VOGEL'S

TEXTBOOK OF MACROAND SEMIMICRO QUAUTATIVE INORGANIC ANALYSIS
FIFTH EOmON

Revised by

G.SVEHLA

VOGEL'S TEXTBOOK OF MACRO AND SEMIMICRO QUALITATIVE INORGANIC ANALYSIS

Fifth Edition Revised by G. Svehla, Ph.D., D.Se., F.R.I.e. Reader in Analytical Chemistry, Queen's University, Belfast

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Longman London and New York

Longman Group Limited London

Associated companies, branches and representatives throughout the world Published in the United States of America by Longman Inc., New York

© Longman Group Limited 1979
All rights reserved. No part of this publication may be reproduced, stored in a retrieval system, or transmitted in any form or by any means, electronic, mechanical, photocopying, recording, or otherwise, without the prior permission of the Copyright owner.
First Published under the title 'A Text-book of Qualitative Chemical Analysis' 1937 Second Edition 1941 Reissue with Appendix 1943 Third Edition under the title 'A Text-book of Qualitative Chemical Analysis including Semimiero Qualitative Analysis' 1945 Fourth Edition under the title 'A Text-book of Macro and Semimicro Qualitative Inorganic Analysis' 1954 New Impression (with minor corrections) 1955 New Impression 1976 Fifth edition 1979
Library of Congress Cataloging in Publication Data Vogel, Arthur I.

Vogel's Macro and semimicro qualitative inorganic analysis. First-3d ed. published under title: A text-book of qualitative chemical analysis; 4th ed. published under title: A text-book of macro and semimicro qualitative inorganic analysis. Includes index. 1. Chemistry, Analytic-Qualitative. 2. Chemistry, Inorganic. I. Svehla, G. 11. Title. Ill. Title: Macro and semimicro qualitative inorganic analysis. QD81.V6 1978 544 77-8290 ISBN 0-582-44367-9 Printed in Great Britain by Richard Clay (The Chaucer Press) Ltd, Bungay, Suffolk
iv

CONTENTS
CHAPTER I THE THEORETICAL BASIS OF QUALITATIVE ANALYSIS
A. Chemical formulae and equations 1.1 Symbols of elements 1.2 Empirical formulae 1.3 Valency and oxidation number 1.4 Structural formulae 1.5 Chemical equations B. Aqueous solutions of inorganic substances 1.6 Electrolytes and non-electrolytes I. 7 Electrolysis, the nature of electrolytic conductance, ions 1.8 Some properties of aqueous solutions 1.9 The theory of electrolytic dissociation 1.10 Degree of dissociation. Strong and weak electrolytes 1.11 The independent migration of ions. Calculation of conductivities from ionic mobilities Modem theory of strong electrolytes 1.12 1.13 Chemical equilibrium; the law of mass action 1.14 Activity and activity coefficients C. Classical theory of acid-base reactions 1.15 Acids, bases, and salts 1.16 Acid-base dissociation equilibria. Strength of acids and bases 1.17 Experimental determination of the dissociation equilibrium constant. Ostwald's dilution law 1.18 The dissociation and ionic product of water 1.19 The hydrogen-ion exponent (PH) 1.20 Hydrolysis 1.21 Buffer solutions 1.22 The experimental determination of pH D. The Brensted-Lowry theory of acids and bases 1.23 Definition of acids and bases
v

1 1 1 3 4 5 6 6 7 9 9 11 15 17 19 22 25 25 28 33 35 36 39 48 53 61 61

1.24 1.25

Protolysis of acids. Strength of acids and bases Interpretation of other acid-base reactions with the Brensted-Lowry theory

64 66 67 67 68 75 83 85 89 89 92 96 97

E. Precipitation reactions 1.26 Solubility of precipitates 1.27 Solubility product 1.28 Applications of the solubility product relation 1.29 Morphological structure and purity of precipitates 1.30 The colloidal state F. Complexation reactions 1.31 The formation of complexes 1.32 The stability of complexes 1.33 The application of complexes in qualitative inorganic analysis 1.34 The most important types of complexes applied in qualitative analysis

G. Oxidation-reduction reactions 100 1.35 Oxidation and reduction 100 101 1.36 Redox systems (half-cells) 1.37 Balancing oxidation-reduction equations 104 1.38 Important oxidizing and reducing agents 108 1.39 Redox reactions in galvanic cells 112 1.40 Electrode potentials 115 1.41 Oxidation-reduction potentials 119 1.42 Calculations based on the Nernst equation 124 1.43 Conclusions drawn from the tables of oxidation-reduction potentials126 1.44 Equilibrium constant of oxidation-reduction reactions 128 H. Solvent extraction 1.45 The distribution or partition law 1.46 The application of solvent extraction in qualitative analysis 130 130 131

CHAPTER 11 EXPERIMENTAL TECHNIQUES OF QUALITATIVE INORGANIC ANALYSIS
11.1 11.2 11.3 11.4 11.5 11.6 Introduction Dry reactions Wet reactions Semimicro apparatus and semimicro analytical operations Micro apparatus and microanalytical operations Spot test analysis

135 135 136 145 153 173 180 191 191 192

CHAPTER III REACTIONS OF THE CATIONS
IIU III.2

Classification of cations (metal ions) into analytical groups Notes on the study of the reactions of ions
vi

111.3 IlIA III.5 . III.6 III.7

III.8 III.9 Ill. 10 Ill. 11 Ill. 12 III.13 Ill. 14 IIU5 Ill. 16 III.17 IIU8 Ill. 19 III.20 111.21 III.22 III.23 III.24 1II.25 III.26 III.27 III.28 III.29 Ill. 30 III.31 III.32 III.33 III.34 111.35 III.36 III.37 111.38

First group of cations: lead(II), mercury(l) and silver(l) Lead, Pb (A r : 207'2) Mercury, Hg (A r : 200'59) - Mercury(l) Silver, Ag (A r : 107'9) Second group of cations: mercury(II), lead(II), bismuth(III), copper(II), cadmium(II), arsenic(III) and (V), antimony(III) and (V), tin(lI) and (IV) Mercury, Hg (A r : 200'59) - Mercury(lI) Bismuth, Bi (A r : 208'98) Copper, Cu (A r : 63'55) Cadmium, Cd (A r : 112'90) Arsenic, As (A r : 74'92) - Arsenic(III) Arsenic, As (A r : 74'92) - Arsenic(V) Special tests for small amounts of arsenic Antimony, Sb (A r : 121'75) - Antimony(III) Antimony, Sb (A r : 121'75) - Antimony(V) Special tests for small amounts of antimony Tin, Sn (A r : 118'69) - Tin(lI) Tin, Sn (A r : 118'69) - Tin(IV) Third group of cations: iron(lI) and (Ill), aluminium, chromium(III), nickel, cobalt, manganese(lI) and zinc Iron, Fe (A r : 55'85) - Iron(ll) Iron, Fe (A r : 55'85) - Iron(III) Aluminium, Al (A r : 26'98) Chromium, Cr (A r : 51'996) - Chromium(III) Oxianions of group III metals: chromate and permanganate Cobalt, Co (A r : 58'93) Nickel, Ni (A r : 58.71) Manganese, Mn (A r : 54'938) - Manganese(lI) Zinc, Zn (A r : 63'58) Fourth group of cations: barium, strontium, and calcium Barium, Ba (A r : 137'34) Strontium, Sr (A r : 87'62) Calcium, Ca (A r : 40'08) Fifth group of cations: magnesium, sodium, potassium, and ammonium Magnesium, Mg (A r : 24' 305) Potassium, K (A r : 39'098) Sodium, Na (A r : 22'99) Ammonium, NH 4 (M r : 18'038)

193 194 199 204

208 209 212 215 221 223 225 228 231 234 236 237 240 241 241 245 250 254 259 259 264 268 272 277 278 281 282 285 285 289 291 293 297 297 298 300

CHAPTER IV REACTIONS OF THE ANIONS
IV.l IV.2 IV.3 Scheme of classification Carbonates, CO~Hydrogen carbonates, HC0 3 vii

IV.4 IV.5 IV.6 IV.7 IV.8 IV.9 IV.lO IV.ll IV.12 IV.13 IV.14 IV.15 IV.16 IV.17 IV.18 IV.19 IV.20 IV.21 IV.22 IV.23 IV.24 IV.25 IV.26 IV.27 IV.28 IV.29 IV.30 IV.31 IV.32 IV.33 IV.34 IV.35 IV.36 IV.37 IV.38 IV.39 IV.4O IV.41 IV.42 IV.43 IV.44 IV.45

Sulphites, SO~Thiosulphates, S20~Sulphides, S2Nitrites, N0 2 Cyanides, CNCyanates, CNOThiocyanates, SCNHexacyanoferrate(II) ions, [Fe(CN)6]4Hexacyanoferrate(III) ions, [Fe(CN)6]3Hypochlorites, OCIChlorides, ClBromides, BrIodides, 1Fluorides, FNitrates, N0 3 Chlorates, CI0 3 Bromates, Br0 3 Iodates, 10 3 Perchlorates, CIO; Borates, BO~-, B40~-, B0 2 Sulphates, soiPeroxodisulphates, S20~­ Silicates, SiO~Hexafluorosilicates (silicofluorides), [SiF6]2Orthophosphates, PO~Pyrophosphates, P20~-, and metaphosphates, P0 3 Phosphites, HPO~Hypophosphites, H 2P0 2 Arsenites, AsO~ -, and arsenates, AsO~­ Chromates, CrOi-, and dichromates, Cr20~­ Permanganates, MnO; Acetates, CH 3COOFormates, HCOOOxalates, (COO)~Tartrates, C4H40~Citrates, C6HsO~Salicylates, C 6H4(OH)COO- or C 7H s0 3 Benzoates, C 6HsCOO- or C 7H s0 2 Succinates, C 4H 40iHydrogen peroxide, H 202 Dithionites, S20iSpecial tests for mixtures of anions

301 305 308 310 313 316 317 319 322 323 325 327 329 332 334 337 339 340 342 343 346 349 350 353 354 358 358 360 361 361

364
366 368 369 371 374 376 377 378 379 382 383

viii

CHAPTER V SYSTEMATIC QUALITATIVE INORGANIC ANALYSIS
V.l V.2 V.3 VA V.5 V.6 V.7 V.8 V.9 V.IO V.11 V.l2 V.13 V.l4 V.15 V.16 V.17 V.18 V.19 Introduction Preliminary tests on non-metallic solid samples Preliminary tests on metal samples Preliminary tests on liquid samples (samples in solution) Preliminary tests on insoluble substances Dissolution of the sample Examination of the insoluble residue Separation of cations into groups Separation and identification of the Group I cations (silver group) Separation of Group 11 cations into Groups IIA and lIB Separation and identification of Group IIA cations Separation and identification of Group lIB cations Removal of interfering ions before the precipitation of the Group III cations Separation and identification of Group IlIA cations Separation and identification of Group IIIB cations Separation and identification of Group IV cations Identification of Group V cations Preliminary tests for and separation of certain anions Confirmatory tests for anions

395 395 395
405 406 407

411 411 413 420 421 424 428 431 436 437
441 444

446 458

CHAPTER VI SEMIMICRO QUALITATIVE INORGANIC ANALYSIS
VI.l VI.2 Introduction The study of reactions of cations and anions on the semimicro scale Systematic analysis on the semimicro scale. General considerations Preliminary tests on the semimicro scale Testing for anions in solution on the semimicro scale Confirmatory tests for anions on the semimicro scale Special tests for mixtures of anions on the semimicro scale Preparation of solution for cation testing on the semimicro scale Separation of cations into groups on the semimicro scale Separation and identification of Group I cations on the semimicro scale Separation of Groups IIA and lIB and separation and identification of Group IIA cations on the semimicro scale Separation and identification of Group lIB cations on the semimicro scale
ix

461 461 461 463 464 470 473 476 479 480 485 485 487

VU
VIA VI.5 VI.6 VI.7 VI.8 VI.9 VI. 10 VI.ll VI.l2

VI.l3 VI.l4 VI.l5 VI.l6 VI.17 VI.l8 VI.l9 VI.20

Separation and identification of Group IlIA cations on the semimicro scale Separation and identification of Group IIIB cations on the semimicro scale Separation and identification of Group IV cations on the semimicro scale Identification of Group V cations on the semimicro scale Modifications of separation procedures in the presence of interfering anions Separations by paper and thin layer chromatography. General introduction Apparatus and technique for chromatographic separations Procedures for selected chromatographic separations

488 489 490 492 493 495 497 500 507 507 507 509 509 511 511 514 516 518 520 521 522 523

CHAPTER VII REACTIONS OF SOME LESS COMMON IONS
VII.l VII.2 VII.3 VII.4 VII.5 VII.6 VII.7 VII.8 VII.9 VII. 10 VII. 11 VII.12 VII.13 VII.14 Introduction Thallium, Tl (A r : 204·34) - Thallium(l) Thallium, Tl (A r : 204·34) - Thallium(III) Tungsten, W (A r : 183·85) - Tungstate Separation and identification of Group I cations in the presence of thallium and tungsten Molybdenum, Mo (A r : 95·94) - Molybdate Gold, Au (A r : 196·97)- Gold(III) Platinum, Pt (A r : 195·09) Palladium, Pd (A r : 106·4) Selenium, Se (A r : 78·96) - Selenites, SeO~Selenium, Se (A r : 78·96) - Selenates, SeOiTellurium, Te (A r : 127·60) - Tellurites, TeO~Tellurium, Te (A r : 127·60) - Tellurates, TeOiSeparation and identification of Group 11 cations in the presence of molybdenum, gold, platinum, palladium, selenium, and tellurium Vanadium, V (A r : 50·94) - Vanadate Beryllium, Be (A r : 9·01) Titanium, Ti (A r : 47·90) - Titanium(lV) Zirconium, Zr (A r : 91·22) Uranium, U (A r : 238·03) Thorium, Th (A r : 232·04) Cerium, Ce (A r : 140·12)- Cerium(III) Cerium, Ce (A r : 140·'12) - Cerium(lV) Separation of Group III cations in the presence of titanium, zirconium, thorium, uranium, cerium, vanadium, thallium, and molybdenum Lithium, Li (A r : 6·94) The borax bead test in the presence of less common cations
x

VII.15 VII. 16 VII.17 VII.18 VII.19 VII.20 VII.21 VII.22 VII.23

524 527 530 532 535 538 540 541 542

VII.24 VII.25

544 546 548

CHAPTER VIII AN ABBREVIATED COURSE OF QUALITATIVE INORGANIC ANALYSIS
VIII. 1 Introduction VIII.2 Reactions of cations and anions VIII. 3 Systematic analysis. General considerations

550 550 550 551 552 553 556 557

VIllA
VIII.5 VIII.6 VIII.7 VIII. 8 VIII. 9

Preliminary tests on solutions Testing for anions in solution Confirmatory tests for anions Special tests for mixtures of anions Separation and identification of cations in solution Modifications in the presence of anions of organic acids, fluoride, and phosphate

560 564
566
566

IX APPENDIX
IX.l IX.2 IX.3 IXA IX.5 IX.6 IX.7 IX.8 Relative atomic masses of the elements Reagent solutions and gases Solid reagents Solubilities of salts and bases in water at 18°C Logarithms Antilogarithms Concentrated acids and bases Periodic table of the elements

568 589 592 593 595 597 598 599

INDEX

xi

FROM PREFACE TO THE FIRST EDITION
Experience of teaching qualitative analysis over a number of years to large numbers of students has provided the nucleus around which this book has been written. The ultimate object was to provide a text-book at moderate cost which can be employed by the student continuously throughout his study of the subject. It is the author's opinion that the theoretical basis of qualitative analysis, often neglected or very sparsely dealt with in the smaller texts, merits equally detailed treatment with the purely practical side; only in this way can the true spirit of qualitative analysis be acquired. The book accordingly opens with a long Chapter entitled 'The Theoretical Basis of Qualitative Analysis', in which most of the theoretical principles which find application in the science are discussed. The writer would be glad to hear from teachers and others of any errors which may have escaped his notice: any suggestions whereby the book can be improved will be welcomed.
Woolwich Polytechnic

A. I. Vogel London S.E.18

xiii

CHAPTER I

THE THEORETICAL BASIS OF QUALITATIVE ANALYSIS

A. CHEMICAL FORMULAE AND EQUATIONS
1.1 SYMBOLS OF THE ELEMENTS To express the composition of substances and to describe the qualitative and quantitative changes, which occur during chemical reactions in a precise, short, and straightforward way we use chemical symbols and formulae. Following the recommendations of Berzelius (1811), the symbols of chemical elements are constructed by the first letter of their international (Latin) names with, in most cases, a second letter which occurs in the same name. The first letter is a capital one. Such symbols are: (oxygen, oxygenium) H (hydrogen, hydrogenium), C (carbon, carbonium), Ca (calcium), Cd (cadmium), Cl (chlorine, chlorinum), Cr (chromium), Cu (copper, cuprum), N (nitrogen, nitrogenium), Na (sodium, natrium), K (potassium, kalium), etc. As well as being a qualitative reference to the element, the symbol is most useful in a quantitative context. It is generally accepted that the symbol of the element represents 1atom of the element, or, in some more specific cases, 1 grammatom. Thus C represents 1 atom of the element carbon or may represents represent 1 grammatom (12'011 g) of carbon. In a similar way, one atom of oxygen or one grammatom (15'9994 g) of oxygen, H represents one atom of hydrogen or 1 grammatom (1'0080 g) of hydrogen etc. Names, symbols, and relative atomic masses of the elements are given in Section IX.l.

°

°

1.2 EMPIRICAL FORMULAE To express the composition of materials whose molecules are made up of more atoms, empirical formulae are used. These are made up of the symbols of the elements of which the substance is formed. The number of atoms of a particular element in the molecule is written asa subscript after the symbol of the element (but 1is never written asa subscript as the symbol of the element on its own represents one atom). Thus, the molecules of carbon dioxide is formed by one carbon atom and two oxygen atoms, therefore its empirical formula is CO 2 , In the molecule of water two hydrogen atoms and one oxygen atom are present, therefore the empirical formula of water is H 2 0 . In the molecule of hydrogen peroxide on the other hand there are two hydrogen and two oxygen atoms present, its empirical formula is therefore H 2 0 2 • Although there are no strict rules as to the order of symbols appearing in a formula, in the case of inorganic substances the symbol of the metal or that of hydrogen is generally written first followed by non-metals and finishing with oxygen. In the formulae of organic substances the generally accepted order is C, H, 0, N, S, P.

= l'()()80+35'453 = 36'4610 and that of sulphuric acid (H 2 S0 4 ) is M. in hydrochloric acid (HCl) the relative amounts of the hydrogen and chlorine are H :Cl = 1'0080: 35·453 = 1'0000: 35'172 and (as the relative molecular mass of hydrochloric acid is 36"461) it contains 1·008 100 x 36'461 = 2'76 per cent H and 35'453 100 x 36'461 = 97'24 per cent Cl Similarly. the relative amounts of the elements in sulphuric acid (H 2S04 ) are H:S:O = 2x 1.2 QUALITATIVE INORGANIC ANALYSIS The determination of the empirical formula of a compound can be made experimentally. and oxygen. From these data the empirical formula can be determined by a simple calculation. the relative molecular mass of hydrochloric acid (HCl) is calculated as follows: M. If the empirical formula of a compound is known. = 2 x 1'0080 + 32·06 + 4 x 15'9994 = 98·0736 and so on. In this summation care must be taken that the relative atomic mass of a particular element is multiplied by the figure which shows the number of its atoms in the molecule. Thus. and four oxygen atoms are present etc. For such calculations the relative atomic masses of the elements in question must be used. If. Sulphuric acid (H 2 S0 4 ) consists of hydrogen. At the same time the relative molecular mass of the compound has to be measured as well. (b) From the empirical formula the relative molecular mass (molecular weight) can be determined simply by adding up the relative atomic masses (atomic weights) of the elements which constitute the compound. and how many atoms of each element form the molecule of the compound. These are as follows: (a) From the empirical formula of a compound we can see which elements the compound contains.1. for some reason. Thus. in its molecule two hydrogen. Thus. the true formula might contain multiples of the atoms given in the assumed formula. it is impossible to determine the relative molecular mass the simplest (assumed) formula only can be calculated from the results of chemical analysis. sulphur. in its molecule one hydrogen and one chlorine atom are present.0080:32'06:4 x 15'9994 = 2'016: 32'06:63'9976 1: 15'903:31'745 2 . hydrochloric acid (HCl) contains hydrogen and chlorine. we can draw several conclusions about the physical and chemical characteristics of the substance. one sulphur. by determining the percentage amounts of elements present in the substance using the methods of quantitative chemical analysis. (c) Based on the empirical formula one can easily calculate the relative amounts of the elements present in the compound or the percentage composition of the substance.

Si). (The gas here is considered to be a perfect gas. for example. if the formula is known . By comparing these formulae one can see that one atom of some of the elements (like Cl.THEORETICAL BASIS 1. bromine. When looking at the empirical formulae of various substances the question arises: are there any rules as to the number of atoms which can form stable molecules? To understand this let us examine some simple compounds containing hydrogen. and iodide are monovalent. The valency of such elements can therefore be determined only in an indirect way. the volume of the gas (v) is v = mRT t pMr where R is the gas constant.1. From this it seems obvious that the valency of an element can be ascertained from the composition of its compound with hydrogen. M. do not combine with hydrogen at all. Br. we can say that chlorine. while others combine with two (0. Thus. Hydrogen itself is a monovalent element. similarly from the composition of aluminium chloride (AIC13 ) or aluminium oxide (A120 3 ) it is obvious that aluminium is a tervalent metal etc. three (N. which represents one of the most important chemical characteristics of the element. by examining the composition of their compounds formed with chlorine or oxygen and finding out the number of hydrogen atoms these elements replace. is the relative molecular mass of the substance in g mol.3 and knowing that the relative molecular mass of sulphuric acid is 98. T is the absolute temperature in degrees kelvins. nitrogen and phosphorus tervalent. Such compounds are.0763. Thus. hydrogen sulphide (H 2S). is called the valency. (d) Finally. carbon and silicon tetravalent elements and so on. water (H 20). from the formulae of magnesium oxide (MgO) and magnesium chloride (MgC12 ) we can conclude that magnesium is a bivalent metal.1 units and m is the weight of the gas in grams. If p is the pressure in atmospheres. and silane (H 4Si).which of course means that the relative molecular mass is available . and I) will bind one atom of hydrogen to form a stable compound. oxygen and sulphur bivalent. for example some of the metals. 0'0823 t atm K . Some of the elements. 3 . phosphine (H 3P). This number. ammonia (H 3N). hydrogen chloride (HCl). hydrogen bromide (HBr). we can calculate its percentage composition which is 2'0160 100 x 98'0736 = 2'06 per cent H 32'06 100 x 98'0736 = 32'69 per cent S and 63'9976 100 x 98'0736 = 65'25 per cent ° and so on. methane (H 4C).1 mol.) 1. S). hydrogen iodide (HI).we can calculate the volume of a known amount of a gaseous substance at a given temperature and pressure. P) or even four (C.3 VALENCY AND OXIDAnON NUMBER In the understanding of the composition of compounds and the structure of their molecules the concept of valency plays an important role.

for example. tri-.. Melior op. becoming thus a species with one positive charge. etc. for example. oxygen. the uptake or release of electrons corresponds to reduction or oxidation (cf. 155 et f. Each valency can be represented by a single line drawn outwards from the symbol of the element. The oxidation number is a number identical with the valency but with a sign. .Cl.35). A three dimensional representation with true directions and proportional distances can most adequately be made with molecular model kits. Some elements.0= N=: C=: The structural formulae of compounds can be expressed with lines drawn between the atoms ~ like * Cf. like er. its oxidation status is different. Section 1. seem always to have the same valency in all of their compounds. 4 . Br. or the alkali metals. It is useful to define the concept of oxidation number and to use it instead of valency. Nor is there any restriction on the distances of atoms. A deeper study of the composition of compounds and of the course of chemical reactions reveals that the classical concept of valency. Structural formulae must therefore be regarded only as a step in the approximation of the true structure. From the theory of chemical bonding'[ we know that when forming hydrochloric acid. through which chemical bonds are formed.4 STRUCTURAL FORMULAE Using the concept of valency the composition of compounds can be expressed with structural formulae. Similarly we can say that the oxidation number of chlorine in chlorous acid (HCI0 2 ) is + 3. if hypochlorous acid is formed. It is true that compounds of the same element with different valencies show different physical and chemical characteristics. in chloric acid (HCI0 3 ) is + 5. we can therefore say that though chlorine is monovalent in these acids. while it is + 1 in hypochlorous acid. as defined above." If necessary the valency of the element is denoted by a roman numeral following the symbol like Cl(I).1. p. N(III) or as a superscript. Thus. but the marked differences in the chemical behaviour of these two acids indicate that the status of chlorine in these substances is completely different. Melior's Modern 1967. Other elements however show different valencies. is not quite adequate to explain certain phenomena. newly revised and edited by G. and in perchloric acid (HCI0 4 ) + 7. Longman t Cf. chlorine can be mono-. the chlorine atom releases an electron.4 QUALITATIVE INORGANIC ANALYSIS In conclusion we can say that the valency of an element is a number which expresses how many atoms of hydrogen or other atoms equivalent to hydrogen can unite with one atom of the element in question. expressing the nature of the charge of the species in question when formed from the neutral atom. There are no restrictions about the direction of these lines (unless differentiation has to be made between stereochemical isomers). Nlll. 1. 99 et f. chlorine is monovalent both in hydrochloric acid (HCl) and in hypochlorous acid (HCIO). Parkes. D. Thus. cit. a chlorine atom takes up an electron. On the other hand. Br(I). As we know. Each valency of an element can be regarded as an arm or hook. The concept of oxidation number will be used extensively in the present text.1. Inorganic Chemistry. penta.or heptavalent in its compounds. like hydrogen. the oxidation number of chlorine in hydrochloric acid is . p. thus. thus acquiring one negative charge. like H.

In the cases of equilibrium reactions'[ when the reaction may proceed in both directions.THEORETICAL BASIS 1. an appropriate stoichiometric number has to be written in front of the formula. This number is a multiplication factor. must be written correctly. 155. the sides generally cannot be interchanged (in this sense chemical equations are not equivalent to mathematical equations). beginners should study appropriate textbooks. When writing chemical equations the following considerations must be kept in mind: (a) Because of the fact that the formulae of the reacting species are on the left-hand side and those of the products are on the right. newly revised and edited by G. p. used in the chemical reactions.* Readers should be reminded that the simple hexagon o (Oor@l represents the benzene ring. These equations contain the formulae of the reacting substances on the left-hand side and the formulae of the products on the righthand side. t Theoretically speaking.5 CHEMICAL EQUATIONS Qualitative and quantitative relationships involved in a chemical reaction can most precisely be expressed in the form of chemical equations. D. for example 2Ca3(P04h means that we have 6 calcium. which applies to all atoms in the formula. 4 phosphorus. 1. This equilibrium however may be shifted completely towards the formation of the products. (b) The individual formulae. the double arrow (+2) sign should be used instead of the equal ( = ) or single arrow ( -+ ) sign. all reactions lead to an equilibrium.5 o . Longman 1%7. Parkes. A more detailed discussion of structural formulae will not be given here.) * Cr. (c) If more molecules (atoms or ions) of the same substance are involved in the reaction. Benzene (C 6H 6 ) can namely be described with the (simplified) ring formula in which double and single bonds are alternating (so-called conjugate bonds): H H-C:~-H I H H-~):'<j:-H I All the aromatic compounds contain the benzene ring.f H-C1 H N H H-O-H H C '\ o I H /"- I H-C-H I H Structural formulae will be used in this text only when necessary. (Thus. Melior's Modern Inorganic Chemistry. mainly when dealing with organic reagents. and 16 oxygen atoms in the equation. 5 .

CO 2(g). AQUEOUS SOLUTIONS OF INORGANIC SUBSTANCES 1. as a charged particle. while the notation aq is used for species dissolved in water. It is useful to denote the physical state of the reaction partners. It is therefore important to have a general knowledge of the characteristics of aqueous solutions of inorganic substances. Doing so we can see that there are 3 calcium. and volumes (of gaseous substances only) can be calculated on the basis of chemical equations. e.2. Now we try to balance the equation by applying suitable stoichiometric numbers: 3Ca(OH)2 + 2H 3P04 = Ca3(P04h + 6H 20 It is advisable to check the equation by counting the numbers of individual atoms on both sides. we can write the formulae of the substances into the yet incomplete equation: Ca(OHh + H 3P04 -+ CaiP0 4h + H 20 (incomplete) (note that the sides of the equation cannot be interchanged. H 3P04aq. For this purpose the letters s. without parenthesis e. and gaseous substances respectively.O(l). B. Following those considerations discussed in Section 1. 12 hydrogen and 14 oxygen atoms on both sides. In the present text we shall use them in some cases. These letters are used in parenthesis after the formula. AgCl(s). will be denoted by e" in this text. The formation of a precipitate will be denoted by a ! sign (indicating that the precipitate settles to the bottom of the solution) while the liberation of gases will be denoted by a i sign. because the reaction will not proceed in the inverse direction). As an example let us express the equation of the reaction between calcium hydroxide and phosphoric acid. Other solvents are rarely employed except for special tests or operations. Such calculations are involved in all kinds of quantitative analyses based on chemical reactions.g. If not otherwise stated. which is strictly valid for all chemical reactions. H?. This means.6 ELECTROLYTES AND NON-ELECTROLYTES Quantitative inorganic analysis is based mainly on the observation of chemical reactions carried out in aqueous solutions. that the equation should be balanced by applying proper stoichiometric numbers in such a way that the numbers of different individual atoms are the same on both sides. the sum of charges on the left-hand side must be equal to the sum of charges on the right-hand side. while the aq follows the formula simply. 2 phosphorus. Knowing that the products of such a reaction are calcium phosphate and water. and g are applied for solid. The systematic use of these notations is important only in thermodynamics.. The electron.6 QUALITATIVE INORGANIC ANALYSIS (d) A chemical equation must be written in such a way that it fulfils the law of conservation of mass. these charges must be clearly indicated (like Fe 3 + or Fe + + +) and properly balanced. that is when the energetics of the reactions are examined. equations will refer to reactions proceeding in dilute aqueous solutions. 6 . liquid. mass balances.g. relative masses. 1. (e) If charged species (ions or electrons) are involved in the reaction.1.

The former substances are termed electrolytes. glucose. all inorganic substances (like acids. metals). as already stated.7 A solution is the homogeneous product obtained when a substance (the solute) is dissolved in the solvent (water). bases. do not conduct electricity and which remain unchanged. while that with the positive charge is termed the anode. Cathode Source of current (battery) Fig I. glycerine. while anions do the same on the anode.c. and salts).----IIII!I!I! t----------. With the aid of a battery (or another d. ethanol. 1. Substances can be classified into two important groups according to their behaviour when an electric current is passed through their solution.THEORETICAL BASIS 1. the latter are designated non-electrolytes. in a battery (like the Daniell-cell) the anode is the negative and the cathode is the positiveelectrode. THE NATURE OF ELECTROLYTIC CONDUCTANCE. are immersed. cathode is the electrode where cations lose their charge.. 1.. The whole process is called electrolysis. mannose. the solutions undergo chemical changes thereby. the so called electrodes. IONS Chemically pure water practically does not conduct electricity.7 ELECTROLYSIS. acids. e. may not yield a conducting solution in another solvent such as ether or hexane. 7 . bases. or salts are dissolved in it. According to Faraday's nomenclature. It must be pointed out that a substance which behaves as an electrolyte in water.l two solid conductors (e. the resultant solution not only conducts the electric current.g. source) a potential difference is applied between the two electrodes. In the first class there are those which conduct electric current. and are exemplified by such organic materials as cane sugar. sodium chloride. The electrolyte solution is placed in a vessel. The second class is composed of materials which. * * It must be emphasized that the terms cathode and anode correspond to the negative and positive electrodes respectively only in electrolysis cells. and urea. In the molten state most electrolytes will conduct electricity. with few exceptions. into which . Phenomena occurring during electrolysis can be studied in the electrolysis cell shown in Fig.1.. but undergoes chemical changes as well. Consequently.. The electrode with the negative charge in the electrolysis cell is called the cathode. ifhowever. when dissolved in water. and these include.g.

while those of chlorine or dichromate must be negatively charged.c.. This solution can be placed in a U-shaped electrolysis cell and topped up with a colourless layer of dilute sulphuric acid on each side (Fig. it is obvious that those particles which move towards one of the electrodes must be charged and that this charge must be opposite to that of the electrode towards which they move. If this solution is then electrolysed.. but they are composed of ions. Faraday termed the charged particles in the electrolyte ions.7 QUALITATIVE INORGANIC ANALYSIS The chemical change occurring-during the course of electrolysis is observable on or in the vicinity of the electrodes.. Cations and anions are present in equivalent amounts and are dispersed evenly in the solution among the molecules of the solvent. P t .-.. As the blue colour is associated with copper and the orange with dichromate. 1.1. iI---Pt Blue (Cu 2"')- - --f. If for example a dilute solution of hydrochloric acid is electrolysed (between platinum electrodes). The migration of such particles is a result of the electrostatic attraction force. the concentration of hydrochloric acid in the solution decreases. 8 .. macroscopic portions of the solution therefore appear to be electrostatically neutral in all cases. Thus the particles of hydrogen or copper. It can be stated generally that solutions of electrolytes do not contain neutral molecules dispersed among the molecules of the solvent. a brownish solution is obtained.. As such a movement can be achieved solely by electrolysis.:. 1. the hitherto colourless solution next to the cathode slowly becomes blue. In many cases such a change is a simple decomposition. which move towards the cathode. must be positively charged. hydrogen gas is liberated on the cathode and chlorine on the anode. It is easy to demonstrate that electrolysis is always accompanied by the transport of material in an electrolysis cell. as solutions of non-electrolytes do. it can be said that copper moves towards the cathode and dichromate towards the anode during the electrolysis. which is created when switching on the current. If for example the blue solution of copper sulphate and the orange solution of potassium dichromate are mixed in equimolar concentrations.2). while d.l Fig. the positively and negatively charged ions were called cations and anions respectively.2 the solution next to the anode becomes orange.

its molecules will be present as individual particles in the solution.8/9 1. Thus. we can say that equal numbers of particles. This dissociation is a reversible process. Since the solution is electrically neutral. To explain these facts. The electrolytic dissociation (ionization) of compounds may therefore be represented by the reaction equations: NaCl +2 Na+ +ClMgS0 4 +2 Mg2+ + SO~­ CaC12 +2 Ca2+ +2ClNa2S04 +2 2Na+ +SO~Ions carry positive or negative charges. dissociate into charged atoms or groups of atoms. while in the case of calcium chloride or sodium sulphate there are three particles present for each molecule. 3 . will show identical osmotic pressure. and have the same effect upon the lowering of vapour pressure. and the elevation of the boiling point. According to 'this theory. etc. we can say that the number of particles in the solution of sodium chloride or magnesium sulphate is twice the number of molecules present. On such a basis it is possible to determine the relative molecular mass of soluble non-electrolyte substances experimentally. by measuring the above quantities. the total number of positive charges must be equal to the total number of negative charges in a solution. dissolved in the same weight of solvent. for example. lowering of vapour pressure. which are in fact the ions which conduct the current in electrolytes by migration. At very great dilutions the dissociation is practically complete for all electrolytes. the degree of dissociation varies with the degree of dilution. will acquire identical osmotic pressures. 1 mole of a non-electrolyte when dissolved in 1aoo g of water lowers. or elevation of the boiling point. seemingly independent.9 THE THEORY OF ELECTROLYTIC DISSOCIATION In Sections 1. when dissolved in water. and that in solutions of electrolyte substances the number of particles are 2.8 two. Arrhenius put forward his theory of electrolytic dissociation (1887). experimental facts were described. Using water as a solvent. present in the same amount of solution. the molecules of electrolytes. the freezing point of water by 1·86°C and elevates its boiling point by a·52°e.7 and 1. with calcium chloride or sodium sulphate these quantities are three times those expected. When substances like sodium chloride or magnesium sulphate are examined. When a non-electrolyte is dissolved in water..8 SOME PROPERTIES OF AQUEOUS SOLUTIONS It has been found experimentally that equimolecular quantities of non-electrolytes. the depression of the freezing point. When electrolyte solutions are subjected to such measurements. These are that electric current is conducted by the migration of charged particles in the solution of electrolytes.THEORETICAL BASIS 1. the depression of freezing point or the elevation of boiling point is about twice that calculated from the relative molecular mass. Consequently. times greater than the number of molecules dissolved. the number of particles present in the solution can be determined. Keeping in mind what has been said above. 9 . The number of charges carried by an ion is equal to the valency of the atom or radical. 1. abnormal results are obtained.. depression of the freezing point.

besides the colourless potassium and sulphate ions: CUS04 +2 Cu2+ + SOiK 2Cr20 7 +2 2K+ +Cr 20iand this is why copper ions (together with potassium ions) moved towards the negatively charged cathode.9 QUALITATIVE INORGANIC ANALYSIS The explanation of the abnormal results obtained when measuring the depression of freezing point or elevation of boiling point is straightforward on the basis of the theory of electrolytic dissociation. when arriving at the cathode first take up an electron to form a neutral hydrogen atom: H+ +e.1. In the solution. while dichromate ions (as well as sulphate ions) moved towards the positively charged anode. while chloride ions will move towards the anode. Returning to the example of the electrolysis of hydrochloric acid. owing to electrostatic forces. containing copper sulphate and potassium dichromate we have the blue copper(II) ions and the orange dichromate ions present. as said before.-+ H Pairs of hydrogen atoms will then form hydrogen molecules. where they are then taken up by hydrogen ions. forming chlorine atoms: -+ Cl+eCl 2(g) which again will form chlorine molecules: 2Cl -+ and are discharged in the form of chlorine gas. which. which are discharged in the form of hydrogen gas: 2H Cl-+ H 2(g) On the anode the chloride ions release electrons. will start to migrate towards the electrode with opposite charge. because both substances yield two ions per molecule when dissociated. The phenomenon of electrolysis also receives a simple explanation on the basis of the theory of electrolytic dissociation. and travel through the electric circuit to the cathode. The conductance of electrolyte solutions is due to the fact that ions (charged particles) are present in the solution. when switching on the current. the electrode processes are as follows: hydrogen ions. Similarly. where. In the case of hydrochloric acid we have hydrogen and chloride ions in the solution: HCl +2 H+ +Cland it is obvious that hydrogen ions will migrate towards the cathode. because these substances yield three ions from each molecule when dissociating. Those changes occurring on the electrodes during electrolysis can also be explained easily on the basis of the theory of electrolytic dissociation. the depression of freezing point or elevation of boiling point of calcium chloride or sodium sulphate solutions are three times as great as of an equimolar solution of a non-electrolyte. hydrogen ions migrate towards the cathode and chloride ions towards the anode. 10 . The electrons are taken up by the anode. In the case of sodium chloride and magnesium sulphate the measured values are twice as great as those calculated from the relative molecular mass. mentioned earlier.

like temperature). It is not necessarily the cation or anion of the dissolved substance. even though these ions carry the electrical current by migration. As hydrogen ions are removed from the vicinity of the cathode. 11 . This rule is true for any kind of electrochemical process. which reacts on the electrodes. where hydrogen ions will be in excess and the solution there becomes acidic. Hydrogen and sulphate ions are left behind in the solution. The degree of dissociation (IX) is equal to the fraction of the molecules which actually dissociate. neither sodium nor sulphate ions (Na2S04 P 2Na + + SOi-) will be discharged. Sections 1. e. If for example sodium sulphate is electrolysed (with platinum electrodes). Finally. it was stated that it is a reversible process and its extent varies with concentration (and also with other physical properties. The discharge of hydroxyl ions on the anode results in the formation of oxygen gas: 40H-+ 4e.+2H 20+02(g) The competition of various ions at the electrodes for discharge may lead to various combinations. hydrogen and chloride ions are discharged in the form of hydrogen and chlorine gas on the cathode and anode respectively. and the successful ion is the one which needs the least energy for discharge. Sodium and hydroxyl ions are left behind. Using electrochemical terms we can say that under given circumstances the ion which requires a lower negative electrode potential will be discharged first on the cathode. In aqueous solutions very small amounts of hydrogen and hydroxyl ions are always present due to the slight dissociation of water (cf. STRONG AND WEAK ELEC- TROLYTES When discussing the theory of electrolytic dissociation. while the one that requires a lower positive potential will be discharged on the anode. making the latter acidic. but hydrogen and hydroxyl ions.THEORETICAL BASIS 1.g. the result of the electrolysis therefore is the formation of hydrogen gas on the cathode and oxygen on the anode. if copper sulphate (CuS0 4 P Cu2+ + SOi-) is electrolysed under the same circumstances. while the release of electrons is associated with oxidation.24): H 20 P H+ +OHThe ions of the dissolved substance and hydrogen as well as hydroxyl ions compete for discharge on the electrodes.18 and 1. The opposite happens around the anode. but it is always true that electrons are taken up by ions on the cathode and electrons are released by ions on the anode. copper and hydroxyl ions will be discharged. In later parts of the present text we shall see that the uptake of electrons always means reduction. it again becomes neutral.10 The phenomena of electrolysis are not always as simple as discussed in connection with hydrochloric acid. while oxygen gas is liberated on the anode. Briefly therefore we can say that during the course of electrolysis reduction takes place on the cathode. while oxidation occurs on the anode. When electrolysing sodium chloride (NaCl P Na" +Cl-) under similar circumstances. and the whole solution becomes alkaline. 1. When after the electrolysis the solution is mixed. making this part of the solution alkaline.10 DEGREE OF DISSOCIATION. the hydroxyl-ion concentration will surpass that of the hydrogen ions. the cathode being coated with a layer of copper metal. the same is true for the operation of electromotive cells (batteries).

The reciprocal of the specific resistance is termed i-I * It is not in fact necessary to use such a particular cell for the measurements. p.o: The sum of these is equal to i. is closely associated with the number of particles present in the solution. provided that its 'cell constant' has been determined by a calibration procedure. as this is an average number. The ratio of these ~ ----= ~ (obs) (theor) I . using an electrolyte (e. is expressed in n cm units.1. If o: = 0. while if o: = 1 dissociation is complete. potassium chloride solution). If 1 mole of this electrolyte is dissolved. will determine the conductivity of the solution. * This cell can then be connected as the unknown resistance in a Wheatstone-bridge circuit. which is fed by a perfectly symmetrical (sinusoidal) alternating current at low voltage. the experimental values of these were found to be higher than the theoretical ones. The cryoscopic and ebullioscopic techniques are based on the measurement of the depression of the freezing point and the elevation of the boiling point respectively. as it cannot be measured as such. we can calculate the total number of particles (ions plus undissociated molecules) in the following way: the number of ions (per molecule) will be na. This number can easily be associated with the degree of dissociation. Conductivity itself is a derived quantity. and the degree of dissociation is a. o: can be computed easily. This method is associated with the fact that the electric current is carried by the ions present in the solution. two parallel faces of which are made of a conductor (platinum). with a known specific resistance. Let us consider an electrolyte which when dissociated gives rise to the formation of n ions per molecule. the van't Hoff coefficient: i=nrx+l-rx= l+(n-l)rx from which the degree of dissociation can be expressed as rx=-n-l Thus. their relative number. The value i (called van't Hoff's coefficient) gives the average number of particles formed from one molecule. The specific resistance. i is not an integer. 12 . An important method of determining the degree of dissociation is based on the measurement of the conductivity of the electrolyte in question (conductivity method). The degree of dissociation can be determined by various experimental methods. It is always greater than unity.10 QUALITATIVE INORGANIC ANALYSIS rx= number of dissociated molecules total number of molecules The value of o: may vary within 0 and 1. To determine conductivity one has to measure the specific resistance (resistivity) of the solution. by calculating i from experimental data.g. Direct current would cause changes in the concentration of the solution owing to electrolysis. any cell of constant dimensions is suitable. This can be done by placing the solution in a cubelike cell of 1 cm side. As mentioned before. no dissociation takes place. which is closely connected to the degree of dissociation. while the number of undissociated molecules 1.

where molar conductivities are plotted as functions of concentration.1 mol. It can be seen from this table that while the variation of molar conductivity of some solutions with Table I. K. 1.3. the limiting value corresponds to complete dissociation.1.1 units. containing 1 mole of the solute. Because the conductance of solutions varies with temperature (at higher temperatures the conductance becomes higher).10 specific conductance or conductivity. The latter is the conductance of a solution which contains 1 mole of the solute between two electrodes of indefinite size. 1 cm apart.1 Molar conductivities of electrolytes at 25°C in cm2 Electrolyte rr J mol. Values shown on Table I. within each of which there is little variation. results from the increasing degree of dissociation.3. The five substances selected for illustration represent five different groups of inorganic compounds. This limiting value of the molar conductivity is denoted here by Ao (the notation Axo is also used).1 units. The increase of molar conductivity.J units Concentration mol t:.1 cm.l were measured at 25°C. The molar conductivity is expressed in crrr' n. in the last century. A.I KCI ->O(=A o) NaCI 126'2 125-3 124'3 123'5 122'2 119'8 117-8 HCI 423'7 422·2 421'1 419'2 414'9 410'5 NaOH 260'9 246·5 244'7 242'5 238'8 234'5 KOH 283-9 CH 3COONa CH 3COOH 91·3 388'6 104·0 64·5 48·7 35'2 22-8 16'2 00001 0-0002 0·0005 0001 0'002 0-005 0-01 150'1 149'2 148'3 147'5 146'5 144'2 141'6 270'1 268·2 266'2 262'1 258·9 89·4 88'7 87-7 85'7 83-7 concentration is slight for most of the electrolytes listed. using a logarithmic scale for the latter to provide a wider range for illustration. the curve for nitric acid would run very close to the curve 13 . c is the concentration in mol cm . in line with the Arrhenius theory. and is expressed in n.THEORETICAL BASIS 1. Kohlrausch discovered. that the molar conductivity of aqueous solutions of electrolytes increases with dilution. The difference in behaviour can be seen better from Fig. while its value at a concentration c will be denoted by A c• The degree of dissociation can be expressed as the ratio of these two molar conductivities (:J. For electrolytic solutions it is customary to define the quantity called molar conductivity. the temperature at which these conductances are measured must be given. The variation of molar conductivity with concentration for a number of electrolytes is shown in Table 1. and reaches a limiting value at very great dilutions. there is a strong dependence on concentration in the case of acetic acid. The specific conductance and molar conductivity are connected by the relation: A =KV = ~ c where V is the volume of the solution in cm:' (ml).g.=- Ac Ao for the given concentration (c) of the electrolyte. e.

.. we can see that there are only two groups showing different behaviour. Some representative results are shown in Table 1. weak electrolytes (weak acids and weak bases) start to dissociate only at very low concentrations. It can be noted that agreement is particularly good for dilute solutions of binary electrolytes (KCl).4 10. I-I Fig. strong bases.2. and salts (including those of weak acids and weak bases). But if we think in terms of degrees of dissociation.. of Ions for one molecule. made up of strong acids.. the more considerable the differences.. and the variation in the degree of dissociation is considerable at this lower concentration range.6 10.7 10-8 c ImoI. despite the substantially different principles involved in the two types of measurements.3 10. 1. Table 1.2 Degree of dissodation of electrolytes... (These dissociate almost completely even at relatively low degrees of dilution O'OIM solutions).HCI (strong acids) CH 3 COOH (weak acids) - __-----. the cryoscopic and ebullioscopic techniques on one hand and the conductivity method on the other hand.3 of hydrochloric acid. On the other hand. calculated from freezing point and conductivity measurements Substance Concentration mol t " ' (J(from freezIng point 0·946 0·915 0'890 0·862 0·949 0'903 0'798 0·939 0'887 0'748 0'946 0'865 0'715 (J(from conductivity 0'943 0·924 0'891 0'864 0·959 0'886 0'754 0'957 0'873 0'716 0'930 0'822 No. The first group... The more concentrated the solutions. The two methods.3 shows the degree of dissociation of Table 1.10 QUALITATIVE INORGANIC ANALYSIS . and there is little variation in the degree of dissociation at further dilution....1.L-------= KOH (strong bases) NH 40H (weak bases) KCI (salts) 100 10-1 10-2 10.. n 2 KCI BaCI 2 K 2S04 K 3[Fe(CNM 0'01 0·02 0·05 0'10 0'001 0·01 0'10 0'001 0'01 0'10 0'001 0'01 0'10 3 3 4 14 . yield strikingly similar values for the degree of dissociation. is termed strong electrolytes..5 10..

1. containing similar anions and always the same two cations. is constant and independent of the nature of the anion. 2CN-) very small Bases Sodium hydroxide (Na+. As a result of prolonged and careful study of the conductance of salt solutions down to low concentrations. SOi-) 0'40 Copper sulphate (Cu2+. may be determined by extending the measurements to low concentrations and then extrapolating the graph of conductivity against concentration to zero concentration. It is however possible to calculate these limiting conductances on the basis of the law of independent migration of ions. Kohlrausch found that the difference in molar conductivities of pairs of salts. 2CI-) <0·01 Mercuric cyanide (Hg2+.) Phosphoric (H+. H 2BO.3 Degree of dissociation of electrolytes in O'IM aqueous solutions Acids Hydrochloric (H +. Ao. From these values we can easily decide whether a particular substance is a strong or a weak electrolyte. CH 3 • COO-) Carbonic (H+. He found for example that the following differences of limiting molar conductivities (measured at 18°C in crrr' 0. OH-) 0'91 0'91 0'81 0'013 a number of electrolytes in O'IM concentrations.. CN-) Boric (H+. OH-) Potassium hydroxide (K ". CALCULATION OF CONDUCTIVITIES FROM IONIC MOBILITIES For strong electrolytes the limiting value of the molar conductivity. this method cannot be employed. For weak electrolytes.11 Table 1.COO-) 0'80 Barium chloride (Ba2+. CI-) Nitric (H ". 20H-) Ammonia (NH.THEORETICAL BASIS 1. CI-) 0'86 Sodium chloride (Na +. HSO. CH 3. HCO.) Sulphuric (H+. HS-) Hydrocyanic (H+. CO~ -) 0'70 Zinc sulphate (Zn2+. such as acetic acid and ammonia. N0 3 ) Sodium acetate (Na".1 mol " ! units) 15 .) Hydrosulphuric (H+.11 THE INDEPENDENT MIGRATION OF IONS. OH-) Barium hydroxide (Ba2+. 2CI-) 0'75 Potassium sulphate (2K ".) 0'82 0'82 Silver nitrate (Ag ".) Salts 0'92 0'92 0'61 0'28 0'085 0·013 0'0017 0'0007 0'0001 0'0001 Potassium chloride (K +. NO. SOi-) 0'39 Mercuric chloride (Hg2+. Cl. SOi-) 0'73 Sodium carbonate (2Na +. CI-) 0'86 Potassium nitrate (K ". since the dissociation is far from complete at the lowest concentrations at which measurements can be conveniently made ('" 1O-4M). F-) Acetic (H+. H 2PO.) Hydrofluoric (H+.

1.11 QUALITATIVE INORGANIC ANALYSIS

Ao(KC1)-Ao(NaCl) = 130'1-109,0 = 21'1 Ao(KN03)-Ao(NaN03) = 126,3-105'3 = 21'0 are very nearly equal. From these and similar results, Kohlrausch drew the conclusion that the molar conductivity of an electrolyte is made up as the sum of the conductivities of the component ions. Mathematically this can be expressed as Ao = A~ +A o where A~ and A are the limiting molar conductivities or mobilities of the cation o and anion respectively. The ionic mobilities are computed from values of A o with the aid of transference numbers. These represent the current carried by the cation and anion respectively, and can be determined experimentally from the difference of concentration of electrolytes between the bulk of the solution and parts of the solution close to the cathode and anode. * Thus, for example, the transference number of chloride ion in a potassium chloride solution was found to be 0'503, while that of potassium is 0·497 (the sum of transference numbers for one particular electrolyte is by definition equal to one). The limiting value of the molar conductivity of potassium chloride solution (at 18°C) is 130'1 crrr' 0- 1 mol-I. Thus the mobility of the potassium ion is
A~(K+) =

0'497 x 130'1 = 64·6 ern" 0- 1 mol " !

and that of the chloride ion is Ao(Cl-) = 0'503 x 130·1 = 65'5 ern" 0- 1 mol- 1
Table 1.4 Limiting Ionic moblllties at lSOC and 25°C in cm 2
18"C H+ Na+ K+ Ag+ 1/2 Ca H 1/2 Sr H 1/2 Ba H 1/2 Pb H 1/2 Cd H 1/2 Zn H 1/2 Cu H 317·0 43'5 64·6 54·4 52-2 51'7 55'0 61'6 46'5 46·0 45'9 25°C

rr J

mol- J units

OW

CI-

N0 3 Br-

r
FCIO; 10 3 CH 3COO-

1/2 SOl1/2 (COO)~-

174·0 65'5 61'8 67'7 66·1 46·8 55·0 34·0 32·5 68·3 61·1

H+ Na+ K+ Ag+

348'0 49'8 73-4 61·9

OW
CI10 3 CH 3COO-

210'8 76'4 42·0 40·6

A selected number of ionic mobilities at 18°C and 25°C is shown in Table 1.4. This table may be utilized for the calculation of the limiting molar conductivities of any electrolytes made up of the ions listed. Thus, for acetic acid at 25°C Ao(CH3COOH) =
= =
A~(H+)+Ao(CH3COO-)

348'0+40'6 388'6 crrr' 0- 1 mol- 1

* For a more delailed discussion of Iransfere nee numbers textbooks of physical chemislry should be consulted (cf.: Wailer J. Moore's Physical Chemistry. 41h edn., Longman 1966, p. 333 el f).
16

THEORETICAL BASIS 1.12

The degree of dissociation can be calculated from the relation
IX

=-

Ac Ao

where Ac is the molar conductivity at the concentration c; this can be measured experimentally. 1.12 MODERN THEORY OF STRONG ELECTROLYTES The theory of electrolytic dissociation can be used to explain a great number of phenomena which are important in inorganic qualitative analysis. The theory, as put forward by Arrhenius, can be applied without much alteration as far as weak electrolytes are concerned but as further evidence - particularly of the structure of matter in the solid state - emerged, it became less and less adequate for strong electrolytes. It became clear that substances which are classified as strong electrolytes are made up of ions even in the solid (crystalline) form. In a crystal of sodium chloride, for example, there are no sodium chloride molecules present, (such molecules exist only in the sodium chloride vapour). The crystal is built up of sodium and chloride ions, arranged in a cubic lattice, one sodium ion being

(a)

(c)

_1----'---__ H
(b)

Fig. 1.4

17

1.12 QUALITATIVE INORGANIC ANALYSIS

surrounded always by six chloride atoms and vice versa (see Fig. I.4a). As the ions are there in the solid state, it is incorrect to suggest that at dissolution 'molecules' dissociate into ions. The dissolution of an ionic crystal in water is a physical process. It has been proved that in the water molecule the two hydrogen and the oxygen atoms are arranged in a triangle with a distance of 0'0958 nm between the centres of the hydrogen and oxygen atoms, and with an angle of 106° between the directions of the two hydrogen atoms (cf. Fig. lAb). Because of this arrangement, that side of the water molecule containing the hydrogen atoms, becomes electrostatically positive, while the opposite end, where the oxygen atom is, becomes negative. Thus, the water molecule has a dipole character. If an ionic crystal is placed in water, these dipoles will orientate around the ions present in the outer layer of the lattice. Electrostatic force will tend to pull these ions away from the crystal (see Fig. lAc). When an ion has been removed from the lattice, a symmetrical sphere of water molecules will orientate around it, and the whole hydrated ion with its sphere of water molecules will be taken away from the crystal by thermal motion. A new ion will thus be exposed to the action of water molecules, and slowly the whole crystal will dissolve. It can be stated therefore that in the solution of a strong electrolyte there are only (hydrated) ions present; in other words, 'dissociation' is complete. When accepting this model for the dissolution of strong electrolytes, further problems have to be faced. As was said in the previous section, the theory of electrolytic dissociation was in excellent agreement with the fact that the molar conductivity of strong electrolytes varies considerably with concentration at higher concentrations (cf. Fig. 1.3). This fact does not seem to be in accordance with the theory outlined above. As the number of ions is constant if a certain amount of electrolyte is dissolved, irrespective of its concentration, one would expect that the molar conductivity of such solutions would be constant. It was not until 1923 that Debye and Hiickel, (followed by Onsager in 1925) tried to interpret these phenomena with their famous interionic attraction theory. This theory was elaborated in a quantitative way and led to a number of important discoveries in solution chemistry. For a fuller treatment textbooks of physical chemistry should be consulted. * In the present text the theory is outlined only to the extent necessary for the better understanding of phenomena occurring in qualitative inorganic analysis. The Debye-Hiickel-Onsager theory accepts the fact that in solutions of strong electrolytes ionization is complete. When at rest, i.e. when there is no electrical potential difference applied on the electrodes, each ion is surrounded by a symmetric 'atmosphere' of ions of the opposite charge. When a potential difference is applied, the ions start to migrate towards the electrode with the opposite charge, owing to electrostatic forces. The migration of an individual ion is however far from being free of obstacles. According to the theory there are two discernible causes to which the retardation of ions can be attributed. The first of these is called the electrophoretic effect, and originates from the fact that the ion under consideration has to move against a stream of ions of the opposite charge moving towards the other electrode. As said before, these ions carry a large number of associated water (or solvent) molecules, and the friction between these hydrated (solvated) ions retards their migration. The higher the

* Cf. Waiter J.
18

Moore's Physical Chemistry. 4th edn., Longman 1966, p. 359 et f.

THEORETICAL BASIS 1.13

concentration, the nearer are these ions to each other and the more pronounced is this effect. The second, the asymmetry or (relaxation) effect, is the result of the breakdown of the symmetrical atmosphere of oppositely charged ions around the ion in question. As soon as the ion starts to move towards the particular electrode, it leaves, the centre of the sphere of its ionic atmosphere, leaving behind more ions belonging to the original sphere. For a while at least an unsymmetrical distribution of ions will develop, those ions, which are 'left behind' will electrostatically attract the ion in question. As this force is exerted in just the opposite direction to that of motion, the migration of the ion isslowed down. This effect is the more pronounced the more concentrated the solution. If the electric circuit is broken, it takes some time for the arrangement of ions to become symmetrical again (in other words, for relaxation to be complete), and this time, called the time of relaxation, can be expressed mathematically as the function of measurable parameters of the solution. It is inversely proportional to the concentration. The change of conductivity with dilution is therefore not attributed to changes in the degree of dissociation, as suggested by Arrhenius, but to the variation of the interionic forces outlined above. The molar conductivity, at a concentration c, can be expressed by the (simplified) equation:

A c = Ao-(A+BAo)jc
where Ao is the limiting value of the molar conductivity at zero concentration. A and B are constants (for a particular ion in a particular solvent at constant temperature) and correspond to the asymmetry and electrophoretic effects respectively. The great merits of the Debye-Hiickel-Onsager theory can be judged from the fact that both A and B can be expressed with measurable parameters of the solution and with some natural constants, and that conductivities calculated with this equation agree well with the experimental values, especially if concentrations are not too high. The ratio A c/ Ao in the modern theory of strong electrolytes, based on complete ionization, no longer gives the degree of dissociation (:J. for a strong electrolyte (for which it should be equal to unity); it is more proper therefore to call it the conductivity coefficientor conductance ratio. It does give the approximate degree of dissociation for weak electrolytes, but even here there are interionic forces contributing towards a lessening of the conductivity, and a correction may be applied with the aid of the Debye-Hiickel-Onsager theory. 1.13 CHEMICAL EQUILmRIUM; THE LAW OF MASS ACTION One of the most important facts about chemical reactions is that all chemical reactions are reversible. Whenever a chemical reaction is initiated, reaction products are starting to build up, and these in turn will react with each other starting a reverse reaction. After a while a dynamic equilibrium is reached; that is as many molecules (or ions) of each substance are decomposed as are formed in unit time. In some cases this equilibrium is almost completely on the side of formation of one or another substance, and the reaction thus seems to proceed until it becomes complete. In other cases it might be the experimenter's task to create the circumstances under which the reaction, which otherwise would reach an equilibrium, will become complete. This is often the case in quantitative analysis. The conditions of chemical equilibrium can most easily be derived from the
19

1.13 QUALITATIVE INORGANIC ANALYSIS

law of mass action.* This law was stated originally by Guldberg and Waage in 1867 in the following form: the velocity of a chemical reaction at constant temperature is proportional to the product of the concentrations of the reacting substances. Let us consider first a simple reversible reaction at constant temperature:
A+B +2 C+D

The velocity with which A and B react is proportional to their concentrations, or
v\=k\x[A]x[B]

where k t is a constant known as the rate constant and the square brackets indicate the molar concentration of the substance enclosed within the brackets. Similarly, the velocity with which the reverse process occurs is given by
V2

= k2

X

[C] x [0]

At equilibrium the velocities of the reverse and forward reactions are equal (the equilibrium is a dynamic and not a static one) and therefore or
k\x[A]x[B] = k 2x[C]x[D]

By rearranging we can write

[C] x [0] [A] x [B]

= kt = K

k2

K is the equilibrium constant of the reaction. Its value is independent of the

concentrations of the species involved; it varies slightly with temperature and pressure. The expression may be generalized for more complex reactions. For a reversible reaction represented by the equation
vAA+vBB+vcC+ ... +2 vLL+vMM+vNN

where vA, VB • . . etc. are the stoichiometric numbers of the reaction, the equilibrium constant can be expressed as:
K=~::-::---.::;~:;-".-~=---==o::---

[L]"L x [M]"M x [N]"N ... [A]"A x [B]"B x [c]"e ...

Expressed in words: When equilibrium is reached in a reversible reaction at constant temperature and pressure, the product of the molecular concentrations of the resultants (the substances on the right-hand side of the equation), divided by the product of the molecular concentrations of the reactants (the substances on the left-hand side of the equation), each concentration being raised to the power equal to the number of species of that substance taking part in the reaction, is constant.

* 11 must be emphasized that the conditions of chemical equilibrium can be derived and explained most exactly on the basis of thermodynamics, that is without involving reaction rates at all. Textbooks of physical chemistry will of course contain the thermodynamical interpretation (er. W. J. Moore's Physical Chemistry. 4th edn., Longman 1966, p. 167 et f.)
20

THEORETICAL BASIS 1.13

The expression for the equilibrium constant given above gives us the clue to the problem one often comes across in qualitative analysis: what to do in order to make a reaction complete, in other words, to shift a chemical equilibrium in a desired direction. To examine this problem, let us consider the reaction of arsenate ions with iodide. If solutions of sodium arsenate, potassium iodide, and hydrochloric acid are mixed, the solution turns yellow or brown, owing to the formation of iodine. The reaction proceeds between the various ions present, arsenite ions and water being formed simultaneously, and can be expressed with the equation AsO~- + 21- + 2H+ P AsO~- + 12 + H 20 Sodium, potassium, and chloride ions, added with the reagents, do not take part in the reaction, and are therefore not included in the equation. This reaction is reversible and leads to an equilibrium. Applying the law of mass action, we can express the equilibrium constant of the reaction as
[AsO~-] x [1 2 ] x [H 20]

K =

[AsO~

] x [I ]2 x [H+]2

Let us suppose we want to reduce all the arsenate to arsenite, that is we want to shift the equilibrium towards the right-hand side of the equation. We can do this in several ways. If we add for example more hydrochloric acid to the solution, we can observe that the yellowish-brown colour deepens, that is more iodine is formed. The explanation of this is obvious from the expression for the equilibrium constant. When adding hydrochloric acid, we increased the hydrogenion concentration of the solution; thus increasing the denominator in the expression for the equilibrium constant. The equilibrium constant must remain constant, and therefore the numerator of the expression must increase as well. This can be achieved only by the increase of the individual concentrations in the numerator, which means that more arsenite, iodine, and water must be formed. In turn this means that the equilibrium has shifted towards the righthand side. The same will happen if we add more potassium iodide to the solution. There are other ways however to achieve the same object. We can for example remove the iodine formed during the reaction by evaporation or by extraction in water-immiscible solvent. In this case the numerator of the expression decreases, and in order to keep K constant, the denominator must decrease also. This again means that more reactants are used up (and more products are formed). Generally, we can say that a chemical equilibrium at constant temperature and pressure can be shifted towards the formation of the products either by adding more reactants, or by removing one of the products from the (homogeneous) equilibrium system. In terms of reactions used in qualitative analysis this means either the addition of reagents in excess, or the removal of reaction products from the solution phase, by some means such as precipitation, evaporation, or extraction. From the argument above it follows that opposite action will shift the equilibrium in the opposite direction. Thus, for example, adding more iodine to the equilibrium system, or removing some of the hydrogen ions with a buffer, or removing iodide ions by precipitating them with lead nitrate in the form of lead iodide will shift the equilibrium towards the formation of arsenate. A different way of shifting equilibria towards one or another direction is based on the fact that the equilibrium constant depends on temperature and,
21

1.14 QUALITATIVE INORGANIC ANALYSIS

at least in some cases, on pressure. Heating is often applied when performing qualitative analyses, though mainly in order to speed up the reactions (that is to influence kinetics) rather than to influence the conditions of equilibrium. In some cases cooling to low temperatures may achieve the object. For example, the equilibrium constant of the reaction Pb2+ + 21- +2 PbI 2(s) varies with temperature in such a way that at lower temperatures the formation of lead iodide is favoured. Thus, if we want to precipitate iodide quantitatively with lead, besides adding the reagent in excess, we should perform the reaction in the cold. The equilibrium of those reactions in solutions in which some of the reactants or products are gases, may be influenced by varying the pressure above the solution. Calcium carbonate precipitate for example can be dissolved by introducing carbon dioxide gas in a closed vessel until the pressure in the vessel increases to a few atmospheres, when the equilibrium CaC0 3(s)+C0 2(g)+H 20 +2 Ca2+ +2HC0 3 shifts towards the formation of calcium hydrogen carbonate. For the same reason, hydrogen sulphide gas is more effective if added at a slightly increased pressure, than when bubbled through a solution in an open vessel. If, on the other hand, the product of the reaction is a gas, the equilibrium can be shifted easily towards the formation of the products by removing the gas at a reduced pressure. 1.14 ACTIVITY AND ACTIVITY COEFFICIENTS In our deduction of the law of mass action we used the concentrations of species as variables, and deduced that the value of the equilibrium constant is independent of the concentrations themselves. More thorough investigations however showed that this statement is only approximately true for dilute solutions (the approximation being the better, the more dilute are the solutions), and in more concentrated solutions it is not correct at all. Similar discrepancies arise when other thermodynamic quantities, notably electrode potentials or chemical free energies are dealt with. To overcome these difficulties, and still to retain the simple expressions derived for such quantities, G. N. Lewis introduced a new thermodynamic quantity, termed activity, which when applied instead of concentrations in these thermodynamic functions, provides an exact fit with experimental results. This quantity has the same dimensions as concentration. The activity, aA' ofa species A is proportional to its actual concentration [A], and can be expressed as
aA <I«>

[A]

Here fA is the activity coefficient, a dimensionless quantity, which varies with concentration. For the simple equilibrium reaction, mentioned in Section 1.13 A+B +2 C+D the equilibrium constant can be expressed more precisely as
K = ae x aD = fe[C] XfD[D] = fe XfD x [C] x [0] aAxaB fA[A]xfB[B] fAXfB [A]x[B]

Activities, and thus activity coefficients, must be raised to appropriate powers, just like concentrations, if the stoichiometric numbers differ from 1. Thus, for
22

THEORETICAL BASIS 1.14

the general reversible reaction, dealt with in Section 1.13:

vAA+vBB+vcC+ ... P vLL+vMM+vNN+ ...
the equilibrium constant should be expressed more precisely as
K =

a"L x a"M x a"N x '" L M N a'AA x aBB x acc x ... (fL[L ])"L x (fM[M])"M x (fN[N])"N x =-'-==-==-~~----=-===--=,------:c..::..::~~--(fA[A])"A x (fB[B])"B x (fc[C])"c x = fL LxfMMxnr x x [L]"L x [M]"M x [N]"N X B cx f'AA xfB xfc [A]"A x [B]"B x [c]"c x

The activity coefficient varies with concentration. This variation is rather complex; the activity coefficient of a particular ion being dependent upon the concentration of all ionic species present in the solution. As a measure of the latter, Lewis and Randall (1921) introduced the quantity called ionic strength, I, and defined it as the half sum of the products of the concentration of each ion multiplied by the square of its charge. With mathematical symbols this can be expressed as

1=1 ~ c;zf
where c, is the concentration of the ith component, and z, is its charge. Thus, if a solution is 0·1 molar for nitric acid and 0'2 molar for barium nitrate, the concentrations of each ion being
CB 2 + a

Cw = 0·1 mol £-1 = 0'2 mol £- 1 CNO] = 0'3 mol £-1

and the charges
ZH+ = 1 ZBa2+ = 2 ZNOj = 1

for the same ions respectively, the ionic strength of the solution will be I = 1<CH+Z~+ +C B +Z~a2+ +CN03Z~03) a2 = 1<0'1 x 1+0'2 x 4+0'3 xl) = 0·6 The correlation between activity coefficient and ionic strength can be deduced from the quantitative relationships of the Debye-Hiickel-Onsager theory. Without giving details of this deduction* it is interesting to quote the final result: log/;

= -0'43e3N2 1000R3e 3T3

2npo

x

Z;

2)I

In this expression e is the charge of the electron, N the Avogadro constant, R the gas constant, Po the density of the solvent, e the dielectric constant of the solvent,

* For details textbooks of physical chemistry should be consulted. Cf. W. J. Moore's Physical Chemistry. 4th edn., Longman 1966, p. 354 et f.
23

1.14 QUALITATIVE INORGANIC ANALYSIS

and T the absolute temperature. Though the expression is rather complicated, it is worth noting that it contains natural constants and some easily measurable physical quantities. This shows the great merit of the Debye-Hiickel-Onsager theory: it is able to provide a quantitative picture of the characteristics of electrolyte solutions. Inserting the adequate values of constants and physical quantities for dilute aqueous solutions at room temperatures (T = 298K) the expression can be
Table 1.5 Mean activity coefficients of various electrolytes
Molar concentration HCI HBr HN0 3 HI0 3 H 2S0 4 NaOH KOH Ba(OHh AgN0 3 AI(N0 3 h BaCI2 Ba(N0 3h CaCI 2 Ca(N0 3h CdCI 2 CdS04 CuCI 2 CUS04 FeCI 2 KF KCI KBr KI KCI0 3 KCI04 K2S04 K 4Fe(CN)6 LiBr Mg(N0 3h MgS0 4 NH 4CI NH 4Br NH 4I NH 4N0 3 (NH 4hS04 NaF NaCI NaBr NaI NaN0 3 Na2S04 NaCI0 4 Pb(N0 3h ZnCI 2 ZnS04
0'001 0'01 0'05 0·1 0'2 0'5 1'0 2'0

0·966 0·966 0·965 0'96 0'830

0'904 0·906 0'902 0'86 0'544 0·90 0'712 0·90

0'830 0'838 0'823 0'69 0·340 0'82 0'82 0'526 0'79 0'56 0'52 0'57 0·54 0'28 0'21 0'58 0·21 0'62 0'88 0'815 0'822 0'84 0'813 0'788 0'52 0'19 0'842 0'55 0'22 0'79 0·78 0'80 0'78 0'48 0'81 0'823 0'844 0'86 0'82 0'53 0'82 0'46 0'56

0'796 0'805 0'785 0'58 0'265 0'80 0'443 0'72 0'20 0'49 0'43 0'52 0'48 0'21 0')7 0'52 0'16 0'58 0·85 0'769 0'777 0'80 0'755 0·43 0'14 0'810 0'51 0'18 0'74 0·73 0'76 0·73 0'40 0'75 0'780 0'800 0'83 0'77 0·45 0'77 0·37 0'50 0'15

0'767 0'782 0'748 0'46 0'209 0·73 0'370 0'64 0'16 0'44 0'34 0'48 0'42 0'15 0'11 0'47 0'11 0'55 0'81 0'719 0'728 0'76 0'36 0'11 0'784 0'46 0'13 0'69 0'68 0'71 0'66 0'32 0'69 0'730 0'740 0'81 0'70 0'36 0'72 0'27 0'45 0'11

0'758 0'790 0'715 0·29 0'154 0'69 0·73 0'51 0'14 0·39 0'52 0·38 0'09 0'07 0'42 0·07 0'59 0'74 0'651 0·665 0'71

0'809 0'871 0'720 0'19 0'130 0·68 0'76 0'40 0'19 0'39 0'71 0'35 0'06 0·05 0'43 0·05 0'67 0'71 0·606 0'625 0'68

1·01 1·17 0'78 0'10 0'12 0'70 0'89 0·28 0·45 0'44 0'35 0·04 0'51 0'70 0'576 0·602 0'69

0'88 0'88 0'89 0'88 0'76 0·73 0'89 0'74 0'89 0'965 0'965 0·965 0'967 0·965 0'89 0·966 0'88 0·96 0'96 0·96 0'96 0'87 0'966 0·966 0·97 0·966 0'89 0'97 0'88 0'88 0'70

0'72 0'71 0'73 0'71 0'47 0'40 0'72 0'41 0'75 0'93 0'901 0'903 0'905 0'907 0'895 0'71 0'909 0'71 0'40 0'88 0'87 0'89 0'88 0'67 0·90 0·904 0·914 0·91 0'90 0'71 0'90 0·69 0'71 0·39

0'67 0'783 0'44 0·09 0·62 0·62 0'65 0'56 0·22 0·62 0·68 0'695 0'78 0'62 0'27 0'64 0'17 0'38 0·07

0'848 0'50 0·06 0'57 0'57 0'60 0'47 0'16 0'66 0'686 0'80 0'55 0'20 0'58 0'11 0'33 0'05

1'06 0·69 0·05

0'67 0'734 0·95 0·48

0'04

24

THEORETICAL BASIS 1.15

simplified to log/; = -0'509z1)1 For the mean activity coefficient of a salt the expression log! = -0'509z+=-)1 is valid, where z + and z: are the charges of the cation and anion respectively. The expression is applicable to solutions oflow ionic strengths (up to 1 = 0'01) in the strictest sense. A number of mean activity coefficients are collected in Table 1.5. Activity coefficients generally first decrease with increasing concentrations, then, after passing through a minimum, rise again, often exceeding the value 1. This is illustrated well on the diagrams of Fig. 1.5 where activity coefficients of some electrolyte solutions are plotted against the square root of concentration.
f
f
HC)
),7 ),6 ),5 ),4 ),5 ),4 )'3 )'2 ).)

LiO

)·3 )·2
).)
)·Ok-----~""'-"..£----

)·0t--------f---0·9 0·8

0·7
0'6

0·5
0·4

0·9 0·8

NaC)

0·7
0·6

0·3 0·2 0·1

0·5'-----:l-:,---...L:----lL..--"*_ ),0 0·5 o

o0L----:l-:,---,.J-,--~'7--=--·

Fig. 1.5

Activity coefficients of non-ionized molecules do not differ appreciably from unity. In dilute solutions of weak electrolytes the differences between activities and concentrations (calculated from the degree of dissociation) is negligible. From all that has been said about activity and activity coefficients, it is apparent that whenever precise results are to be expected, activities should be used when expressing equilibrium constants or other thermodynamic functions. In the present text however we shall be using simply concentrations. For the dilute solutions of strong and weak electrolytes that are mainly used in qualitative analysis, errors introduced into calculations are not considerable.

C. CLASSICAL THEORY OF ACID-BASE REACTIONS
1.15 ACIDS, BASES, AND SALTS Inorganic substances can be classified into three important groups: acids, bases, and salts.
25

1.15 QUALITATIVE INORGANIC ANALYSIS

An acid is most simply defined as a substance which, when dissolved in water, undergoes dissociation with the formation of hydrogen ions as the only positive ions. Some acids and their dissociation products are as follows: HCI +2 H+ +CIhydrochloric acid chloride ion HN0 3 +2 H+ + N0 3 nitric acid nitrate ion CH 3COOH +2 H+ +CH 3COOacetic acid acetate ion Actually, hydrogen ions (protons) do not exist in aqueous solutions. Each proton combines with one water molecule by coordination with a free pair of electrons on the oxygen of water, and hydronium ions are formed: H+ +H 20
-+

H 30+

The existence of hydronium ions, both in solutions and in the solid state has been proved by modern experimental methods. The above dissociation reactions should therefore be expressed as the reaction of the acids with water: HCI+H 20 +2 H 30+ +CIHN0 3+H20 +2 H 30+ +N0 3 CH 3COOH+H 20 +2 H 30+ +CH 3COOFor the sake of simplicity however we shall denote the hydronium ion by H+ and call it hydrogen ion in the present text. All the acids mentioned so far produce one hydrogen ion per molecule when dissociating; these are termed monobasic acids. Other monobasic acids are: perchloric acid (HCl0 4 ) , hydrobromic acid (HBr), hydriodic acid (HI) etc. Polybasic acids dissociate in more steps, yielding more than one hydrogen ion per molecule, Sulphuric acid is a dibasic acid and dissociates in two steps: H 2S04 +2 H+ + HS04: HSO; +2 H+ + SO~yielding hydrogen sulphate ions and sulphate ions after the first and second step respectively. Phosphoric acid is tribasic: H 3P04 p H+ + H 2PO; H 2PO; +2 H+ + HPO~­ HPO~- +2 H+ +PO~The ions formed after the first, second, and third dissociation step, are termed dihydrogen phosphate, (mono)hydrogen phosphate, and phosphate ions respectively. The degree of dissociation differs from acid to acid. Strong acids dissociate almost completely at medium dilutions (cf. Section 1.10), these are therefore strong electrolytes. Strong acids are: hydrochloric, nitric, perchloric acid, etc. Sulphuric acid is a strong acid as far as the first dissociation step is concerned, but the degree of dissociation in the second step is smaller. Weakacids dissociate only slightly at medium or even low concentrations (at which, for example, they are applied as analytical reagents). Weak acids are therefore weak electrolytes.
26

THEORETICAL BASIS 1.15

Acetic acid is a typical weak acid; other weak acids are boric acid (H 3B03 ) , even as regards the first dissociation step, carbonic acid (H 2C0 3 ) etc. Phosphoric acid can be termed as a medium strong acid on the basis of the degree of the first dissociation; the degree of the second dissociation is smaller, and smallest is that of the third dissociation. There is however, no sharp division between these classes. As we will see later (cf. Section 1.16) it is possible to express the strength of acids and bases quantitatively. A base can be most simply defined as a substance which, when dissolved in water, undergoes dissociation with the formation of hydroxyl ions as the only negative ions. Soluble metal hydroxides, like sodium hydroxide or potassium hydroxide are almost completely dissociated in dilute aqueous solutions: NaOH p Na+ +OHKOH p K++OHThese are therefore strong bases. Aqueous ammonia solution, on the other hand, is a weak base. When dissolved in water, ammonia forms ammonium hydroxide, which dissociates to ammonium and hydroxide ions: NH 3+H 20 p NH 40H p NHt+OHIt is however more correct to write the reaction as

NH 3+H 20 p NHt+OHStrong bases are therefore strong electrolytes, while weak bases are weak electrolytes. There is however no sharp division between these classes, and, as in the case of acids, it is possible to express the strength of bases quantitatively. According to the historic definition, salts are the products of reactions between acids and bases. Such processes are called neutralization reactions. This definition is correct in the sense that if equivalent amounts of pure acids and bases are mixed, and the solution is evaporated, a crystalline substance remains, which has the characteristics neither of an acid nor of a base. These substances were termed salts by the early chemists. If reaction equations are expressed as the interaction of molecules, HCI+NaOH acid base
-+

NaCI+H 20 salt

the formation of the salt seems to be the result of a genuine chemical process. In fact however this explanation is incorrect. We know that both the (strong) acid and the (strong) base as well as the salt (cf. Section 1.10) are almost completely dissociated in the solution, viz. HCI p H++ClNaOH p Na+ +OHNaCI p Na+ +CIwhile the water, also formed in the process, is almost completely undissociated. It is more correct therefore to express the neutralization reaction as the chemical combination of ions: H+ +CI- +Na+ +OH-+

Na+ +CI- +H 20

In this equation, Na + and Cl- ions appear on both sides. As nothing has there27

among others. reacts with strong acids.1. if the dissociation of a monobasic acid HA takes place according to the equilibrium HA P H++Athe dissociation equilibrium constant can be expressed as 28 .16 QUALITATIVE INORGANIC ANALYSIS fore happened to these ions. On the other hand.4). Its value for acetic acid is 1·76 x 10. In this reaction aluminium hydroxide behaves as an acid. 1. the crystal lattice is held together by electrostatic forces due to the charges of the ions (cf. aluminium hydroxide can also be dissolved in sodium hydroxide: when tetrahydroxoaluminate ions are formed. The salt in the solid state is built up of ions. This is indicated by the fact. arranged in a regular pattern in the crystal lattice. Sodium chloride. both with hydrogen and hydroxyl ions). or ampholytes. are able to engage in neutralization reactions both with acids and bases (more precisely. The amphoteric behaviour of certain metal hydroxides is often utilized in qualitative inorganic analysis. Aluminium hydroxide. for example.5 at 25°C. for instance. In general. we can express the equilibrium constant as K = [H+] [CH 3COO-] [CH 3COOH] The constant K is termed the dissociation equilibrium constant or simply the dissociation constant.16 ACID-BASE DISSOCIAnON EQUILIBRIA. for example. 1. yields hydrogen and acetate ions: CH 3COOH p CH 3COO. Amphoteric substances. notably in the separation of the cations of the third group. the equation can be simplified to H+ +OH-+ H 20 showing that the essence of any acid-base reaction (in aqueous solution) is the formation of water. The dissociation of acetic acid. when it dissolves and aluminium ions are formed: Al(OHh(s) + 3H+ -+ Al3+ + 3H 20 In this reaction aluminium hydroxide acts as a base. that the heat of neutralization is approximately the same (56·9 kJ) for the reaction of one mole of any monovalent strong acid and base. STRENGTH OF ACIDS AND BASES The dissociation of an acid (or a base) is a reversible process to which the law of mass action can be applied.+ H+ Applying the law of mass action to this reversible process. Fig. is built up of sodium ions and chloride ions so arranged that each ion is surrounded symmetrically by six ions of the opposite sign.

Ammonium hydroxide (i.P H++HA 2 HA 2 . while the third is the least complete. The dissociation of the dibasic acid H 2A can be represented by the following two equilibria: H 2A P H++HAHA. It must be noted that Kt > K 2 . the aqueous solution of ammonia) dissociates according to the equation: NH 40H P NH1 +OH- The dissociation equilibrium constant can be expressed as K = [NH1] x [OH-] [NH 40H] 29 . the more it dissociates. that is the first dissociation step is always more complete than the second. hence the greater is the value of K. Similar considerations can be applied to bases. that is the first dissociation step is the most complete. It must again be noted that K 1 > K 2 > K 3 . A tribasic acid H 3A dissociates in three steps: H 3A P H+ +H 2AH 2A. and both dissociation equilibria can be characterized by separate dissociation equilibrium constants.THEORETICAL BASIS 1.P H++A 2 - Applying the law of mass action to these processes we can express the two dissociation equilibrium constants as and K 1 and K 2 are termed first and second dissociation equilibrium constants respectively.P H+ +A 3 - and the three dissociation equilibrium constants are K1 K2 = = [H+] [H 2A] [H 3A] .16 The stronger the acid. second. Dibasic acids dissociate in two steps. the dissociation equilibrium constant.e. and third steps respectively. [H+] [HA 2 ] [H 2A-] [H+][A 3 [HA 2 ] ] K3 = for the first.

is independent of the concentration (more precisely of the activity) of the acid.6. Longman 1967. 5th edn. if a monovalent base BOH* dissociates as BOH +:t [B+] + [OH-] the dissociation equilibrium constant can be expressed as [B+] x [OH-] K = [BOH] It can be said again that the stronger the base the better it dissociates. because their dissociation constants are so large that they cannot be measured reliably. Accurate values for strong acids do not appear in the table. The value of the dissociation equilibrium constant.. The usefulness of pK will become apparent when dealing with the hydrogen-ion exponent or pH. 30 . When dissolved in water. and therefore provides the most adequate quantitative measure of the strength of the acid or base. The values of dissociation constants can be used with advantage when calculating the concentrations of various species (notably the hydrogen-ion concentration) in the solution. Finar's Organic Chemistry. The Fundamental Principles. p. L. The exponent of the dissociation equilibrium constant. We saw already that the value of the dissociation constant is correlated with the degree of dissociation. and there- fore the larger the value of the dissociation equilibrium constant. A selected list of K and pK values is given in Table 1. Generally. The general formula of a monoamine is R-NH 2 (where R is a monovalent organic radical). called pK. and so with the strength of the acid or base. I. 343 et f. amines hydrolyse and dissociate as RNH 2+H 20 <:! RNH 30H <:t RNHj +OH- and the law of mass action can be applied to this dissociation just like for that of ammonia. and therefore it cannot be used to characterize the strength of the acid or base without stating the circumstances under which it is measured.1.16 QUALITATIVE INORGANIC ANALYSIS The actual value of this dissociation constant is 1'79 x 10-5 (at 25°C). The degree of dissociation depends on the concentration. Their behaviour can be explained along similar lines as the basic character of ammonia. showing that one hydrogen of the ammonia is replaced by the radical R. The dissociation of acetic acid takes place according to the equilibrium: CH 3COOH +:t H+ +CH 3COOthe dissociation equilibrium constant being K = [H+] x [CH 3COO-] = 1'75 X 10-5 [CH 3COOH] * Organic amines behave like monovalent weak bases. For more detailed account see I. Vol. A few examples of such calculations are given below: Example 1 Calculate the hydrogen-ion concentration in a O'OIM solution of acetic acid. on the other hand. is defined by the equations pK = -logK I = log- K Its value is often quoted instead of that of K.

10 2·2 x 10.7 5·61 x 10.5 2·25 6·77 11'53 9·28 12·74 13080 2'13 7-21 12·32 3'14 4·77 4·39 31 .13 7·21 X 10.12 5·27 X 10.2 5·4 x 10.34 4·76 3'75 2'86 1'29 9'98 4'20 4-87 H 2C03 H 2S H 2S0 3 H 2S04 (COOHh C4H606 (tartaric acid) 25 25 20 20 18 18 20 20 20 20 I 2 I 2 I 2 I 2 I 2 I 2 4·31 x 10.4 1·42 x 10.5 9'04 X 10.4 4·79 x 10.10 7 X 10.2 1'05 x 10.5 6'37 10'25 7'04 14'92 1·78 1'99 0·4 1'9 1·62 4·27 3·04 4·37 Tribasic acids H 3As04 H 3B03 H 3P04 C6H s0 7 (citric acid) 18 18 18 20 20 20 20 20 20 20 20 20 I 2 3 I 2 3 I 2 3 I 2 3 5·62 x 10.3 1'70 x 10.3 5·1 x 10.14 7'46 X 10.10 1'8xlO.4 1'39xI0.3 6'12xlO.2 1'02x 10.5 4'09 X 10.2 -4xlO.10 6'24 x 10.15 1·66 x 10.-9.s 4·9 x 10.7 2·95 x 10.1 1'27 x 10.1 3'2 x IO.4 22 1·75 x 10.THEORETICAL BASIS 1.5 1'77xlO.48 3'17 3-32 3-66 0'85 7'49 2-31 9'70 3'15 -1.4 1'70 x 10.6 Dissociation constants of acids and bases Acid QC DIssociation step K pK Monobasic acids HCI HBr HI HF HCN HCNO HCNS HCIO HCI0 2 HIO HN0 2 HN0 3 CH 3COOH HCOOH CH 2CI-COOH CHCI 2-COOH C 6H 5OH C 6H 5COOH C 2H5COOH Dibasic acids 25 25 25 25 18 25 25 15 25 25 20 30 20 20 20 25 20 20 20 _10 7 _10 9 -3 x 109 6·7 x 10.s 4·8 X 10.11 9'1 X IO.16 Table 1.2 2'4xlO.5 --7 --9 .s 1'2xlO.13 1·6 X 10.3 2 x 10.5 1'34x 10.4 4·25 x 10.

4 5·69 X 10.) 32 .1 (The second root of equation (i) with a minus sign in front of the square root leads to a negative concentration value.10 1'15 x 10. while some molecules dissociate.3 2·6 x 10.60 0'18 4·77 1'40 2-43 2·58 3-38 3-24 4·24 3'52 3'07 3-25 9-40 8·94 9'23 Neglecting the small amounts of hydrogen ions originating from the dissociation of water (cf.4 m o l t . The total concentration c (O'OlM) of the acid is therefore the sum of the concentration of undissociated acetic acid and that of acetate ions: c = [CH 3COOH] + [CH 3COO-] = 0'01 These equations can be combined into [H+]2 K = c. Hence the hydrogen-ion concentration is equal to the concentration of acetate ions: [H+] = [CH 3COO-] Some of the acetic acid in the solution will remain undissociated. which has no physical meaning.4 4x 10.1.s 4 x 10.4 5·75 x 10.2 3'74 x 10.1 1'7IxlO.4 8·57 x 10.6 Dissociation constants of acids and bases Acid QC DIssociatIon step K pK Bases NaOH LiOH NH 40H Ca(OHh Mg(OHh CH 3-NH 2 (CH 3h NH (CH 3 h N C 2H s-NH 2 (C 2H sh NH (C 2H sh==N C 6H s-NH 2 (aniline) CsHsN (pyridine) C 9H 7N (quinoline) 25 25 20 25 25 25 20 20 20 20 25 25 20 20 20 I I I I 2 2 I I I I I I I -4 6·65 x 10.4 5·6 x 10. Section 1.3 4·17 X 10.9 5·9 x 1010 -0. we can say that all hydrogen ions originate from the dissociation of acetic acid.[H+] Rearranging and expressing [H+] we obtain [H+] = -K+JK 2 2+4cK (i) Inserting K = 1'75 x 10.s 3·02 X 10.16 QUALITATIVE INORGANIC ANALYSIS Table 1.18).sand c = 0·01 we have [H+] = -1'75xlOs+J3'06xlO 2 IO+7xlO 7 =4'lOxlO.

and S2.] = K 2 . The dissociation constants of hydrogen sulphide are K = [H+] x [HS-] = 8'73 x 10-7 1 [H 2S] and (i) K = [H+] x [S2-] = 3'63 x 10-12 2 [HS ] (ii) (for 20°C). the total concentration (0'1 mol t . Because of the small degree of even the first ionization. (the precise figure is 0'1075 mol r 1).4 and the combination of (ii) and (iii) yields the value of [S2-]: [ HS.] = 3'17 x 10[H+]2 18 one finds that the concentration of sulphide ions is inversely proportional to the square of hydrogen-ion concentration. (iii). centration are interlinked. by adjusting the hydrogen-ion concentration by adding an acid or a base to a solution.17 EXPERIMENTAL DETERMINATION OF THE DISSOCIATION EQUILIBRIUM CONSTANT. Thus.] [ S2.= K 2 = 3'63 X 10. when the correlation [H+] = [HS-] (iii) holds.I) can be regarded as equal to the concentration of undissociated hydrogen sulphide: [H 2S] = 0'1 (iv) Combining equations (i). Thus only the first ionization step may be taken into consideration. the value of [S2-] is exceedingly small.. 1. preferential value. The dissociation reaction can be written as HA P H++A33 . To find this correlation let us consider the dissociation of a weak monobasic acid. OSTWALD'S DILUTION LAW The dissociation equilibrium constant and the degree of dissociation at a given con-. and (iv) we have [HS-] = JK 1[H 2S] = J8'73 x 10 7 x 0·1 = 2'95 x 10.12 [H+] If one multiplies equations (i) and (ii) together and transposes [ S2. A saturated aqueous solution of hydrogen sulphide (at 20°C and 1 atm pressure) is about O'lM. This principle is used in the separation of metal ions of the 2nd and 3rd groups.in a saturated solution of hydrogen sulphide. As the second dissociation constant is very small.17 From this example we can see that in a 0'01Msolution of acetic acid only about 4 % of the molecules are dissociated. Example 2 Calculate the concentrations of the ions HS. the concentration of sulphide ions can be adjusted to a predetermined.THEORETICAL BASIS 1.

(ii).c-crx .7 Calculation of the dissociation equilibrium constant of acetic acid from measured values of molar conductivity Concentration 5 X 10 1'873 5'160 9-400 24'78 38'86 56·74 68'71 92'16 112'2 0 A (J( rx 2 Kx 105 1'78 1'76 1'83 1'82 1·83 1·84 1'84 1·84 1'84 102'5 65'95 50·60 31·94 25'78 21·48 19'58 16'99 15'41 388'6 0'264 0'170 0·130 0'080 0'066 0·055 0·050 0·044 0·040 34 . The average value Table 1. 1. As the latter is proportional to the molar conductivity of the solution. K can be calculated by these equations. x ex _ crx 2 . The concentration of hydrogen ions and that of the dissociated anion will be equal. as they express the correlation between dilution and the degree of dissociation. and can be expressed as [H+] = [A-] = ea Combining equations (i). in which the dissociation equilibrium constant of acetic acid is computed from molar conductivities.17 QUALITATIVE INORGANIC ANALYSIS with the dissociation equilibrium constant (i) The total concentration of the (undissociated plus dissociated) acid is c.3. These equations are often referred to as Ostwald's dilution law. The degree of dissociation is a.7.10.l-rx (iii) or. The way in which dissociation constants are obtained from experimental data is illustrated in Table 1. the above correlation describes the particular shapes of the conductivity curves shown in Fig.1. using the notation V for the dilution of the solution V=c 1 (in t mol " ! units) the equilibrium constant can be written as K=--V(l-rx) If c or V is known and o: is determined by one of the experimental methods mentioned in Section 1. thus the correlation (ii) holds. and (iii) we can write K _ ea.

THEORETICAL BASIS 1.18

0'82 x 10- 5) of the equilibrium constant agrees well with the true value 0'78 x 10- 5 at 25°C).

1.18 THE DISSOCIAnON AND IONIC PRODUCT OF WATER Kohlrausch and Heidweiller (894) found, after careful experimental studies, that the purest water possesses a small, but definite conductance. Water must therefore be slightly ionized in accordance with the dissociation equilibrium: H 20 +2 H+ + OHApplying the law of mass action to this dissociation, we can express the equilibrium constant as [H+] x [OH-]
K =

[H 20]

From the experimental values obtained for the conductance of water the value of K can be determined; this was found to be 1·82 x 10- 1 6 at 25°C. This low value indicates that the degree of dissociation is negligible; all the water can therefore in practice be regarded as undissociated. Thus the concentration of water (relative molecular mass = 18) is constant, and can be expressed as [H 20] = 1000 = 55.6 mol
18

r

1

We can therefore collect the constants to one side of the equation and can write Kw = [H+] x [OH-] = 1'82 x 10- 16 x 55'6 = 1'01 x 10- 1 4 (at 25°C) the new constant, Kw is called the ionic product of water. Its value is dependent
Table 1.8 The Ionic product of water at various temperatures
Temperature
(QC)

s;« 1014
0'12 0·19 0'29 0·45 0·68 1·01 1·47

Temperature
(QC)

s;« 1014
2'09 2-92 4·02 5'48 7'30 9-62

0 5 10 15 20 25 30

35 40 45 50 55 60

on temperature (cf. Table 1.8); for room temperature the value Kw = 10- 1 4 is generally accepted and used. The importance of the ionic product of water lies in the fact that its value can be regarded as constant not only in pure water, but also in diluted aqueous solutions, such as occur in the course of qualitative inorganic analysis. This means that if, for example, an acid is dissolved in water, (which, when dissociating, produces hydrogen ions), the concentration of hydrogen ions can increase only at the expense of hydroxyl-ion concentration. If, on the other hand, a base is dissolved, the hydroxyl-ion concentration increases and hydrogen-ion concentration decreases.
35

1.19 QUALITATIVE INORGANIC ANALYSIS

We can define the term neutral solution more precisely along these lines. A solution is neutral if it contains equal concentrations of hydrogen and hydroxyl ions; that is if [H+] = [OH-] In a neutral solution therefore [H+] = [OH-] = ~ = 10- 7 mol

r

J

In an acid solution the hydrogen-ion concentration exceeds this value, while in an alkaline solution the reverse is true. Thus [H+] > [OH-] and [H+] > 10- 7 in an acid solution in an alkaline solution [H+] < [OH-] and [H+] < 10- 7 In all cases the acidity or alkalinity of the solution can be expressed in quantitative terms by the magnitude of the hydrogen-ion (or hydroxyl-ion) concentration. It is sufficient to use only one of these for any solution; knowing one we can calculate the other using the equation + 10- 14 [H ] = [OH] In a M solution of a strong monobasic acid (supposing that the dissociation is complete) the hydrogen-ion concentration is 1 mol r l . On the other hand, in a M solution of a strong monovalent base the hydroxyl-ion concentration is 1 mol t - 1, thus the hydrogen-ion concentration is 10- 1 4 mol r 1. The hydrogen-ion concentration of most of the aqueous solutions dealt with in chemical analysis (other than concentrated acids, used mainly for dissolution of samples), lies between these values.
1.19 THE HYDROGEN-ION EXPONENT (pH) In the practice of chemical analysis one frequently deals with low hydrogen-ion concentrations. To avoid the cumbersome practice of writing out such figures with factors of negative powers of 10, Sorensen (1909) introduced the hydrogen-ion exponent or pH, defined by the relationship:

pH = -log [H+] = log

[~+]

or

[H+] = 1O- pH

Thus, the quantity pH is equal to the logarithm of the hydrogen-ion concentration* with negative sign, or the logarithm of the reciprocal hydrogen-ion concentration. It is very convenient to express the acidity or alkalinity of a solution by its pH. From the considerations of Section 1.18 it follows that the pHs of aqueous solutions will in most cases lie between the values of 0 and 14. In a IM solution of a strong monobasic acid pH = -log 1 = 0 while the pH of a IM strong monovalent base is pH = -log 10- 1 4 = 14

* more precisely: hydrogen-ion activity, i.e.
pH
=

-log UH'

or

0H+

=

IQ-pH

36

THEORETICAL BASIS 1.19

If a solution is neutral, pH = -log 10- 7 = 7 From the above definition it follows that for an acid solution pH < 7 for an alkaline solution pH > 7 The term pOH is sometimes used in an analogous way for the hydroxyl-ion exponent, that is
pOH

= -log [OH-] = log [O~] or [OH-] = lO-poH

For any aqueous solution the correlation pH+pOH = 14 holds. Figure 1.6 will serve as a useful mnemonic for the relation between [H+], pH, [OH-], and pOH in acid and alkaline solutions.
4 2 [H+ 1 1(1(J°)Io-1 10- 2 10- 3 10- 4 10- 5 10- 6 10- 7 10- 8 10- 9 10- 10 10-11 10-1 10-13 10- 1

pH

0

1

2

3

4

5

6

7

8

9

10

11

12

13

14

13 12 11 10 9 8 7 6 5 4 3 2 0 1 10-1 10- 1 10-11 10- 10 10-9 10-8 10-7 10-6 10-5 10-4 10-3 10-2 10-11(10- °) 4 3 2 [OH-l 10pOH
14

Acid

Alkaline
Neutral
Flg.I.6

Example 3 Calculate the pH of a solution of 0·01M acetic acid (cf. Example 1 in Section 1.16). In Example 1 we found that the hydrogen-ion concentration is [H+] = 4·lOx 1O-4 mo l t - 1

Thus, pH = -log(4·1O x 10- 4 ) = -(log4·1O+1og 10- 4 ) = -(0·61-4) = 3·39
Example 4 Calculate the molarity of an ammonia solution with a pH of 10·81. The dissociation of ammonium hydroxide takes place according to the equilibrium

NH4 0 H +2 NHt +OH-

(i)

with the dissociation equilibrium constant (cf. Table 1.6):
K
b

= [NHt] x [OH-] = 1.71 x 10- 5
[NH 40H]

(ii)
37

1.19 QUALITATIVE INORGANIC ANALYSIS

In a solution of pure ammonia the concentrations of ammonium and hydroxyl ions are equal (cf. (i) above) [NHt] = [OH-] (iii) The unknown concentration, c, of ammonia is equal to the sum of the concentrations of the ammonium ions and the undissociated ammonia c = [NHt] + [NH 40H] Finally, we have the correlation [H+] x [OH-] = 10- 14 valid for all dilute aqueous solutions. From the definition of pH pH = -log[H-] we can calculate the hydrogen-ion concentration in the following way: pH = 10'81 = -log[H+] = -(0'19-11) [H+] = 1'55 x 10- 11 From equation (v) the hydroxyl-ion concentration can be calculated 10- 1 4 10- 14 4 [OH-] = [H+] = 1'55 x 10 11 = 6'45 X 10- mol f -1 Equations (ii), (iii), and (iv) can be combined to [OH-]2 «, = c-[OH ] from which c can be expressed as
c =
= =
=-----=---------"'---=

(iv) (v)

(vi)

(vii)

[OH-]2 + Kb[OH-]

Kb

[OH-]2

+
4

[OH-]
)2

Kb
(6'54 x 10l'71xlO +6'45x 10- 4 2'5
X

5

=

2·495 X 10- 2

~

10- 2

Thus the solution is 0'025 molar. The method using the exponent rather than the quantity itself has been found useful for expressing other small numerical quantities which arise in qualitative analysis. Such quantities include (cf. Section 1.16) (i) dissociation constants and (ii) other ionic concentrations. (i) For any acid with a dissociation constant K,
pKa
38

=

-log K;

1 = logs,

THEORETICAL BASIS 1.20

Similarly, for any base with a dissociation constant K b
1 pKb = -log K b = log-

Kb

Example 5 The dissociation constant of acetic acid is 1'75 x 10- 5 (at20°C). Calculate its pKa value. pKa = -logKa = -log l'75x 10-5
= -

=

(log 1'75 x log 10- 5) -(0'24-5) = 4'75

Example 6 The pKb value of dimethyl amine is 3'24 (at 20°C). Calculate the K b dissociation constant. pKb

= -log K b = 3'24 = 4-0'76 = -(0'76-4)

log K b = 0'76-4 K b = num log(0'76-4) = 5'76 x 10- 4 The correct value (cf. Table 1.6) is 5.69 x 10- 4 • The difference comes from the fact, that pK values are usually rounded off to the third significant figure. (The accurate value of pKb would be 3'24489.) (ii) For any ion I of concentration [I]
pI = -log [I] = log

[~]

Example 7 Find the pNa value of a solution in which [Na+] =

8 x 10-5 mol
pNa

r

l .

= -log[Na+] = -(log 8 x 10- 5) = -(log 8+1og 10- 5)
=

-(0'90-5) = 4'10.

When salts are dissolved in water, the solution is not always neutral in reaction. The reason for this phenomenon is that some of the salts interact with water; hence it is termed hydrolysis. As a result, hydrogen or hydroxyl ions remain in the solution in excess, the solution itself becoming acid or basic respectively. . In order to understand the phenomenon of hydrolysis better, it is useful to examine the behaviour of four categories of salts separately. All existing salts fall into one of the following categories: I. Those derived from strong acids and strong bases, e.g. potassium chloride. 11. Those derived from weak acids and strong bases, e.g. sodium acetate. Ill. Those derived from strong acids and weak bases, e.g. ammonium chloride. IV. Those derived from weak acids and weak bases, e.g. ammonium acetate. These groups behave differently with respect to hydrolysis. I. Salts of strong acids and strong bases, when dissolved in water, show a neutral reaction, as neither the anion nor the cation combines with hydrogen or hydroxyl ions respectively to form sparingly dissociated products. The dissociation equilibrium of water
H 20 +2 H+

1.20 HYDROLYSIS

+ OH39

1.20 QUALITATIVE INORGANIC ANALYSIS

is therefore not disturbed. The concentration of hydrogen ions in the solution equals that of hydroxyl ions; thus, the solution reacts neutral. 11. Salts of weak acids and strong bases, when dissolved in water, produce a solution which reacts alkaline. The reason for this is that the anion combines with hydrogen ions to form a sparingly dissociated weak acid, leaving hydroxyl ions behind. In a solution of sodium acetate for example the following two equilibria exist: H 2 0 +2 H+ +OHCH 3COO- + H+ +2 CH 3COOH Thus, the hydrogen ions, formed from the dissociation of water, will partly combine with acetate ions. The two equations can therefore be added, which results in the overall hydrolysis equilibrium: CH 3COO- + H 2 0 +2 CH 3COOH + OHIn the solution, hydroxyl ions will be in excess over hydrogen ions, and the solution will react alkaline. In general, if the salt of a monobasic weak acid HA is dissolved in water, the A-anion will combine with hydrogen ions to form the undissociated acid: A- + H+ +2 HA The hydrogen ions are produced by the dissociation of water: H 2 0 +2 H+ + OH(ii) Although the dissociation of pure water is almost negligible, when dissolving the salt, more and more water molecules become ionized, because the removal of hydrogen ions from equilibrium (ii) will, according to the law of mass action, shift the equilibrium to the right. The two equilibria can be combined by addition into A- + H 2 0 +2 HA + OH(iii) The equilibrium constant of this process is called the hydrolysis constant, and can be written as: (iv) The concentration of water, as in the case of its dissociation equilibrium, can be regarded as constant and can therefore be involved in the value of the K h hydrolysis constant. The greater the value of K h , the greater is the degree of hydrolysis and the more alkaline the solution. Values of the hydrolysis constant need not be measured and tabulated separately, because they are correlated to the dissociation constants of the weak acid (cf. equation (i))and the ionization constant of water (cf. equation (ii)):
(v)

(i)

and (vi)
40

THEORETICAL BASIS 1.20

Dividing (vi) by (v) we have

Kw
K =
a

«;

[HA] [OH-]
=

[A ]

(vii)

Thus, the hydrolysis constant is equal to the ratio of the ionization constants of water and of the acid. The degree of hydrolysis can be defined as the fraction of each mole of the anion hydrolysed in the equilibrium. If c is the total concentration of the anion (i.e. of the salt) and x is the degree of hydrolysis, the actual concentrations of the species involved in the hydrolysis equilibrium are as follows: [OH-] = xc [HA] = xc [A-] = c-cx = cO-x) With these values the hydrolysis constant can be expressed as cx 2 Kh = - I-x By rearranging equation (viii) we can express the degree of hydrolysis as

(viii)

s;
X

= -

2c

+

K~

4c2

«; +~

(ix)

If x is small (2-5 per cent), equation (viii) reduces to
K h = x'c

from which

x

=,j~h

(ixa)

The hydrogen-ion concentration of a solution obtained by dissolving c moles of a salt per litre can be calculated easily. From the stoichiometry of equilibrium (iii) it follows that, if the amount of hydroxyl ions originating from the selfdissociation of water is negligible, the hydroxyl-ion concentration and the concentration of the undissociated acid are equal:

[OH] = [HA]

(x)

If the degree of hydrolysis is not too great, the total concentration, c, of the salt is equal to the concentration of the anion: (xi) Combining equations (iv), (x), and (xi) we can express the hydrolysis constant as
~=

[OH-]2
c

~

Now we can combine this expression with expressions (v) and (vi), when the hydrogen-ion concentration of the solution can be expressed as follows: [H+] =
KwK a = 10- 7 /Ka c

v:

(xiii)
41

1.20 QUALITATIVE INORGANIC ANALYSIS

It is easier to memorize the expression of pH, obtained by logarithmization of equation (xiii) : pH = 7+-!pKa+! log e (xiv)

Example 8 Calculate the hydrolysis constant, the degree of hydrolysis, and the hydrogen-ion concentration and pH of a O'lMsolution of sodium acetate at room temperature. From Table Le x, = 1·75x 1O-s,pKa = 4'76. The hydrolysis constant can be calculated from equation (vii): K 10- 14 K =~= = 5'72 x 10- 10 h Ka 1'75 x 10- S The degree of hydrolysis is calculated from equation (ix) :

x=

h --+ 2e

K

5'72 x 10- 10 2 x O' 1 + x = 7·56 X 1O-s

3'28x1O- 19 5'72 x 10- 10 4 x 0'01 + 0'1

Thus the degree of hydrolysis is slight, only 0'0075 per cent. The same result is obtained therefore from the simplified expression (ixa):
X

=jK
e

h

=/5'72 x 10 10 =7'56x1O- s 0'1

The hydrogen-ion concentration is obtained from equation (xiii): H+ = 10- 7 [«, = 10-7 /1'75xlO S = l-32x1O- 9 e 0'1 The pH of the solution is pH = -log l'32x 10- 9 = -(0'12-9) = 8'88

V

V

The same result is obtained from equation (xiv):
pH = 7+!pKa+-!loge = 7+2--! = 8·88

4'76

Example 9 Calculate the hydrolysis constant, the degree of hydrolysis, and the pH of a O'lM solution of sodium sulphide. From Table 1.6 the two ionization constants for hydrogen sulphide are K a 1 = 9'1 x 10- 8; pKa 1 = 7·04 and K a 2 = 1'2 X 1O- IS; pKa 2 = 14'92. The hydrolysis of sulphide ions take place in 2 steps: S2- +H 20 +::t HS- +OH(Kh l ) HS- + H 20 +::t H 2S+ OH(Kh 2 ) The two hydrolysis constants for the two steps are calculated from equation (vii) : Kw 10- 1 4 h1 = K K = l'2x 1O-1S = 8·33
a2

42

THEORETICAL BASIS 1.20

and
Kh2

= K = 9.1 x 10
al

Kw

10- 1 4

8

= l·1Ox 10-

7

Since K hl » K h 2 the second hydrolysis step can be neglected in the calculations. The degree of hydrolysis is calculated from equation (ix) :

Khl x=-+
2e
x = 0·988 or 99 per cent

- - + 0·1 0·04

69·44

8·33

Because of this high degree of hydrolysis, the simplified equation (ixa) cannot be used any more.
Example 10 Calculate the degree of hydrolysis and the pH of a O·lM solution of (a) sodium carbonate and (b) sodium hydrogen carbonate. From Table 1.6 for H 2C0 3 K a 1 = 4·31 X 10- 7 ; pKa 1 = 6·37 and K a2 = 5·61 X 10- 11; pKa2 = 10·25. (a) The hydrolysis of the carbonate ion takes place in two stages:
CO~-

+ H 20 +2 HC0 3 + OH-

(Kh 1 ) (Kh 2 )

and HC0 3 + H 20 +2 H 2C0 3 + OHThe two hydrolysis constants for the two steps are calculated from equation (vii): Kw 10- 1 4 4 K h l = K = 5.61 X 10-11 = 1·79 X 10a2

and
Kh 2

=

Kw
K
a1

= 4.31 x 10

10- 1 4

7

= 2·32 X 10-

8

Again K h l » K h 2 meaning that the second hydrolysis step can be neglected in the calculations. The degree of hydrolysis can be calculated from equation (ix) :

K x= - -hl +
2e 1·79 X 10- 4 0·2

+

3·20 X 10- 8 1·79 X 10- 4 4xO·Ol + 0·1

x = 4·22 x 10- 2 or 4·22 per cent

The approximate expression (ixa) yields a figure close to the above:
x =

J J
K ~ e

=

1·79x 10 0·1 1

4

= 4·23 X 10- 2 or 4·23 per cent

The pH of the solution is calculated from equation (xiv):
PH

=

7+ 2PKa 2+ 2 oge

I

I

10·25 1 = 11·63 = 7+2 2-43

1.20 QUALITATIVE INORGANIC ANALYSIS

The solution is again strongly alkaline (b) The hydrolysis of the hydrogen carbonate ion proceeds as HC0 3 +H 20 +::t H 2C0 3+OHThe hydrolysis constant has already been calculated (cf. Example lO (a)):
K h 2 = 2'32
X

(xv)

lO-8

the degree of hydrolysis can be calculated from equation (ix): x=
2 - -h+ 2e

K

2'32 X lO-8 2 x 0'1 +

5'39 X lO-16 2'32 X lO-8 4 x 0'01 + 0'1

x

=

4'82

X

lO-4 or 0'048 per cent

The same result is obtained from the approximate expression (ixa):
x =

jK

h2

=

e

)2'32 X lO-8 = 4'82 0'1

X

lO-4

The calculation of pH needs more consideration, as apart from the hydrolysis (equation xv), the dissociation equilibria: HC0 3 +::t CO~- + H+ H 20 +::t H+ + OHand H 2C0 3 +::t HC0 3 + H+ (xviii) produce hydrogen and hydroxyl ions also. A mathematically correct treatment, taking all these equilibria into consideration, yields a complex expression for the hydrogen-ion concentration, which can only be solved by successive approximation. An approximate expression can be obtained by combining equilibria (xv), (xvi), and (xvii) to obtain 2HC0 3 +::t H 2C0 3 + CO~showing that in the solution the concentrations of carbonic acid and carbonate ions are equal: [H 2C0 3 ] =
[CO~-]

(xvi) (xvii)

(xix)

Combining the expressions for the primary and secondary dissociation constants of carbonic acid we obtain:
Ka 1 x Ka 2
=

[H+] [HC0 3] [H 2C0 3]

X

[H+] [CO~-] [HC0 3 ] (cf. xix)

[H+]2[CO~-] = [H+]2 [H 2 C0 3 ]
x 5'61 x lO

and thus the hydrogen-ion concentration [H+] = JKa 1Ka2 = J4'31 x lO
44
7 11

=

4·95 X lO-9 mol £-1

THEORETICAL BASIS 1.20

For the pH we obtain

pH = -log(4'95 x 10- 9 ) = -(0'69-9) = 8'31
The experimental value, obtained by glass electrode measurements is pH = 8'18, indicating that the error introduced by the simplified way of calculation together with the error due to the use of concentrations instead of activities is very small indeed. DI. Salts of strong acids and weak bases, when dissolved in water, produce a solution, which reacts acidic. The M+ cation of the salt reacts with hydroxyl ions, produced by the dissociation of water, forming the weak base MOH and leaving hydrogen ions behind: H 20 +2 H+ +OHM+ + OH- +2 MOH
/

The overall hydrolysis equilibrium can be written as
M+ + H 2 0 +2 MOH + H+
(i)

Since hydrogen ions are formed in this reaction, the solution will become acid. The hydrolysis constant can be defined as
K _ [MOH] [H+] _ Kw h [M+] - Kb

(ii)

showing that the hydrolysis constant is equal to the ratio of the ionization constants of water and the weak base. The degree of hydrolysis (x) for the salt of a monovalent weak base can again be correlated to the hydrolysis constant as

Kh

X

2

e

= I-x.

~

from which the degree of hydrolysis can be expressed as

x = 2e

s,

+ 4c2 + ~

jK~

s,

(iv)

If x is small (2-5 per cent), this reduces to

x =

j~h

(iva)

In these equations e represents the concentration of the salt. The hydrogen-ion concentration can be obtained from the equation of the hydrolysis constant (ii) because, according to the stoichiometry of equation (i), the concentration of the undissociated weak base is equal to that of the hydrogen ions:
(v)

In this assumption we neglected the small concentration of hydrogen ions originating from the dissociation of water. We can also say that, provided that the degree of hydrolysis is not too great, the concentration of the cation M+ is equal to the total concentration of the salt: (vi)
45

LW QUALITATIVE INORGANIC ANALYSIS

Combining equations (ii), (v), and (vi) we can express the hydrogen-ion concentration as: [H+]

= v~C = ~

10- 7

~ vI(;,

(vii)

The pH of the solution is
pH = 7-!pKb - ! log c

(viii)

Example 11 Calculate the degree of hydrolysis and the pH of a O'lM solution of ammonium chloride. From Table 1.6 the dissociation constant of ammonium hydroxide K b = 1'71 X 10- 5 , pKb = 4'77. The hydrolysis equilibrium can be written as

NH1 +H 20 +2 NH 40H+H+ The hydrolysis constant
Kh = -

Kw

«,

=

10- 14 1'71 x 10

= 5' 86 x 105

10

As the value of this constant is small, the degree of hydrolysis can be calculated from the approximate formula (iva):
x =

jK
C

h

=

100'1 = 7'66 x 10- 5 or 0'0077 per cent
5·86
X

10

The pH of the solution can be calculated from equation (viii):
1 1 p H = 7 --rPKb - 2 1 c = 7- 4·77 0g 1 2 +2

= 5. 17

IV. Salts of weak acids and weak bases, when dissolved in water, undergo hydrolysis in a rather complex way. The hydrolysis of the cation leads to the formation of the undissociated weak base. M+ + H 20 +2 MOH + H+ while the hydrolysis of the anion yields the weak acid: A- +H 20 +2 HA+OH(ii) The hydrogen and hydroxyl ions formed in these processes recombine in part to form water: H+ + OH- +2 H 20 (iii) These equations may however not be added together, unless the dissociation constants of the acid and the base happen to be equal. Depending on the relative values of these dissociation constants, three things may happen: If K, > K b (the acid is stronger than the base), the concentration of hydrogen ions will exceed that of hydroxyl ions, the solution will become acid. If K, < K b (the base is stronger than the acid), the reverse will happen and the solution becomes alkaline.
46

(i)

(ii). and the solution will be neutral. c. and (iii) in that order respectively.20 If K. In this case the hydrolysis can be described by the equation: NH1 +CH 3COO. because all the equilibria prevailing in the solution have to be taken into consideration. = l'75x 10. the sum of the concentrations of cations and anions in the solution must be equal (the so-called 'charge balance' condition) : (viii) The total concentration of the salt.5 ) and of ammonium hydroxide tK. equations (i) and (ii) can be added. it is equal to the sum of concentrations of the anion and the undissociated acid: (ix) Second. = K b (the acid and the base are equally weak).THEORETICAL BASIS 1. it is also equal to the sum of the concentrations of the cation and of the undissociated base: (x) 47 . another three equations must be found therefore to solve the problem.+2 H 20 These three equilibria correspond to the general equations (i). = 1'71 x 10. One of these can be derived from the fact that. when the overall hydrolysis equilibrium can be expressed as M+ +A + +2H 20 +2 MOH+HA+H+ +OHThe hydrolysis constant can be expressed as: (iv) s. in fact. First. as the dissociation constants of acetic acid (K. is the sum of the three equilibria : NH1 +H 20 +2 NH 40H+H+ CH 3COO.+H 20 +2 NH 40H+CH 3COOH which. because of electroneutrality. can be expressed in two ways. The calculation of hydrogen-ion concentration is rather difficult. = [MOH] [HA] [H+] [OH-] Kw [H+] [A ] = KaK b The degree of hydrolysis is different for the anion and for the cation (unless the two dissociation constants are equal).5 ) are practically equal. = [H+] [A-] [HA] [M+][OH-] [MOH] (v) «. = (vi) (vii) Kw = [H+] [OH-] contain altogether six unknown concentrations. The equations defining the equilibrium constants K. the two concentrations will be equal. In general. Such is the case of ammonium acetate.+ H 20 +2 CH 3COOH + OHH+ + OH.

will shift the equilibrium towards the formation of undissociated acetic acid (that is towards the left in the above equation).+ H+ is however almost negligible. As a first approximation the value [H+]. and to maintain this hydrogen-ion concentration during the course of the analysis. is almost completely dissociated. It is impossible therefore to maintain the pH in a weakly acid. and can be easily changed by reaction with traces of alkaline dissolved from the glass or by ammonia traces. the above method will not help. when we need to maintain a pH of 4 in a solution during our analytical operations. present in the atmosphere of the laboratory. 1. especially if K. use this in the right-hand side of equation (xi). and use this new value in a successive approximation. or weakly alkaline solution simply by the addition of a calculated amount of a strong acid or base.1. This is a very small amount. To solve it. This solution will possess a certain pH.21 QUALITATIVE INORGANIC ANALYSIS Combining the six equations (v)-(x). We may add hydrochloric acid to the (originally neutral) solution in such an amount. because the presence of large amounts of acetate ions (which originate from the dissociation of sodium acetate). Let us consider for example a case. that the concentration of the free acid should be O·OOOlM in the final mixture. neutral. The dissociation of acetic acid CH 3COOH +2 CH 3COO. like any other salt. Similarly.= j Kw ~: may be used. we have to find an approximate value of [H+].+ H+ -+ CH 3COOH the hydrogen-ion concentration of the solution remains therefore virtually unchanged. Let us consider now a mixture of a weak acid and its salt.21 BUFFER SOLUTIONS In the practice of inorganic qualitative (and quantitative) analysis it is often necessary to adjust the hydrogen-ion concentration to a certain value before a test.[H+] Kb C [~+] 1) (xi) This equation is implicit for [H+]. If however the pH of the solutions has to be kept between say 2 and 12. all that happened is that the amount of acetate ions decreased while 48 . solve for [H+]. In such a solution the sodium acetate. this means that we must have 0·036 mg free hydrochloric acid present. Given a solution of say 10 ml. the addition of sufficient amounts of a strong acid or a strong base can achieve this task. and K b do not differ too considerably. such as a mixture of acetic acid and sodium acetate. we can express the hydrogen-ion concentration as [H+] = Ka~ + [H ] + Kw Kw+Kb[H+] . solutions containing small amounts of alkali hydroxides are sensitive to carbon dioxide present in the air. If a strongly acid (pH 0-2) or strongly alkaline (pH 12-14) medium is necessary. these will combine with the acetate ions in the solution to form undissociated acetic acid: CH 3COO. and this pH will be kept remarkably well even if considerable amounts of acids or bases are added. If hydrogen ions (that is a strong acid) are added.

The hydrogen-ion concentration can be calculated from considerations of the chemical equilibrium which exists in such solutions. buffer solutions contain a mixture of a weak acid and its salt or a weak base and its salt. Such solutions show therefore a certain resistance towards both acids and alkalis. because the latter react with the (undissociated) ammonium hydroxide: NH 40H+H+ -+ NH1 +H 20 while the resistance against hydroxyl ions is based on the formation of the undissociated base from ammonium ions (which originate from the salt): NH1 +OH-+ NH 40H In general. The equilibrium constant can be expressed as from which the hydrogen-ion concentration can be expressed as (i) The free acid present is almost completely undissociated. A mixture of ammonium hydroxide and ammonium chloride shows resistance again hydrogen ions. will be (approximately) equal to the concentration of the anion: (iii) Combining equations (i). hence they are termed buffer solutions. because the presence of large amounts of the anion A-. hydroxyl ions are added. A buffer solution can also be prepared by dissolving a weak base and its salt together. on the other hand. (ii) For the same reason the total concentration of the salt. If. the dissociation equilibrium HA +2 H++Aexists in the solution. The total concentration of the acid.THEORETICAL BASIS 1. c. will therefore be (approximately) equal to the concentration of the undissociated acid.21 the amount of undissociated acetic acid increased. which originates from the salt. c.+ H 20 again the hydrogen. only the number of acetate ions will increase while the amount of acetic acid will decrease.(and hydroxyl-) ion concentration will not change considerably. Considering a buffer made up of a weak acid and its salt. these will react with the acetic acid: CH 3COOH + OH-+ CH 3COO. (ii). and (iii) we can express the hydrogen-ion concentration as (iv) 49 .

Section 1. (x) Cb or the pH as pH = 14-pKb . we know that in any aqueous solution the ionic product of water (cf.S. (viii).1 4 (ix) By combining equations (vi). Thus [H+] = 1'75 x 10.l o g Cb Cs (xi) where 14 = -log Kw = pKw ' Example 12 Calculate the hydrogen-ion concentration and pH of a solution prepared by mixing equal volumes ofO'lM acetic acid and 0'2M sodium acetate. the dissociation equilibrium which prevails in such a solution is MOH +2 M+ +OHfor which the dissociation equilibrium constant can be expressed as (vi) With similar considerations. c.Kw xc.5 x 0'05 = 8'75 x 10. containing the cation M+. we can write for the total concentration of the base. 50 . that (vii) and (viii) Finally. (vii).21 QUALITATIVE INORGANIC ANALYSIS or thepH as c. = 1'75 x 10. - «. and (ix) we can express the hydrogenion concentration of such a buffer as _ [H +] . c. = 0'1 mol £-1 (note that both original concentrations were halved when the solutions were mixed).6 K. and for the concentration of the salt. We use equation (iv): [H+] = «. Ca = 0'05 mol £-1 and c. ~a s From Table 1. if the buffer is made up from a weak base MOH and its salt.18): Kw = [H+] [OH-] = 10.6 ) = -(0'94-6) = 5'04.1.6 0'1 and pH = -log(8'75 x 10. pH = pKa+logCa (v) Similarly.

1 The relative molecular mass ofNH 4Cl being 53'49.21 Example 13 We want to prepare 100 ml of a buffer with pH = 10.log(0·83 .2H20 O'IM HCI+0'09M KCI Saturated solution of potassium hydrogen tartrate. Standard buffer solutions The following standards are suitable for the calibration of pH meters and for other purposes which require an accurate knowledge of pH. are shown in Table 1. For 100 ml we need one-tenth of this. 1937). KHC sH404 O'IM CH 3COOH+0'IM CH 3COONa 0'025M KH 2P04 + 0'025M Na 2HP04 . diluted to 100·0 ml. B.log( -1'17) = num.12H 2O 0'05M Na 2B40 7. The compositions of a number of typical buffer solutions are given below. Table 1.2) = 6·76 x 10. Solutions for the pH range 1'40-2'20 at 25°C (German and Vogel.2 x 53'49 = 3'59 g.2 mol t.H2C204.12H 2O Solutions of known pH for colorimetric determinations are conveniently prepared by mixing appropriate volumes of certain standard solutions.9 Compositionof buffer solutions A. the weight of salt needed for 1 t is 6'76 X 10. that is 0'359 g. KHC 4H40 6 0'05M potassium hydrogen phthalate. pKb = 4'77 (from Table 1. How much ammonium chloride must be added and dissolved before diluting the solution to 100 ml? We use equation (xi): pH = 14-pKb-log Cs Vb Here pH = 10.I).9. X(ml) 48·9 37·2 27-4 19·0 16·6 Y(ml) 1'1 12-8 22"6 31·0 33-4 pH 1·40 1'50 1'60 1'70 1·80 X (ml) Y(ml) 36'8 40·0 42·4 45·6 pH 1·90 2·00 2'10 2-20 13"2 10·0 7-6 4'4 51 . X mI of O'IM p-toluenesulphonic acid monohydrate (19'012 gel) and Y ml of O'IM sodium p-toluenesulphonate (19'406 g (. There are several buffer systems which can easily be prepared and used in the laboratory. Rearranging and inserting the above values we obtain log Cs = 14-4'77+1og0'4-1O = -1'17 c.6). covering the pH range from 1'5 to 11. We have 50 ml 0'4M ammonia solution. Compositions of some of these. = num. and Cb = 0'2 (that is if 50 ml 0'4 molar solution is diluted to 100 ml it becomes 0'2 molar). Solution pH at 12°C 25°C 1'48 2'07 4'()()() (15°C) 4·65 3'57 4·005 4-64 6'85 9'18 38°C 1'50 2·08 4·015 4·65 6·84 9'07 O'IM KHC204.THEORETICAL BASIS 1.

3'893 g of A. Solutions for the pH ranges 2'2-3·8. (A) pH 2'2-3'8. 50 ml 0'2M KHphthalate + Q ml 0'2M NaOH. diluted to 200 ml (C) pH 5'8-8. The pH values of mixtures of lOO ml of this solution with various volumes (X) of O'2M sodium hydroxide solution (free from carbonate) are tabulated below. 1916).R.9 C. 1939) A mixture of 6·008 g of A.21 QUALITATIVE INORGANIC ANALYSIS Composition of buffer solutions Table 1.1. 50 ml 0'2M KH 2P04 + R ml 0'2M NaOH. 4'0--6'2.R. 7'8-10'0 at 20"C Lubs. diluted to 200 ml A B C D P(ml) HCI 46·60 39'60 33-00 26'50 20-40 14·80 9·65 6·00 2-65 pH 2·2 2·4 2-6 2-8 3·0 3'2 3-4 3'6 3'8 Q(ml) NaOH 0'40 3'65 7-35 12·00 17'50 23'65 29'75 35'25 39'70 43-10 45'40 47·00 pH 4·0 4·2 4·4 4·6 4·8 5·0 5·2 5·4 5-6 5·8 6·0 6'2 R (ml) NaOH pH 5'8 6'0 6'2 6'4 6'6 6'8 7'0 7-2 7'4 7-6 S(ml) NaOH 2-65 4·00 5·90 8·55 12·00 16'40 21·40 26'70 32'00 36'85 40'80 43-90 pH 7-8 8'0 8·2 8·4 8·6 8·8 9·0 9·2 9·4 3'66 5-64 8'55 12-60 17·74 23'60 29'54 34·90 39·34 42·74 45'17 46'85 ss 7-8 8·0 9'8 10·0 * That is a solution containing 12·369 g H 3B02 and 14'911 g KCI per litre. potassium dihydrogen phosphate. diluted to 200 ml (B) pH 4. 5'8-8'0. 1921).0.2. 50 mI 0'2M KHphthalate + P mI 0·2M HCI. 50 ml 0'2M H 3B03 and 0'2M KCI*+S ml 0'2M NaOH.R. diluted to 200 ml (0) pH 7-8-10'0. Solutions for the pH range 2'2-8'0 (McIlvaine. boric acid and 5'266 g of pure diethylbarbituric acid is dissolved in water and made up to I litre. E. X (ml) Na 2HP04 Y(ml) Citric acid 1%0 18'76 17-82 16·83 15-89 15'06 14·30 13·56 12·90 12·29 11·72 11'18 10·65 10'14 9'70 pH 2·2 2-4 2-6 2-8 3'0 3'2 3-4 3'6 3-8 4'0 4·2 4'4 4·6 4-8 5'0 X(ml) Na2HP04 10·72 11'15 11·60 12·09 12-63 13-22 13'85 14·55 15·45 16·47 17-39 18'17 18·73 19·15 19'45 Y(ml) Citric acid 9·28 8'85 8·40 7-91 7·37 6'78 6'15 5'45 4·55 3'53 2-61 1·83 1·27 0'85 0'55 pH 5·2 5·4 5·6 5'8 6·0 6'2 6·4 6'6 6'8 7·0 7-2 7·4 7-6 0'40 1·24 2'18 3'17 4·11 4·94 5'70 6'44 7'10 7'71 8'28 8·82 9'25 9'86 10·30 7-8 8·0 (Clark and D. Solutions for the pH range 2'6-12'0 at lSOC . 52 . 20'00 ml mixtures of X mI ofO'2MNa 2HP04 and Y mI ofO'IM citric acid.universal bulTer mixture (Johnson and Lindsey.0-6. citric acid. 1'769 g of A.

wecan easily determine the approximate pH of a test solution.22 Table 1. the equilibrium will be shifted towards the formation of the indicator anion.THEORETICAL BASIS 1. A few of these will be discussed here. is different from the indicator acid. that is hydrogen ions are removed. dissociation takes place according to the equilibrium HInd +2 H+ --Ind" The colour of the indicator anion. If the solution to which the indicator is added is acid. the above equilibrium will be shifted towards the left. while methyl orange a red (acid) one. The use ofindicators and indicator test papers An indicator is a substance which varies in colour according to the hydrogen-ion concentration. and observe the colour. If however the solution becomes alkaline. and the colour of the solution changes. we can be sure that the pH of the solution is between 2·8 and 3·1. that is the colour of the undissociated indicator acid becomes visible. The undissociated indicator acid or base has a different colour to the dissociated product. In the case of an indicator acid. It is generally a weak organic acid or weak base employed in a very dilute solution. A.22 THE EXPERIMENTAL DETERMINAnON OF pH In some instances it may be important to determine the pH of the solution experimentally. but definite range of pH. and with such the approximate pH of the solution can be determined with one single test. The colour change takes place in a narrow. that is it contains large amounts of hydrogen ions. Iffor example we find that under such circumstances thymol blue shows a yellow (alkaline) colour.9 Composition of buffer solutions pH 2-6 X (ml) pH 5·8 6'0 6·2 6'4 6·6 6·8 7'0 7-2 X(mI) pH 9·0 9·2 9'4 9·6 9·8 10'0 10'2 10'4 10'6 10'8 11'0 11·2 1104 11'6 11·8 12·0 X (ml) 2-8 3'0 3'2 N 3'6 H 4·0 4·2 4·4 4·6 4-8 5·0 5·2 5'4 5-6 2·0 4'3 6·4 8·3 10'1 11·8 13·7 15·5 17-6 19·9 22·4 24-8 27·1 29·5 31·8 34·2 7·4 7-6 7-8 8·0 8·2 8'4 8·6 8·8 36'5 38·9 41·2 43'5 46·0 48'3 50'6 52-9 55·8 58·6 61·7 63'7 65-6 67·5 69'3 71'0 72'7 74·0 74'9 77-6 79'3 80'8 82'0 82-9 83'9 84·9 86'0 87·7 89'7 92'0 95·0 99·6 1. Some of the indicators listed in Table 1. According to the accuracy we need and the instrumentation available we can have a choice of several techniques. Such a 'universal' indicator may 53 . HInd. If we possess a set of such indicator solutions.10 summarizes the colour changes and the pH ranges of indicators within which these colour changes take place. On a small strip of filter paper or on a spot-test plate we place a drop of the indicator and then add a drop of the test solution.10 may be mixed together to obtain a so-called 'universal' indicator. Ind -. Table 1.

and 1 g thymol blue in 1 t absolute ethanol. the approximate pH values with their corresponding colours are given in the following small table: pH colour 2 red 4 orange 6 yellow 8 green la blue 12 purple Small strips of filter paper may be impregnated with this solution and dried.6 3'1-4·4 3'0-5'0 H-5'4 4'2-6·3 4-8-6'4 5·0-8'0 6'0-7-6 7.1.0-0'8 0. According to the pH of the solution this 'universal' indicator shows different colours. 0·6 g dimethylazobenzene.6 7-2-8'8 7-3-8'7 8'0-% 8'2-10. 0'4 g methyl red.2-2-8 2-8-4.0 BriIliant cresyl blue (acid) z-Naphtholbenzein (acid) Methyl violet Cresol red (acid) Thymol blue (acid) Meta cresol purple Bromophenol blue Methyl orange Congo red Bromocresol green Methyl red Chlorophenol red Azolitmin (litmus) Bromothymol blue Diphenol purple Cresol red (base) IX-Naphtholphthalein Thymol blue (base) z-Naphtholbenzein (base) Phenolphthalein Thymolphthalein Brilliant cresyl blue (base) Amino-diethylamine-methyl diphenazonium chloride Pentamethyl p-rosaniline hydrochloride o-Cresolsulphone-phthalein Thymol-sulphone-phthalein m-Cresol sulphone-phthalein Tetrabrornophenol-sulphone phthalein Dimethylamino-azo-benzenesodium sulphonate Diphenyl-bls-azo-znaphthylamine-4-sulphonic acid Tetrabromo-m-cresol-sulphonephthalein o-Carboxybenzene-azodimethylaniline Dichlorophenol-sulphonephthalein Dibromo-thymol-sulphonephthalein o-Hydroxy-diphenyl-sulphcnephthalein o-Cresol-sulphone-phtbaletn e-Naphthol-phthalein Thymol-sulphone-phthalein (See above) be prepared.0-1'8 1'2-2-8 1'2-2-8 1. by dissolving 0'2 g phenolphthalein. The solution must be neutralized by adding a few drops of dilute sodium hydroxide solution until its colour turns to pure yellow.0 0. 0·8 g bromothymol blue.0 8'3-10.0 9'3-10'5 10'8-12.10 IndIcator pH range 0. For 54 .0-1.22 QUALITATIVE INORGANIC ANALYSIS Colour changes and pH range of some Indicators ChemIcal name Colour In acid solutIon Redorange Colourless Yellow Red Red Red Yellow Red Violet Yellow Red Yellow Red Yellow Yellow YelIow Yellow Yellow Yellow Colourless Colourless Blue Colour In alkaline solution Blue Yellow Blue-green Yellow Yellow Yellow Blue Yellow Red Blue Yellow Red Blue Blue Violet Red Blue Blue Blue-green Red Blue Yellow Table 1.0-8. after Bogen. Such an indicator test paper may conveniently be stored for longer times.

Firms manufacturing and selling chemicals. On the other hand. within the pH range of 1-11. the approximate pH of the test solution is determined by one of the methods described in Section 1. Then a series of buffer solutions is prepared (cf. by which the pH can be determined with an accuracy of 0'1-0'2 pH unit.21. say 5 or 10 ml. The colorimetric determination of pH The principle outlined under Section 1.differing successively inpH by about 0'2 and covering the range around the approximate value. Section 1. The appropriate narrow-range test paper to use must be selected by a preliminary test with a wide-range paper. having approximately the same dimensions.-=I 1--::-A I 1 c- I 1 1 1 1 I I I 1 1 I =11lS:S:S =t--=1 1 = 1 I C 1 I 1 1 I 1 1 1 -I -r::r-=-: I- l:SS:S __ 1 1 B 1 1 1 1 =1 I-~ I 1 1 1 1 1 1 D 11 1 I 1 1 I I le Light ~I l:SS:S Fig. but a convenient colour chart is supplied with the paper strips. by the aid of which the approximate pH can easily be determined by comparing the colour of the paper with that shown on the chart.Table 1. normally market wide-range universal pH test papers.22 a test one strip of this paper should be dipped into the solution. With a single paper the approximate pH of a test solution may be determined with an accuracy of O· 5-1'0 pH units. 1. while in alkaline ones it shows a blue colour. B.22. Equal volumes. and a small. and the colour examined. A series of different colours corresponding to the different pH values is thus obtained. Some firms also market series of papers. identical quantity of a suitable indicator for the particular pH range is added to each tube. When a complete (or almost com- -. In acid solutions litmus turns to red. The composition of the indicator mixture is generally not disclosed. of the buffer solutions are placed in test tubes of colourless glass.A can be made more precise by using known amounts of buffers and indicator solutions and comparing the colour of the test solution with a set of reference standards under identical experimental circumstances. First.THEORETICAL BASIS 1. and the resulting colour is compared with that of the individual coloured reference standards. in some cases we may only have simply to test whether the solution is acid or alkaline. For this test a strip oflitmus paper may be used.22.7 55 . An equal volume of the test solution is then treated with an equal volume of indicator to that used for the buffer solutions.9). The transition pH range lies around pH = 7.A.

). the simple comparison method described above. fitted on a revolving disc. As the disc revolves. and D are glass cylinders with plain bottoms standing in a box. The preparation of reference standards in this procedure is a tedious task and may require considerable time. For turbid or slightly coloured solutions. A. The glass discs in the two instruments are not interchangeable. prepared from buffer solutions. There is also an opal glass screen against which colours can be compared. 56 . England.) indicators. from The British Drug Houses Ltd. Viewing through the two pairs of tubes from above. of Long Island City).. * shown on Fig. A contains the solution to be tested with the indicator. N.A. B.f r .22 QUALITATIVE INORGANIC ANALYSIS plete) match is found.. and each colour standard passes in turn in front of an aperture through which the solution in the cell (or cells) can be observed. U. Time can be saved by applying what is called a permanent colour standard method. Salisbury. which requires a special device. shown in Fig. which is painted dull black in the inside. The device is fitted r r . 1.... C. can no longer be applied..S. Inc. A similar apparatus is marketed by Hellige. the pH of the colour standard visible in the * Manufactured by The Tintometer Ltd.O Fig. The Lovibond comparator. this utilizes Merck's (U.Y. C contains the solution of known pH with the indicator..g. the test solution is then moved from hole to hole until the best colour match is obtained. When making the measurements. B contains an equal volume of water. the test solution and the corresponding buffer solution have the same pH ± 0·2 unit. the so-called comparator. The commercial standards. Milford. the colour of the test solution is compensated for.. The interference due to the coloured substance can be eliminated in a simple way by a device introduced by H. For matching the colours the buffer solutions may be arranged in the holes of a test tube stand in order of increasing pH. Walpole (1916).7.A.8 with low compartments to receive small test tubes or rectangular glass cells. are not permanent and must be checked every few months.1.. The disc can revolve in the comparator." rr--. only tube C has to be removed and replaced by another standard for better matching..8 employs nine permanent glass colour standards. 1. Special stands with white background and standards for making the comparison are available commercially (e. 1. but indicator is not added to D.S. while D contains the same volume of the solution to be tested as was originally added to A.

on the other hand. The colour discs available include cresol red (acid and base range).10.THEORETICAL BASIS 1. of the cell can thus be expressed as e. E ca1 = const The potential of the saturated calomel electrode is + 0'246 V at 25°C (measured against the standard hydrogen electrode). bromocresol blue. Longman 1966. A specified amount (with the Lovibond comparator 10 ml) of the unknown solution is placed in the glass test tube or cell.39). E gb the potential of the glass electrode.A) and then the suitable disc is selected and inserted into the comparator.m. The treatment in this section is factual. thymol blue. e. 379 et f. One of the electrodes. of an electrochemical cell can be regarded as the absolute value of the difference of the electrode potentials of the two electrodes. the appropriate quantity of indicator (normally 0'5 ml) is added and the colour is matched against the glass disc. A determination of the approximate pH of the solution is made with a 'universal' or 'wide range' indicator or with an indicator test paper (see under Section I. most often called simply a pH-meter. on the other hand. The e. bromocresol green.f. 'universal' indicator. The electrodes are connected to the terminals of an electronic voltmeter.. It is claimed that results accurate to 0'2 pH unit can be achieved.D. methyl red.D. p. termed the indicator electrode acquires a potential which depends on the pH of the solution.m. and two electrodes. Moore's Physical Chemistry.m. depends on the pH of the solution. The potentiometric determination of pH* The most advanced and precise method of the measurement of pH is based on the measurement of the electromotive force (e. The pH ranges of these indicators are listed in Table 1.m. diphenol purple. chlorophenol red.H.f. to which the potential of the indicator electrode therefore can be compared in various solutions. 4th edn. bromocresol purple. and aims to describe the necessary knowledge required for a proper measurement of pH. independent of the pH of the solution.H. has to have a constant potential. the pH of the unknown solution can be read directly from the scale. cresol red.f.22. Section 1. thymol blue (acid and base range). indicators. The Lovibond comparator is employed with B. t For a detailed discussion of electrochemical cells textbooks of physical chemistry should be consulted. W. The measured e. hence the term reference electrode is applied for this second electrode. and must be chosen adequately. If properly calibrated with a suitable buffer of a known pH.) of an electrochemical cell.f. In practice the glass electrode is used as the indicator electrode. 57 . t The two electrodes applied in building the electrochemical cell have different roles in the measurement. In pH measurements the (saturated) calomel electrode is applied as an indicator electrode. which is discussed later in this book (cf. J. phenol red. bromothymol blue. and the B. For the pH region 2-11 * The full understanding of this section implies some knowledge of electrode potentials. Provision is made in the apparatus for the application of the Walpole technique by the insertion of a 'blank' containing the solution. The second electrode.22 aperture appears in a special recess. which contains the solution of the unknown pH as electrolyte. C. = IE g1 - Ecad Here E ca1 is the electrode potential of the calomel electrode. which is constant. bromophenol blue.g.

.4 : Connecting plug Fig. 1.. The pH-sensitive glass is made by manufacturers according to various specifications.11.9 Table 1.. placed somewhere between the bulb and the top of the glass tube. as the pH can be read directly from the pH-meter. it is not necessary to measure the standard potential and to deduct the potential of the calomel electrode from the results. Cap Support Screening---H 'r-++t----r' Screen (earth) . B. which is connected to the circuit by a platinum wire..11 Composition of glasses used in the manufacture of glass electrodes" Ll 20 Na 20 21-4 28 24 Cs 20 CaO 6·4 BaO La 20 3 4 8 810 2 72·2 65 68 Dole glass Perley glass Lithium-barium glass 3 . Within one set of measurements it can be regarded as constant.. Chim.. This internal reference electrode is switched in series with the wire leading to the electrolyte in the bulb. Bouquet: Anal. Acta. Csakvary. 56 (1971) p.+-. The role of the internal reference 58 . 1. The composition of the most important glasses used in glass electrodes are listed in Table 1. Boksay and G.-J connector Inner reference electrode Ag/AgCl/M Metal conductor Buffer . The glass electrode (Fig. This quantity varies from specimen to specimen. The bulb is filled with an acid solution or with an acid buffer. described below.1. Z. it depends also on the age and on the pretreatment of the electrode. and is connected to the input of the pH-meter..22 QUALITATIVE INORGANIC ANALYSIS (where the accurate determination is most important) the pH-dependence of the potential of the glass electrode can be expressed as E g = Eg~-O'059 pH 1 Here Eg~ is the standard potential of the glass electrode.9) contains the pH-sensitive glass in the form of a small bulb.. which is fused to an ordinary glass tube.. Usually there is an internal reference electrode (a silver-silver chloride electrode) included in the circuit. 279. If we adapt the usual calibration process.

This should be removed by dipping the electrode into an organic solvent (specified in the instruction leaflet). (The current must also be low with electrodes of low resistances. it will not give reproducible readings on the pH-meter. As a rule. Through one of the holes a glass tube is fitted. When not in use. to the instrument body and through this it is earthed. making its response non-linear to pH. in most cases together with the input of the calomel electrode. In the saturated calomel electrode a saturated solution of potassium chloride is applied. is shown in Fig. and therefore reliable results cannot be obtained even with the most careful calibration. the electrical signal being passed through the inside lead. The bulb of a new glass electrode is sometimes coated with a wax layer for protection. As long as both calomel and potassium chloride are present in solid form. This electrode is therefore non-polarizable. into which a rubber stopper with two bores is placed.26). The potential of a saturated calomel electrode at 25°C is + 0·246 V against the standard hydrogen electrode. saturation is maintained by keeping undissolved crystals of potassium chloride in the solution. to avoid polarization. a constant potential.22 electrode is to protect the glass electrode from an accidental loading by electricity. A calomel electrode is basically a mercury electrode. Over pH 2 and below pH 11 the glass electrode operates reliably. and then soaking the electrode in dilute hydrochloric acid for a few days. each measurement should be preceded by a calibration with a buffer. (In such cases the electrode has to be soaked in O'lM hydrochloric acid for 1-2 days.) Though the swollen glass of the electrode is capable of conducting. The concentration of mercury(l) ions is kept constant (though low) by adding mercury (I) chloride precipitate (Hg 2Cl 2 • calomel) to the solution. The resistance of a glass electrode is usually about 108_109 n.) The cable leading from the glass electrode is therefore screened. and thus the electrode potential remains constant too. At constant temperature the chloride-ion concentration is constant. suitable for elementary work. 59 . just like the calomel electrode. this means that the concentration of mercury(l) ions remains constant (cf. The glass bulb itself is made of a very thin glass and is therefore very delicate. which means that the current in the circuit is extremely low. Section 1. (at high hydrogen-ion concentrations). A simple form of calomel electrode. glass electrodes therefore must be kept always dipped in water or in dilute acid. If the glass electrode is left to dry out. the glass electrode is suitable for the accurate measurement of pH within the range 2 to 11. this concentration of mercury(I) ions will remain constant even if a considerable current passes through the electrode. 1. It is non-polarizable and has.f. it must be handled with the greatest care. and by applying a large concentration of potassium chloride. the electrode potential of which depends solely on the concentration of mercury(I) (Hg~+) ions in the solution with which it is in contact. At pH values above 11 the so-called alkaline error of the glass electrode occurs. while the screening cable is switched.m. The proper operation of the glass electrode requires that the electrode glass itself should be wet and in a 'swollen' state. the pH of which should stand as near to the pH of the test solution as possible. It can be made of a simple reagent bottle. when its response usually returns.THEORETICAL BASIS 1. This varies considerably with the hydrogen-ion concentration itself. the electrode should be kept in distilled water or in dilute hydrochloric acid. a rather high so-called diffusion potential is superimposed on the measured e. it represents a high resistance in the circuit.10. As was said before. Below this pH.

Washing can be done by shaking the precipitate with distilled water and decantation. When cooling the solution freezes into the tube but remains conductive. The mercury must be of the purest available quality. Over the mercury a freshly precipitated and carefully washed layer of calomel must be placed.c.. to 100 ml of which 0'5 g of agar has been added. With both instruments the amplified signal is then displayed on a meter. KCI+Hg CI 2 Hg Fig. component filtered. More expensive instruments convert the d. The platinum wire is then connected to the circuit. The end of the salt bridge should be kept dipped into concentrated potassium chloride solution when storing. . the d. 1. signal. This salt bridge then has to be fitted into the second hole of the rubber stopper. if possible trebly distilled.10 with a platinum wire fused through its bottom. A liberal amount of analytical grade solid potassium chloride should be added and the vessel filled with saturated potassium chloride solution. On cooling the level of solution decreases because of contraction. . the procedure being repeated 8-10 times. Cheaper instruments contain a differential amplifier. with this the electric signal coming from the cell is compensated by turning a potentiometer knob until a galvanometer shows zero deflection. the d.1. calibrated in pH units (and in most cases also in millivolts). and finally the amplified signal is rectified. signal. thus enabling electrical contact between the electrode and the test solution. The wire leading from the electrode to the pH-meter need not be screened. The electrode is now ready for use. which is then amplified. into an a.c.10) should be filled with a hot solution of concentrated potassium chloride. (The input resistance of a good pH-meter is in the region of 1012_1013 n. such an instru60 . input signal being amplified directly in the instrument. it should therefore either be topped up. or the empty parts of the U-tube cut away. The pH-meter is an electronic voltmeter with a high input resistance. bent in U-shape (see Fig. coming from the measuring cell.c. A third type of electronic pH-meter is also known.) Both valve and transistorized instruments are in use. 1. which is in direct contact with the mercury in the bottom of the electrode vessel. They generally operate from the mains.c.22 QUALITATIVE INORGANIC ANALYSIS - -1- . Because of the low currents which circulate in the cell. Then a small tube. and contain their own power supply circuit with a rectifier.

and a sufficient time.23 ment needs also an amplifier between the galvanometer and the potentiometric circuit. on the other hand. (In any case the instruction manual should be followed or an experienced person consulted.23 DEFINITION OF ACIDS AND BASES The classical concepts of acids and bases. marked 'reference' or 'calomel'. the galvanometer is zeroed with the potentiometer knob. It was. the 'selector' must be switched to 'zero' position. the pH-meter is switched off. The glass and calomel electrodes are dipped into the buffer. The 'temperature selector' must be set to the room temperature. With pH-meters based on the principle of compensation. The glass electrode must be kept in water or dilute hydrochloric acid. and the pH of the test solution read from the scale.) The 'range selector' switch should then be set from 'zero' (or 'standby') position to the range which incorporates the pH of the buffer. D. rather than switched on and off frequently. must be allowed until complete thermal and electrical equilibrium is achieved. and the 'buffer adjustment' knob operated until the meter deflects to a position on the pH-scale identical to the pH of the buffer. the operations are similar to those mentioned above. the electrodes are taken out of the buffer. which become most apparent if acid-base phenomena in non-aqueous solutions have to be interpreted. ranging from a few minutes to half an hour. 61 . but the potentiometer knob (with the pHscale) is set to a position corresponding to the pH of the buffer. and the galvanometer zeroed with the 'buffer adjustment' knob. Nevertheless this theory has limitations. When the test solution is measured.22 are sufficient to explain most of the acid-base phenomena encountered in qualitative inorganic analysis carried out in aqueous solutions. Then.15-1. and the electrodes connected to the relevant input terminals. and the pH of the solution read from its scale. (but not always) the 'zero' knob must be adjusted until the meter shows a deflection given in the instruction manual (generally 0 to 7 on the pH-scale). as outlined in Sections 1. with pH nearest to the expected pH of the test solution. When measuring the pH the instrument has to be switched on first. The input of the calomel electrode. When the measurement is finished. is generally an ordinary banana socket. When finishing for the day.THEORETICAL BASIS 1. however. In the classical acid-base theory two ions. and immersed in the test solution. Usually. and the electrodes rinsed with distilled water and stored away. the input terminal of the glass electrode looks somewhat special to accommodate a plug with a screened cable. On such instruments the pH is read from the position of the potentiometer knob. THE BRPNSTED-LOWRY THEORY OF ACIDS AND BASES 1. Now a suitable buffer is chosen. rinsed carefully with distilled water. and is marked 'glass' or 'indicator'. while the salt bridge of the calomel electrode should be left dipped into concentrated potassium chloride. The 'selector' is again set to the same position as before. The 'selector' switch is then switched to 'zero' position. the hydrogen ion (that is the proton) and the hydroxyl ion are given special roles. otherwise it should be left on.

which was proposed independently by J. This point can be illustrated with some experimental facts. acetate. Brensted and T. Such considerations led to a more general definition of acids and bases. is taken up by another base. sodium acetate. Sodium hydroxide.+ H+ H3P04 +2 H 2POi + H+ H 2POi +2 HPOi. A and B are termed a conjugate acid-base pair. Lowry in 1923. while it acts as a strong base in water. Other experimental facts indicate that in glacial acetic acid all soluble acetates. or amide (NH 2). released by the acid. They defined acid as any substance (in either the molecular or the ionic state) which donates protons (H+). shows properties of a true base. while sodium amide (NaNH 2 ) takes up such a role in liquid ammonia. can be singled out as solely responsible for base behaviour. and in liquid ammonia all soluble amides possess base properties.+H+ CH 3COOH +2 CH 3COO. M.it can be regarded as a 'half reaction' which takes place only if the proton.23 QUALITATIVE INORGANIC ANALYSIS pointed out that while the proton has indeed exceptional properties. Denoting the acid by A and the base by B.+ H+ HPOi.+2 PO~. It is reasonable to suggest therefore that the proton (the only common ion present in both acids) is responsible for their acid character. shows no special base characteristics in the other solvents (though it reacts readily with glacial acetic acid). on the other hand. However none of the three ions. but also in glacial acetic acid or liquid ammonia as solvents. In glacial acetic acid. It was found for example that perchloric acid acts as an acid not only in water. The equation expresses a hypothetical scheme for defining the acid and base . and a base as any substance (molecular or ionic) which accepts protons. and hence the new definition is in no way connected to any solvent.1. Some acid-base systems are as follows: Acid +2 Base+H+ HCl +2 Cl.+ H+ HN0 3 +2 N0 3 + H+ H 2S04 +2 HSOi + H+ HSOi +2 SOi.+ H+ NHt +2 NH 3 + H+ NH 3 +2 NH 2 + H+ H 30+ +2 H 20 + H+ H 20 +2 OH. N. the hydroxyl ion possesses no exceptional qualities entitling it to a specific role in acid-base reactions. to which acid-base function can be attributed. hydroxyl. the acid-base equilibrium can be expressed as A +2 B+H+ Such an equilibrium system is termed a conjugate (or corresponding) acid-base system.+ H+ 62 . So does hydrochloric acid. It is important to realize that the symbol H+ in this definition represents the bare proton (unsolvated hydrogen ion).

H 2S04 . bases are substances which are able to accept protons (and not. + Acid. Some substance (like HS0 4. N0 3. like HS0 4. like NHt. the product of such a dissociation. In the classical acid-base theory various types of acid-base reactions (like 63 .THEORETICAL BASIS 1. The following are included: (a) uncharged molecules. OH. the form Na". These equations represent a transfer of a proton from Al (Acid. HN0 3 . (b) anions.etc. The free proton is therefore taken up by a base of a second acid-base system. an acid-base reaction can be written as Acid I + Base. H 2POi-. the formula NaOH is illogical. like HCl. These substances are called amphoteric electrolytes or ampholytes. which produce hydroxyl or any other ion). it is more proper to express these together in one equation as Al +B 2 -+ B I +A 2 -+ Generally. OH. The basic nature of these strong bases is due to the OH. in some cases the equilibrium may be shifted almost completely in one or another direction. (c) cations. especially those with un shared electrons. H 20 etc. Thus. H 3P04 etc. forming an acid A 2 B2+H+ A2 As these two reactions can proceed only simultaneously (and never on their own). H is important to note that those substances (alkali hydroxides) which are. All these reactions lead to equilibrium.) can function both as acids and bases.23 From these examples it can be seen that according to the Brensted-Lowry theory.ions which are present in the solid state or aqueous solution. like cr.etc. strong bases are in fact not forming uncharged molecules. H 30+ etc. Reactions between acids and bases are hence termed protolytic reactions. According to this theory. and therefore cannot exist as such to any appreciable extent in solution. NH2". HPoi.or Na+ +OHwould really express the composition of sodium hydroxide. (b) anions. CH 3COOH. As already pointed out. acids can be: (a) uncharged molecules known as acids in the classical acid-base theory. the free proton. Thus. because of its small size and the intense electric field surrounding it. for example. like NH 3 and H 20 etc. those. Base. HPOi-. depending on the circumstances. Al produces a proton according to the equation: Al -+ B1 +H+ -+ this proton is taken up by B2 . H 2P0 4. the equation A +2 B+H+ does not represent a reaction which can take place on its own. according to the classical acid-base theory. but are invariably ionic in nature even in the solid state. NH 3 . The overall direction of these reactions depends on the relative strengths of acids and bases involved in these systems. as in the classical acid-base theory.) to B2 (Basey). will have a great affinity for other molecules.

24 THE PROTOLYSIS OF ACIDS. Hydrogen chloride in the gaseous or pure liquid state does not conduct electricity. the resulting solution is found to be an excellent conductor of electricity. This equilibrium is completely shifted towards the right. Some of these reactions will be discussed in more detail in subsequent chapters. Of the two 64 . and therefore contains a high concentration of ions. and possesses all the properties of a covalent compound. HCI+H 20 p H 30+ +CI(i) (ii) CH 3COOH+H20 p H 30+ +CH 3COOH 2S04 + H 20 P H 30+ + HS0 4 (iii) HS0 4 + H 20 P H 30+ + SO~(iv) H 30+ +OH.P H 20+H 20 (v) (vi) CH 3COOH+NH 3 P NHt +CH 3COOH 20+CH 3COO. To elucidate these processes. first of all in water. 1. + Base. reactions (vii) to (ix) represent 'hydrolysis' reactions. reaction (v) is the common reaction. describes the 'dissociation' (or. which is the same as reaction (v) but in the opposite direction. the autoprotolysis) of water. when dissolved in water. their protolysis yields hydronium ions. H 2S04 .P CH 3COOH+OH(vii) NHt +H 20 P H 30+ +NH 3 (viii) H 20 + HPO~.P H 2P0 4 + OH(ix) H 20 + H 20 P H 30+ + OH(x) Reactions (i) to (iv) represent 'dissociations' of acids. all the hydrogen chloride is transformed into hydronium ions. STRENGTHS OF ACIDS AND BASES It is of interest to examine the processes which take place when an acid is dissolved in a solvent. has reacted with hydrogen chloride to form hydronium and chloride ions: HCI+H 20 P H 30+ +CIFrom the original acid (HCl) and base (H 20) a new acid (H 30+) and a new base (CI-) have been formed. + Base. The great advantage of the Brensted-Lowry theory is that all these different types of reactions can be interpreted commonly as simple protolytic reactions. more properly. neutralization and hydrolysis) had to be postulated to interpret experimental facts. According to the BrenstedLowry theory this dissolution is accompanied by a protolytic reaction. reaction (vi) describes the neutralization reaction between acetic acid and ammonia which takes place in the absence of water. Some examples of protolytic reactions are collected below: Acid. of strong acids with strong bases. Similar conclusions can be drawn for other strong acids (like HN0 3 . called 'neutralization'. p Acid. HCI0 4 ) . When the gas is dissolved in water. the theory can easily be extended to acid-base reactions in non aqueous solvents.1. where the classical acid-base theory has proved to be less adaptable. Evidently water. while reaction (x).24 QULAITATIVE INORGANIC ANALYSIS dissociation. in which the solvent (water) acts as a base. let us examine what happens if a strong acid (hydrochloric acid) and a weak acid (acetic acid) undergo protolysis. behaving as a base. Moreover.

which gives up its protons less readily. what is equivalent to the former statement. An acid.e. Thus. When acetic acid is dissolved in water. For the protolysis of acetic acid this equilibrium constant can be expressed as [H 3 0 +] [CH 3COO-] K. like acetic acid. Thus the value of K. hydronium ion is the weaker acid. the resulting solution has a relatively low conductivity indicating that the concentration of ions is relatively low. Ionization constants of acids are listed in Table 1. Melior's Modern Inorganic Chemistry. the stronger the acid. 434 et f. defined and described in Section 1. the conjugate base is strong. Water as a solvent has thus a levelling effect on strong acids. The strength of an acid thus depends upon the readiness with which the solvent can take up protons as compared with the anion of the acid. this has been proved beyond doubt by various physicochemical measurements. or. The reaction CH 3COOH+H2 0 +2 H 3 0 + +CH 3COOproceeds only slightly towards the right. = [CH 3COOH] the expression being identical to that of the ionization constant.. = [Acid] The higher the ionization constant. affording a solution with a relatively low concentration of H 30+ is called a weak acid. like hydrogen chloride. listed in Table 1. The protolysis of acids in water can be described by the general equation: Acid + H 20 +2 H 30+ + Base and the protolysis constant (or ionization constant) can be expressed in general terms as [H 30+] [Base] «. The strength of acids can be measured and compared by the value of their protolysis equilibrium constant. hydrochloric acid is a stronger acid than acetic acid.16. * NH 3 + H 20 +2 NHt + OH- * This statement does not contradict the fact that ammonium hydroxide does really exist. Base dissociation constants. 6th edn. that if the acid is strong. In the view of the Brensted-Lowry theory the dissociation of ammonium hydroxide is more properly the reaction of ammonia with water. is at the same time a measure of the strength of the base. revised and edited by G. its conjugate base must be weak and vice versa: if the acid is weak. (the strong acid and H 30+). each strong acid is levelled to the strength of hydronium ions. involved in each protolytic reaction. which gives up H+ readily to the solvent to yield a solution with a high concentration of H 30+ is termed a strong acid. p. Cf. Parkes. the acetate ion is a stronger base than the chloride ion. D.6. An acid.THEORETICAL BASIS 1. and consequently the weaker the base. 65 . i. It is clear also. are related to the protolysis constant of their conjugate acid through the equation Kw K=a K b This expression can easily be derived from the case of ammonia. Longman 1967.24 acids.6. there is no need to define a base ionization constant separately. possesses a powerful tendency to combine with H+.

p Base. Displacement reactions. can be described as NHt + H 20 P NH 3 + H 30+ with the protolysis constant K = [NH 3 ] [H 30+] a [NHt] (ii) The ionization constant (or autoprotolysis constant) of water (cf. in such a case the 'undissociated' acid reacts directly with hydroxyl ions. (ii). Section 1. + Acid! 66 . Neutralization reactions may proceed in the absence of water.25 QUALITATIVE INORGANIC ANALYSIS the K b base dissociation constant for this process can be expressed by K _ [NHt] [OH-] b - [NH 3 ] (i) The protolysis of the ammonium ion. on the other hand. 1. P Base! + Acid.P H 20+CH 3COOH Acid! + Base.1. and the conjugate base (H 20) of the stronger acid is formed: H 30+ +CH 3COO.is Kw = [H 30+] [OH-] (iii) Combining the three expressions (i). the great advantage of the Brensted-Lowry theory lies in the fact that any type of acidbase reaction can be interpreted with the simple reaction scheme Acid! + Base.25 INTERPRETATION OF OTHER ACID-BASE REACTIONS WITH THE BRf3NSTED-LOWRY THEORY As already outlined. are easy to understand. which are present in the solid phase. and (iii) the correlation K = Kw a Kb can easily be proved. The following examples serve to elucidate the matter: Neutralization reactions between strong acids and metal hydroxides in aqueous solutions are in fact reactions between the hydronium ion and the hydroxide ion: H 30+ +OH. The stronger acid (H 30+) reacts with the conjugate base (CH 3COO-) of the weaker acid (CH 3COOH). like the reaction of acetate ions with a strong acid.P H 20+H 20 Acid! + Base. Such reactions have little if any practical importance in qualitative analysis. p Base! + Acid. The displacement of a weak base (NH 3 ) with a stronger base (OH-) from its salt can be explained also: OH.18). p Base! + Acid.+ NHt p NH 3 + H 20 Base! + Acid.

in which one molecule of water plays the role of an acid. In the hydrolysis of acetate ions water acts as an acid: CH 3COO. and these ions are conjugate acids of the corresponding metal hydroxides. and will not be repeated here. proton-containing) solvents. E. The solubility (S) of a precipitate is by definition equal to the molar concentration of the saturated solution. pressure. is formed. Results and expressions are indeed identical if aqueous solutions are dealt with.THEORETICAL BASIS 1.15-1. A precipitate is a substance which separates as a solid phase out of the solution. the autoprotolysis) of water. for example. The dissociation (more properly. p Acid. and can be removed from the solution by filtration or by centrifuging. Solubility depends on various circumstances. and on the composition of the solvent. The great advantage of the Brensted-Lowry theory is that it can be adapted easily for acid-base reactions in any protic (that is. A precipitate is formed if the solution becomes oversaturated with the particular substance. PRECIPITATION REACTIONS 1.22 of this chapter. p Base! + Acid. concentration of other materials in the solution. in which water can play the part of a weak acid or a weak base. is in fact the reversal of the process of neutralization. This hydrolysis may proceed further until aluminium hydroxide. p Base! + Acid.+H 20 P CH 3COOH+OHBase! + Acid. by the acid-base reaction [AI(H 20)4]3+ +H 20 P [AI(H20hOH]2+ +H 30+ Acid! + Base. P Acid! + Base. like temperature.26 Hydrolysis is an equilibrium between two conjugate acid-base pairs. The variation of solubility with pressure has little practical importance in 67 . The precipitate may be crystalline or colloidal. + Base! The quantitative treatment of these equilibria is formally similar to those described in Sections 1. The first step of the hydrolysis of the aluminium ion can be explained. keeping in mind that these heavy metal ions are in fact aquacomplexes (like [Cu(H 20)4]2+ [AI(H 20)4]3+ etc.26 SOLUBILITY OF PRECIPITATES A large number of reactions employed in qualitative inorganic analysis involve the formation of precipitates. while in the hydrolysis of the ammonium ion it acts as a weak base: NHt + H 20 P NH 3 + H 30+ Acid! + Base. the other that of a base: H 20 + H 20 P H 30+ + OHAcid! + Base.). The hydrolysis of heavy metal ions can also be explained easily.

etc. but all other ions are foreign. when the increase of solubility is more marked. the precipitate dissolves completely owing to the formation of dicyanoargentate [Ag(CNhJ. serve as the basis of separation. The latter will dissolve lead chloride. for example. silver chloride precipitate is in equilibrium with its saturated solution. In the presence of a foreign ion. In other cases the reagent used in the test is dissolved in a non-aqueous solvent. the following equilibrium is established: AgCl +2 Ag" + ClThis is a heterogeneous equilibrium. that solubilities of precipitates increase with temperature. that the solubility of a precipitate decreases considerably if one of the common ions is present in excess though this effect might be counterbalanced by the formation of a soluble complex with the excess of the common ion. both silver and chloride ions are common ions. while the 68 . The solubility of silver cyanide. followed by treating the mixture with hot water. though in exceptional cases (like calcium sulphate) the opposite is true. in some cases it is marginal. ethers. slight variations of the latter do not have marked influence on the solubility. The variation of solubility with temperature can. can be suppressed by adding silver ions in excess to the solution. mainly ions. After filtration of the hot solution. but will leave silver and mercury(l) chlorides practically undissolved. A common ion is an ion which is also a constituent of the precipitate.complex ion. More important is the variation of the solubility with temperature. Solubility depends also on the nature and concentration of other substances. in some cases. in the mixture. as all operations are carried out in open vessels at atmospheric pressure.1. Because of the importance of the effects of common and foreign ions on the solubility of precipitates in qualitative inorganic analysis. There is a marked difference between the effect of the so-called common ions and of the foreign ions. If. but this increase is generally slight. It can be said in general. these will be dealt with in more detail in subsequent sections. as the AgCl is in the solid phase.27 QUALITATIVE INORGANIC ANALYSIS qualitative inorganic analysis. which contains also an excess of the undissolved substance. If. The rate of increase of solubility with temperature varies. and the addition of the reagent to the test solution in fact changes the composition of the medium.27 SOLUBILITY PRODUCT The saturated solution of a salt. With silver chloride for example. in other cases considerable. The variation of solubility with the composition of the solvent has some importance in inorganic qualitative analysis. on the other hand. for example. by precipitating the three ions first in the form of chlorides. Though most of the tests are carried out in aqueous solutions.) as solvents. is an equilibrium system to which the law of mass action can be applied. in some cases it is advantageous to apply other substances (like alcohols. The separation of lead from silver and mercury(I) ions can be achieved. The separation of alkali metals can for example be achieved by the selective extraction of their salts by various solvents. 1. lead ions will be found in the filtrate and can be identified by characteristic reactions. for example. cyanide ions are added in excess. first the solubility decreases slightly. unless a chemical reaction (like complex formation or an acidbase reaction) takes place between the precipitate and the foreign ion. but when larger amounts of cyanide are added. the solubility of a precipitate increases. In general it can be said.

at constant temperature (and pressure) the product of concentration of silver and chloride ions is constant. For the saturated solution of an electrolyte A'AB'B which ionizes into vAAm+ and vBB n.27 Ag+ and Cl.2 8 has been computed from thermal and other data (Latimer. do not always give consistent results. for nickel sulphide three forms (IX. and hence the solubility. In some cases the physical structure. 1949). /3. The values of solubility products are determined by various means. What has been said for silver chloride can be generalized. the ion concentration being raised to powers equal to the respective numbers of ions of each kind produced by the dissociation of one molecule of the electrolyte. The values were selected from the most trustworthy sources in the literature. whilst direct determination leads to a solubility product of S·Sx 10.2 4 • The o-form is said to be that of the freshly precipitated substance: the other forms are produced on standing.ions: A'AB'B P vAAm+ +vuB nthe solubility product (Ks ) can be expressed as «.m. this may be due to the process known as 'ripening'. such as measurements of electrical conductivity. Nernst in 1889. = [Am+r A x [Bn-rB Thus it can be stated that. This principle was stated first by W. Some of the most important values are collected in Table 1. which is a sort of recrystallization. using data obtained by calorimetry. The various methods however.12. and this may be attributed to various causes including the following. 1938).2 5 (Belcher.THEORETICAL BASIS 1. Because the concentration of the common ion is high. of the precipitate at the time of precipitation is not the same as that of an old or stabilized precipitate. termed the solubility product: s. or it may be due to a real change of crystal structure. values of solubility products of precipitates are useful. The solubility product relation explains the fact that the solubility of a substance decreases considerably if a reagent containing a common ion with the substance is added. The unit of K. 1 X 10.ions are in the dissolved phase. The equilibrium constant can be written as [Ag+] [Cl-] K = [AgCl] The concentration of silver chloride in the solid phase is invariable and therefore can be included into a new constant K. The ion concentrations in the expression of the solubility product are to be given in mol t -1 units. of cells. and the student is referred to textbooks of physical chemistry for a description of these methods. Thus. in a saturated solution of a sparingly soluble electrolyte. the product of concentrations of the constituent ions for any given temperature is constant. and ')I) have been reported with solubility products of 3 x 10.2 1.2 6 and 2 x 10. 69 . itself is therefore (mol r 1 )'A+'B. = [Ag+] [Cl-] Thus in a saturated solution of silver chloride. For cadmium sulphide a value of 1-4x 10. the e.f. Many of these constants are obtained by indirect means. In order to explain many of the precipitation reactions in qualitative inorganic analysis.2 8 respectively. that of the other ion must become low in the saturated solution of the substance. another source gives the value of 1·4 x 10. or from thermodynamic calculations.

I S 8-7 x 10.23 3-5 X 10.28 1'6xI0.8 .29 2·2 X 10. as it may increase the solubility of the precipitate because of complex formation.12 0'9 x 10.14 1'8xI0. the individual Ion concentrations the excess of the substance will therefore be precipitated.s 8-6 x 10.17 1)( 10.4 2'8xlO.8 2·8 x 10.9 2·5 X 10.72 4·8 x 10.S 1.S io« IO.13 3'4 x 10.7 1-6x 10.11 1-6 X 10.14 3-7xlO.26 2-9 x 10.8 1-6x 10. For the saturated solution of the electrolyte A. which ionizes into vAA m+ and vuBn.1.32 5 x 10.s 8·5 x 10.16 3-8 x 10.9 3'2 x 10.18 1·6 X 10. A B.7 1'5 x 10.8 1'8 X 10.S 7-0 X 10.12 I X 10.28 I X 1O-4s 4 x 10.22 I x 10.44 2 X 10.23 8'1 x 10.12 1-5xlO.16 2-0 X 10.11 4·8 x 10.9 2-6 x 10.10 9·2 x 10.38 Substance FeS Hg 2Br2 Hg 2CI2 Hg 2I2 Hg 2S HgS K 2[PtCI6] MgC0 3 MgC 20 4 MgF 2 Mg(NH 4)P04 Mg(OHh Mn(OHh MnS Ni(OHh NiS PbBr 2 PbCI 2 PbC0 3 PbCr04 PbF 2 PbI 2 Pb 3(P04h PbS PbS04 SrC0 3 SrC 204 SrS04 TICI TH TI 2S Zn(OHh ZnS Solubility product 4-0 x 10.24 7'9 x IO.4 1·4 x 10.27 QUALITATIVE INORGANIC ANALYSIS Table 1.23 The dimension of the solubility product is (mol therefore are always expressed in mol f .19 1-4 x 10.29 1'6 x 10.s 2-4 x 10.9 5'0 x 10.S4 I-I x 10.2x 10. the reagent must be applied in excess.9 1-5xlO.43 3 x 10.11 2'3 x 10. in the strictest sense. The effect of foreign ions on the solubility of precipitates is just the opposite. has to be expressed in terms of activities.9 1·7 x 10.14 1'4x IO.8 I X 10. CI)VA+VS.47 1-6 x 10.4 3'3 X 10.ions 70 . the solubility increases slightly in the presence of foreign ions.11 l'Ox 10.13 5'0 x 10.18 2'5 x 10. one has to bear in mind that the solubility product relation. To explain the effect of foreign ions on the solubility of precipitates.49 7·7 X IO.18 1-2 X 10.I units.8 8-7xlO. If therefore one ion has to be removed from the solution by precipitation.6 5'0 x 10.12 Solubility products of precipitates at room temperature Substance AgBr AgBr0 3 AgCNS AgCI Ag 2C204 Ag 2Cr04 AgI AgI0 3 Ag3P04 Ag 2S Ag 2S04 AI(OH)3 BaC0 3 BaC 204 BaCr04 BaS04 Bi2S3 CaC0 3 CaC 204 CaF 2 CaS04 CdS Co(OHh Co(OHh CoS Cr(OHh CuBr CuCI CuI CuS CU2S CuSCN Fe(OHh Fe(OHh Solublllty product 7-7 x 10.12 2·4 x 10. Too great excess of the reagent may however do more harm than good.19 5·2 x 10.10 5'0 X 10.11 4·0 x 10.

-----0'10 0·12 0'14 BaCI2 0'18 00 (a) 002 0·04 ~£....l.THEORETICAL BASIS 1.) must be expressed as K.11 illustrate the effects of common and foreign ions S2 x 24 ~_ _.--... 0'06 Concentration of added salt/mol l " ! 80 70 $: ~ x L "6 E- . 0 a ~ ~ E- KN0 3 >...... consequently the lower the activity coefficients (cf... The higher the total concentration of the ions in the solution.14).) Concentration of added salt/moll-I (b) Fig. '---0·08 ... the concentrations [Am+] and [Bn-] must increase to counterbalance the decrease of the activity coefficients. Section 1.----l Ag+ added 0'02 0·04 0·06 0·08 0'10 (Calc...27 the solubility product (K... < .---L----IL.---:-l:-.. 0 O ell ~ 60 50 40 30 1i =' ~ 20 AgN0 3 100L. - TlN0 3 ---.+ x [Am+]"A x [Bn-]OB The activity coefficients fAm+ and fBn. hence the increase in solubility. =' 8 4 '-. 1....11 71 . = aA~+ x au~- = fA~+ xfuI!. 1..depend however on the concentration of all ions (that is common and foreign ions) in the solution...- :::::"6 20 p . As the solubility product must remain constant. the higher the ionic strength... The graphs on Fig.

4 m o l r 1 331·7 The dissociation Ag 2Cr0 4 +2 2Ag+ +CrOiis complete.= 1·076x1O. Calculate the solubility product.1.4 72 . 1 mole of Ag 2Cr04 yields 2 moles of Ag" and 1 mole of CrOi-. Z. Section 1.27 QUALITATIVE INORGANIC ANALYSIS more quantitatively. the divalent sulphate exerting the greater effect. This is quite predictable.4 [CrOi-] = S = 1·076 X 10. = [Ag+]x [Cl-] = 1·045 x 1O-5x 1·045 x 10. In the case of Ag 2S0 4 the excess of AgN0 3 decreases the solubility somewhat less than simple theory (which does not take activity coefficients into consideration) predicts. on the other hand. Note that in these examples activities are not taken into consideration. has an emphasized role. Thus. The two salts with no common ions. increase the solubility. solubility products are everywhere expressed in terms of concentrations. though somewhat less than the solubility product predicts (dotted line). In the case of TICl the three salts with common ions decrease the solubility of the salt considerably.1)2 Example 15 Calculate the solubility product of silver chromate. The solubility (S) therefore is S = 0·0015 = 1·045 x 10. hence the solubility 2 S=3·57x1O. The relative molecular mass of AgCl is 143·3. Hence = 1·1 x 10. because of the simultaneous decrease of the activity coefficient (the so-called salt effect). one mole of AgCl produces 1 mole each of Ag" and [Ag"] = 1·045 x 10. The following examples may help the student to understand the subject more fully. knowing that 1litre of the saturated solution contains 3·57 x 10. as in the expression (cf.mol£-I [Cl-] = 1·045 x 10. The effects of MgS0 4 and K 2S0 4 are obviously the results of simultaneous common-ion and salt effects.5 mol £-1 143·3 In the saturated solution the dissociation is complete: AgCl +2 Ag+ +ClThus. the concentrations of the two ions are as follows: [Ag+] = 2S = 2·152x 10.jI the charge of the ion. MgS0 4 and K 2S0 4 decrease the solubility only slightly.2 g of dissolved material. The relative molecular mass of Ag 2Cr04 is 331·7.14) log/.10 (mol £. = -Az. whilst KN0 3 and Mg(N0 3 h markedly increase the solubility with the divalent magnesium ion causing the greater increase.5 mol £-1 and K.5 5 cr. Example 14 A saturated solution of silver chloride contains 0·0015 g of dissolved substance in 1 litre.

Thus the amount of substance dissolved per litre (m) is m = 811'5xl'68xlO.12 (mol £-1)3 Example 16 The solubility product of lead phosphate is l. we have [Pb3+] = 3 S and or or 1'5 X 10.32 = 108 SS Thus Sl'5x1O.4g£-1 Example 17 Given that the solubility product of magnesium hydroxide is 3'4 x 10.5 x 10.THEORETICAL BASIS 1. The dissociation equation is Pb 3(P0 4h +2 3Pb2+ +2PO~If S is the solubility (in mol £-1).11. = l'5x 10.27 The solubility product s.7 mol < [PO~-] = 2 S r l The relative molecular mass of Pb 3(P04h is 811'5.32.4 mol r 1 and as [OH-] = 2x. calculate the concentration of hydroxyl ions in a saturated aqueous solution. = [Mg2+] X [OH-]2 = X(2X)2 = 4x 3 = 3-4 X 10.11 Hence X= 1 3'4 x 10 4 11 = 2'04 X 10-.7 = l-37x1O.32 S = 108 1'68 X 10. Calculate the concentration of its saturated solution in g £. then [OH-] = 2x.10 = [Ag+]x [Cl-] 73 .4 mol r 1 Example 18 What is the concentration of silver ions (in mol £-1 units) remaining in a solution of AgN0 3 after the addition of HCl to make the final chloride-ion concentration 0'05 molar? The solubility product of AgCl is «. we may put [Mg2+] = x.1 units.4 = 4'08 X 10. = [Ag+]2 x [CrO~-] = (2'152 x 10. The solubility product can thus be written as K. The dissociation Mg(OHh +2 Mg2+ + 20Hbeing complete. we can calculate [OH-] = 2 x 2'04 X 10.4)2 x 1'076 X 10.4 = 5'Ox 10.

Thus. as it would yield negative concentration values for both ions in the expression of the solubility product.4 x 7 x 10 8 x=------"--------::-------2 which yields the two roots. because each solution is diluted to twice its original volume.2 mol £.8 and the relative atomic mass of Pb is 207'2.9 mo 1£-1 [Cl-] 5x Example 19 To 100 ml of a solution. the molar concentration of Pb2+ in the original solution is [Pb2+]or = 8'2~. 100 ml of 10.I.7 x 10-4 x+7'8x 10. = [Pb2+] [SOi-] (i) can therefore be expressed as 2'2 x 10.3 -x = 5 X 1O-4-x mol £-1 The solubility product s.3M sulphuric acid is added. this will carry again x mol of SOi.+2 PbS0 4 The solubility product of PbS0 4 is 2'2 X 10.4 and X 2 = 1'4 X 10. PbSO 4 is precipitated: Pb2+ +SOi. At the same time precipitation occurs. these concentrations are halved. How much lead remains in the solution unprecipitated? When mixing the reagents. the concentrations of these ions can be expressed as 4 X = 2 X 1O-4-x mol £-1 [Pb2+] = 4x 102 and [SOi-] = 10.4. but of these Xl has obviously no physical meaning. If x mol of Pb2+ is precipitated. when equilibrium is reached.8 = (2 x 1O-4-x)(5 x 1O-4-x) Rearranging the above equation we obtain x 2 .4 mol £-1 while that of sulphate ions is. The value X 2 = 1'4 X 10.8 = 0 From which x can be expressed as 7 x 10-4 ± J 49 x 10 8 . Thus 10 10[ A g "l = ~ = l'5x 10 2 = 3 X 10. XI = 5'61 X 10. The two roots both fulfil equation (i). as given in the question [SOi-]or = 10.4 is therefore the one which 74 .1. 1 litre of the same solution would contain 8'29 x 10./20-2 = 4 X 10.3 g lead ions.2 g of Pb2+.3 mol r 1 At the instant of mixing.into the precipitate. which contains 8·29 x 10.27 QUALITATIVE INORGANIC ANALYSIS In the final solution [Cl-] = 5 x 10.

It should be pointed out. the system will seek to adjust itself in such a manner that the ionic product attains the value of the solubility product. for instance. The solubility product is in reality an ultimate value which is attained by the ionic product when equilibrium has been established between the solid phase of the slightly soluble salt and the solution.28 APPLICAnONS OF THE SOLUBILITY PRODUCT RELAnON In spite of its limitations (as outlined in the previous section) the solubility product relation is of great value in qualitative analysis. as.10 Let us suppose that to a solution which is 0·1 molar in silver ions we add enough potassium chloride to produce momentarily a chloride concentration 0·01molar. Example 19).3 > 1·5x 10.29). until [Ag "] x[Cl-] = 1·5x 10.5 mol £-1 In 200 ml of solution we have one-fifth of this number of moles.3. for example by the addition of another salt with a common ion.28 has to be taken into consideration. The concentration of lead ions in the final solution thus becomes [Pb2+] = 2x 1O-4-1·4x 10. = [Ag+] x [cr] = 1·5 x 10. Multiplying by the relative atomic mass we can calculate the amount of lead which was left un precipitated : mp b 2 + = 202·7 x 1·2 x 10.Such a solution is now saturated for silver chloride.THEORETICAL BASIS 1. Attention must also be drawn to the fact that complete precipitation of a 75 . that the solubility product defines a state of equilibrium. equilibrium in the system is attained by some of the solid salt passing into solution. 1·2 x 10. If then we add either a soluble chloride or a silver salt in small quantity.1 °. if the ionic product is arbitrarily made greater than the solubility product.5 = 2·43 x 10. but does not provide information about the rate at which this equilibrium is established.5 mol Pb2+.e. The ionic product in such a case would be 0·1 x 0·01 = 10. Section 1. by diminishing the concentration of one of the ions. since with its aid it is possible not only to explain but also to predict precipitation reactions.13).e. At this point equilibrium is reached (cf. If conditions are such that the ionic product is different from the solubility product. 1. The rate of formation of precipitates will be discussed in a separate section (cf. As an example of the formation of a precipitate. i. As 10. The actual ionic concentrations can easily be calculated (cf. Conversely.1 °. the adjustment of the system results in the precipitation of the solid salt. let us consider the case of silver chloride. a slight further precipitation of silver chloride takes place.3 g) remains dissolved.3 g showing that under such circumstances about one-third of the original amount of lead (8·29 x 10. until equilibrium is reached again and so on. that is the rate of formation of silver chloride precipitate equals the rate of its dissolution. Section 1. The solubility product is s.4 = 6x 10. Thus. equilibrium will not exist and precipitation of silver chloride will take place Ag" + Cl- +2 AgCl until the value of ionic product has been reduced to that of the solubility product. if the ionic product is made smaller than the solubility product. i.

While the concentration of metal ions usually does fall into the range of 1-10.13 The effect of sodium chloride 011 the solubility of sliver chloride NaCI present mol E" ! 0·933 1·433 2·272 3·000 4·170 5·039 DIssolved Ag+ mol i-I 8·6 x 10.5 1·84x 10. we can now consider some direct applications of the solubility product principle to quantitative inorganic analysis.27) or as a result of complex ion formation (for more details. the concentration of the other ion cannot be decreased to zero since the solubility product has a constant value.31). a further excess of precipitant does not materially increase the weight of precipitate. see Section 1. When hydrogen sulphide gas is passed into a solution. On the basis of this general discussion.3 3·34 X 10.3 mol r 1. This variation of the sulphide ion concentration with pH is due to the fact that hydrogen sulphide is a weak acid itself.13.4 1·19 x 10.9 mol r 1 (or 3 x 10.4 5·74 x 10. and can easily be selected by the adjustment of the pH of the solution to a suitable value.1. In practice. For this precipitation the rule mentioned above can be applied: precipitation may take place only if the product of concentrations of metal ions and sulphide ions (taken at proper powers) exceed the value of the solubility product.3 of silver chloride illustrate this point. collected in Table 1. it is found that. after a certain point. because no matter how much the concentration of one ion is arbitrarily increased (and there are physical limitations in this respect too).9 x 107·87 = 3·236 x 10.1) which is negligible for most practical purposes.3 6·04 X 10. with two dissociation steps: H 2S +2 H+ +HSwith 76 . on the effect of larger amounts of sodium chloride on the solubility Table 1. These results show why only a moderate excess of the reagent should be used when carrying out precipitation reactions. the concentration of sulphide ion may vary considerably.7 g t . metal sulphides are precipitated. Some results of Forbes (1911). The concentration of the ion can of course be reduced to a very small value indeed: in Example 18 the silver-ion concentration is as low as 3 x 10.28 QUALITATIVE INORGANIC ANALYSIS sparingly soluble electrolyte is impossible. Precipitation of sulphides Hydrogen sulphide gas is a frequently used reagent in qualitative inorganic analysis. either as a result of increased salt effect (see Section 1. a large excess of the precipitant may cause some of the precipitate to dissolve. Indeed.

28 with K2 = [H+] [S2-] [HS] = 1'2 x 10. With proper mathematical treatment the sulphide ion exponent even for pH above 8 can be calculated.9 mol t -1. and the value [H 2S] = 0'1 inserted into the above equation: [H+]2[S2-] -=---=--=-_= = 10. over pH = 8 the dissociation of hydrogen sulphide cannot be disregarded any more. which adjusts the pH to 1O? The solubility products of CuS and MnS are 77 . Under such circumstances only the most insoluble sulphides can be precipitated. It can be seen that the sulphide-ion concentration is inversely proportional to the square of hydrogen-ion concentration. and therefore the simple treatment outlined above cannot be used. In strongly acid solutions ([H+) = 1) the sulphide-ion concentration may not be greater than 10. The equation is strictly valid for the pH range 0-8. This is illustrated in the following examples. This graph can be used if predictions on the precipitation of sulphides are required.THEORETICAL BASIS 1. results of such calculations are summarized on the graph of Fig.22 [H 2S] 1 2 '" At room temperature (25°C) and atmospheric pressure the saturated aqueous solution of hydrogen sulphide is almost exactly 0'1 molar. As the substance is a weak acid.15 Multiplying the two equations we obtain [H+]2[S2-] = K K = 1·09 X 10.22 '" 10.22 0'1 The expression can be rearranged to give 23 210[S ] = [H+]2 (i) This equation shows the correlation between hydrogen-ion concentration and the concentration of sulphide ions. its dissociation may be ignored. enabling the precipitation of metal sulphides with higher solubility products. Its definition is analogous to that of pH: pS = -10g[S2-] Using such a notation.23 mol t..7 ) the sulphide-ion concentration rises to 10. Example 20 Given is a solution containing O'lM CUS04 and O'lM MnS0 4. What happens if (a) the solution is acidified to achieve pH = 0 and saturated with hydrogen sulphide gas. equation (i) becomes pS = 23-2pH This equation can easily be memorized and used for quick calculations. Equation (i) can be simplified further if we introduce the quantity pS.12. 1. and (b) if ammonium sulphide solution is added. In a neutral solution ([H+] = 10. the sulphide ion exponent.

78 .12). that is [S2-J = 10. at pH = 0 the value of pS is 23. what is the lowest pH at which ZnS can be precipitated? From Table 1. copper sulphide will be precipitated.2 and pS = 21.I. the product of ion concentrations is 10.23 mol £-1. As 10. This corresponds to [S2-J = 10.44 and 1'4 x 10. while as 10.12.24 > 1 X 10. 1. Thus [Zn 2+J[S2-J = 10.23 and [Zn2+] = 10.44. At pH 4 to 5. that is from a solution containing an acetate buffer. Table 1.U 1 X 10.23 [ S2.5 for both metal ions. the sulphide-ion concentration in the saturated solution is 10.1 mol r 1 in both cases.2.29 for both ions.= 10.24 < 1'4 x 10. Example 21 Given a O'OlM solution of ZnC12.5 > 1·4 X 10. 1.15 > 1 X 10. (a) From Fig. Because 10.44. The product of ion concentrations is 10. both CuS and MuS will be precipitated under such conditions. we find atpH = 10the value 4 for pS.J = ----.12 the solubility product of ZnS is taken as 1 x 10.23 .15 manganese sulphide will not be precipitated at all.28 QUALITATIVE INORGANIC ANALYSIS 2 o 2 4 6 8 4 pH Fig.21 10.4 mol £-1.15 respectively (cf. if we want to precipitate ZnS quantitatively. the pH must be raised even higher. It is possible therefore to separate copper and manganese at pH = O.12. (b) Using Fig.1. The metal-ion concentrations being 10. From the equation pS = 23-2pH the minimum value of pH at which precipitation occurs is pH = 23-pS = 23-21 = 1 2 2 In fact. ZnS will precipitate easily.

..THEORETICAL BASIS 1. Precipitates will be formed only if the concentrations of the metal and hydroxyl ions are momentarily higher than those permitted by the solubility product. and Zn H cannot be precipitated from acid solutions. AsH and Sb H form sulphides under virtually any circumstances e. Metal ions like Ag". Sn H . but they will form sulphides in neutral or even slightly acid (buffered) solutions. Because of the fact that in aqueous solutions the product of hydrogen. The separation of these ions is based on the same phenomenon. the formation of a metalhydroxide precipitate depends mainly on the pH of the solution. CUH . Bi3 +. these are also made use of in qualitative inorganic analysis..1 .1 4 Kw [ H +] = [OH] .= 6'41 1'56 x 10 12 and the pH pH X 10.3 ) = 2'19 Thus.14 at 25°C. Pb H .. Hg~+.3 8 10 2 = l'56x 10. The value of the solubility product (cf. it is possible to calculate the (minimum) pH required for the precipitation of a metal hydroxide..5 = l'56x 10.3 = -log[H+] = -10g(6'41 x 10. Mn H . like Fe H .5 M that is to say. Section 1. the hydroxyl-ion concentration [OH-] = V~ = 3~ 33'8 X 10. and (b) the pH at which the concentration of . Precipitation and dissolution of metal hydroxides The solubility product principle can also be applied to the formation of metal hydroxide precipitates.5 . Fe H ions in the solution does not exceed 10. Ni H . the hydroxyl-ion concentration ] [OH-] = V~ = 3~ 33'8 X 10.28 If similar calculations are carried out for a number of other metal sulphide precipitates it is easy to classify these metals into two distinct groups.--.and hydroxyl-ion concentrations is strictly constant (Kw = 10. The difference is used in the analytical classification of these ions. it is the hydroxyl-ion concentration which has the decisive role in the formation of such precipitates. Example 22 Calculate the pH (a) at which the precipitation of Fe(OHh begins from a O'OlM solution of FeC13 .12) is Kg = [Fe H [OH-r = 3'8 x 10.g.1 2 The hydrogen-ion concentration is 10..11 79 .3 8 (a) With [Fe H] = 10. (b) With [Fe H] = 10. while the second set are members of the third group.. the first set of ions mentioned form the so-called first and second groups of cations. they can be precipitated from strongly acid (pH = 0) solutions.--..3 mol t -1 is the usual range).3 8 10. when the precipitation is practically complete.. Fe(OHh will start to precipitate atpH = 2'19. Cd H . Other metal ions.2 .. As the metal-ion concentration in actual samples does not vary much (l 0.10.18). Fe H. Using the solubility product principle..-------. Co H .. cf.. Table 1.

H 2Mo0 4 V////III.13. pH ///1111..13 80 .14 [H+] = [oti] 1'56 x 10 11 = 6'41 X 10- 4 and the pH pH = -log[H+] = -10g(6'41 x 10.28 QUALITATIVE INORGANIC ANALYSIS The hydrogen-ion concentration K 10. """<. 1.... Ta(OH)s Ce(OH)4 1 -c 2 3 4 5 6 7 8 9 10 11 12 13 ~////I/' 'II I 1/////// / / / //. 'Ill/.. -../ "////// Zr(OH) 4 Sn(OH)4 '1111.L -.::: ~/////////////./// / / / / //11. on the other hand. correspond to solutions containing 10. are summarized on the graphs of Fig. ///////IIIIIII~ -. ~/ //////«.. '(//. 'II/. The shaded area in each graph shows the pH region in which the precipitate is formed... The upper ends of the oblique lines. the areas left white correspond to circumstances under which the ions are in the dissolved phase. 'Ill.4 ) = 3'19 Thus at pH = 3'19 Fe(OHh is completely precipitated.... I/I/' -c 'J '111////. The lower ends.. "<0" . ~/.::.0//htY ~////////~ 'Ill/.. -. Results of similar calculations. 1963). 'I////ftY 'III//////~ ~ ~//I.:...2 mol r 1 metal ions. 1. "/. <c.. (Erdey. '/ /'/////ff 3 4 5 1 2 6 7 8 9 10 11 12 13 FIg.1.. Ti(OH)4 Th(OH) 4 Fe(OHh A1(OH)3 Cr(OHh U0 2(OH)2 Be(OH) 2 Zn(OHl 2 Fe(OH) 2 Cd(OH)2 NI(OH)2 Co(OH)2 AgOH Pb(OH)2 Re(OH)3 HgO Mn(OHh Mg(OH) 2 H 2W0 4 '11. V..... 'IP'1111111111// '1/ 1'//////// // / / / h'/. I/..::. 1//////... these are therefore the pH values at which precipitation begins./ '1111. / / 'I////' 'I/' '1/ .. '1/ 'IIII//. mark pH TI(OH) 3 Sn(OH)2 Nb(OH)s VI. "«'I/' """'<. made on several metal-hydroxide precipitates..:... 'Ill. "'<L///. drawn as boundaries.

Because of the constancy of the solubility product (equation (iv)) some of the calcium oxalate must dissolve to produce oxalate ions. By adjusting the pH to 12-13 in this way. Solubility of sparingly soluble salts of weak acids in strong mineral acids The solubility product principle enables us to give a simple explanation of this phenomenon. the following method could be used for their separation: first the pH is adjusted to 4. Ni(OHh is precipitated. formed during the addition of the reagent. Dashed lines correspond to irreversible precipitation and dissolution. it will decrease [(COO)~-] by forming H(COO)2 (and subsequently (COOHh in a saturated solution of calcium oxalate. and the filtrate treated with an excess of sodium hydroxide.THEORETICAL BASIS 1. but the Zn(OHh. the separation of ions within the third group of cations. 81 . The precipitate is filtered. based entirely on the separation of metal hydroxides.9 (iv) For equilibria (ii) and (iii) the following ionization equilibrium constants will be valid K a2 and K = [H+] [(COO)~-] = 5'4 10-5 x 10-+ [H(COO)2] (v) a1 = [H+] [H(COO)2] = 2'4 [(COOHh] x (vi) It is evident from equation (v) that if [H+] is large. As it will be seen later. the following equilibria will occur simultaneously: (i) Ca(COO)2(S) +2 Ca2+ +(COO)~(COO)~. Some of the hydroxides (like AgOH or Cu(OHh) may dissolve in ammonia solution at even lower pH values owing to the formation of ammine complexes.28 the pH at which precipitation becomes complete (Le.+H+ +2 H(COO)2 (ii) H(COO)2 + H + +2 (COOH)2 (iii) Equilibrium (i) can be characterized with the solubility product: «. The Ni(OHh precipitate can then be filtered and washed. If the hydrogen-ion concentration is high enough. washed. is redissolved. omitting the use of sulphides altogether. Ni2+ and Zn2+ ions. If for example we have a solution which contains Fe 3+ . and even separation schemes may be devised. The three ions are thus separated. It is useful to state that there are complete separation systems of cations devised.5 mol r 1). Typical examples are the solubilities of calcium oxalate or barium carbonate in hydrochloric acid. = [Ca2+] x [(COO)~-] = 2'6 X 10. or to uncertain values in general. is almost entirely based on the differences in the solubilities of their hydroxides. These however will not be discussed here. The figure also shows the dissolution pH values of amphoteric hydroxides in alkalis. the whole amount of precipitate may dissolve. when Fe(OHh is precipitated. From the diagram important conclusions may be drawn. where the concentration of metal ions in the solution decreases below 10. which is of relatively frequent occurrence in quantitative analysis. When dilute hydrochloric acid is added to a suspension of calcium oxalate. these pH values however are not shown on the diagram.

because of the low values of the two ionization constants of carbonic acid. and (unless pumped back into the solution at higher pressure) the latter is removed from the system by bubbling out of the solution.11 (xii) 2 [HC0 3 ] Now. Here two sparingly soluble salts may be formed. the whole set of equilibria gets shifted towards the right-hand sides. = and [Ba2+] x [CO~-] = 8'1 X 10.28 QUALITATIVE INORGANIC ANALYSIS Similarly.7 [H 2C0 3 ] (xi) K = [H+] [CO~-] = 5. An example of great practical importance is the Mohr method for the estimation of halides. hydrogen ions will immediately combine with carbonate ions present in the solution (owing to process vii) forming first hydrogen carbonate (equation viii).l o = [Ag+]2 x [CrO~-] = 2·4 x 10. silver chloride (a white precipitate) and silver chromate (which is red): Ag" + Cl. From the two equations we can therefore obtain 82 .12).+2 HC0 3 H+ + HC0 3 +2 H 2C0 3 +2 H 20 + CO 2(g) These equilibria can be characterized with the solubility product (vii) (viii) (ix) (x) s. ending up in the complete decomposition and dissolution of barium carbonate. Any other metal carbonate undergoes similar decomposition when treated with an acid. This decomposes to water and carbon dioxide. then ultimately carbonic acid (equation ix). if hydrochloric acid is added to a solution containing barium carbonate precipitate.+2 AgCl(s) and 2Ag+ +CrO~Ks(AgCl) K s(Ag 2Cr04 ) +2 Ag 2Cr0 4(s) (i) (ii) The solubility products of these precipitates are as follows (cf. Even an acid as weak as acetic acid will decompose carbonates. a small quantity of potassium chromate being added to serve as an indicator. viz. If there are enough hydrogen ions added.1. Table 1. = «.9 and with the ionization constants of carbonic acid [H+] [HC0 3] = 4'31 x 10. [Ag+] x [cr] = l'5x1O. Fractional precipitation The calculation as to which of two sparingly soluble salts will be precipitated under given experimental conditions may be also made with the aid of the solubility product principle.61 X 10.12 = In the saturated solution of the mixture of both precipitates these solubility equilibria will prevail simultaneously. the following equilibria will exist in the solution: BaCOis) +2 Ba2+ +CO~­ H+ + CO~. In this process a solution of chloride ions is titrated with a standard solution of silver nitrate.

silver ions are added.29 [Cl-]2 (1'5 X 10. first BaS04 will be precipitated until the ratio [Sr2+]j[Ba2+] = 3000 is reached. SrS04 will be precipitated until the ratio given in equation (vi) is reached.1°)2 1 12 [CrOi-] = 2'4 x 10= 1·1 X 108 (iii) This expression shows that under equilibrium conditions the concentration of chromate ions in the solution is always much greater than that of the chloride ions.7 Ks(BaS04) = [Ba2+] x [SOi-] = 9'2 x 10. If a O'lM solution of sodium chloride is titrated with silver nitrate in the presence of O'002M potassium chromate. Table 1. On the other hand. It follows therefore that if in a solution [Sr2+] > 3000[Ba2+] and sulphate ions are added. If therefore to a mixture of chloride and chromate ions.12): K s(SrS04 ) = [Sr2+] x [SOi-] = 2·8. As previously pointed out.1 1 (iv) (v) These two expressions and also the relation 3000 [Sr2+] 2·8 x 10. particularly where there is some doubt as to the exact magnitude of the solubility product. In the supernatant liquid the ratio expressed in equation (vi) will be maintained.x 10.7 [Ba2+] = 9'2 x 10 11 ~ -1(vi) must be satisfied for the equilibrium between the two precipitates. the results have an important bearing on the separation of Group IV cations.THEORETICAL BASIS 1. that the ratio expressed in equation (iii) is achieved. these will combine with chloride ions. the concentration of chloride ions at which silver chromate starts to precipitate can be expressed from equation (iii): 1 [ 2-] 1'1 X 108 Cr04 = Therefore practically all chloride ions are removed from the solution before silver chromate is formed. the values of many solubility products are not known with any great accuracy: for this reason considerable caution must be exercised in predicting whether or not a given ion can be separated from one or more ions on the basis of solubility product equations. The occurrence of a precipitate as the result of the addition of a certain reagent may be used as a test for a given ion. Similar calculations may be carried out for the pairs SrS04 and CaS04. and BaS04 and CaS0 4. In such 83 . from then onwards both precipitates will be formed together. Another example of some practical interest is the precipitation with sulphate of a solution containing strontium and barium ions. if originally [Sr2+] < 3000[Ba2+] and sulphate ions are added again.29 MORPHOLOGICAL STRUCTURE AND PURITY OF PRECIPITATES Precipitation is probably the most frequently used method in the practice of qualitative analysis. forming silver chloride precipitate until the concentration of chloride ions in the solution decreases to such an extent. The solubility products of the precipitates SrS04 and BaS04 are as follows (cf. From then onwards the two precipitates will be formed simultaneously. from then onwards the two ions will precipitate simultaneously. 1.

the larger the crystals that are formed during the course of precipitation. and very probably (though not necessarily) the quicker they will settle out of the solution. thus a recrystallization occurs. which again will assist filtration. a great number of crystals are formed. Obviously. will retain some of the mother liquid. while others are to be found in the precipitate. the small particles will slowly dissolve in the mother liquor. the greater is the probability of forming new nuclei. It is advisable however. 84 Erdey's Gravimetric Analysis. which forms precipitate(s) with only one or a few of the ions present. Such a supersaturated solution may stay for quite a long time in this metastable state. but none of these will grow too large. containing dents and cavities. This process * Cf. even after thorough washing. to create circumstances under which supersaturation is moderate. the easier they can be filtered. The morphological structure of precipitates can often be improved by aftertreatment.1. Some of the ions remain dissolved. It is known* that the solubility of very small particles is considerably greater than that of a larger crystal of the same substance. octahedrons. Simple structures. a suitable reagent is added. while the larger particles will in turn grow. inoculation with a crystal) to promote crystallization. Pergamon Press 1963. thus the higher the rate of nucleation. Le. a precipitate made up of small particles is formed. are advantageous. allowing only a relatively small number of nuclei to be formed. which in turn can grow into large crystals. Vol. With precipitates made up of such crystals quantitative separations are less likely to be achieved. often special procedures are required (shaking. Experience has shown that the formation of crystals from a homogeneous solution often does not start at the concentration of ions allowed by the solubility product. Precipitates may however be produced for the sake of separation. but is delayed until the concentration of the solute is much higher than that of the saturated solution. 81 et f. The shape of crystals is also important. that is the shape and size of its crystals. If the rate of nucleation is high. The higher the degree of supersaturation. Doing so. observing their effects on the precipitate. like cubes. . or needles. The rate of nucleation depends on the degree of supersaturation of the solution. Crystals with more complex structures. The size of crystals formed during the course of precipitation depends mainly on two important factors: these are the rate of nucleation and the rate of crystal growth. L. p.29 QUALITATIVE INORGANIC ANALYSIS cases we simply observe whether the precipitate formed has the proper colour and general appearance and sometimes carry out tests with further reagents. because it is easy to wash them after filtration. The rate of crystal growth depends also on the degree of supersaturation. In order to achieve as far as possible a quantitative separation. After the addition of a suitable amount of the reagent the precipitate is filtered and washed. I. The rate of nucleation can be expressed by the number of nuclei formed in unit time. If this rate is high. the precipitate must be easily filterable and must be free of contamination. If a mixture made of the mother liquor and the precipitate is simply allowed to stand for a longer time. scratching the wall of the vessel with a glass rod. large crystals are formed. The rate of crystal growth is the other factor which influences the size of crystals formed during the course of precipitation. The ease with which a precipitate can be filtered and washed depends largely upon the morphological structure of the precipitate.

After such treatment the precipitate becomes more easily filterable and washable. i.30 of ageing or ripening can be considerably accelerated by keeping such mixtures at higher temperatures. magnesium oxalate forms slowly (and the presence of calcium oxalate precipitate tends to accelerate this process). Some precipitates are deposited slowly and the solution is in the state of supersaturation for a considerable time. Thus when hydrogen sulphide is passed into a cooled solution of arsenic(III) oxide. The solution. no precipitate is discernible when one looks through the resulting mixture. Adsorption. which become contaminated. this is why this step is included in almost all procedures of gravimetric analysis. Clearly the reaction has taken place forming arsenic(III) sulphide but particles are in such a fine state of division that they do not appear as a precipitate. The first is the adsorption of foreign particles on the surface of a growing crystal. while if aged. They are in fact 85 .THEORETICAL BASIS 1. is greatest with gelatinous precipitates and least for those of pronounced macrocrystalline character. e. be soluble in acids or bases. If a powerful beam of light is passed through the solution and the latter viewed through a microscope at right angles to the incident light. Post-precipitation often occurs with sparingly soluble substances which tend to form supersaturated solutions. Thus. has acquired a deep-yellow colour and when viewed by reflected light shows a marked opalescence. When dealing with the reactions of ions attention will be drawn to such cases.30 THE COLLOIDAL STATE It sometimes happens in qualitative analysis that a substance does not appear as a precipitate when the reactants are present in such concentrations that the solubility product of the substance is greatly exceeded and precautions are taken against supersaturation of the resulting solution. it becomes resistant to such agents. The process of ageing precipitates in this way is often called digestion. evidently due to the light reflected by the particles in suspension in the solution. when calcium oxalate is precipitated in the presence of larger amounts of magnesium ions. A freshly obtained precipitate might. When a precipitate is separating from a solution it is not always perfectly pure. ageing of a precipitate might have an unwanted effect. the precipitate is practically pure at first. 1. dependent upon the nature of the precipitate and conditions of precipitation.g. while the second is the occlusion of foreign particles during the process of crystal growth. a scattering oflight (bright spots of light against a dark background) is observed.e. in general. however. Thus. but if it is allowed to remain in contact with the solution. allowing them to stand on a water bath. if zinc ions are present. they usually have an ion in common with the primary precipitate. On the other hand. those with particles of molecular dimensions do not exhibit a Tyndall effect. it may contain various amounts of impurities. True solutions. by post-precipitation of zinc sulphide. The contamination of the precipitate by substances which are normally soluble in the mother liquor is termed coprecipitation. the calcium oxalate precipitate becomes contaminated owing to post-precipitation of magnesium oxalate. Two important processes may be distinguished which cause coprecipitation. The scattering of light is called the TyndaU effect. Zinc ions alone may not be precipitated with sulphide ions under identical circumstances. Another typical example is the precipitation of copper or mercury(II) sulphide in dilute acid solution. for example. whilst the device suitable for viewing the Tyndall beam in a microscope is termed the ultramicroscope.

and a more detailed account of the phenomenon will therefore be given. thereby making the pores small enough to retain particles of colloidal dimensions. the particles are found to pass right through the filter paper.30 QUALITATIVE INORGANIC ANALYSIS in the colloidal state or in colloid solution. say.separation can be effected by the use of special devices. Close examination shows that they are not homogeneous. Ordinary filter paper will retain particles up to a diameter of 10-20 Ilm 0-2 x 10. Potassium chloride solution produces the same effect but considerably more of it must be added. Also. The total surface area of 1 ml of material in the form of a cube of 1 cm side is 6 crrr'.7 and 5 x 10. aluminium sulphate solution however brings about immediate precipitation of arsenic(III) sulphide. The colloidal state of matter is distinguished by a certain range of particle size. Any electrolyte. pass through an ordinary filter paper (the size of ions is of the order of 0'1 nm = 10. The addition of. The procedure known as dialysis utilizes the fact that substances in true solution. causes precipitation. An important consequence of the smallness of the size of the particles in a colloidal solution is that the ratio of the surface to the volume is extremely large. The effect of particle size upon the area of the surface will be apparent from the following example. silver chloride and silicic acid. When it is divided into cubes of 10. Other colloidal solutions which may be encountered in qualitative analysis include iron(III). thus ruling out the possibility of supersaturation. the liquid (usually water in qualitative analysis) is called the dispersion medium and the colloid the disperse phase. Phenomena which depend upon the size of the surface. The separation can also be effected by ultra-filtration. The ultimate size of the pores depends upon the particular 86 .1 0 m). can pass through membranes of parchment or collodion.9 m). and nickel sulphides. Colloidal solutions are therefore not true solutions. although there is no apparent reaction between the Al3+ or SOi. coagulation or tlocculation of the colloidal material.8 m) size (which approximates to many colloidal systems). such as adsorption. Although colloidal particles cannot be separated from those of molecular dimensions by the use of ordinary filter papers . Such a mixture is known as a disperse system. will therefore play an important part. and aluminium hydroxides. provided the molecules are not too large. copper(II). The limit of vision under the microscope is about 5-10 nm (5-10 x 10.and any ion in the solution.the best quantitative filter papers retain particles larger than about l um in diameter .5 m). as a consequence of which certain characteristic properties become apparent. chromium(III). or with gelatin subsequently hardened by formaldehyde. but consist of suspension of solid or liquid particles in a liquid. It is evident that the colloidal state must be avoided in qualitative analysis. Filter papers are impregnated with collodion. Colloidal properties are in general exhibited by substances of particle size ranging between 0'2 Ilm and 5 nm (2 x 10. no appreciable settling takes place. Heating the solution also favours coagulation. manganese(II).6 cm 00. i. Further examination of the colloidal solution of arsenic(III) sulphide brings to light other peculiar properties. just like true solutions. when the colloidal solution is allowed to stand for a long time. while colloidal particles are retained. no precipitation takes place upon shaking with solid arsenic(III) sulphide.e. so that colloidal solutions. When an attempt is made to filter the solution. the total surface area of the same volume of material is 6 x 106 ern".9 m).1. in fact.

30 paper used and upon the concentration of the solution employed to impregnate it. The change is. whereas others refer to them as coagels. which can be observed by the ultramicroscope. aquasols. When placed into an electric field.14. when water is the dispersion medium. etc. Negatively charged colloids include the sols of metals. they set to jelly-like masses. and proteins. and barium sulphate. Table 1.14 Some properties of colloid systems Hydrophobic sols 1. which can be changed only by special methods. formed from sols. A comparatively minute quantity of an electrolyte results in flocculation.g. alcosols. water has no effect upon the flocculant. 2.g. ordinarily. The chief properties of each class are summarized in Table 1. designated as lyophobic(Greek: solvent hating) and lyophilic(Greek: solvent loving). Examples: sols of silicic acid. in general. Hydrophlllc sols 1. 5. often termed gels (or coagels). showing that the colloid particles possess a distinct charge. irreversible. The particles. The process of dispersing a flocculated solid or gel (or coagel) to form a colloidal solution is called peptization. 'salting out'. the terms hydrophobic and hydrophilic are employed. silver halides. particularly sols of metallic hydroxides. starch. 4. Only a diffuse light is exhibited in the ultramicroscope. 4. Small quantities of electrolytes have little effect: large amounts may cause precipitation. 2. Colloidal systems. starches. The viscosity of the sols is similar to that of the medium. but the name is now generally restricted to those cases in which the whole system sets to a semi-solid state without any supernatant liquid initially. Colloid particles in solution exhibit the phenomenon called the Brownian motion. The solution is poured on the filter and the passage of the liquid is accelerated by suction or by pressure. The particles migrate in one direction in an electric field (cataphoresis or electrophoresis). metallic sulphides. such as aluminium and iron(III) hydroxides. Some authors employ the word gel to include gelatinous precipitates. in which a liquid is the dispersion medium. sulphur. silver halides. 3. The particles may migrate in either direction or not at all in an electric field. 5. tin(IV). The ultramicroscope reveals bright particles in vigorous motion (Brownian movement). have an electric charge of definite sign. silicic acid. rates of diffusion and adsorption) in addition to pore size determine whether or not particles of a given size will pass through an ultra-filter. e.g. This charge can be both positive and negative. gelatin. but it must be emphasized that the distinction is not an absolute one since some. gums.THEORETICAL BASIS 1. Examples: sols of the metals. Colloidal solutions may be divided roughly into two main groups. in general. The surface tension is often lower than that of water: foams are often produced readily. they usually migrate towards one of the electrodes. exhibit intermediate properties. The particles change their charge readily. stannic acid. 3. The solid produced upon coagulation or flocculation of a sol was originally described as a gel. metallic hydroxides. they are positively charged in acid medium and negatively charged in a basic medium. The surface tension is similar to that of water. Uncharged particles are also known. The viscosity is very much higher than that of the medium. It may be mentioned that other factors (e. and 87 . The change is. are often termed sols to distinguish them from true solutions: the nature of the liquid is indicated by the use of a prefix. e. reversible upon the addition of water.

As a consequence. and in the formation of coloured lakes from colloidal metallic hydroxides and certain soluble dyes (see Section 111. If two sols of opposite charge are mixed (e. being present in large concentrations. It has been found that the latter depends upon the valency of the ions of the opposite charge to that on the colloidal particle. It appears that ions of opposite charge to those primarily adsorbed on the surface are necessary for coagulation. e. the colloid coagulates. This can be achieved. In all cases. e. Thus in the formation of an arsenic(III) sulphide sol by precipitation with hydrogen sulphide in faintly acid solution.13).30 QUALITATIVE INORGANIC ANALYSIS certain acid dyestuffs. sulphide ions are primarily adsorbed (since every precipitate has a tendency to adsorb its own ions).g. and in order to maintain the electroneutrality of the solution. the nature of the ions has some influence also. the higher the valency the smaller the coagulation value.1. which are therefore not inhibited further from coagulation. with the same charge).g. e. which might form a protective colloid. Thus. however. There is. The adsorptive properties of colloids find some application in analysis. then the latter appears to be strongly protected against the flocculating action of electrolytes. Hydrophilic sols are generally much more difficult to coagulate than hydrophobic sols. For this reason organic matter. The ions of the electrolyte. with the positive side facing the solution. The above remarks apply largely to hydrophobic sols. of gold. The minimum amount of electrolyte necessary to cause flocculation is called the tlocculation or coagulation value. an electrical double layer is created around each particle. gelatin. and a new difficulty may arise. preventing the formation of larger (microscopic or macroscopic) particles. the precipitate will be contaminated by surface adsorption. If this double layer is destroyed.23 and 111. mutual coagulation usually occurs because of the neutralization of charges. the colloid particles repel each other. The electrolyte concentration in the supernatant liquid may fall below the coagulation value. the more strongly is it adsorbed. The stability of a colloidal solution is intimately associated with the electrical charge on the particles. An explanation is thus provided of the relative stability of the otherwise unstable gold (or other noble metal) sols produced by the addition of a little gelatin or of the salts of protalbic or lysalbic acids (the latter are obtained by the alkaline hydrolysis of albumin). whilst sols of metallic hydroxides and of certain basic dyestuffs usually carry a positive charge. It may be that the particles of the lyophilic sol are adsorbed by the lyophobic sol and impart their properties to the latter. the higher the valency of the ion. It can be prevented by washing the precipitate with a suitable electrolyte. some evidence 88 . by adding larger amounts of an electrolyte to the solution (salting-out effect). If a small amount of a hydrophilic sol (preferably. an equivalent quantity of hydrogen ions is secondarily adsorbed. Upon washing the precipitate with water. part of the adsorbed electrolyte is removed. During the coagulation of a colloid by an electrolyte. interfere with the formation of a spherical electrical double layer around the particles. and the precipitate will pass into colloidal solution again. The hydrophilic substance is known as a protective colloid. in the removal of phosphates by tin(IV) hydroxide oxide in the presence of nitric acid (Section V. the ion of opposite sign to that of the colloid is adsorbed to a varying degree on the surface.35 for aluminium and magnesium respectively). but not necessarily. for example. must generally be destroyed before proceeding with an analysis. iron(III) hydroxide and arsenic(III) sulphide). is added to a hydrophobic sol.g.g.

where the central ion is in the centre of a square and the four ions occupy the four corners of the latter. The central atom can be characterized by the coordination number. To the coordination number 4 a tetrahedric symmetry normally corresponds. each of which can be occupied by one (monodentate) ligand. a complex with a central atom of a coordination number of6. an integer figure. which shows the number of (monodentate) ligands which may form a stable complex with one central atom. but bidentate (like the dipyridyl ion). Longman 1966. Cu". F.THEORETICAL BASIS 1. while the six ligands occupy the spaces defined by the vertices of the octahedron. The relative amounts of these components in a stable complex seems to follow a well-defined stoichiometry. in the centre of an octahedron.. Pt2+). Complexes made of polydentate ligands are often called chelates. Zn2+. Fe3+. Vogel's A Text-Book of Quantitative Inorganic Analysis. The arrangement of ligands around the central ion is symmetrical. p. comprises the central ion. but the numbers 2(Ag+) and 8 (some of the ions in the platinum group) do occur. The addition of macerated filter paper is beneficial in assisting the filtration of colloidal precipitates. although this cannot be interpreted within the classical concept of valency. In most cases the coordination number is 6 (as in the case of Fe2+. and also tetradentate ligands are known. The macerated filter paper increases the speed of filtration by retaining part of the precipitate and thus preventing the clogging of the pores of the filter paper. NF+. is common as well. A complex ion (or molecule) comprises a central atom (ion) and a number of ligands closely attached to the former. Thus. CN-. H 20 form monodentate ligands. if the solubility permits. which bites into an object like the polydentate ligand 'catches' the central ion. the name originating from the Greek word for the claw of the crab. * Formulae and names of some complex ions are as follows: [Fe(CN)6]4hexacyanoferrate(II) * cr. Simple inorganic ions and molecules like NH 3 . The formation of chelate complexes is used extensively in quantitative chemical analysis (complexometric titrations). Precipitates obtained from dilute or very concentrated solutions are often in the form of very fine crystals.415etf. although a planar (or nearly planar) arrangement.31 that lake formation may be partly chemical in character. Cd2+) sometimes 4 (Cu2+. A. 89 . tridentate. These fine precipitates will generally become filterable if allowed to stand for some time in contact with the mother liquor. preferably. The coordination number represents the number of spaces available around the central atom or ion in the so-called coordination sphere. COMPLEXATION REACTIONS 1.31 THE FORMAnON OF COMPLEXES In the practice of qualitative inorganic analysis ample use is made of reactions which lead to the formation of complexes. Cr3+. cr. I. that is one ion or molecule occupies one of the spaces available around the central ion in the coordination sphere. near the boiling point of the solution. Co3+. 3rd edn.

Ag) is followed by the formula of the ligand (CN. 90 4th edn. followed by the name of the central atom and its oxidation number (valency).. which were prepared in great numbers at that time. which in turn produces the energy responsible for the stabilization of the complex (ligand field stabilization energy). Although the Lewis theory offers a comprehensive explanation of chemical structures in relatively simple terms. in the case of monodentate ligands is equal to the coordination number). Werner suggested that.. . brackets of the type { } will be used to avoid confusion. S203)' with the stoichiometric index number. * * Cf. 545 et f. then the name of the ligand is expressed. and thereby could explain the existence of stereoisomers. For a more detailed study of the ligand field theory. (which. explained the formation of complexes by the donation of a whole electron pair by an atom of the ligand to the central atom. H 20. As early as 1893. p. first the (Greek) number.1. a deeper understanding of the nature of the chemical bond necessitated the formulation of new theories. In the name of the ion. various theories have been developed. Cu. In the structural formula of the tetramminecuprate(ll) ion NH3 H 3N .. Lewis (1916). He attributed directions to these secondary valencies. and the charge of the ion is shown outside the brackets in the usual way. The classical rules of valency do not apply for complex ions. The formula is placed inside square brackets. Co. A. NH 3. showing the direction of donation of electrons. when describing his theory of chemical bonds based on the formation of electron pairs. When expressing concentrations of complexes. Later G. This ligand field causes the splitting of the energy levels of the d-orbitals of the central atom.31 QUALITATIVE INORGANIC ANALYSIS [Fe(CN)6r[Cu(NH 3)4]2+ [CU(CN)4r[Co(H 20)6]3+ [Ag(CNhr [Ag(S203hr- hexacyanoferrate(III) tetramminecuprate(II) tetracyanocuprate(I) hexaq uoco baltate(II I) dicyanoargentate(l) dithiosulphatoargentate(I) From these examples the rules of nomenclature are apparent.. appropriate textbooks should be consulted. This so-called dative bond is sometimes denoted by an arrow. apart from normal valencies. elements possess secondary valencies which are used when complex ions are formed. Among these the ligand field theory explains the formation of complexes on the basis of an electrostatic field created by the coordinated ligand around the inner sphere of the central atom. N. Longman 1962. W. The central atom (like Fe. [ ~u ]2+ <- NH 3 NH 3 the arrows indicate that an electron pair is donated by each nitrogen to the copper ion. To explain the particularities of chemical bonding in complex ions. J. Moore's Physical Chemistry.

Some examples are: Cu2+ +4NH 3 -+ blue Fe2+ +6CN.-+ yellow [Cu(NH 3)4J2+ deep. dark blue [Fe(CN)6J 4yellow [Ni(NH 3)6J2+ blue' [FeF 6rcolourless Another important phenomenon often observed when complexes are formed.31 The charge on a complex ion is the sum of the charges on the ions which form the complex: Ag" +2CNCu2+ +4CNFe2+ +6CNFe3+ + 6CN-+ -+ -+ -+ [Ag(CNhJ[CU(CN)4J 2[Fe(CN)6J 4[Fe(CN)6r- If neutral molecules are involved as ligands in the formation of complexes.+1Complex formation is responsible for the dissolution of precipitates in excess of the reagent: AgCN(s)+CNBiI 3(s) + 1-+ -+ [Ag(CN)2J[Bilj]" There are differences in the stabilities of complexes.-+ pale green Ni2+ + 6NH 3 -+ green Fe3+ +6F. One of the most common phenomena occurring when complex ions are formed is a change of colour in the solution.THEORETICAL BASIS 1. copper(II) sulphide can be precipitated from a solution of copper ions with hydrogen sulphide: Cu2+ +H 2S -+ CuS(s)+2H+ 91 . many precipitates may dissolve because of complex formation: AgCl(s)+2NH 3 -+ [Ag(NH 3hJ+ +ClAgi(s)+2S20~. the charge on the complex ion remains the same as that on the central atom: Ag" +2NH 3 -+ [Ag(NH 3)2J+ Ni2+ +6NH 3 -+ [Ni(NH 3)6J2+ Complexes with mixed ligands may have quite different charges: Co3+ +4NH 3 +2N0 2 Co3+ + 3NH 3 + 3N0 2 Co3+ +2NH 3 +4N0 2 -+ -+ -+ [Co(NH 3)4(N02)2J+ [Co(NH 3h(N02hJ [Co(NH 3)2(N02)4J- (positive) (neutral) (negative) The formation of complexes in qualitative inorganic analysis is often observed and is used for separation or identification. is an increase of solubility.-+ [Ag(S203hr. Thus.

even though cadmium sulphide is more soluble than the copper(I) sulphide precipitate (cf. Section 1. obtained by applying the law of mass action to these dissociation equilibria. By applying the law of mass action to the dissociation mentioned above.32 THE STABILITY OF COMPLEXES . cadmium(I1) ions form both tetrammine [Cd(NH 3)4]2+ and tetracyano [Cd(CN)4]2. (all of which have importance in qualitative inorganic analysis) is shown in Table 1. the silver ion concentration in the solution must be very small. The lower the value of the instability constant.complexes. A selected list of instability constants. This was done on the basis of their dissociation constants (cf. but hydrogen sulphide gas can precipitate the yellow cadmium sulphide from both solutions. the higher the concentration of free central ion (metal ion) in the solution. This ion dissociates to form silver and cyanide ions: [Ag(CNh]. we can express the dissociation constant or instability constant as [Ag+] x [CN-]2 K = {[Ag(CNh]} The constant has a value of 1·0 x 10. Silver ions (which are the product of this dissociation) can be precipitated by hydrogen sulphide gas as silver sulphide Ag 2S.complex is less stable than the tetracyanocuprate(I) [CU(CN)4rIn the previous section hints were made about the differences in stabilities of various complexes.16). to a solution which contains the complex ion. It is obvious that the higher the value of the instability constant.complex. under normal circumstances. In order to be able to make more quantitative statements and comparisons. indicating that the tetracyano complex is more stable than the tetrammine complex. The problem in many ways is similar to that of expressing the relative strength of acids and bases.15.32 QUALITATIVE INORGANIC ANALYSIS The same precipitate is formed if hydrogen sulphide gas is introduced into the dark-blue solution of tetramminocuprate(I1) ions: [Cu(NH 3)4]2+ +H 2S -+ CuS(s)+2NHt +2NH 3 From the colourless solution of tetracyanocuprate(l) [CU(CN)4r. a suitable way has to be found to express the stability of complexes. would form a precipitate with the central ion. By inspection of this expression it must be evident that if cyanide ions are present in excess.12). a reagent is added which. and also silver metal can be deposited on the cathode from such a solution by electrolysis (note that the dicyanoargentate ion.21 at room temperature. On the other hand. and therefore the more probable it is that the product of ion concentrations in the solution will exceed the value of the solubility product of the precipitate and hence the precipitate 92 1. with its negative charge moves towards the anode when electrolysed). This fact indicates that the tetracyanocadmiate(II) [Cd(CN)4Y.ions however. A similar principle can be applied for complexes. hydrogen sulphide does not precipitate copper sulphide.1. Let us consider the dicyanoargentate(I) [Ag(CNh].+2 Ag+ +2CNThe fact that such a dissociation takes place can be proved easily by experiments. Table 1. It is interesting to compare these values and to predict what happens if. the more stable is the complex and vice versa.

the more probable that the precipitate will in fact be formed. Obviously.2 3·3xlO. the more probable it is that the precipitate will dissolve.and tetracyanocadmiate(II) [Cd(CN)4]2. and [Cd2+] [CN-]4 K 2 = {[Cd(CN)4]2 } = 1'4 X 1017 (i) (ii) We have to calculate the concentrations of the various species present in the 93 .+1 2 [Fe(SCN)]2+ ~ Fe3+ +SCN[Zn(NH3)4]2+~Zn2+ +4NH 3 [Zn(CN)4]2. The lower this solubility product. both in 0'5M concentration.THEORETICAL BASIS 1.~ Zn 2.7 6·0 X 10.0x 10.1 8 I·OxI0.2 2 2·2 X 10.ions.34 1·3xlO.4 7 Ks(CdS) = 1'4 x 10.32 Table 1. On the other hand.1 7 r will start to form.~ Ag" +2CN[CU(CN)4]3. The solution has a pH of9 and contains 0'1 mol t -1 free cyanide ions.1 7 5 X 10.2 8 4·6 X 10.S 1·4x 10. the more difficult it will be to find a suitable complexing agent to dissolve it. the more stable the complex. +4CN6·8 x 10. Firm predictions can easily be made on the basis of simple calculations. the less soluble the precipitate.42 I·OxlO.28 and from Table 1.12 we have the solubility products K s ( CU2 S) = 2 x 10.~ Hg 2+ +4CN[Hg(SCN)4]2-~Hg2+ +4SCN[Co(NH3)6]3+~Co3+ + 6NH 3 [Co(NH3)6]2+~ Co 2+ +6NH 3 [13 ~ 1.3 1 4·0 X 10.~ Cd2+ +4CN[CdI 4]2~ Cd2+ +41[HgCI 4]2~ Hg2+ +4CI[HgI 4]2~ Hg2+ +41[Hg(CN)4]2. Equally an assessment can be made of the possibility of being able to dissolve an existing precipitate with a certain complexing agent.15 we take the values of the following instability constants: [Cu+] [CN-]4 -28 K 1 = {[CU(CN)4r } = 5 x 10 . Can copper(I) sulphide CU2 and/or cadmium sulphide CdS be precipitated from this solution by introducing hydrogen sulphide gas? From Table 1.10 2 X 10.14 2·5 X 10.7 1·4 X 10.2 2·6 X 10.0x 10.15 Instability constants of complex Ions [Ag(NH 3hr ~ Ag" +2NH 3 [Ag(S203h]3-~ Ag" +2S20~­ [Ag(CNh].1 7 5.2 1 5·0 X 10.~ CU++4CN[Cu(NH3)4]2+~CU2+ +4NH 3 [Cd(NH3)4]2+~ Cd2+ +4NH 3 [Cd(CN)4]2. The following examples illustrate the way in which these calculations are made: Example 23 A solution contains tetracyanocuprate(l) [CU(CN)4r.3 1.

14 X 10. it is obvious that copper(l) sulphide will not be precipitated under such circumstances.5 = 7 X 10.53 < K. therefore cadmium(II) sulphide will be precipitated from such a solution. Then potassium cyanide is added to the solution. This difference in the behaviour of copper and cadmium ions is utilized for the separation of copper and cadmium. and the concentrations of free ammonia and free potassium cyanide are 2 mol £-1 and 0·05 mol £.32 QUALITATIVE INORGANIC ANALYSIS solution. thus the concentration of both complex ions are 0·5 mol £-1.53 As 6·25 x 10. For copper(I) ions we have [CU+]2 x [S2-] = (2·5 x 10.(CdS) the concentrations of the ionic species are higher than permitted by the solubility product. The concentration of cyanide ions being 10. when the tetrammine complexes of copper(II) and cadmium are formed (and hydroxides of other ions may be precipitated). On the other hand. excess ammonia is added to the solution. by this the presence of cadmium ions is proved. By filtering the mixture the separation of copper and cadmium is achieved.5 mo 1£-1 rI.28 x 0·5 1 u and [ [CN ]4 (10 = 2·5x1O. If hydrogen sulphide gas is now introduced.1 respectively.14 mol r 1 Now we compare the products of concentrations with the solubility products.28): 10-23 10. to a mixture which contains 0·1432 g silver chloride and 0·2348 g silver iodide.5 = 6·25 X 10.19 As 7 X 10. the yellow precipitate of cadmium(II) sulphide is formed. and at the same time copper(II) ions are reduced to copper(I). By comparing the relative molecular masses of AgCl (143·2) and AgI (234·8) with the actual weights we can see that the amount of each precipitate present 94 . Example 24 What happens if. the concentrations of the free metal ions can be expressed from (i) and (ii) as [C "l = K x {[Cu(CN)4]3-} = 5 x 10. The deep-blue colour of the tetrammine cuprate(II) ions (which serves as a test for copper) disappears. First. The hydrogen-ion concentration being 10. and a colourless solution is obtained.1.9 mol ion concentration can be expressed as (cf. the complexes are practically undissociated.1 mol r 1. (a) ammonia and (b) potassium cyanide solution is added? The final volume of the solution is 100 ml.23 [ S2. Section 1.(Cu 2S).24)2 x 10. the sulphide Because of the low values of the instability constants.19 > K. when the tetracyano complexes are formed.17 x 0·5 [CN ]4 (10 It = 7 x 10. for cadmium ions we have [Cd2+] x [S2-] = 7 x 10.] = [H+]2 = (10-9)2 = 10.24mol£-1 t Cd2+ ] = K 2 x {[Cd(CN)4]2-} = 1·4 x 10.

THEORETICAL BASIS 1. the concentrations of chloride and iodide ions will be 10.1 6 With these data in hand.2 mol r 1 [Cl-] = 10.2 mol £-1 Er] = 1O-2 mol£-1 Comparing the products of concentrations with the solubility products. if therefore they dissolve completely in the 100 ml solution. The instability constants of these complex ions are taken from Table l15.2 mol £-1 The concentration of free silver ions can be calculated from equation (iii) [Ag"] = K 1 {[ Ag(NH 3h] +} = 6·8 x 10. the concentrations of chloride and iodide ions would be [cr] = 10.8 K 1 = {[Ag(NH = .2 mol r 1.10 and K. From the stoichiometry of the dissociation reactions.8 X 10. (a) If ammonia is added. we have the concentrations [NH 3 ] = 2 mol £-1 {[Ag(NH 3h]+} = 10.7 X 10-10 mol £-1 [NH 3 ] 2 22 If the precipitates were completely dissolved.21 2 {[Ag(CNh]} x (il·l°) (iv) From Table 1.I oxlO. On the other hand [Ag+]x[I-] = 1·7xlO.10xlO. x 3h]+} and K = [Ag+] [CN-r = 1 10.2 mol r 1 95 .12 > Ks(AgI) This result shows that silver iodide will not dissolve in ammonia (though some of the silver ions will be complexed). we have [Ag+]x [Cl-] = 1·7xlO.2 = 1.2 = 1·7xlO.32 is 10.12 < K. (b) A similar procedure can be adapted for the case of cyanide.2 mol r 1 [1-] = 10.2 mol £-1 in these solutions.12 we take the solubility products of AgCl and AgI : K. These results are in good agreement with experimental facts.2 mol £-1 {[Ag(CNh]-} = 10.3 mol.(AgCl) Thus the silver chloride precipitate will dissolve in ammonia. it follows that their concentrations will also be 10. they are [Ag+] [NH 3]2 6 8 10.(AgCl) = 1·5 X 10. Here [CN-] = 5 x 10.2 = 1·7xlO. which lead to the formation of [Ag(NH 3h]+ and [Ag(CNhr complex ions.(AgI) = 0·9 x 10. we can solve the problems.

leading to the formation of complexes. like the bright-red precipitate formed between nickel(II) ions and dimethylglyoxime: 96 . The test in fact is often used to test for iron(III) in the presence of iron(II) ions.33 QUALITATIVE INORGANIC ANALYSIS From equation (iv) the concentration of free silver ions can be calculated: 21 2 A +] = K2{[Ag(CN)2]-} = 10. both precipitates will dissolve in potassium cyanide.1. even iron(II) ions do not react with thiocyanate. it can be readily extracted into ether or amyl alcohol. In slightly acid medium a deep-red colouration is formed.2 = 4 X 10.21 1 £-1 [ g [CN ]2 (5 x 10-2)2 mo Comparing the products of ion concentrations with the solubility products [Ag"] x [cr] = 4 x 10.21 X 10. With some experience however copper and nickel can be distinguished from each other. This reaction is specific for iron(III) ions.X 10. which forms a hexamminenickelate(II) [Ni(NH 3)6]1 + ion. Consequently.+ SCN[Fe(SCN)s]2. 1.23 < Ks(AgI) we can see that these concentrations are less than 'allowed' by the solubility product for a saturated solution of these silver halides.21 X 10. The complexes with positive charges are cations and migrate towards the cathode if electrolysed.= 4x 10. while those with negative charges are anions. owing to the stepwise formation of a number of complexes: Fe3+ + SCN[FeSCN]2+ + SCN[Fe(SCN)2] + + SCN[Fe(SCNh] + SCN[Fe(SCN)4]. this reasoning can be verified by experiment. when the dark-blue tetramminocuprate ions are formed: Cu2+ +4NH 3 +2 [Cu(NH 3)4]2+ blue dark blue the only other ion which gives a somewhat similar reaction is nickel. Another important application is the test for iron(III) ions with thiocyanate. Thus. Again. Some complexes are precipitates.2 = 4 X 10.33 THE APPLICATION OF COMPLEXES IN QUALITATIVE INORGANIC ANALYSIS The formation of complexes has two important fields of application in inorganic qualitative analysis: (a) Specific tests for ions Some reactions.23 < Ks(AgCl) [Ag "] x [1-] = 4 x 10.+ SCN+2 [FeSCN]2+ +2 [Fe(SCN)2]+ +2 [Fe(SCNh] +2 [Fe(SCN)4r +2 [Fe(SCN)s]2+2 [Fe(SCN)6r- of these [Fe(SCNh] is a non-electrolyte. can be applied as tests for ions. moving towards the anode when electrolysed. a very sensitive and specificreaction for copper is the test with ammonia.

Some important examples of these are: (a) Aquocomplexes Most common ions exist in aqueous solution (and some also in the crystalline state) in the form of aquocomplexes. Such solutions may then be made alkaline without the danger of these metals being hydrolysed. if carried out under proper experimental circumstances (cf.-+ PbCl 2(s) If ammonia is added.32). Masking may also be achieved by dissolving precipitates or by the selective dissolution of a precipitate from a mixture. 1. which also react with the reagent.34 OH 0 N=C-CH 3 2 CH'l N--oH + Ni" CH 3 .O H CH 3 .-+ AgCl(s) Pb2+ +2Cl. the presence of lead can be confirmed.27). and therefore the time for the test can be cut considerably.C N I t I ~N( I o ! OH +2W CH 3 . interferences may occur owing to the presence of other ions in the solution. when testing for lead in the presence of silver. There is no need for the physical separation of the ions involved. Thus.34 THE MOST IMPORTANT TYPES OF COMPLEXES APPLIED IN QUALITATIVE ANALYSIS In qualitative inorganic analysis complexes (both ions and molecules) are often encountered.C = N N=C-CH 3 I (the arrows represent coordinative bonds). In some cases it is possible to prevent this interference with the addition of reagents. This reaction is specific and sensitive for nickel.THEORETICAL BASIS 1. Another example of the use of masking is the addition of organic reagents containing hydroxyl groups (like tartaric or citric acid) to solutions containing iron(III) or chromium(III) ions to prevent the precipitation of their hydroxides. Section 1. without any further test. so-called masking agents. Section 111. Such ions are [Ni(H 20)6]2+ [Al(H 20)6]3+ hexaquonickelate(II) hexaquoaluminato 97 . silver chloride dissolves in the form of the diammineargentate ion: AgCl(s)+2NH 3 -+ [Ag(NH 3h]+ +Clwhile lead chloride (mixed with some lead hydroxide) remains as a white precipitate. and tests for other ions can be made. A classical example of masking has already been mentioned: for the test of cadmium with hydrogen sulphide copper can be masked with cyanide ions (cf. which form stable complexes with the interfering ions.C = N . In this way.31 and also Example 23 in Section 1. we may produce a mixture of silver and lead chloride precipitates: Ag+ +Cl. (h) Masking When testing for a specific ion with a reagent.

we normally ignore the coordinated water molecules in formulae and equations. (c) Hydroxocomplexes (amphoteric hydroxides) Certain metal hydroxide precipitates. For this reason these precipitates are often termed amphoteric hydroxides. may be dissolved either by acids or by bases. Zn2+. AI3+. some of these are mixed aquo-hydroxo complexes. like sulphate. that is they display both acid and base character. 98 . CuS04. is normally regarded as the simple metal ion (like Zn2+). and the proper formulae of the tetrahydroxocomplexes are [Pb(H 20h(OH)4]2-. at around 120°C.5H20 does not account for the fact that there are two different types of water molecules (copper-water and sulphate-water) in the crystal structure. instead of using the formulae mentioned.34 QUALITATIVE INORGANIC ANALYSIS [Cu(H 20)4]2+ [Zn(H 20)4]2+ [S04(H 20)]2- tetraquocuprate(II) tetraquozincate(II) monoaquosulphate(ll) Some of the anions. ZnO~-. unless the formation or decomposition of the aquocomplex plays a specific role in the chemical reaction. as in the process ZU(OH)2+20H. 240°C. the addition of mineral acids decomposes them. While their dissolution in acid results in the formation of the aquocomplex of the metal which. Such complexes are diammineargentate(I) [Ag(NH 3h]+ [Cu(NH 3)4]2+ tetramminecuprate(II) [Co(NH 3)6]2+ hexamminecobaltate(II) These ions exist only at high (> 8) pH. Note that the formula of solid copper sulphate pentahydrate for example should be written precisely as [Cu(H 20)4] [S04(H 20)]. The usual formula. SOi-. Cu2+. form aquocomplexes as well: The hydronium ion H 30+ is in fact an aquocomplex itself.1. Thus. (h) Ammine complexes These have already been mentioned.+2 [Zn(OH)4]2The tetrahydroxozincate(II) ion is sometimes (mainly in older texts) represented as the zincate anion. In spite of the fact that these aquocomplexes exist. first four molecules of water are released from crystalline copper sulphate. in turn. Similar soluble hydroxocomplexes are as follows: [Pb(OH)4]2[Sn(OH)4]2 [but [Sn(OH)6]2[AI(OH)4]tetrahydroxoplumbate(Il) tetrahydroxostannate(Il) hexahydroxostannate(IV)] tetrahydroxoaluminate In fact. They are formed if excess ammonia is added to the solution of certain metal ions. and H+ in the text. This can easily be proved. On heating. the dissolution in excess base is in fact due to the formation of hydroxocomplexes. we shall write simply Ni2+. like zinc hydroxide Zn(OHh. while the fifth molecule can only be removed at a much higher temperature. and could be written as [H(H 2 0 )r .

34 (d) Halide complexes. the colourless hexafluoroferrate(II1) [FeF6r. An excess of potassium iodide dissolves the black bismuth iodide BiI 3 precipitate under the formation of the tetraiodobismuthate(II1) [BiI 4]. like IX-IX' -bipyridyl for iron(II) and dimethylglyoxime for nickel(II). like citric or tartaric acids. 3rd edn.ion. Thiocyanate is used in some cases for the detection of ions. For this reason.THEORETICAL BASIS 1. on the other hand.415etf. Longman 1966. Oxalate is probably the simplest bidentate ligand.. If. the solution turns yellow. forming chelate complexes such as [Fe(C 20 4h] 3[Sn(C 204h]2trioxalatoferrate(II1) ion trioxalatostannate(IV) ion Oxyacids. fluorine is often used as a masking agent both in qualitative and quantitative analysis. The deep-red colour observed is due to the formation of a number of thiocyanatoferrate(II1) ions and also of the chargeless molecule [Fe(SCNhJ.ions. p. Especially stable are some of the fluoride complexes like hexafluoroaluminate [AlF6r-.ions. Silver chloride precipitate may be dissolved in concentrated hydrochloric acid. These are termed ehelates or chelate complexes. In Example 23 its use for masking copper for the identification of cadmium has been discussed. for example. In quantitative analysis the formation of chelates is frequently utilized (complexometric titrations). an excess of hydrochloric acid is added to a solution which contains iron(II1) ions (in a suitably high concentration). Cyanide is often used as a masking agent. Halide ions are often coordinated to metal ions. The blue tetrathiocyanatocobaltate(II) [CO(SCN)4]2. I.copper is monovalent. The action of some specific reagents. (e) Cyanide and thiocyanate complexes Cyanide ions form stable complexes with a number of metals. Polydentate ligands. This colour change (or deepening of colour) is due to the formation of hexachloroferrate(II1) [FeCl 6r. mainly as masking agents. are quite common and form very stable complexes. is also based on the formation of chelate complexes. and polyols. forming halide complexes. A.and the hexafluorozirconate(IV) [ZrF6]2.ions are formed. Its reaction with iron(II1) ion is characteristic and can be used for detecting both ions. (/) Chelate complexes The ligands in complexes listed under (a) to (e) are all monodentate. Vogel's A Text-Book of Quantitative Inorganic Analysis. in qualitative analysis. 99 . Such complexes are [Ag(CNh][Cu(CN)4] 3 [Fe(CN)6]4[Fe(CN)6rdicyanoargentate tetracyanocuprate(I) hexacyanoferrate(II) hexacyanoferrate(II1) Note that in [CU(CN)4r. like saccharose are also used.complex is sometimes used for the detection of cobalt. * * Cf. when dichloroargentate(I) [AgCl 2].

100 . a nail) is dropped into the solution of copper sulphate.1. The reaction which takes place is Fe+Cu2+ -+ Fe2+ +Cu In this case the iron metal donates electrons to copper(II) ions. such as combustion or extraction of metals are not treated here as these fall outside the scope of this book. In this reaction Fe3+ is reduced to Fe2+ and Sn2+ oxidized to Sn 4+. accompanied by the interchange of electrons between the reactants. in short. the uptake of hydrogen was also called reduction so the loss of hydrogen had to be called oxidation." (a) The reaction between iron(lll) and tin(II) ions leads to the formation of iron(II) and tin(lV): 2Fe3+ + Sn 2+ -+ 2Fe2+ + Sn 4+ If the reaction is carried out in the presence of hydrochloric acid.35 QUALITATIVE INORGANIC ANALYSIS G. it gets coated with red copper metal.+31 2 + 3H 20 It is not so easy to follow the transfer of electrons in this case. Here Zn is oxidized to Zn2+ and H+ is reduced to H 2 • (d) In acid medium. Again. OXIDATION-REDUCTION REACTIONS 1.g. the chargeless hydrogen atoms combine to H 2 molecules and are removed from the solution. had to be classified as oxidation or reduction until the most general definition of oxidation and reduction. In this section only such oxidation-reduction reactions are dealt with as have importance in qualitative analysis. while the presence of iron(II) can be identified in the solution. in which neither oxygen nor hydrogen take part. because an acid- base reaction (the neutralization of H+ to H 20) is superimposed on the redox .or uptake of electrons. other reactions. with technological or historical importance. Other processes. Later on. What in fact happens is that Sn2+ donates electrons to Fe3+. was arrived at. redox reactions. These are called oxidationreduction reactions or. Fe becomes oxidized to Fe2+ and Cu2+ reduced to Cu. thus an electron transfer takes place. let us examine a few of these reactions. the disappearance of the yellow colour (characteristic for Fe3+) can easily be observed. reduction was considered to be a process in which oxygen was removed from a compound. There are however a number of reactions in which the state of oxidation changes. based on the release. where the oxidation number (valency) of the reacting species did not change. (c) The dissolution of zinc in hydrochloric acid is also an oxidationreduction reaction: Zn+2H+ -+ Zn2+ +H 2 Electrons are taken up by H + from Zn.. bromate ions are capable of oxidizing iodide to iodine. Before trying to define more precisely what these terms mean. Historically speaking the term oxidation was applied to processes where oxygen was taken up by a substance. themselves being reduced to bromide: Br0 3 +6H+ +61-+ Br.35 OXIDATION AND REDUCTION All the reactions mentioned in the previous sections were ion-combination reactions. (b) If a piece of iron (e. In turn.

or molecules). It is logical therefore to talk about oxidation-reduction reactions (or redox reactions) when referring to processes which involve transfer of charges. Section 1. because the electron(s) released by a substance must be taken up by another one. its oxidation state changes to more positive values. we can draw a few general conclusions and can define oxidation and reduction in the following ways: (i) Oxidation is a process which results in the loss of one or more electrons by substances (atoms. it therefore applies also to processes in the solid. on the other hand. its oxidation state changes to more negative (or less positive) values. this cannot always be seen immediately from the reaction equations. or gaseous states. Let us look into the examples quoted in the previous section. A reducing agent is accordingly one that loses electrons and becomes oxidized during the process. ions. When an element is being reduced. which in turn is reduced to manganese(II) : 2MnO.. This definition of reduction is again quite general and applies also to processes in the solid.36) shows that altogether ten electrons are donated by (five molecules of) hydrogen peroxide to (two) permanganate ions in this process. (ii) Reduction is. If we talk about the oxidation of one substance. Looking at these examples. the oxidation of one substance and the reduction of another one. or gaseous states.36 step. It is easy to see from these steps what actually happens if the reaction proceeds: the electrons released by Sn2+ are taken up by Fe3+. we must keep in mind that at the same time the reduction of another substance also takes place.36 REDOX SYSTEMS (HALF-CELLS) Although all oxidation-reduction reactions are based on the transfer of electrons. 1. This definition of oxidation is quite general. (e) Even more complicated is the oxidation of hydrogen peroxide to oxygen and water by permanganate. These processes can be better understood if they are split into two separate steps. and is reduced during the process. (iii) From all the examples quoted it can be seen that oxidation and reduction always proceed simultaneously. (a) The reaction between iron(III) and tin(II) ions 2Fe3+ + Sn2+ 2Fe3+ +2e-+ 2Fe2+ + Sn 4 + (i) (ii) is made up of the reduction of iron(III) ions -+ 2Fe2+ and the oxidation of tin(II) ions Sn2+ -+ Sn 4 + +2e- (iii) In these steps it is necessary to write down the exact number of electrons which are released or taken up in order to balance the charges. molten. + 5H 202 + 6H+ -+ 2Mn2+ + 50 2 + 8H 20 A more detailed examination (cf. This is quite obvious. molten. a process which results in the gain of one or more electrons by substances (atoms. which in turn are taken up by a single bromate ion. ions. When an element is being oxidized. An oxidizing agent is one that gains electrons. It can be seen however that six iodide ions lose six electrons.THEORETICAL BASIS 1. It can also be seen that equation (i) is 101 . or molecules).

In general therefore.. These individual reduction or oxidation steps. but the electrons are cancelled out during the summation. each oxidation-reduction reaction can be regarded as the sum of an oxidation and a reduction step.-+ 2Mn2+ +8H 20 and of the oxidation of hydrogen peroxide 5H 20 2 -+ 50 2 + IOH+ + IOe" The electrons released by H 20 2 are taken up by MnO:.1. (b) The reaction between iron metal and copper ions Fe+Cu2+ Cu2+ +2eFe -+ -+ Fe2+ +Cu Cu consists of the reduction of Cu2+ -+ and of the oxidation of Fe Fe2+ +2eThe two electrons released by Fe are taken up by Cu2+ in this process. The latter aspect of oxidation-reduction reactions 102 . the reaction between permanganate and hydrogen peroxide in an acid medium 2MnO:. It has to be emphasized that these individual steps cannot proceed alone. + 16H+ + lOe.36 QUALITATIVE INORGANIC ANALYSIS the sum of (ii) and (iii). which involve the release or uptake of electrons are often called half-cell reactions (or simply half-cells) because from combinations of them galvanic cells(batteries) can be built up. each oxidation step must be accompanied by a reduction and vice versa. (c) The dissolution of zinc in acids Zn+2H+ 2H+ +2eZn -+ -+ Zn2+ +H 2 H2 involves the reduction of H+ -+ and the oxidation of Zn Zn2+ +2eAgain. (e) Finally. the two electrons released by Zn are taken up by H+ . (d) In the reaction between bromate and iodide Br0 3 + 6H+ + 61 Br0 3 + 6H+ + 6e61-+ -+ Br' + 312 + 3H 20 Br" + 3H 20 we have the reduction of bromate -+ and the oxidation of iodide 312 + 6eand the electrons released by the iodide are taken up by bromate ions. + 5H 20 2 + 6H+ -+ 2Mn2+ + 50 2 + 8H 20 is made up of the reduction of permanganate 2MnO:.

(i) Simple redox systems are those in which. That is why the single arrow was used in all the reactions. Section 1. including the half-cell processes as well. but the opposite process.g. while Fe3+ can be reduced (e.g. as Fe3+ +e. in other cases as (vi) and (vii) it is called inhomogeneous. we can speak about the iron(III)-iron(II) or about the tin(IV)tin(II) or the permanganate-manganese(II) system and so on. In the simplest cases a = b = I. only electrons are exchanged. Of the systems mentioned above (i) to (vii) fall into this category. 103 . Fe3+ can be reduced by Sn2+. between the oxidized and reduced forms of the substance. If the numbers of moles on the two sides of the equilibrium are equal (that is a = b) we have a homogeneous redox system like those (i) to (v).) Fe2+ can be oxidized to Fe3+.+=t Fe2+ and also Sn 4+ +2eFe2+ + 2eCu2+ +2eZn2+ +2eH+ + e" 12 + 2eBr0 3 + 6H+ + 6eMnO:. In a redox system therefore. +8H+ +5eO 2 + 2H+ + 2e+=t Sn2+ +=t Fe +=t Cu +=t Zn +=t tH 2 +=t 21+=t Br" + 3H 20 +=t Mn2+ +4H 20 +=t H 20 2 (i) (ii) (iii) (iv) (v) (vi) (vii) (viii) (ix) (x) The substances which are involved in such an equilibrium form a redox system. e.THEORETICAL BASIS 1. by Sn2+) to Fe2+.+2e). For practical purposes we will classify these redox systems in two categories. but also protons (hydronium ions) are exchanged.g.39). Such systems can generally be described by the following equilibrium: a Ox+ne +=t bRed Here Ox and Red represent the oxidized and reduced form of the substance respectively. in which electrons (and in some cases protons) are exchanged.--+ S40~. an oxidized and a reduced form of a substance are in equilibrium. MnO:. it is also true that with a suitable agent (e. the oxidation of Fe2+ by Sn 4+ will not take place. Thus. which also involve electrons.vill be dealt with later (cf. while n is the number of electrons exchanged. when the system can be written as Ox-j-xe" +=tRed (ii) Combined redox and acid-base systems involve not only the exchange of electrons.* Thus. the oxidation of thiosulphate to tetrathionate: 2S20~. that not all half-cell reactions are thermodynamically speaking reversible (e. All the oxidation-reduction reactions used in examples (a) to (e) proceed in one definite direction. It is quite logical to express these half-cell reactions as chemical equilibria. as in any acid- * It must be emphasized however. we can say that normally it is reversible.36 .g. a and b are stoichiometric numbers. If however we examine one half-cell reaction on its own.

+=t Mn2+ (xi) which indeed represents the pure redox step. + 8H+ MnO:. Balancing of oxidation-reduction equations however is a quite difficult task.+H 202+6H+ 2MnO:. has already studied elementary chemistry and would therefore be quite familiar with this procedure. the dichromate-chromium(III) system: .37 BALANCING OXIDATION-REDUCTION EQUATIONS In Section 1.+=t C 6H s0 6 does not contain ions (other than hydrogen). because when Cr 20~. Such are the systems (viii) to (x) among the examples given above. Although most inorganic systems are made up wholly or partly of ions. Many of the organic redox systems are in fact irreversible.5 the ways in which chemical equations can be balanced were outlined. because from one permanganate ion. The electrons which are released are taken up by manganese atoms. the use of double arrows in the equations in such cases is not really justified. +8H+ +5e. and water we might end up with a wrong equation. for example.is reduced to Cr3+ there is an increase in the number of moles containing chromium. bearing in mind that whoever studies qualitative inorganic analysis. +3H 202+6H+ 104 ---+ ---+ 2Mn2++30 2+4H20 2Mn 2+ +40 2+6H20 . The dehydroascorbic acid (C 6H 606 ) and ascorbic acid (C 6H s06 ) redox system for example C 6H 60 6+2H+ +2e. the reaction between permanganate ions and hydrogen peroxide in acid medium. a number of organic redox systems are in fact equilibria between molecules.-Mn2+ system is homogeneous. one can easily be mistaken. The oxidation number (valency) of manganese in permanganate being + 7.37 QUALITATIVE INORGANIC ANALYSIS base system. 1. The following equations 2MnO:. Let us examine. for example. the exchange of electrons could be expressed as Mn 7+ + 5e. It must be emphasized that redox systems do not necessarily consist of ions.1. they hydrolyse in the acid-base step to form permanganate ions: Mn 7+ + 4H 20 +=t MnO:. as there are 2 protons and 2 electrons involved. Unless one knows the number of electrons exchanged in the process.Cr70~- + 14H+ +6e. oxygen gas. one manganese(II) ion is formed. Many other organic redox systems (like the quinone-hydroquinone system) follow a similar pattern. Even if we know that the products of the reaction are manganese(I1) ions. Mn 7+ ions are however unstable in water. Let us consider for example the permanganate-manganese(II) system.+=t Mn2+ +4H 20 (xii) (ix) The combination of these two steps yields the equation quoted under (ix): The MnO:. These systems are indeed combinations of redox and acid-base steps. there is no change in the number of moles An inhomogeneous combined redox and acid-base system is.+=t 2Cr3+ + 7H 20 (xiii) This system is considered to be inhomogeneous.

only the third equation produces equal numbers of electrons in these steps.THEORETICAL BASIS 1. water. 1. In general. Thus.+3H 20 (iii) 105 . 4. 1. only one of these (the third) is truly correct. + 7H 202 +6H+ --+ ----+ 2Mn2+ + 50 2 + 8H 20 2Mn2+ +60 2 + lOH20 etc. Ascertain the products of the reaction. The half-cell reactions are as follows: Fe3+ + « +=t Fe2+ Sn2+ +=t Sn 4+ +2e3. add these equations and cancel out substances which appear on both sides of the resulting equation. if we write up the two half-cell equations: H 20 2 +=t O 2 +2H+ +2eand MnO:. we express the half-cell reactions as Br0 3 +6H+ +6e-+ Br. +8H+ +5e. and. balancing of oxidation-reduction equations should be made by taking the following steps: 1. The following examples may serve as illustrations: Example 25 Describe the reaction which proceeds between Fe3+ and Sn2+. In order to balance oxidation-reduction equations. From this ratio the equation then can be balanced quite easily.37 2MnO:. 2. we must therefore find out how many electrons are released by the reducing agent and taken up by the oxidizing agent. 2. We know that the products of this reaction are bromide ions. which in turn will be taken up by 2 permanganate ions. Finally. This can easily be done if the half-cell reaction equations of the redox systems involved are known. If we multiply (i) by 2.+=t Mn2+ +4H 20 we can see at once that 5 molecules of hydrogen peroxide will release 10 electrons. iodine.+Sn2+ 2Fe3+ + Sn2+ -+ (i) (ii) 2Fe2+ +Sn 4+ +2e2Fe2+ + Sn 4+ which can be simplified to -+ Example 26 Bromate ions can be reduced by iodide in acid medium. Multiply each half-cell equation by a factor so that both equations contain the number of electrons. 2. Express the half cell reaction equations of the reduction and oxidation steps involved. We must know that the products are Fe2+ and Sn 4+. probably. + 5H 20 2 + 6H+ 2MnO:. are formally all correct: the numbers of atoms and charges are equal on both sides in all these equations. Express the reaction equation. we can add the two equations: 2Fe3+ +2e. In the above example. In fact. 3. and expresses the stoichiometry of this process adequately. If we examine the oxidation and reduction steps separately.

and cadmium ions remain dissolved. as the S2. 2. The product of the reaction is manganese dioxide precipitate. From the cadmium sulphide. I.: S2--+ S! + 2e- (vii) 3.37 QUALITATIVE INORGANIC ANALYSIS and 12 + 2e3. When nitric acid acts as an oxidizing agent.-4.) This is followed by the oxidation of S2. 2. sulphur is formed (unless the acid is too concentrated and hot). almost neutral solution.+3CdS! +3S 2--+ 2NOj + 4H 20 + 3Cd2+ + 3S2. permanganate ions are capable of oxidizing manganese(II) ions. First the dissociation of the precipitate takes place: CdS! ~ Cd2+ + S2- (vi) (This dissociation becomes complete. I. Combining 2 x (viii) + 3 x (ix) we obtain 6 electrons on both sides: 2MnO:.+ 3Mn2+ + 6H 20 --+ 2Mn0 2! +4H 20+3Mn02! + 12H+ +6e106 .ions are removed continuously from the solution by reaction vii. + 8H+ + 6e.+ 3S! + 6eAfter simplification the equation becomes 2HN0 3 + 6H+ + 3CdS! --+ 2NOj + 3Cd2+ + 3S! + 4H 20 Example 28 In slightly acid. Summing (iii) + 3 x (iv) we obtain: 21--+ (iv) Br0 3 + 6H+ + 6e. The sum of 2 x (v) + 3 x (vi) and 3 x (vii) provides equal numbers of electrons on both sides: 2HN0 3 +6H+ +6e. The half-cell reaction of the reduction of permanganate is a three-electron process: (viii) while at the oxidation of manganese(II) 2 electrons are liberated: Mn2+ +2H 20 --+ Mn0 2!+4H+ +2e- (ix) 3. Express the reaction equation. Let us try to express the equation of this reaction. nitrogen monoxide (NO) is formed.-4.+ 61Br0 3 + 6H+ + 61- --+ Br" + 3H 20 + 312 + 6eBr' + 312 + 3H 20 which after simplification becomes: --+ Example 27 Cadmium sulphide precipitate can be dissolved in hot nitric acid.-4.1. Again water is probably formed. The half-cell reaction of the nitric acid-nitrogen oxide system is HN0 3+3H+ +3e--+ NOj+2H 20 (v) We can discuss the oxidation of cadmium sulphide in two steps.

Express the equation of the reaction.+80H+ +60e+ IOC0 2t + 5N 2t +40H+ + 50e107 .+CN. 4. The half-cell equation of the reduction of permanganate is well known: MnO:.+4H 20 -+ SOi. Thus.+ IOSCN. and 4. when zinc oxide is used as a buffer. As (x) involves 6 electrons and (xi) involves 14.37 This equation can be simplified to 2MnO:. which may be dealt with in two separate steps. After simplification we get a much less complicated equation: 7Cr20~. 7 x (x) + 3 x (xi) yields 42 electrons on both sides: 7Cr20~- +98H+ + 42e. N 2. In order to make the reaction complete. + 176H+ + 1l0e. The half-cell equation of the reduction of dichromate is Cr20~- + 14H+ +6e- -+ 2Cr3+ + 7H 20 (x) while oxidation of each glycerol molecule produces 14 electrons (note that this reaction is not reversible): C 3H s0 3 + 3H 20 -+ 3C0 2i + 14H+ + 14e- (xi) 3. CO 2. l.+3C 3H s0 3 +56H+ -+ 14Cr3++9C0 2i+40H 20 Example 30 The oxidation of thiocyanate ions by permanganate in acid solution is applied in quantitative analysis. Example 29 Glycerol CH 2(OH)-CH(OH)-CH2(OH) or simply C 3H s0 3 can slowly be oxidized by dichromate ions in hot acid solution. l.+40H 20+ IOCN. H 20 as well as Cr3+ ions. Express the reaction equation. First.+20H 20 -+ 22Mn2+ +88H 20+ IOSOi.THEORETICAL BASIS 1. the solution must be buffered. 2. +3Mn2+ +2H 20 -+ 5Mn0 2+4H+ It is worth while noting that hydrogen ions are formed during the reaction. Mn2+. The products of the reaction are: CO 2. 2. we have to find their lowest common multiple.+3C 3H s0 3+9H 20 -+ 14Cr3++49H 20+9C02l +42H+ + 42e- One must not be puzzled by the unusually high stoichiometric numbers.+ IOCN. which is 42.+8H+ +6e- (xiii) In a second step cyanide ions are oxidized to nitrogen and carbon dioxide: (xiv) 3. and H 20. +8H+ +5e-+ Mn2+ +4H 20 (xii) The oxidation of thiocyanate is a rather complex process. sulphate and cyanide ions are formed: SCN. and if these build up to a higher concentration they may reverse the process. A combination of 22 (xii) + 10 (xiii) + 5 (xiv) provides equal numbers of electrons on both sides: 22MnO:. The products of the reaction are SOi-. The reaction is utilized for the titrimetric determination of manganese by the socalled Volhard-Wolff method.

ions exhibit a characteristic green colour. Potassium permanganate.+ 56H+ --+ 22Mn2+ + lOSOi. (c) In strongly alkaline solutions (at pH 13 or over) permanganate can be reduced to manganate in a one-electron process: MnO'.+2H 20+0 2 t . buffers have to be used. such a reduction takes place and oxygen is formed: 4MnO'.+ lOC0 2i+5N 2i+28H 20 It is very important that users of this book should acquire a routine knowledge of balancing oxidation-reduction equations. For reference purposes a number of such reactions have been collected in the present chapter. A careful study of Section 1. Potassium permanganate is a strong oxidizing agent. grouped around substances which are used in practice as oxidizing and reducing agents.--+ Mn0 2! + 2H 20 Mn0 2 is a darkish-brown precipitate.+ 16H+ 2MnO'. +5Fe2+ +8H+ 2MnO'. + lOSCN. + 3Mn2+ + 2H 20 --+ 5Mn0 2! + 4H+ As H+ ions are formed. when in a three-electron process the oxidation number of manganese changes from + 7 to + 4 : MnO'. when ZnO is normally used as buffer. which produces a violet solution when dissolved in water. which acts differently according to the pH of the medium. When permanganate is heated with alkalis. (a) In acid solution permanganate ions are reduced by a five-electron process. for which the half-cell reactions can easily be checked from the numbered equations. which might reverse the reaction. which is characteristic for permanganate ions.38 QUALITATIVE INORGANIC ANALYSIS On simplifying the final equation becomes 22MnO'.38 IMPORTANT OXIDIZING AND REDUCING AGENTS A large number of oxidation-reduction reactions will be listed among the reactions used for the identification of ions.38 which follows might also help. + 5H 2S + 6H+ (b) In neutral or slightly alkaline solution permanganate is reduced to manganese dioxide. As an example the oxidation of manganese(II) salts can serve: 2MnO'. 1. +8H+ +5e- --+ Mn2+ +4H 20 Mn2+ +5Fe3+ +4H 20 --+ 2Mn2+ + 51 2 + 8H 20 --+ 2Mn2+ + 5S! + 8H 20 --+ Some important oxidations carried out with permanganate ions are as follows: MnO'. +e--+ MnOi- The oxidation number of manganese in manganate is + 6. The reaction is utilized for the titrimetric determination of manganese. KMnO 4 This is a dark-brown solid. Further practice may be obtained by combining various oxidizing and reducing agents mentioned in Examples 25 to 30.1. + 101. +40H108 --+ 4MnOi. MnOi. when the oxidation number of manganese changes from + 7 to + 2 : MnO'. + 4H+ + 3e.

Br2.+ 3Sn2++ 14H+ Cr20~Cr20~- 2Cr3+ +6Fe3+ + 7H 20 --+ 2Cr3+ + 312 + 7H 20 --+ 2Cr3+ + 3Sn4+ + 7H 20 --+ --+ + 3HCHO + 8H+ (formaldehyde) 2Cr3+ + 3HCOOH + 4H 20 (formic acid) Nitric acid HN0 3 The oxidizing action of nitric acid depends on the concentration of the acid and the temperature of the solution. which produces an orange solution in water. one can see that the dissolution produces a colourless gas inside the flask: Fe+HN0 3+3H+ --+ Fe3+ +NOi+2H 20 Over the neck of the flask.THEORETICAL BASIS 1. and12 The action of halogens is dependent upon the conversion of electrically neutral halogen molecules into halogen ions by accepting electrons: Cl 2+2eBr 2 +2e12 + 2e- 2CI--+ 2Br--+ 21--+ 109 . a I + I mixture of concentrated acid with H 20) on iron filings and heating the mixture. Normally. C12. or half-concentrated HN0 3 is mostly used to dissolve metals and precipitates. the dissolution of iron metal) in a flask with a narrow neck.+ 14H+ +6e. In strongly acid solutions dichromate ions are reduced to chromium(III): Cr20~. exposed to atmospheric oxygen turns brownish red. Concentrated.38 Potassium dichromate K 2Cr20 7 This strong oxidizing agent is an orange-red solid. the formula HN0 3 is therefore used in the above equations The Halogens.+ 14H+ Cr20~. the colour originating from Cr3+ ions. but readily reacts with atmospheric oxygen. nitrogen oxide is formed in a three-electron process: HN0 3+3H+ +3e.g. when the reddish-brown nitrogen dioxide is formed: 2NO + O 2 --+ 2N0 2 (i) It is instructive to carry out-such an oxidation (e.g. the gas. because reaction (i) proceeds.+ 61. The solution becomes light green. Such reactions are: 3Ag+HN0 3+3H+ 3CuS+2HN0 3+6H+ --+ --+ 3Ag++NOi+2H 20 3Cu2+ +3S!+2NOi+4H 20 Under the conditions in which these reactions are carried out nitric acid is far from being completely dissociated. Some important oxidations with dichromate are as follows: +6Fe2+ + 14H+ Cr 20~. Pouring not too concentrated nitric acid (e.--+ NO+2H 20 The NO gas is colourless.--+ 2Cr3+ + 7H 20 The oxidation number of Cr changes from + 6 to + 3.

+21- Aqua regia. Iodine is a mild oxidant. + 6H+ 3H 202+2Au3+ H 202 +2[Fe(CN)6]3110 -+ -+ -+ 50 2i + 2Mn2+ + 8H 20 2Au+30 2i+6H+ 2[Fe(CN)6]4. Its oxidizing action is based on a two-electron process. The oxidative action of chlorine is based on the process described in the previous section. The dissolution of gold can be expressed with the equation: 3HN0 3+9HCI+2Au -+ 3NOCI+6CI. An alkaline solution containing chromium(III) in the form oftetrahydroxochromate(III) [Cr(OH)4]can be oxidized to chromate(VI) with H 202: 3H 202+2[Cr(OH)4]-+ 2CrO~-+2H++6H20 Reductions with hydrogen peroxide can also be achieved both in acid (i) and (ii) and alkaline medium (iii) : 5H 202 + 2MnO:. H 20 2 Although often quoted as a strong oxidizing agent. Some oxidations with halogens. hydrogen peroxide may act both as an oxidizing and as a reducing agent. used in qualitative analysis. is a strong oxidizing agent. Its action is based on the formation of chlorine: HN0 3 + 3HCI -+ NOCli + Cl 2i + 2H 20 This equation is somewhat simplified. hydrogen peroxide releases 2 electrons and oxygen gas is formed: H 202 -+ O 2 +2H+ +2eIts role in redox reactions depends on the relative oxidizing or reducing strength of the reaction partner. NOCl.+H 20 12 +2S20~-+ -+ -+ 2CI-+2Fe3+ AsO~. Nitrosyl chloride.+2Au3+ +6H 20 Hydrogen peroxide.38 QUALITATIVE INORGANIC ANALYSIS The oxidizing power of halogens decrease with increasing relative atomic mass. which results in the formation of water: H 202 +2H+ +2e-+ 2H 20 As a reducing agent. for example. H 202 + 2H+ + 21H 202+2H+ +2Fe2+ -+ -+ 12 + 2H 20 2Fe3+ +2H 20 It can however act as oxidant in alkaline medium too.+2H+ S40~. are as follows: CI2+2Fe2+ Br 2 +AsO~. which is able to oxidize (and to dissolve) noble metals like gold and platinum. The mixture of three volume of concentrated HCI and one volume of concentrated HN0 3. in fact there are more products formed during the process. while the iodide ion often acts as reducing agent. Oxidations with hydrogen peroxide in acid medium are.1. is one of the products which can easily be identified. called 'aqua regia' or the kingly water. and also on the pH of the solution.+2Br.+2H+ +0 2t (i) (ii) (iii) .

I to o.+2H+ 3H 2S + 2HN0 3 --+ 3S! + 2NOj + 4H 20 Hydriodic acid HI (the iodide ion Ir ) Iodide ions reduce a number of substances.+ Cl 2 --+ 12 +2CI6r + Cr 20~. like Cr 20~-. AsOl. forms sulphurous acid. S02. its action is based on the transformation of sulphite ion to sulphate.+ Br0 3 +6H+ --+ 312 +Br.+21. + 16H+ --+ 512 +2Mn2+ + 8H 20 If a solution of potassium iodide is acidified with concentrated hydrochloric acid and the solution is left exposed to air.+ 14H+ --+ 312 + 2Cr3+ + 7H 20 101.+2H+ --+ 3S0i..+8H+ SO~.are as follows: +2Fe3+ +H 20 SO~. it undergoes oxidation. +6H+ --+ 5S! +2Mn2+ +8H 20 H 2S+2Fe3+ --+ S!+2Fe2++2H+ H 2S+CI2 --+ S!+2CI.+2H+ +2e- The reagent is sometimes employed by adding sodium sulphite Na 2S0 3 to the acidified solution to be reduced.+1 2 +H 20 3S0~.or substances like HN0 3 or Cl 2 are present. it slowly turns to yellow and later brown.38 Sulphur dioxide. when dissolved in water. If oxidizing ions.+Cr3+ +4H 20 --+ SOi. The oxidation number of sulphur changes from + 4 to + 6.+ 10 3 . MnO:. when elementary S is formed: H 2S --+ S! +2H+ +2eThe sulphide precipitates formed will therefore also contain some free sulphur. The reaction equations are as follows: 3S!+2Cr3++7H 20 5H 2S+2MnO:.+3H 20 51. because of oxidation by atmospheric oxygen: 4r +02+4H+ --+ 212+2H20 111 . : 21--+ 3H2S+Cr20~-+8H+ --+ 61. Fe3+.+ 6H+ --+ 312 + 3H 20 21.+2Fe2+ +2H+ --+ SOi.g. Reductions with I" are e.+2MnO:.THEORETICAL BASIS 1. Iodide ions are mostly added in the form of potassium iodide KI. hence 2 electrons are released during the process: So~- +H 20 --+ SOi.+Cr20~.+ AsOlSO~- SOi. and sulphurous acid H 2S0 3 Sulphur dioxide gas. Some reductions with SO~. themselves being oxidized to iodine: 12 + 2eThe oxidation number of iodine changes from .+AsO~--+ Hydrogen sulphide H 2S Hydrogen sulphide gas or its saturated solution is used as a precipitant in qualitative inorganic analysis. It is a strong reducing agent.

+ 6H 20 -+ Zn] + N0 3 + 2H+ -+ Fe! + CUH -+ Fe! + Sn4+ -+ 4[Zn(OH)4]2.+ H 2t 2AI! + 20H. In other words. In this and the next few sections the problem will be dealt with in some detail.39 REDOX REACTIONS IN GALVANIC CELLS When discussing oxidation-reduction reactions we have not mentioned ways in which the directions of such reactions can be predicted. Their action is due to the formation of ions. and aluminium These are often used as reducing agents. When oxidized to tin(IV) the oxidation number of tin increases from + 2 to + 4. The direction of chemical reactions can always be predicted from thermodynamical data. as: Zn!+2H+ -+ Zn H +H 2i Fe! + 2H+ -+ Fe H + H 2i 2AI! + 6H+ -+ 2AP+ + 3H 2i Zn! +20H. corresponding to the release of 2 electrons: Sn H -+ Sn4+ + 2e- Some reductions with tin(1I) are Sn H + 2HgCl 2 -+ Sn4+ + Hg 2Cl2 + 2CISn H + Hg 2Cl2 -+ Sn4+ +2Hg+2CISnH +C1 2 -+ Sn4+ +2CISnH +Fe3+ -+ Sn4+ +2Fe H Solutions of SnCl 2 do not keep well because atmospheric oxygen oxidizes the tin(II) ion: 2Sn H +02i+4H+ -+ 2Sn4+ +2H 20 Metals like zinc.+ 6H 20 -+ 2[ AI(OH)4].+2H 20 -+ [Zn(OH)4]2.39 QUALITATIVE INORGANIC ANALYSIS Tin(11) chloride SnCl2 Tin(II) ions are strong reducing agents. discussions in the previous chapters were aimed at understanding how oxidation-reduction reactions proceed. if the Gibbs free energy change of a reaction is calculated. but there was no mention of why they take place.+ 3H 2l 1. iron.+ NH 3 Zn H + N02" + H 20 Cut + Fe H SnH + Fe H The reactions in which metals dissolve in acids or alkalis are also reductions of the dissolving agents. Thus. 112 . normally of their lowest oxidation state: Zn -+ Zn H + 2eFe -+ Fe H +2e- Al -+ AI3+ + 3e- Zinc can be used for reduction both in acid and alkaline medium: 3Zn! + 2Sb3+ -+ 2Sb! + 3Zn H 4Zn! + N0 3 + 70H.1.

meaning that the reaction in fact will proceed in one or another direction. if the value of such a constant is high or low. galvanic cells were extensively studied before theories of redox reactions were formulated.14. precipitation. e. It is possible. 1. and complexation reactions.14 the electrodes are connected by wires. each made up of an electrode and an electrolyte. Such a treatment has been used when dealing with acid-base. to pass these electrons through electrodes and leads from one ion to the other.g. For this reason. however. In the previous chapters therefore the problem of the directions of chemical reactions was dealt with on the basis of the equilibrium constant. electrons will flow from the negative electrode through the lead towards the positive electrode. if v NaCl A B Fig. To perform such calculations a good working knowledge of thermodynamics is needed. which however is not expected from the readers of this book. electrons will flow in the direction indicated. 1. and this tradition is observed in this text also. The movement of electrons in the lead means that an electrical current is flowing. one ion collides with another and during this the electron is passed on from one ion to the other. and therefore conclusions as to the direction of reactions may be drawn from the knowledge of equilibrium constants. the equilibrium between the reactants and products is shifted to one or another extreme. This has both historical and practical reasons. From the value of the equilibrium constant one can easily make semiquantitative estimations. A galvanic cell consists of two halt-cells. in oxidation-reduction processes electrons are transferred from one species to another. The magnitudes of electrode potentials 113 . interpretation of redox reactions is traditionally based on phenomena occurring in galvanic cells. The direction of this electron flow in the cell is strongly associated with the direction of the chemical reaction(s) involved in the process. Because of their practical importance. This transfer may occur directly.e. Electrically speaking. Although the law of mass action is equally valid for oxidation-reduction processes. one of which is shown in Fig.39 we can definitely state whether a given chemical reaction may proceed or not. As pointed out in the previous sections.THEORETICAL BASIS 1. The two electrolytes are connected with a salt bridge and. A suitable device in which this can be achieved is a galvanic cell. the direction of electron flow depends on the sign of the potential difference between the electrodes. traditionally a different approach is used for such processes. i.

The latter consists of an inverted U'-tube filled with a solution of a conducting electrolyte. corresponding to the flow of the electrons from the negative electrode (A) towards the positive one (B). and stoppered at each end with a plug of cotton wool to arrest mechanical flow. a current will flow. The electrolyte in a solution in the salt bridge is always selected so that it does not react chemically with either of the solutions which it connects. the measured voltage is equal to the electromotive force or e. tin(IV) ions can be detected in solution A while iron(II) ions can be found in solution B. and are connected to a voltmeter V ofa high internal resistance. such as potassium chloride. which would proceed normally if the reactants were mixed. are placed in separate beakers A and B. on the other hand. Let us examine the operation of a few galvanic cells. The solutions of tin(II) chloride and iron(III) chloride. the voltmeter shows a deflection corresponding to the difference of the voltages of the two electrodes.39 QUALITATIVE INORGANIC ANALYSIS are therefore of primary importance when trying to interpret oxidationreduction processes in a quantitative way.1.m. When the circuit is closed. Platinum foil electrodes are introduced into each of the solutions. It connects the two solutions while preventing mixing.f. which leads to the formation of iron(II) and tin(lV) ions: 2Fe3+ + Sn2+ -+ 2Fe2+ + Sn 4 + (i) If solutions of iron(III) chloride and tin(II) chloride are mixed. and the two solutions are connected by means ofa 'salt bridge' containing sodium chloride. this reaction proceeds instantaneously. The chemical reaction which takes place can be described by the following equation: CuZ+ +Zn! -+ Cut +ZnZ+ (iv) In this process. If. of the cell. In solution B therefore the reaction 2Fe3+ +2e-+ 2Fe2+ (iii) will proceed. The same reaction proceeds in the galvanic cell shown in Fig. its surface becomes coated with copper metal and the presence of zinc ions in the solution can be detected. electrons donated by zinc atoms were taken up by copper ions. (b) If a piece of zinc is dipped into a solution of copper sulphate.14. 1. The basis difference between the two processes is that the reactants (Fe3+ and Sn2+) in the galvanic cell are separated from each other. If the current flows for a while. the resistance of the circuit is low. The sum of equations (ii) and (iii) being equal to (i) we can see that the basis of the operation of this galvanic cell was an oxidation-reduction process. These are then conducted to the other electrode where they are taken up by iron(III) ions. 114 . each acidified with dilute hydrochloric acid to increase conductivity. If the resistance of the meter is so high that no current can flow in the circuit. This indicates that the following processes took place during the operation of the cell : In solution A: (ii) and the two electrons are taken up by the electrode. (a) We have already dealt with the reduction of iron(III) ions with tin(II).

the chemical reactions which took place in vessels E and D respectively were Zn and Cu2+ +2e-+ -+ Zn2+ +2eCu (v) (vi) Note that the sum of equations (v) and (vi) equals (iv).f. Thus. Zn in a solution of ZnS0 4 ) .40 ELECTRODE POTENTIALS When a galvanic cell is constructed. metal ions from the solution will take up electrons from the metal 115 .m. = IE 1 -E2 1 These electrode potentials are potential differences themselves. The latter can be regarded as the absolute value of the difference of two individual electrode potentials. The voltmeter V measures the e. which are formed between the electrode (solid phase) and the electrolyte (liquid phase). If a piece of metal is immersed in a solution which contains its own ions (e. and slowly diffuse into the solution as metal ions. this potential difference is equal to the electromotive force (e. leaving electrons on the metal itself.mJ. immersed in a solution of copper sulphate. while in vessel E the zinc foil. only if there is practically no current flowing in the circuit). it is possible to detect that the weight of the zinc electrode has decreased.15. current will flow which can be measured on the ammeter A. First. at the same time the concentration of zinc ions in the vessel E has increased. the atoms of the outside layer of the metal will dissolve. two processes will immediately start. Eland E 2 • e. In vessel D a copper foil.f. of the cell (the measured voltage being equal to the e. a potential difference is measurable between the two electrodes.g. 1.THEORETICAL BASIS 1. 1. 1.ZnS0 4 The same process takes place in the DanieU cell.m. and that of copper ions in vessel D has decreased. If the electrodes are connected through a resistor. The role and construction of the salt bridge B is the same as in the previous cell. is the -ve pole. If the flow of current is negligible. dipped into zinc sulphate.m.J Fig.40 v B CU------1fD CUS04--t:=-_---.) of the cell.15 -/---Zn E L_-==t--. which is shown in Fig. forms the + ve pole of the cell. If the cell has been operating for a while. while the weight of the copper electrode has increased. Their occurrence can be most easily interpreted by the formation of double layers on the phase boundaries.f. meaning that the chemical processes in both cases were the same. Second.

Soon the rates of the two processes will become equal and an equilibrium state will come into being. the rate of dissolution becomes slower because of the repulsion of the ionic layer at the phase boundary. e. R = 8'314 J K.22 is also reversible to chloride ions. As seen before. that is to a cation. and as a result the metal becomes positive with respect to the solution. the number of ions discharged equals the number of ions produced.e. a constant. the electrons in the metal phase and the ions in the solution will accumulate at the phase boundary. If the rate of dissolution is higher than the rate of deposition. is immersed into a solution of potassium chloride. On the phase boundary another electrical double layer will be formed and in fact another. is the algebraic difference of the two electrode potentials. a piece of another metal must be dipped into it. In the equation R is the gas constant F is the Faraday (expressed in suitable units. It is not possible to measure the potential difference between the solution and the electrode. It is impossible therefore to measure absolute electrode potentials. described in Section 1. Building up cells from two electrodes. the e. the potential will depend on the concentration of the chloride ion.f.g. the net result of this process will be that an excess of positively charged ions will get into the solution. in contact with solid silver chloride.m. on the other hand. when silver. because in order to do this the solution must be connected to a conductor. i. while the rate of deposition increases because of the electrostatic attraction forces between the negatively charged metal and the positively charged ions. The potential difference established between a metal and a solution of its salt will depend on the nature of metal itself and on the concentration of the ions in the solution. These two processes have different initial rates.1 mol number (F = 9'6487 x 104 C mol-I). leaving behind an excess of electrons on the metal. This equation was first deduced by Nernst in 1888. of a cell can be measured relatively easily. when.f. It is possible to construct electrodes which are reversible with respect to an anion. only their differences. This is the case with the copper electrode in the Daniell cell. For a reversible metal electrode with the electrode reaction Me -+ Me n + +ne- the E electrode potential can be expressed as E = E' + RFT In aMen+ n ~ E' + RT In[Me n +] nF where the activity aMen+ can in most practical cases be replaced by the concentration of the metal [Me? "]. and this e. I ") 116 . and the electrode will be reversible to this ion. If.m. Thus.40 QUALITATIVE INORGANIC ANALYSIS and get deposited in the form of metal atoms. T is the absolute temperature (K). The calomel electrode. Because of the electrostatic attraction between the opposite charged particles. and is therefore called the Nemst equation. As a result a welldefined potential difference will develop between the metal and solution.1. in a given time. the electrical double layer will be formed just in the opposite sense. the initial rate of deposition is higher than the initial rate of dissolution. which is characteristic for the metal in question. The electrodes just referred to are reversible with respect to the metallic ion. Once this double layer is formed. E is the standard potential. forming an electrical double layer. unknown electrode potential is developed. and the metal will acquire a negative potential with respect to the solution.

and the measured e.40 ofwhich one is always the same. This is a reversible hydrogen electrode. its sign will be equal to the polarity of the electrode in question in this cell. A standard hydrogen electrode can easily be built from a platinum foil.THEORETICAL BASIS 1. and it permits the change from the gaseous form into the ionic form and the reverse without hindrance: 2H+ + 2e. 117 . When using the standard hydrogen electrode as a reference electrode time must be allowed for the system to reach equilibrium.16. The gas is introduced D C H 2A '-----' Molar - B -. we can determine the relative values of electrode potentials. with hydrogen gas of 1·0133 x 105 Pa (= I atm) pressure being in equilibrium with a solution of hydrogen ions of unit activity. the foil is thus kept saturated with the gas. All electrode potentials are then calculated on this hydrogen scale. The hydrogen gas. The potential of this electrode is taken arbitrarily as zero. by bubbling it through solutions of KMn04 and AgN0 3 • Connection between the platinum foil sealed in tube D and an outer circuit is made with mercury in D..16 through side tube C and escapes through openings B in the surrounding gas tube A. to which all electrode potentials can be related. which can be used then for practical purposes.- H+ - - - Fig. All that has to be done is to select a suitable standard reference electrode. a galvanic cell is obtained. Hydrogen gas at a pressure of I atm is passed over the foil. normally 30-60 min should elapse before the final measurement is taken. will be equal to the electrode potential of the unknown electrode. 1.+:t H 2 This electrode therefore behaves as if composed entirely of hydrogen. that is as a hydrogen electrode.f. must be meticulously purified. The platinum black has the remarkable property of adsorbing large quantities of hydrogen. used for this purpose.g. By connecting this standard hydrogen electrode through a salt bridge to an electrode of an unknown potential. and immersed in a solution of hydrochloric acid containing hydrogen ions of unit activity (a mixture of 1000 g water and 1·184 mol hydrogen chloride can be used in practice). In practice the standard reference electrode used for comparative purposes is the standard hydrogen electrode. coated by platinum black by an electrolytic process. 1. A convenient form of the standard hydrogen electrode is shown on Fig. e.m.

Thus.16 Standard potentials of metal electrodes at 2SOC Electrode reaction Li++e+:t Li +:tK +:t Ba +:t Sr +:t Ca +:tNa +:t Ce +:t Mg +:t Th +:t Be +:t Y +:t Al +:t Mn E" (Volts) Electrode reaction Zn2+ +2eCr3+ + 3eFe2+ +2eCd2+ +2eCo2+ + 2eNi2+ + 2eSn2+ + 2ePb2+ + 2e2H+ + 2eCu2+ +2e+:t +:t +:t +:t +:t +:t +:t Zn Cr Fe Cd Co Ni Sn Pb H 2 (Pt) Cu 2Hg Ag Pd Au E" (Volts) -0. Table 1.16 contains values of standard potentials of metal electrodes. mercury or silver.04 -2-92 -2-90 -2'89 -2'87 -2. Longman 1966. If the activity of ions in the solution is unity (l mol f -1). other electrodes are used. The more negative the potential of a metal.66 -1. The sign of the potential is the same as the polarity of the electrode in this combination.. the greater the tendency of the metal to pass into the ionic state and vice versa.1. aluminium.44 -0. * From the Nernst equation we can see that the electrode potential of a metal electrode. Table 1. . activity) of these ions. For more details on such electrodes. Moore's Physical Chemistry. Section 1.90 -1'85 -1. In this table metals are arranged in the order of their standard potentials. and iron will all displace copper from solutions. J. zinc. p.g.+:t Au3+ + 3e. the standard hydrogen electrode is only occasionally used in practice as a reference electrode.22) or the silver-silver chloride electrode. The standard electrode potential of a metal can therefore be defined as the e. 379 et f. depends on the concentration (more precisely. produced when a half-cell consisting of the element immersed in a solution of its ions possessing unit activity is coupled with a standard hydrogen electrode.71 -2-48 -2-37 -1.13 0'00 +0'34 +0'79 +0'80 +0'99 +1'50 K++eBa2+ +2eST2+ + 2eCa2+ +2eNa++eCe3+ + 3eMg2+ +2eTh 4 + +4eBe2+ + 2ey3+ + 3eAI3+ + 3eMn2+ +2e- -3. magnesium.m. These are easy to manipulate and their electrode potentials are constant. E = E' thus the electrode potential becomes equal to the standard electrode potential itself. having been determined once and for all by direct reference to the standard hydrogen electrode.28 -0'25 -0. copper will displace silver and mercury and so on.18 -= +:t +:t Hg~+ +2e. A metal with a more negative potential will displace any other metal below it in the series from solutions of its salts.40 -0.+:t Ag" + e: +:t Pd2+ +2e.74 -0. 118 4th edn.76 -0.80 -1. the expression becomes. Metals with negative standard potentials displace hydrogen and can * See e.+:t starting with negative values and finishing with positive potentials.40 QUALITATIVE INORGANIC ANALYSIS Because of slowness of response and elaborate equipment needed for handling hydrogen gas. immersed in a solution of its ions. textbooks of physical chemistry should be consulted. such as the calomel electrode (cf.f. W. lead will displace copper. Instead.14 -0. What is obtained is the so-called electrochemical series of the metals.

m. is capable of measuring potentials originating from oxidation-reaction equilibria. we can construct a half-cell by immersing a platinum foil as an electrode into it. The standard electrode potential is a quantitative expression of the readiness of the element to lose electrons. If we have a solution in which both iron(II) and iron(III) ions are present. but from the practical point of view very important. is how such a potential can be measured. like platinum. was adsorbed on a platinum electrode (with an exceptionally high surface. 119 . (c) combined redox and acid-base systems and (d) gas electrodes. secured by the electrolytically deposited platinum black). hydrogen. with the aid of a reference electrode. can be measured and expressed on the hydrogen scale.+=t Fe2+ Although oxidation-reduction potentials can be treated in a general way. a mere sonde). It is quite logical therefore to conclude that not only those redox systems which involve a solid metal in the half-cell reaction will give rise to an electrode potential but that any oxidation-reduction system can be characterized with a sort of potential. the more powerful its action as a reductant. class.41 therefore be dissolved in acids with the evolution of hydrogen.THEORETICAL BASIS 1. a standard hydrogen or calomel electrode) and the e. a so-called bright platinum electrode must therefore be used. These are often called oxidation-reduction potentials. (b) simple redox systems. The platinum electrode. We have also seen how the electrode potential. The question. Experience has shown that an inert electrode. and it was shown that the equilibrium between the metal ion and the metal (i) gives rise to a potential difference between the electrode and the solution. which in fact acted as an inert electrode (Le. of this cell can be measured.f. here we shall first classify redox systems and then deal separately with the potentials within each class. and connecting the platinum electrode to the electrical circuit. With a suitable salt bridge we can connect this solution to another half-cell (e. representing a special. those with positive standard potentials can be dissolved only in oxidizing acids (like HN03 ) . the electrode potentials discussed in Section 1. The platinum should not be coated with platinum black in this case as we do not want any adsorption to take place on the surface. The potential of the half-cell corresponds to the half-cell equilibrium: Fe3+ +e. This not only suits the beginner but has been proved most useful for the study of inorganic qualitative and quantitative analysis. Equation (i) above represents a redox half-cell with the metal ion as the oxidized form and the metal itself as the reduced form. 1. When discussing the standard hydrogen electrode we have already seen such a system.41 OXIDAnON-REDUCTION POTENTIALS In the previous section metal electrodes were dealt with. As it will be clear later. the reduced form. gold (or in some cases mercury). was able to take up or provide electrons released or accepted by the hydrogen gas or hydrogen ions respectively.g. The more negative the electrode potential of a metal. (as in most textbooks of physical chemistry and electrochemistry). of course.40 are themselves oxidation-reduction potentials. The four classes dealt with here are (a) metal electrodes. It is therefore a measure of the strength of a metal as a reducing agent.

36) can be written as Ox+mH+ +ne. The implications of these statements will be discussed in more detail in Section 1.+H 20 Cr20~. The relation between ion concentrations (activities) and the oxidation-reduction potential can be expressed by the Nernst equation as nF [Red] The E standard potential can be measured in a solution containing the oxidized and reduced form in equal (molar) concentrations (activities).+=t Me and the electrode potential can be calculated from the expression: ~ E + RT In[Me n+] n nF Standard electrode potentials are collected in Table 1.40.+ 14H+ +6e. Section 1. The more positive this standard potential. (c) Combined redox and acid-base systems systems (cf. Such half-cells are MnO'. and these electrodes were discussed in details in Section 1. gold. the stronger an oxidant is the oxidized form. can be written as Me n+ +ne. Such systems are Fe3+ + « +=t Fe2+ 12 + 2e. Thus. the more negative the standard potential. The oxidationreduction potential can be measured with an inert electrode (platinum.+2H+ +2e-+=t AsO~.41 QUALITATIVE INORGANIC ANALYSIS '(a) Metal electrodes The half-cell reaction on which their operation is based.+=t 2Cr3+ + 7H 20 Br0 3 + 6H+ + 6e. or in some cases mercury).+=t Red + ~ H 20 Ox again represents the oxidized and Red the reduced form of the system.+=t Sn2+ Both the oxidized and reduced forms are in the dissolved phase. E = E' + RFT In aMen + 6 (b) Simple redox systems terms as Ox-l-xe" +=t Red The half-cell reaction can be symbolized in general Ox represents the oxidized form and Red the reduced form of the redox couple. Standard oxidation-reduction potentials of simplex redox systems are shown in Table 1. +8H+ +5e. Sn 4 + 2e.1.16. the standard oxidation-reduction potential of the iron(III)-iron(II) system could be measured in a solution containing O'IM FeCl 3 and O'IM FeCl2 or O'OIM FeCl 3 and 0'01 M FeCl 2 etc.+=t Br" + 3H 20 etc.17. the stronger a reductant is the reduced form. 120 E = E + RT In aox nF a Re d 6 ~ E' + RT In [Ox] The half-cell reaction of such .43.+=t Mn2+ +4H 20 AsOi.+=t 21etc.

Inhomogeneous redox systems The forms of Nernst equation quoted in Section 1. but the 121 .+e2Hg2+ +2eMn3++ eMn04 +ePb 4+ + 2eS20~.43).) at pH O.+2eS40~.1 hydrogen ions (that is. Standard oxidation-reduction potentials of combined redox and acid-base systems are shown in Table 1. For inhomogeneous systems. The E" standard oxidation-reduction potential can be measured in a solution containing the oxidized and reduced forms in equal concentrations and I mol t. strictly speaking. Thus.THEORETICAL BASIS 1. for example. and (c) are.18. where there is no change in the number of molecules (or ions) when the substance is reduced or oxidized.41 Table 1. The correlation between concentrations (activities) and the oxidation-reduction potential can be expressed with the Nerst equation as E=L De RT aoxai'i+ RT [Ox] [H+]m + .In---~E" + . atpH 0). where this is not the case. Predictions as to the direction of reactions can again be made on the basis of the values of oxidationreduction potentiaIs (cf.42 and also see Section 1.41 +0'16 +0'76 +0'36 +0'91 + 1'51 +0'56 + 1·69 +2'05 +0'\7 +0'15 +0'10 ±o·OQ + I·O! + 1·36 +0·52 The oxidation-reduction potential can again be measured with a platinum or gold (inert) electrode.nF aRed nF [Red] From this expression it can be seen clearly that the oxidation-reduction potential of such systems depends as well on the hydrogen-ion concentration(pH) of the solution. the standard potential of the permanganate-manganese(I1) system could be measured in a solution containing O'IM KMn0 4 and O'IM MnS0 4 (or O'OIM KMn04 and O'OIM MnS0 4 etc.17 Standard oxidation-reduction potentials of simple redox systems at 2SOC Redox system E" (Volts) Au3+ +2eCe4+ +eCo3+ +eCr3+ +eCu2+ +eFe3+ + e: [Fe(CN)6]3. (b). general equations would be too complex to quote. Example 33 in Section 1.+2eSn4+ +2eTi4+ + e: H 2+2eBr2 +2eCI2 +2e12 + 2e- +:t Au" +:t Ce3+ +:t Co2+ +:t Cr2+ +:t Cu" +:t Fe 2+ +:t [Fe(CN)6]4+:t Hg~+ +:tMn2+ +:t MnO~+:t Pb2+ +:t 2S0~+:t 2S20~+:t Sn2+ +:t TP + +:t 2H+ +:t 2Br+:t 2CI+:t2r + 1·29 + 1'62 + 1·84 -0. The dependence of the oxidation-reduction potential on the pH must always be kept in mind when trying to make deductions from the values of this Table.41(a). valid only for homogeneous redox systems.In--==-=""""-=-".

41 QUALITATIVE INORGANIC ANALYSIS Table 1.+=t 212Hg2+ +2e.18.18 Standard oxidation-reduction potentials of combined redox and .+3H 20 Cl-+3H 20 Cl.+ 14H+ +6e.+=t 2Cr3+ + 7H 20 Cr20~- The oxidation-reduction potentials of these systems can be expressed as " RT [1-]2 E = E . Such inhomogeneous systems are for example 12 + 2e. a suitable inert electrode (e.17 and 1. E".6F In [Cr20~ ][H+J14 "RT " RT [Hg~+] and [Cr3+]2 E respectively. The potential of gas electrodes can easily be calculated with a suitable form of the Nernst equation.acid-base systems at 25°C +% +% CIO)"+6H++6e+% CIO.+=t H 2 122 .+4H 20 2Cr3+ + 7H 20 2H 20 r +3H 20 Mn0 2(s)+2H 20 Mn2+ +4H 20 AsO~- E" (Volts) +0'56 + 1'42 + 1'45 + 1·34 + 1·36 + 1'77 + 1·09 + 1·70 +1'52 +0'20 +1'15 + 1·23 +% SeO~-+H20 potential can be easily expressed if the half-cell reaction is known. The solid inert electrode may act as the catalyst of the ionization process.2F In [1 ] 2 E = E .+=t Hg~+ + 14H+ + 6e. Standard potentials. (d) Gas electrodes Gaseous substances.+% MnO. as we have already seen with the hydrogen electrode. As the gases themselves do not conduct electricity. +8H+ +5e. platinum or graphite) must be used as a link to the electrical circuit.+% H 202 + 2H+ + 2e+% 10)" +6H+ +6e+% MnO. (i) The hydrogen electrode operates on the basis of the half-cell reaction: 2H+ +2e. +8H+ +8e+% Cr20~. The rule is that in the argument of the logarithm in the Nernst equation the concentration must be taken at powers corresponding to their stoichiometrical numbers.2F In [Hg2+]2 = E . may act as electrodes. This will be elucidated in connection with three electrodes of practical importance. for these systems can be taken from Tables 1.+2H+ +2eBrO)" +6H+ +6e- +%SO~-+H20 +H 20 Br. +4H+ +3e. when donating or accepting electrons.g.1.+% SO~-+2H++2eSeO~-+2H++2e- Redox system AsO~.

41 This can be regarded as a simple redox system. being constant. The importance of these quantities will become apparent later (Cf. as. k. We have seen that the standard potential. its potential can be expressed as E = E e ' _ RT In aH2 se E. we can write E = E e.43). E". two. E." _ RT In [H 2] 2F a~+ 2F [H+]2 In this expression the activity (or concentration) of hydrogen gas cannot easily be measured. which is a combined redox and acid-base reaction. E". (iii) The chlorine electrode operates on the basis of the half-cell reaction Cl 2 +2e~ 2Cl- Its electrode potential can be expressed as E = E'" _ RT In [Cl-=1 = E" _ RT In [Cl-]2 2F [CI 2 ] 2F PCl 2 The value of the E" standard potential is + 1'36 V. ~ [H 2 ] = k PH 2 The proportionality factor. Thus. (ii) The operation of the oxygen electrode is based on the half-cell reaction O 2 +4H+ +4e- ~ 2H 20 Applying the Nernst equation for such a process. can be measured in a system where the activity of hydrogen ions is unity in the solution and the pressure of hydrogen gas over the solution is I atm. _ RT Ink = E" 2F can be used to define the standard potential. one. It can however be replaced by its pressure. of such an electrode is by definition O. for a given temperature. The concentration of water is regarded as constant in dilute aqueous solutions. the expression E e . The overall conclusions we can draw from the examples mentioned are that the potential of gas electrodes depends on the concentration of the particular 123 . The standard potential. the potential of the hydrogen electrode can be expressed as E = E" _ RT In 2F PH2 a~+ ~ E" _ RT In ~ 2F [H+]2 Thus the potential of the hydrogen electrode depends on the hydrogen-ion concentration in the solution and on the pressure of hydrogen gas above the solution. three). - RT I 4F n [0 ] [H+]4 [H 20 ] 2 2 = E e RT I [+]4 + 4F n (Po 2 H ) The final expression is arrived at in a similar way to that for the hydrogen electrode. It is useful and easy to memorize the standard potentials of the hydrogen electrode (E" = 0 V) and of the oxygen electrode (E" = 1'23 V. Section 1.THEORETICAL BASIS 1. aH. the activity (or concentration) is proportional to the pressure. The value of E~ measurable at pH = 0 with P02 = I atm (where P02 is pressure of oxygen over the solution) is + 1'23 V.

42 QUALITATIVE INORGANIC ANALYSIS ion in the solution which is involved in the half-cell reaction and on the pressure of the gas in the electrode system. varies with temperature also. These are E Cu E = E' + 0'0592 log [Me""] = E'" Cu + 0'0592 1og [C u 2+] 2 0'0592 = 0'34 + -2-1og0'15 = 0'316V and E zn = r. 124 . With R = 8'3143 J K.m. S. like those shown in Tables 1. p.16 to 1. The correlation between electrode potential and temperature is given by the appropriate form of the Gibbs-Helmholtz equation (er. The following examples may illustrate the ways in which oxidation-reduction potentials can be calculated. 1964.m.f. MacMillan. and lO-based T = 298'15 K. 924).76 -0'778 V * When calculating potentials for other than room temperature. Glasstone's Textbook of Physical Chemistry. Example 31 Calculate the e.+=t Zn The e. Calculations based on the Nernst equations are therefore usually restricted to this temperature. logarithms can be introduced. in other words. 2nd edn.oe L Zn 0'0592 + --2. of a Daniell cell.42 CALCULATIONS BASED ON THE NEAREST EQUATION Values of standard potentials are normally available for room temperatures (25°q. London..f.f. = IEcu.+=t Cu and E"'zn = -0'76 V for Zn2+ +2e.1. 1. it is not enough simply to insert the appropriate temperature into the prelogarithmic factor of the Nernst equation.m. of the cell can be expressed as e. because the standard potential. made up by immersing a copper foil into a 0'15M CuS04 solution and a zinc rod into 0'25M ZnS04 solution and linking the two half-cells together. E". * The prelogarithmic factor of the Nernst equation can thus be simplified. can be obtained. which.1 mol 4C mol-I. is the pressure of gas measurable above the solution. and In 10 = 2'0326 the constantRJ In 10 = 0'0592 F = 9'6487 X 10 t '.EznI Thus first the two electrode potentials have to be calculated.Iog [ Zn 2+] 0'0592 + -2-1og 0·25 = -0. According to Table 16 the values of the standard potentials are as follows: E"'cu = 0'34 V for Cu2+ + 2e. Thus the potential of a metal electrode becomes n and the same prelogarithmic factor can be used in all other forms of the Nernst equation.18.

. is.0'OS92 log = 0'788 V [Fe3+] 0'15 Example 33 20 ml 0'02M KMn0 4.log 3(0' 1)8 = I'431 V * The amount of hydrogen ions. 10 ml O'SM H 2S04 and S ml O'IM FeS0 4 solutions are mixed and diluted with water to 100 ml. the oxidationreduction potential will be that of the permanganate-manganese(II) system: MnO.-S-Iog [Mn0 [H+]8 4] Now we have to calculate the concentrations in the argument of the logarithm.]. To calculate the potential the Nernst equation can be written as 6 0'OS92 [Mn2+] E = E .. 8 x 10. Table 1. E = 0'76 V.. Calculate the oxidationreduction potential of the solution. : e.15 .= 0'76 . Thus the ratio can be expressed as [Mn2+] _ S _ I [Mn0 4] .3 Now the oxidation-reduction potential can be calculated: 0'OS92 I E = I·S2 .18) E = I. of the original 20 ml 0'02M KMn0 4. 125 . + 8H+ + Se.-S. IS ml is left unreacted while the equivalent of S ml is reduced to Mn2+..THEORETICAL BASIS 1. = IEcu-Eznl = 10'316-(-0'778)1 = 1'094 V Example 32 A solution contains O'OSM FeCI 2 and O'ISM FeCI 3 • What is the oxidation-reduction potential measurable in the solution? From Table LI7 the standard potential for the half-cell Fe3+ + « +=t Fe2+ is taken. it is sufficient to calculate the ratio [Mn2+]/[MnO. used up in this reaction.4 mol.+=t Mn2+ + 4H 20 for this the standard potential is (cf. the solution therefore will contain both MnO.m. Disregarding the slight decrease of the hydrogen-ion concentration* due to the reaction.m.. and Mn2+ ions (while practically all the Fe2+ disappears and equivalent amounts of Fe3+ are formed).] and [Mn2+] is more complicated but in fact we do not need their actual values.42 and the e. The appropriate form of the Nernst equation (n = I): O'OS [Fe2+] 0'OS92 log . This can be done easily. +SFe2+ +8H+ --+ SFe3+ +Mn2+ +4H 20 E = E 6 - 6 it can be seen that only a portion of the KMn04 will be reduced.f. according to the stoichiometry of the reaction. Thus. we can calculate [H+] as [H+] = 2x IOxO'S = 0'1 mol t " ! 100 To calculate [MnO.f.. From the reaction equation MnO. From the stoichiometry of the reaction it follows that.S2.

Of the 20 ml O·lM NaCl the equivalent of 2 ml has been removed by precipitation. To calculate the electrode potential we have to calculate [Ag "]. thus [Cl-] = J!0·1 = 0·018molr 1 100 The potential can now be calculated: E = 0·80+0·0592 log (~~~11:) = 0·313 V Example 35 What is the potential of the oxygen electrode in a solution having a pH of 8? The potential of this electrode (cf.43 QUALITATIVE INORGANIC ANALYSIS Example 34 20 ml O·IM NaCl and 2 ml O·IM AgN0 3 are mixed and diluted to 100 ml.8 . the potential is. Those conclusions can now be extended and generalized.~ Ag is 0·80 V (cf. The potential of a silver electrode can be expressed by the Nernst equation as E =E"+0·059 log [Ag+] E"for the half-cell Ag+ +e. Calculate the potential of a silver electrode dipped into this solution. It can be said that the more positive the oxidation-reduction 126 . E = 1·23 + 0. and the feasibility of dissolving metals in acid with the liberation of hydrogen.43 CONCLUSIONS DRAWN FROM THE TABLES OF OXIDATIONREDUCTION POTENTIALS From the values of oxidation-reduction potentials we can easily find out whether a particular oxidation-reduction reaction is feasible or not.16). For pH = 8 we have [H+] = 10. The pressure of oxygen over the solution is P02 = 0·21 atm 92 under atmospheric conditions. because practically all the silver is precipitated by the sodium chloride: Ag+ +Cl- ~ AgCl! For this precipitate the solubility product can be taken from Table 1.12: «. = [Ag"] [Cl-] = 1·5 x 10. We have already seen the rules that govern the displacement of metals by one another. Section 1.1 0 This expression can be combined with the Nernst equation to yield E = E" +0·059 log [~"-] The concentration of chloride ions can be calculated quite easily. Table 1.1.01 log {0·21(1O-8)4} = 0·748 V 1.41d) can be expressed as E = E" + 0·0592 Iog (P02 [H+]4) 4 Here E"= 1·23 V. This concentration will be extremely low. Thus.

+H 20 12 + 2e.12.l8 for example: AsO~- +2H+ +2e. 127 . the direction of a reaction will depend on the actual values of oxidation-reduction potentials. reaction 5). and never in the opposite direction. reaction 5 and Section 111. the stronger an oxidant is its oxidized form and vice versa: the more negative its oxidation-reduction potential. iron(II). the stronger a reducing agent is its reduced form.0'0592 H 2 og [AsO~ ] P At pH = 6 the potential of a solution containing arsenate and arsenite ions at equal concentrations decreases to +0'20 V. bromide. From Table 1. From the data. iron(lI) ions can never reduce tin(IV). The oxidation-reduction potential of the arsenate-arsenite system depends on the pH: . Section 111. iodide. that is. Under such circumstances therefore the opposite reaction will occur: 12+AsO~.THEORETICAL BASIS 1.43 potential of a redox system.+=t Fe2+ Sn4+ +2e. The direction of an oxidation-reduction reaction can also easily be predicted.+=t AsO~.. for example.l7 and I. quote the following two systems: Fe3+ +e. Similarly. iron(lIl) ions will oxidize tin(lI) ions. for example. It must be emphasized that the standard potentials are to be used only as a rough guide.--+ 12+AsO~-+H20 but the reaction cannot go in the opposite direction.+=t Sn2+ E = +0'76 V E = +0'15 V Because of the relative values of the oxidation-reduction potentials. and hexacyanoferrate(lI) ions.. The concentrations of the various species must be taken into consideration especially if combined redox and acid-base systems are involved. These.13. also that iron(llI) ions may oxidize arsenite or iodide ions but never chromium(lIl) or chloride ions etc. taken from Table 1. if the concentrations of the species are known. This in fact is true only if the solution is strongly acid (pH ~ 0).0'0592 [AsO~-] E = E .2 .17 we can. the reaction 2Fe3+ + Sn2+ --+ 2Fe2+ + Sn4+ can proceed only in this direction. the oxidized form of the system with a more positive potential will oxidize the reduced form of a system with the more negative potential. can be calculated easily by means of the Nernst equation. that permanganate ions (in acid medium) can oxidize chloride.1og [AsOl ] [H+]2 = E" - 0'0592 I [AsO~ -] .17 and I.+H 20 --+ AsO~- +2H+ +21- Both reactions are indeed used in qualitative inorganic analysis (cf. from the Tables I. and never the other way round.+=t 21- E E = = 0'56 V 0'52 V one could draw the conclusion that arsenate ions will oxidize iodide: AsO~-+2H++21.l8 we can see.

the feasibility of such reactions can most properly be decided on the basis of their equilibrium constant. are used up in this reaction. for a more detailed understanding the reader should consult textbooks of physical chemistry. If a moles of OX l and b moles of Red. Equations (iii) and (iv) can be combined to logK = Flogloe n(E 6-E!.4 mol-I.l and R = 8'314 J K. A few examples may illustrate how such calculations should be carried out. Moore's Physical Chemistry. F = 9'6487. and E1 are the standard oxidation-reduction potentials of systems I and 2 respectively. 128 4th edn. with log e = 0'4343. expressed with concentrations is (ii) This equilibrium constant is related to the standard free energy change.) RT 1 2 For room temperature (T = 298'15 K). are used up). In the following factual treatment this is assumed.1. we can obtain the expression logK= 16'905n(E'. Example 36 Calculate the equilibrium constant of the reaction (2e-) 2Fe3+ + Sn2+ +=t 2Fe2+ + Sn4 + * See e. This standard free energy change is equal to the electrical work done by a galvanic cell built from the two half-cells which are involved in reaction (i)... and n is the number of electrons exchanged during the reaction (more precisely. The proper explanation of this correlation needs a good working knowledge of chemical thermodynamics. !1(j..g. in turn. The equilibrium constant of such a reaction (Section 1. 174 and 385.44 QUALITATIVE INORGANIC ANALYSIS 1. Longman 1966. 104 C mol. * Let us consider the general form of a redox reaction (ne-) aOx t +bRed 2+ . of this reaction: -!1(j = RTln K (iii) The negative sign originates from the sign conventions usually adopted in chemical thermodynamics.13). the number of Faradays passing through the electrical circuit if a moles of OX l and b moles of Red.-E. W.. pp. (i) Here the subscripts I and 2 refer to the individual redox systems. . +=t cOx2+dRedl + . the electrical work done is (iv) where Et. The equilibrium constant of oxidationreduction reactions is.44 EQUILIBRIUM CONSTANT OF OXIDATION-REDUCTION REACTIONS The law of mass action being valid for oxidation-reduction reactions. J. strongly related to the differences in the standard oxidation-reduction potentials of the systems involved..) (v) which can be used for practical calculations.

17 and U8)... Et = 1'52 V. From expres- 16'905 x 2 x (0'76-0'15) K = 1020'62 = 4'21 X 1020 (5e-) = = 20'62 Example 37 Calculate the equilibrium constant of the reaction MnO'.1og [Mn0 [H+]8[Fe2+]5 4] . equation (v) we have or (vi) 0'76 V (cf. the oxidation-reduction potentials of both systems are equal: ~=~ W (xi) 129 Equations (vii).. + 8H+ + 5Fe2+ ~ Mn2+ + 5Fe3+ + 4H 20 For this reaction [Mn2+] [Fe3+]5 K = [Mn0 4] [H+]8[Fe2+]5 Here n = 5.44 The equilibrium constant can be written as [Fe2+]2 [Sn 4+] K = [Fe 3+]2[Sn 2+] Here n = 2. = log K = 16'905 x 5 x (1'52-0'76) = 64'24 K = 1064'24 = 1'73 X 1064 Using this example we can show the correlation between standard oxidationreduction potentials without applying the thermodynamical concepts mentioned above. The oxidation-reduction potential of the system MnO'..5 .~ Fe2+ by [Fe2+] E2 = 0'0592 log [Fe3+] (vii) m.. +8H+ +5e~ Mn2+ +4H 20 can be expressed as 0'0592 [Mn2+] El = Et . (ix). Tables 1.5 . Et = +0'76 V and sion (v) we obtain log K or E. - (viii) Equation (viii) can be transformed easily to E2 = E2 0'0592 [Fe2+]5 .THEORETICAL BASIS 1. Table 1. Using E.E 2 = .5 . and (x) can then be combined to give .17). = +0'15 V (cf.1og [Fe3+]5 (ix) If the reaction reaches equilibrium.1og [Mn0 4][H+]8 and that of the system Fe3+ +e. 0'592 [Mn2+] [Fe3+]5 E.

A state of equilibrium exists between the solution of iodine in carbon disulphide and the solution of iodine in water. the nature of the solute.19. or distribution.) which is identical with expression (v) deduced earlier (n = 5 for this particular reaction). and also ether and water. The value of the ratio varies with the nature of the two solvents.4S QUALITATIVE INORGANIC ANALYSIS As the concentrations in the argument of the logarithm are equilibrium concentrations. Thus iodine is very much more soluble in carbon disulphide. The removal of a solute from an aqueous solution by a water-immiscible solvent is called solvent extraction. H. It is important to note that the ratio C2/Cl is constant only when the dissolved substance has the same relative molecular mass in both solvents. The distribution or partition law may be formulated thus: when a solute distributes itself between two immiscible solvents there exists for each molecular species. that is the reactions become the more complete. on the other hand. the iodine will be found to be distributed between the two solvents. From such examples it becomes apparent that the greater the difference between the standard oxidation-reduction potentials. as defined by equations (i) and (v) is negative. 130 . That is: Concentration of iodine in carbon disulphide _ Concentration of iodine in water C2 _ G- K d The constant K d is known as the partition. which means that in practical terms the reaction will take place quantitatively. chloroform. If. the difference of standard potentials. It has been found that when the amount of iodine is varied. and this distribution ratio is independent of any other molecular species which may be present. when certain liquids such as carbon disulphide and water.I. the higher the value of the equilibrium constant. equations (vi) and (xi) can be combined. This technique is often applied for separations. are shaken together in a vessel and the mixture allowed to stand. Such liquids are said to be immiscible (carbon disulphide and water) or partially miscible (ether and water). coefficient. the two liquids separate out into two layers. In practice.45 THE DISTRIBUTION OR PARTITION LAW It is a well-known fact that certain substances are more soluble in some solvents than in others. a constant ratio of distribution between the two solvents. SOLVENT EXTRACTION 1. the reaction is not feasible. or carbon tetrachloride than it is in water. the ratio of the concentrations is constant at any given temperature. Some experimental results are collected in Table 1. a difference of O· 3 V for n = I secures a value for K greater than 105 . and the temperature. at a given temperature. Furthermore. in fact it will proceed in the opposite direction. according as to whether they are almost insoluble or partially soluble in one another. If iodine is shaken with a mixture of carbon disulphide and water and then allowed to settle. leading to log K = 16·905 x 5 x (Er-E5.

phase: chloroform 0·338 x 10.3 10.1 1'54x 10.2 7·84x 10.4 10.3 10. although theoretically it cannot be reduced completely to zero. phase: carbon disulphide 1·387 1'017 0'520 0'323 3'231 x 2·522 x 1·261 x 0'788 x 10.2 6·01 X 10.x 12 in mol t.THEORETICAL BASIS 1.2 4'lOx 10. Example 38 Ten milligrams iodine are suspended in 12 ml water. In this way the concentration of iodine in the aqueous solution may be reduced to a very small value.2 12'17xlO.4 135'2 128·3 126·1 132-6 130·6 Average: 75'8 76·3 80·0 81·3 82-6 84·1 80·1 1. Its concentration will become [I 2 ]aq = 253'.(or mmol ml"") 131 1 .4 10.4 10.46 Table 1.2 1'64 x 10. The carbon disulphide layer may be removed with the aid of a separatory funnel and the process repeated.3 10.3 10.3 10. Calculate the weight of iodine remaining in the aqueous layer.19 The distribution of iodine between water and organic solvents at 25°C Concentration of iodine Kd in the organic phase mol £-1 in the aqueous phase mol £-1 Org.3 Average: Org.3 429 403 412 410 413·5 Average: Org.4 10. and shaken with 2 ml CC1 4 until equilibrium is reached.3 10. the concentration of iodine in the resulting carbon disulphide layer is about 400 times that in water. The following calculation will illustrate the point.2 1·332 X 2'151 X 5'130 x 7'391 X 9·448 x 14·38 x 10. phase: carbon tetrachloride I·O! x 10.46 THE APPLICATION OF SOLVENT EXTRACTION IN QUALITATIVE ANALYSIS A few examples of the application of solvent extraction in qualitative analysis are as follows: (a) Removal of bromine and of iodine from aqueous solution When an aqueous solution of iodine is shaken with carbon disulphide.1 3'21 x 10-1 0'25 X 1·20 x 1·84 x 2·42 x 10. Let x be the weight (in milligrams) of iodine which remains in the aqueous phase.4 10.1 2'32xlO.

(253·g = 2 x 126·9 is the relative molecular mass of iodine). It can be shown that after a third extraction 3.46 QUALITATIVE INORGANIC ANALYSIS units. with the formula (NH 4h[Co(CNS)4]' produced by the action of a concentrated solution of ammonium thiocyanate upon a cobalt(II) ion is more soluble in amyl alcohol than in water.5 mg iodine is left behind. y.19 we have K d = gO· I for the distribution coefficient: (lO-x) 253·g x 2 x 253·g x 12 IO-x 2 . (b) Various tests in qualitative analysis (i) Chromium pentoxide is more soluble in amyl alcohol (or in ether) than in water.62 x 10.= gO·1 x 12 from this x = 0·70 mg. can be computed from the equation 0·70-y 2 Y 12 from which y = 0·052 mg. in performing extractions. the quantity of iodine still remaining in the aqueous layer. If the CC1 4 layer is withdrawn with the aid of a separatory funnel and the residual aqueous layer is shaken with a second 2 ml batch fresh CCI4. the original 10 ml of the aqueous suspension were treated with a single 6 ml extraction CCI4. the blue colouration of the amyl alcohol layer.g x 2 mol f -1 From Table 1. This is a simple illustration of the fact that. is a sensitive and characteristic test for cobalt. If instead of three successive extractions with 2 ml portions of CCI4. it is more efficient and also more economical to carry out a number of successive extractions with small portions of the solvent rather than a single extraction with a large quantity.. In the CC1 4 10-x mg iodine will be found. as can be shown by a calculation similar to the above. and the presence of chromate or of hydrogen peroxide is indicated by the blue colour. by shaking the dilute aqueous solution with amyl alcohol (or with ether). due to the formation of a concentrated solution of this compound.3 mg and after a fourth one only 2·1 x 10.. Use is made of the partition principle in the detection of bromides. of iodides. (ii) The compound ammonium tetrathiocyanatocobaltate. 132 . its concentration being (lO-x) [I 2 ] CCl 4 = 253.1. and in the detection of bromides and iodides in the presence of each other. the weight of iodine remaining in the aqueous layer would be reduced only to 0·24 mg. a concentrated solution in the latter solvent is obtained.

and the free base. The initial concentration of aniline hydrochloride is known. however. is deduced. of course. for our present purpose. such as benzene or chloroform. the concentration of the free iodine in the aqueous solution can be calculated from the known distribution coefficient. the partition coefficient of the acid or base between the water and the other solvent must. in which iodine alone is appreciably soluble. Sufficient data are then available for the calculation of the degree of hydrolysis. Subtracting this from the total iodine. On shaking the aqueous solution with benzene the aniline will distribute itself between the water and benzene in the ratio of the distribution coefficient. may be written: Salt + Water +=t Acid + Base The concentration of the weak acid or of the weak base can be determined by distribution between water and another solvent. and from this the total concentration of aniline. A similar method has been used for the investigation of the equilibrium between bromine and bromides: 133 . both as free 12 and combined as 13". and therefrom the total concentration of the free iodine present at equilibrium. by subtracting the latter value from the initial concentration of potassium iodine the concentration of the free KI is deduced. (d) The determination of the constitution of complex halide ions Iodine is much more soluble in an aqueous solution of potassium iodide than it is in water.46 ( c) Study ofhydrolysis In the hydrolysis of a salt of a weak base and a strong acid or of a weak acid and a strong base.+=t 13" If the solution is titrated with standard sodium thiosulphate solution. This is partially hydrolysed into aniline and hydrogen chloride. the free acid. be known. a fresh amount of iodine is liberated from the tri-iodide in order to maintain the equilibrium. If. By determining the concentration of the iodine in the carbon tetrachloride solution. the concentration of the free aniline in the aqueous solution can be computed from that found in the benzene solution. The following equilibrium exists in such a solution: 12+1. produced by hydrolysis. is obtained. the solution is shaken with carbon tetrachloride.THEORETICAL BASIS 1. The equilibrium constant: K = [1-] x [12 ] [13 ] is then computed. The hydrolysis. this is due to the formation of tri-iodide ions. as soon as some iodine is removed by interaction with the thiosulphate. the total concentration of the iodine. then the iodine in the organic layer is in equilibrium with the free iodine in the aqueous solution. An example of such a salt is aniline hydrochloride. The degree of hydrolysis may then be calculated from the concentration of the salt and the determined concentration of the weak acid or base. there is an equilibrium between the salt. since. 13". the concentration of the combined iodine (as 13") is obtained.

1.46 QUALITATIVE INORGANIC ANALYSIS Distribution measurements have also been used to prove the existence of the tetramminecuprate(II) ion. the partition of the free ammonia being studied between chloroform and water: [Cu(NH 3)4]2+ +:! Cu2+ +4NH 3 134 . in an aqueous ammoniacal solution of copper sulphate. [Cu(NH 3)4]2+.

decantation.g. For micro analysis the factor is of the order of 0'01 or less. with hydrogen sulphide.I INTRODUCTION Before the student attempts to carry out the analytical reactions of the various cations and anions detailed in Chapters III and IV. evaporation. the choice lies between macro and semimicro analysis. etc. filtration. he should be familiar with the operations commonly employed in qualitative analysis. the concentrations of the ions remain unchanged. (ii) The greater speed of the analysis. to about 0'05 gram and the volume of solution to about I ml. There are many advantages in adopting the semimicro technique. evaporation. and these will be described in some detail. e. (v) Much space is saved both on the reagent shelves and more especially in the lockers provided immediately below the bench for the housing of the 135 . the quantity used for analysis is reduced by a factor of 0'1-0'05. but these terms indicate only very approximately the amounts used in the analysis. saturation. boring of corks. due to working with smaller quantities of materials and the saving of time in carrying out the various standard operations of filtration. Qualitative analysis may be carried out on various scales. In macro analysis the quantity of the substance employed is 0'5-1 gram and the volume of solution taken for the analysis is about 20 ml. distillation. In what is usually termed semimicro analysis. precipitation. and construction of a wash bottle. It will be noted that only the scale of the operations has been reduced.e. washing of precipitates can be carried out rapidly and efficiently when a centrifuge replaces a filter. These will therefore be either very briefly discussed or not described at all in the following pages. (iv) The amount of hydrogen sulphide used is considerably reduced. that is with the laboratory technique involved. crystallization.CHAPTER 11 EXPERIMENTAL TECHNIQUES OF QUALITATIVE INORGANIC ANALYSIS II. For routine analysis by students. bending of glass tubes. he should be familiar with such operations as solution. (iii) Increased sharpness of separation. these include: (i) Reduced consumption of chemicals with a considerable saving in the laboratory budget. i. preparation of ignition tubes. Special experimental techniques have been developed for handling the smaller volumes and amounts of precipitate. There is no sharp line of demarcation between semimicro and micro analysis: the former has been called centigram analysis and the latter milligram analysis. washing. It is assumed that the student has had some training in elementary practical chemistry.

no serious difficulty should be encountered in adapting a macro procedure to the semimicro scale. Most of the dry reactions to be described can be used with only minor modifications for semimicro analysis.2 QUALITATIVE INORGANIC ANALYSIS individual student's apparatus. Crystalline salts break into smaller pieces. and also other. Blowpipe tests A luminous Bunsen flame (air holes completely closed). may also be employed. More frequently the powdered substance is mixed with twice its bulk of anhydrous sodium carbonate or. with 'fusion mixture' (an equimolecular mixture of sodium and potassium carbon136 . or the material may melt or may decompose with an attendant change in colour. or a gas may be evolved which can be recognized by certain characteristic properties. prepared from soft glass tubing. however. the extreme tip of the flame is allowed to play upon the substance. The tests are carried out upon a clean charcoal block in which a small cavity has been made with a penknife or with a small coin. Dry tests appear to have lost their popularity in certain quarters. and blowing gently so as to cause the inner cone to play on the substance under examination. nitrite. chlorate. Qualitative analysis utilizes two kinds of tests. which are readily obtainable and are cheap. 11. Different techniques are employed for wet reactions in macro. A little of the substance is placed in the cavity and heated in the oxidizing flame. An oxidizing flame is obtained by holding the. Heating The substance is placed in a small ignition tube (bulb tube). Both macro and semimicro procedures will be given separately in this book in order that the requirements of all types of students may be met. preferably. Instructions for such operations are given below. semimicro. and micro analysis. dry reactions and wet reactions. burning indicates the presence of an oxidizing agent (nitrate.11.). few applications of the micro technique will be described in the text. is employed for these tests. that is without dissolving the sample. when the semimicro technique is adopted. Small test-tubes. Nevertheless. It may be said that when the general technique of semimicro analysis has been mastered and appreciated. particularly for the elementary courses. about 5 cm long. (vi) The desirability of securing a training in the manipulation of small amounts of material. they do. l.nozzle of the blowpipe about onethird within the flame and blowing somewhat more vigorously in a direction parallel with the burner top. gently at first and then more strongly.2 DRY REACTIONS A number of useful tests can be carried out in the dry. The former are applicable to solid substances and the latter to substances in solution. 60-70 mm x 7-8 mm. and heated in a Bunsen flame. Apart from drop reactions. For these. this latter merit may be turned to good use by reducing the size of the bench lockers considerably and thus effectively increasing the accommodation of the laboratory. 2. reasons many laboratories now employ semimicro analysis. students are recommended to read the sections dealing with macro technique. etc. Figure ILl illustrates the oxidizing and reducing flames. often provide useful information in a comparatively short time and a knowledge as to how they are carried out is desirable for all students of qualitative analysis. A reducing flame is produced by placing the nozzle of a mouth blowpipe just outside the flame. Sublimation may take place.

which probably consists of either a compound or a solid solution of cobaltous and aluminium oxides (Thenard's blue) indicates the presence of aluminium. II. and antimony) or to a sintered mass (copper) or to glistening metallic fragments (iron.1 ates. silicates. The oxides of lead. and zinc are readily reduced to the metal. this has a lower melting point than sodium carbonate alone) in the reducing flame. is indicative of zinc oxide. bismuth. The oxides of cadmium. that of cadmium is brown and is moderately volatile. but these are so volatile that they vaporize and are carried from the reducing to the oxidizing zone of the flame. The oxides thus formed are deposited as an incrustation round the cavity of the charcoal block. The oxides of the metals may further decompose. nickel. they are infusible and glow brightly when strongly heated. bismuth. strontium. and magnesium are not reduced by charcoal. iron. and a pale pink mass is formed when magnesium oxide is present. If the white residue or white incrustation left on a charcoal block is treated with a drop of cobalt nitrate solution and again heated. tin. nickel. bismuth. 11. and antimony. A characteristic incrustation accompanies the globules of lead. tin. arsenates. probably of similar composition (Rinmann's green). decomposed into the oxides and carbon dioxide. or be reduced to the metals. that of arsenic is white and is accompanied by a garlic odour due to the volatilization of the arsenic. to the metal. or oxides. The oxides of the noble metals (silver and gold) are decomposed. 137 . The final products of the reaction are therefore either the metals alone. and cobalt are reduced either to a fused metallic globule (lead. The alkali salts are largely adsorbed by the porous charcoal. calcium. The initial reaction consists in the formation of the carbonates of the cations present and of the alkali salts of the anions. which is often obtained as a globule.* a pale-green colour.2 Reducing Fig. 3.2). The oxides of aluminium.EXPERIMENTAL TECHNIQUES 11. * A blue colour is also given by phosphates. and cobalt). antimony. it is necessary to have some knowledge of the structure of the non-luminous Bunsen flame (Fig. arsenic. for the most part. where they are converted into difficulty volatile oxides. and oxygen. Flame tests In order to understand the operations involved in the flame colour tests and the various bead tests to be described subsequently. a bright-blue colour. without the aid of the charcoal. and the carbonates are. barium. or borates. copper. or they may remain unchanged. Zinc yields an incrustation which is yellow while hot and white when cold. metals and their oxides.

11.Upper reducing zone (e) r+--. in testing the relative volatilities of substances or of a mixture of substances.Lower reducing zone (f) (h) P-----.11. The principal parts of the flame. The procedure is as follows.2 QUALITATIVE INORGANIC ANALYSIS The non-luminous Bunsen flame consists of three parts: (i) an inner blue cone ADB consisting largely of unburnt gas. and these are prepared in situ by mixing the compound with a little concentrated hydrochloric acid before carrying out the tests. 11. and also.. here a large excess of oxygen is present and the flame is not so hot as'at c. (ii) a luminous tip at D (this is only visible when the air holes are slightly closed). sodium carbonate... it is especially useful for reducing oxide incrustations to the metal.2 hottest part of the flame is the fusion zone at b and lies at about one-third of the height of the flame and approximately equidistant from the outside and inside of the mantle. this is employed for testing volatile substances to determine whether they impart any colour to the flame.Upper oxidizing zone (d) 10+----1--. it is employed for testing the fusibility of substances. it is a less powerful reducing zone than e..Lower oxidizing zone (c) ~--. A thin 138 . It may be used for all oxidation processes in which the highest temperature is not required. in conjunction with a. or microcosmic salt. The chlorides are among the most volatile compounds. The lower reducing zone (f) is situated in the inner edge of the mantle next to the blue cone and it is here that the reducing gases mix with the oxygen of the air.. The c 1 0 + . and may be employed for the reduction of fused borax and similar beads. according to Bunsen. The upper oxidizing zone (d) consists of the non-luminous tip of the flame. We can now return to the flame tests.Lower temperature zone (a) Fig.Hottest portion of flame 0 . and (iii) an outer mantle ACBD in which complete combustion of the gas occurs. The upper reducing zone (e) is at the tip of the inner blue cone and is rich in incandescent carbon. are clearly indicated in Fig.. The lower oxidizing zone (c) is situated on the outer border of b and may be used for the oxidation of substances dissolved in beads of borax.2 The lowest temperature is at the base of the flame (a). Compounds of certain metals are volatilized in the non-luminous Bunsen flame and impart characteristic colours to the flame.

and barium in the fusion zone. potassium. bent into a small loop at one end and inserted into a cork (to serve as a handle) at the other. When cool. The testtube is about half filled with concentrated hydrochloric acid so that when the cork is placed in position. It is a good plan to store the wire permanently in the acid. The resulting bright clean platinum wire imparts no colour to the flame. strontium. and a tube D. The yellow colouration due to the sodium masks that of the potassium. may be used. A table showing the colours imparted to the flame by salts of different metals is given in Section V. fused into the end of a short piece of glass tubing or glass rod which serves as a handle. View the flame through two thicknesses of cobalt glass. strontium.2(3).EXPERIMENTAL TECHNIQUES 11. mounted on a turntable. Less volatile substances are heated in the fusion zone (b). a short length of chromel (or nichrome) wire. Carry out flame tests with the chlorides of sodium. It is then best to employ fused potassium hydrogen sulphate. and the colour imparted to the flame observed. the platinum wire should be cleaned with concentrated hydrochloric acid. It is then introduced into the lower oxidizing zone (c). A platinum wire sometimes acquires a deposit which is removed with difficulty by hydrochloric acid and heat. the bead of potassium pyrosulphate which forms travels along the wire. This is first thoroughly cleaned by dipping it into concentrated hydrochloric acid contained in a watch glass and then heating it in the fusion zone (b) of the Bunsen flame. followed by heating. Any small residue of pyrosulphate dissolves at once in water.2 platinum wire* about 5 cm long and 0'03-0'05 mm diameter. calcium. It is therefore possible to detect potassium in the lower oxidizing flame and the calcium. The wire is dipped into concentrated hydrochloric acid on a watch glass. Flame spectra The only worthwhile way to employ flame tests in analysis is to resolve the light into its component tints and to identify the cations present by their characteristic sets of tints. The instrument employed to resolve light into its component colours is called a spectroscope. in this way it is possible to make use of the difference in volatilities for the separation of the constituents of a mixture. the platinum wire is immersed in the acid. which contains a scale of reference lines which may be superposed upon the spectrum. whilst the last traces are usually removed by a single moistening with concentrated hydrochloric acid. then into a little of the substance being investigated so that a little adheres to the wire. 4. the bead is readily dislodged. is employed. Upon passing the wire slowly through a flame. and barium and record the colours you observe. 139 . Repeat the test with a mixture of sodium and potassium chlorides. the yellow sodium colour is absorbed and the potassium flame appears crimson. the wire is clean when it imparts no colour to the flame. 11.3. Spectroscopic tests. A coating of potassium hydrogen sulphate is made to adhere to the wire by drawing the hot wire across a piece of the solid salt. A simple form is shown in Fig. dissolving the contaminating deposits. The spectroscope * If a platinum wire is not available. A cork is selected that just fits into a test-tube. It consists of a collimator A which throws a beam of parallel rays on the prism B. This is not as satisfactory as platinum wire and is not recommended. the telescope C through which the spectrum is observed. Potassium chloride is much more volatile than the chlorides of the alkaline earth metals. After all the tests. and a hole is bored through the cork through which the glass holder of the platinum wire is passed.

which is adjustable by a milled knob at the side. relatively inexpensive. which is more useful for routine tests in qualitative analysis. half the length of the slit is covered and thus light from a source in a position at right angles to the axis of the instrument will fall on one-half of the slit adjacent to the direct light which enters the other half. a lighted Bunsen burner is placed in front of the collimator A at a distance of about 10 cm from the slit. shown in Fig.2 QUALITATIVE INORGANIC ANALYSIS c Fig. The slit should also be made narrow in order that the position of the lines on the scale can be noted accurately. the scale D is illuminated by placing a small electric lamp in front of it. such as sodium chloride.11. potassium chloride. 140 . as seen through the telescope C. and the tube containing the adjustable slit rotated until the sodium line. Finally. When the comparison prism is interposed. The wavelength curve may then be employed in obtaining the wavelength of all intermediate positions and also in establishing the identity of the component elements of a mixture.3 is calibrated by observing the spectra of known substances. The light from the 'flame' source passes through the central axis of the instrument through the slit. A smaller. Some sodium chloride is introduced by means of a clean platinum wire into the lower part of the flame. is the direct vision spectroscope with comparison prism. such as is marketed by the General Electric Company: this constitutes a high-intensity sodium light source. (If available.) The sodium line is then sharply focused by suitably adjusting the sliding tubes of the collimator and the telescope. thallium chloride.4. it is more convenient to employ an electric discharge 'sodium lamp'. and lithium chloride. 11. and more compact instrument. is in a vertical position. The conspicuous lines are located on a graph drawn with wavelengths as ordinates and scale divisions as abscissae. 11. and the scale sharply focused. To adjust the simple table spectroscope described above (which is always mounted on a rigid stand).

7 m.. is observed through the window. It is focused by means of a lens system comprising two achromatic combinations between which is a right angle prism.9 m. An adjusting screw is provided to alter the position of the right angle + . The old units of Angstrom (A. where it is seen superimposed upon the spectrum. By narrowing the slit.. If a sodium compound is introduced into the colourless Bunsen flame.1 0 m) and millimicron (mu = 10...for stand Clamp Window Comparison prism -Light . two fine yellow lines may be seen. and the adjusting screw is locked into position by means of a locking nut. [Wavelengths are generally expressed in nanometers (nm). The train of prisms gives an angular dispersion of about 110 between the red and the blue ends of the spectrum. --ciiatiCUie plate Adjustable slit ' .g. which can be focused by means of a sliding tube adjustment.] The mean wavelength of the two sodium lines is therefore 589'3 nm. This prism turns the beam of light so that it falls on the face of the end prism (of the train of five prisms) and is reflected into the observer's eye. The mean wavelength corresponding to these two lines is 5'893 x 10.. which is illuminated either from the same source of light as that being observed or from a small subsidiary source (e. There is a subsidiary tube adjacent to the main tube: the former contains a graticule on a glass disc. The elements which are usually identified by the 141 ... it colours it yellow... if the light is examined by means of a spectroscope.. The scale is calibrated directly into divisions of 10 nanometers (or 100 A in older instruments) and has also an indication mark at the D-line: it is 'calibrated' by means of a sodium source. identical to nm) are now obsolete. The resulting spectrum. I nm = 10.9 m. a flash lamp bulb). three being of crown glass and the alternate two of flint glass.EXPERIMENTAL TECHNIQUES 11.Objective lens Focusing adjustment for scale Adjusting --E::::J screen Lens focusing for graticule plate Fig.. 10.4 prism in order to adjust the scale relative to the spectrum. The instrument can be mounted on a special stand.2 This light passes through an achromatic objective lens and enters a train offive prisms of the 600 type. a bright yellow line is visible. 11.

A more extended discussion is outside the scope of this volume. S. The free end of the platinum wire is coiled into a small loop through which an ordinary match will barely pass. 589'6 766'5. especially in the hands of beginners. calcium.513'7 487-4 Double yellow Double red Double violet Red Orange (faint) Green Orange band Yellowish-green Violet (faint) Red band Orange Blue Green band Blue (faint) The spectra of the various elements are shown diagrammatically in Fig. the salt swells up as it loses its water of crystallization and shrinks upon the loop forming a colourless.. strontium. As already stated.11.769'9 404-4. less frequently. H. thallium and. Wiley 1971.1 Element Sodium Potassium Lithium Thallium Calcium Strontium Barium Commonly occurring spectrum lines Description of !ine(s) Wavelength in nm 589'0. AddisonWesley 1961 or M. The danger of the bead falling off is reduced by holding the wire horizontally. t Na2B407 = 2NaB0 2+ B20 3 The bead is moistened and dipped into the finely powdered substance so that a minute amount of it adheres to the bead. because of the comparative complexity of their spectra.534'7.1. is used for the borax bead tests. the wavelengths of the brightest of these are given. and is less time-consuming. are collected in Table 11. and the reader is referred to the standard works on the subject. 662'8 606·0 460·7 553-6. they will appear as bands.2 QUALITATIVE INORGANIC ANALYSIS spectroscope in qualitative analysis are: sodium. The wavelengths of the brightest lines. It is important to employ a minute * See for example: 1. the positions of the lines have been drawn to scale. Ahrens and R. t Some authors do not recommend the use of a loop on the platinum wire as it is considered that too large a surface of the platinum is thereby exposed. 142 . It is the author's experience that the loop method is far more satisfactory.404'7 670'8 610·3 535'0 618'2-620'3 555-4 422·7 674'4. lithium. The adhering solid is held in the hottest part of the flame. potassium. and barium. According to their procedure. 2nd edn. Borax bead tests A platinum wire. * 5. transparent.5. If the resolution of the spectroscope is small. visible through a good-quality direct vision spectroscope. Taylor: Spectrochemical Analysis. Slavin: Emission Spectrochemical Analysis. Table 11. The loop is heated in the Bunsen flame until it is red hot and then quickly dipped into powdered borax Na2B407' IOH20. glass-like bead consisting of a mixture of sodium metaborate and boric anhydride. 11. similar to that referred to under flame tests.524'3. the alternate dipping into borax and heating is repeated until a bead I·5-2 mm diameter is obtained. the spectra of the alkaline earth metals are relatively complex and consist of a number of fine lines.

allowed to cool and the colour observed again. 143 .2 RED GREEN BLUE VIOLET I I I I I I I ~ Fig.5 amount of substance as otherwise the bead will become dark and opaque in the subsequent heating. The bead and adhering substance are first heated in the lower reducing flame.EXPERIMENTAL TECHNIQUES 11. They are then heated in the lower oxidizing flame. allowed to cool and the colour observed. 11.

Phosphate (or microcosmic salt) bead tests The bead is produced similarly to the borax head except that microcosmic salt. the bead is removed from the wire by heating it again to fusion. In the reducing flame (i. in those cases where different coloured beads are obtained in the oxidizing and the reducing flames. The student should carry out borax bead tests with salts of these metals and compare his result with those given in Chapter Ill. Some authors assume that the metal metaborate may combine with sodium metaborate to give complex borates of the type Na2[Cu(B02)4]' Na2[Ni(B02)4] and Na 2[Co(B02)4]: Cu(B0 2h +2NaB0 2 = Na2[Cu(B02)4] 6. a borax bead is run backwards and forwards along the wire by suitably heating. and nickel. 4H 20. the so-called silica 144 . iron. is used. one has: Na2B407 = 2NaB0 2 + B20 3 CuO+B 20 3 = Cu(B0 2h (copper(I1) metaborate) The reaction: CuO+NaB0 2 = NaCuB0 3 (orthoborate) probably also occurs. is not dissolved by the phosphate bead. which are often coloured. in particular. so that the bead appears red and opaque: 2Cu(B0 2h +4NaB0 2 +2C = 2Cu+ 2Na2B407 +2COi With iron salts. silica is liberated and this remains suspended in the bead in the form of a semi-translucent mass.11. transparent bead contains sodium metaphosphate: Na(NH 4)PH04 = NaP0 3+H 20i+NH 3i This combines with metallic oxides forming orthophosphates. The borax bead also provides an excellent method for cleaning a platinum wire. Silica. sodium ammonium hydrogen phosphate tetrahydrate Na(NH 4)HP04. manganese. Thus a blue phosphate bead is obtained with cobalt salts: NaP0 3 + CoO = NaCoP0 4 The sodium metaphosphate glass exhibits little tendency to combine with acidic oxides.2 QUALITATIVE INORGANIC ANALYSIS Characteristic coloured beads are produced with salts of copper. After each test. The colourless. and then jerking it off the wire into a vessel of water. Thus with copper salts in the oxidizing flame. in the presence of carbon). Fe(B0 2h and Fe(B0 2h are formed in the reducing and oxidizing flames respectively. and is then shaken off by a sudden jerk. chromium.e. cobalt. two reactions may take place: (i) the coloured copper(I1) salt is reduced to colourless copper(I) metaborate: 2Cu(B0 2h +2NaB0 2 +C = 2CuB0 2 +Na 2B407 +COi (ii) the copper(I1) borate is reduced to metallic copper. borates corresponding to varying stages of oxidation of the metal are produced. When a silicate is strongly heated in the bead. The coloured borax beads are due to the formation of coloured borates.

145 . violet" when cold. They accordingly adhere better to the platinum wire loop. a green bead of sodium manganate is formed: MnO + Na2C03 + O 2 = Na2Mn04 + CO 2l A yellow bead is obtained with chromium compounds. Sodium carbonate bead tests The sodium carbonate bead is prepared by fusing a small quantity of sodium carbonate on a platinum wire loop in the Bunsen flame. hot and cold. a white.EXPERIMENTAL TECHNIQUES 11. Green when cold. Pale yellow when hot. blue when cold. The various colours of the phosphate beads are collected in the following table. hot and cold. Green when hot. Table 11. hot and cold. • Blood red when fused with a trace ofiron(II) sulphate. colourless when cold Colourless. 7. Green. colourless to green when cold.3 WET REACTIONS These tests are made with substances in solution. are usually more pronounced. Violet. hot and cold. Brown. hot and cold. due to the production of sodium chromate: 2Cr 203 +4Na2C03 +30 2 = 4Na 2Cr04 +4C0 2i 11. or (c) by a change of colour. and the whole heated in the oxidizing flame. hot and cold. red when cold. hot and cold. which are generally similar to those of the borax beads. The colours of the phosphates. it may be stated that the borax beads are more viscous than the phosphate beads. yellowgreen when cold. however. If this is moistened. yellow when cold. Yellow when hot. Blue. Yellow when hot. hot and cold. The majority of the reactions of qualitative analysis are carried out in the wet way and details of these are given in later chapters.2 Microcosmic salt bead tests Oxidizing flame Reducing flame Metal Copper Iron Chromium Manganese Cobalt Nickel Vanadium Uranium Tungsten Titanium Green when hot. hot and cold. blue" when cold. Blue. In general.3 'skeleton' is seen in the bead during and after fusion. dipped into a little potassium nitrate and then into a small quantity of a manganese compound. Green. (b) by the evolution ofa gas. A reaction is known to take place (a) by the formation of a precipitate. Colourless when hot. Green. be pointed out that many silicates dissolve completely in the bead so that the absence of a silica 'skeleton' does not conclusively prove that a silicate is not present. opaque head is produced. hot and cold. Yellow when hot. This reaction is employed for the detection of silicates: CaSi0 3 + NaP0 3 = NaCaP0 4 + Si0 2 It must. Yellow.or reddish-brown when hot. Grey when cold. The following notes upon the methods to be adopted in carrying out the tests will be found of value and should be carefully studied. Colourless. Yellowish.

and are useful for decompositions and evaporations. the so-called 'boiling tube' is recommended.19d) can be operated by pressing the elastic walls of the bottle. is cut into suitable lengths and the ends rounded in the Bunsen flame. A rod pointed at one end.19b: this form of wash bottle is highly convenient and is more hygienic than the type requiring blowing by the mouth. prepared by heating a glass rod in the flame. 146 . It is useful to remember that 10 ml liquid fills a test-tube of this size to a depth of about 5'5 cm. 2. Conical or Erlenmeyer flasks These should be of 50. 1I.19a). As the air bubbles through the liquid. by means of V-shaped glass rods.11. about 18 x 2'5 cm. the clock glass should be supported on the rim of the beaker. and 250 ml capacity and of the Griffin form are the most useful in qualitative analysis. and 250 ml capacity. whose stem has been cut off. A rubber-tipped glass rod or 'policeman' is employed for removing any solid from the sides of glass vessels. 100. 5. 3. A rubber bulb may be attached to the short tube as in Fig. Open glass tubes must not be used as stirring rods.3 QUALITATIVE INORGANIC ANALYSIS 1. Asbestos string or cloth should be wound round the neck of the flask in order to protect the hand. Stirring rods A length of glass rod. For evaporations and chemical reactions which are likely to become vigorous. and although they will take hot liquids. The introduction of a funnel. 100. Polyethylene wash bottles (Fig. of about 4 mm diameter. it is very inconvenient to use them because one has to grip the hot walls. 1I. and the stopper carrying the two tubes should be preferably of rubber (cf. The rods should be about 20 cm long for use with test-tubes and 8-10 cm long for work with basins and small beakers. The pressure pushes the liquid out through the tube. A test-tube brush should be available for cleaning the tubes. Test-tubes The best size for general use is 15 x 2 cm with 25 ml total capacity. this runs through the filter paper rapidly and has a greater solvent power than cold water. These flasks cannot be heated. The flow rate can easily be regulated by changing the pressure exerted by the hand. Smaller test-tubes are sometimes used for special tests. 4. so that less is required for efficient washing. Clock glasses of the appropriate size should be provided. A stirring rod of polythene (polyethylene) with a thin fan-shaped paddle on each end is available commercially and functions as a satisfactory 'policeman' at laboratory temperature: it can be bent into any form. prevents loss of liquid through the neck of the flask and permits the escape of steam. Wash bottle This may consist of a 500 ml flat-bottomed flask. For heating moderate volumes of liquids a somewhat larger tube. It is recommended that the wash bottle be kept ready for use filled with hot water as it is usual to wash precipitates with hot water. is employed for piercing the apex of a filter paper to enable one to transfer the contents of a filter paper by means of a stream of water from a wash bottle into another vessel. the latter will always be saturated with dissolved oxygen and this might interfere with some of the tests. 1I. When set aside the walls flatten out again and air is sucked into the bottle through the tube. Fig. drawing it out when soft as in the preparation of a glass jet and then cutting it into two. Beakers Those of 50.

followed by D) so as to displace most of the air in the flask: this will take not more than about 30 seconds. particularly in acid solution. a sufficient excess of the reagent has been added. most of it escapes into the air of the fume chamber and is wasted. B is a wash bottle containing water and serves to remove any hydrochloric acid spray that might be carried over from the Kipp's apparatus in the gas stream. It should always be borne in mind that a large excess of the precipitating agent may lead to the formation of complex ions and consequent partial solution of the precipitate. Precipitation with hydrogen sulphide This operation is of such importance in qualitative analysis that it merits a detailed discussion. consists in passing a stream of gas in the form of bubbles through the solution contained in an open beaker. In order to ensure that all the air has been expelled. The 'bubbling' method is not recommended and should not be used for macro analysis. absorption of the gas takes place at the surface of the bubbles and. it is advisable to loosen the stopper in A again to sweep out the gas and then to stopper the flask tightly. The stopper is first loosened in the neck of the flask and the gas stream turned on (C first. this does not mean that an excessive amount should be employed. if no further precipitation occurs. furthermore. Passage of the gas is continued with gentle rotation of the flask untilthe bubbling ofthe gas in B has almostceased. splashing of the liquid on to the hydrogen sulphide delivery tube should be avoided. The efficiency of the method is low. In most cases. When studying the reactions of ions the concentrations of the reagents are known and it is possible to judge the required volume of the reagent by quick mental calculation. The solution is contained in a small conical flask A.t At this point the solution in A should be saturated with hydrogen sulphide and precipitation of the sulphides should be complete: this will normally require only a few minutes. which is sometimes employed.3 6.EXPERIMENTAL TECHNIQUES 11. t It must be borne in mind that the gas may contain a small proportion of hydrogen due to the usually present in the commercial iron(II) sulphide. whilst stopcock D provides an additional control* for the gas flow. It must be remembered that the gas is highly poisonous. this procedure is sometimes termed the 'bubbling' method. One method. only a moderate amount over that required to bring about the reaction is necessary. 7. 147 . The conical flask is connected to the wash bottle by a short length of rubber tubing.6. Precipitation When excess of a reagent is to be used in the formation of a precipitate. With the gas flowing. The most satisfactory procedure (the 'pressure' method) is best described with the aid of Fig. unless specifically stated. Complete precipitation should be tested for by separating the precipitate by filtration. Displacement of the gas in the flask (by loosening the stopper) when the bubbling has diminished considerably will ensure complete precipitation. or conical flask. it prevents diffusion of air into the wash bottle and thus ensures an almost immediate supply of hydrogen sulphide. 11. C is a stopcock which controls the flow of gas from the generator. which is provided with a stopper and lead-in tube. since the gas is absorbed slowly. and repeating the procedure with the filtrate until the hydrogen sulphide produces * Stopcock D is optional. the stopper is inserted tightly and the flask is gently shaken with a rotary motion. test-tube. an unnecessary excess of the reagent is wasteful and may lead to complications at a subsequent stage of the analysis. This is usually best detected by filtering a little of the mixture and testing the filtrate with the reagent.

g. It should never be more than about two-thirds full of the solution. The delivery tube must be thoroughly cleaned after each precipitation. 1I. This can most easily be prepared in the bottle B of the apparatus shown in Fig. (b) a filtration 'accelerator' or 'ashless tablet' (Whatman). The filter paper pulp may consist of (a) filter paper clippings. 11. for example that of lead chloride which is markedly more soluble in hot than cold water. 8. it is shown (with the stopper) in (b).S. ashless grade.9b or c).3 QUALITATIVE INORGANIC ANALYSIS B (a) (h) Fig. The advantages of the 'pressure' method are: (i) a large surface of the liquid is presented to the gas and (ii) it prevents the escape of large amounts of unused gas. a saturated aqueous solution of hydrogen sulphide can be used as a reagent. or (c) 'dry-dispersed'. analytical filter paper pulp (Schleicher and Schuell.6 no further precipitate. For a quantitative precipitation of sulphides (e. Occasionally a test-tube replaces the conical flask.II. A moderately fine-textured filter paper is generally employed. for separation of metals) the use of hydrogen sulphide gas is however recommended.A. this procedure may be used when the quantity of the precipitate is large and it is to be discarded. The upper edge of the filter paper should be about 1 cm from the upper rim of the glass funnel.6. Alternatively. to separate the mother liquor and excess of reagent from the precipitate. Liquids containing precipitates should be heated before filtration except in special cases. The best method is to add a little filter paper pulp to the solution and then to filter in the normal manner. The size of the filter paper is controlled by the quantity of precipitate and not by the volume of the solution. of course. which usually clog the pores of the filter paper and thus considerably reduce the rate of filtration. may be filtered through fluted filter paper or through a pad of filter papers resting on the plate of a Buchner funnel (Fig. Such a reagent can most conveniently be used in teaching laboratories or classroom demonstrations when studying the reactions of ions. All the various forms of pure filter paper pulp increase the speed of filtration by re148 . Filtration The purpose of filtration is. Gelatinous precipitates.).11. U. ash-free.

the filter is filled about one-half to twothirds full at each washing. 10. If the amount of precipitate is small. crystalline. 9. one or two methods may be employed. In the first. When only a small quantity of the precipitate is available. Where large quantities of liquids and/or precipitates are to be handled. this will help to prevent the formation of colloidal solutions. such as ammonium chloride or nitrate. preferably whilst hot. A precipitate may be washed by decantation. the filter paper is removed from the funnel. filtration under diminished pressure is employed: a metal or glass water pump may be used to provide the reduced pressure. and the precipitate then transferred to the filter paper. The completion of washing Le. and scraped with a spatula. Other test papers are employed similarly. If it is desired to maintain a small volume of the liquid. It is frequently necessary to dissolve a precipitate completely. If the solution is to be tested for acidity or alkalinity. Aids to filtration The simplest device is to use a funnel with a long stem. silver nitrate solution is used. removed upon the end of a glass rod. about 45 cm long and bent as shown in Fig. through the other hole. the removal of the precipitating agent is tested for by chemical means.7. a drop of the thoroughly stirred solution. The addition of a Whatman filtration 'accelerator' may also be advantageous. if necessary. until all the precipitate has passed into solution.3 taining part of the precipitate and thus preventing the clogging of the pores of the filter paper. is placed in contact with a small strip of 'neutral' litmus paper or of 'wide range' or 'universal' test paper (Section 1. it is often a good plan to add an ammonium salt. carrying a glass stopcock at its upper end. The lower end of the tube or of the funnel should touch the side of the vessel in which the filtrate is being collected in order to avoid splashing. thus if a chloride is to be removed. the filtrate may be poured repeatedly through the filter until all the precipitate has passed into solution. A filter flask of 250-500 ml capacity is fitted with a two-holed rubber bung. to the funnel by means of rubber tubing. Removalofthe precipitatefrom the filter If the precipitate is bulky. or if rapid filtration is desired. The speed of filtration depends inter alia upon the length of the water column. 11. When a precipitate tends to pass through the filter paper. on to the filter and repeating the process. sufficient amounts for examination can be removed with the aid of a small nickel or stainless steel spatula. This is most readily done by pouring the solvent. or better to attach a narrow-bored glass tube. as much as possible being retained in the vessel during the first two or three washings. into 149 . a small hole is pierced in the base of the filter paper with a pointed glass rod and the precipitate washed into a test-tube or a small beaker with a stream of water from the wash bottle. The side arm of the flask is connected by means of thick-walled rubber tubing ('pressure' tubing) to another flask. a long glass tube is passed through one hole and a short glass tube. opened out on a clock glass.22) on a watch glass. This procedure is unnecessary for coarse. In the second. to the solution. easy filterable precipitates as the washing can be carried out directly on the filter paper.EXPERIMENTAL TECHNIQUES 11. the filter paper and precipitate may be heated with the solvent and filtered. This is best done by directing a stream of water from a wash bottle first around the upper rim of the filter and following this down in a spiral towards the precipitate in the apex.

Both types of support are folded with the filter paper to form the normal type of cone (Fig. 11. it may be collected in a test-tube placed inside the filter flask. 11. is available commercially.) filter paper support (No. * shown in c. made from a muslin-type material which will not retard filtration. Two thicknesses of wellfitting filter paper cover the plate. Fig. They may be filtered through a small pad of glass wool or of asbestos placed in the apex of a glass funnel. is to employ a sintered glass funnel (Fig. the filter plate. This consists of a porcelain funnel in which a perforated plate is incorporated. the filter funnel may now be removed from the filter flask. filtration may be carried out in the usual manner under the partial vacuum created by the pump.8). applicable to strongly acidic and mildly basic solutions. particularly when the volume of the liquid in the funnel is small. The Jena 'slit sieve' funnel. its great advantage over the porcelain Buchner funnel is that it is easy to see whether the funnel is perfectly clean.3 QUALITATIVE INORGANIC ANALYSIS @) Fig. or a Schleicher and Schuell (U. IL8 For a large quantity of precipitate. Strongly acidic or alkaline solutions cannot be filtered through ordinary filter paper. For this purpose either a Whatman filter cone (No.9d). 51) made of a specially hardened filter paper. may be used. When the volume ofliquid is small.7 the mouth of which a glass funnel is fitted by means of a rubber bung. air thereby entering the apparatus which thus attains atmospheric pressure. To surmount the difficulty. (Fig. is fused into a resistance glass (borosilicate) funnel. a small Buchner funnel (b in Fig. 123). Upon applying suction to the filter paper fitted into the funnel in the usual way. the stopcock T being closed. the stopcock T is opened. is essentially a transparent Buchner funnel.SA. the filter paper must be supported in the funnel.11. When filtration is complete.9. which is available in various porosities. 1I. shown enlarged for the sake of clarity) is employed. it will be punctured or sucked through. A more convenient method. The Buchner funnel is fitted into the filter flask by means of a cork. * A Pyrex 'slit sieve' funnel. 1I.9a). 150 with 65 mm disc. Filtration is carried out under reduced pressure exactly as with a Buchner funnel. 11. . After the filter paper has been supported in the funnel.

For many purposes a water bath (a beaker half-filled with water maintained at the boiling point is quite suitable) will serve as a source of heat. When evaporating to dryness. etc. to remove the dish whilst there is still a little liquid left. the rate of evaporation will of course be slower than by direct heating with a flame. Evaporation The analytical procedure may specify evaporation to a smaller volume or evaporation to dryness.9 11. the capacity of the vessel should be as small as possible for the amount of liquid being reduced in volume. The reduction in volume of a solution may also be accomplished by direct heating in a small beaker over a wire gauze or by heating in a wide test-tube (. Both operations can be conveniently carried out in a porcelain evaporating dish or casserole. 11. sulphur dioxide. in the latter case care must be taken that the liquid does not bump violently.IO. The most rapid evaporation is achieved by heating the dish directly on a wire gauze.EXPERIMENTAL TECHNIQUES 11.boiling-tube'). it is frequently desirable. Should corrosive fumes be evolved during the evaporation. the process must be carried out in the fume cupboard. II. in order to minimize spattering and bumping. by a free flame. applicable to solutions from which gases (hydrogen sulphide. held in a holder.3 (a) (h) (c) (d) Fig. the heat capacity of the evaporating dish is usually sufficient to complete the operation without further heating. is shown in Fig.) are to be removed by boiling. It consists of a length 151 . A useful anti-bumping device.

which rapidly dries the filter and precipitate. followed by a liberal washing with tap water. the student should remember that wet dirt is very much easier to remove than dry dirt. laying it upon several dry filter papers and allowing them to absorb the water. Drying ofprecipitates Partial drying. Other apparatus. Avoid using unnecessary excess of reagents. It should be extinguished when no longer required. Great care must be taken not to char the filter paper. Reagents should always be added portion-wise. that is a cloth which has been washed at least once and contains no dressing.3 QUALITATIVE INORGANIC ANALYSIS )C Fig. is accomplished by opening out the filter. A test-tube brush should be used to clean test-tubes and other glass apparatus. A string duster is useful to wipe up liquids spilt upon the bench. Remember a tidy bench is indicative of a methodical mind. make sure that both the solution to be tested and the reagent are absolutely free from suspended particles. Glass apparatus which appears to be particularly dirty or greasy is cleaned by soaking in chromosulphuric acid (concentrated sulphuric acid containing about 100 g of potassium dichromate per litre). filter the solutions first. The device must not be used in solutions that contain a precipitate. If a reagent bottle is empty. The size of the Bunsen flame should be no larger than is absolutely necessary. Test-tubes may be inverted in the test-tube stand and allowed to drain. 14. (b) Reagent bottles and their stoppers should not be put upon the bench. which is inserted into the solution.10 -. 13. should be wiped dry with a 'glass cloth'. 12. They should be returned to their correct places upon the shelves immediately after use. A safer but slower method is to place the funnel and filter paper. which is sufficient for many purposes.jl cm f-- of glass tubing sealed off about I cm from one end. it should be returned to the store-room for filling. The funnel is thus exposed to a current of hot air. (d) Do not waste gas or chemicals. (c) When carrying out a test which depends upon the formation of a precipitate. All glass and porcelain apparatus must be scrupulously clean. which rests either upon a sand bath or upon a wire gauze and is heated by means of a small flame.1I. Cleaning ofapparatus The importance of using clean apparatus cannot be too strongly stressed. after rinsing with distilled water. If this is not the case. Some working hints (a) Always work in a tidy. and then with distilled water. All glassware should be put away clean. systematic manner. or the filter paper alone resting upon a clock glass. 11. 152 . inside a steam oven. More complete drying is obtained by placing the funnel containing the filter paper in a 'drying cone' (a hollow tinnediron cone or cylinder). A few minutes should be devoted at the end of the day's work to 'cleaning up'.

. etc. filter paper. 11.4 (e) Pay particular attention to the disposal of waste... 11. etc. label an solutions and precipitates clearly. must be conducted in the fume chamber. (ii) the evaporation of concentrated acids. (f) All operations involving (i) the passage of hydrogen sulphide into a solution. Solids (corks.) should be placed in the special boxes provided for them in the laboratory....EXPERIMENTAL TECHNIQUES 11. negative. whether positive.4 SEMIMICRO APPARATUS AND SEMIMICRO ANALYTICAL OPERATIONS The essential technique of semimicro analysis does not differ very greatly from that of macro analysis. Neither strong acids nor strong alkalis should be thrown into the sink. e . It is a good plan to cover these with filter paper to prevent the entrance of dust. these two factors are of great importance when time and money are limited.. it may be said at once that as soon as the simple technique has been acquired and mastered. or inconclusive. The various operations occupy less time and the consumption of chemicals and glassware is reduced considerably. N t X 1 ~ X j 4ml (a) I ~ r- '" j 20ml (c) j 3ml (d) Sml (h) Fig. the habit of performing experiments and recording them immediately is one that should be developed from the very outset.11 153 . Particular care must be directed to having both the apparatus and the working bench scrupulously clean. and the sink flushed with much water. (iii) the evaporation of solutions for the removal of ammonium salts. Since volumes of the order of 1 ml are dealt with.. they must be largely diluted first.. (g) All results. The writing up of experiments should not be postponed until after the student has left the laboratory.. and (iv) the evolution of poisonous or disagreeable vapours or gases. On no account may they be thrown into the sink. (h) If the analysis is incomplete at the end of the laboratory period. the scale of the apparatus is reduced. the student will find it just as easy to manipulate these small volumes and quantities as to work with larger volumes and quantities in ordinary test-tubes (I 50 x 20 mm) and related apparatus. -1~ e 1 r- x . s:: e e !::! x ~ e e . must be recorded neatly in a notebook at the time they are made. Apart from inaccuracies which may thus creep in.

the capillary of the latter (b) is long enough to reach to the bottom of a 3 ml centrifuge tube. and then stirring the suspension. These can readily be made by cutting 2 mm diameter glass rod into 12 cm lengths. 4 ml. For rapid concentration of a solution by means of a free flame. II. In washing a precipitate with water or other liquid.lI c) will be found convenient. also. if desired. t :==:) ::::=----------1 Fig.. Stirring rods Solutions do not mix readily in semimicro test-tubes and centrifuge tubes. it is essential to stir the precipitate so that every particle is brought in contact with as large a volume ofliquid as possible: this is best done by holding the tube almost horizontal.13a and b..12 momentarily in a flame. the 3 ml centrifuge tube is the most widely used and will be adopted as standard throughout this book. 11. II. Various sizes are available. 11.. sometimes 100 x 12 mm. The former one finds application. Droppers For handling liquids in semimicro analysis. 3. II. Two varieties are shown in Fig. I-----lOcm----~. known as a centrifuge tube (Fig. by heating about I cm from the end and bending it back at an angle of 45° (see Fig.. the semimicro boiling tube (60 x 25 mm. a dropper (also termed a dropper pipette) is generally employed.4 QUALITATIVE INORGANIC ANALYSIS 1.. 8 ml) are used for reactions which do not require boiling.. Pyrex.12b).1 Id) is generally employed. mixing is effected by means of stirring rods.13 154 .. 11. and is used for removing supernatant liquids from test-tubes and centrila f)-Scm- ::::::: ---scm-h::J '------. to spread the precipitate over a large surface. the contents cannot be boiled as 'bumping' will occur. The sharp edges are fire-polished by heating {a} (h) Fig.11. a test-tube with a tapered bottom. 8cm----. Test-tubes and centrifuge tubes Small Pyrex test-tubes (usually 75 x 10 mm. A handle may be formed. 2. (h) .. When a precipitate is to be separated by centrifuging. Fig. in 30 or 60 ml (l or 2 fluid ounce) reagent bottles and may therefore be called a reagent dropper.. here.

24-25. the softened end of the tube may be quickly pressed down on an asbestos or uralite sheet or upon some other inert surface. concentrated nitric acid. the number of drops per ml of other liquids will be very approximately as follows: dilute aqueous solutions. When cold. Dropper b will be referred to as a capillary dropper. II. if this dropper is used. Introduce some distilled water into the clean dropper by dipping the capillary end into some distilled water in a beaker and compressing and then releasing the rubber teat or bulb. concentrated hydrochloric acid. and this as well as the rubber teat (or bulb) are attacked by concentrated inorganic acids. Fire-polish the capillary ends by rotating in a flame for a moment or two.e.4 fuge tubes and for the quantitative addition of reagents. but the size of the drop (c. 63. and gently press the rubber bulb.as in Fig. Reagent bottles and reagents A semimicro reagent bottle may be easily constructed by inserting a reagent dropper through a cork or rubber stopper that fits a 30 or 60 ml bottle . When the centre is soft. II. rotating it slowly all the time. concentrated sulphuric acid. This dropper is somewhat more robust than that shown in Fig. 20-22. 23-24.14b) may be purchased and are inexpensive. 4. Attach a small label to the upper part of the dropper giving the number of drops per ml. acetic acid. delivers drops of dilute aqueous solutions about 0'05 ml in volume. Count the number of drops until the meniscus reaches the 2 ml mark.EXPERIMENTAL TECHNIQUES 11. If the dropper delivers 20 drops of distilled water. of the liquid. To make a capillary dropper. The standard commercial form of medicine dropper. i. with a tip of 1'5 mm inside diameter and 3 mm outside diameter. A dropping 155 . In order that a rubber bulb (teat) may fit securely on the wide end. allow the glass to thicken slightly by continuing the heating and rotating whilst exerting a gentle inward pressure from the ends. heat it cautiously in a flame until just soft.14a. The dropper should deliver between 30 and 40 drops per ml. 20 per ml) may be slightly too large when working with volumes of the order of I ml. A reagent dropper is made in a similar manner except that it is unnecessary to appreciably thicken the middle of the tube before drawing out. surface tension.l3a. 36-37. etc. However.. take a piece of glass tubing about 20 cm long and of 7 mm bore and heat it near the middle of a Bunsen or blowpipe flame. Whilst both types of dropper may be purchased. and whilst rotating slowly open it up with a file or glass-worker's triangular 'reamer'. Hold the dropper vertically over a clean dry 5 ml measuring cylinder. it is quite a simple operation (and excellent practice) to make them from glass tubing. Repeat the calibration until two results are obtained which do not differ by more than 2 drops. II. 36-37. It must be remembered that the volume of the drop delivered by a dropper pipette depends upon the density. Remove the tube from the flame and slowly draw out the softened portion to form a fairly thick-walled capillary about 20 cm long and 2 mm diameter. Calculate the volume of a single drop. as it has a shorter and thicker capillary: this may be an advantage for elementary students. it should be calibrated as described in the previous paragraph. the volume of the drop delivered must be known. cut the capillary at the mid-point with a file. about 20 drops per ml. Before use the droppers must be calibrated. alternatively. These dropping bottles (Fig. the stoppers of these bottles are usually made of a hard rubber or plastic composition. Le. and concentrated ammonia solution.

Nitric acid.4 QUALITATIVE INORGANIC ANALYSIS (b) Fig. 2M M 2M The other reagents. cone. Nitric acid. dil. The following are used in the author's laboratory. in a T. of 2'5-3M strength. dropping bottles (Fig. II. II. dil. great care should be taken that the drop156 . and the dilute mineral acids in the reagent bottles fitted with reagent droppers. bottle. which are used less frequently. These are questions of personal preference. The bottles a and b cannot be used for concentrated acids and other corrosive liquids because of their action upon the stoppers. Each student should be provided with a solid wooden stand housing a set of reagents in 30 ml or.3 Reagents for semimicro work (Fig. dil. dil.14 (d) bottle of 30 ml capacity with an interchangeable glass cap (Fig.14d).K. n. cone. 2M Potassium hexacyanoferrate(II) Q'Q25M Potassium chromate Q·IM Ammonium carbonate M Reagent Bottles Fitted with Reagent Droppers Sodium hydroxide Ammonium sulphide Potassium hydroxide Barium chloride Silver nitrate lron(III) chloride T.11. are kept in 60 or 125 ml dropping bottles (30 ml for expensive or unstable reagents) on the reagent shelf (side shelf or side rack reagents). and the decision will rest with the teacher. dil. cone. cone. When using these side shelf reagents. Some may prefer to have the Ammonia solution. 12M ISM 16M 2M M 2M Q'25M Q·IM Q'5M Hydrochloric acid.14c) is also marketed. preferably. 15M Ammonia solution. 2M Ammonia solution.K. Two sets of these bottles should be available in each laboratory. II.I4a or b) Acetic acid. further details of these will be found in the Appendix. 60 ml bottles.K. cone. dil. Sulphuric acid. Table 11. The simplest containers for these corrosive liquids are 30 or 60 ml T. Dropper Bottles Hydrochloric acid. Sulphuric acid. Others may like to have the Hydrochloric acid.

Under no circumstances should the capillary end of the dropper be dipped into any foreign solution. it will be found that the precipitate has separated at the bottom of the tube. This is an apparatus for the separation of two substances of different density by the application of centrifugal force which may be several times that of gravity. the droppers must be thoroughly rinsed with distilled water and then dried. The tube and its contents. Fine crystalline particles tend to increase in size when allowed to stand in the liquid in which they are precipitated. If accidental contact should be made. This operation (centrifugation) replaces filtration in macro analysis. (ii) the precipitate is concentrated into a small volume so that small precipitates are observed readily and their relative magnitudes estimated. The rate of settling t« (cm S-1) of spherical particles of density dp and of radius a (cm) in a medium of dynamic viscosity '1 (poise) and of density dm is given by Stokes' law: r = 2a 2g(d p- dm) (i) • 9'1 where g is the acceleration due to gravity (981 cm s" 2). The supernatant liquid can be readily removed by means of a capillary dropper. and the cover is placed in position. and an increase in the acceleration due to gravity g. the clear liquid may be called the centrifugate or 'centrate'. The theory of the centrifuge is given below. (iii) the washing of the precipitate can be carried out rapidly and efficiently.4 pers do not come into contact with the test solutions. and (iv) concentrated acids. thus contaminating the reagents. upon rotation for a short time and after allowing the buckets to come to rest and removing the cover. and a similar tube containing an equal weight of water are placed in diagonally opposite buckets of the centrifuge. an increase in difference between the density of the particles dp and that of the medium dm . IUS 157 . In practice. The advantages of centrifugation are: (i) speed. a decrease in the viscosity of the medium. The centrifuge The separation of a precipitate from a supernatant liquid is carried out with the aid of a centrifuge. It is evident from the equation that the rate of settling is increased by: an increase in the size of the particles a. Fig. the liquid containing the suspended precipitate is placed in a semimicro centrifuge tube. bases. and other corrosive liquids can be manipulated easily.EXPERIMENTAL TECHNIQUES 11. 5.

It is supplied with a dual purpose head. 11. comparatively small. 450 times the force of gravity. 4n 2rn2 g mg Expressing rotations per second n in rotations per minute N. The buckets can either 'swing out' to the horizontal position or.E.4n 2rn2 r. however. say.S. and substituting for n. and also by the addition of certain electrolytes.dm ) . Several types of centrifuge are available for semimicro analysis. An inexpensive constant speed. To accelerate greatly the rate of settling.5 X 10 X (2000)2 = 447. The centrifugal force Fe upon a particle of effective mass m (grams) moving in a circle of diameter r (cm) at n revolutions per second is given by: mv 2 m(2nrn)2 Fe r r = ma = .11.33) is marketed and has a working speed of 1450 rev min" ". we have: Fe 4n2r~ I 118 10.g their ratio Fe = m . v is the velocity (cm s" 2). say. where a is the acceleration (cm S-2). The relative rates of settling in a centrifuge tube and in a stationary test-tube may be derived as follows.33). B. in the latter case. by means of a rubber adapter. Moreover.) or 510 (International).an extremely rare occurrence. an increase in temperature reduces the viscosity and also increases the difference (dp .= = 4n 2mrn2. the force on the particle g (acceleration due to gravity) must be changed. A precipitate which settles in. A small 2-tube hand centrifuge with protecting bowl and cover (Fig.16 and Fig. the instrument acts as an 'angle' centrifuge. The central spindle should be provided with a locking screw or nut: this is an additional safeguard against the possibility of the head carrying the buckets flying off . the buckets can be held at a fixed angle of 450 (M. if properly constructed it will give speeds up to 2-3000 rev min" 1 with 3 ml centrifuge tubes.4 QUALITATIVE INORGANIC ANALYSIS particularly when the solution is maintained at elevated temperatures and shaken occasionally. The great advantage of a centrifuge is thus manifest. These are: A. 158 . electrically-driven centrifuge (see Figs 11. and n = 3'1416. The coagulation of colloidal and gelatinous precipitates is also accelerated by high temperatures and stirring.32 and 11. This explains why centrifuge tubes or test-tubes in which precipitates are formed are usually placed in a hot water bath and shaken from time to time before separation of the mother liquor. The effect of these factors is. This is readily and conveniently achieved with the aid of a centrifuge. The hand-driven centrifuge is inexpensive and is satisfactory for elementary courses. This is an alternative to the hand centrifuge.5 N 2 F g = 9 8 1 x 6 0 2=' X r (it') Thus a centrifuge with a radius of 10 cm and a speed of 2000 revolutions per minute has a comparative centrifugal force of 1'118 x 10. 11.. The gravitational force F g on a particle of mass m is given by: F g = m. 10 minutes by the force of gravity alone will settle in 10 x 60/450 or in 1'3 seconds in such a centrifuge.

4 C.L-+tr. It is of the utmost importance to avoid strains or vibrations as these may result in stirring up the mixture and may damage the apparatus. Do not attempt to retard the speed of the centrifuge with the hand. but is relatively expensive. . the following points should be borne in mind: (a) The two tubes should have approximately the same size and weight.. Removable lid .33) with speed indicator is the ideal instrument for centrifugation.... Maintain the maximum speed for 30-45 seconds.=§1=i--l. Fix the cover in place. ... i . (c) Before centrifuging a precipitate contained in a centrifuge tube.. electrically-driven centrifuge (see Fig..J:.---------Centrifuge head r. A little practice will enable one to judge the exact time required to pack the precipitate tightly at the bottom of the tube.------:J1if-t__ Position of centrifuge tube when running Position of centrifuge tube at rest ... II.. ...h ... 159 . ..EXPERIMENTAL TECHNIQUES 11.. prepare a balancing tube by adding sufficient distilled water from a dropper to an empty tube of the same capacity until the liquid levels in both tubes are approximately the same. and bring it to the maximum speed with a few turns of the handle. A variable speed. (d) Insert the tubes in diametrically opposite positions in the centrifuge.. (e) Start the centrifuge slowly and smoothly.. . (b) The tube should not be filled beyond I cm from the top.. and then allow the centrifuge to come to rest of its own accord by releasing the handle. It is recommended that at least one of these should be available in every laboratory for demonstration purposes....O i l here Fig.. the head (sometimes known as a rotor) will then be balanced and vibration will be reduced to a minimum. Spilling may corrode the buckets and produce an unbalanced head...16 When using a hand-driven centrifuge.. 11.. .

In difficult cases. Allow 30 seconds for the centrifuge to come to rest. the precipitate is more clearly visible (and the relative quantity is therefore more easily estimated) in a centrifuge tube (Fig. it is neither necessary nor desirable to utilize the full speed of the centrifuge. (i) If a variable speed. it can be transferred to another vessel by merely compressing the rubber bulb. switch the current on with the resistance fully in circuit. Surface tension effects prevent surface particles from settling readily. 11.17). II. To remove the supernatant liquid. gradually move the resistance over until the necessary speed is attained. a capillary dropper is generally used. An unusual sound may be due to the breaking of a tube. then raise the lid and remove the tubes. The advantages of the latter include easier removal of the mother liquor with a dropper.18). Agitate the surface with a stirring rod if necessary.A capillary dropper. The solution in the dropper should be perfectly clear. turn off the current at once and report the matter to the teacher. with small quantities of solids. and. If a suspicious sound is heard. electrically-driven centrifuges are similar to those given above with the addition of the following: (h) Never leave the centrifuge while it is in motion. the rubber teat or nipple of the Precipitate _ _--L Fig. (g) Never use centrifuge tubes with broken or cracked lips. see whether any particles are floating on the surface of the liquid or adhering to the side of the tube. make certain that the current is switched off. vibration suggests an unbalanced condition. or you observe that the instrument is vibrating or becomes unduly hot. The centrifuge tube is held at an angle in the left hand. move the slider (rheostat arm) back to the original position.4 QUALITATIVE INORGANIC ANALYSIS (f) Before commencing a centrifugation. The instructions for use of constant speed. held in the right hand.) After 30-45 seconds. is compressed to expel the air and the capillary end is lowered into the tube until it is just below the liquid (Fig. Most semimicro centrifuges will accommodate both semimicro test-tubes (75 x 10 mm) and centrifuge tubes (up to 5 ml capacity). Great care should be taken as the capillary approaches the bottom of the centrifuge tube that its tip does not touch the precipitate..11. electrically-driven centrifuge is employed. 11.17 . As the pressure is very slowly released the liquid rises in the dropper and the latter is lowered further into the liquid until all the liquid is removed. and wash down the side of the centrifuge tube using a capillary dropper and a small volume of water or appropriate solution. a little cotton wool may be inserted 160 . (For most work.

6. any excess of cotton wool should be cut off with scissors. IU8 in the tip of the dropper and allowed to protrude about 2 mm below the glass tip. to peptize the precipitate.EXPERIMENTAL TECHNIQUES 11.l4a or b) may be used. Transferring of precipitates In some cases precipitates can be transferred from semimicro test-tubes with a small spatula (two convenient types in nickel or monel metal are shown in Fig. Wash bottles For most work in semimicro analysis a 30 or 60 ml glass stoppered bottle is a suitable container for distilled water. and is mouth-operated. rubber bulb. c is a Pyrex 50 ml graduated wash bottle. II. The wash liquid is usually water. and the washing is repeated at least once. A small conical flask (25 or 50 ml) may be used for hot water.20). This operation is usually difficult. Le. 8. various types are available (Fig. The wash liquid is a solvent which does not dissolve the precipitate but dilutes the quantity of mother liquor adhering to it. 11.4 Fig. 5-10 drops of water or other reagent are added and the mixture thoroughly stirred (stirring rod or platinum wire). The supernatant liquid is removed by a capillary dropper. 50 ml). otherwise it will be contaminated with the ions present in the centrifugate. the centrifuge tube is then counterbalanced against another similar tube containing water to the same level and centrifuged. For those who prefer wash bottles. Washing the precipitates It is essential to wash all precipitates in order to remove the small amount of solution present in the precipitate. and d is a polythene bottle. Alternatively. 161 . It is best to wash the precipitate at least twice. and to combine the first washing with the centrifugate. the latter is handled with a reagent dropper. 7.19): a is a 100 or 250 ml flat-bottomed flask with a jet of 0'5-1 mm diameter. 125 ml. 11. but may be water containing a small amount of the precipitant (common ion effect) or a dilute solution of an electrolyte (such as an ammonium salt) since water sometimes tends to produce colloidal solutions. a bottle carrying its own dropper (Fig. from which the wash solution can be obtained by squeezing. To wash a precipitate in a centrifuge tube. b is a hand-operated wash bottle (flask.

Indeed. ----~--------l .4 QUALITATIVE INORGANIC ANALYSIS (a) (h) Fig. by heating the side of the test-tube (8 ml) and not the ----------. 4mmt_ .120mm 5mmt (a) (========================1D . II. . the mixture vigorously stirred and the resulting suspension transferred to a reagent dropper.. if required. . However. the precipitate brought into suspension by agitation with a stirring rod. . 9... a wash liquid or the reagent itself is added... for some reason.... and the suspension is thenpoured into the open dish or crucible... the liquid is removed by centrifugation..19 (c) (d) particularly for centrifuge tubes..11.70mm ..... If the precipitate in a test-tube is to be treated with a reagent in an evaporating dish or crucible...20 mm 162 . . Heating of solutions Solutions in senurmcro centrifuge tubes cannot be heated over a free flame owing to the serious danger of 'bumping' (and consequent loss of part or all of the liquid) in such narrow tubes.. ... The test-tube may be washed by holding it in an almost vertical (upside down) position with its mouth over the receptacle and directing a fine stream of solution or water from a capillary dropper on to the sides of the test-tube.35mm. Similar remarks apply to semimicro test-tubes.. in semirmcro analysis it is rarely necessary to transfer actual precipitates from one vessel to another.... and the contents of the latter ejected into the other vessel. If. 11. the reagent is added first.....1-15-.. (h) Fig. The 'bumping' or spattering of hot solutions may often be dangerous and lead to serious burns if the solution contains strong acids or bases... . transfer of the precipitate is essential..

11. three-quarters filled with water and covered with a lead or galvanized iron plate (Fig. It is a good plan to wind a thin rubber band Fig. furthermore. 11. however. the rubber band can be used for attaching small pieces of folded paper containing notes of contents. 11. is Barber's water bath rack (Fig. A more elaborate arrangement which will.22) drilled with two holes to accommodate a test-tube and a centrifuge tube.21.EXPERIMENTAL TECHNIQUES 11. this will facilitate the removal of the hot tube from the water bath without burning the fingers and. 11. meet the requirements of several students. The danger of 'bumping' may be considerably reduced by employing the anti-bumping device shown in Fig.21 On the whole it is better to resort to safer methods of heating.10. 'bumping' does not usually occur. the tube should be about I cm longer than the test-tube to facilitate removal. The dimensions of a 163 .4 bottom alone with a micro burner. as indicated in Fig. The mouth of the test-tube must be pointed away from the students nearby. etc. The simplest procedure is to employ a small water bath. 11. The latter heating operation requires very careful manipulation and should not be attempted by elementary students.23). 11. Fig.22 about 5 mm from the top of the tube. and withdrawing from the flame periodically and shaking gently. This may consist of a 250 ml Pyrex beaker.

11. This may be placed in an air bath consisting of a 30 ml nickel crucible and supported thereon by an asbestos or uralite ring (Fig. or beaker on a water bath. crucible.23 Fig 11. b is to be preferred as the boiling tube cannot fall out by mere pressure on the holder at the point where it is usually held. 6 ml) or crucible (3-8 ml) may be employed. IUI) may be employed. 11. a plastic material which is unaffected by water at lOOOC. Alternatively. constructed of a light metal alloy. 1I. . stainless steel. or of brass which is subsequently tinned.25. If evaporation to dryness is required. a small Pyrex beaker (say. the semimicro boiling tube (c in Fig. 11. Evaporations Where rapid concentration of a liquid is required or where volatile gases must be expelled rapidly.--5 mm 6cm Fig 11. This rack will accommodate four centrifuge tubes and four semimicro test-tubes. are shown in Fig. Two useful holders. * Slow evaporation may be achieved by heating in a test-tube. of 50 or 100 ml capacity) may be used with a silica or nichrome * A small wooden clothes-peg 164 (spring type) may also be used for holding semimicro test-tubes. a small casserole (c.4 QUALITATIVE INORGANIC ANALYSIS 15mm 14--+--12 mm 9cm 9mm 0'8mm 9mm )4. The brass may be tinned by boiling with 20 per cent sodium hydroxide solution containing a few lumps of metallic tin.24 rack of suitable size are given in Fig. 10.26a) and heated with a semimicro burner. The apparatus is constructed of monel metal.24.

the heat capacity of the vessel usually suffices to complete the evaporation without further heating. the operation should be conducted in the fume cupboard. too hot a flame should not be used. 11.4 o (a) 0 (a) 0 (h) sI Fig. (h) Fig.26 Evaporation to dryness may also be accomplished by direct intermittent heating with a micro burner of a crucible (supported on a nichrome or silica triangle) or of a semimicro beaker (supported on a wire gauze). II.EXPERIMENTAL TECHNIQUES 11. If corrosive fumes are evolved.25 triangle to support the crucible or casserole (Fig. In many cases the flame may be removed whilst a little liquid remains. 165 . A little practice is required in order to achieve regular boiling by intermittent heating with a flame and also to avoid 'bumping' and spattering.26b): this device may also be applied for evaporations in semimicro beakers. 11.

The perfectly clean delivery tube is connected to the source of hydrogen sulphide as in Fig. a 25 ml Erlenmeyer flask may be necessary. Precipitation may be carried out in a centrifuge tube. The tube dipping into the liquid in the wash bottle should preferably be a heavy-walled capillary. this will give a better control of the gas flow and will also help to prolong the life of the charge in the generator.27) or conical flask. and VII. and a slow stream of gas is passed through the liquid for about 30 seconds in order to expel the air. overnight). This can result in an increased resistance against the reagent used for dissolution.27 • For a 3 ml centrifuge tube or a 4 ml test-tube.11. It is advisable to arrange the timetable of work with these precipitates in such a way that dissolution can be attempted soon after precipitation. 1I.4 QUALITATIVE INORGANIC ANALYSIS 11. Dissolving of precipitates The reagent is added and the suspension is warmed. Some precipitates may undergo an ageing process when set aside for longer times (e. when dealing with the particulars of reactions. 12. 166 . IV.6a). If only partial solution occurs. the vessel is shaken gently from time to time. 11. such a tendency of a precipitate is always noted. these generators are always kept in a fume cupboard (draught chamber or hood.6. if necessary. 11. and may be employed for groups of students. In Chapters Ill. on the water bath until the precipitate has dissolved. The tap in the gas Fig.g. but a semimicro testtube or 10 ml conical flask is generally preferred. the cork is pushed into position and the passage of hydrogen sulphide is continued until very few bubbles pass through the liquid. Precipitations with hydrogen sulphide Various automatic generators of the Kipp type are marketed. the suspension may be centrifuged. Owing to the highly poisonous and very obnoxious character of hydrogen sulphide. for a large volume of solution. the top part of the rubber teat (bulb) from a dropper makes a satisfactory stopper: a small hole is made in the rubber bulb and the delivery tube is carefully pushed through it. 11. The delivery tube is drawn out to a thick-walled capillary (1-2 mm in diameter) and carries at the upper end a small rubber stopper which fits the semimicro test-tube" (Fig.) A wash bottle containing water should always be attached to the generator in order to remove acid spray (compare Fig.

the vessel placed in the water bath for a few minutes.. a Pyrex test-tube (150 x 20 mm) charged with 'Aitch-tu-ess' or an equivalent mixture (essentially an intimate mixture of a solid paraffin hydrocarbon. and the gas introduced again. sulphur. The method is not strongly recommended because 'pressure' precipitation (cf. 11.4 generator is then turned off.Fig. 11. tube is just above the surface of the solution.--. an absorption bottle (Fig. The testtube type of generator is depicted in Fig. the stopper is loosened. The small hole (vent) is covered Fig. It consists of a 60 ml bottle containing 10 per cent sodium hydroxide solution: the lower end of the longer.29 167 . the delivery tube is disconnected and immediately rinsed with distilled water. introduces an element of danger.28.3) is difficult and. Since the hydrogen sulphide evolution does not cease abruptly with the removal of the flame. and asbestos) is utilized: this yields hydrogen sulphide when heated by a micro burner and the evolution of gas ceases (but not usually abruptly) when the source of heat is removed. the capillary pipette and cotton wool bulb are removed and the absorption bottle is attached. 11. If an individual generator is desired. 6 mm. When saturation of the solution with the gas is completed.EXPERIMENTAL TECHNIQUES 11.29) is generally employed to absorb the unused gas. Section 11. If the liquid must be warmed.28 with the finger during the passage of the gas. if attempted. . 11.

All the above apparatus. Apparatus b is employed when the test reagent is a liquid. 11. sulphite. sulphide. may be warmed by placing in the hot water rack (e. 11. The double bulb ensures that all the evolved gas reacts. carbonate. all the evolved gas may be swept through the reagent by a stream of air introduced by a rubber bulb of about 100 ml capacity.30 (c) short length of wide-bore rubber tubing is fitted over the mouth of a semimicro test-tube with about I cm protruding over the upper edge. A drop or two of the liquid reagent is introduced into the absorption tube.11. The sample under test is placed in B. The simplest form (a) consists of a semimicro test-tube with the accompanying 'filter tube' :* a strip of test paper (or of filter paper moistened with the necessary reagent) about 3-4 mm wide is suspended in the 'filter tube'.g. A (a) (h) Fig. 168 . the filter plug again packed down with a 4 mm glass rod. the apparatus of Fig. and hypochlorite) are usually identified by the volatile decomposition products obtained with the appropriate reagents. An alternative apparatus for liquid reagents is shown in c: it is a type of absorption pipette and is attached to the 4 ml test-tube by a rubber stopper or a tightly-fitting paraffined cork. thiosulphate. The smaller size is satisfactory for most purposes. Suitable apparatuses for this purpose are shown in Fig. and 0'5-1 ml of the reagent introduced. whilst the complete assembly is depicted in b. a-c. The chemical reaction is started in the test-tube and a 'filter tube' containing a tightly-packed plug of cotton wool is inserted through the rubber collar. Fig. ** The bulb of a commercial rectum or ear syringe is satisfactory. they are inexpensive and therefore eminently suitable for elementary and other students. They will meet all normal requirements for testing gases evolved in reactions in qualitative analysis. and it also prevents the test reagent from being sucked back into the reaction mixture. Identification of gases Many anions (e.4 QUALITATIVE INORGANIC ANALYSIS 13.23). the test reagent is introduced into the 'filter tube' A over a tightly-packed * Test-tubes (75 x IQ mm and 100x 12 mm) together with the matching 'filter tubes' (55 x 7 mm and 80 x 9 mm) are standard products.g. In those cases where spray is likely to affect the test paper.30. ** The approximate dimensions of the essential part of the apparatus are given in a. 11. a loose plug of cotton wool should be placed at the narrow end of the 'filter tube'.31 may be used. When the amounts of evolved gas are likely to be small. 11.

-""""----8 (a) Fig. 14.EXPERIMENTAL TECHNIQUES 11. 11. Cleaning of apparatus It is essential to keep all apparatus scrupulously clean if trustworthy results are to be obtained. thus sweeping out the gases through the test reagent in A.31 (h) plug of cotton wool (or other medium). The apparatus is then rinsed several times with tap water. and repeatedly with distilled water. is added through the 'filter tube' C. The apparatus may be warmed by placing it in a hot water bath. All apparatus must be thoroughly cleaned with chromosulphuric acid (concentrated sulphuric acid containing about 100 g of potassium dichromate per litre) or with a brush and cleaning powder. 11. Special brushes (Fig.4 r lOO mm 1 2mm A c 9mm 45 mm t -.32) are available for semi- Fig. The rubber bulb is inserted into C.32 169 . and by depressing it gently air is forced through the apparatus. 11. and the acid or other liquid reagent.

To calculate the volume of the precipitating agent required.3 mol chloride ion.g. and incidentally providing a permanent record of the test. 120) is a soft variety of pure.11. so that exact calculations cannot be made. the total amount of the cations is 1'93 x 10. The tubes may be allowed to drain in a special stand or else they may be inverted in a small beaker on the bottom of which there are several folds of filter paper or a filter paper pad to absorb the water. so that the volume of acid required will be (1'93 x 10. Now I ml of 2M hydrochloric acid contains 2 x 10.4 QUALITATIVE INORGANIC ANALYSIS micro test-tubes and centrifuge tubes.3)/200'6 = I x 10. the teats are cleaned by repeatedly filling them with distilled water and emptying them. and also for testing the pH of a solution colorimetrically. Spot plates with a number of circular cavities are marketed. Nos. either black or white. At the end of the laboratory period.g. Whatman. The precipitate does not spread very far into the paper because of the filtering action of the pores of the paper. The capillary dropper delivers a drop of about 0'03 ml (30-40 drops per ml). water-repelling barrier which constricts the spot reaction to a uniform area of fixed dimensions. they are allowed to dry on a linen glass cloth.6 for a full discussion). for it will assist the student to appreciate fully the significance of the quantities of reagent employed in semimicro analysis.S. Let us assume that a sample contains I mg of silver ions and 2 mg of mercury(I) ions.3)/107'9 = 9'3 x 10. 15. and that the precipitating agent is 2M hydrochloric acid. However.6 mol silver ion and (2 x 10. U. The former are employed for white or light-coloured precipitates. if the weight of 170 . and the latter for dark-coloured precipitates. Drop-reaction or spot-test paper (e.A. 211Y and 597Y): these are prepared with a chemically inert. Droppers are best cleaned by first removing the rubber bulbs or teats and allowing distilled water to run through the tubes. When clean. hence I drop of 2M hydrochloric acid contains sufficient chloride ions to precipitate the silver and mercury(I) ions and also to provide a large excess to reduce the solubility of the sparingly soluble chlorides (common ion effect). highly porous paper which is used for reactions that result in highly coloured precipitates.3) = 0'00965 ml. Spot plates. the commercial 'pipe cleaners' are also satisfactory. In the present sample there will be (I x 10. the weights of the ions in a solution of the sample are usually not known. Calculation ofthe volume ofprecipitating reagents This type of calculation is instructive. Le. Drop-reaction paper These are employed chiefly for confirmatory tests (see Section 11. Semi-quantitative results may be obtained by the use of the Yagoda 'confinedspot-test' papers (Schleicher and Schuell. In practice.5)/(2 x 10. Spot plates are useful for mixing small quantities of reagents. the white paper serving as an excellent background for dark or highly coloured precipitates.5 mol mercury(I) ion.5 mol. 16. consequently the spot test technique is employed in highly sensitive identification tests. the clean apparatus is placed in a box with cover. Transparent spot plates (e.. the number of moles of the ion or ions to be precipitated and the number of moles per ml of the precipitating agent must be ascertained. Jena) and combination black and white spot plates (with line of demarcation between the black and white running exactly through the centres of the depressions) are also available commercially. No. so that it remains clean until required. Larger apparatus may be allowed to drain on a clean linen towel or glass cloth.

K. beaker. we require 3'4 x 10. dry watch glass. Never return the reagent to the bottle. personal injury may result from the use of the wrong reagent. Never place them on the 171 . (I) Do not introduce your spatula into a reagent bottle to remove a little solid. the possible introduction of impurities is thus avoided.4 mol. The 35mg of lead constitutes 35x 10.3 /207'2 = 1'7x 10. chlorine. etc.) or of poisonous or disagreeable gases (hydrogen sulphide. and use this. for which 3'4 x 10. arrange the more common and frequently used apparatus in an orderly manner on your bench. it is better to waste a little of the reagent than to take the risk of contaminating the whole supply. This volume equals approximately 6 drops. of which about 35 mg constitutes a Group I cation. (g) All operations resulting in the production of fumes (acid vapours.4 f or 0'17 ml of the acid. Pour a little of the reagent (e. we cannot err on the wrong side.addition of reagents.4 sample employed is known. etc. (c) Read the laboratory directions carefully and be certain that you understand the purpose of each operation . (h) Record your observations briefly in your note-book in ink immediately after each operation has been completed. and the addition of 8-10 drops will suffice for complete precipitation. (d) When transferring a liquid reagent with a reagent dropper always hold the dropper just above the mouth of the vessel and allow the reagent to 'drop' into the vessel. Let us consider an actual sample.4 /2 = 1'7 x 10. Some practical hints (Cf. dropper bottles.EXPERIMENTAL TECHNIQUES 11.) and introduce your dropper into this. 14) (a) Upon commencing work. possibly. taking into account the common ion effect as well. (i) Keep your droppers scrupulously clean. Do not allow the dropper tip to touch anything outside the reagent bottle. (e) Never dip your own dropper into a reagent.) must be performed in the fume chamber. (b) Weigh the sample for analysis (if a solid) to the nearest milligram: 50 mg is a suitable quantity. If a 2M solution of hydrochloric acid is available. a corrosive liquid) into a small clean vessel (test-tube. Do not return the solid reagent to the stock bottle. This is one of the reasons for taking a known weight (weighed to the nearest milligram) of the sample for analysis. Section 11. All apparatus should have been cleaned during the previous laboratory period. Thus. Pour or shake a little of the solid on to a clean. Each item of apparatus should have a definite place so that it can be found readily when required. Similar remarks apply to the use ofT. etc. Serious errors leading to a considerable loss of time and. if we base our calculation on lead. etc. the maximum amount of precipitating agent required can be easily calculated. Try to estimate your requirements and pour out only the amount necessary. with the relative atomic mass of 207'2 requires the largest amount of hydrochloric acid for complete precipitation.g. crucible.3. Simple stoichiometric considerations reveal that among such ions lead. Examine the label on the bottle before adding the reagent. 17. We may assume that 50 mg of the solid sample (or a solution containing the same amount of dissolved material) is taken for analysis. sulphur dioxide.4 mol hydrochloric acid is needed. volatile ammonium salts. Return each reagent bottle to its proper place immediately after use.

) I wash bottle. 20 ml I wooden stand (to house test-tubes. Griffin form. or if you suspect any apparatus (e. and one 50ml rubber bulb (for wash bottle.) * Semimicro test-tubes (100 x 12'5 mm. 11. (The liquid reagents recommended for each student are given in Section 11. The smaller 4 ml test-tubes will generally suffice: their great advantage is that they can be used directly in a semimicro centrifuge in the buckets provided for the 3 ml centrifuge tubes. in a definite place. This task can often be done while waiting for a solution to evaporate or for a precipitate to dissolve while being heated on a water bath.33 18. conical flasks. U) During the course of the work place dirty centrifuge tubes. and wash them at convenient intervals. 11. consult the teacher.11. 25 ml 6 test-tubes." 4 ml.19d) I beaker. 8 ml) and the appropriate 'filter tubes' (80 x 9 mm) are marketed.24) or I lead cover (Fig. 11. 11. preferably in a beaker. At the end of each laboratory period. 60 x 25 mm.30) I gas absorption pipette (with 75 x 10 mm test-tube and rubber stopper. lOOml. 5 ml I beaker.19) 2 conical flasks.. Semimicro apparatus The apparatus suggested for each student is listed below. 11. 11. 'filter tubes'. 3 ml (Fig. 250 ml I hot water rack constructed of tinned copper (Figs. Rinse the droppers several times with distilled water after use. etc. 11. (I) When in difficulty. remove the rubber teat or cap and rinse it thoroughly. etc. with rim 2 test-tubes. 75 x 10 mm. polythene (Fig.23 and 11.g.22) for water bath I beaker. 1I. 75 x 10 mm. 10 ml I conical flask.4 QUALITATIVE INORGANIC ANALYSIS bench. the centrifuge) is not functioning efficiently. without rim 2 'filter tubes'.4(4). 172 . gas absorption pipette. Fig.1 Id) 2 semimicro boiling tubes.30) 4 centrifuge tubes. 10 ml I conical flask. (k) Adequately label all solutions and precipitates which must be carried over to the next laboratory period." 4 ml. test-tubes. and these may find application in analysis. Fig. 55 x 7 mm" (Fig. Fig.

silica 1 triangle. n. It must be pointed out that whilst the weight of the sample for analysis has been reduced. n.S 2 medicine droppers.EXPERIMENTAL TECHNIQUES II. 5 mm (for 'filter tubes') 30 cm glass rod. test-tube. 6 ml (28 x 20 mm) I crucible. 25 ml filled with cotton wool I wide-mouthed bottle. Fig. two 0'5 x 1'5 cm. in micro analysis the corresponding quantities are about 5 mg and 0'1 ml. 4 mm outside diameter (for H 2S apparatus) 10 cm rubber tubing.13a) 2 capillary droppers (Fig. Bunsen or Tirrill I semimicro burner n. complete with rubber teats (bulbs) 2 reagent droppers (Fig. n. 8 ml (32 x 19 mm) 3 rubber stoppers (one I x 2 cm. and other species. is maintained. A special 173 . 3 x 3 cm 2 microscope slides I platinum wire (5 cm of 0'3 mm diameter) I forceps. n.25) I semimicro test-tube brush (Fig. 3 mm (for H 2S apparatus) 5 cm rubber tubing. Thus whereas in macro analysis the weights and volumes for analysis are 0'5-1 g and about 10 ml. and gas absorption pipette) 30 cm glass tubing. 5 ml I watch glass. n. n. Micro analysis is sometimes termed milligram analysis to indicate the order of weight of the sample employed.lO) I crucible. to fit 25 ml conical flask. porcelain.12) I measuring cylinder. labelled DISTILLED WATER I packet blue litmus paper I packet red litmus paper I triangular file (small) I tripod and wire gauze (for water bath) I retort stand and one iron ring 7·5 cm I wire gauze (for ring) I triangle.31) I pipe cleaner I spot plate (6 cavities) I wide-mouthed bottle. porcelain. the ratio of weight to volume has been retained and in consequence the concentration of the individual ions. 3 mm (for stirring rods. and in semimicro analysis 50 mg and I ml respectively. 3 ml (23 x 15 mm) I crucible. porcelain. n.13b) I stand for droppers 2 anti-bump tubes (Fig.20a or b) I semimicro test-tube holder (Fig. 3'5 cm diameter 2 cobalt glasses. 10 cm I semimicro spatula (Fig.5 MICRO APPARATUS AND MICROANALYTICAL OPERATIONS In micro analysis the scale of operations is reduced by a factor of 0'0 I as compared with macro analysis. nichrome I burner. 25 ml filled with strips (2 x 2 cm) of drop reaction paper I dropping bottle.

In general.). by what is commonly called spot analysis.). Chamot and C.e. less susceptible to slight variations of experimental conditions. also A. can be used. Micro centrifuge tubes (Fig. Volume 1 (1938) and Volume 11 (1940) (J. are pedagogically unsound.). The dimensions for other capacities are: Type a:0'5 ml.34) of 0'5-2 ml capacityt replace test-tubes. After centrifuging. M. No attempt will be made to deal with operations centred round the microscope (magnification up to 250) as the specialized technique is outside the scope of this volume. Furthermore. 2 ml. Some of the modifications. Wiley. Wiley. Benedetti-Pichler : Introduction to the Microtechnique of Inorganic Analysis (1942) (J. in the long run. Spot analysis has been developed as a result of the researches of numerous chemists: the names ofTananaeff. There is no sharp line of demarcation between semimicro and micro analysis and much of the technique described for the former can. help in the development of micro qualitative analysis. particularly. A. Chapman and Hall.S QUALITATIVE INORGANIC ANALYSIS technique must be used for handling such small quantities of materials. either hand-operated or electrically-driven. spot reactions are preferable to tests which depend upon the formation and recognition of crystals under the microscope. Wenger. Solutions are separated from precipitates by centrifuging. Semimicro centrifuges (Section 11. Feigl and their collaborators must be mentioned in this connection. 8'5 mm (ext. Chapman and Hall). evenly spaced. 68 x 11'25 mm (ext. the precipitate collects in the bottom of the tube. * The small amounts of material obtained after the usual systematic separations can be detected. beakers and flasks for most operations. W. of 1'5 cm diameter and 1'3 cm deep. 60 x 6·3 mm (ext. Adapters are provided inside the buckets (baskets) in order to accommodate micro centrifuge tubes with narrow pen ends. van Niewenburg. followed by the utilization of spot tests after the group or other separation has been effected. in many cases. will be described.4. Gutzeit and. such schemes. Type b: 0'5 rnl. Mason: Handbook ofChemical Microscopy. however.) t The dimensions given ensure that the centrifuge tubes fit into the buckets of a semimicro centrifuge.).II. involving comparatively simple apparatus.5). Incomplete schemes of qualitative inorganic analysis have been proposed which are based largely upon spot tests: these cannot. 76 x 11'25 mm (ext. be regarded as entirely satisfactory for very few spot tests are specific for particular ions and also the adoption of such schemes will not. see E. Centrifuge tubes are conveniently supported in a rack consisting of a wooden block provided with 6 to 12 holes. Krumholz. be utilized for the latter. Two types of centrifuge tubes are shown: b is particularly useful when very small amounts of precipitate are being handled. 3 rnl. with suitable modifications to allow for the reduction in scale by about one-tenth. Hence the following pages will contain an account of the methods which can be used for performing macro operations on a micro scale and also a discussion of the technique of spot analysis. when considered from the point of view of training of students in the theory and practice of analysis. and can be interpreted more readily. 174 .). i. Precipitations are usually carried out in micro centrifuge tubes. 63 mm. The supernatant liquid * For a detailed account. It seems to the writer that the greatest potential progress lies in the use of the common macro procedures (or simple modifications of them) to effect the preliminary separations for which the specialized micro technique is adopted. analysis which utilizes spots of solutions (about 0'05 ml or smaller) or a fraction of milligram of solids. in that they are easier and quicker to carry out. 2'5 mm (int. 11.

II. The centrifuge cone is held in the right hand and the capillary pipette is pushed slowly towards the precipitate so that the point of the capillary remains just below the surface of the liquid.S 13-14mm 13-14mm 63 x8·5mm 1 68 x llmm j Iml (a) j Iml Fig. 3·5mm may be removed either by a capillary dropper (Fig. another centrifuge tube will be evident upon reference to Fig. always keeping the tip just below the =========t---~ =========[ Fig. The latter consists of a thin glass tube (internal diameter about 2 mm: this can be prepared from wider tubing) 20 to 25 cm in length with one end drawn out in a micro flame to a tip with a fine opening.3S l2iJ9 surface of the liquid until the entire solution is in the pipette and the tip is about I mm above the precipitate.37. upon removing the finger. 11.35. the latter is gradually lowered. say. 11. The siphon is made of thermometer capillary and is attached to the capillary pipette by means of a short length of rubber tubing of 1 mm bore. For the washing of precipitates the wash solution is added directly to the precipitate in the centrifuge tube and stirred thoroughly either by a platinum wire or by means of a micro stirrer. Only gentle suction is applied and the opening A is closed with the finger. diarn. the action of the capillary siphon ceases immediately. 11. As the liquid rises in the pipette. 11. The pipette is removed and the liquid blown or drained out into a clean dry centrifuge tube.EXPERIMENTAL TECHNIQUES II. The correct method of transferring the liquid to the capillary pipette will be evident from Fig.36. the side arm of the small test-tube is situated near the bottom so as to reduce spattering of the liquid in the centrifuge tube inside the test-tube when the vacuum is released.13) or by means of a transfer capillary pipette. the latter can 175 .34 (h) Int. The small hole A in the side of the tube permits perfect control of the vacuum. such as is shown in Fig. 11. Another useful method for transferring the centrifugate to.

11.5 QUALITATIVE INORGANIC ANALYSIS

A

\

Fig. 11.36

readily be made from thin glass rod. The mixture is then centrifuged, and the clear solution removed by a transfer capillary pipette as already described. It may be necessary to repeat this operation two or three times to ensure complete washing. The transfer of precipitates is comparatively rare in micro qualitative analysis. Most of the operations are usually so designed that it is only necessary to transfer solutions. However, if transfer of a precipitate should be essential and the precipitate is crystalline, the latter may be sucked up by a dry dropper pipette and transferred to the appropriate vessel. If the precipitate is gelatinous, it may be transferred with the aid of a narrow glass, nickel, monel metal, or platinum

10 cm

O'3cm bore

D-l cm
4cm
bore

1
176

O'2cm dia,

Fig. 11.37

EXPERIMENTAL TECHNIQUES II.S

spatula. The centrifuge tube must be of type a (Fig. 11.34) if most of the precipitate is to be removed. The heating of solutions in centrifuge tubes is best carried out by supporting them in a suitable stand (compare Figs. 11.22-23) and heating on a water bath. When higher temperatures are required, as for evaporation, the liquid is transferred to a micro beaker or micro crucible; this is supported by means of a nichrome wire triangle as indicated in Fig. 11.38. Micro beakers may be heated

c::::;::=~==f=::;::=}-Wiretriangle
~-+---

Micro beaker or cruch or crucible

f----Nickel crucible

Fig.II.38

by means of the device shown in Fig. 11.39, which is laid on a water bath.

Section A-B

.!!
Steam jacket-for micro beaker

QBl

Water bath rings
Fig.II.39

Another valuable method for concentrating solutions or evaporating to dryness directly in a centrifuge tube consists of conducting the operation on a water bath in a stream of filtered air supplied through a capillary tube fixed just above the surface of the liquid. The experimental details will be evident by reference to Fig. 11.40. Micro centrifuge tubes are cleaned with a feather, 'pipe cleaner' or small testtube brush (cf. Fig. 11.31). They are then filled with distilled water and emptied by suction as in Fig. 11.41. After suction has commenced and the liquid removed, the tube is filled several times with distilled water without removing the suction device. Dropper pipettes are cleaned by repeatedly filling and emptying them with distilled water, finally separating rubber bulb and glass tube, and rinsing both with distilled water from a wash bottle. A transfer capillary pipette is cleaned by blowing a stream of water through it. The passage of hydrogen sulphide into a solution in a micro centrifuge tube
177

II.S QUALITATIVE INORGANIC ANALYSIS

----Rubber stopper

: : 1 - - - - - Purified

{:(,

cotton wool

Fig. 11.40

is carried out by leading the gas through a fine capillary tube in order not to blow the solution out of the tube. The delivery tube may be prepared by drawing out part of a length of glass tubing of 6 mm diameter to a capillary of 1-2 mm bore and 10-20 cm long. A plug of pure cotton wool is inserted into the wide part of the tubing, and then the capillary tube is drawn out by means of a micro burner to a finer tube of 0'3-0'5 mm bore and about 10 cm long. The complete arrangement is illustrated in Fig. 11.42. Such a fine capillary delivers a stream of very small bubbles of gas; large bubbles would throw the solution out of the micro centrifuge tube. The flow of the hydrogen sulphide must be commenced before introducing the point of the capillary into the centrifuge cone. If this is not done, the solution will rise in the capillary and when hydrogen sulphide is admitted, a precipitate will form in the capillary tube and clog it.

Fig. 11-41

178

EXPERIMENTAL TECHNIQUES II.S

I r - - - - Rubber

stopper

L
~~i~

c lamp Purified cotton wool

Fig. 11.42

The point of saturation of the solution is indicated by an increase in the size of the bubbles; this is usually after about two minutes. The identification of gases obtained in the reactions for anions may be conducted in an Erlenmeyer (or conical) flask of 5 or 10 ml capacity; it is provided with a rubber stopper which carries at its lower end a 'wedge point' pin, made preferably of nickel or monel metal (Fig. 11.43). A small strip of impregnated test paper is placed on the loop of the pin. The stoppered flask, containing the reaction mixture and test paper, is placed on a water bath for five minutes. An

Fig. 11.43

improved apparatus consists of a small flask provided with a ground glass stopper on to which a glass hook is fused (compare Fig. 11.55); the test paper is suspended from the glass hook. If the evolved gas is to be passed through a
179

11.6 QUALITATIVE INORGANIC ANALYSIS

liquid reagent, the apparatus of Fig. II.29b or c. proportionately reduced, may be employed. Confirmatory tests for ions may be carried out either on drop reaction paper or upon a spot plate. The technique of spot tests is fully described in Section 11.6. The following micro apparatus* will be found useful: Micro porcelain, silica, and platinum crucibles of 0'5 to 2 ml capacity Micro beakers (5 ml) and micro conical flasks (5 ml) Micro centrifuge tubes (0'5, 1'0 and 2·0 ml) Micro test-tubes (40-50 x 8 mm) Micro volumetric flasks (I, 2, and 5 ml) Micro nickel, monel, or platinum spatula, 7-10 cm in length and flattened at one end Micro burner Micro agate pestle and mortar Magnifying lens, 5 x or lax A pair of small forceps A small platinum spoon, capacity 0'5-1 ml, with handle fused into a glass tube. (This may be used for fusions.) 11.6 SPOT TEST ANALYSIS The term 'spot reaction' is applied to micro and semimicro tests for compounds or for ions. In these chemical tests manipulation with drops (macro, semimicro, and micro) play an important part. Spot reactions may be carried out by any of the following processes: (i) By bringing together one drop of the test solution and of the reagent on porous or non-porous surfaces (paper, glass, or porcelain). (ii) By placing a drop of the test solution on an appropriate medium (e.g. filter paper) impregnated with the necessary reagents. (iii) By subjecting a strip of reagent paper or a drop of the reagent to the action of the gases liberated from a drop of the test solution or from a minute quantity of the solid substance. (iv) Byplacing a drop of the reagent on a small quantity of the solid sample, including residues obtained by evaporation or ignition. (v) By adding a drop of the reagent to a small volume (say, 0'5-2 ml) of the test solution and then extracting the reaction products with organic solvents. The actual 'spotting' is the fundamental operation in spot test analysis, but it is not always the only manipulation involved. Preliminary preparation is usually necessary to produce the correct reaction conditions. The preparation may involve some of the operations of macro analysis on a diminished scale (compare Section 11.5), but it may also utilize certain operations and apparatus peculiar to spot test analysis. An account of the latter forms the subject matter of the present section. Before dealing with the apparatus required for spot test reactions, it is necessary to define clearly the various terms which are employed to express the sensitivity of a test. The limit ofidentification is the smallest amount recognizable, and is usually expressed in micrograms (~g) or gamma (y), one micro gram or one gamma being one-thousandth part of a milligram or one-millionth part of a gram: I ~g = I y = 0'001 mg = 10- 6 g

* All glass apparatus must
180

be of resistance (e.g. Pyrex) glass.

EXPERIMENTAL TECHNIQUES 11.6

Throughout this text the term sensitivity will be employed synonymously with limit of identification. The concentration limit is the greatest dilution in which the test gives positive results; it is expressed as a ratio of substance to solvent or solution. For these two terms to be comparable, a standard size drop must be used in performing the test. Throughout this book, unless otherwise stated, sensitivity will be expressed in terms of a standard drop of 0'05 ml. The removal and addition of drops of test and reagent solutions is most simply carried out by using glass tubing, about 20 cm long and 3 mm external diameter; drops from these tubes have an approximate volume of 0'05 ml. The capillary dropper (Fig. 1I.13b)may also be employed. A useful glass pipette, about 20 cm long, may be made from 4 mm tubing and drawn out at one end in the flame (Fig. 11.44); the drawn-out ends of these pipettes may be made of varying bores. A liberal supply of glass tubes and pipettes should always be kept at hand. They may be stored in a beaker about 10 cm high with the constricted end downwards and resting upon a pad of pure cotton wool; the beaker and pipettes can be protected against dust by covering with a sheet of polythene. Pipettes which are used frequently may be supported horizontally on a stand constructed of thin glass rod. After use, they should be immersed in beakers filled with distilled water: interchanges are thus prevented and subsequent thorough cleaning is facilitated.

Fig. 11.44

Very small and even-sized drops can be obtained by means of platinum wire loops; the size of the loop can be varied and by calibrating the various loops (by weighing the drops delivered), the amount of liquid delivered from each loop is known fairly accurately. A number of loops are made by bending platinum wire of suitable thickness; the wires should be attached in the usual manner to lengths of glass rod or tubing to act as handles. They are kept in
181

11.6 QUALITATIVE INORGANIC ANALYSIS

Pyrex test-tubes fitted with corks or rubber stoppers and labelled with particulars of the size of drop delivered. It must be pointed out that new smooth platinum wire allows liquids to drop off too readily, and hence it is essential to roughen it by dipping into chloroplatinic acid solution, followed by heating to glowing in a flame; this should be repeated several times. Micro burettes sometimes find application for the delivery of drops. Reagent solutions can be added from dropping bottles of 25-30 ml capacity (see Section 11.4.4). A stock bottle for water and for solutions which do not deteriorate on keeping, is shown in Fig. 11.45; it permits facile addition in drops.

Fig. 11.45

This stock bottle is constructed from a Pyrex flask into which a tube with a capillary end is fused; a small rubber bulb is placed over the drawn-out neck, which has a small hole to admit air. Digestion of solid samples with acid or solvent may be performed in small crucibles heated on a metal hot plate, or in an air bath (Fig. 11.38), or in the glass apparatus illustrated in Fig. 11.46. The last-named is heated over a micro burner, and then rotated so that supernatant liquid or solution may be poured off drop-wise without danger or loss. Spot tests may be performed in a number of ways: on a spot plate, in a micro

Fig. 11.46

182

EXPERIMENTAL TECHNIQUES 11.6

crucible, test tube, or centrifuge tube, or on filter paper. Gas reactions are carried out in special apparatus. The commercial spot plates are made from glazed porcelain and usually contain 6 to 12 depressions of equal size that hold 0'5 to I ml of liquid. It is advisable, however, to have several spot plates with depressions of different sizes. The white porcelain background enables very small colour changes to be seen in reactions that give coloured products; the colour changes are more readily perceived by comparison with blank tests in adjacent cavities of the spot plate. Where light-coloured or colourless precipitates or turbidities are formed, it is better to employ black spot plates. Transparent spot plates of resistance glass (e.g. Jena) are also available; these may be placed upon glossy paper of suitable colour. The drops of test solution and reagent brought together on a spot plate must always be mixed thoroughly; a glass stirrer (Fig. 11.37) or a platinum wire may be employed. Traces of turbidity and of colour are also readily distinguished in micro test-tubes (50 x 8 mm) or in micro centrifuge tubes. As a general rule, these vessels are employed in testing dilute solutions so as to obtain a sufficient depth of colour. The liquid in a micro centrifuge tube or in a test-tube may be warmed in a special stand immersed in a water bath (compare Figs. 11.22-23) or in the apparatus depicted in Fig. 11.47. The latter is constructed of thin aluminium or

Fig. 11.47

nickel wire; the tubes will slip through the openings and rest on their collars. The wire holder is arranged to fit over a small beaker, which can be filled with water at the appropriate temperature. For heating to higher temperatures (> 100°C) micro porcelain crucibles may be employed: they are immersed in an air bath (Fig. 11.38) and the latter heated by a micro burner, or they can be heated directly on an asbestos mat. Small silica watch glasses also find application for evaporations. It must be emphasized that all glass and porcelain apparatus, including spot plates and crucibles, must be kept scrupulously clean. It is a good plan to wash all apparatus (particularly spot plates) immediately after use. Glassware and porcelain crucibles are best cleaned by immersion in a chromic acid-sulphuric acid mixture or in a mixture of concentrated sulphuric acid and hydrogen peroxide, followed by washing with a liberal quantity of distilled water, and drying. The use of chromic acid mixture is not recommended for spot plates. The great merit of glass and porcelain apparatus is that it can be employed with any strength of acid and base: it is also preferred when weakly coloured compounds (especially yellow) are produced or when the test depends upon
183

11.6 QUALITATIVE INORGANIC ANALYSIS

slight colour differences. Filter paper, however, cannot be used with strongly acidic solutions for the latter cause it to tear, whilst strongly basic solutions produce a swelling of the paper. Nevertheless, for many purposes and especially for those dependent upon the application of capillary phenomena, spot reactions carried out on filter paper possess advantages over those in glass or porcelain: the tests generally have greater sensitivity and a permanent (or semi-permanent) record of the experiment is obtained. Spot reactions upon filter paper are usually performed with Whatman drop reaction paper No. 120, but in some cases Whatman No. 3 is utilized: the Schleicher and Schuell (U.S.A.) equivalents are Nos. 601 and 598. These papers possess the desirable property of rapidly absorbing the drops without too much spreading, as is the case with thinner papers. Although impurities have been reduced to minimum values, these papers may contain traces of iron and phosphate: spot reactions for these are better made with quantitative filter paper (Whatman No. 42 or, preferably, the hardened variety No. 542). The paper should be cut into strips 6 x 2 cm or 2 x 2 cm, and stored in petri dishes or in vessels with tightly-fitting stoppers. Spot test papers are marketed in which the spot reaction is confined to a uniform area of fixed dimensions, produced by surrounding the area by a chemically inert, water-repelling barrier. These papers are developed by H. Yagoda and may be employed for semi-quantitative work. The Schleicher and Schuell (U.S.A.) No. 2IlY 'confined spot test' paper is intended for use with single drops of solution, and No. 597Y for somewhat larger volumes. They are often referred to as Yagoda test papers. Spot reactions on paper do not always involve interaction between a drop of test solution and one of the reagent. Sometimes the paper is impregnated with the reagent and the dry impregnated reagent paper is spotted with a drop of the solution. Special care must be taken in the choice of the impregnating reagent. Organic reagents, that are only slightly soluble in water but dissolve readily in alcohol or other organic solvents, find extensive application. Water-soluble salts of the alkali metals are frequently not very stable in paper. This difficulty can often be surmounted by the use of sparingly soluble salts of other metals. In this way the concentration of the reactive ion can be regulated automatically by the proper selection of the impregnating salt, and the specificity of the test can be greatly improved by thus restricting the number of possible reactions. Thus potassium xanthate (see under Molybdenum, Section VII.6) has little value as an impregnating agent since it decomposes rapidly and is useless after a few days. When, however, cadmium xanthate is used, a paper is obtained which gives sensitive reactions only with copper and molybdenum and will keep for months. Similarly the colourless zinc hexacyanoferrate(I1) offers parallel advantages as a source of hexacyanoferrate(I1) ions: it provides a highly sensitive test for iron(I1) ions. A further example is paper impregnated with zinc, cadmium, or antimony sulphides: such papers are stable, each with its maximum sulphide-ion concentration (controlled by its solubility product) and hence only those metallic sulphides are precipitated whose solubility products are sufficiently low. Antimony(I1I) sulphide paper precipitates only silver, copper, and mercury in the presence of lead, cadmium, tin, iron, nickel, cobalt and zinc. It might be expected that the use of 'insoluble' reagents would decrease the reaction rate. This retardation is not significant when paper is the medium because of the fine state of division and the great surface available. Reduction
184

EXPERIMENTAL TECHNIQUES II.6

in sensitivity becomes appreciable only when the solubility products of the reagent and the reaction product approach the same order of magnitude. This is naturally avoided in the selection of reagents. Filter paper may be impregnated with reagents by the following methods: (i) For reagents that are soluble in water or in organic solvents, strips of filter paper are bathed in the solutions contained in beakers or in dishes. Care must be taken that the strips do not stick to the sides of the vessel or to one another, as this will prevent a uniform impregnation. The immersion should last about 20 minutes and the solution should be stirred frequently or the vessel gently rotated to produce a swirling of the solution. The strips are removed from the bath, allowed to drain, pinned to a string (stretched horizontally), and allowed to dry in the air. Uniform drying is of great importance. Alternatively, the reagent may be sprayed on to the filter paper. The all-glass spray shown in Fig. 11.48 (not drawn to scale) gives excellent results. A rubber

,
~~

/'"

,I' ,
Rubber bulb,__C::::: attached here 40mm Hole about.-.L 3 mm diam. B

<,'"

-Outer tube 3'5 mm diarn. Outer tube 10 mm diarn. Inner tube 2mm diarn.

A

- - Seal Note: tubing of I mm wall

o
Fig. 11.48

bulb is attached at C; the cork is fitted into a boiling tube or small flask charged with the impregnating solution. The paper is sprayed first on one side and then on the other. (ii) For reagents that are precipitated on the paper, the strips are soaked rapidly and uniformly with the solution of one of the reactants, dried and then immersed similarly in a solution of the precipitant. The excess reagents are then removed by washing, and the strips dried. The best conditions (concentration of solutions, order in which applied, etc.) must be determined by experiment. In preparing highly impregnated paper, the precipitation should never be made with concentrated solutions as this may lead to an inhomogeneous precipitation and the reagent will tend to fall off the paper after it is washed and dried. It is essential to carry out the soaking and precipitation separately with dilute solutions and to dry the paper between the individual precipitations. Sometimes it is preferable to use a reagent in the gaseous form, e.g. hydrogen sulphide for sulphides and ammonia for hydroxides; there is then no danger of washing away the precipitate.
185

11.6 QUALITATIVE INORGANIC ANALYSIS

The reactions are carried out by adding a drop of the test solution from a capillary pipette, etc., to the centre of the horizontal reagent paper resting across a porcelain crucible or similar vessel; an unhindered capillary spreading follows and a circular spot results. With an impregnated reagent paper, the resulting change in colour may occur almost at once, or it may develop after the application of a further reagent. It is usually best not to place a drop of the test solution on the paper but to allow it to run slowly from a capillary tip (0·2-1 mm diameter) by touching the tip on the paper. The test drop then enters over a minute area, precipitation or adsorption of the reaction product occurs in the immediate surrounding reagion, where it remains fixed in the fibres whilst the clear liquid spreads radially outwards by capillarity. A concentration of the coloured product, which would otherwise be spread over the whole area originally wetted by the test drop, is obtained, thus rendering minute quantities distinctly visible. A greater sensitivity is thus obtained than by adding a free drop of the test solution. Contact with the fingers should be avoided in manipulation with drop-reaction papers; a corner of the strip should be held with a pair of clean forceps. The problem of separating solid and liquid phases either before or after taking a sample drop or two of the test solution frequently arises in spot test analysis. When there is a comparatively large volume of liquid and the solid matter is required, centrifugation in a micro centrifuge tube (Fig. 11.34) may be employed. Alternatively, a micro sintered glass filter tube (Fig. 11.49), placed in a test-tube

Fig. 11.49

of suitable size, may be subjected to centrifugation: this device simplifies the washing of a precipitate. If the solid is not required, the liquid may be collected in a capillary pipette by sucking through a small pad of purified cotton wool placed in the capillary end; upon removing the cotton wool and wiping the pipette, the liquid may be delivered clear and free from suspended matter. A useful filter pipette is shown in Fig. 11.50. It is constructed of tubing of 6 mm diameter. A rubber bulb is attached to the short arm A; the arm B is ground flat, whilst the arm C is drawn out to a fine capillary; a short piece of rubber tubing is fitted over the top ofB. For filtering, a disc of filter paper of the same diameter as the outside diameter of the tube (cut out from filter paper by means of a sharp cork borer or by a hand punch) is placed on the flat ground surface of B, the tube F placed upon it and then held in position by sliding the rubber tubing just far enough over the paper to hold it when the tube F is removed. The filter pipette may be used either by placing a drop of the solution
186

EXPERIMENTAL TECHNIQUES 11.6
D
c:>

B

F

F

C)E
A

C

Fig. 11.50

I

D

on the filter disc or by immersing the tube end B into the crucible, test-tube, or receptacle containing the solution to be filtered. The bulb is squeezed by the thumb and middle finger, and the dropper point closed with the forefinger thus allowing the solution to be drawn through the paper when the bulb is released. To release the drops of filtered liquid thus obtained, the filter pipette is inverted over the spot plate, in an inclined position with the bulb uppermost. Manipulation of the bulb again forces the liquid in the tip on to the spot plate. The precipitate on the paper can be withdrawn for any further treatment by simply sliding the rubber tubing D down over the arm B. Another method involves the use of an Emich filter stick fitted through a rubber stopper into a thick-walled suction tube; the filtrate is collected in a micro test-tube (Fig. 11.51). The filter stick has a small pad of purified asbestos above the constriction.

Fig. 11.51

187

11. the apparatus can be used for treating the filter paper with the respective gases or vapours.6 QUALITATIVE INORGANIC ANALYSIS Fig. 11. 11. and a drop of the reagent for Fig. which can be closed with a small ground glass stopper fused to a glass knob.52 The apparatus illustrated in Fig. 11. Gas reactions may be performed in specially devised apparatus. By charging the flask with hydrogen sulphide solution. it is required to absorb the gas liberated in a drop of water or reagent solution. chlorine or bromine water. 11. The apparatus is shown in Fig. sulphides. 11.52 may be employed when the filter paper (or drop reaction paper) must be heated in steam.54 Fig.and consists of a micro test-tube of about I ml capacity. ammonia solution. etc.53. Fusion and solution of a melt may be conducted either in a platinum wire loop or in a platinum spoon (0'5-1 ml capacity) attached to a heavy platinum wire and fused into a glass holder. Thus in testing for carbonates.55 188 . The reagent and test solution or test solid are placed in the bottom of the tube. 11.. the filter paper is placed on the side arm support.53 Fig.

it may be desirable to suspend a small strip of reagent paper from a glass hook fused to the stopper as in Fig. 11. here the stopper for the micro test-tube consists of a small glass funnel on top of which the impregnated filter paper is laid in order to absorb the gas. Where hightemperatures or glowing are necessary for the evolution of the gas. In some reactions. 11. 11. The apparatus depicted in Fig. the gas is dissolved.EXPERIMENTAL TECHNIQUES 11.57. and is absorbed by the reagent on the knob. A micro crucible or a micro centrifuge tube may be employed as a receiver. The impregnated filter paper permits the passage of other gases and only retains the gas to be tested by the formation of a non-volatile compound that can be identified by means of a spot test.58 placed a loosely-fitting glass tube narrowed at both ends. 11.g. the glass tube.57 Fig. whilst the change of colour and reaction products may be rendered more easily visible by filling the bulb with gypsum or magnesia powder. the drop may be washed on to a spot plate or into a micro crucible and treated with the reagent. The gas is evolved in the tube. e. 11. e. in the chromyl chloride test for a chloride (see Section IV. in testing for ammonia. which is closed by a rubber stopper. The open end of the tube should be covered by a small piece of reagent paper and kept in position by means of a glass cap.55.56 Fig. The apparatus. and if sufficient time is allowed it is absorbed quantitatively by the reagent.14). if necessary. Micro distillation is sometimes required.54. if the gas liberated forms a coloured compound with the reagent. Since the apparatus is closed.g. When a particular gas has to be identified in the presence of other gases. A drop of water may replace the reagent on the stopper. Another useful apparatus is shown in Fig. 189 .6 the gas is suspended on the knob of the stopper. the apparatus shown in Fig. is sometimes preferable. shown in Fig.58) may be used. 11. 11. 11.56 should be used. The lower capillary end is filled to a height of about I mm with a suitable reagent solution. a simple hard glass tube supported in a circular hole in an asbestos or 'uralite' plate (Fig. may be raised or lowered at will. blown into a small bulb at the lower end. 11. it can easily be seen in the capillary. it consists of a micro test-tube into which is Fig. by gently warming. no gas can escape.59 is suitable for the distillation of very small quantities of a mixture. particularly when minute quantities of gas are concerned.

as a general rule. It is important to draw attention to the difference between the terms 'specific' and 'selective' when used in connection with reagents or reactions. whilst those reactions (and reagents) which are characteristic of a comparatively small number of substances are classified as selective. It must be remembered that this is the most favourable case.6 QUALITATIVE INORGANIC ANALYSIS Fig. 11.59 In Chapters Ill. The sensitivities given are. Reactions (and reagents). involves a loss of sensitivity. more often than not. and that in actual practice the presence of other ions usually necessitates a modification of the procedure which is frequently indicated. Furthermore. IV and VII the experimental details are given for the detection of a number of ions by spot tests. which under the experimental conditions employed are indicative or one substance (or ion) only are designated as specific. and the possibility of these interferences occurring must be taken into consideration when a test is applied. Hence we may describe reactions (or reagents) as having varying degrees of selectivity. a reaction (or reagent) can be only specific or not specific. The figures given in the text have been obtained largely with the Schleicher and Schuell spot paper: substantially similar results are given by the equivalent Whatman papers.11. 190 . and which. Almost without exception each test is subject to interference from the presence of other ions. for a solution containing only the ion in question. however. the sensitivities when determined upon drop-reaction paper will depend upon the type of paper used.

cadmium. zinc. aluminium. While sulphides of cations in Group lIa are insoluble in ammonium polysulphide. it makes the study of these reactions easier because ions of analogous behaviour are dealt with within one group. or with hydrogen sulphide in dilute mineral acid medium. antimony(V). 191 . cations are classified into five groups on the basis of their behaviour against some reagents. Systematic qualitative analysis by separations will be dealt with extensively in Chapter V. Group 11 The cations of this group do not react with hydrochloric acid. mercury(l). arsenic(III). copper. Ions of this group are lead. and can also separate these groups for further examination. and manganese(II).CHAPTER III REACTIONS OF THE CATIONS III. those of cations in Group lib are soluble.l CLASSIFICATION OF CATIONS (METAL IONS) INTO ANALYTICAL GROUPS For the purpose of systematic qualitative analysis. The five groups of cations and the characteristics of these groups are as follows: Group I Cations of this group form precipitates with dilute hydrochloric acid. but form precipitates with hydrogen sulphide in dilute mineral acid medium. antimony(III). Ions of this group are mercury(II). tin(II). iron(III). However they form precipitates with ammonium sulphide in neutral or ammoniacal medium. Classification is based on whether a cation reacts with these reagents by the formation of precipitates or not. Cations of this group are cobalt(II). The first four form the subgroup lIa and the last six the sub-group lib. iron(II). arsenic (V). ammonium sulphide. It can therefore be said that classification of the most common cations is based on the differences of solubilities of their chlorides. sulphides. but the reactions of cations will be dealt with here according to the order defined by this group system. bismuth. and carbonates. nickel(II). and silver. and ammonium carbonate. hydrogen sulphide. Apart from being the traditional way of presenting the material. By the systematic use of these so-called group reagents we can decide about the presence or absence of groups of cations. The group reagents used for the classification of most common cations are hydrochloric acid. Group III Cations of this group do not react either with dilute hydrochloric acid. chromium(III). and tin(III)(IV).

The second column (still on the left-hand page). and the majority of the reactions can be applied as a spot test as well. Group V Common cations. Since. and (c) the equation of the reaction or some other explanation of what had happened. and barium. however. including the reagent and experimental circumstances. Although it would be wrong to copy the text of this book. which include magnesium. In some cases it is impossible or impractical to prepare a M reagent. One should not use these reagents when working alone in a laboratory. ammonium. Chapter 11). (b) the changes observed. together with their reactions will be given in Chapter VII. Hints on the preparation of reagents are given in the Appendix of this book. meaning that it is easy to calculate the relative volumes of the reactant and the reagent needed to complete the reaction. which do not react with reagents of the previous groups. headed 192 . with notes on their stability.IIU QUALITATIVE INORGANIC ANALYSIS Group IV Cations of this group do not react with the reagents of Groups I. and should therefore be handled with care. The concentration of reagents is in most cases chosen to be molar. Most reagents are poisonous to some extent. In the list of reactions these reagents will be marked as (POISON) or (HAZARD). A useful way of making notes is the following. the supervisor or a colleague should always be notified before using them. It is not advisable to add the calculated amount of reagent at once to the solution (cf. The left page of an open notebook is divided into two equal sections by a vertical line. It is easy to predict the volume of a particular reagent needed to complete the reaction from the concentrations. Taking notes when studying these reactions is absolutely necessary for a student. Some systems of group classification exclude ammonium chloride besides ammonium carbonate as the group reagent. A logical. but the final amount should be equal or more than the equivalent. experimental techniques described in Chapter 11 should be applied. The reagents are listed there in alphabetical order. III. Acids and bases are applied mostly in 2M concentrations in order to avoid unnecessary dilution of the mixture. thus 0'5 or even O'IM reagents have to be used sometimes.2 NOTES ON THE STUDY OF THE REACTIONS OF IONS When studying the reactions of ions. and hydrogen ions. lithium. and Ill. in such cases magnesium must also be included in this group. potassium. Those reagents which are exceptionally poisonous or hazardous must be specially labelled and must be used with utmost care. 11. Cations of this group are: calcium. in the course of systematic analysis considerable amounts of ammonium chloride will be present when the cations of the fourth group are to be precipitated. The reactions can be studied both in macro and semimicro scale. The left column can be headed 'TEST' and should contain a brief description of the test itself. They form precipitates with ammonium carbonate in the presence of ammonium chloride in neutral or slightly acidic medium. clear way of making notes is essential. and any special experimental circumstances applied when performing the test. strontium. it is more logical not to include magnesium into Group IV. This group system of cations can be extended to include less common ions as well. it is important to note (a) the reagent. sodium. Classification of these ions. form the last group of cations.

--+ PbS04! Pb2++2NH 3+2H 20 --+ Pb(OHh!+2NHt Pb2+ does not form ammine complexes Pb2+ +20H. It is also advisable to summarize reactions within one group in the form of tables. helps the student actually to learn the subject as well. dissolves yellow ppt. Bromides and iodides are Table IIU Test Group I Pb 2 + I. and silver chloride AgCl. KI + excess Pb2+ +2CI. by dealing with the one particular reaction altogether four times.--+ PbCI 2! no ammine complexes (but Pb(OHh!) 33·4 g PbCI 2 dissolves per litre at lOO"C Pb2+H 2S --+ PbS!+2H+ 3PbS! + 8HN0 3 --+ 3Pb 2+ + 2NOj + 4H 20 + 3S! S!+2HN0 3 --+ SOi-+2H++2NOj Pb2+ +SOi. The 'OBSERVATION' column should be filled when actually making the experiments.l. Group reaction: white precipitate of lead chloride PbCI 2 . The solubility of mercury(I) sulphate lies in between. When writing this up. no change + excess 4. (different) white ppt. Nitrates of these cations are very soluble. H 2S(+ HCI) +conc. AND SILVER(I) Group reagent: dilute (2M) hydrochloric acid. mercury(I) chloride Hg 2C1 2 . Cations of the first group form insoluble chlorides. the entire right-hand page should be reserved for 'EXPLANATION'. The column 'TEST' should be made up before making the actual experiments. MERCURY(I). when the reactions of the particular group have been studied and explained.REACTIONS OF CATIONS ms 'OBSERVATION' should contain the visible change which occurred when carrying out the test.--+ Pb(OHh! Pb(OHh! + 20W +:t [Pb(OH)4]2Pb(OHh: amphoteric Pb2+ +2r --+ PbI 2! no iodo complexes 193 . and. while the 'EXPLANATION' page should be made up after leaving the laboratory. white ppt. the reaction tables should be made up. I1L3 FIRST GROUP OF CATIONS: LEAD(II). the student will be able to devise his experiments and to make best use of the time available in the laboratory. This systematic way of study enables us to devote precious laboratory time entirely to experiments. NaOH + excess 5. where the reaction equation can be entered. A typical page of a notebook containing some of the reactions of lead(II) ions is shown on Table III. is slightly soluble in water and therefore lead is never completely precipitated when adding dilute hydrochloric acid to a sample. no change white ppt. while silver sulphate dissolves to a much greater extent. HCI One page of a laboratory notebook Observation Explanation +NH 3 +hot water 2. Lead chloride. the rest of the lead ions are quantitatively precipitated with hydrogen sulphide in acidic medium together with the cations of the second group. Finally. Among sulphates lead sulphate is practically insoluble. as shown on Table 111. however.HN0 3 + boiling 3. white ppt. no change dissolves black ppt.2 for the first group of cations. NH 3 white ppt. Finally.

IlIA QUALITATIVE INORGANIC ANALYSIS Table 111. small amounts + excess Na 2C0 3 + boiling Na2HP04 Specific reaction white PbCI2! no change dissolves black PbS! white PbS04! white Pb(OHh! no change white Pb(OHh! dissolves [Pb(OH)4J 2yellow PbI 2! no change yellow PbCr04! no change white Pb(CNh! no change white PbO. and nitrogen oxide is formed also: 3Pb+8HN0 3 --+ 3Pb2++6N03"+2NOj+4H 20 The colourless nitrogen oxide gas.2 Tabulating reactions of Group I cations Pb2+ Hg~+ Ag+ white AgCl! dissolves [Ag(NH 3 h r no change black Ag 2S! dissolves Ag" brown Ag2O! dissolves [Ag(NH 3 h r brown. Acetates are more soluble. Hydroxides and carbonates are precipitated with an equivalent amount of the reagent. I1I. though precipitation of lead halides is incomplete. small amounts + excess K 2Cr04 +NH 3 KCN. an excess however might act in various ways. small amounts + excess NaOH. It readily dissolves in medium concentrated nitric acid (8M).HgNH 2N0 3! no change black. Hg 2O! no change green Hg 21 2! grey Hg!+[HgI4J 2red Hg 2Cr04! black Hg] + HgNH 2N0 3! black Hg] + Hg(CNh no change yellowish-white Hg 2C0 3! black Hg] + HgO! white Hg 2HP04! Diphenyl carbazide violet colour also insoluble. Sulphides are insoluble.PbC0 3! no change white Pb 3(P04h! Benzidine ( + Br2) blue colour white Hg 2Cl2! black Hg] + HgNH 2Cl! no change black Hg] + HgS! white HgiN0 3hS! black Hg] + HgO. Ag 2O! no change yellow AgI! no change red Ag 2Cr04! dissolves [Ag(NH 3 h r white AgCN! dissolves [Ag(CNhJyellowish-white Ag2C0 3! brown Ag 2O! yellow Ag 3P04! p-dimethylaminobenzylidenerhodanine (+HN0 3 ) violet colour HCI +NH -i-hot water H 2S(+HCI) +ccHN0 3 .1 at room temperature).4 LEAD. 194 . Pb (Ar : 207'19) Lead is a bluish-grey metal with a high density (11'48 g ml. There are differences in their behaviour towards ammonia as well. small amounts + excess KI. when mixed with air. and the precipitates dissolve quite easily in hot water. though silver acetate might be precipitated from more concentrated solutions. boiling NH 3 . is oxidized to red nitrogen dioxide: 2NOj(colourless) + O 2 j --+ 2N0 2 j(red) With concentrated nitric acid a protective film of lead nitrate is formed on the surface of the metal and prevents further dissolution. Dilute hydrochloric or sulphuric acid have little effect owing to the formation of insoluble lead chloride or sulphate on the surface.

--+ [PbCI 4 ] 2 If the precipitate is washed by decantation and dilute ammonia is added.--+ Pb 2SCI 2!+2H+ This however decomposes on dilution (a) or on further addition of hydrogen sulphide (b) and black lead sulphide precipitate is formed: Pb 2SCI 2! Pb 2SCI 2! + H 2S PbS! + PbCI 2! --+ 2PbS! +2CI--+ (a) (b) Lead sulphide precipitate decomposes when concentrated nitric acid is added. the latter is converted into (black) lead sulphide in a precipitate-exchange reaction: PbCI 2! +H 2S --+ PbS! +2H+ +2CI- If the test is carried out in the presence of larger amounts of chloride [potassium chloride (saturated)]. finely divided elementary sulphur is precipitated: 3PbS! + 8HN0 3 --+ 3Pb 2 + + 6N0 3 + 3S! + 2NOj + 4H 20 If the mixture is boiled. initially a red precipitate of lead sulphochloride is formed when introducing hydrogen sulphide gas: 2Pb2+ +H 2S+2CI. though a precipitate-exchange reaction takes place and lead hydroxide is formed: PbCI 2!+2NH 3+2H 20 --+ Pb(OHh!+2NH! +2CI- 2. Dilute hydrochloric acid (or soluble chlorides): a white precipitate in cold and not too dilute solution: Pb2+ +2CI.4 Reactions of lead(11) ions A solution of lead nitrate (O'25M) or lead acetate (O'25M) can be used for the study of these reactions. which forms immediately white lead sulphate precipitate (b) with the lead ions in the solution: . Introducing hydrogen sulphide gas into a mixture which contains white lead chloride precipitate. needle-like crystals when cooling. 1.1 at 20oq . and white. Because hydrogen ions are formed in the above reaction. no visible change occurs [difference from mercury(I) or silver ions].~ PbCI 2! The precipitate is soluble in hot water (33'4 g t. It is also soluble in concentrated hydrochloric acid or concentrated potassium chloride when the tetrachloroplumbate(II) ion is formed: PbCI 2!+2CI.REACTIONS OF CATIONS ill. it is advisable to buffer the mixture with sodium acetate. Hydrogen sulphide in neutral or dilute acid medium: black precipitate of lead sulphide: Pb2+ +H 2S --+ PbS!+2H+ Precipitation is incomplete if strong mineral acids are present in more than 2M concentration.1 at 100°C while only 9·9 g t. but separates again in long. S!+2HN0 3 Pb2+ + soi: --+ --+ soi: +2H+ +2NOj PbS0 4! (a) (b) 195 . sulphur is oxidized by nitric acid to sulphate (a).

+S20~. Every precaution must be observed to prevent the escape of hydrogen sulphide into the air of the laboratory. lead hydroxide has an amphoteric character.4 QUALITATIVE INORGANIC ANALYSIS Boiling lead sulphide with hydrogen peroxide (3 %). when added to a solution oftetrahydroxoplumbate(I1) forms a black precipitate oflead dioxide by oxidizing bivalent lead to the tetraveIent state: [Pb(OH)4]2.-+ [Pb(OH)4]2Thus. Hot. when tetraacetateplumbate(I1) and ditartratoplumbate(I1) ions are formed: PbS0 4! + 4CH 3COO. and why it can be detected in the filtrate from the separation of the sparingly soluble lead chloride in dilute hydrochloric acid. concentrated sulphuric acid dissolves the precipitate owing to formation of lead hydrogen sulphate: PbS04! + H 2S04 -+ Pb2+ + 2HSO:. can precipitate lead chromate from their solution. chromate ions. Lead sulphate precipitate is soluble in more concentrated solutions of ammonium acetate (lOM) (a) or ammonium tartrate (6M) (b) in the presence of ammonia. and all operations with the gas must be conducted in the fume chamber. 3.+ H 202 -+ Pb0 2! + 2H 20 + 20H[Pb(OH)4]2. Note: Hydrogen sulphide is a highly poisonous gas. for example.-+ Pb0 2! +2H20+2S0~SO~. Sodium hydroxide: white precipitate of lead hydroxide Pb2+ +20H- -+ Pb(OHh! The precipitate dissolves in excess reagent. the black precipitate turns white owing to the formation of lead sulphate: PbS!+4H 202 -+ PbS0 4!+4H20 The great insolubility of lead sulphide in water (4'9 x 10. Dilute sulphuricacid (or soluble sulphates) : white precipitate oflead sulphate: Pb2+ + PbS0 4! The precipitate is insoluble in excess reagent. Ammonia solution: white precipitate of lead hydroxide Pb2++2NH 3+2H20 -+ Pb(OHh!+2NHt The precipitate is insoluble in excess reagent. Solubility is much lower in the presence of ethanol. 4.III.+SO~(b) The stabilities of these complexes are not very great.-+ [Pb(C 4H40 6h]2.1 1 g f -1) explains why hydrogen sulphide is such a sensitive reagent for the detection of lead. 196 .-+ [Pb(CH3COO)4]2~+ SO~(a) PbS04!+2C4H40~. Hydrogen peroxide (a) or ammonium peroxodisulphate (b). when tetrahydroxoplumbate(I1) ions are formed: Pb(OHh! + 20H.-+ (a) (b) 5.

--+ [Pb(OH)4]2.4 When boiled with sodium carbonate the lead sulphate is transformed into lead carbonate in a precipitate-exchange reaction: PbS0 4! + CO~ --+ PbC0 3! + SO~- By washing the precipitate by decantation with hot water. Sodium carbonate: white precipitate of a mixture of lead carbonate and lead hydroxide 2Pb2+ + 2CO~. The precipitate dissolves in dilute nitric acid and even in acetic acid and CO 2 gas is liberated: Pb(OHh! + PbC0 3! + 4H+ --+ 2Pb2+ + 3H 20 + CO 2i 10. Disodium hydrogen phosphate: white precipitate of lead phosphate 3Pb2+ +2HPO~. on diluting with water the precipitate reappears. acetic acid or ammonia solution: yellow precipitate of lead chromate Pb2+ + CrO~.+=t [PbI 4]2The reaction is reversible. Potassium chromate in neutral. 8.--+ PbCr0 4! Nitric acid (a) or sodium hydroxide (b) dissolve the precipitate: 2PbCr04! +2H+ +=t 2Pb2+ +Cr20~.+ SO~(b) 9. though it can be dissolved by both dilute nitric acid (a) and sodium hydroxide (b). sulphate ions can be removed and the precipitate will dissolve in dilute nitric acid PbC0 3! + 2H+ --+ Pb2+ + H 20 + CO 2i 6. lead chromate precipitates again. An excess of a more concentrated (6M) solution of the reagent dissolves the precipitate and tetraiodoplumbate(II) ions are formed: Pb12! +21.+=t [Pb(OH)4]2-+CrO~- (a) (b) Both reactions are reversible. from which it separates on cooling in golden yellow plates. Potassium iodide: yellow precipitate of lead iodide Pb2+ +21- --+ Pb12! The precipitate is moderately soluble in boiling water to yield a colourless solution.REACTIONS OF CATIONS 1II.+2H 20 PbCr04!+40H.+=t PbiP0 4h!+2H+ 197 . PbS0 3!+2H+ --+ Pb2++H 20+S02i (a) PbS0 3! + 40H. Sodium sulphite in neutral solution: white precipitate oflead sulphite Pb2+ + SO~- --+ PbS0 3! The precipitate is less soluble than lead sulphate. by buffering the solution with ammonia or acetic acid respectively.+ H 20 --+ Pb(OHh! + PbC0 3! + CO 2i On boiling no visible change takes place [difference from mercury(l) and silver(l) ions]. 7.

This reaction can be used to distinguish lead(II) ions from mercury(I) and silver(I). thallium. manganese. Tetramethyldiamino-diphenylmethane (or 'tetrabase') (0'5 %) (CH3hN-Q-CH2-Q-N(CH3h): a blue oxidation product {hydrol: -CH 2 --+ -CH(OH)} is formed under the conditions given below. Potassium cyanide (POISON): white precipitate of lead cyanide Pb2+ +2CN- --+ Pb(CNh! which is insoluble in the excess of the reagent. add I ml 2M potassium hydroxide and 0'5-1 ml3 per cent hydrogen peroxide solution. nickel. and nickel give a similar reaction: iron and large quantities of copper interfere. 12. Benzidine (0'05 %) (DANGER: THE REAGENT IS CARCINOGENIC) the so-called 'benzidine blue' is produced upon oxidation with lead dioxide. cobalt. with a tetrahydroxoplumbate(II) solution). Place I ml test solution in a 5 ml centrifuge tube. Allow to stand for 5 minutes. The ions of bismuth.. Concentration limit: I in 50. only thallium interferes. remove the excess ammonia by waving the paper over a small flame. the excess of the latter is destroyed by ammonia [2NH 3 + 30Br.--+ N 2 i + 3Br. shake and centrifuge.000. Place a drop of the test solution upon drop-reaction paper. strong acids (nitric acid) dissolve the precipitate. and thallium give a similar reaction. silver. The supernatant liquid is coloured blue. Sensitivity: I ~g Pb. Gallocyanine (1 %) ~ ( 198 o4c)C)"NlCH. and wash once with cold water. Add 2 drops reagent: a blue colour develops.III. cerium. Add 2 drops I: 1 ammonia solution.4 QUALITATIVE INORGANIC ANALYSIS The reaction is reversible. manganese. 11.. but by performing the test in an alkaline extract (Le. and treat successively with 2 drops 3M sodium hydroxide and I drop saturated bromine water. Separate the precipitate by centrifugation. cobalt. The ions of bismuth. cerium. . Oxidation is conveniently carried out by sodium hypobromite. ~ COOHN ~ I ) . The precipitate is also soluble in sodium hydroxide.HCI .000. which react in different ways. Concentration limit: I in 10.+ 3H 20]. Add 2 ml reagent. 13. 14..

liquid metal at ordinary temperatures and has a density of 13'534 g ml. but it is not very selective. Concentration limit: I in 50. and then 2 drops of the reagent. cadmium.REACTIONS OF CATIONS II1. Blowpipe test. bismuth.1 at 25°C. nickel. (which is soft and will mark paper). Pale blue (inconclusive). Hg (Ar : 200·59) . In the presence of silver.MERCURY(I) Mercury is a silverwhite. Sensitivity: 1-6 ~g Pb. Dry the paper on a water bath. followed by a little 96 per cent ethanol. alkaline. cadmium. antimony.S deep-violet precipitate of unknown composition. Shake for 30 seconds. copper. Concentration limit: I in 1. surrounded with a yellow incrustation oflead monoxide is obtained. The test is applicable to finely divided lead sulphate precipitated on filter paper. 15. a malleable bead of lead. Diphenylthiocarbazone (or Dithizone) (0 '005 %) brick-red complex salt in neutral. Dry tests a.000. Heavy metals (silver. Remove the soluble sulphates of the other metals by washing with about 3 drops of M sulphuric acid.000. move the filter papers to a fresh position after each addition of pyridine. ammoniacal. or alkalicyanide solution. The green colour of the reagent changes to red. A deep violet spot is produced. III. Flame test. Transfer a drop of the test solution to a drop-reaction paper and add a drop of M sulphuric acid to fix the lead as lead sulphate. but reacts readily with nitric acid. When a lead salt is heated with alkali carbonate upon charcoal. and then apply the test as detailed above. The reagent is prepared by dissolving 2-5 mg dithizone in 100 ml carbon tetrachloride or chloroform. Place I ml of the neutral or faintly alkaline solution in a micro test-tube. proceed as follows. mercury. medium concentrated (8M) nitric acid with an excess of mercury yields mercury(I) ions: 6Hg+8HN0 3 --+ 3Hg~+ +2NOi+6N03" +4H 20 199 . It is unaffected when treated with hydrochloric or dilute sulphuric acid (2M). etc. but this effect may be eliminated by conducting the reaction in the presence ofmuch alkali cyanide: excess ofalkali hydroxide is also required for zinc.5 MERCURY. and zinc. The reaction is extremely sensitive. followed by a drop each of I per cent aqueous pyridine and the gallocyanine reagent (blue). Remove the excess of the reagent by placing several filter papers beneath the drop-reaction paper and adding drops of the pyridine solution to the spot until the wash liquid percolating through is colourless. Place a drop of the test solution upon drop-reaction paper. or copper. It does not keep well. introduce a few small crystals of potassium cyanide. b.250. Sensitivity: 0'1 ~g Pb (in neutral solution).) interfere. 16. Cold.

concentrated sulphuric acid dissolves mercury as well. Sodium sulphide (colourless). their reactions will therefore be treated here. This reaction can be used to differentiate mercury(l) ions from lead(II) and silver(I). dissolves the mercury(II) sulphide (but leaves mercury metal) and a disulphomercurate(II) complex is formed: HgS+S 2.). The name calomel. but the finely divided mercury makes it shiny black. The mercury(II) amidochloride is a white precipitate. Hydrogen sulphide in neutral or dilute acid medium: black precipitate.M = nice black) refers to this characteristic of the originally white mercury(l) chloride precipitate. both insoluble precipitates: Hg 2Cl2 + 2NH 3 -+ Hg] + Hg(NH 2)CI! + NHt + CI- the reaction involves disproportionation. are in the second cation group. forming undissociated but soluble mercury(II) chloride: 3Hg 2C12! + 2HN0 3 + 6HCI -+ 3HgCl 2 + 2NOi + 4H 20 2. Reactions ofmercury(I) ions A solution of mercury (I) nitrate (O·05M) can be used for the study of these reactions. together with the other members of that group.S QUALITATIVE INORGANIC ANALYSIS with an excess of hot concentrated nitric acid mercury(II) ions are formed: 3Hg+8HN0 3 -+ 3Hg2+ +2NOi+6N0 3 +4H 20 Hot. mercury(I) and mercury(II) behave quite differently against reagents used in qualitative analysis.+ S02 l +2H 20 while if the acid is in excess. 1.-+ [HgS 2]2200 .f. mercury(I) is converted partly to mercury(II) and partly to mercury metal. Mercury(II) ions. their reactions will therefore be dealt with later. Dilute hydrochloric acid or soluble chlorides: white precipitate of mercury(I) chloride (calomel) Hg~+ +2CI- -+ Hg 2C12! The precipitate is insoluble in dilute acids. coming from Greek (Kaov J1. mercury(II) ions are formed: 2Hg+2H 2S0 4 Hg+2H 2S0 4 -+ Hg~+ -+ Hg2++s0i-+S02i+2H 20 The two ions. and hence belong to two different analytical groups. Mercury(I) ions belong to the first group of cations. The product is mercury(I) ion if mercury is in excess + SOi. Ammonia solution converts the precipitate into a mixture of mercury(II) amidochloride and mercury metal. Mercury(I) chloride dissolves in aqua regia.III. which is a mixture of mercury(II) sulphide and mercury metal Hg~+ +H 2S -+ Hg! +HgS! +2H+ Owing to the extremely low solubility product of mercury(II) sulphide the reaction is very sensitive. on the other hand.

--+ HgS! + S2- (a) Mercury(II) sulphide then dissolves in the (mono) sulphide formed in the previous reaction HgS! + S2. N0 3 !+2Hg!+3NHt 201 . Aqua regia dissolves the precipitate.+ S~This rather complicated reaction can be understood more easily by breaking it down into the following steps: First mercury is oxidized by the disulphide.+S~- (c) Combining the reactions (a).--+ 2[HgS 2]2.REACfIONS OF CAnONS ms After removing the mercury metal by filtration.+ 2H+ --+ HgS! + H 2Sj Sodium disulphide (yellow) dissolves both mercury and mercury(II) sulphide: HgS! + Hg] + 3S~. yielding undissociated mercury(II) chloride and sulphur: l2HCI + 4HN0 3 + 3Hg! + 3HgS! = 6HgCl 2 + 3S! + 4NOj + 8H 20 This reaction can be understood as the sum of the following steps: When making up aqua regia chlorine atoms are formed: 3HCl+HN0 3 --+ 3CI+NOj+2H 20 These react partly with mercury. yielding mercury(II) sulphide and (mono)sulphide ions: Hg] + S~. Ammonia solution: black precipitate which is a mixture of mercury metal and basic mercury(II) amidonitrate.Hg / NH 2 -. (which itself is a white precipitate) 2Hg~+ +N0 3 +4NH 3+H 20 --+ HgO. reacts with disulphide ions yielding disulphomercurate(II) and trisulphide ions: HgS+2S~- --+ HgS~.--+ [HgS 2]2(b) Mercury(II) sulphide. black mercury(II) sulphide can again be precipitated by acidification with dilute mineral acids: [HgS 2]2. (b) and (c) together we obtain the reaction described above. which was originally present in the precipitate. forming mercury(II) chloride: (a) (b) (c) Hg] + 2Cl --+ HgCl 2 Another part of chlorine reacts with mercury(II) sulphide HgS!+2CI--+ HgCI 2+S! Combination of 4(a) + 3(b) + 3(c) yields the equation 12HCI + 4HN0 3 + 3Hg! + 3HgS! = 6HgCl 2 + 3S! + 4 NOj + 8H 20 When heated with aqua regia. sulphur is oxidized to sulphuric acid and the solution becomes clear: S!+6HCI+2HN0 3 --+ Si-+6CI-+8H++2NOj 3.

Sodium carbonate in cold solution: yellow precipitate of mercury(l) carbonate: + CO~- --+ Hg 2C0 3! The precipitate turns slowly to blackish grey. 8. the colour of the precipitate turns to grey.+H 20 6. When heating the precipitate turns to red.m. added slowly in cold solution: green precipitate of mercury(l) iodide Hg~+ +21- --+ Hg 212! If excess reagent is added a disproportionation reaction takes place. crystalline mercury(l) chromate. but dissolves readily in dilute nitric acid. disproportionation again takes place.s QUALITATIVE INORGANIC ANALYSIS This reaction can be used to differentiate between mercury(l) and mercury(II) ions. Potassium chromate in hot solution: red crystalline precipitate of mercury(l) chromate Hg~+ + CrOi- --+ Hg 2Cr04! If the test is carried out in cold. owing to disproportionation. when mercury(II) oxide and mercury are formed: Hg 2C0 3! --+ HgO! +Hg! +C0 2l The decomposition can be speeded up by heating the mixture. Potassium iodide. Sodium hydroxide turns the precipitate into black mercury(l) oxide: Hg 2Cr04!+20H- --+ Hg 20!+CrOi. and a mixture of red mercury(II) iodide precipitate and finely distributed black mercury is formed: Hg 212! Hg~+ --+ Hg12! + Hg] 7. Sodium hydroxide: black precipitate of mercury(l) oxide Hg~+ + 20H- --+ Hg 20! + H 20 The precipitate is insoluble in excess reagent. a brown amorphous precipitate is formed with an undefined composition. soluble tetraiodomercurate(II) ions and a black precipitate of finely divided mercury being formed: Hg 212!+2r --+ [HgI 4]2-+Hg! When boiling the mercury(l) iodide precipitate with water. Disodium hydrogen phosphate: white precipitate of mercury(l) hydrogen phosphate: Hg~+ + HPOi- --+ Hg 2HP0 4! 202 . 4. When boiling. when mercury(II) oxide and mercury metal are formed: Hg 20! --+ HgO! + Hg] 5.

Potassium cyanide (POISON) produces mercury(II) cyanide solution and mercury precipitate: Hg~+ +2CN. Place a drop of the faintly acid test solution upon dropreaction paper and add a drop of 50 per cent potassium nitrite solution. leaving the black spot. in the form of a greyish-black precipitate: Hg~+ +N02" +H 20 --+ 2Hg!+N0 3 +2H+ Under similar circumstances mercury(II) ions do not react. Mercury(II) solutions react in a similar way. Heating the spot in a Bunsen-flame. Aluminium sheet If a drop of mercury(I) nitrate is placed on a clean aluminium surface. silverish spot is obtained. thus considerable amounts of aluminium get corroded. which again is oxidized. 14 Diphenylcarbazide (1 %in alcohol) /NH__NH) c=o ( -. 11. mercury evaporates and the red copper surface becomes visible again. aluminium amalgam is formed and aluminium ions pass into solution: 3Hg~+ +2AI --+ 2AIH +6Hg! The aluminium which is dissolved in the amalgam is oxidized rapidly by the oxygen of the air and a voluminous precipitate of aluminium hydroxide is formed.REACTIONS OF CAnONS ms 9. : NH--NH 203 forms a violet-coloured compound with mercury(I) or mercury(II) ions. The remaining mercury amalgamates a further batch of aluminium. Tin(II) chloride reduces mercury(I) ions to mercury metal. The spot test technique is as follows. Coloured ions yield a brown colouration which may be washed away. In the presence of 0'2M nitric . and rubbing the surface with a dry cloth. is practically undissociated. drying. which appears in the form of a greyish-black precipitate: Hg~+ + Sn2+ --+ 2Hg! + Sn 4+ Mercury(II) ions react in a similar way. a glittery. 12. 10. a deposit of mercury metal is formed: Cu+Hg~+ --+ Cu2+ +2Hg! Rinsing. 13.--+ Hg!+Hg(CNh Mercury(II) cyanide. A black (or dark grey) spot is produced. the composition of which is not quite understood. The test is highly selective. Glossy copper sheet or copper coin If a drop of mercury(I) nitrate is placed on a glossy copper surface. Potassium nitrite reduces mercury metal from a solution of mercury(I) ions in cold. though soluble.

silver acetate. 15. malleable. The test is most sensitive if the filter paper is left to dry at room temperature. and on top of the latter one drop of the test solution. 204 . Silver complexes are however soluble. consisting of fine drops of mercury. Silver(II) compounds are unstable. Drop test: Impregnate a piece of filter paper with the freshly prepared reagent. which is colourless. 2Ag+2H 2S04 --+ 2Ag++SO~-+S02j+2H20 (b) Silver forms monovalent ion in solution. but play an important role in silver-catalysed oxidationreduction processes. when diammineargentate complex ion is formed: AgCI!+2NH 3 --+ [Ag(NH 3h]+ +Cl- Dilute nitric acid or hydrochloric acid neutralizes the excess ammonia.--+ AgCl] With concentrated hydrochloric acid precipitation does not occur. it dissolves in concentrated hydrochloric acid. and not more than 0'1 gram of the substance should be used in the test. the equilibrium shifts back to the left and the precipitate reappears. and ductile metal.+=t [AgCI 2]By diluting with water. Note: Mercury vapour is extremely poisonous. Dilute ammonia solution dissolves the precipitate. Add I drop 0'4M nitric acid. Silver halides are sensitive to light. Decanting the liquid from over the precipitate. The globules coalesce when they are rubbed with a glass rod. Ag (Ar : 107'868) Silver is a white. Silver nitrate is readily soluble in water.6 SILVER. Dry test. Reactions of silver(I) ions A solution of silver nitrate (O'IM) can be used to study these reactions. these characteristics are widely utilized in photography. when a dichloroargentate complex is formed: AgCl! + Cl. nitrite and sulphate are less soluble. In the presence of mercury a violet colour is observable. All compounds of mercury when heated with a large excess (7-8 times the bulk) of anhydrous sodium carbonate in a small dry test-tube yield a grey mirror. In more concentrated nitric acid (8M) (a) or in hot. It is insoluble in hydrochloric.l ) and melts at 960·5°C. Dilute hydrochloric acid (or soluble chlorides): white precipitate of silver chloride Ag" +CI. 10.s QUALITATIVE INORGANIC ANALYSIS acid the test is selective for mercury. dilute sulphuric (M) or dilute nitric (2M) acid. and the precipitate reappears because the equilibrium is shifted back towards the left. in the upper part of the tube. 1. Under these circumstances the sensitivity is I ~g Hg~+ or Hg2+ with a concentration limit of I in 5 x 104. It has a high density (10'5 g ml.m. concentrated sulphuric acid (b) it dissolves: 6Ag+8HN0 3 --+ 6Ag+ +2NOj +6N0 3 +4H 20 (a) . while all the other silver compounds are practically insoluble.

which turns to greyish or black owing to the formation of silver metal: 2AgCI! (hv) ) 2Ag! +C1 2j The reaction is slow and the actual reaction mechanism is very complicated. Then apply the reagent. Hydrogen sulphide (gas or saturated aqueous solution) in neutral or acidic medium: black precipitate of silver sulphide 2Ag+ +H 2S --+ Ag 2S!+2H+ Hot concentrated nitric acid decomposes the silver sulphide.+CI- The safest way to study this reaction is as follows: decant the liquid from the precipitate. The excess of silver halide has to be removed (to make the developed negative insensitive to light) by fixation. ammonium poly sulphide. or sodium thiosulphate. and sulphur remains in the form of a white precipitate: 3Ag 2S!+ 8HN0 3 --+ S!+2NOj+6Ag+ +6N0 3 +4H 20 The reaction can be understood better if written in two steps: 3Ag 2S!+2HN03 --+ S!+2NOj+3Ag 20!+H20 3Ag 20! + 6HN0 3 --+ 6Ag+ + 6N0 3 + 3H 20 If the mixture is heated with concentrated nitric acid for a considerable time. and wash it 2-3 times with water by decantation. In the camera these processes are only initiated. dicyanato. a 'negative' image of the object is therefore obtained. Photography is based on these reactions.6 Potassium cyanide (POISON) dissolves the precipitate with formation of the dicyanoargentate complex: AgCI!+2CN--+ [Ag(CNh]. Ammonia solution: brown precipitate of silver oxide 2Ag+ + 2NH 3 + H 20 --+ Ag 20! + 2NHt 205 . 2. Sodium thiosulphate dissolves the precipitate with the formation of dithiosulphatoargentate complex: AgCI! +2S20~--+ [Ag(S203h]3. potassium cyanide. ammonia.or dithiosulphatoargentate complexes with hydrogen sulphide. Sunlight or ultraviolet irradiation decomposes the silver chloride precipitate. 3. sulphur is oxidized to sulphate and the precipitate disappears: S!+2HN0 3 --+ SOi-+2NOj+2H+ The precipitate is insoluble in ammonium sulphide. the photographic material has to be 'developed' to complete the reaction. Silver SUlphide can be precipitated from solutions containing diammine-. Other silver halides show similar behaviour. Greyish or black silver particles appear on places irradiated by light.REACTIONS OF CATIONS III.+CI- This reaction takes place when fixing photographic negatives or positive prints after development.

The precipitate dissolves in ammonia solution (a) and in nitric acid (b): Ag 20!+4NH3+H20 Ag 20! + 2H+ Ag+ +r -+ -+ 2[Ag(NH 3hr +20H2Ag+ + H 20 (a) (b) 5. A red ring of silver chromate is obtained. Potassium chromate in neutral solution: red precipitate of silver chromate 2Ag+ +CrO~- -+ Ag2Cr04! Spot test: place a drop of the test solution on a watch glass or on a spot plate. (If ammonium nitrate is present in the original solution or the solution is strongly acidic no precipitation occurs.-+ [Ag(CNh]. Potassium iodide: yellow precipitate of silver iodide -+ AgI! The precipitate is insoluble in dilute or concentrated ammonia.+1[Ag(S203h]3.) The precipitate dissolves in excess of the reagent. The precipitate is soluble in dilute nitric acid (a) and in ammonia solution (b): (a) 2Ag2Cr04! +2H+ +=t 4Ag+ +Cr20~.+H 20 (b) Ag 2Cr04!+4NH3 -+ 2[Ag(NH 3h]+ +CrO~The acidified solution turns to orange because of the formation of dichromate ions in reaction (a). Remove one drop of the clear liquid and place it on drop-reaction paper together with a drop of the potassium chromate reagent. but dissolves readily in potassium cyanide (POISON) (a) and in sodium thiosulphate(b): AgI+2CN-+ AgI+2S20~. 206 .6 QUALITATIVE INORGANIC ANALYSIS The reaction reaches an equilibrium and therefore precipitation is incomplete at any stage. Sodium hydroxide: brown precipitate of silver oxide: 2Ag+ +20H- -+ Ag 20!+H 20 A well-washed suspension of the precipitate shows a slight alkaline reaction owing to the hydrolysis equilibrium: Ag 20! + H 20 +=t 2Ag(OHh! +=t 2Ag+ + 20HThe precipitate is insoluble in excess reagent. and diammineargentate complex ions are formed: Ag 20t+4NH 3+H 20 -+ 2[Ag(NH 3h]+ +20H- The solution should be disposed of quickly.+1- (a) (b) 6. The reaction can be used for microscopic test. add a drop of ammonium carbonate solution and stir (this renders any mercury(I) or lead ions unreactive by precipitation as the highly insoluble carbonates). which explodes readily even in a wet form.III. The formation of needle-like red crystals of silver chromate can be observed distinctly. when a piece of potassium chromate crystal has to be dropped into the test solution. because when set aside silver nitride Ag 3N precipitate is formed. 4.

formed in reaction (a) is a medium-strong acid.REACTIONS OF CATIONS III. The solution should be discarded after the test (cf. while gaseous nitrogen is evolving: 4[ Ag(NH 3h]+ + H 2N-NH 2 • H 2S04 --+ --+ 4Ag!+N 2i+6NH1 +2NH 3+SOiIf the vessel in which the reaction is carried out is clean. until the last traces of the silver oxide precipitate disappear. The silver mirror forms within a few seconds. the precipitate disappears owing to the formation of dicyanoargentate ions: AgCN!+CN--+ [Ag(CNh]- 8. Into this test-tube pour 2 ml silver nitrate (O·IM) and 2 ml distilled water. the precipitate decomposes and brown silver oxide precipitate is formed: Ag 2C0 3! --+ Ag 20!+C0 2i 2Ag+ + CO 2 i + H 20 --+ 2[Ag(NH 3h]+ +CO~--+ Nitric acid (a) and ammonia solution (b) dissolve the precipitate Ag 2C0 3! + 2H+ Ag 2C0 3!+4NH 3 (a) (b) Carbon dioxide gas is evolved in reaction (a). Potassium cyanide (POISON) when added dropwise to a neutral solution of silver nitrate: white precipitate of silver cyanide: Ag" + CN--+ AgCN! When potassium cyanide is added in excess. then with distilled water. Then add dilute ammonia (2M) dropwise. rinse cautiously with running cold water. Then add 2 ml saturated hydrazine sulphate solution and shake the mixture vigorously. 9. 10. silver adheres to the glass walls forming an attractive mirror. mixing the solution vigorously by shaking. Next day empty the test-tube. forms finely divided silver metal. and set aside overnight. Disodium hydrogen phosphate in neutral solution: yellow precipitate of silver phosphate: 3Ag+ + HPOi--+ Ag 3P04!+H+ --+ --+ Nitric acid (a) and ammonia solution (b) dissolve the precipitate: Ag 3P04! + 3H+ Ag 3P04! +6NH 3 3Ag+ + H 3P04 3[Ag(NH 3h]+ +POl(a) (b) Phosphoric acid. Hydrazine sulphate (saturated): when added to a solution of diammineargentate ions. 207 .6 7. which is only slightly dissociated if nitric acid is present in excess. Sodium carbonate: yellowish-white precipitate of silver carbonate: 2Ag+ + CO~--+ Ag 2C0 3! When heating. Procedure: Fill two-thirds of a test-tube with chromosulphuric acid (concentrated).

a white malleable bead without an incrustation of the oxide results. p-Dimethylaminobenzylidene-rhodanine (in short: rhodanine reagent. but not by very dilute sulphuric acid (difference from lead). in the latter case the excess of the reagent is extracted with diethyl ether or amyl alcohol. Group reaction: precipitates of different colours. the copper sub-group and the arsenic sub-group. HIGHLY POISONOUS) solution to the test solution then follow the procedure given above. LEAD(lI). antimony(III) sulphide Sb 2S3 (orange). While 208 . and palladium salts form similar compounds and therefore interfere. antimony(V) sulphide (orange). a little of the clear filtrate is treated on a spot plate with a drop of the reagent and 2 drops nitric acid (2M). copper. CADMIUM(II). and silver chloride) (Group I).III. The basis of this division is the solubility of the sulphide precipitates in ammonium polysulphide. tin(II) sulphide SnS (brown). 0'3 % solution in acetone): reddish-violet precipitate in slightly acidic solutions: HN-CO I SC \ / I C=CH 0/ ~ \\ I. II CH 3 AgN-CO N \ I + Ag" . mercury(l) chloride. this is readily soluble in nitric acid. Cations of the second group are traditionally divided into two sub-groups. Alternatively. copper(II) sulphide CuS (black). Dry test (blowpipe test) When a silver salt is heated with alkali carbonate on charcoal. COPPER(lI). bismuth(III) sulphide Bi2S3 (brown). 12. the mixture is treated with 10 per cent potassium cyanide solution whereby mercury(II) cyanide. then I drop of the reagent. mercury. platinum. cadmium sulphide CdS (yellow). gold. or palladium first add 1 drop potassium cyanide (10 %. AND TIN (11) AND (IV) Group reagent: hydrogen sulphide (gas or saturated aqueous solution).7 QUALITATIVE INORGANIC ANALYSIS reaction 3). ARSENIC (Ill) AND (V). gold. when violet specks of the silver complex will be visible under the yellow solvent layer. platinum. The silver mirror can be removed most easily by dissolving it in nitric acid (8M). Spot test: To I drop of the test solution add I drop nitric acid (2M). and tin(lV) sulphide SnS 2 (yellow). To detect silver in a mixture of lead chloride. and dicyanoargentate [Ag(CN 2]-are formed: after filtration (or centrifugation). or in a semimicro test tube. lead(II) sulphide PbS (black). A red-violet precipitate or stain is formed if silver ions are present. 11. ANTIMONY (Ill) AND (V). nI..7 SECOND GROUP OF CATIONS: MERCURY(II).SC \ / I C=CH -Q-'\:: / _ CH 3 N \ S CH 3 S CH 3 Mercury. BISMUTH(lII). The solution is immediately precipitated by dilute hydrochloric acid. mercury(II) sulphide HgS (black). arsenic(V) sulphide (yellow). arsenic(III) sulphide AS2S3 (yellow). In the presence of mercury. the test may be performed on a spot plate. A red colouration is formed in the presence of Ag in weakly acid solution.

MERCURY(II) The most important physical and chemical properties of the metal were described in Section 111. nitrates. which acts partly as an oxidizing agent. it is tetravalent in the thiostannate ion.5. arsenic(III) oxide can be dissolved in hydrochloric acid. 209 . Reactions oflead(II) ions were already described with those of the cations of the first group (see Section I1I. copper(II). and carbonates are insoluble. The copper sub-group consists of mercury(II). arsenic(V). antimony(V).4). and cadmium(II).+ 3H 20 The dissolution of sulphides in ammonium polysulphide can be regarded as the formation of thiosalts from anhydrous thioacids. Thus the dissolution of arsenic(III) sulphide (anhydrous thioacid) in ammonium sulphide (anhydrous thiobase). (6M) and arsenic(III) cations are formed: AS20 3 + 6HCI -+ 2As H + 6CI. On the other hand. The sulphides. cyanide ions. yields the formation of ammonium. etc. to dissolve the latter. antimony(III). copper(II). antimony(V). The chlorides. The oxidation-reduction potentials of the arsenic(V)-arsenic(III) and antimony(V)-antimony(III) systems vary with pH. ammonium polysulphide is needed. The arsenic sub-group consists of the ions arsenic(III). Some of the cations of the copper sub-group (mercury(II). antimony(III).8 MERCURY. and sulphates of the cations of the copper sub-group are quite soluble in water. tin(II) and tin(IV). These ions have amphoteric character: their oxides form salts both with acids and bases.and thio-arsenite ions (ammonium thioarsenite: a thiosalt): AS2S 3! + 3S2 -+ 2AsS~- All the sulphides of the arsenic sub-group dissolve in (colourless) ammonium sulphide except tin(II) sulphide. and cadmium(II)) tend to form complexes (ammonia. and tin(IV) ions respectively. Arsenic(III).). I1I. this precipitation is rather incomplete owing to the relatively high solubility of lead(II) chloride. lead(II). and tin(II) ions can be oxidized to arsenic(V).REACTIONS OF CAnONS ms sulphides of the copper sub-group are insoluble in this reagent. therefore the oxidation or reduction of the relevant ions can be assisted by choosing an appropriate pH for the reaction. those of the arsenic sub-group do dissolve under the formation of thiosalts. Although the bulk oflead(II) ions are precipitated with dilute hydrochloric acid together with other ions of Group I. Thus. hydroxides.+ 3H 20 At the same time arsenic(III) oxide dissolves in sodium hydroxide (2M). In the course of systematic analysis therefore lead ions will still be present when the precipitation of the second group of cations is the task. Hg (A r : 200·59) . thiostannate ions being formed: SnS! + S~-+ SnS~- Note that while tin is bivalent in the tin(II) sulphide precipitate. the latter three can be reduced by proper reducing agents. bismuth(III). when arsenite anions are formed: AS 20 3 +60H-+ 2AsO~.

essentially it consists of mercury(II) oxide and mercury(II) amidonitrate: 2Hg2+ + N0 3 + 4NH 3 + H 20 --+ HgO. Sodium sulphide (2M) dissolves the precipitate when the disulphomercurate(II) complex ion is formed: HgS! + S2.54). Hydrogen sulphide (gas or saturated aqueous solution): in the presence of dilute hydrochloric acid.III. alkali hydroxides. to form sulphuric acid: 2HN0 3 + S! --+ SOi + 2H+ + 2NOj 2. if added in stoichiometric amounts the precipitate turns to yellow when mercury(II) oxide is formed: Hg2+ + 20H- --+ HgO! + H 20 The precipitate is insoluble in excess sodium hydroxide. hot dilute nitric acid. sublimes at atmospheric pressure.--+ [HgS 2]2Adding ammonium chloride to the solution. Sodium hydroxide when added in small amounts: brownish-red precipitate with varying composition. Acids dissolve the precipitate readily. = 4 x 10. The precipitate is insoluble in water. Potassium iodide when added slowly to the solution: red precipitate of mercury(II) iodide: Hg2+ +21210 --+ Hg12! . Ammonia solution: white precipitate with a mixed composition. 1. and can be used to differentiate mercury(II) from mercury(I). which however dissolves readily if the solution is heated. initially a white precipitate of mercury(II) chlorosulphide (a). (a) 3Hg2+ +2CI. like most of the mercury compounds. 3. Aqua regia dissolves the precipitate: 3HgS! + 6HCI + 2HN0 3 --+ 3HgCl 2 + 3S! + 2NOj + 4H 20 Mercury(II) chloride is practically undissociated under these circumstances. Hg(NH 2)N0 3! + 3NH1 The salt. 4. which decomposes when further amounts of hydrogen sulphide are added and finally a black precipitate of mercury(II) sulphide is formed (b). mercury(II) sulphide precipitates again. This reaction is characteristic for mercury(II) ions.+2H 2S --+ Hg 3S 2CI2!+4H+ Hg 3S 2CI2!+H2S --+ 3HgS!+2H+ +2CI(b) Mercury(II) sulphide is one of the least soluble precipitates known (K. Sulphur remains as a white precipitate.8 QUALITATIVE INORGANIC ANALYSIS Reactions ofmercury( /I) ions The reactions of mercury(II) ions can be studied with a dilute solution of mercury(II) nitrate (O·05M). or (colourless) ammonium sulphide.

If more reagent is added. Tetraiodomercurate(lI) ions are first produced: Hg2+ +4r --+ [HgI 4] 2- these react with the complex diencuprate ions.38. Aniline adjusts the pH of the solution to an appropriate value. and molybdenum do interfere. mercury(l) chloride is further reduced and black precipitate of mercury is formed: Hg 2C1 2! + Sn2+ --+ 2Hg! + Sn 4 + + 2Cl- Spot test in the presence of aniline: Treat a drop of the test solution on a filter paper or a spot plate with a drop of tin(lI) chloride solution and a drop of aniline. A brown or black stain of mercury metal is produced.5. Potassium cyanide (POISON): does not cause any change in dilute solutions (difference from other ions of the copper sub-group). 5.5. in oxidation-reduction titrations. Copper sheet or coin reduces mercury(lI) ions to the metal: Cu + Hg2+ --+ Cu2+ + Hg] For practical hints for the test see Section 111. silky precipitate of mercury(l) chloride (calomel) : 2Hg2+ + Sn2+ + 2Cl--+ Hg 2C1 2! + Sn 4 + This reaction is widely used to remove the excess of tin(lI) ions. Tin(II) chloride: when added in moderate amounts: white.8 The precipitate dissolves in excess reagent. 8. when colourless tetraiodomercurate(lI) ions are formed: Hgl 2 +21--+ [HgI 4 ] 2 - An alkaline solution of potassium tetraiodomercurate(lI) serves as a selective and sensitive reagent for ammonium ions (Nessler's-reagent cf. reaction 14. Diencuprato(II) sulphate* reagent in the presence of potassium iodide: dark blue-violet precipitate in neutral or ammoniacal solution. 6. gold. Section 111. silver. Diphenylcarbazide reacts with mercury(lI) ions in a similar way to mercury(I). forming diencuprato(II)tetraiodomercurate(lI) precipitate: [Cu(enh]2+ + [HgI 4 ] 2 --+ [Cu(enh] [HgI 4 ] ! The reaction is a sensitive one but cadmium ions. * 'en' is the usual short form of ethylenediamine H 2N-CH 2--CH 2--NH 2 " 211 . 9.REACTIONS OF CATIONS III. For details see Section 111. 7. interfere. reaction 2). at which antimony does not interfere. Bismuth and copper also have no effect. which form a similar complex salt. reaction 12. used for prior reduction.

Bi(OHh is a weak base. 11.5. 1. reddishwhite metal. A deep-blue crystalline precipitate of cobalt tetrathiocyanatomercurate(II) is formed: Hg2+ +Co2+ +4SCN- --+ Co[Hg(SCN)4]! Drop test: Place a drop of the test solution on a spot plate.+ 3H 2Si Hot dilute nitric acid dissolves bismuth sulphide.9 QUALITATIVE INORGANIC ANALYSIS 10.+3S0 2i+6H 20 (a) (b) (c) Bismuth forms tervalent and pentavalent ions. bismuth salts therefore hydrolyse readily. which contains about 3-4 per cent nitric acid. BiO+ forms insoluble salts. For practical hints see Section 10. like bismuthyl chloride. irrespective of their valency state. The hydroxide. Concentration limit: I in 105. 10. A blue colour is produced in the presence of mercury(II) ions. leaving behind sulphur in the form of a white precipitate: Bi2S3!+8H+ +2N0 3 212 --+ 2Bi3+ +3S!+2NOi +4H 20 . Bi2S3! +6HCl --+ 2Bi3+ + 6Cl. Sensitivity: O' 5 ~g Hg2+.+NOi+2H 20 2Bi+6H 2S04 --+ 2Bi3+ +3S0i. when the following process occurs: Bi3+ +H 20 +=t BiO+ +2H+ The bismuthyl ion. Boiling concentrated hydrochloric acid dissolves the precipitate.III. 2Bi + 8HN0 3 --+ 2Bi3+ + 6N0 3 + 2NOi + 4H 20 Bi+3HC1+HN0 3 --+ Bi3+ +3Cl. aqua regia (b). or hot. Hydrogen sulphide (gas or saturated aqueous solution): black precipitate of bismuth sulphide: 2Bi3+ + 3H 2S --+ Bi2S3! + 6H+ The precipitate is insoluble in cold. when hydrogen sulphide gas is liberated. form mercury metal when heated with excess anhydrous sodium carbonate. but dissolves in oxidizing acids such as concentrated nitric acid (a). Cobalt (ll) thyocyanate test To the test solution add an equal volume of the reagent (about 10 %' freshly prepared). and stir the wall of the vessel with a glass rod. If we want to keep bismuth ions in solution.9 BISMUTH. Pentavalent bismuth forms the bismuthate Bi0 3 ion. we must acidify the solution. Reactions ofbismuth (Ill) ions These reactions can be studied with a O'2M solution of bismuth(III) nitrate. Bi (A r : 208'98) Bismuth is a brittle. dilute acid and in ammonium sulphide. add a small crystal of ammonium thiocyanate followed by a little solid cobalt(II) acetate. It is insoluble in hydrochloric acid because of its standard potential (O'2V). concentrated sulphuric acid (c). reaction IS. BiOC1. Tervalent bismuth ion BP+ is the most common. It melts at 271'5°C. Dry test All mercury compounds. when the above equilibrium shifts towards the left. crystalline. with most ions. Most of its salts are insoluble in water.

-+ Bi(OHh!+3HCNj The precipitate is insoluble in excess reagent (distinction from cadmium ions). when yellowish-brown bismuthate ions are formed: BiO. Sodium tetrahydroxostannate(II) (O'125M. when bismuth metal and hexahydroxostannate(IV) ions are formed (b): (a) BP+ + 30H. 3.9 2. cf. reaction 3). freshly prepared): in cold solution reduces bismuth(III) ions to bismuth metal which separates in the form of a black precipitate.-+ 2Bi! + 3[Sn(OH)6]2(b) 213 . it turns orange. the precipitate loses water and turns yellowish-white: Bi(OHh! -+ BiO. The approximate chemical reaction is: BP+ + N0 3 + 2NH 3 + 2H 20 -+ Bi(OHhN0 3! + 2NHt The precipitate is insoluble in excess reagent (distinction from copper or cadmium). Heating the precipitate with water.REACTIONS OF CATIONS 111. OH! + H 202 -+ Bi0 3 + H+ + H 20 4. Potassium cyanide (POISON): white precipitate of bismuth hydroxide. The precipitate is soluble in acids: Bi(OHh! + 3H+ -+ Bi3+ + 3H 20 When boiled. when orange-coloured tetraiodo-bismuthate ions are formed: Bi1 3! + 1. First the sodium hydroxide present in the reagent reacts with bismuth(III) ions (a. the above reaction is reversed and black bismuth iodide is reprecipitated. 2-3 mg bismuth dissolved per 100 ml sodium hydroxide (2M). Sodium hydroxide: white precipitate of bismuth(III) hydroxide: Bi3+ + 30H- -+ Bi(OHh! The precipitate is very slightly soluble in excess reagent in cold solution.+=t [BiI 4]When diluted with water.-+ Bi1 3! The precipitate dissolves readily in excess reagent. Ammonia solution: white basic salt of variable composition. owing to the formation of bismuthyl iodide: Bi1 3! + H 20 -+ BiOI! + 2H+ + 215. 6. OH! + H 20 Both the hydrated and the dehydrated precipitate can be oxidized by 4-6 drops of concentrated hydrogen peroxide. The reaction is a hydrolysis: Bi3+ +3H 20+3CN. Potassium iodide when added dropwise: black precipitate of bismuth(III) iodide: Bi3+ + 31.-+ Bi(OHh! 2Bi(OHh! + 3[Sn(OH)4]2. bismuth(III) hydroxide then is reduced by tetrahydroxostannate(II) ions.

one drop lead nitrate. On a spot plate. which is soluble in dilute mineral acids. as in a catalytic process). that the inductor is used up itself in the course of the reaction (and not regenerated. I drop potassium cyanide (POISON). A brown to black colouration (precipitate) is characteristic for bismuth. Disodium hydrogen phosphate: white. Section 111. and 2 drops freshly prepared sodium tetrahydroxostannate(lI) reagent. In the presence of bismuth the reaction is accelerated. when tin metal is formed as a black precipitate: 2[Sn(OH)4]2--+ Sn] + [Sn(OH)6]2. and mercury interfere with the reaction. copper. lead(II).+ 20H- Note that tin is tetravalent in the hexahydroxostannate(IV) ion. mix a drop of the test solution. bismuth induces the reduction oflead).+ [Sn(OH)4]2(slow») Pb! + [Sn(OH)6]2. Test by induced reaction: In the absence of bismuth(lIl) ions the reaction between tetrahydroxoplumbate(II) ions (cf. crystalline precipitate of bismuth phosphate: Bi3+ + HPO:. at the same time bismuth is also precipitated: [Pb(OH)4]2. a white precipitate of the corresponding basic salt is produced. They have to be distinguished from catalytic processes by the fact. --+ BiP04! + H+ the precipitate is only sparingly soluble in dilute mineral acids (distinction from mercury(II). and the test must be carried out in cold. Water When a solution of a bismuth salt is poured into a large volume of water. Induced reactions are quite common among oxidationreduction processes.4. Disodium hydrogen arsentate reacts in an analogous way.+ 20H2Bi! + 3[Sn(OH)6]2- Such reactions are called induced reactions (that is. but is insoluble in tartaric acid (distinction from antimony) and in alkali hydroxides (distinction from tin). Heating accelerates the decomposition. and cadmium ions).+ 20H- With dilute solutions (using O'25M lead nitrate and O'125M sodium tetrahydroxostannate(lI) reagent) the formation of the black precipitate of lead metal is not observable within an hour.111. Silver. 7. Bi3+ +N0 3 +H 20 Bi3++CI-+H 20 --+ --+ BiO(N0 3)!+2H+ BiO. The reagent slowly decomposes by disproportionation. 214 --+ BiAs04! + H+ .9 QUALITATIVE INORGANIC ANALYSIS The reagent must be freshly prepared.CI!+2H+ 8. reaction 4) and tetrahydroxostannate(lI) is slow: [Pb(OH)4]2. copper(II).+ [Sn(OH)4]22Bi(OHh! + 3[Sn(OH)4]2 (fast») (fast») Pb! + [Sn(OH)6]2. Copper can be made inactive by the addition of some potassium cyanide. the product is the white bismuth arsenate precipitate: Bi3+ + HAsO:.

lead. 13. iron(III). The thicknesses of the rings will depend upon the relative concentrations of the various metals. Antimony interferes and should be absent. Sensitivity: 6 ~g Bi3+. due to bismuth. (ii) an orange ring. Medium-concentrated nitric acid (8M) dissolves copper readily: 3Cu + 8HN0 3 -+ 3Cu2+ + 6N0 3 + 2NOj + 4H 20 215 .REACTIONS OF CATIONS 111.freshly prepared) reagent. When a bismuth compound is heated on charcoal with sodium carbonate in the blowpipe flame. containing the mercury. Thiourea (10 %): intense yellow complex with bismuth(III) ions in the presence of dilute nitric acid. Concentration limit: I in 350. Test onfilter paper: Moisten a piece of drop-reaction paper with the reagent and place a drop of the slightly acid test solution upon it.000. silver(I). when added in slight excess to a hot.10 9. H BiI4 ! If other halide ions are absent. Lead. and chromate ions interfere and should therefore be absent. Nevertheless. 10. The test is a very sensitive one. or in a micro test-tube. copper. and mercury salts interfere because they react with the iodide. When a drop of the test solution containing bismuth. An orange-red spot is obtained. four zones can be observed: (i) a white central ring. surrounded by a yellow incrustation of the oxide. faintly acid solution of bismuth ions: yellow precipitate of bismuth pyrogallate: Bi + C 6HiOHh -+ Bi(C6H 303 )! + 3H+ It is best to neutralize the test solution first by ammonia against litmus paper. Cinchonine-potassium iodide reagent (1 %): orange-red colouration or precipitate in dilute acid solution. which is soft. and (iv) a brown ring of iodine liberated by the reaction with copper. and mercury ions is placed upon absorbent paper impregnated with the reagent. although in the presence of oxygen some dissolution might take place. III. and ductile. 8-Hydroxyquinoline (5 %) and potassium iodide (6M) in acidic medium: red precipitate of 8-hydroxyquinoline-tetraiodobismuthate Bi3++ C 9H 70N + H+ + 4r -+ C 9H 70N. is obtained. (iii) a yellow ring of lead iodide. Concentration limit: I in 3 x 104 . The test may be carried out on drop-reaction paper. It melts at 1038°C. Sensitivity: 0'15 ~g Bi. and then the reagent. the reaction is characteristic for bismuth. Because of its positive standard electrode potential (+0'34 V for the Cu(Cu2+ couple) it is insoluble in hydrochloric acid and in dilute sulphuric acid. The test may also be carried out on a spot plate. 11. then add some drops of dilute nitric acid. 12. Cu (A r : 63'54) Copper is a light-red metal. antimony(III). a brittle bead of metal. Pyrogallol (lO%. on a spot plate.tO COPPER. Mercury(I). Dry test (blowpipe test). malleable. and are fixed in distinct zones. copper. bismuth may be detected in the presence of salts of these metals as they diffuse at different rates through the capillaries of the paper.

when colourless tetracyanocuprate(I) ions and disulphide ions are formed: 2CuS! + 8CN.+ 2NOj + 4H 20 There are two series of copper compounds. ammonium sulphide.-+ 2[Cu(CN)4r. brownish-black precipitate or colouration is obtained. Copper(II) salts are generally blue both in solid. for the sake of simplicity they will be denoted in this text as the bare copper(II) ions CUH. therefore only the reactions of the copper(II) ion are described. 1.10 QUALITATIVE INORGANIC ANALYSIS Hot. Anhydrous copper(II) salts. most of the copper(I) salts are insoluble in water their behaviour generally resembling that of the silver(I) compounds. Concentration limit: I in 5 x 106 .e. Hydrogen sulphide (gas or saturated aqueous solution): black precipitate of copper(II) sulphide: CUH + H 2S -+ CuS! + 2H+ Ks(CuS. The limit of visibility of the colour of the tetraquocupratefll)' complex (i. CuO. The solution must be acidic (M in hydrochloric acid) in order to obtain a crystalline. like anhydrous copper(II) sulphate CuS04. Copper(II) compounds contain the copper(II) ions Cu H. hydrated form and in dilute aqueous solution. Copper(I) compounds are derived from the red copper(I) oxide Cu 20 and contain the copper(I) ion Cu+. well-filterable precipitate.44 • Sensitivity: I ~g Cu H. sulphur is oxidized to sulphuric acid and a clear. They are readily oxidized to copper(II) compounds. in sodium hydroxide. In practice only the copper(II) ions is important.+2NOj Potassium cyanide (POISON) dissolves the precipitate. leaving behind sulphur as a white precipitate: 3CuS! + 8HN0 3 -+ 3Cu 2+ + 6N0 3 + 3S! + 2NOj + 2H 20 When boiled for longer. The precipitate is insoluble in boiling dilute (M) sulphuric acid (distinction from cadmium). the colour of copper(II) ions in aqueous solutions) is 500 ~g in a concentration limit of I in 104. which are derivable from the black copper(II) oxide. concentrated nitric acid dissolves the copper(II) sulphide.111. blue solution is obtained: S!+2HN0 3 -+ 2H+ +SO~. In the absence of acid. By adding some acid and boiling coagulation can be achieved. Reactions of copper( /I) ions These reactions can be studied with a 0'25M solution of copper(II) sulphate. concentrated sulphuric acid dissolves copper also: Cu + 2H 2S04 -+ CUH + SO~. These compounds are colourless.+ S~216 . 25°) = 10. or in very slightly acid solutions a colloidal. are white (or slightly yellow). Hot. In aqueous solutions we always have the tetraquo complex ion present. the colour is characteristic really for the teatraquocuprate(II) ion [Cu(H 20)4]2+ only.+ S02 j + 2H 20 Copper is readily dissolved in aqua regia as well : 3Cu + 6HCI + 2HN0 3 -+ 3Cu H + 6CI. and only very slightly soluble in polysulphides. sodium sulphide.

The reduction with thiosulphate yields tetrathionate ions: 13" +2S20~-+ 31. owing to the formation of tetramminocuprate(II) complex ions: Cu(OHh. but the solution is intensely brown because of the formation of tri-iodide ions (iodine): 2Cu2+ +51- -+ 2Cul!+I3" Adding an excess of sodium thiosulphate to the solution. 3. When heated. sulphur is oxidized) coupled with a formation of a complex.tO Note that this is an oxidation-reduction process (copper is reduced. If the alkaline solution is treated with certain reducing agents. 4. and acetaldehyde. which is white. copper(II) sulphide tends to oxidize to copper(II) sulphate: CuS!+20 2 -+ CuS04 and therefore becomes water soluble. 2. When exposed to air.-+ Cu(OHh! The precipitate is insoluble in excess reagent.+S40~217 .+ 20H- If the solution contains ammonium salts (or it was highly acidic and larger amounts of ammonia were used up for its neutralization). which is converted into red copper(l) oxide Cu 20 on boiling. precipitation does not occur at all. hydrazine. in the moist state. CuS0 4! + 8NH 3 -+ 2[Cu(NH 3)4]2+ + SOi. it contains the complex ion [Cu(COO. with paper or other inflammable substances in it. when a deep blue colouration is obtained. the precipitate is converted to black copper(II) oxide by dehydration: Cu(OHh! -+ CuO! + H 20 In the presence of a solution of tartaric acid or of citric acid. A filter paper with copper(II) sulphide precipitate on it should never be thrown into a waste container. The alkaline solution of copper(II) salt containing tartaric acid is usually known as Fehling's solution. Ammonia solution when added sparingly: blue precipitate of a basic salt (basic copper sulphate): 2Cu2++S0i-+2NH 3+2H 20 -+ Cu(OHh·CuS0 4!+2NHt which is soluble in excess reagent. but the precipitate should be washed away first with running water. Potassium iodide: precipitates copper(l) iodide. Sodium hydroxide in cold solution: blue precipitate of copper(II) hydroxide: Cu2+ +20H. copper(II) hydroxide is not precipitated by solutions of caustic alkalis. such as hydroxylamine. yellow copper(l) hydroxide is precipitated from the warm solution. tri-iodide ions are reduced to colourless iodide ions and the white colour of the precipitate becomes visible. A considerable amount of heat is liberated during this process. but the solution is coloured an intense blue. glucose.CHO)]2-.REACTIONS OF CATIONS m. The reaction is characteristic for copper(II) ions in the absence of nickel. but the blue colour is formed right away.

the concentration of copper(I) ions is so low) that hydrogen sulphide cannot precipitate copper(I) sulphide from this solution (distinction from cadmium. cf. 6. when dark-blue copper tetrammine ions are formed: Cu 2[Fe(CN)6]! + 8NH 3 --+ 2[Cu(NH 3)4]2+ + [Fe(CN)6]4Sodium hydroxide decomposes the precipitate. Potassium cyanide (POISON): when added sparingly forms first a yellow precipitate of copper(lI) cyanide: Cu2+ +2CN- --+ Cu(CNh! the precipitate quickly decomposes into white copper(I) cyanide and cyanogen (HIGHLY POISONOUS GAS): 2Cu(CNh! --+ 2CuCN!+(CNhi In excess reagent the precipitate is dissolved. The electrode potential of copper 218 .11. Section 111. Copper(lI) thiocyanate can be transformed to copper(I) thiocyanate immediately by adding a suitable reducing agent. 2Cu2+ + [Fe(CN)6]4- --+ Cu 2[Fe(CN)6]! The precipitate is soluble in ammonia solution. 5.e. A saturated solution of sulphur dioxide is the most suitable reagent: 2Cu(SCNh!+S02 +2H 20 --+ 2CuSCN!+2SCN. Potassium hexacyanoferrate(II): reddish-brown precipitate of copper hexacyanoferrate(lI) in neutral or acid medium. when blue copper(lI) hydroxide precipitate is formed: Cu 2[Fe(CN)6]! + 40H--+ 2Cu(OHh! + [Fe(CN)6]4- 7.42): Cu2+ +Fe --+ Fe2+ +Cu and an equivalent amount of iron dissolves. a red deposit of copper is obtained: (See Section 1. reactions I and 5).+4H+ 8. Iron If a clean iron nail or a blade of a penknife is immersed in a solution of a copper salt.10 QUALITATIVE INORGANIC ANALYSIS These reactions are used in quantitative analysis for the iodometric determination of copper. Potassium thiocyanate: black precipitate of copper(lI) thiocyanate: Cu2+ +2SCN- --+ Cu(SCNh! The precipitate decomposes slowly to form white copper(I) thiocyanate and thiocyanogen is formed: 2Cu(SCNh! --+ 2CuSCN! + (SCNh l thiocyanogen decomposes rapidly in aqueous solutions.+SOi. and colourless tetracyanocuprate(I) complex is formed: CuCN!+3CN--+ [CU(CN)4]3- The complex is so stable (i.111.

REACTIONS OF CATIONS I1I. are present. soluble in mineral acids. their precipitation can be prevented by the addition of sodium potassium tartrate (10 %). A green colouration is obtained. Place a drop of the neutral test solution upon drop-reaction paper. Mercury(I) should be absent as it gives a black stain with ammonia.CHOH. Only nickel and cobalt ions react under similar conditions yielding blue and brown precipitates respectively. but not in alkali-cyanide solutions. Sensitivity: O· 5 ~g Cu. The precipitate is formed in the presence of alkali tartrates. If other ions. Only palladium and gold interfere giving Pd(C 7H 60 2Nh and metallic gold respectively in acetic acid solution. be detected in the presence of these elements by utilizing the capillary separation method upon filter paper. In the presence of metallic salts which are precipitated by ammonia. and then hold it over ammonia vapour. 11. Treat some drop-reaction paper with a drop of the weakly acid test solution and a drop of the reagent. Sensitivity: 0'1 ~g Cu. insoluble in dilute ammonia. expose it to ammonia vapour and add a drop of the reagent.tO (more precisely of the copper--eopper(II) system) is more positive than that of iron (or the iron-iron(II) system). Place a drop of the test solution. Concentration limit: I in IOS . 10. Salicylaldoxime (1 %) forms a greenish-yellow precipitate of copper salicylaldoxime Cu(C 7H 60 2Nh in acetic acid solution. precipitable by ammonia solution. 219 .C 6H s): forms a green precipitate of copper(II) benzoinoxime CU(C1 4H ll 02N). which has been neutralized and then acidified with acetic acid in a micro test-tube and add a drop of the reagent. A yellowgreen precipitate or opalescence (according to the amount of copper present) is obtained.Benzoinoxime (or cupron) (5 %in alcohol) (C 6H s . Large amounts of ammonium salts interfere and should be removed by evaporation and heating to glowing: the residue is then dissolved in a little dilute hydrochloric acid. Copper may however.C( NOH). 9. a. Concentration limit: I in 5 x IO s. a drop of Rochelle salt solution (10 %) is placed upon the paper before the reagent is added. Rubeanic acid (or dithio-oxamide ) (0'5) H2N-C-C--NH2) ( 11 11 : S S black precipitate of copper rubeanate Cu[C( NH)S]2 from ammoniacal or weakly acid solution. they should therefore be absent. The reagent is specific for copper in ammoniacal tartrate solution. A black or greenish-black spot is produced.

then the reaction velocity. Concentration limit: I in 2 x 106 . In the presence of cobalt. hence a blank test must be carried out with the distilled water. but is enormously accelerated by traces of copper.000 times that amount of nickel. is surrounded by a yellow-brown ring of cobalt rubeanate. For smaller amounts of copper. Add to each I drop iron(III) thiocyanate (0'05M) and 3 drops sodium thiosulphate (0·5M).000 times that amount of eo balt. the composition of the precipitate is approximately Zn[Hg(SCN)4] . Concentration limit: I in 2 x 106 . the interference of iron(III) is avoided by carrying out the precipitation in the presence of alkali fluorides or oxalates. the central green or black ring. to a lesser extent. Place a drop of the acid test solution upon a spot plate. 13. Catalytic test. Iron(III) salts react with thiosulphate according to the equations Fe3+ +2S20~[Fe(S203h]. Concentration limit: I in 5 x 105 .m. The decolourization of the copper-free solution is complete in 1'5-2 minutes: if the test solution contains I ~g copper. 220 .+Fe3+ --+ --+ [Fe(S203hr 2Fe2+ +S40~- (a) (b) Reaction (a) is fairly rapid. If the reaction is carried out in the presence of a thiocyanate. Two zones or circles are formed: the central olive-green or black ring is due to copper and the outer blue-violet ring to nickel. Sensitivity: 0'25 ~g Cu in the presence of 20. In the presence of nickel. has no effect. crystalline precipitate in the presence of zinc or cadmium ions. Concentration limit: I in 2 x 105 • 12. Cobalt and nickel interfere since they yield green or blue precipitates of the corresponding tetrathiocyanatomercurates(II). The addition of copper ions to a precipitate of zinc tetrathiocyanatomercurate(II). Sensitivity: 0'05 ~g Cu in the presence of20. Concentration limit: I in 106 . which is proportional to the time taken for complete decolourization. Sensitivity: 0·1 ug Cu2+.CU[Hg(SCN)4J. add I drop zinc acetate (l %) solution and I drop of the reagent. which serves as an indicator for the presence of iron(III) ions and also retards reaction (b). may be employed for detecting minute amounts of copper(II) ions. Upon adjacent cavities of a spot plate place a drop of the test solution and a drop of distilled water. Tungsten and. The precipitated zinc tetrathiocyanatomercurate(II) is coloured violet owing to the coprecipitation of the copper complex. Sensitivity: 0·2 ~g Cu2+. the difference in times between the two tests is still appreciable. the decolourization is instantaneous.ie QUALITATIVE INORGANIC ANALYSIS Sensitivity: 0'01 ~g Cu. Impregnate drop-reaction paper with the reagent and add a drop of the test solution acidified with acetic acid. Traces of copper in distilled water give a positive reaction. selenium cause a catalytic acceleration similar to that of copper: they should therefore be absent. already formed. due to copper. reaction (b) is a slow one. proceed as follows. Ammonium tetrathiocyanatomercuratet I/) : {(NH 4h[Hg(SCN)4]} : deep-violet. (2M).

2. Ammonia solution when added dropwise: white precipitate of cadmium(II) hydroxide: Cd2+ +2NH 3+2H20 ~ Cd(OHh!+2NHt The precipitate dissolves in acid. An excess of the reagent dissolves the precipitate. e. 1.11 CADMIUM. if the concentration of strong acid in the solution is above O'5M. when the equilibrium shifts towards left. Dilute acids dissolve the precipitate by shifting the equilibrium to the left. by moistening with concentrated hydrochloric acid before heating. Borax bead Green while hot. The precipitate is insoluble in potassium cyanide (POISON) this distinguishes cadmium ions from copper. Concentrated acids dissolve the precipitate for the same reason. Cd (Ar : 112'40) Cadmium is a silver-white. Flame test Green especially in the presence of halides. precipitation is incomplete. It melts at 321°C. the sulphide is insoluble with a characteristic yellow colour. red in the reducing flame. best obtained by the addition of a trace of tin. Dry tests a.g. b. It dissolves slowly in dilute acids with the evolution of hydrogen (owing to its negative electrode potential) : Cd+2H+ -+ Cd2++H 2 i Cadmium forms bivalent ions which are colourless. HI. and sulphate are soluble in water. c. when tetramminecadmiate(II) ions are formed: Cd(OHh!+4NH 3 -+ [Cd(NH 3)4]2+ +20H- the complex is colourless. Blowpipe test When copper compounds are heated with alkali carbonate upon charcoal red metallic copper is obtained but no oxide is visible. 221 . Hydrogen sulphide (gas or saturated aqueous solution): yellow precipitate of cadmium sulphide: Cd2+ +H 2S -+ CdS!+2H+ The reaction is reversible. Sodium hydroxide: white precipitate of cadmium(II) hydroxide: Cd2+ +20H- ~ Cd(OHh! The precipitate is insoluble in excess reagent. its colour and composition remains unchanged when boiled. and blue when cold after heating in the oxidizing flame. nitrate. Reactions ofthe cadmium(lI) ions These reactions can be studied most conveniently with a O'25M solution of cadmium sulphate. 3.REACTIONS OF CATIONS HUI 14. malleable and ductile metal. Cadmium chloride.

the sensitivity is 4 ~g Cd in the presence of 400 times that amount of copper.m. 3 drops each of the potassium cyanide and formaldehyde solution should be used.u QUALITATIVE INORGANIC ANALYSIS 4. when tetracyanocadmiate(II) ions are formed: Cd(CNh!+2CN-+ [Cd(CN)4]2- The colourless complex is not too stable. 7. Introduce 1 drop of the reagent and 2 drops formaldehyde solution (40 %).+H 2S -+ CdS!+2H+ +4CNThe marked difference in the stabilities of the copper and cadmium tetracyanato complexes serves as the basis for the separation of copper and cadmium ions (cf. A brown precipitate is formed. 6. which contrasts with the blue tint of the latter. hence it is advisable to compare the colour produced in a blank test with pure water when searching for minute amounts of cadmium. when hydrogen sulohide gas is introduced. neutral or ammoniacal test solution on a spot plate and mix it with I drop sodium hydroxide (2M) solution and I drop potassium cyanide (10 %) solution.000. In the presence of considerable amounts of copper. Section 1. Sensitivity: 0'8 ~g Cd. Potassium thiocyanate: forms no precipitate (distinction from copper). which turns greenish-blue with formaldehyde. 4-Nitronaphthalene-diazoamino-azo-benzene ('Cadion 2B') (0'02 %) Cadmium hydroxide forms a red-coloured lake with the reagent. 8. Potassium cyanide (POISON): white precipitate of cadmium cyanide. cadmium sulphide is precipitated: [Cd(CN)4]2. which very rapidly becomes greenish-blue. 222 . Potassium iodide: forms no precipitate (distinction from copper). Place a drop of the acid. 5. Dinitro-p-diphenyl carbazide (0'1 %) ( 'NH-NH-Q-N0 C~:-NH-Q-N02) : 1 forms a brown-coloured product with cadmium hydroxide. when added slowly to the solution: Cd2+ +2CN~ -+ Cd(CNh! An excess ofthe reagent dissolves the precipitate.32). The reagent alone is red in alkaline solution and is coloured violet with formaldehyde. Concentration limit: 1 in 60.

Ignition test Cadmium salts are reduced by sodium oxalate to elementary cadmium. The reagent is prepared by dissolving 0'02 g 'cadion 2B' in 100 ml ethanol to which I ml 2M potassium hydroxide is added. It sublimes on heating. and magnesium is prevented by adding sodium potassium tartrate to the test solution: only silver (removed as silver iodide by the addition of a little KI solution) and mercury then interfere. the metal is converted into yellow cadmium sulphide. garlic-like odour is apparent. The interference of copper. Arsenic(III) compounds can be derived from the amphoteric arsenic trioxide AS 20 3 . In strongly acidic solutions therefore the arsenic(III) ion ASH is stable. The metallic mirror is gradually converted into the orange-coloured sulphide. iron. Allow to cool. A bright-pink spot. Sensitivity: 0'025 ~g Cd.REACTIONS OF CATIONS m. followed by sodium hydroxide solution until alkaline. a few crystals of hydroxylamine hydrochloride.g. A mirror of metallic cadmium with brown edges is produced. which is usually obtained as a metallic mirror surrounded by a little brown cadmium oxide. on heating in a free supply of air. sodium arsenite. AsCI 3 ) . and then one drop potassium hydroxide (2M). arsenic burns with a blue flame yielding white fumes of arsenic(III) oxide AS 406 . chromium. and heat. is produced.12 Place a drop of the reagent upon drop-reaction paper. nickel. The solution must not be warmed.12 ARSENIC. Blowpipe test All cadmium compounds when heated with alkali carbonate on charcoal give a brown incrustation of cadmium oxide CdO.+ 3H 20 -+ 2AsO~. Upon heating with sulphur. Mercury is best removed by adding a little sodium potassium tartrate. It is destroyed by mineral acid. surrounded by a blue circle. the mercury is precipitated as metal. and a characteristic. cobalt. 10. The element is insoluble in hydrochloric acid and in dilute sulphuric acid: it dissolves readily in dilute nitric acid yielding arsenite ions and concentrated nitric acid or in aqua regia or in sodium hypochlorite solution forming arsenate: As + 4H+ + N0 3 -+ ASH + NOj + 2H 20 3As+5HNOiconc)+2H 20 -+ 3AsO~-+5NOj+9H+ 2As + 50CI. b. Tin(II) chloride is not suitable for this reduction since most of the cadmium is adsorbed on the mercury precipitate. arsenic(III) chloride. Na 3As03 ) . add one drop of the test solution (which should be slightly acidified with acetic acid (2M) containing a little sodium potassium tartrate). Arsenic(V) compounds 223 . which yields salts both with strong acids (e. As (Ar : 74'92) . 9.ARSENIC(III) Arsenic is a steel-grey. Dry tests a. which becomes yellow after cooling.+ 5Cl. add a little flowers of sulphur and heat again.g. Do not confuse this with the yellow sublimate of sulphur. AsO~. brittle solid with a metallic lustre.+ 6H+ Two series of compounds of arsenic are common: that of arsenic(III) and arsenic(V). In strongly basic solutions the arsenite ion. and with strong bases (e. Place a little of the cadmium salt mixed with an equal weight of sodium oxalate in a small ignition tube.is the stable one. All arsenic compounds are poisonous.

ions are formed: --+ 2AsS~. which is contaminated with sulphur because of the decomposition of the excess polysulphide reagent: 2AsS~- + 6H+ --+ As 2SS! + 3H 2Sj S~. (NH4hS2 dissolves the precipitate.+AsS~- +3H 20 Ammonium sulphide also dissolves the precipitate: AS2S3 + 3S2.+2H+ --+ H 2t + S! 2. Arsenic(V) therefore exists in solutions predominantly as the arsenate AsO~. Hydrogen sulphide: yellow precipitate of arsenic(III) sulphide: 2As H + 3H 2S --+ AS2S3! + 6H+ The solution must be strongly acidic. when arsenic(III) sulphide and hydrogen sulphide are formed: AS2S3! + 3H 2Sj Yellow ammonium sulphide (ammonium polysulphide).+ 6H+ AS2S3! + 4S~. which forms salts such as sodium arsenate Na 3As04. owing to the formation of colloidal AS2S3 .III. Arsenic(III) oxide does not dissolve in cold water. As 20 S ' This is the anhydride of arsenic acid.12 QUALITATIVE INORGANIC ANALYSIS are derived from arsenic pentoxide. if there is not enough acid present a yellow colouration is visible only. Silver nitrate: yellow precipitate of silver arsenite in neutral solution (distinction from arsenates) : AsO~- + 3Ag+ --+ Ag 3As03! H 3As03 + 3Ag+ 3[Ag(NH 3h]+ +AsO~(a) (b) The precipitate is soluble both in nitric acid (a) and ammonia (b): Ag 3As03! + 3H+ Ag 3As03! + 6NH 3 224 --+ --+ . when thioarsenate AsS~. but dissolves in hot concentrated nitric acid: 3As2S3 + 26HN0 3 + 8H 20 AS 2S3+60H--+ 6AsO~. and ammonia: --+ AsO~.+9S0~- +42H+ + 26NOj It is also readily soluble in solutions of alkali hydroxides. H 3As0 4. On reacidifying these both decompose. but by boiling the mixture for 30 minutes. Na 3As03 . or sodium arsenite. The mixture can be cooled without the danger of precipitating the oxide. AS 20 3 .--+ 2AsS~In both cases thioarsenite (AsS~-) ions are formed. Reactions ofarsenic ( Ill) ions A O'IM solution of arsenic(III) oxide. dissolution is complete. 1. The precipitate is insoluble in concentrated hydrochloric acid (din tinction and method of separation from Sb 2S3 and SnS2).+ S~Upon acidifying this solution yellow arsenic(V) sulphide is precipitated.ion.--+ 2AsS~. can be used for these experiments.

copper(l) oxide is precipitated. Concentration limit: 1 in 50. and an equilibrium is reached. and the solution gently warmed. are removed by adding sodium hydrogen carbonate as a buffer. The precipitate also dissolves in sodium hydroxide solution. and 2 drops Mmagnesium sulphate solution. A brown or black precipitate or colouration is obtained. Potassium tri-iodide (solution ofiodine in potassium iodide) : oxidizes arsenite ions while becoming decolourized: AsO~- +1. Magnesia mixture (a solution containing MgCI 2 .xH 20. due to the separation of elementary arsenic. 2 drops 'lO-volume' hydrogen peroxide.+2H+ The reaction is reversible. a mixture of arsenic(III) 225 . the solution becomes dark brown and finally black. from neutral solutions. If the hydrogen ions formed in this reaction. This forms the basis of a delicate test for arsenic. Tin ( I/) chloride solution and concentrated hydrochloric acid (Bettendorff's Test) A few drops of the arsenite solution are added to 2 ml concentrated hydrochloric acid and O· 5 ml saturated tin(II) chloride solution. 6. NH 4N0 3 .000. Hydrogen sulphide: no immediate precipitate in the presence of dilute hydrochloric acid. soluble in acids. Sensitivity: 1 ~g As. by converting the arsenic into magnesium ammonium arsenate and heating to redness.7H 20 can be used for the study of these reactions.n 3.REACTIONS OF CATIONS m. NH4CI. 1. Evaporate slowly and finally heat until fuming ceases. upon boiling. Mix a drop of the test solution in a micro crucible with 1-2 drops concentrated ammonia solution.13 ARSENIC.ARSENIC(V) The properties of arsenic were summarized in Section 01. and warm slightly. variously formulated as CuHAs0 3 and CuiAs0 3 h . 10. the reaction becomes complete. Copper sulphate solution: green precipitate of copper arsenite (Scheele's green). 2As H + 3Sn2+ --+ 2As! + 3Sn4+ If the test is made with the sulphide precipitated in acid solution. 4. As (Ar : 74·92) . The solution should contain some dilute hydrochloric acid. and a little NH 3 ) . the pyroarsenate Mg 2As 207 remains and any mercury salts present are volatilized.12. 5. Treat the residue with 1-2 drops of a solution of tin(II) chloride in concentrated hydrochloric acid. and a little NH 3 ) : no precipitate (distinction from arsenate). only mercury will interfere. Reactions of arsenate ions A O·lM solution of disodium hydrogen arsenate Na 2HAs04. +H 20 --+ AsO~- +31. and also in ammonia solution forming a blue solution. If the passage of the gas is continued. A similar result is obtained with the magnesium nitrate reagent (a solution containing Mg(N0 3 h.

+ 6H+ AsO~. hexacyanoferrate(lI) and (Ill) ions.+ 3C0 2 --+ (a) (b) (c) (d) Upon acidifying these solutions with hydrochloric acid. say. like the trisulphide. on conducting hydrogen sulphide into the warm reduced solution immediate precipitation of arsenic trisulphide occurs. ammonium polysulphide (c). AsO~. in the hot solution. and sulphur is slowly precipitated.+ S! 2. AsO~- + 3Ag+ --+ Ag 3As04! This reaction may be adapted as a delicate test for arsenic in the following manner.+ AS0 3S 3 . sodium or ammonium carbonate (d): As 2SS! + 60HAs 2SS! + 3S2As 2Ss! + 6S~As 2SS! + 3CO~--+ AsS~- + AS0 3S 3 . to iodide: 12 + H 2S --+ 2H+ + 21. The iodide acts as a catalyst in that it reduces the arsenic acid thus: --+ 2AsS~. 2AsO~-+5H2S+6H+ --+ As 2SS!+8H 20 Arsenic pentasulphide.+21- +2H+ --+ AsO~- +1 2 +H 20 The iodine liberated is reduced. ammonium sulphide (b). Silver nitrate solution: brownish-red precipitate of silver arsenate Ag 3As04 from neutral solutions (distinction from arsenite and phosphate which yield yellow precipitates). The precipitation can be greatly accelerated by the addition of small amounts of an iodide. sulphur dioxide may be passed into the slightly acid solution in order to reduce the arsenic to the tervalent state and then the excess of sulphur dioxide is boiled off. Precipitation is more rapid in hot solution. the precipitate consists of a mixture of the tri. yellow arsenic pentasulphide As 2SS is precipitated. and a little concentrated hydrochloric acid.+ 3H 20 --+ 2AsS~- 2AsS4 + 3S~--+ AsS~. is readily soluble in alkali hydroxides or ammonia (a). in turn. The test is applicable only in the absence of chromates.111. which also give coloured silver salts insoluble in acetic acid. 226 .13 QUALITATIVE INORGANIC ANALYSIS sulphide. soluble in acids and in ammonia solution but insoluble in acetic acid. I ml of a 10 per cent solution.and penta-sulphides. arsenic pentasulphide is reprecipitated: As 2SS! + 3H 2Sj For the rapid precipitation of arsenic from solutions of arsenates without using a large excess of hydrochloric acid.+H 2S --+ AsO~2AsO~.+ 3H 2S + 6H+ --+ +S!+H 20 AS2S3! + 6H 20 If a large excess of concentrated hydrochloric acid is present and hydrogen sulphide is passed rapidly into the cold solution. AS2S3 .

reaction 5). oxidizing agents must be absent. the latter is coloured blue by the iodine.+ 12MoO~. Sensitivity: 6 ~g As.+2H+ +21. AsOl. The composition of the precipitate should be written as (NH 4h[As(Mo 30 1 0 ) 4 ]. the precipitate is obtained in granular form.+1 2!+H 20 The reaction is reversible (cf.+3NHt +24H+ --+ (NH 4h AsMo 1204 0!+ 12H20 The precipitate in fact contains trimolybdate (Mo 30io) ions. The reaction may be used for the detection of arsenate in the presence of arsenite. iodine is precipitated. This test provides an excellent method of distinction from arsenites. red silver arsenate is formed (distinction from phosphate) : MgNH 4As04! + 3Ag+ --+ Ag 3As04! + Mg2+ + NHt 4. each replacing one oxygen in AsOl-. Section 111. reaction 3): white.12. a yellow crystalline precipitate of ammonium arsenomolybdate.+Mg2+ +NHt --+ MgNH 4As04! For some purposes (e.g. but dissolves in ammonia solution and in solutions of caustic alkalis. and a little NH 3 ) .be present to complete this reaction. and warm.+ UO~+ + NHt --+ U0 2NH4As04! 227 . which do not give a precipitate with the reagent (an approximately O'IM solution ofuranyl acetate).n Place a drop of the test solution in a micro crucible. the detection of arsenate in the presence of phosphate). 3. Ammonium molybdate solution: when the reagent and nitric acid are added in considerable excess to a solution of an arsenate. and from phosphates which yield a precipitate in the cold or upon gentle warming). add a few drops of concentrated ammonia solution and of'IO-volume' hydrogen peroxide. 6.12. A brownish-red precipitate or colouration appears. Concentration limit: I in 8. Uranyl acetate solution: light yellow. Magnesia mixture (see Section 111. 5. soluble in mineral acids but insoluble in acetic acid. (NH 4h AsMo 1204 0 is obtained on boiling (distinction from arsenites which give no precipitate.~ AsO~. Potassium iodide solution: in the presence of concentrated hydrochloric acid. a large amount of acid must. gelatinous precipitate of uranyl ammonium arsenate UOiNH 4)As04 . Upon treating the white precipitate with silver nitrate solution containing a few drops of acetic acid. AsOl. upon shaking the mixture with 1-2 ml of chloroform or of carbon tetrachloride. it is better to use the magnesium nitrate reagent (a solution containing Mg(N0 3 h. NH 4CI. The precipitate is insoluble in nitric acid. Acidify with acetic acid and add 2 drops silver nitrate solution. AsOl.REACTIONS OF CAnONS m. xH 20 in the presence of excess of ammonium acetate.000. crystalline precipitate of magnesium ammonium arsenate Mg(NH 4)As04 • 6H 20 from neutral or ammoniacal solution (distinction from arsenite): AsOl. If precipitation is carried out from a hot solution of an arsenate.

arsenic compounds.+6H+ The Marsh test is best carried out as follows. composed of hydrogen and arsine (after all the air has been expelled from the apparatus). constricted twice near the middle to about 2 mm diameter. The following reactions take place during these operations. On igniting the mixed gases. c. (i) Marsh's test This test.1 228 . mixed with hydrogen.l. a colourless. The apparatus is fitted up as shown in Fig. if desired. 25 cm long and 7 mm diameter. extremely poisonous gas with a garlic-like odour. If the gas. a black deposit of arsenic is obtained on the cool surface.+4Zn+ IIH+ 4AsH 3 i -+ (heat) 2AsH 3 i + 30 2 2As!+50Cl. A B C CaCl 2 ~iL---Glass wool moistened with Pb (CH 3COOh solution Fig.14 QUALITATIVE INORGANIC ANALYSIS III.111. they burn with a livid blue flame and white fumes of arsenic(I1I) oxide are evolved. which must be carried out in the fume chamber. and play an important role in forensic analysis. the distance between the constrictions being 6-8 cm. A conical flask of about 125 ml capacity is fitted with a two-holed rubber stopper carrying a thistle funnel reaching nearly to the bottom of the flask and a 5-7 mm right-angle tube. is based upon the fact that all soluble compounds of arsenic are reduced by 'nascent' hydrogen in acid solution to arsine. then to a small tube containing anhydrous calcium chloride of about 8 mesh. AsH 3 . if the inside of a small porcelain dish is pressed down upon the flame. the latter is attached by a short piece of 'pressure' tubing to a U-tube filled with glass wool moistened with lead acetate solution to absorb any hydrogen sulphide evolved (this may be dispensed with. I1I. The drying tubes and the tube ABC are securely supported by means of clamps.+5CI. ASH + 3Zn + 3H+ AsO~. as its efficacy has been questioned). which is deposited as a brownish-black 'mirror' just beyond the heated part of the tube. and the deposit is readily soluble in sodium hypochlorite or bleaching powder solution (distinction from antimony).14 SPECIAL TESTS FOR SMALL AMOUNTS OF ARSENIC These tests are applicable to all. is conducted through a heated glass tube.+3H 20 -+ -+ -+ -+ -+ AsH 3 i + 3Zn2+ AsH 3 i+4Zn2+ +4H 20 4As! + 6H 2 i AS 20 3 + 3H 20 2AsO~. III. it is decomposed into hydrogen and metallic arsenic. then to a hard glass tube.

g. Heat the tube at A to just below the softening point. Filter paper moistened with AgN0 3 solution Cotton wool =t---Dilute H 2S04 'l!S:!ii". When a satisfactory mirror has been obtained. III. and test the solubility of the black or brownish deposit in sodium hypochlorite solution. if necessary. Hold a cold porcelain dish in the flame. The silver nitrate reaction (sometimes known as Hofmann's test) is very useful as a confirmatory test.Zinc Fig. The purity of the reagents is tested by passing the gases.Zo\>'--. a mirror of arsenic is deposited in the cooler.14 All reagents must be arsenic-free. the absence of a black precipitate or suspension proves that appreciable quantities of arsenic are not present. the chief difference being that only a test-tube is required and the arsine is detected by means of silver nitrate or mercury(I1) chloride. Place 15-20 grams of arsenic-free zinc in the flask. If much arsenic is present. by means of a delivery tube attached by a short piece of rubber tubing to the end of C. A second flame may be applied at B to ensure complete decomposition (arsine is extremely poisonous). loosely plug the tube with purified cotton wool and then place a piece of filter paper moistened with 20 per cent 229 . Nowadays the mirror test is usually applied. e. The black precipitate is silver: AsH 3 i + 6Ag+ -+ ASH + 3H+ + 6Ag! The solution containing the arsenic compound is then added in small amounts at a time to the contents of the flask. add 5-7 ml dilute sulphuric acid. by hydrogen sulphide after removing the excess of silver nitrate with dilute hydrochloric acid. (ii) Gutzeit's test This is essentially a modification of Marsh's test.2 The original Marsh test involved burning and deposition of the arsenic upon a cold surface. through silver nitrate solution for several minutes. add dilute sulphuric acid (l : 3) until hydrogen is vigorously evolved. Smaller amounts of arsenic may be present in the silver nitrate solution as arsenious acid and can be detected by the usual tests. Place 1-2 g arsenic-free zinc in a test-tube. less constricted portion of the tube. Disconnect the rubber tube at C.REACTIONS OF CAnONS III. there will be an almost immediate blackening of the silver nitrate solution. remove the flames at A and B and apply a light at C. or by neutralizing and adding further silver nitrate solution.

The use of mercury(lI) chloride paper. It may be necessary to warm the tube gently to produce a regular evolution of hydrogen. and on top of this place a disc of drop-reaction paper impregnated with 20 per cent silver nitrate solution. Hydrogen sulphide. A blank test must be performed with the reagent in all cases.3. remove the filter paper and examine the two spots. 3AgN0 3 . replace the cotton wool and silver nitrate paper. In this reaction gold is formed: AsH + 2Au H -+ ASH + 2Au! + 3H+ 3 The test may be performed on the semimicro scale with the aid of the apparatus shown in Fig. and allow to stand.2). prepared by immersing filter paper in a 5 per cent solution of mercuric chloride in alcohol and drying in the atmosphere out of contact with direct sunlight.l4 QUALITATIVE INORGANIC ANALYSIS silver nitrate solution on top of the tube (Fig. If much arsenic is present. Warm the test-tube gently (if necessary) on a water bath to accelerate the reaction. 111. will appear black.1II. and stibine SbH 3 . due to the complex Ag 3As. 230 . phosphine PH 3 . constitutes an improvement. remove the filter paper and examine the part that covered the test-tube. say 2 minutes. givea similar reaction. the latter displaced so that a fresh portion is exposed. Insert a loose wad of pure cotton wool moistened with lead nitrate solution in the funnel. the paper may be held in position by a watch glass or microscope slide. Filter paper.2H 20. A grey spot will be obtained. may also be employed when a dark-red to blue-red stain is produced. At the end of a definite period. 111. add I ml of the solution to be tested. Place 10 drops of the test solution in the semimicro test- Fig. this is occasionally yellow. usually a light-brown spot is obtained owing to the traces of arsenic present in the reagents. add a few granules of arsenic-free zinc and I ml dilute sulphuric acid. I1L3 tube. impregnated with a 0'3M aqueous solution of 'gold chloride' NaAuCI4. This is turned yellow by a little arsine and reddish-brown by larger quantities. They may be removed by means of a purified cotton-wool plug impregnated with copper(I) chloride. Remove the cotton-wool plug. Examine the silver nitrate paper after about 5 minutes. assuming that the rate of evolution of gas is approximately the same. After 2 minutes. the second spot (due to metallic silver).

A more sensitive test is provided by drop-reaction paper impregnated with gold chloride reagent (a 0'3M solution of NaAuCI 4 • 2H 2 0 ). when it will be seen to consist of colourless octahedral and tetrahedral crystals. and place a small piece of drop-reaction paper moistened with 20 per cent silver nitrate solution on the flat surface. it may also be dissolved in water and tested for arsenic by Fleitmann's or Bettendorff's test. which melts at 630°C. 11I. The strip is washed with distilled water. Mix a drop of the test solution with a few grains of zinc and a few drops of dilute sulphuric acid in the micro test-tube. except that zinc or aluminium and sodium hydroxide solution replace zinc and dilute sulphuric acid. This test depends upon the fact that nascent hydrogen generated in alkaline solution. silver-white metal. Sb (Ar : 121'75) . silver. A black stain of silver is produced by the action of the arsine. The modus operandi is as for the Gutzeit test. it is convenient to use the apparatus depicted in Fig. and then gently heated in a test-tube.ANTIMONY(III) Antimony is a lustrous. mercury. 11. A yellow or grey stain is produced after several minutes. reduces arsenic(III) compounds to arsine. It is necessary to warm the solutions. e.g. Sensitivity: 0'05 ~g As. Blowpipe test Arsenic compounds when heated upon charcoal with sodium carbonate give a white incrustation of arsenic(III) oxide.REACTIONS OF CATIONS m. It is therefore necessary to test for arsenic in the deposit in the dry way. but only slowly even on boiling.15 ANTIMONY. It is essential to perform a blank test with the reagents to confirm that they are arsenic-free. Arsenates must first be reduced to the tervalent state before applying the test. When heated with excess of potassium cyanide and of anhydrous sodium carbonate in a dry bulb tube. add some pure aluminium turnings. The latter is identified by examination with a hand lens. It is insoluble in hydrochloric 231 . A method of distinguishing arsenic and antimony compounds is thus provided. dried between filter paper. The apparatus of Fig. Insert the funnel with a flat rim. Gentle warming is usually necessary.000. a white crystalline deposit of arsenic(III) oxide is obtained.000.is For minute quantities of arsenic. and other metals are precipitated under similar conditions. Concentration limit: I in 100. Perform the test as described in the previous paragraph: a blue to blue-red stain of metallic gold is obtained after standing for 10-15 minutes. from aluminium or zinc and sodium hydroxide solution. b. soluble in sodium hypochlorite solution. (v) Dry tests a. but does not affect antimony compounds. (iii) Fleitmann's test (iv) Reinsclr's test If a strip of bright copper foil is boiled with a solution of an arsenic(III) compound acidified with at least one-tenth of its bulk of concentrated hydrochloric acid. A grey stain will be obtained. Sensitivity: I ug As. a black mirror of arsenic. IIU may be used on the semimicro scale.56. Place I ml test solution in the test-tube. and I ml 2M potassium hydroxide solution. the arsenic is deposited upon the copper as a grey film of copper arsenide Cu sAs 2 • Antimony. is produced in the cooler part of the tube. Arsenates are also reduced by copper. and an odour of garlic is apparent while hot. Concentration limit: I in 50.

and in alkali hydroxide solutions (forming antimonite and thioantimonite). hydrolysis occurs when antimonyl. or the concentration of hydrogen ions is decreased by dilution. in ammonium polysulphide (forming a thioantimonate).III.+S~2Sb 2S3! + 40H . can be used to study these reactions. when the ion Sb3+ is stable. Reactions of antimony( Ill) ions A O'2M solution of antimony(III) chloride. from solutions which are not too acid. when antimony(III) ions are formed: Sb+HN0 3+3HCI-+ Sb3+ +3CI.+NOj+2H 20 Two series of salts are known. The precipitate is soluble in warm concentrated hydrochloric acid (distinction and method of separation from arsenic(III) sulphide and mercury(II) sulphide). SbO+. can be dissolved in tartaric acid. If the solution is made alkaline. SbO~-. these are derived from the oxides Sb 203 and Sb 20 S ' Antimony(III) compounds are easily dissolved in acids. which can be regarded as a mixture of Sb 203 and Sb 20 S ' These anhydrides.lS QUALITATIVE INORGANIC ANALYSIS acid.-+ 2SbS~. In hot. concentrated sulphuric acid it dissolves slowly forming antimony(III) ions: 2Sb + 3H 2S0 4 + 6H+ -+ 2Sb3+ + 3S0 2j + 6H 20 Nitric acid oxidizes antimony to an insoluble product. 1. antimony pentasulphide is precipitated initially but usually decomposes partially into the trisulphide and sulphur: 6H+ -+Sb 2SS! + 3H 2Sj Sb 2SS! -+ Sb 2S3! +2S! Acidification of the antimonite-thioantimonite mixture leads to the precipitation of the trisulphide: Sb02" +3SbS2" +4H+ -+ 2Sb 2S3!+2H20 232 2SbS~. This can be prepared either by dissolving the solid antimony(III) chloride or antimony(III) oxide. and in dilute sulphuric acid. in dilute hydrochloric acid. in turn. SbCI 3. Sb 2S3. A mixture of nitric acid and tartaric acid dissolves antimony easily.-+ Sb02" + 3SbS2" + 2H 20 Upon acidification of the thioantimonate solution with hydrochloric acid. ions are formed: Sb3+ +H 20 +=t SbO+ +2H+ Antimony(V) compounds contain the antimonate ion. Sb 203. 2Sb3+ + 3H 2S -+ Sb 2S3! + 6H+ Sb 2S3! + 6HCI -+ 2Sb3+ + 6CI. with antimony(III) and antimony(V) ions in them. Hydrogen sulphide: orange-red precipitate of antimony trisulphide. Their characteristics are similar to the corresponding arsenic compounds.+ 3H 2Sj Sb2S3!+4S~. Aqua regia dissolves antimony.+ .

Potassium iodide solution: yellow colouration owing to the formation of a complex salt. an orange precipitate of antimony trisulphide will be obtained. a black stain of antimony is formed upon the platinum. it is preferable to employ tin. 3. 2Sb3+ + 3Zn! --+ 2Sb! + 3Zn2+ Some stibine SbH 3 may be evolved when zinc is used. Rhodamine-B (or tetraethylrhodamine) reagent violet or blue colouration with quinquevalent antimony. a black spot will form on the coin. Iron wire: black precipitate of antimony. 2Sb3+ + 3Fe --+ 2Sb! + 3Fe2+ 6.REACTIONS OF CATIONS m. Zinc: a black precipitate of antimony is produced.xH 20 soluble in concentrated (5M) solutions of caustic alkalis forming antimonites. 2Sb3+ + 3Sn! --+ 2Sb! + 3Sn2+ A modification of the above test is to place a drop of the solution containing antimony upon a genuine silver coin and to touch the coin through the drop with a piece of tin or zinc. the stain (or deposit) should be dissolved in a little warm dilute nitric acid and hydrogen sulphide passed into the solution after dilution. Cl is formed. soluble in hydrochloric acid and in tartaric acid solution (difference from bismuth). In Group lIB SbCl 3 is always formed together with SnCl 4 when the precipitate is treated with 233 . If a little of the antimony trichloride solution is poured upon platinum foil and a fragment of metallic zinc is placed on the foil. This may be confirmed as described in reaction 4. Tervalent antimony does not respond to this test. 5. 2Sb3+ + 60HSb203! + 20H- --+ --+ Sb20 3! + 3H 20 2Sb02" + H 20 4. Sb3+ + 61- --+ [SbI 6]3- 7. hence it must be oxidized with potassium or sodium nitrite in the presence of strong hydrochloric acid. Sodium hydroxide or ammonia solution: white precipitate of the hydrated antimony(lIl) oxide Sb 20 3. With a large excess of water the hydrated oxide Sb 20 3 • xH 20 is produced. a white precipitate of antimonyl chloride SbO.is 2. Water: when the solution is poured into water.

A more concentrated reagent is obtained by dissolving 0'05 g of rhodamine-B in a 15 per cent solution of potassium chloride in 2M hydrochloric acid.500 times that amount of Sn. A blue colouration appears within a few minutes. The reagent is reduced to a blue compound.is QUALITATIVE INORGANIC ANALYSIS hydrochloric acid: by oxidizing Sb(III) to Sb(V) with a little solid nitrite. Place a drop of the test solution upon drop-reaction paper which has been impregnated with the phosphomolybdic acid reagent and hold the paper in steam.Sb3+ and the tin as Sn4+. The test solution may consist of the filtered solution obtained by treating the Group lIB precipitate with hydrochloric acid: the antimony is present as. Concentration limit: I in 100. Sensitivity: 0'03 ~g Sn.000. Phosphomolybdic acid reagent (H3[PMo 1204 0 ] ) : 'molybdenum blue' is produced by antimony(III) salts. place 1 ml test solution in a semimicro test-tube. and tungstates in solution give similar colour reactions. which can be extracted with amyl alcohol. Concentration limit: I in 650. The bright-red colour of the reagent changes to blue. ammonium or potassium) salts to 'molybdenum blue'. 234 . which has no effect upon the reagent. Tin(lI) chloride reduces not only the reactive phosphomolybdic acid but also its relatively unreactive (e. Of the ions in Group 11. Mercury. antimony(llI) salts do not reduce ammonium phosphomolybdate: Sn2+ may thus be detected in the presence of Sb3+. molybdates.16 ANTIMONY.g. Place I ml reagent on a spot plate and add I drop test solution.15. Sensitivity: 0'2 ~g Sb. Concentration limit: I in 250. dry. 8.000. add 0'5-1 ml reagent. thallium. gold. Alternatively.000. Reactions of the antimony( V) ions Antimony(V) ions are derived from the amphoteric oxide Sb20 s' In acids this oxide dissolves under the formation of the antimony(V) cation Sbs + : Sb 20 s + 10H+ +=t 2Sb s+ + 5H 20 In acid solutions therefore we have the Sb s+ ion present. Place a drop of the test solution on this paper: a blue spot appears if tin(lI) is present. However. an excellent means of testing for Sb in the presence of a large excess of Sn is available.m. sparingly soluble ammonium salt. Sb (Ar : 121·75) . The reagent is prepared by dissolving 0'01 g of rhodamine-B in 100 ml of water. only tin(lI) interferes with the test. III. Sensitivity: 0'5 ~g Sb and applicable in the presence of 12. vanadates. Impregnate drop-reaction paper with a solution of phosphomolybdic acid and then hold it for a short time over ammonia gas to form the yellow. The test solution should be strongly acid with hydrochloric acid and the antimony(III) oxidized by the addition of a little solid sodium or potassium nitrite: a large excess of nitrite should be avoided.ANTIMONY(V) The physical and chemical properties of antimony have been described in Section 111. The reagent consists of a 5 per cent aqueous solution of phosphomolybdic acid. It does not keep well. and heat for a short time.

and is also dissolved by concentrated hydrochloric acid with the formation of antimony trichloride and the separation of sulphur. SbO~­ is a simplified expression of the composition of the antimonate ion. The precipitate is soluble in ammonium sulphide solution (yielding a thioantimonate) in alkali hydroxide solutions.+ SbS~. When heated the characteristic violet vapour of iodine appears.(and has nothing whatsoever to do with the sulphite ion SO~-). ultimately antimonic acid is formed: +=t H + SH+ Sb s+ +4H 20 3Sb04! The precipitate dissolves both in acids and alkalis (but not in alkali carbonates) : +=t Sb s+ +4H H 3Sb04!+SH+ 20 H 3Sb04! + 30H. iodine crystals precipitate out and float on the surface of the solution. Its formation from Sb 20 S with alkalis may be described by the reaction: Sb 20 S + 20H. an acidified O'2M solution of potassium hexahydroxoantimonate K[Sb(OH)6J can be used. Sb 2S S .+13" 235 .present in solutions.+ 3H 20 --+ 2Sb3+ +2S!+3H 2Sj --+ Sb 2S S! + 3H 2Sj --+ Sb 2SS ! + 3H 20 Note that the thioantimonate SbSO~. If the reagent is added in excess.+ SH20 +=t 2[Sb(OH)6JFor the study of these reactions.+ 6H+ SbSO~. in moderately acid solutions. Hydrogen sulphide: orange-red precipitate of antimony pentasulphide.ion is the derivative of the antimonate ion SbO~. The thio-salt is decomposed by acids. 1. on the other hand. in fact it exists in the hydrated form. the pentasulphide being precipitated.ion is formed: Sb 20 S + 30H. antimony pentoxide Sb 20 S may be dissolved in concentrated hydrochloric acid.+=t SbO~- + 3H 20 3. the antimonate SbO~.+=t Sb3+ +1 2! If the Sb5+ ions are in excess. Potassium iodide solution: in acidic solution iodine is separated: Sb s+ +21. brown tri-iodide ions are formed which screen the yellow colour of hexaiodoantimonate(III) ions: Sb5+ +91--+ [SbI 6J 3 . which may be termed hexahydroxoantimonate(V). 2. Alternately.is In alkalis.+=t 2SbO~- + 3H+ In alkaline medium therefore we have the SbO~.REACTIONS OF CATIONS m. Water: white precipitate of basic salts with various compositions.+ 6H+ --+ 2SbS~--+ SbSO~- + SbS~. + IOH+ 2Sb s+ + SH --+ Sb 2S 2S S! Sb 2S S! + 3S2 Sb 2S S! + 60HSb2S S!+6H+ 2SbS~.

this is decomposed by the excess of silver nitrate into silver and antimony(III) oxide: (i) Marslr's test SbH 3 + 3Ag+ 2Ag3Sb!+6Ag+ +3H 20 -+ -+ Ag 3Sb! + 3H+ l2Ag!+Sb 20 3!+6H+ It is best to dissolve the precipitate in a solution of tartaric acid and to test for antimony with hydrogen sulphide in the usual manner.15. In.rr QUALITATIVE INORGANIC ANALYSIS 4. (iv) Reinsclr's test A grey to black deposit is formed upon the copper. but it is deposited on both sides of the heated portion of the tube because of the greater instability of the stibine. (ii) Gutzei~s test A brown stain is produced which is soluble in 80 per cent alcohol. SbH 3 (mixed with hydrogen). reaction 7). hydrogen sulphide precipitates orange-red antimony sulphide from this solution. Ignition of this deposit in a dry test-tube gives a non-crystalline sublimate of antimony(III) oxide. A lustrous mirror of antimony is formed in a similar manner to the arsenic mirror. When the stibine-hydrogen mixture is passed into a solution of silver nitrate (Hofmann's test) a black precipitate of silver antimonide Ag 3Sb is obtained. Rhodamine-B reagent: see antimony(III) compounds (Section 111. this deposit in insoluble in sodium hypochlorite or bleaching powder solution. (v) Dry test (blowpipe test). a brittle metallic bead. soluble in potassium hydrogen tartrate solution. which is evolved burns with a faintly bluish-green flame and produces a dull black spot upon a cold porcelain dish held in the flame. acidified with hydrochloric acid.17 SPECIAL TESTS FOR SMALL AMOUNTS OF ANTIMONY This test is carried out exactly as described for arsenic. 236 . When antimony compounds are heated with sodium carbonate upon charcoal. This mirror may be converted into orange-red antimony trisulphide by dissolving it in a little boiling hydrochloric acid and passing hydrogen sulphide into the solution. is obtained. The stibine.m. Zinc or tin: black precipitate of antimony in the presence of hydrochloric acid: 2Sb s+ +SZn! -+ 2Sb!+ SZn2+ 2Sb5+ + SSn! -+ 2Sb! + SSn2+ Some stibine (SbH 3 ) is produced with zinc. (ili) Fleitman. but is dissolved by a solution of tartaric acid (difference from arsenic). provided the antimony concentration of the solution is not too high. 5. There is no need for preliminary oxidation in this case. surrounded by a white incrustation. The gas is also decomposed by passage through a tube heated to dull redness.rs or Bettendorffs tests Negative results are obtained when these are applied to antimony compounds (distinction from arsenic).

In their aqueous solution they can be present as the tin(IV) ions Sn4+ or as hexahydroxostannate(IV) (or simply stannate) ions [Sn(OH)6]2-.is 111. a white solid.+4NOj+8H 20 Tin can be bivalent and tetravalent in its compounds. from not too acid solutions (say in the presence ofO'25-0'3M hydrochloric acid or pH c. it is also soluble in yellow 237 . 2H 20. 1.+2S0 2t +4H 20 Aqua regia dissolves tin readily. SnS. In hot. It melts at 231·8°C. SnCI2. tin(II) and ammonium ions being formed: 4Sn + lOH+ + N0 3 -+ 4Sn2+ + NHt + 3H 20 With concentrated nitric acid a vigorous reaction occurs. but at low temperatures it becomes brittle due to transformation into a different allotropic modification. when again tin(IV) (stannic) ions are formed: 3Sn+4HN03+ l2HCI-+ 3Sn4+ + 12Cl. while in alkaline medium it is shifted towards the right. In acid solution the tin(II) ions Sn2+ are present. while in alkaline solutions tetrahydroxostannate(II) or stannite ions [Sn(OH)4]2.Tio(II) Tin is a silver-white metal which is malleable and ductile at ordinary temperatures. Hydrogen sulphide: brown precipitate of tin(II) sulphide. The solution should contain at least 4 per cent free hydrochloric acid (lOO ml concentrated HCI per litre). If larger amounts of iron are present. the formation of metastannic acid is again prevented. Reactions of tin(11) ions A 0'25M solution of tin(II) chloride.are to be found. being produced: 3Sn+4HN03+(x-2)H 20 -+ 4NOj+3Sn0 2·xH20! In the presence of antimony and tartaric acid tin dissolves readily in nitric acid (induced dissolution) because of complex formation. can be used for studying these reactions.+=t [Sn(OH)4]2Tin(II) ions are strong reducing agents. The metal dissolves slowly in dilute hydrochloric and sulphuric acid with the formation of tin(II) (stannous) salts: Sn+2H+ -+ Sn2+ +H 2j Dilute nitric acid dissolves tin slowly without the evolution of any gas. Tin(IV) or stannic compounds are more stable.+=t [Sn(OH)6]2In acid solutions the equilibrium is shifted towards the left.18 TIN. The precipitate is soluble in concentrated hydrochloric acid (distinction from arsenic(III) sulphide and mercury(II) sulphide). usually formulated as hydrated tin(IV) oxide Sn02 . 0'6).xH 20 and sometimes known as met astannic acid. These two are" readily transformed into each other: Sn2+ + 40H. concentrated sulphuric acid tin(IV) ions are formed at dissolution: Sn+4H 2S04 -+ Sn4+ +2S0i. So (Ar : 118·69) . They again form an equilibrium system: Sn 4+ + 60H. The tin(II) or stannous compounds are usually colourless.REACTIONS OF CATIONS m.

This procedure may be used with the Group lIB precipitate after treatment with hydrochloric acid. 3. Bismuth nitrate and sodium hydroxide solutions: black precipitate of bismuth metal (cf. The precipitate should be dissolved in concentrated hydrochloric acid and the mercury(lI) chloride test applied. as described in Section 111. reaction 4. Sn2+ +H 2S -+ SnS!+2H+ SnS! + S~ .+=t Sn(OHh! Sn(OHh! + 20H. Mercury(Il) chloride solution: a white precipitate of mercury(I) chloride (calomel) is formed if a large amount of the reagent is added quickly: Sn2+ +2HgC1 2 -+ Hg 2CI2!+Sn4+ +2CIIf however tin(lI) ions are in excess. palladium. the ions of copper. is formed. chromium. white tin(lI) hydroxide is precipitated. and nickel ions give a similar reaction. Sodium hydroxide solution: white precipitate of tin(lI) hydroxide. hence. the tin must be oxidized to the quadrivalent state with hydrogen peroxide before precipitation with hydrogen sulphide. the precipitate turns grey. 6. gold. Dimethylglyoxime-irontIll) chloride test" No colouration is produced when iron(III) ions are mixed with the dimethylglyoxime reagent and a little ammonia solution. but if a trace of iron(lI) is present (produced by reduction with tin(lI) ions). cobalt. due to the iron(lI) dimethylglyoxime complex. see Section 111. reaction 6).+2H+ -+ SnS 2!+H2Sj Tin(lI) sulphide is practically insoluble in solutions of caustic alkalis. Section 111. reaction 8. which cannot be dissolved in excess ammonia. 2. Metallic zinc: spongy tin is deposited which adheres to the zinc. especially on warming.27.+=t [Sn(OH)4]2With ammonia solution. platinum. the tin is partially deposited upon the zinc in a spongy form but does not stain the platinum. SnS 2. owing to further reduction to mercury metal: Sn2+ + Hf2C12! -+ 2Hg! + Sn4+ + 2CI4. ammonium sulphide solution to form a thiostannate.18 QUALITATIVE INORGANIC ANALYSIS [(NH4hSx]. Vanadium. uranyl. Treatment of the solution of ammonium thiostannate with an acid yields a yellow precipitate of tin(IV) sulphide. which is soluble in excess alkali: Sn2+ +20H. If tin is present in the quadrivalent state. titanium.15. If the zinc rests upon platinum foil. manganese. and the solution is weakly acid.m. but not in colourless [(NH 4hS]. selenium. * For formulae.-+ 'SnS~SnS~. 5.9. if potassium hydroxide solution is employed for separating Group IIA and Group lIB. a deep red colouration. it is reduced to Sn(lI) by treatment with aluminium or magnesium filings and hydrochloric acid and the solution is filtered. 238 .

Concentration limit: I in 1. but is fairly sensitive: it can be used in the analysis of the Group lIB precipitate. Sensitivity: 2 ~g Sn.REACTIONS OF CATIONS m. add a drop of the test solution. A red colouration is produced. 3 drops dimethylglyoxime reagent. before the paper is quite dry.000 The reagent consists of a I per cent solution of dimethylglyoxime in ethanol.000.250. Sensitivity: 0'2 ~g Sn. The reagent consists of a 0'25 per cent aqueous solution of cacotheline. followed by 0·3 ml 5 per cent tartaric acid solution (to prevent the formation of iron(III) hydroxide). it may be applied to the tin solution which has been reduced with iron wire. W. hence the colour change is blue -+ violet -+ red. Sensitivity: 0·05 ~g Sn. must be absent. C21H2107N3): violet colouration with stannous salts. Alternatively. Te. V. Pd. 7. U. and about 0'5 ml 2M ammonia solution. dithionites. A violet (purple) colouration is produced. Cacotheline reagent (a nitro-derivative of brucine. 8. treat a little of the test solution in a micro test-tube with a few drops of the reagent. Co and Ni. Concentration limit: I in 250. Bi. and if tin is in the quadrivalent state. The reagent is therefore useful in testing for tin in the mixed sulphides of antimony and tin obtained in routine qualitative analysis. acidify (if necessary) with dilute hydrochloric acid. as do also molybdates and tungstates. 4-Methyl-I. It is advisable to carry out a blank test. Se.is and tellurium interfere. or magnesium powder and a drop of the reduced solution employed for the test.000. A violet spot. add 0'2 ml O'IM iron(III) chloride solution. Mo. Mix I drop of the test solution on a spot plate with I ml of the reagent. appears on the yellow paper. Hg. surrounded by a less coloured zone. aluminium. Te. Titanium(III) chloride reacts similarly. it should be reduced previously with aluminium or magnesium. sulphites and selenites). Since iron(lI) ions have no influence on the test. Reducing agents. Concentration limit: I in 25. The colour changes from blue to violet or red. but iron(lI) salts and similar reducing agents have no effect. Diazine green reagent (dyestuffformed by coupling diazotized safranine with dimethylaniline): tin(II) chloride reduces the blue diazine green to the red safranine. reduced with magnesium) in a micro test-tube. which affect iron(III) chloride.2-dimercapto-benzene (or 'dithiol") reagent 239 . Au. Impregnate some drop-reaction paper with the reagent and. The test solution should be acid (2M HCI). Place 0'2 ml test solution containing tin(II) ions (this may consist of the solution obtained from the Group lIB precipitate. and the solution filtered. 9. Sb. The reagent consists of a 0·01 per cent aqueous solution of diazine green. The solution of the sulphides in hydrochloric acid is reduced with iron wire. The following interfere with the test: strong reducing agents (hydrogen sulphide. The reaction is not selective.

+=t [Sn(OH)6]2With ammonia and with sodium carbonate solutions.111.19 QUALITATIVE INORGANIC ANALYSIS red precipitate when warmed with tin(lI) salts in acid solution.19 TIN. a similar precipitate is obtained which. 1. Reactions of tin( IV) ions To study these reactions use a 0'25M solution of ammonium hexachlorostannate(IV) by dissolving 92 g (NH 4h[SnC16] in 250 ml concentrated hydrochloric acid and diluting the solution to 1 litre with water.18. The reagent is prepared by dissolving 0'2 g 4-methyl-1. is insoluble in excess reagent.-+ SnS~­ SnS2!+2S~. phosphates and nitrites. and antimony (yellow precipitates). Place 2 drops of the test solution.-+ SnS~. but it serves to facilitate the reduction of any tin(IV) ions present. bismuth (red precipitate). The use of the latter in the reagent is not imperative. Sn4+ + 2H 2S -+ SnS 2! + 4H+ SnS2! + S2. 3. 2-dimercapto-benzene in 100 m1 I per cent sodium hydroxide solution and adding 0'3-0'5 g thioglycollic acid. III. Concentration limit: 1 in 500. due to the formation ofthe stable complex ion of the type [Sn(C204MH20h]4. nickel. etc.. in a micro crucible and add 3 drops of the reagent. mercury. in solutions of alkali hydroxides.). Mercury(Il) chloride solution: no precipitate (difference from tin(II)). lead. So (Ar : 118'69) . Metallic iron: reduces tin(IV) ions to tin(II): Sn4+ -i-Fe -+ Fe2+ +Sn2+ 240 .000. acidified with dilute hydrochloric acid. arsenic. 2. copper. and also in ammonium sulphide and ammonium polysulphide. colloidal organic substances (starch. The hydrochloric acid concentration of the solution should not exceed 15 per cent.-+ Sn(OH)4! Sn(OH)4! + 20H. 4. and cobalt (black precipitates). The reagent is discarded if a white precipitate of the disulphide forms.+ 2H+ -+ SnS2i + H 2S3! No precipitation of tin(IV) sulphide occurs in the presence of oxalic acid. Yellow tin(IV) sulphide is precipitated upon acidification. Sodium hydroxide solution: gelatinous white precipitate of tin(IV) hydroxide Sn(OH)4' soluble in excess of the precipitant forming hexahydroxostannate(IV) Sn4+ + 40H. however. this forms the basis of a method of separation of antimony and tin. Hydrogen sulphide: yellow precipitate of tin(IV) sulphide SnS 2 from dilute acid solutions (0·3M). The precipitate is soluble in concentrated hydrochloric acid (distinction from arsenic(III) and mercury(II) sulphides). Warm (not above 600C): a red colour or precipitate develops. The following interfere: silver. cadmium.+S~­ SnS~.TIN(IV) The properties of metallic tin were discussed at the beginning of Section 111.

Borax bead test A borax bead which has been coloured pale blue by a trace of copper salt becomes a clear ruby red in the reducing flame if a minute quantity of tin in added. cobalt sulphide (black). Iron. The commercial metal is rarely pure and usually contains small quantities of carbide. tenacious.21 IRON. preferably in the presence of potassium cyanide. AND ZINC Group reagent: hydrogen sulphide (gas or saturated aqueous solution) in the presence of ammonia and ammonium chloride. and the mixture is filtered. by hydrogen sulphide from their solutions made alkaline with ammonia solution. It melts at 1535°C. tin(lI) ions can be detected with mercury(lI) chloride reagent. Dilute or concentrated hydrochloric acid and dilute sulphuric acid dissolve iron. ALUMINIUM. but are all precipitated. Dry tests a. and sulphide of iron. The metals. NICKEL. concentrated sulphuric acid yields iron(lIl) ions and sulphur dioxide: 2Fe + 3H 2S04 + 6H+ -+ 2Fe3+ + 3S0 2 i + 6H 20 241 . 5.REACTIONS OF CAnONS ill. which forms a white incrustation upon the charcoal. manganese(lI) sulphide (pink). A similar result is obtained on boiling the solution with copper or antimony. manganese. It is therefore usual to subdivide the group into the iron group (iron. Part of the metal is oxidized to tin(lV) oxide.IRON{lI) Chemically pure iron is a silverwhite. and some graphite. with the exception of aluminium and chromium which are precipitated as the hydroxides owing to the complete hydrolysis of the sulphides in aqueous solution. silicide. and chromium (often accompanied by a little manganese) are also precipitated as the hydroxides by ammonia solution in the presence of ammonium chloride. and chromium) or Group IliA and the zinc group (nickel. ID.20j21 If pieces of iron are added to a solution. nickel sulphide (black). Fe (Ar : 55·85) . malleable and metallic globules of tin which do not mark paper. aluminium. and ductile metal. or ammonium sulphide solution. are precipitated as the sulphides. aluminium hydroxide (white). CHROMIUM(1I1) AND (VI). in the presence of ammonium chloride. COBALT. The metals of this group are not precipitated by the group reagents for Groups I and 11. 111. when iron(lI) salts and hydrogen gas are produced. especially on strong heating. cobalt. aluminium. whilst the other metals of the group remain in solution and may be precipitated as sulphides by hydrogen sulphide.20 THIRD GROUP OF CATIONS: IRON(II) AND (Ill). Blowpipe test All tin compounds when heated with sodium carbonate. These contaminants play an important role in the strength of iron structures. and zinc sulphide (white). phosphide. Iron can be magnetized. chromium(III) hydroxide (green). on charcoal give white. MANGANESE(II) AND (VU). Fe+2H+ -+ Fe2+ +H 2 i Fe+2HCI-+ Fe2++2CI-+H 2 i Hot. Group reaction: precipitates of various colours: iron(lI) sulphide (black). and zinc) or Group IIIB. b.

The iron(II) (or ferrous) salts are derived from iron(lI) oxide FeO. 6H 20). (cf. yielding ultimately reddish-brown iron(III) hydroxide. Fe(OHh. for the study of these reactions. they are therefore strong reducing agents. zinc and manganese and also to magnesium. or hot. larger amounts of ammonium ions are present.15). Reducing agents convert iron(III) ions to iron(II). in neutral or alkaline media even atmospheric oxygen will oxidize iron(lI) ions. iron(lI) hydroxide is rapidly oxidized. Intensively coloured ion-association and chelate complexes are also common. Sodium hydroxide solution: white precipitate of iron(lI) hydroxide. by the addition of 242 . is not attained and precipitation does not occur. Similar remarks apply to the other divalent elements of Group Ill. 1. I + I Nitric acid. Fe2+ + 20H. insoluble in excess. the addition of hydrogen peroxide immediately oxidizes it to iron(III) hydroxide. In solution they contain the cation Fe2+ and normally possess a slight-green colour. and the concentration of hydroxyl ions is lowered to such an extent that the solubility product of iron(lI) hydroxide. the colour becomes stronger. Iron(lI) solutions must therefore be slightly acid when kept for a longer time. If the hydrogen-ion concentration is reduced. in this state it does not react with dilute nitric acid nor does it displace copper from an aqueous solution of a copper salt. nickel.7H 20 or iron(II) ammonium sulphate (Mohr's salt.n QUALITATIVE INORGANIC ANALYSIS With cold dilute nitric acid. Ammonia solution: precipitation ofiron(lI) hydroxide occurs (cf. If. reaction I). Hydrogen sulphide: no precipitation takes place in acid solution since the sulphide ion concentration. and the sulphide-ion concentration correspondingly increased. [S2 -]. acidified with 50 ml MH2S04 per litre. Upon exposure to air. cobalt. is insufficient to exceed the solubility product of iron(lI) sulphide. the dissociation of ammonium hydroxide is suppressed.m. They are more stable than the iron(lI) salts.-+ Fe(OHh! 4Fe(OHh +2H 20+02 -+ 4Fe(OHh! 2Fe(OHh + H 202 -+ 2Fe(OHh! 2. Under ordinary conditions it appears as a dirty-green precipitate. however. Iron(III) (or ferric) salts are derived from iron(III) oxide Fe203. in the complete absence of air. Reactions of iron(Il) ions Use a freshly prepared 0·5M solution of iron(lI) sulphate FeS0 4. Section 1. (NH 4hS04. 3. iron(lI) and ammonium ions are formed: 4Fe + lOH+ + N0 3 -+ 4Fe2+ + NHt + 3H 20 Cold. but soluble in acids. Iron(II) ions can be oxidized easily to iron(III). if the solution contains chloride. In their solution the pale-yellow Fe3+ cations are present. concentrated nitric acid dissolves iron with the formation of nitrogen oxide gas and iron(III) ions: Fe + HN0 3 + 3H+ -+ Fe3+ + NOr + 2H 20 Iron forms two important series of salts. FeS0 4. The less acidic the solution the more pronounced this effect. Fe(OHh. concentrated nitric acid renders iron passive.

alkali cyanide. and nitrogen. Earlier it was suggested that its composition was iron(II) hexacyanoferrate(III). soluble in excess reagent when a pale-yellow solution of hexacyanoferrate(lI) (ferrocyanide) [Fe(CN)6]4. By dissolving the residue in acid iron can be detected in the solution (all these operations must be carried out in a fume cupboard).33). occurs. The iron present in such solutions may be detected by decomposing the complex ion by boiling the solution with concentrated sulphuric acid in a fume cupboard with good ventilation. Potassium cyanide solution (POISON): yellowish-brown precipitate of iron(lI) cyanide. The moist precipitate becomes brown upon exposure to air.22. First 'hexacyanoferrate(III) ions oxidize iron(lI) to iron(III).--+ FeS! FeS! + 2H+ --+ Fe2+ + H 2Sj 4FeSO! + 90 2 --+ 2Fe20(S04h! 5. Ammonium sulphide solution: black precipitate of iron(lI) sulphide FeS.ions is obtained: Fe2+ +2CNFe(CNh! + 4CN- Fe(CNh! --+ [Fe(CN)6]4--+ The hexacyanoferrate(lI) ion being a complex ion does not give the typical reactions of iron(lI) (cf. 7. readily soluble in acids with evolution of hydrogen sulphide. Potassium hexacyanoferrate(Il) solution: in the complete absence of air a white precipitate of potassium iron(lI) hexacyanoferrate(lI) is formed: Fe2+ +2K+ + [Fe(CN)6]4- H K 2Fe[Fe(CN)6]! under ordinary atmospheric conditions a pale-blue precipitate is obtained (cf. partial precipitation of black iron(lI) sulphide. due to its oxidation to basic iron(lIl) sulphate Fe 20(S04h.+ 6H 2S04 + 6H 20 --+ Fe2+ + 6COj + 6NHt + 6S0i- A dry sample which contains alkali hexacyanoferrate(II).REACTIONS OF CAnONS m. if potassium cyanide is present in excess): [Fe(CN)6]4.21 sodium acetate solution. The identical composition and structure of Turnbull's blue and Prussian blue has 243 . Fe 3[Fe(CN)6]2' hence the different name. when hexacyanoferrate(lI) is formed: Fe2+ + [Fe(CN)6]3- --+ Fe3+ + [Fe(CN)6]4--+ and these ions combine to a precipitate called Turnbull's blue: 4Fe3+ + 3[Fe(CN)6]4Fe 4[Fe(CN)6]3 Note. reaction 7). that the composition of this precipitate is identical to that of Prussian blue (cf. Potassium hexacyanoferrate(Ill) solution: a dark-blue precipitate is obtained. 4. 6. FeS. Sections 1. when carbon monoxide gas is formed (together with hydrogen cyanide. Section 111. Fe2+ + S2.31 to 1. reaction 6). decomposes on ignition to iron carbide.

9.n QUALITATIVE INORGANIC ANALYSIS recently been proved by Mossbauer spectroscopy. Other metallic ions react with the reagent in acid solution.rX -Dipyridyl reagent (0-0): deep-red complex bivalent cation [Fe(CsH4Nh]2+ with iron(lI) salts in mineral acid solution. The colouration fades on standing owing to the oxidation of the iron(lI) complex.000. with a drop of the test solution: a red or pink spot is produced. Concentration limit: I in 125. but the intensities of the resulting colours are so feeble that they do not interfere with the test for iron provided excess reagent is employed. they must first be reduced by a little hydroxylamine hydrochloride. but nickel.. Sensitivity: 0·04 ~g Fe2+. 10. Treat a drop of the faintly acidified test solution with I drop of the reagent on a spot plate: a red colouration is obtained.000. Alternatively. Iron(III) salts give no colouration.M.600.rX -dipyridyl in 0·5 ml alcohol or in O· 5 ml O·IM hydrochloric acid. A red colouration appears. introduce a drop of the reagent. lY.. Section 111. The reagent consists of a I per cent solution of dimethylglyoxime in alcohol.m. o-Phenanthroline reagent 244 . iron(III) hydroxide being precipitated. If appreciable quantities of iron(III) salts are present and traces of iron(lI) salts are sought. Mix a drop of the test solution with a small crystal of tartaric acid. Sensitivity: O: 3 ~g Fe2+.27. 11. The precipitate is decomposed by sodium or potassium hydroxide solution. The test may be carried out in the presence of potassium cyanide solution in which nickel dimethylglyoxime (cf. If it is desired to detect iron(llI) ions by this test. Iron(III) ion does not react. The reagent is prepared by dissolving 0·01 g lY. it is best to carry out the reaction in a micro crucible lined with paraffin wax and to mask iron(III) ions as [FeF 6] 3. Large amounts of halides and sulphates reduce the solubility of the iron(lI) dipyridyl complex and a red precipitate may be formed. 3 M. cobalt. treat dropreaction paper (Whatman No. and large quantities of copper salts interfere and must be absent.. Ammonium thiocyanate solution: no colouration is obtained with pure iron(lI) salts (distinction from iron(III) ions). 8. 1st quality) which has been impregnated with the reagent and dried. Dimethylglyoxime reagent: soluble red iron(lI) dimethylglyoxime in ammoniacal solution.by the addition of a few drops of potassium fluoride solution. Concentration limit: I in 1. reaction 8) dissolves. followed by 2 drops ammonia solution.

Fe (A r : 55·S5). Iron(III) hydroxide is converted on strong heating into iron(III) oxide. 1. If it turns brown.REACTIONS OF CAnONS m. zinc.22 IRON. A red colour is obtained. Precipitation does not occur in the presence of certain organic acids (see reaction 8 below). nickel. the ignited oxide is soluble with difficulty in dilute acids. Fe3+ + 3NH 3 + 3H 20 -+ Fe(OHh! + 3NHt The solubility product of iron(III) hydroxide is so small (3·8 x 1O. Iron(lIl) has no effect and must first be reduced to the bivalent state with hydroxylamine hydrochloride if the reagent is to be used in testing for iron. gelatinous precipitate of iron(III) hydroxide Fe(OHh. 4.21. The reagent consists of a 0·1 per cent solution of o-phenanthroline in water. Ammonia solution: reddish-brown.IRON(OI) The most important characteristics of the metal have been described in Section 111. Reactions of iron( IIl) ions Use a 0·5M solution of iron(III) chloride FeCI 3.000. insoluble in excess of the reagent (distinction from aluminium and chromium): Fe3+ + 30H- -+ Fe(OHh! 3. 10. due to hydrolysis.500. Hydrogen sulphide gas: in acidic solution reduces iron(III) ions to iron(II) and sulphur is formed as a milky-white precipitate: 2Fe3+ +H 2S -+ 2Fe2+ +2H+ +S! If a neutral solution of iron(III) chloride is added to a freshly prepared. a few drops of hydrochloric acid should be added. saturated solution of hydrogen sulphide. a bluish colouration appears first. but dissolves on vigorous boiling with concentrated hydrochloric acid. followed by the precipitation of sulphur.6H20. The solution should be clear yellow. Concentration limit: I in 1. Ammonium sulphide solution: a black precipitate. This reaction can be used to test the freshness of hydrogen sulphide solutions. Sodium hydroxide solution: reddish-brown precipitate ofiron(III) hydroxide. manganese. cobalt. insoluble in excess of the reagent. but soluble in acids. due to the complex cation [Fe(C 1SHsN 2h]2+ in faintly acid solution. By boiling the solution with a few torn pieces of filter paper the precipitate coagulates and can be filtered. The blue colour is due to a colloid solution of sulphur of extremely small particle size. Place a drop of the faintly acid test solution on a spot plate and add I drop of the reagent. 2Fe(OHh! Fe 203 + 6H+ -+ -+ Fe203 + 3H 20 2Fe3+ + 3H 20 2. and magnesium).-+ 2FeS! + S! 245 .n red colouration. consisting of iron(II) sulphide and sulphur is formed: 2Fe3+ + 3S2.3S) that complete precipitation takes place even in the presence of ammonium salts (distinction from iron(II). The finely distributed sulphur cannot be readily filtered with ordinary filter papers.

produces a reddishbrown precipitate of iron(III) cyanide: Fe3+ + 3CN.-+ [Fe(CN)6rThese reactions should -be carried out in a fume cupboard. Section 111. only the filter paper should be thrown away. A large excess of the reagent dissolves it partly or entirely. as described with hexacyanoferrate(lI) (cf. as iron(III) oxide and hexacyanoferrate(lI) ions are formed: Fe 4[Fe(CN)6]3! + 120H-+ 4Fe(OHh! + 3[Fe(CN)6]4- Oxalic acid also dissolves Prussian Blue forming a blue solution. and the filter paper. when exposed to air. this process was once used to manufacture blue writing inks. 246 . Sodium hydroxide turns the precipitate to red.22 QUALITATIVE INORGANIC ANALYSIS In hydrochloric acid the black iron(lI) sulphide precipitate dissolves and the white colour of sulphur becomes visible: FeS! + 2H+ -+ H 2Sj + Fe2+ From alkaline solutions black iron(III) sulphide is obtained: 2Fe3+ + 3S2 . as the free acid present in the iron(III) chloride solution forms hydrogen cyanide gas with the reagent: H+ + CN. with the finely distributed sulphur on it. but should rather be washed away under running water.-+ Fe 2S 3! On acidification with hydrochloric acid iron(III) ions are reduced to iron(lI) and sulphur is formed: Fe 2S 3! + 4H+ -+ 2Fe2+ + 2H 2Sj + S! The humid iron(lI) sulphide precipitate. Under certain conditions so much heat may be produced that the precipitate dries out. The complex has to be decomposed first by evaporating with concentrated sulphuric acid or by igniting a solid sample. reaction 5).21. Potassium cyanide (POISON): when added slowly. Sulphide precipitates therefore should never be disposed of into a waste bin.-+ Fe(CNh! In excess reagent the precipitate dissolves giving a yellow solution.-+ Fe 4[Fe(CN)6]3 (cf. is slowly oxidized to brown iron(III) hydroxide: 4FeS!+6H 20+30 2 -+ 4Fe(OHh!+4S! The reaction is exothermal. 6. Potassium hexacyanoferrate(II) solution: intense blue precipitate of iron(III) hexacyanoferrate (Prussian blue): 4Fe3+ + 3[Fe(CN)6]4. The precipitate is insoluble in dilute acids. Section 111.-+ HCNj Iron(III) ions cannot be detected in a solution of hexacyanoferrate(III) with the usual reactions.III. when hexacyanoferrate(III) ions are formed: Fe(CNh! + 3CN. when an intensive blue solution is obtained. 5. catches fire.21. but decomposes in concentrated hydrocholoric acid. reaction 7).

which acts as a buffer against the strong acid: CH 3COO. It is advisable to add small amounts of sodium acetate. attributed to the formation of a complex ion with the composition [FeiOHh(CH3COO)6J+.REACTIONS OF CAnONS m. 10. due to the formation of an undissociated complex. Reactions 8 and 9 are combined for the removal of the phosphate ion from solutions in which it interferes with the normal course of analysis (cf. in the presence of sodium acetate.+2H 20 +=t [Fe 3(OHh(CH3COO)6J+ +2H+ leads to an equilibrium. Potassium hexacyanoferrate(Ill): a brown colouration is produced. does not dissolve the precipitate. the ammonium salt of nitrosophenylhydroxylamine. Sodium acetate solution: a reddish-brown colouration is obtained. If the reagent is added in excess. This tends to form colloid solutions ('Soluble Prussian Blue') and cannot be filtered. The overall reaction. sodium acetate acts as a buffer and the reaction becomes complete.+ H+ +=t CH 3COOH Acetic acid. formed in this reaction. 8. If the solution is diluted and boiled.--+ Fe[Fe(CN)6J Upon adding hydrogen peroxide or some tin(II) chloride solution. can be written Fe3+ + HPOi. Disodium hydrogen phosphate solution: a yellowish-white precipitate of iron(III) phosphate is formed: Fe3+ + HPOi--+ FeP04! + H+ The reaction is reversible. the hexacyanoferrate(III) part of the compound is reduced and Prussian blue is precipitated.+ CH 3COO--+ FeP04! + CH 3COOH 9.13). a reddish-brown precipitate of basic iron(III) acetate is formed: [FeiOHh(CH3COO)6J+ + 4H 20 --+ --+ 3Fe(OHhCH 3COO! + 3CH 3COOH + H+ The excess of acetate ions acts again as a buffer and the reaction becomes complete.n If iron(III) chloride is added to an excess of potassium hexacyanoferrate(II) a product with the composition of KFe[Fe(CN)6J is formed. C6H sN(NO)ONH4 : reddish-brown precipitate is formed in the presence of hydrochloric acid: Fe3+ + 3C 6HsN(NO)ONH 4 --+ Fe[C 6HsN(NO)OJ3! + 3NHt 247 . because a strong acid is formed. Section V. which decomposes the complex. 7. because a strong acid is formed which dissolves the precipitate. The reaction 3Fe3+ +6CH 3COO. iron(III) hexacyanoferrate(III): Fe3+ + [Fe(CN)6J 3. Cupferron reagent.

complex and the nondissociated mercury(II) thiocyanate species: Fe(SCNh + 6F2Fe(SCNh + 3Hg2+ --+ --+ [FeF6]3. In addition to this a set of complex ions.are also formed. [Fe(SCN)4]-' [Fe(SCNh]2-. 12. It is insoluble in acids. tartrates. The reagent is prepared by dissolving 2 g solid in 100 ml distilled water: it does not keep well.000. similar to that with iron (Ill). Ammonium thiocyanate solution: in slightly acidic solution a deep-red colouration is produced (difference from iron(II) ions). Sensitivity: 0'25 g Fe 3+. Place a drop of the test solution on a spot place and add I drop of I per cent ammonium thiocyanate solution.+=t {Fe[(COOh]3} Fluorides and mercury(II) ions bleach the colour because of the formation of the more stable hexafluoroferrate(III) [FeF6]3. cobalt. oxalates. and [Fe(SCN)6]3. chromium. A deep-red colouration appears. disappearing on heating. It is recommended that a piece of ammonium carbonate be placed in the stock bottle.g. 11. [Fe(SCNh]+ .22 QUALITATIVE INORGANIC ANALYSIS The precipitate is soluble in ether. Place a few drops of the slightly acid test solution in a micro test-tube and add 1 drop of the reagent. Iron(II) does not react: only copper interferes. reduce the sensitivity of the test. citrates. e. 7-Iodo-8-hydroxyquinoline-5-sulphonic acid (or ferron reagent) green or greenish-blue colouration with iron(III) salts in faintly acid solution (pH 2'5-3'0). but can be decomposed by ammonia or alkali hydroxides. iodates. due to the formation of a non-dissociated iron(III) thiocyanate complex: Fe3+ + 3SCN- --+ Fe(SCNh This chargeless molecule can be extracted by ether or amyl alcohol. when iron(lII) hydroxide precipitate is formed. Concentration limit: 1 in 200. Coloured salts. those of copper. A green colouration appears. The dibasic organic acids form complex ions of the type: Fe3+ + 3(COO)~. borates. arsenates.III. this enhances the stability.+ 3SCN2Fe3+ + 3Hg(SCNh The presence of nitrites should be avoided for in acid solution they form nitrosyl thiocyanate NOSCN which yields a red colour. 248 . Phosphates. sulphates. and nickel. and the corresponding free acid interfere due to the formation of stable complexes with iron(III) ions. such as [Fe(SCN)]2+ . The reaction is well adapted as a spot test and may be carried out as follows. acetates. The composition of the product in aqueous solution depends mainly on the relative amounts of iron and thiocyanate present.

e.21).n Sensitivity: O·S ~g Concentration limit: 1 in 1.REACTIONS OF CAnONS m. aqua regia. potassium dichronate. Rapid oxidation is effected by concentrated nitric acid. In turn. In acid solutions these metals will dissolve further with liberation of hydrogen. Oxidation of iron(Il) ions to iron(Ill): oxidation occurs slowly upon exposure to air.+3H 20 2Fe2+ +HN0 3+3HC1-+ 2Fe3+ +NOClj +2Cl. hydrogen peroxide. It must be remembered that even freshly prepared solutions of pure iron(II) salts contain some iron(III) 249 . potassium iodide.000. Distinctive tests for iron(Il) and iron(IlI) ions. alloys with mercury) may be used: 2Fe3+ + Zn -+ Zn2+ + 2Fe2+ 2Fe3+ +Cd -+ Cd2+ +2Fe2+ The solution will contain zinc or cadmium ions respectively after the reduction.+2H 20 SFe2+ + MnO:. reaction 11). potassium permanganate. concentrated hydrochloric acid with potassium chlorate. they should therefore be removed from the solution once the reduction has been accomplished. Section 111. Reduction of iron(Ill) to iron(Il) ions In acid solution this may be accomplished by various agents. hydrazine sulphate.000. reaction 9. hydroxylamine hydrochloride. or ascorbic acid can also be used: 2Fe3+ + Sn2+ 2Fe3+ + 214Fe3+ +2NH 20H 4Fe3+ + N 2H 4 2Fe3+ +C 6H s0 6 -+ 2Fe2+ + Sn 4+ -+ 2Fe2+ + 12 -+ 4Fe2+ +N 20+H20+4H+ -+ 4Fe2+ + N 2 +4H+ -+ 2Fe2+ +C 6H 606+2H+ the product of the reduction with ascorbic acid being dehydroascorbic acid. Zinc or cadmium metal. reaction 3) and sulphur dioxide gas reduce iron(III) ions also: 2Fe3+ + H 2S -+ 2Fe2+ + S! + 2H+ 2Fe3+ +S02 +2H 20 -+ 2Fe2+ +SOi.+4H+ 14. Hydrogen sulphide (cf. 4Fe2+ +0 2 +4H+ -+ 4Fe3+ +2H 20 3Fe2+ + HN0 3 + 3H+ -+ NOj + 3Fe3+ + 2H 20 2Fe2+ +H 202 +2H+ -+ 2Fe3+ +2H 20 6Fe2+ +CI0 3 +6H+ -+ 6Fe3+ +Cl. the test is conclusive also in the presence of iron(III). Iron(II) can be detected most reliably with a. and cerium(lV) sulphate in acid solution. The reagent consists of a 0'2 per cent aqueous solution of 7-iodo-8-hydroxyquinoline-S-sulphonic acid. 13. + 8H+ -+ SFe3+ + Mn2+ + 4H 20 Fe2+ + Ce 4+ -+ Fe3+ + Ce3+ 15.cx'-dipyridyl (cf. or their amalgams (i. iron(lm ions can be detected with ammonium thiocyanate solution (cf. Tin(II) chloride.

AI(OHh. Dry tests a. Aluminium sulphide can be prepared in the dry state only.+ 3H 2 i Aluminium is tervalent in its compounds. AICI3 . and sulphate are water-soluble. ductile and malleable metal. 10.m. to study these reactions.AI2(S04h . Dilute hydrochloric acid dissolves the metal readily. 250 . or potash alum. Aluminium ions (AI3+) form colourless salts with colourless anions. The solubility is decreased in the presence of ammonium salts owing to the common ion effect (Section 1.23 ALUMINIUM. 16H 20. Reactions ofaluminium ( Ill) ions Use a O' 33M solution of aluminium chloride. dissolution is slower in dilute sulphuric or nitric acid: 2AI+6H+ -+ 2AI3++3H 2i The dissolution process can be speeded up by the addition of some mercury(II) chloride to the mixture. the powder is grey. With alkali hydroxides a solution of tetrahydroxoaluminate is formed: 2AI + 20H. slightly soluble in excess of the reagent.27). 1. these solutions display acidic reactions owing to hydrolysis. If however iron(III) is reduced by one of the ways described in reaction 13. and pale green in the reducing flame. these are ordinarily difficult to see. K 2S04 . Aluminium sulphate forms double salts with sulphates of monovalent cations with attractive crystal shapes. Ammonium solution: white gelatinous precipitate of aluminium hydroxide. grey metallic particles of iron are produced. with large quantities of iron the bead is reddish-brown in the oxidizing flame. or a O'166M solution of aluminium sulphate. b. the bead is yellowish-brown while hot and yellow when cold in the oxidizing flame. It melts at 659°C. nitrate.24H 20.+ 6H 20 -+ 2[ AI(OH)4]. but the oxide layer protects the object from further oxidation.za QUALITATIVE INORGANIC ANALYSIS and the thiocyanate test will be positive with these. these are called alums. Borax bead test With a small quantity of iron. Exposed to air. aluminium objects are oxidized on the surface. Its halides. Blowpipe test When iron compounds are heated on charcoal with sodium carbonate. but can be separated from the charcoal by means of a magnet. AI(OHh. Concentrated hydrochloric acid also dissolves aluminium: 2AI+6HCI-+ 2AI3++3H 2i+6CIConcentrated sulphuric acid dissolves aluminium with the liberation of sulphur dioxide: 2AI+6H 2S04 -+ 2AI3++3S0i-+3S0 2i+6H 20 Concentrated nitric acid renders the metal passive. the thiocyanate test will become negative. AliS04h. AI (Ar : 26·98) Aluminium is a white. is formed. in aqueous solutions it hydrolyses and aluminium hydroxide. 16.

when tetrahydroxoaluminate ions are formed: AI(OHh + OH-+ [AI(OH)4]- The reaction is a reversible one (compare Section 1. the aluminium solution is added in slight excess and the mixture boiled until the liquid has a slight odour of ammonia.+ 6H 20 -+ 2AI(OHh! + 3H 2Si The characteristics of the precipitate are the same as mentioned under reaction 2. sugars. but on boiling with excess reagent. because of the formation of soluble complex salts. [AI(OH)4]. 4. Sodium hydroxide solution: white precipitate of aluminium hydroxide: AIH + 30H- -+ AI(OHh! The precipitate dissolves in excess reagent. These organic substances must therefore be decomposed by gentle ignition or by evaporating with concentrated sulphuric or nitric acid before aluminium can be precipitated in the ordinary course of qualitative analysis. a voluminous precipitate of basic aluminium acetate AI(OHhCH 3COO is formed: AIH +3CH 3COO. it dissolves readily in strong acids and bases. Ammonium sulphide solution: a white precipitate of aluminium hydroxide: 2AIH + 3S2 . ammonium chloride) yielding a precipitate of aluminium hydroxide. in the latter case a large excess of acid causes the precipitated hydroxide to redissolve. known as aluminium hydroxide gel.n A small proportion of the precipitate passes into solution as colloidal aluminium hydroxide (aluminium hydroxide sol): the sol is coagulated on boiling the solution or upon the addition of soluble salts (e. This may be effected with a solution of ammonium chloride (the hydroxyl-ion concentration is reduced owing to the formation of the weak base ammonia.28).+NHt -+ AI(OHh!+NH 3i+H20 [AI(OH)4]. neutral solutions. sulphosalicylic acid. but after boiling it becomes sparingly soluble: AIH + 3NH 3 + 3H 20 -+ AI(OHh! + 3NHt 2. citric acid. which can 'be readily removed as ammonia gas by heating) or by the addition of acid. Sodium acetate solution: no precipitate is obtained in cold. and other organic hydroxy compounds.+ H+ +=t AI(OHh! + H 20 AI(OHh + 3H+! +=t AIH + 3H 20 The precipitation of aluminium hydroxide by solutions of sodium hydroxide and ammonia does not take place in the presence of tartaric acid. malic acid.and any reagent which will reduce the hydroxyl-ion concentration sufficiently should cause the reaction to proceed from right to left with the consequent precipitation of aluminium hydroxide.+2H 20 -+ AI(OHhCH 3COO!+2CH3COOH 251 . To ensure complete precipitation with ammonia solution.g.REACTIONS OF CATIONS m. 3. When freshly precipitated.

+ HC0 3 7. The test is applied to the precipitate of aluminium hydroxide obtained in the usual course of analysis. Phosphates.D QUALITATIVE INORGANIC ANALYSIS 5. Dissolve the aluminium hydroxide precipitate in 2 ml 2M hydrochloric acid. Beryllium gives a lake similar to that formed by aluminium. Sodium phosphate solution: white gelatinous precipitate of aluminium phosphate: AI3+ + HPOi.III. add I ml IOM ammonium acetate solution and 2 ml 0'1 per cent aqueous solution of the reagent. strong acids dissolve the precipitate. the precipitate is insoluble in acetic acid (difference from phosphates of alkaline earths.+2H+ --+ H 2C0 3 --+ H 20+COj The precipitate dissolves in excess reagent: AI(OHh l + CO~. Chromium forms a similar lake in acetate solution. Shake. and the test applied in the usual way. but this is rapidly decomposed by the addition of the ammoniacal ammonium carbonate solution.+=t AIP0 4!+H+ The reaction is reversible.+ H 20 --+ [Al(OH)4]. Sodium carbonate solution: white precipitate of aluminium hydroxide. persisting in the alkaline solution. since certain other elements interfere. is obtained. when carbon dioxide gas is formed: AI3+ + 3H 20 +=t AI(OHh! + 3H+ CO~. which are soluble). A bright-red precipitate (or colouration). It is then best to precipitate the aluminium phosphate by the addition of ammonia solution. 252 .+PO~- 6. Iron interferes with the test and should be absent. However. when present in considerable quantity. allow to stand for 5 minutes. The precipitate can also be dissolved in sodium hydroxide: AIP0 4! +40H--+ [AI(OH)4]. 'Aluminon' reagent (a solution of the ammonium salt of aurine tricarboxylic acid) COONH 4 H 4NOOC OOH HO-b-CQ=o COONH 4 this dye is adsorbed by aluminium hydroxide giving a bright-red adsorption complex or 'lake'. because the sodium carbonate neutralizes the acid liberated at the hydrolysis of aluminium. the resultant precipitate is redissolved in dilute acid. and add excess of ammoniacal ammonium carbonate solution to decolourize excess dyestuff and lakes due to traces of chromium(III) hydroxide and silica. prevent the formation of the lake. The reagent is prepared by dissolving 0'25 g of 'aluminon' in 250 ml of water.

Place a drop of the test solution (which has been treated with just sufficient of M sodium hydroxide solution to give the tetrahydroxaluminate ion [AI(OH)4]-) on a spot plate. Alizarin reagent red lake with aluminium hydroxide. Concentration limit: I in 333. Ca. Be. It is best to dry the paper at 100°C when the violet colour due to ammonium alizarinate disappears owing to its conversion into ammonia and alizarin: the red colour of the alizarin lake is then clearly visible. A blank test should be made on the sodium hydroxide solution. add I drop of the reagent.000. this difficulty is surmounted by dipping the paper after the alizarin treatment in ammonium carbonate solution which dissolves the uranium hexacyanoferrate(II). but this may be obviated by using paper previously treated with potassium hexacyanoferrate(II). The reagent consists of a 0'1 per cent aqueous solution of alizarin-So 253 . Zr. titanium. Place a drop of the acid test solution on the paper and hold it over ammonia fumes until a violet colour (due to ammonium alizarinate) appears. Sr. Bi. In the presence of large amounts of aluminium. Concentration limit: I in 80. owing to its slimy nature. Salts of Cu. chromium. and manganese interfere. rare earths. Zn. Sensitivity: 0'7 ~g AI. then drops of acetic acid until the violet colour just disappears and I drop in excess. The interfering ions are thus 'fixed' on the paper as insoluble hexacyanoferrate(II)s. Ce. Upon adding a drop of a saturated alcoholic solution-of alizarin. Soak some quantitative filter (or drop-reaction) paper in a saturated alcoholic solution of alizarin and dry it.REACTIONS OF CATIONS m.000. exposing to ammonia vapour and drying. the colour is visible almost immediately. has a tendency to spread outwards from the spot and thus obscure the aluminium lake. Co. Iron. Ti. and the aluminium solution diffuses beyond as a damp ring. thorium. Fe. Th. which is fairly stable to dilute acetic acid.n 8. uranium. A red precipitate or colouration appears. Sensitivity: 0'15 ~g AI. U. Alizarin-S (or sodium alizarin sulphonate) reagent red precipitate or lake in ammoniacal solution. and Ba interfere. 9. Uranium hexacyanoferrate(II). a red ring of the alizarin-aluminium lake forms round the precipitate.

III.24 QUALITATIVE INORGANIC ANALYSIS 10. 254 . The reagent paper is prepared by soaking quantitative filter paper in a solution obtained by dissolving 0·01 g quinalizarin in 2 ml pyridine and then diluting with 18 ml acetone. 2Al 20 3 +2Co2+ +4N0 3 -+ 2CoAl 20 4 +4N0 2i +0 2t An alternative method for carrying out this test is to soak some ashless filter paper in aluminium salt solution. with the formation of hydrogen. concentrated sulphuric acid chromium dissolves readily.8-tetrahydroxyanthraquinone) reagent red precipitate or colouration under the conditions given below.+H 2i In the presence of atmospheric oxygen chromium gets partly or wholly oxidized to the tervalent state: 4Cr2+ + O 2 +4H+ -+ 4Cr3+ +2H 20 Dilute sulphuric acid attacks chromium slowly. It melts at 1765°C. chromium(II) ions are formed: Cr+2H+ -+ Cr2+ +H 2i Cr+2HC1-+ Cr2+ +2Cl. or cobalt meta-aluminate) is obtained. crystalline metal and is not appreciably ductile or malleable. A red-violet or red spot is formed.000.CHROMIUM(III) Chromium is a white. The metal is soluble in dilute or concentrated hydrochloric acid. which glows when hot. concentrated sulphuric acid and aqua regia.5. a blue infusible mass (Thenard's blue. 11. add a drop or two of cobalt nitrate solution and then to ignite the filter paper in a crucible. Sensitivity: 0·005 ~g Al (drop ofO·l ml). In hot. which masks the colour of the Thenard's blue. the residue is coloured blue. Concentration limit: I in 2. Cr (A r : 51·996) . so does cold. If air is excluded. when chromium(III) ions and sulphur dioxide are formed: 2Cr+6H 2S0 4 -+ 2Cr3++3S0~-+3S02i+6H20 Both dilute and concentrated nitric acid render chromium passive.000. Dry tests (blowpipe test) Aluminium compounds when heated with sodium carbonate upon charcoal in the blowpipe flame give a white infusible solid.24 CHROMIUM. Quinalizarin (or 1. III. hold it for a short time over a bottle containing concentrated ammonia solution and then over glacial acetic acid until the blue colour (ammonium quinalizarinate) first formed disappears and the unmoistened paper regains the brown colour of free quinalizarin. Place a drop of the test solution upon the reagent paper. It is important not to use excess cobalt nitrate solution since this yields black cobalt oxide C0 304 upon ignition. If the residue be moistened with one or two drops of cobalt nitrate solution and again heated.2.

they will not be dealt with here. Chromium(II) ions are rather unstable. 6H 20 or a O'166M solution of chromium(III) sulphate CriS04h .they decompose even water slowly with the formation of hydrogen. In solution they are either green or violet.+2H+ ~ Cr20~. Chromate ions are yellow while dichromates have an orange colour. while in the violet solutions the hexaquochromate(III) ion [Cr(H 20)6]3+ is present. Reaction ofchromium(Ill) ions To study these reactions use a O'33M solution of chromium(III) chloride CrCl 3 .+H 20 The reaction is reversible. Chromate and dichromate ions are strong oxidizing agents. Their reactions will be dealt with among the reactions of anions. Chromium(III) (or chromic) ions (Cr3+) are stable and are derived from dichromium trioxide (or chromium trioxide. In the chromate. Atmospheric oxygen oxidizes them readily to chromium(III) ions. upon boiling the solution. As they are only rarely encountered in inorganic qualitative analysis. chromium(III) hydroxide is not precipitated. like aluminium sulphide. dichromate ions will be predominant. can be prepared only in dry. it hydrolyses readily with water to form chromium(III) hydroxide and hydrogen sulphide. Chromates are readily transformed into dichromates on addition of acid: 2CrOi. or dichromate.15H 20. anions chromium is hexavalent with an oxidation state of + 6. Cr20~-. Cr 203. Sodium hydroxide solution: precipitate of chromium(III) hydroxide Cr3+ + 30H- --+ Cr(OHh! 255 . These ions are derived from chromium trioxide Cr0 3. These ions form blue coloured solutions.REACTIONS OF CATIONS mza In aqueous solutions chromium forms three types of ions: the chromium(II) and chromium(III) cations and the chromate (and dichromate) anion. Chromium(III) sulphide. it is essential that the solution be boiling and excess aqueous ammonia solution be avoided. In the green solutions the pentaquomonochlorochromate(III) [Cr(H20hCI]2+ or the tetraquodichlorochromate [Cr(H20)4CI2]+ complex is present (chloride may be replaced by another monovalent cation). as they are strong reducing agents . in which chromium has an oxidation state of + 6. 1. CrOi-. 2. chromium hydroxide is precipitated. Hence for complete precipitation of chromium as the hydroxide. Ammonia Solution: grey-green to grey-blue gelatinous precipitate of chromium(III) hydroxide. In neutral (or alkaline) solutions the chromate ion is stable. slightly soluble in excess of the precipitant in the cold forming a violet or pink solution containing complex hexamminechromate(III) ion. Cr 3+ + 3NH 3 + 3H 20 --+ Cr(OHh! + 3NHt Cr(OHh! + 6NH 3 --+ [Cr(NH 3)6]3+ + 30HIn the presence of acetate ions and the absence of other tervalent metal ions. The precipitation of chromium(III) hydroxide is also prevented by tartrates and by citrates. Cr(OHh. while if acidified. The chromium(II) (or chromous) ion (Cr2+) is derived from chromium(II) oxide CrO.

Sodium phosphate solution: green precipitate of chromium(III) phosphate: Cr3+ + HPOi- ~ CrP04!+H+ The precipitate is soluble in mineral acids but is practically insoluble in cold dilute acetic acid. This reaction is reversible. chromate ions may be identified in the solution by one of its reactions (cf. Section IV. whilst some aluminium. Section V. Sodium carbonate solution: precipitate of chromium(III) hydroxide: 2Cr3+ + 3CO~. The excess of hydrogen peroxide can be removed by boiling the mixture for a few minutes. In excess reagent the precipitate dissolves readily. Ammonium sulphide solution: precipitate of chromium(III) hydroxide: 2Cr3+ +3S 2 . reaction 2). and chromium will remain in the filtrate. If the chromium is present in excess.+ 8H 20 After decomposing the excess of hydrogen peroxide by boiling.13) is therefore uncertain in the presence of a large concentration of chromium. Note.+ 3H 20 --+ 2Cr(OHh! + 3C0 2 j 4. (a) Adding an excess of sodium hydroxide to a chromium(III) salt followed by a few ml of 6 per cent ('20-volume') hydrogen peroxide (cf. Formerly sodium peroxide was employed to effect this oxidation. On adding hydrogen peroxide to the alkaline solution of tetrahydroxochromate(III). tetrahydroxochromate(III) ions (or chromite ions) being formed: Cr(OHh +OH~ [Cr(OH)4]- The solution is green. owing to the oxidation of chromium(III) to chromate: 2[Cr(OH)4]. only a fraction of all the metals will be precipitated as basic acetates.+6H 20 --+ 2Cr(OHh!+3H 2Sj 5. The basic acetate method of removal of phosphates (see Section V. on the addition of acids the precipitate dissolves. in hot solution it reacts almost explosively. iron. on (slight) acidification and also on boiling chromium(III) hydroxide precipitates again. 6. Chromate test Chromium(III) ions can be oxidized to chromate in several ways. The sodium peroxide must be added to the cold solution. The use of sodium peroxide is not recommended. 3.13). The precipitation of chromium(III) hydroxide is prevented by the presence of certain organic compounds in solution (see under aluminium. (b) Hydrogen peroxide can be replaced by a little solid sodium perborate 256 .33). the precipitate of basic acetates obtained on boiling contains the basic acetate Cr(OHh. a yellow solution is obtained.ill. Sodium acetate solution: no precipitate even on boiling the solution.+ 3H 20 2 + 20H--+ 2CrOi. CH 3COO.24 QUALITATIVE INORGANIC ANALYSIS The reaction is reversible. In the presence of considerable amounts of iron and aluminium salts. 7.

when hydrolysed. The name peroxochromic acid is less appropriate. form hydrogen peroxide. Acidifying the solution with dilute sulphuric acid. Silver ions act as catalysts. adding 2-3 ml of ether or amyl alcohol to the mixture and finally adding some hydrogen peroxide.--+ BaCr04 ! b. Barium chloride test After acidifying the solution with acetic acid and adding barium chloride solution. because the compound does not contain hydrogen at all. the solution can be diluted and the test carried out. the catalytic action is due to the transitional formation of silver(III). Chromium pentoxide (chromium peroxide. which gives tribromophenol. In aqueous solution the blue colour fades rapidly.4H 20 in experiment (a). Identification of chromium after oxidation to chromate. they can be removed easily by evaporating the solution with concentrated sulphuric acid until fumes of sulphur trioxide appear. Halides must be absent.e. by hypobromite): 2Cr3+ + 30Br. a yellow precipitate of barium chromate is formed: Ba2+ +CrOi. because chromium pent oxide decomposes to chromium(III) and oxygen: 4CrO s + 12H+ --+ ° 4Cr3+ + 70 2i + 6H 20 257 .+ 2H+ + 2H 202 --+ CrO s + 3H 20 Chromium pentoxide has the following structure: 0 0 Cr 1 0110 I Because of the two peroxide groups the compound is often called chromium peroxide.+ 8H 20 --+ 2CrOi.+ 100H. which can be extracted into the organic phase by gently shaking.24 NaB0 3. (d) In acid solution chromium(III) ions can be oxidized by potassium (or ammonium) peroxodisulphate: 2Cr3+ + 3S20~. Ag3+. During the reaction chromium pent oxide is formed: CrOi. chromate ions may be identified with one of the following tests: a. After cooling.+ 3Br. In alkaline medium this reaction can be written: as B0 3 + 20H--+ BO~- + H 202 (c) Oxidation can be carried out with bromine water in alkaline solution (i. Perborate ions.--+ 2CrOi. a blue colouration is formed. The excess of peroxodisulphate can be decomposed by boiling: 2S20~- + 2H 20 --+ 4S0i.REACTIONS OF CATIONS III.+ 5H 20 The excess of bromine can be removed by the addition of phenol.+ 4H+ + O 2l 8.+ 16H+ + 6S0iOne drop of dilute silver nitrate has to be added to speed up the reaction. Having carried out the oxidation with one of the methods described under reaction 7. peroxochromic acid) test.

000. During the reaction chromate is reduced to chromium(II). Copper. and finally M sulphuric acid dropwise until the red colour (from the reaction between diphenylcarbazide and alkali) disappears. in this case the preliminary oxidation to chromate can also be made on the spot plate. and vanadates. and allow to stand for 2-3 minutes. A blue-violet colouration is obtained.24 QUALITATIVE INORGANIC ANALYSIS c. Concentration limit: I in 2. molybdates. Alternatively. Concentration limit: I in 600. these reaction products in turn produce a complex with the characteristic colour: / C==O ~ NH-NH-C6H s / +crO~---->C==O ~ N=N-C6H s +Cr2+ +4H 20 NH-NH-C6H s diphenylcarbazide 6H s /N=N--C C==O +Cr2+ N=N-C6H s diphenylcarbazone [ IN=N.000.J gives a red colouration (by transmitted light) with an alkali chromate in the presence of nitric acid. A violet or red colour is formed. manganese. and cobalt salts interfere in this procedure because of their precipitation by the alkali. Chromotropic acid test.~ C6HS] 2+ C-O-Cr \ I N-N-C6H s "<. (or chromotropic acid) 1. The influence of molybdates can be eliminated by the addition of saturated oxalic acid solution thereby forming the complex H 2[Mo0 3(C204 ) ]. Add a drop of the diphenylcarbazide reagent.III. Sensitivity: 0'8 ~g Cr. and diphenylcarbazone is formed.000. then a drop of the diphenylcarbazide reagent. N=N--C6H s diphenlycarbazone-chromium(lI) complex The reaction can be applied as a drop test for chromium. Manganese ions interfere (oxidized to permanganate) as do also mercury(II) salts.Sroro. add a crystal of phenol.8-dihydroxynaphthalene-3. which give blue to violet compounds with the reagent in acid solution. Chromium(III) salts may be oxidized with hydrogen 258 .6-disulphonic acid (HO. mix a drop of the acidified test solution on a spot plate with 2 drops O'lM potassium peroxodisulphate solution and I drop O'lM silver nitrate solution. d. Sensitivity: 0'25 ~g Cr. Mix thoroughly. Diphenylcarbazide test In dilute mineral acid solution diphenylcarbazide produces a soluble violet colour. The reagent consists of a I per cent solution of diphenylcarbazide in alcohol. which is a characteristic test for chromium. nickel. Place a drop of the test solution in mineral acid on a spot plate. introduce a drop of saturated bromine water followed by 2-3 drops 2M potassium hydroxide (the solution must be alkaline to litmus).

Place a drop of the test solution in a semimicro test-tube. and Ti.34. sometimes. If therefore chromium(lIl) and/or manganese(lI) are found. Anhydrous or undissociated cobalt(lI) compounds are blue.000. like chromate CrOi.25J26 peroxide and alkali to chromate. the cobalt(llI) ion Co3+ is encountered. The metal dissolves readily in dilute mineral acids: Co + 2H+ --+ COH + H 2i The dissolution in nitric acid is accompanied with the formation of nitrogen oxide: 3Co + 2HN0 3 + 6H+ --+ 3Co H + 2NOi + 4H 20 In aqueous solutions cobalt is normally present as the cobalt(lI) ion COH . the initial oxidation states of these metals should be tested in the original sample. Dry tests 8.REACTIONS OF CATIONS III. The reactions of these ions are described in Chapter IV. those of chromates and dichromates in Section IV.33. add a drop of the reagent. The reagent consists of a saturated solution of chromotropic acid in water.(and dichromate. U. 9. Chromates give a red colouration: this is best observed with a white light behind the tube. especially in complexes. It melts at 1490°C. but is not very characteristic. slightly magnetic metal. The nitric acid serves to eliminate the influence of Fe. Co (Ar : 58·93) Cobalt is a steel-grey. If the 259 . and then acidified with nitric acid before applying the test. are reduced by hydrogen sulphide in hydrochloric acid media to chromium(III) and manganese(lI) ions respectively. Chapter V) these anions will already be converted into the corresponding Group III cations when the separating process reaches this stage. Blowpipe test All chromium compounds when heated with sodium carbonate on charcoal yield a green infusible mass of chromium(lIl) oxide Cr 20 3 • b. and dilute to about 2 ml. which otherwise interfere.26 COBALT. Borax bead test The bead is coloured green in both the oxidizing and reducing flames.25 OXOANIONS OF GROUP In METALS: CHROMATE AND PERMANGANATE The oxoanions of certain Group III metals. Fusion with sodium carbonate and potassium nitrate in a loop of platinum wire or upon platinum foil or upon the lid of a nickel crucible results in the formation of a yellow mass of alkali chromate. and the reactions of permanganates in Section IV. Concentration limit: I in 5. These two ions are derived from the oxides CoO and C0 20 3 respectively. c. The cobalt(II)--eobalt(lIl) oxide C0 304 is also known. In the course of the systematic analysis of an unknown sample (cf. a drop of dilute nitric acid (l: I). Cr20~-) as well as permanganate MnOi. 111. In the aqueous solutions of cobalt(lI) compounds the red COH ions are present. Cr2(S04h + 5Na 2C0 3 + 3KN0 3 = 2Na 2Cr04 + 3KN0 2 + 3Na2S04 + 5C0 2i 111.

6H 20.--+ [Co(NH 3)6]2+ + 6H 20 The yellowish-brown solution of hexamminecobaltate(II) ions turns slowly to brownish-red if exposed to air. the colour of the solution turns gradually to blue. 2. but their complexes are stable both in solution and in dry form.26 QUALITATIVE INORGANIC ANALYSIS dissociation of cobalt compounds is suppressed. Ammonia solution: in the absence of ammonium salts small amounts of ammonia precipitate the basic salt as in reaction I : Co2+ + NH 3 + H 20 + N0 3 260 --+ Co(OH)N0 3! + NHt . alkali hydroxides do not precipitate cobalt(II) hydroxide at all. 1. The same is true for solutions containing citrates or tartrates. Reactions ofthe cobalt(II) ions The reactions ofcobalt(II) ions can be studied with a O'5M solution of cobalt(II) chloride CoCI 2. Cobalt(III) ions Co3+ are unstable.+H 20 --+ 2Co(OHh!+CICobalt(II) hydroxide precipitate is readily soluble in ammonia or concentrated solutions of ammonium salts. 6H 20 or cobalt(II) nitrate Co(N0 3h . The hydroxide is slowly transformed into the brownish-black cobalt(III) hydroxide on exposure to the air: 4Co(OHh!+02+2H20 --+ 4Co(OHh! The change takes place more rapidly if an oxidizing agent. Sodium hydroxide solution: In cold a blue basic salt is precipitated: Co2+ + OH. provided that the mother liquor is alkaline: Co(OHh! +6NH 3 --+ [Co(NH 3)6]2+ +20HCo(OHh! + 6NHt + 40H. like sodium hypochlorite or hydrogen peroxide is added: 2Co(OHh! + H 202 --+ 2Co(OHh! 2Co(OHh!+OCI.III. hydrogen peroxide oxidizes the complex ion more rapidly to hexamminecobaltate(III) ions: 4[Co(NH 3)6]2+ +0 2 +2H 20 --+ 4[Co(NH 3)6J3+ +40H2[Co(NH 3)6]2+ +H 202 --+ 2[Co(NH 3)6J3+ +20HIn the presence of ammonium salts. Cobalt(II) complexes can easily be oxidized to cobalt(III) complexes.+ N0 3 --+ Co(OH)N0 3! Upon warming with excess alkali (or sometimes merely upon addition of excess reagent) the basic salt is converted into pink cobalt(II) hydroxide precipitate: Co(OH)N0 3! + OH--+ Co(OHh! + N0 3 Some of the precipitate however passes into solution.

+ 40H2[Co(CN)6]4.+20H261 . Hot. If the brown solution is boiled for a longer time in air. but the complex is formed in one step.+4H+ -+ Co(CNh! +4HCNj The experiment must be carried out in a fume cupboard with good ventilation. when hexamminecobaltate(II) ions are formed: Co(OH)N0 3!+6NH3 -+ [Co(NH 3)6]2+ +N0 3 +OHThe precipitation of the basic salt does not take place at all if larger amounts of ammonium ions are present. Under such conditions the equilibrium Co2+ +6NHt +=t [Co(NH 3)6]2+ +6H+ gets shifted towards the right by the removal of hydrogen ions by ammonia: H+ +NH 3 -+ NHt The characteristics of the precipitate and the complex are identical to those described under reaction I.REACfIONS OF CAnONS rnze The excessof the reagent dissolves the precipitate.-+ CoS! The precipitate is insoluble in dilute hydrochloric or acetic acids (though precipitation does not take place from such media).+3NOClj+8H+ +2H 20 4.+6CI. Potassium cyanide solution (POISON): reddish-brown precipitate of cobalt(II) cyanide: Co2+ +2CN. a brown solution of hexacyanocobaltate(II) is formed: Co(CNh! + 4CN. concentrated nitric acid or aqua regia dissolve the precipitate. when white sulphur remains: 3CoS!+2NH03+6H+ -+ 3Co2+ +3S!+2NOj+4H 20 CoS! + HN0 3 + 3HCI -+ Co 2+ + S! + NOCI j + 2ClOn longer heating the mixture becomes clear because sulphur gets oxidized to sulphate: S!+2HN0 3 -+ SO~-+2H+ 2NOj S!+3HN0 3+9HC1-+ s01. or if some hydrogen peroxide is added and the solution heated. 3. it turns yellow because hexacyanocobaltate(III) ions are formed: 4[Co(CN)6]4. Ammonium sulphide solution: black precipitate of cobalt(II) sulphide from neutral or alkaline solution: Co2+ +S2.-+ [CO(CN)6]4On acidification in the cold with dilute hydrochloric acid the precipitate reappears: [CO(CN)6]4.+ O 2 + 2H 20 -+ 4[Co(CN)6]3.+H 202 -+ 2[Co(CN)6]3.-+ Co(CNh! The precipitate dissolves in excess reagent.

Ammonium thiocyanate test (Vogel reaction): adding a few crystals of ammonium thiocyanate to a neutral or acid solution of cobalt(II) a blue colour appears owing to the formation of tetrathiocyanatocobaltate(II) ions: Co2+ +4SCN- -+ [CO(SCN)4]2- If amyl alcohol or ether is added the free acid H 2[Co(SCN)4] is formed and dissolved by the organic solvent (distinction from nickel).000.000. the precipitate appears immediately. The reaction may be employed as a spot test as follows. Concentration limit: I in 100. If the concentration of cobalt(II) in the test solution is high enough. then a freshly prepared saturated solution of potassium nitrite. The colourless hexafluoroferrate(III) [FeF 6]3. Alternately. A green to blue colouration appears. 262 . iron(III) can be reduced with sodium thiosulphate or ascorbic acid (a few ml of a O'IM solution of either). formed in the reduction. A blue colouration is produced. Otherwise the mixture should either be slightly heated. The reaction is also characteristic for potassium and for nitrite ions. If iron is present mix 1-2 drops of the slightly acid test solution with a few milligrams of ammonium or sodium fluoride on a spot plate and then add 5 drops saturated solution of ammonium thiocyanate in acetone. Nickel ions do not react if acetic acid is present. nitrite oxidizes cobalt(II) to cobalt(III) : Co2+ +N02" +2H+ -+ Co 3++NOj+H 20 K 3[Co(N0 2)6] (b) then cobalt(III) ions react with nitrite and potassium ions: Co3+ +6N02" +3K+ -+ (c) Adding reactions (b) and (c) we obtain reaction (a). or the wall of the vessel should be rubbed with a glass rod. Sensitivity: 0'5 ~g Co. 6. Interference of iron(III) ions can be eliminated by adding some potassium fluoride. when the equilibrium 2H+ + [CO(SCN)4]2~ H 2[Co(SCN)4] shifts towards the formation of the free acid. Potassium nitrite solution: yellow precipitate of potassium hexanitritocobaltate(III) K 3[Co(N0 2)6] ' 3H 20: Co2+ + 7N02" +2H+ + 3K+ -+ K 3[Co(N0 2)6] ! + NOj + H 20 (a) This reaction takes place in two steps. do not interfere any more. mix I drop test solution with 5 drops saturated solution of ammonium thiocyanate in acetone. The test can be carried out most conveniently as follows: to a neutral solution of cobalt(II) add acetic acid. and iron(II) ions. First. Sensitivity: I ~g Co in the presence of 100 times that amount of Fe.complex does not interfere. Upon a spot plate. which then can be extracted with amyl alcohol or ether.mzs QUALITATIVE INORGANIC ANALYSIS 5. Concentration limit: I in 50. The test is rendered more sensitive if the solution is acidified with concentrated hydrochloric acid.

Large quantities of ammonium salts reduce the sensitivity. 263 . and add 2-3 drops of the reagent. Rubeanic acid (or dithio-oxamide ) reagent H 2N -C. Place a drop of the test solution upon drop-reaction paper.000. Sodium l-nitroso-I-hydroxynaphthalene-B: 6-disulphonate (nitroso-Rvsalt) reagent deep-red colouration. «-Nitroso-Bsnaphthol reagent reddish-brown precipitate of slightly impure cobalulflj-nitroso-ji-naphthol Co(C 1 o H 6 0 2 N h (a chelate complex) in solutions acidified with dilute hydrochloric acid or dilute acetic acid: the precipitate may be extracted by carbon tetrachloride to give a claret-coloured solution. Precipitates are also given by iron (Fe2+ and Fe3+). Concentration limit: I in 1. or in acetone. The test is applicable in the presence of nickel.000. The reagent consists of an O· 5 per cent solution of rubeanic acid in alcohol. A red colouration is obtained. or in ethanol. Sensitivity: 0·03 ~g Co.N H 2) ( 11 11 : Co. The technique for using the reaction as a spot test is as follows. nickel and uranyl salts in Group Ill. Concentration limit: I in 660. A brown spot or ring is formed. The reagent consists of a I per cent solution of «-nitroso-ji-naphthol in 50 per cent acetic acid.000. The nickel complex is soluble in dilute hydrochloric acid. The reagent consists of a I per cent solution of nitroso-R-salt in water. and then add a drop of the reagent. 9. and many other metals interfere. Copper. The reaction may. 8. palladium.000. be used as a confirmatory test for cobalt among the Group(I1I) ions. by ammonium phosphate solution. the uranyl iron may be removed. hold it in ammonia vapour. and add a drop of the reagent.REACTIONS OF CAnONS ill. Place a drop of the faintly acid test solution on drop-reaction paper. mercury(I1). Under similar conditions nickel and copper salts give blue and black precipitates respectively (see Section 111.sw:J S S yellowish-brown precipitate. the colouration produced by iron is prevented by the addition of an alkali fluoride.10).26 7. however. A brown stain is produced. Sensitivity: 0·05 ~g Co.C. iron(I1I) is rendered innocuous by the addition of sodium fluoride. as uranyl phosphate. Concentration limit: I in 500. tin and iron interfere and should be removed. Place a drop of the neutral test solution (buffered with sodium acetate) on a spot plate.

hot sulphuric acid dissolves nickel with the formation of sulphur dioxide: Ni+ H 2S0 4 +2H+ -+ Ni2+ + S02 t +2H 20 Dilute and concentrated nitric acid dissolve nickel readily in cold: 3Ni+2HN0 3 +6H+ -+ 3Ni2+ +2NOi +4H 20 The stable nickel(II) salts are derived from nickel(II) oxide. silver-white metal. The presence of a large proportion of nickel does not interfere.-+ [Ni(NH 3)6]2+ +6H 20 The solution of hexamminenickelate(II) ions is deep blue. A brownish-black nickel(III) oxide Ni 203 also exists. a few drops of concentrated hydrochloric acid added and the filter paper dried. Borax bead test This gives a blue bead in both the oxidizing and reducing flames. or the complex salt Na 2Co(B02)4' is formed. With dilute hydrochloric acid this reaction yields chlorine gas: Ni 20 3 +6H+ +2CI. it is ductile. It is slightly magnetic. Ni (Ar : 5S·71) Nickel is a hard. Sodium hydroxide solution: green precipitate of nickel(II) hydroxide: Ni2+ +20H. Concentrated. Cobalt metaborate Co(B0 2h. in the presence of excess alkali hydroxide ammonium salts will also dissolve the precipitate: Ni(OHh!+6NH 3 -+ [Ni(NH 3)6]2+ +20HNi(OHh!+6NH! +40H. 111. If these are removed.27 QUALITATIVE INORGANIC ANALYSIS 10 Dry tests a. Blowpipe test All cobalt compounds when ignited with sodium carbonate on charcoal give grey. 1.27 NICKEL.10).-+ 2Ni2+ +C1 2t +3H 20 Reactions of the nickelt Il] ions For the study of these reactions use a O·5M solution of nickel sulphate NiS0 4 • 7H 20 or nickel chloride NiCI 2.III. 264 . b. but this dissolves in acids forming nickel(II) ions. The dissolved nickel(II) salts are green. The solution does not oxidize on boiling with free exposure to air or upon the addition of hydrogen peroxide (difference from cobalt). malleable and very tenacious. which is a green substance. placed upon filter paper. NiO. which form the blue tetramminecuprate(II) ions in an analogous reaction (cf. it can be easily mistaken for copper(II) ions. owing to the colour of the hexaquonickelate(II) complex [Ni(H 20)6]2+ . the latter is coloured blue by the cobalt chloride produced. Ammonia dissolves the precipitate.-+ Ni(OHh! The precipitate is insoluble in excess reagent. 6H 20. Section 111. slightly metallic beads of cobalt. this will be regarded as the simple nickel(II) ion Ni2+. in short however. It melts at I455°C. owing to complex formation. and dissolved by the addition of a few drops of dilute nitric acid. No precipitation occurs in the presence of tartrate or citrate. Hydrochloric acid (both dilute and concentrated) and dilute sulphuric acid dissolve nickel with the formation of hydrogen: Ni+2H+ -+ Ni2++H 2i Ni+2HCI-+ Ni2++2CI-+H 2i These reactions accelerate if the solution is heated.

+ H 20 --+ 2Ni(OHh! + ClHydrogen peroxide solution however does not oxidize nickel(II) hydroxide.17 The green nickel(II) hydroxide precipitate can be oxidized to black nickel(III) hydroxide with sodium hypochlorite solution: 2Ni(OHh + ClO. If ammonium salts are present. but the complex is formed immediately. Ammonia solution: green precipitate of nickel(II) hydroxide: NF++2NH 3+2H 20 --+ Ni(OHh!+2NHt which dissolves in excess reagent: Ni(OHh! + 6NH 3 --+ [Ni(NH 3)6] H + 20Hthe solution turns deep blue (cf.--+ Ni(CNh! 265 . Nickel sulphide is practically insoluble in cold dilute hydrochloric acid (distinction from the sulphides of manganese and zinc) and in acetic acid. 5. however. or from solutions containing excess of alkali acetate made slightly acid with acetic acid (compare Section 1. no precipitation occurs from solutions containing mineral acid or much acetic acid. The presence oflarge quantities of ammonium chloride usually prevents the formation of the sol. reaction I). 3.+2H 20 On longer heating sulphur dissolves and the solution becomes clear: S! +2HN0 3 --+ SOi. Potassium cyanide solution (POISON): green precipitate of nickel(II) cyanide NF+ +2CN.+2H+ +2NOj S!+3HN0 3+9HCI--+ soi. a dark-brown colloidal solution is formed which runs through the filter paper. Hydrogen sulphide (gas or saturated aqueous solution): only part of the nickel is slowly precipitated as nickel sulphide from neutral solutions. no precipitation occurs.+3NOClj+8H+ +2H 20 4.+6CI. but dissolves in hot concentrated nitric acid and in aqua regia with the separation of sulphur: 3NiS! + 2HN0 3 + 6H+ --+ 3Ni H + 2NOj + 3S! + 4H 20 NiS! +HN0 3 +3HCI--+ Ni H +S!+NOClj +2CI. Ammonium sulphide solution: black precipitate of nickel sulphide from neutral or slightly alkaline solutions: Ni H + S2. If the colloidal solution is boiled or if it is rendered slightly acid with acetic acid and boiled.REACfIONS OF CATIONS ill.--+ NiS! If the reagent is added in excess. but the precipitate catalyses the decomposition of hydrogen peroxide to oxygen and water 2H 202 Ni(OHh! I 2H 20 + O 2t without any other visible change. from solutions made alkaline with ammonia solution. the colloidal solution (hydrosol) is coagulated and can then be filtered. Complete precipitation occurs. 2.28).

Potassium nitrite solution: no precipitate is produced in the presence of acetic acid (difference from cobalt). which is poisonous and causes watering of the eyes: CN. when a yellow solution appears owing to the formation of tetracyanonickelate(lI) complex ions: Ni(CNh! +2CN--+ [Ni(CN)4]2- Dilute hydrochloric acid decomposes the complex. The spot test technique is as follows. 8. The influence of interfering elements (Fe2+ must be oxidized to Fe 3+. which produces a reddish-brown precipitate.+ H 20 --+ 2Ni(OHh! + 8CN. the complex decomposes and a black nickel(III) hydroxide precipitate is formed (difference from cobalt ions): 2[Ni(CN)4]2.26.27 QUALITATIVE INORGANIC ANALYSIS The precipitate is readily soluble in excess reagent.+ Br" Excess potassium cyanide and/or excess bromine water should be avoided.III. and the precipitate appears again. Palladium. Oxidizing agents must be absent.+2H+ --+ Ni(CNh! +2HCNj If the solution of tetracyanonickelate(II) is heated with sodium hypobromite solution (prepared in situ by adding bromine water to sodium hydroxide solution).+ OBr. because these react with the formation of cyanogen bromide. by hydrogen peroxide) can be eliminated by the addition of a tartrate. a-Nitroso-B-naphthol reagent (cf Section 111. which is soluble in hydrochloric acid (different from cobalt. When large quantities of cobalt salts are present. A fume cupboard with good ventilation must be used for this test: [Ni(CN)4]2. platinum. 7. say.+ Br2 --+ BrCNj + Br" 6. The reagent is prepared by dissolving I g dimethylglyoxime in looml ethanol. Place a drop of the test solution on drop266 . Dimethylglyoxime reagent (C 4Hs0 2N2 ) : red precipitate of nickel dimethylglyoxime from solutions just alkaline with ammonia or acid solutions buffered with sodium acetate: Iron(II) (red colouration). and larger amounts of cobalt (brown colouration) interfere in ammoniacal solution.+ 40H. insoluble in dilute hydrochloric acid). reaction 7): brown precipitate of composition Ni(C 1oH 60 2Nh. bismuth (yellow precipitate). and gold give precipitates in acid solution. they react with the dimethylglyoxime and a special procedure must be adopted (see below).

as well as iron salts interfere with the reaction and should be absent. place a drop of the test solution and a drop of the reagent on a spot plate. cobalt(III) ions represss the sensitivity and should be oxidized to the tervalent state with hydrogen peroxide. The reagent consists of a 10 per cent solution of «-furil-dioxime in alcohol. and add a drop of dilute ammonia solution.000. slightly magnetic scales of metallic nickel. [Ni(CN)4]2. Dry tests a. Copper and cobalt. Rubeanic acid reagent (CS . Upon adding 40 per cent formaldehyde solution the hexacyanocobaltate(III) is unaffected (and hence remains inactive to dimethylglyoxime) whereas the tetracyanatonickelate(II) decomposes with the formation of nickel cyanide. hold it over ammonia vapour and add a drop of the reagent. If these are placed upon a strip of filter paper. A red precipitate or colouration is formed. or by iron(III). ammonium chloride should first be added. Concentration limit: I in 1.000. a few drops of concentrated hydrochloric acid added and the filter paper dried by moving it back and forth in the flame or by placing it on the outside of a test-tube containing water which is heated to boiling point. chromium or aluminium in the presence of ammoniacal tartrate solution: if zinc is present. The solution containing the cobalt and nickel is treated with excess concentrated potassium cyanide solution.000. which reacts immediately with the dimethylglyoxime. Alternatively. «-Furil-dioxime reagent red precipitate in slightly ammoniacal solution.+2HCHO --+ Ni(CNh! +2CHiCN)ONi(CNh!+2C 4Hs 0 2N2 --+ Ni(C 4H 7 0 2N2h!+2HCNj 9.27 reaction paper. dissolved by means of a few drops of nitric acid. Sensitivity: 0·02 Jlg Ni. The reagent consists of a I per cent solution of rubeanic acid in alcohol. 267 .250. followed by 30 per cent hydrogen peroxide whereby the complex cyanides [CO(CN)6]3. the reaction may be carried out on a spot plate. Blowpipe test All nickel compounds when heated with sodium carbonate on charcoal yield grey. 10. A red spot or precipitate (or colouration) is produced.respectively are formed. Detection of traces of nickel in cobalt salts. 11. Alternatively. A blue or blue-violet spot is obtained. Place a drop of the test solution upon drop-reaction paper. Sensitivity: 0·03 Jlg Ni. Concentration limit: I in 6. iron(II) interferes and should be oxidized and alkaline tartrate solution added before applying the test.000. add a drop of the above reagent and hold the paper over ammonia vapour. Sensitivity: 0·16 Jlg Ni.and [Ni(CN)4]4. Place a few drops of the slightly ammoniacal test solution in a micro test-tube and add a few drops of the reagent.REACTIONS OF CATIONS m. Concentration limit: I in 300. The reaction is not disturbed by silver or copper.NH2 ) 2: blue or violet precipitate or colouration in ammoniacal solution.

They form colourless salts. when treated with mineral acids. 10. and the manganate(lV) (or manganite) ion. or of the complex metaborate Na 2[Ni(B02)4]' and grey. Borax bead test This is coloured brown in the oxidizing flame. It melts at about 12500C. Manganese(III) ions are unstable. MnO~-. some complexes. are easily reduced to manganese(II).MANGANESE(II) Manganese is a greyish-white metal. Mn203' Mn0 2. while the last. b. manganese(lV) oxide produces manganese(II) ions as well as chlorine and oxygen gas respectively: Mn0 2!+4HCI-+ Mn2++CI 2i+2CI-+2H20 2Mn0 2! + 2H 2S04 -+ 2Mn2+ + O 2i + 2S0i. with the exception of the manganese(IV) oxide (or manganese dioxide). oxygen is formed: 2Mn 203 +4H 2S04 -+ 4Mn2+ +0 2t +4S0i. They are easily reduced to manganese(II) ions. due to the formation of nickel metaborate. are however known. Although they can be derived from the manganese(III) oxide. concentrated sulphuric acid. they are slightly pink. similar in appearance to cast iron. [Mn(H 20)6]2+. sulphur dioxide is evolved: Mn+2H 2S04 -+ Mn2+ +SOi. When dissolved in concentrated hydrochloric or sulphuric acid. containing manganese in the + 3 oxidation state.+4H 20 Manganese(lV) compounds. and in solutions.+3H 20 With sulphuric acid. produces manganese(II) ions. Mn304' is a manganese(II)manganese(III) oxide. (MnO. Mn 203. On moistening the filter paper with ammonia solution and adding a few drops dimethylglyoxime reagent. Mn (Ar : 54·938) . the latter. It reacts with warm water forming manganese(II) hydroxide and hydrogen: Mn+2H 20 -+ Mn(OHh!+H 2i Dilute mineral acids and also acetic acid dissolve it with the production of manganese(II) salts and hydrogen: Mn+2H+ -+ Mn2+ +H 2i When it is attacked by hot. as both the manganese(IV) ion. +6 and + 7 respectively.28 MANGANESE.+S02 l +2H 20 Six oxides of manganese are known: MnO. Mn203)' The manganese(II) cations are derived from manganese(II) oxide. and Mn 304. in the reducing flame. a red colour is produced. + 3. chlorine is the by-product: Mn 203!+6HCI-+ 2Mn2+ +CI 2i+4Cl. Mn 4+. If hydrochloric acid is used. Ni(B0 2h.mzs QUALITATIVE INORGANIC ANALYSIS the paper acquires a green colour owing to the formation of nickel(II) chloride.+ 2H 20 268 . this is due to the presence of the hexaquomanganate(II) ion. Mn03' Mn 20 7 . though if the compound contains water of crystallization. Mn0 2. are unstable. due to metallic nickel. + 4. The first five of these correspond to oxidation states + 2.

269 . MnO(OHh. and possesses a green colour.+2H 20 takes place. In precipitating iron.+2H 20 --+ Mn0 2!+2MnO'. 4H 20 or manganese(I1) sulphate MnS0 4 • 4H 20 can be used. concentrated sulphuric acid.REACTIONS OF CATIONS mzs Manganese(VI) compounds contain the manganate(VI) MnO~. Ammonia solution: partial precipitation of (initially) white manganese(I1) hydroxide: Mn2++2NH 3+2H 20 ~ Mn(OHh!+2NHt The precipitate is soluble in ammonium salts. Reactions of manganese(lI) ions For the study of these reactions a O·25M solution of manganese(I1) chloride MnCI 2. 1. and chromium.anion. manganese(I1) ions are produced. producing violetcoloured solutions. and be boiled to expel most of the dissolved air. They are all strong oxidizing agents.. The precipitate rapidly oxidizes on exposure to air. In this section the reactions of manganese(I1) ions will be dealt with. Manganese(VII) compounds contain the manganate(VII) or permanganate ion. With hot. Upon neutralization a disproportionation reaction takes place. MnO. the reaction 2Mn0 3+2H 2S0 4 --+ 2Mn2+ +02i+2S0~.. when the reaction proceeds towards the left. manganese dioxide precipitate and manganate(VII) (permanganate) ions are formed: 3MnO~. This is important in connection with the separation from the Group IlIA metals. then a slight excess of ammonia solution should be added and the precipitate filtered as quickly as possible. is formed: Mn(OHh!+02+H20 --+ MnO(OHh!+20H- Hydrogen peroxide converts manganese(I1) hydroxide rapidly into hydrated manganese dioxide: Mn(OHh! + H 202 --+ MnO(OHh! + H 20 2. Under these conditions very little manganese will be precipitated. becoming brown. when hydrated manganese dioxide. No precipitation takes place in the presence of ammonium salts owing to the lowering of the hydroxyl-ion concentration and the consequent failure to attain Mn(OHh On exposure to air. while reactions of permanganates will be described among the reactions of anions. Sodium hydroxide solution: an initially white precipitate of manganese(I1) hydroxide: Mn2+ +20H- --+ Mn(OHh! The precipitate is insoluble in excess reagent. brown hydrated manganese dioxide is precipitated from the ammoniacal solution.. This is stable in alkaline solutions. +40H- If manganese(VI) oxide is treated with acids. aluminium. Alkali permanganates are stable compounds. the solution should contain a large excess of ammonium chloride.

add I drop O'IM silver nitrate solution. which yields the dioxide in the presence of nitric acid) and a little concentrated nitric acid. 7H 20. Boiling the pink precipitate with excess reagent. and/or silver(III). free from hydrochloric acid and chlorides. + IOSOi. with lead dioxide (or red lead. Ammonium sulphide solution: pink precipitate of manganese(II) sulphide: Mn2+ + S2- --+ MnS! The precipitate also contains loosely-bound water.+ 8H 20 --+ 2MnO. diluting somewhat and allowing the suspended solid containing unattacked lead dioxide to settle. + 5Pb2+ +2H 20 6. in the presence of ammonia (or ammonium ions): Mn2+ + NH 3 + HPoi3Mn2++2HPOi--+ --+ Mn(NH 4)P04! If ammonium salts are absent.+ 16H+ The catalytic action of silver is due to the transitional formation of silver(II). Lead dioxide and concentrated nitric acid On boiling a dilute solution of manganese(II) ions. on boiling a reddish-violet solution is formed. oxidize manganese(II) to permanganate. The precipitate turns slowly brown on exposure to air. as powerful oxidants. the supernatant liquid acquires a violet-red (or purple) colour due to permanganic acid. otherwise manganese dioxide precipitate is formed. and a few drops of dilute silver nitrate (which acts as a catalyst) are added. owing to the presence of permanganate: 2Mn2+ + 5S20~. The solution must be dilute (max O'02M). 4. it has a salting-out effect on the colloidal precipitate. 5. Introduce a few mg solid ammonium 270 . Ag 3+. cobalt. less hydrated sulphide (3MnS + H 20) is formed. owing to oxidation to manganese dioxide. 5Pb0 2 +2Mn2+ +4H+ --+ 2MnO. and stir. a yellowish-green. Spot test. free of chloride. The solution is acidified with dilute sulphuric acid. Sodium phosphate solution: pink precipitate of manganese ammonium phosphate Mn(NH 4)P04. The precipitate is readily soluble in mineral acids (different from nickel and cobalt) and even in acetic acid (distinction from nickel.IIU8 QUALITATIVE INORGANIC ANALYSIS 3. The latter is decomposed by hydrochloric acid and hence chlorides should be absent. Place a drop of the test solution in a micro crucible. and zinc): MnS!+2H+ MnS!+2CH 3COOH --+ --+ Mn2+ +H 2Sj Mn2+ +H 2Sj+2CH 3COO- The presence of ammonium chloride assists precipitation. ions. manganese(II) phosphate is formed: Mn3(P04h!+2H+ Both precipitates are soluble in acids. Ammonium or potassium peroxodisulphate Solid (NH4hS20S or K 2S20 S is added to a dilute solution of manganese(II) ions. which. Ag2+.

A solution of permanganate is formed. which yield a similar colour with the 'tetrabase'. which has been rendered just alkaline with 2M sodium hydroxide. + 5Bi3+ + 5Na+ + 7H 20 The spot-test technique is as follows. 11. Formaldoxime reagent (HCR NOH): red colouration with alkaline solution of manganese(II) salts. in a semimicro test-tube and add I drop of the reagent. add a drop of concentrated nitric acid and then a little sodium bismuthate. 2Mn2+ + 5NaBi0 3 + 14H+ -+ 2MnO:.28 peroxodisulphate and heat gently. Sensitivity: 0'25 ~g (in 5 ml). Dry tests a.'tetrabase' test A solution of the 'tetrabase' (tetramethyl-diamono-diphenylmethane) in chloroform is employed as a sensitive test to identify very small amounts of manganese as permanganic acid. 7. Concentration limit: I in 20. Chlorides must be absent. A deep-blue colour is formed. Potassium periodate .000.000. if present. 10. followed by a drop of saturated potassium periodate solution and 2 drops I per cent solution of the 'tetrabase' in chloroform. a solution of permanganate is produced.REACTIONS OF CATIONS III. Iron is best removed before applying the test (e. 8. Sodium bismuthate (NaBi0 3 ) When this solid is added to a cold solution of manganese(II) ions in dilute nitric acid or in dilute sulphuric acid. with a suspension of zinc hydroxide or as the basic acetate). the mixture stirred and excess reagent filtered off (preferably through asbestos or glass wool or a sintered glass funnel). and the solution boiled for I minute. The latter oxidizes the 'tetrabase' to an intensely blue compound.g. cobalt. Concentration limit: I in 500.000. Potassium periodate (KIO 4) The manganese(II) sulphate solution is rendered strongly acid with sulphuric or nitric acid or (best) phosphoric acid. Copper gives a blue-violet colouration. Chromium. + 3H 20 -+ 2MnO:. A red colouration is obtained. Sensitivity: 25 ~g Mn (in 5 ml). dilute the mixture with water until the colour appears.000. 0'2-0'3 g potassium periodate added. 2Mn2+ + 510:. although it may be rendered inactive by the addition of a tartrate. Place 2 ml test solution. The reagent consists of a 2'5 per cent solution of formaldoxime in water. Borax bead test The bead produced in the oxidizing flame by small amounts of manganese salts is violet whilst hot and amethyst-red 271 . The purple colour of permanganic acid appears. The characteristic colour of permanganate appears. Chromium salts should be absent for they are oxidized by periodates to chromates. and nickel salts give colourations with the reagent and must therefore be absent. Concentration limit: I in 200. + 510 3 + 6H+ 9. Place a drop of the test solution on a spot plate. If the solution is so dark that the colour cannot be detected. they must be removed by evaporation with sulphuric or nitric acid before applying the test. but the interference can be overcome by the use of alkali cyanide. Place a drop of the test solution on a spot plate. Sensitivity: 0'1 ~g Mn.

derived from zinc oxide. these contain the zinc(II) cation. In the reducing flame the manganese bead is colourless whilst that due to nickel is grey. The pure metal dissolves very slowly in acids and in alkalis. when no gas is evolved: 4Zn + IOH+ + N0 3 -+ 4Zn2+ + NHt + 3H 20 With increasing concentration of nitric acid. MnS04 + 2KN03 + 2Na2C03 = Na2Mn04 + 2KN02 + Na2S04 + 2C02i 3MnS04 + 2KCI03 + 6Na2C03 = 3Na2Mn04 + 2KCI + 3Na2S04 + 6C02i III. concentrated sulphuric acid. Section 11.+=t Zn(OHh! 272 . the presence of impurities or contact with platinum or copper. Fusion test Fusion of any manganese compound with sodium carbonate and an oxidizing agent (potassium chlorate or potassium nitrate) gives a green mass of alkali manganate. b. when tetrahydroxozincate(II) is formed: Zn+20H. or by fusing a bead of sodium carbonate with a small quantity of the manganese compound in the oxidizing flame and dipping the fused mass whilst hot into a little powdered potassium chlorate or nitrate and reheating (cf. Reactions of zinc ions A O·25M solution of zinc sulphate ZnS0 4.+H 2t Zinc forms one series of salts only. With hot. The latter dissolves readily in dilute hydrochloric acid and in dilute sulphuric acid with the evolution of hydrogen: Zn+2H+ -+ Zn2++H 2i Solution takes place in very dilute nitric acid. with larger amounts of manganese the bead is almost brown and may be mistaken for that of nickel. sulphur dioxide is evolved: Zn+2H 2S04 -+ Zn2++S0 2i+SOi-+2H20 Zinc also dissolves in alkali hydroxides. 1. Sodium hydroxide solution: white gelatinous precipitate of zinc hydroxide: Zn2+ +20H.1). 7H 20 can be used to study these reactions. ZnO.29 ZINC. dinitrogen oxide (N 20) nitrogen oxide (NO) are formed: 4Zn+ IOH+ +2N0 3 -+ 4Zn2+ +N 20i+5H20 3Zn + 8HN0 3 -+ 3Zn2+ + 2NOi + 6N0 3 + 4H 20 Concentrated nitric acid has little effect on zinc because of the low solubility of zinc nitrate in such a medium. It melts at 410°C and boils at 906°C.zs QUALITATIVE INORGANIC ANALYSIS when cold. produced by the addition of a few drops of the solutions of the salts of these metals. a piece of broken porcelain may be employed). accelerates the reaction.m. Zn (Ar : 65·38) Zinc is a bluish-white metal. it is fairly malleable and ductile at I 10-1 50°C.+2H 20 -+ [Zn(OH)4]2. The test may be carried out either by heating upon a piece of platinum foil with potassium nitrate and sodium carbonate (if platinum foil is not available. This explains the solubility of commercial zinc.

Ammonia solution: white precipitate of zinc hydroxide. the precipitate is washed with dilute ammonium chloride solution containing a little ammonium sulphide. 2. The precipitate thus obtained is partially colloidal. but dissolves in dilute mineral acids. and consequently precipitation ceases. Zn2+ + 2NH 3 + 2H 20 ~ Zn(OHh! + 2NH 4 Zn(OH)2! + 4NH 3 ~ [Zn(NH 3)4]2+ + 20H3. and in solutions of caustic alkalis. the sulphide-ion concentration derived from the hydrogen sulphide is depressed so much by the hydrogen-ion concentration from the acid that it is too low to exceed the solubility product of ZnS. Zn2+ +H 2S ~ ZnS!+2H+ Upon the addition of alkali acetate to the solution. Disodium hydrogen phosphate solution: white precipitate of zinc phosphate: 3Zn2+ +2HPOi- ~ ZniP0 4h!+2H+ 273 .REACTIONS OF CATIONS 111. in acetic acid. readily soluble in excess reagent and in solutions of ammonium salts owing to the production of tetramminezincate(II). The non-precipitation of zinc hydroxide by ammonia solution in the presence of ammonium chloride is due to the lowering of the hydroxyl-ion concentration to such a value that the solubility product of Zn(OHh is not attained. it is insoluble in excess reagent. it is difficult to wash and tends to run through the filter paper. Hydrogen sulphide: partial precipitation of zinc sulphide in neutral solutions. from neutral or alkaline solutions. when the concentration of acid produced is about 0'3M (pH about 0'6). the precipitation is conveniently carried out in boiling solution in the presence of excess ammonium chloride. particularly on washing. the sulphide-ion concentration is correspondingly increased. the hydrogen-ion concentration is reduced because of the formation of the feebly dissociated acetic acid. and precipitation is almost complete Zn2++H 2S+2CH 3COO--+ ZnS!+2CH 3COOH Zinc sulphide is also precipitated from alkaline solutions of tetrahydroxozincate: 5. Ammonium sulphide solution: white precipitate of zinc sulphide. ZnS. Zn2+ + S2- --+ ZnS! 4. To obtain the zinc sulphide in a form which can be readily filtered.29 the precipitate is soluble in acids: Zn(OHh! + 2H+ ~ Zn2+ + 2H 20 [Zn(OH)4]2- and also in the excess of the reagent: Zn(OHh! + 20H~ Zinc hydroxide is thus an amphoteric compound.

form a white precipitate: Zn2+ + [Hg(SCN)4]2. uranium. Potassium hexacyanoferrate(II) solution: white precipitate of variable composition. The faintly acid (sulphuric acid or acetic acid) solution is treated with 0·1 ml 0'25M copper sulphate solution. Copper salts alone do not form a precipitate with the ammonium tetrathiocyanatomercurate(II) reagent. if the reagent is added in some excess the composition of the precipitate is K 2Zn3[Fe(CN)6]2 : 3Zn2+ + 2K + + 2[Fe(C~~)6]4- --+ K 2Zn3[Fe(CN)6]2 The precipitate is insoluble in dilute acids. a white precipitate of the zinc complex Zn(C t oH6N02h .+2K+ This reaction can be used to distinguish zinc from aluminium.~ Zn(NH4)P04!+H+ Both precipitates are soluble in dilute acids. but is reprecipitated on neutralization.III. A violet precipitate is obtained.= Zn[Hg(SCN)4] In the presence of copper ions. Iron salts produce a red colouration. when the reactions are reversed. The reagent is. Ammonium tetrathiocyanatomercurate(II)-copper sulphate test. this disappears when a little alkali fluoride is added. Quinaldic acid reagent (quinoline-a-carboxylic acid. if present alone. the copper complex eoprecipitates with that of zinc. the violet precipitate collects at the interface. both precipitates are soluble in ammonia: Zn3(P04h + 12NH 3 --+ 3[Zn(NH 3)4]2+ +2PO~­ Zn(NH 4)P04 + 3NH 3 --+ [Zn(NH 3)4]2+ + HPOi6. The reaction is best carried out on the semimicro scale or as a spot test. CO 2H) Upon the addition of a few drops of the reagent to a solution of a zinc salt which is faintly acid with acetic acid. The ammonium tetrathiocyanatomercurate(II) reagent is prepared by 274 . Cobalt. but dissolves readily in sodium hydroxide: K 2Zn3[Fe(CN)6]2 + 120H--+ 2[Fe(CN)6]4. This is an extremely sensitive test for zinc ions. and the violet (or blackish-purple) precipitate consists of mixed crystals of Zn[Hg(SCN)4] + CU[Hg(SCN)4J. H 20 is obtained. followed by 2 ml ammonium tetrathiocyanatomercurate(II) reagent. cooling and shaking with a little amyl alcohol.29 QUALITATIVE INORGANIC ANALYSIS In the presence of ammonium ions zinc ammonium phosphate is formed: Zn2++NH!+HPOi. The test is rendered still more sensitive by boiling the mixture for I minute. Copper. cadmium. and is a useful confirmatory test for zinc isolated from the Group IIIB separation. nickel. C gH6N. however. 7. iron. Also. The precipitate is soluble in ammonia solution and in mineral acids. expensive.+3[Zn(OH)4]2. and manganese ions have no effect. The reagent is prepared by neutralizing I g quinaldic acid with sodium hydroxide solution and diluting to 100 ml. and chromium ions give precipitates with the reagent and should be absent. 8. whilst zinc ions.

white. the oxidation proceeds rapidly: the white zinc hexacyanoferrate(II) is deeply coloured by the adsorption of the coloured oxidation products.) which give coloured precipitates with potassium hexacyanoferrate(II) should be absent. and 6 drops 2 per cent p-phenetidine hydrochloride solution. Place a drop of the test solution (which should be slightly acid. except that a minute amount of a dilute solution of a cobalt salt (nitrate. A blue precipitate is formed. Place a drop or two of the test solution. Prepare the reagent by mixing 10 drops 0'033M potassium hexacyanoferrate(III) solution. To 0'1 ml freshly prepared reagent on a spot plate. AI. 11. Ni 2+ . The reaction may also be conducted in a semimicro test-tube: here 0. 3K+ + [CO(CN)6]3. Ammonium tetrathiocyanatomercurate(II)-cobalt sulphate test This test is similar to that described under reaction 8.ions are formed). Copper salts should be absent. If the hexacyanoferrate(II) formed is removed by zinc ions as the sparingly soluble. Optimum experimental conditions are obtained by converting the zinc into the hexacyanocobaltate(III). and a drop of the ammonium tetrathiocyanatomercurate(II) reagent on a spot plate or in a micro crucible. Sensitivity: O' 2-0' 5 ~g Zn. Rinmann's green test The test depends upon the production of Rinmann's green (largely cobalt zincate CoZn0 2 ) by heating the salts or oxides of zinc and cobalt.+. The test is especially useful in the presence of Cr. add a drop of the test solution. etc.3-0'5 ml amyl alcohol is added.+Zn2+ = KZn[Co(CN)6]+2K+ 275 . and Mg.REACTIONS OF CATIONS mzs dissolving 8 g mercury(II) chloride and 9 g ammonium thiocyanate in 100 ml water. Concentration limit: I in 100. Concentration limit: I in 10. A blank test is desirable. 10. 2 drops Msulphuric acid. a drop of 0'5M cobalt nitrate solution. A purple to blue colouration or precipitate appears in the presence of zinc. on a spot plate. Sensitivity: lug Zn. Potassium hexacyanoferrate(III)-p-phenetidine test Potassium hexacyanoferrate(III) oxidizes p-phenetidine (4-ethoxyaniline) and other aromatic amines slowly with change of colour and the formation of potassium hexacyanoferrate(II). The reaction may also be carried out in a semimicro test-tube in the presence of 0'3-0'5 ml of amyl alcohol. Iron(II) salts give a red colouration but this can be eliminated by the addition of a little alkali fluoride (colourless [FeF6]3. zinc hexacyanoferrate(II).000. 9. preferably with dilute sulphuric acid). which is slightly acid (preferably with sulphuric acid). C0 2. Cations (Cu2+. An excess of cobalt(II) oxide must be avoided for it leads to a red-brown colouration: oxidation to cobalt(III) oxide produces a darkening of colour. Fe2+. The violet precipitate collects at the interface.000. Coprecipitation of the cobalt tetrathiocyanatomercurate(II) yields a blue precipitate composed of mixed crystals of Zn[Hg(SCN)4] + Co[Hg(SCN)4J. Concentration limit: I in 100. add I drop 0'25M copper sulphate solution and I drop ammonium mercurithiocyanate reagent. sulphate or acetate) is added.000. A violet (or blackish-purple) precipitate appears.

Upon adding sodium hydroxide solution to the mixture and shaking.29 QUALITATIVE INORGANIC ANALYSIS Ignition of the latter leads to zinc oxide and cobalt(II) oxide in the correct proportion for the formation of cobalt zincate. Sensitivity: 0·6 ~g Zn. and add a few drops of the reagent. Concentration limit: I in 3. The test can be applied in the presence of 2. which can be extracted with carbon tetrachloride. and Pd2+ ions interfere. and drying at room temperature or at lOOOC. Hg~+. (In alkaline solutions the sensitivity of the test is less. Cu2+. The paper is yellow and keeps well. Dry tests (blowpipe test) Compounds of zinc when heated upon charcoal with sodium carbonate yield an incrustation of the oxide. alkaline or acetic acid solutions. 13. formed in neutral. Rinmann's green) test paper. If the incrustation is moistened with a drop of cobalt 276 . The potassium hexacyanocobaltate(III) (or cobalticyanide) test paper is prepared by soaking drop-reaction paper or quantitative filter paper in a solution containing 4 g potassium hexacyanocobaltate(III) and I g potassium chlorate in 100ml water. All other metals must be removed. is red: Acidify the test solution with acetic acid. This reaction is characteristic for zinc only. whilst carbon from the filter paper (see below) prevents the formation of cobalt(III) oxide. The reagent is freshly prepared by dissolving 1-2 g of dithizone in 100 ml carbon tetrachloride. Observe the colour of the ash against a white background: part of it will be green. The zinc complex.) Limit of detection: in neutral medium: 0·025 ~g Zn2+ in acetic acid or sodium hydroxide medium: 0·9 ~g Zn2+. The organic phase turns red in the presence of zinc. Ag". Au 3+. Hg2+. Dry the paper over a flame and ignite in a small crucible. Place a few drops of the neutral (litmus) test solution upon potassium hexacyanocobaltate(III) (or cobalticyanide.000. the aqueous phase turns to red also. Dithizone test Dithizone (diphenyl thiocarbazone) forms complexes with a number of metal ions.111. 12. The metal cannot be isolated owing to its volatility and subsequent oxidation. which is yellow when hot and white when cold.000 times those amounts of Ni and AI.

while calcium hydroxide is the least soluble among them. and calcium carbonate CaC0 3 • The three alkaline earth metals decompose water at different rates. add I drop cobalt nitrate solution and to ignite in a crucible or in a coil of platinum wire. In the absence of ammonia or ammonium ions. the salts form colourless solutions. These compounds have to be removed before attempting the group reaction as the the alkaline earth salts of both are soluble in water.REACTIONS OF CATIONS 111. and oxalates are insoluble. a green mass (Rinmann's green).30 FOURTH GROUP OF CATIONS: BARIUM. when carbon dioxide gas is formed: Co~- + 2CH 3COOH --+ CO 2l + H 20 + 2CH 3COO- The reagent has to be used in neutral or slightly alkaline media. AND CALCIUM Group reagent: IM solution of ammonium carbonate. but ammonium carbonate (in the presence of moderate amounts of ammonia or ammonium ions) forms white precipitates. Their hydroxides are strong bases. 111. and displays an alkaline reaction because of hydrolysis: CO~- +H 20 +:t HC03 +OH- The reagent is decomposed by acids (even by acetic acid). The white precipitates formed with the group reagent are: barium carbonate BaC0 3 . 277 . it is very difficult to distinguish them and especially to separate them. hydrogen sulphide nor ammonium sulphide. The reagent is colourless. Commercial ammonium carbonate always contains ammonium hydrogen carbonate (NH 4HC03 ) and ammonium carbamate NH 40(NH 2)CO. consisting largely of cobalt zincate CoZn02 is obtained. 2BaS+2H 20 --+ 2Ba2+ +2SH. they all hydrolyse in water. Alkaline earth chlorides and nitrates are very soluble. This can be done by boiling the reagent solution for a while.g. The test has to be carried out in neutral or alkaline solutions. The residue is coloured green. Because the alkaline earth ions behave very similarly to each other in aqueous solutions. e. magnesium will also be precipitated. sulphates. forming hydrogen sulphides and hydroxides. although with different solubilities: barium hydroxide is the most soluble. forming hydroxides and hydrogen gas. The sulphides can be prepared only in the dry. both ammonium hydrogen carbonate and ammonium carbamate are converted to ammonium carbonate in this way: Group reaction: cations of the fourth group react neither with hydrochloric acid. strontium carbonate SrC0 3 . the carbonates. phosphates. STRONTIUM. An alternative method is to soak a piece of ashless filter paper in the zinc salt solution.+20H- Unless the anion is coloured.30 nitrate solution and again heated.

If the alkaline solution is exposed to the atmosphere. Ammonium carbonate solution: white precipitate of barium carbonate. and only 0·012 g barium chloride (all anhydrous salts). 1.7). as a consequence of the law of mass action. 111. These differences can be utilized for separations. often present in an aged reagent. soluble in acetic acid and in dilute mineral acids. It melts at 710°C. some carbon dioxide is absorbed and a turbidity.III. HC0 3 . the solubilities of anhydrous strontium and barium nitrates in this solution are negligible. or NHt + CO~NHt + BaC0 3 ! -+ -+ NH 3 i + HC0 3 NH 3 i + HC0 3 + Ba2+ If the amount of barium carbonate precipitate is very small. 3. and hence the carbonate-ion concentration of the solution is decreased. = 1'7 x 10. barium chloride or nitrate may precipitate out. it may well dissolve in high concentrations of ammonium salts.31 QUALITATIVE INORGANIC ANALYSIS There are however differences in the solubilities of some of their salts in nonaqueous media. Thus. malleable and ductile metal. Ammonium oxalate solution: white precipitate of barium oxalate Ba(COOh. CO~-. K. Its chloride and nitrate are soluble. which is stable in dry air. Ba (Ar : 137·34) Barium is a silver-white. It reacts with the water in humid air forming oxide or hydroxide. this is due to small amounts of ammonium carbonate. but readily dissolved 278 . One hundred grams of a I: I mixture diethyl ether and anhydrous ethanol dissolve more than 40 g anhydrous calcium nitrate. 2. It reacts with water at room temperature forming barium hydroxide and hydrogen: Ba+2H 20 Ba+2H+ -+ Ba2+ +H 2i+20H- Dilute acids dissolve barium readily with the evolution of hydrogen: -+ Ba2+ +H 2 t Barium is bivalent in its salts forming the barium(lI) cation Ba2+. due to barium carbonate. Reactions ofbarium ions Use a 0'25Msolution of barium chloride BaCI 2 • 2H 20 or barium nitrate Ba(N0 3 h for the study of these reactions. 0·91 g strontium chloride. leading to the formation of the hydrogen carbonate ion. 100 g anhydrous ethanol dissolve 12·5 g calcium chloride. is produced. this is because the ammonium ion. but on adding concentrated hydrochloric or nitric acids to barium solutions. the carbonate ion. being a strong acid. A slight turbidity may occur when adding the reagent. reacts with the base. Ammonia solution: no precipitate of barium hydroxide because of its relatively high solubility. slightly soluble in water (0'09 g per litre.31 BARIUM. Ba2+ +CO~-+ BaC0 3 ! The precipitate is slightly soluble in solutions of ammonium salts of strong acids.

and filtered. Dilute sulphuric acid: heavy. By repetition of this process.11 ) . and appreciably soluble in boiling concentrated sulphuric acid.REACTIONS OF CATIONS msr by hot dilute acetic acid (distinction from calcium) and by mineral acids (cf. practically all of the sulphate can be converted into the corresponding carbonate. A more expeditious method of obtaining the same result is to fuse the barium sulphate with 4 to 6 times its weight of anhydrous sodium carbonate.+Ba2+ +:! BaS04! 279 . Saturated calcium sulphate solution: immediate white precipitate of barium sulphate. K. It has been stated that by boiling barium sulphate with a 15 fold excess of sodium carbonate solution of at least 1'5 mol r. more of the barium sulphate will be converted into barium carbonate. Barium sulphate precipitate may also be dissolved in a hot 3 to 5 per cent solution of disodium ethylenediamine tetraacetate (Na2EDTA) in the presence of ammonia.1 concentration. Ba2+ +(COO)~+:! Ba(COOh! 4. If the mixture is filtered and washed (thus removing the sodium sulphate). The carbonate may be dissolved in acids. extracted with boiling water. white.) --+ --+ BaS0 4! Ba2+ + 2HSO'. The melt is allowed to cool. 5. and the residue boiled with a fresh volume of sodium carbonate solution. In the solutions of saturated calcium or strontium sulphate the concentration of sulphate ions is high enough to cause precipitation with larger amounts of barium.1 . Section 1. = 9'2 x 10.28). 99 per cent is converted into barium carbonate in I hour. the transformation is incomplete. because the product of ion concentrations exceeds the value of the solubility product: SO~. finely divided precipitate of barium sulphate BaS04' practically insoluble in water (2'5 mg t. this process therefore provides a method for bringing insoluble sulphates into solution. The explanation of these reactions is as follows: of the three alkaline earth sulphates barium sulphate is the least soluble. the residue of barium carbonate can then be dissolved in the appropriate acid. partial transformation into the less soluble barium carbonate occurs in accordance with the equation: BaS04! + CO~+:! BaC0 3! + SO~- Owing to the reversibility of the reaction. Ba2+ +SO~BaS04! + H 2S04(conc. A similar phenomenon occurs if saturated strontium sulphate reagent is used. the maximum concentration of carbonate is thus obtained and the reaction proceeds almost to completion in one operation. By precipitation in boiling solution or preferably in the presence of ammonium acetate. Ifbarium sulphate is boiled with a concentrated solution of sodium carbonate. almost insoluble in dilute acids and in ammonium sulphate solution. a more readily filterable form is obtained.

g. but readily soluble in mineral acids (cf. The reaction is best carried out on drop-reaction paper as above. should be absent.g. strong acids must be removed or neutralized. In the presence of a large concentration of hydrogen ions. the spot disappears. The addition of sodium acetate acts as a buffer by reducing the hydrogen-ion concentration and complete precipitation of BaCr04 will take place.ions) to dichromate solutions. The reagent should be confined to testing for elements in Group IV.ONa : reddish-brown precipitate of the barium salt of rhodizonic acid in neutral solution.000. Concentration limit: I in 90.+H 20 Upon adding a base (e. It does not keep well so only small quantities should be prepared at a time. Hence to precipitate Ba2+ ions as BaCr04 . The reagent consists of a 0'5 per cent aqueous solution of sodium rhodizonate.1 °) : Ba2++ CrOi- --+ BaCr04 ! The precipitate is insoluble in dilute acetic acid (distinction from strontium and calcium).+2H+ +=t Cr20~. whilst the barium derivative is converted into the brilliant-red acid salt. The addition of acetic acid to the K 2Cr04 solution lowers the CrOiion concentration sufficiently to prevent the precipitation of SrCr04 and CaCr04 but it is maintained high enough to precipitate BaCr04 • 7. OH. the reaction will proceed from right to left as the hydrogen ions are removed. Concentration limit: I in 200. A brown or reddish-brown spot is obtained. = 1'6 x 10.111. Sodium rhodizonate reagent CO-CO-C. Section 1.ion concentration to precipitate them. but only the precipitate due to the former is completely soluble in dilute hydrochloric acid. If barium is absent. Potassium chromate solution: a yellow precipitate of barium chromate. the strontium rhodizonate dissolves. In the presence of strontium the reddish-brown stain of barium rhodizonate is treated with 0'5M hydrochloric acid. ONa) 1 11 ( CO-CQ--C. those precipitated by hydrogen sulphide and by ammonium sulphide. The addition of acid to potassium chromate solution causes the yellow colour of the solution to change to reddish-orange. the chromate-ion concentration will be reduced to such a value that the solubility product of BaCr04 will not be attained. Treat the reddish-brown spot with a drop ofO'5M hydrochloric acid when a bright-red stain is formed if barium is present. e.28). Calcium and magnesium salts do not interfere. and thus chromate will form.000. K. The solubility products for SrCr04 and CaCr04 are much larger than for BaCr04 and hence they require a larger CrOi. 280 . Place a drop of the neutral or faintly acid test solution upon drop-reaction paper and add a drop of the reagent. Other elements. strontium salts react like those of barium. owing to the formation of dichromate: 2CrOi. Sensitivity: 0'5 ~g Ba in the presence of 50 times that amount of Sr. practically insoluble in water (3'2 mg r-1.31 QUALITATIVE INORGANIC ANALYSIS 6. Sensitivity: 0'25 ~g Ba.

It melts at 771°C. decomposition with acids) are similar to those of the latter.9 at room temperature). The precipitate is insoluble in ammonium sulphate solution even on boiling (distinction from calcium) and slightly soluble in boiling hydrochloric acid. The salts must be heated to 180°C before the test to remove all water of crystallization. malleable and ductile metal. Ammonium oxalate solution: white precipitate of strontium oxalate Sr2+ +(COO)~- --+ Sr(COOh! 281 . impart a yellowish-green colour to the flame.1 . Saturated calcium sulphate solution: white precipitate of strontium sulphate. Sr (Ar : 87·62) Strontium is a silver-white. 5.+=t SrC03!+SO~- Strontium carbonate is less soluble than strontium sulphate (solubility: 5'9 mg SrC0 3 r-1. K. the platinum wire is moistened with concentrated hydrochloric acid before being dipped into the substance. After filtering the solution the precipitate can be dissolved in hydrochloric acid. = 1'6 x 10. are non-volatile.32 STRONTIUM. It is almost completely converted into the corresponding carbonate by boiling With a concentrated solution of sodium carbonate: SrS04+CO~. This test can be applied for the separation of barium from strontium and/or calcium. 3.7 ) . = 2'8 x 10. then moistened with concentrated hydrochloric acid. The sulphate is first reduced to the sulphide in the reducing flame. 9. 1. with the exception of the chloride. 111. Reactions of strontium ions For the study of these reactions a 0'25M solution of strontium chloride SrCl 2 . formed slowly in the cold but more rapidly on boiling (distinction from barium). 4. Since most barium salts. Dry test (flame colouration) Barium salts. Ammonium carbonate solution: white precipitate of strontium carbonate: Sr2+ +CO~- --+ SrC0 3! Strontium carbonate is somewhat less soluble than barium carbonate. 2. K. Its properties are similar to those of barium. Dilute sulphuric acid: white precipitate of strontium sulphate: Sr2+ +SO~- --+ SrS0 4! The solubility of the precipitate is not negligible (0'097 g r. otherwise its characteristics (slight solubility in ammonium salts. Ammonia solution: no precipitate.REACTIONS OF CATIONS ill. thus strontium ions can be transferred into the solution.6H 20 or strontium nitrate Sr(N0 3h can be used.32 8 Anhydrous ethanol and ether: a I + I mixture of these solvents does not dissolve anhydrous barium nitrate or barium chloride (distinct from strontium and calcium). and reintroduced into the flame. when heated in the nonluminous Bunsen flame.

31. Dry test (flame colouration) Volatile strontium compounds. Sensitivity: 4 ~g Sr. Anhydrous ethanol and ether: a I + I mixture of these solvents does not dissolve anhydrous strontium nitrate. reaction 6). The test can be utilized for the separation of calcium. for the same reasons as described under barium (cf. but does dissolve anhydrous strontium chloride. Section ID. Calcium forms the calcium(II) cation CaH in aqueous solutions. reaction 7). 7. and try to dissolve the residues in a few millilitres of the solvent. K. III. reaction 7. and add a drop of the reagent. Its salts are 282 . To detect strontium in the presence of barium.33 CALCIUM. especially the chloride. A brownish-red colouration or precipitate is produced. If barium is present. see Section 111.8). place a drop of the neutral test solution on drop-reaction paper or on a spot plate. Calcium decomposes water under the formation of calcium hydroxide and hydrogen.000.111. no precipitate occurs therefore in dilute solutions of strontium. A brownish-red spot or ring is formed. when calcium oxide and/or calcium hydroxide is formed. Ca (Ar : 40·08) Calcium is a silver-white. Concentration limit: I in 13. Filter the precipitate.31. If barium is absent. Place a drop of the test solution on this paper and. 9. Impregnate some quantitative filter paper or drop-reaction paper with a saturated solution of potassium chromate. It melts at 845°C. Sensitivity: 4 ~g Sr in the presence of 80 times that amount of Ba. place I drop of the reagent on the moistened spot. Potassium chromate solution: yellow precipitate of strontium chromate: Sr H +CrOi. = 3'5 x 10. 8. and barium. another in nitric acid. rather soft metal. after a minute. The test is applied to the elements of Group IV. proceed as follows. It is attacked by atmospheric oxygen and humidity. Concentration limit: I in 13. The test can be carried out as follows: precipitate strontium as the carbonate. The precipitate is soluble in acetic acid (distinction from barium) and in mineral acids. = 5 x 10. For further details of the reagent.31. Evaporate the two solutions on separate watch-glasses to dryness. and dry it. Sodium rhodizonate reagent: reddish-brown precipitate of strontium rhodizonate in neutral solution. K. Barium chromate does not react with sodium rhodizonate. Acetic acid does not attack it. mineral acids however dissolve the precipitate.000.33 QUALITATIVE INORGANIC ANALYSIS The precipitate is sparingly soluble in water (0'039 g r-1.5). 6. impart a characteristic carmine-red colour to the non-luminous Bunsen flame (see remarks under Barium). dissolve one part of it in hydrochloric acid. but the more soluble strontium chromate reacts normally. strontium. heat the residue to 1800C for 30 minutes.--+ SrCr0 ! 4 The precipitate is appreciably soluble in water (1'2 g £-1. Barium reacts similarly and a method for the detection of barium in the presence of strontium has already been described (Section 01. the latter is converted into the insoluble barium chromate.

Solid calcium chloride is hygroscopic and is often used as a drying agent. With an aged precipitant a turbidity may occur owing to the formation of calcium carbonate (cf. reaction 2). The precipitate dissolves in hot. Ammonia solution: no precipitate. after neutralization with ammonia. Section 111.REACTIONS OF CATIONS m. Barium and strontium ions react in a similar way.4). reaction I). even in acetic acid: CaC0 3!+2H+ CaC0 3!+2CH3COOH --+ --+ Ca2+ +H 20+C02i Ca2+ +H 20+C02i+2CH 3COO- Calcium carbonate is slightly soluble in solutions of ammonium salts of strong acids (cf.33 normally white powders and form colourless solutions. calcium ions can be detected in the filtrate with oxalate.+=t [Ca(S04h]2Although dissolution in ammonium sulphate may not be complete. freshly prepared soda water).g. that is more soluble than barium or strontium sulphate. Calcium chloride and calcium nitrate dissolve readily in ethanol or in a I + I mixture of anhydrous ethanol and diethyl ether. The precipitate is soluble in acids. Saturated calcium sulphate: no precipitate strontium and barium). Reactions ofcalcium ions To study these reactions a 0'5M solution of calcium chloride CaCI 2. concentrated sulphuric acid: CaS04 + H 2S04 +=t 2H+ + [Ca(S04h]2The same complex is formed if a precipitate is heated with a 10 per cent solution of ammonium sulphate: CaS04 +soi. The precipitate is soluble in water which contains excess carbonic acid (e. because carbon dioxide is removed during the process and the reaction proceeds towards left. 1. = 2'3 x 10.2H20 £-1. as calcium hydroxide is fairly soluble. IS formed (difference from 283 . 2. 4. 2'06 g CaS04 or 2'61 g CaS04.31. Section 111. K. 3. 6H 20 can be used.31. unless the anion is coloured. Dilute sulphuric acid: white precipitate of calcium sulphate Ca2+ +soi- --+ CaS04! The precipitate is appreciably soluble in water (0'61 g Ca 2+. Ammonium carbonate solution: white amorphous precipitate of calcium carbonate: Ca2+ +CO~- --+ CaC0 3! On boiling the precipitate becomes crystalline. because of the formation of soluble calcium hydrogen carbonate: CaC0 3!+H 20+C02 +=t Ca2+ +2HC0 3 On boiling the precipitate appears again. In the presence of ethanol the solubility is much less.

Magnesium does not interfere provided its concentration does not exceed 10 times that of the calcium. 8.28). The precipitate is practically insoluble in water (6'53 mg Ca(COOh £-1. barium and magnesium ions however interfere.33 QUALITATIVE INORGANIC ANALYSIS 5. Place a drop of the neutral test solution on a black spot plate or upon a black watch glass. Concentration limit: I in 5. Picrolonic acid (or I-p-nitrophenyl-3-methyl-4-nitro-5-pyrazolone) reagent 284 . nor from concentrated solutions in the presence of acetic acid (cf. 9. Section 1. 7. All other metals. with the exception of alkali and ammonium salts. NH--N=C-COONa yellow sparingly-soluble precipitate of the calcium salt. Potassium hexacyanoferrate(II) solution: white precipitate ofa mixed salt: Ca2+ + 2K + + [Fe(CN)6]4--+ K 2Ca[Fe(CN)6J! In the presence of ammonium chloride the test is more sensitive. Ammonium oxalate solution: white precipitate of calcium oxalate. Potassium chromate solution: no precipitate from dilute solutions. and add a tiny fragment of the solid reagent.9 ) . K. the reagent dissolves completely. 6. immediately from concentrated and slowly from dilute solutions: Ca2+ + (COO)~--+ Ca(COOht Precipitation is facilitated by making the solution alkaline with ammonia.31. Sodium dihydroxytartrate osazone reagent C6H S ' NH--N=i--cOONa): ( C6H s . This reagent is useful inter alia for the rapid differentiation between tap and distilled water: a positive result is obtained with a mixture of I part of tap water and 30 parts of distilled water. If calcium is absent. insoluble in acetic acid. = 2'6 x 10.III. The test can be used to distinguish calcium from strontium. Section 111. must be absent. reaction 6).000.000. Sensitivity: 0'0 I ~g Ca. but readily soluble in mineral acids (cf. In this case potassium is replaced by ammonium ions in the precipitate. The presence of calcium is revealed by the formation over the surface of the liquid of a white film which ultimately separates as a dense precipitate.

(It may be necessary to warm the slide gently on a water bath until crystallization just sets in at the edges. 12. malleable and ductile metal. SODIUM. Concentration limit: I in 6. iron. ammonium sulphide or (in the presence of ammonium salts) with ammonium carbonate. Characteristic rectangular crystals are produced. Dry test (flame colouration) Volatile calcium compounds impart a yellowish-red colour to the Bunsen flame (see remarks under Barium). Group reagent: there is no common reagent for the cations of this group. The reactions of ammonium ions are quite similar to those of the potassium ion. Numerous elements. Sensitivity: I00 ~g (in 5 ml). 10. Place a drop of the test solution (either neutral or acidified with acetic acid) in the depression of a warm spot plate and add I drop of a saturated solution of picrolonic acid.) Upon observation through a microscope. Concentration limit: I in 50.000. For practical details see Section 111. reaction 8. nickel. It burns readily in air or oxygen with a brilliant white light. The metal is slowly decomposed by water at ordinary temperature. but at the boiling point 285 . including copper. III. hydrogen sulphide. Special reactions or flame tests can be used for their identification. because the ionic radii of these two ions are almost identical. magnesium carbonate. dissolves both anhydrous calcium chloride and calcium nitrate. bundles of needles or elongated prisms will be visible if calcium is present. Mg (A r : 24·305) Magnesium is a white. The sensitivity is 0'0 I ~g (in 0-01 ml) under the microscope. POTASSIUM. dissolve the residue in a few drops of water. and barium. it involves the use of a microscope (magnification about 110 x ). aluminium. forming the oxide MgO and some nitride Mg 3N 2. lead. thorium. and therefore during the course of systematic analysis (when considerable amounts of ammonium salts are building up in the solution) magnesium will not precipitate with the cations of the fourth group. It melts at 650°C. AND AMMONIUM. Anhydrous ethanol.REACTIONS OF CATIONS III. or a I + I mixture of anhydrous ethanol and diethyl ether.34J35 characteristic rectangular crystals of calcium picrolonate Ca(CloH70sN4h·8H20! in neutral or acetic acid solutions. in the presence of ammonium salts.35 MAGNESIUM. and add a minute drop of dilute sulphuric acid.000.32. 11. is soluble. The salts should preferably be present as nitrates. cobalt. Evaporate a few drops of the test solution on a watch glass to dryness on a water bath. III. interfere. Calcium sulphate dihydrate (microscope) test This is an excellent confirmatory test for calcium in Group IV.34 FIFTH GROUP OF CATIONS: MAGNESIUM. Group reaction: cations of the fifth group do not react with hydrochloric acid. Of the cations of this group. transfer to a microscope slide. Strontium and barium give precipitates but of different crystalline form. magnesium displays similar reactions to those of cations in the fourth group. However.

is practically insoluble. gelatinous magnesium hydroxide: Mg2+ + 2NH 3 + 2H 20 -+ Mg(OHh! + 2NHt The precipitate is very sparingly soluble in water (12 mg t -1. In the presence of a sufficient concentration of ammonium salts. but readily soluble in solutions of ammonium salts: Mg2+ + 20H- -+ Mg(OHh! 3. 1. is decreased still further so that much of the magnesium salt remains in solution. if ammonium salts are absent. Section 1. The small hydroxyl-ion concentration. already low. Sodium carbonate solution: white. Ammonium carbonate solution: in the absence of ammonium salts a white precipitate of basic magnesium carbonate: 5Mg2+ + 6CO~.27).+ 7H 20 -+ 4MgC0 3 . Ammonia solution: partial precipitation of white. carbonate. Section 1. because the equilibrium NHt + CO~. They taste bitter. The solubility product of the precipitate being high (Kg of pure MgC0 3 is I x 10. insoluble in excess reagent. Kg = 3'4 x 10.1 1 ) . 4. increases and consequently the concentration of the hydroxyl ions decreases owing to the commonion effect (cf.5). Magnesium dissolves readily in acids: Mg+2H+ -+ Mg2++H 2 i Magnesium forms the bivalent cation Mg2+. hence magnesium is not precipitated by ammonia solution in the presence of ammonium chloride or other ammonium salts.35 QUALITATIVE INORGANIC ANALYSIS of water the reaction proceeds rapidly: Mg+2H 20 -+ Mg(OHh!+H 2 t Magnesium hydroxide. voluminous precipitate of basic carbonate 286 . As the reaction progresses. hydroxide.28). Reactions of magnesium ions To study these reactions a 0'5M solution of magnesium chloride MgCI 6 • 6H 20 or magnesium sulphate MgS0 4 • 7H 20 can be used. Mg(OHh. the concentration of the ammonium ions. Sodium hydroxide solution: white precipitate of magnesium hydroxide. 2. due to the dissociation of the completely ionized ammonium salt.1lI. the concentration of carbonate ions necessary to produce a precipitate is not attained. the hydroxylion concentration is reduced to such an extent that the solubility product of Mg(OHh is not exceeded (cf. Some of the salts are hygroscopic. Its oxide. and phosphate are insoluble. the other salts are soluble.+:t NH 3 + HC0 3 is shifted towards the formation of hydrogen carbonate ions. but readily soluble in ammonium salts. 5H 20! + 2HC0 3 In the presence of ammonium salts no precipitation occurs.

insoluble in solutions of bases. but readily soluble in acids and in solutions of ammonium salts.then with a few drops of the diphenylcarbazide reagent and the solution filtered. 5. this may usually be overcome by cooling and by rubbing the test-tube or beaker beneath the surface of the liquid with a glass rod. Disodium hydrogen phosphate solution: white crystalline precipitate of magnesium ammonium phosphate Mg(NH 4)P04 . due to the formation of a complex salt or an adsorption complex. MgHP0 4 . is produced in neutral solutions.Oh. a yellow precipitate of the complex salt Mg(C 9H6N . The reagent is prepared by dissolving 2 g oxine in 100 ml 2M acetic acid. is treated with 1-2 ml reagent which has been rendered strongly ammoniacal by the addition of 3-4 ml dilute ammonia solution and the mixture heated to the boiling point. All other metals.+ NH 3 i + H 20 This tendency is reduced by moderate amounts of ammonia (it is found that the compound is very sparingly soluble in 2'5 per cent ammonia solution). must be absent.35 (cf.NH. 287 .a precipitate of magnesium hydroxide will be formed . The normal solubility of Mg(NH 4)P04.NH. containing a little ammonium chloride. The precipitate separates slowly from dilute solutions because of its tendency to form supersaturated solutions. 7.REACTIONS OF CAnONS m. On washing the precipitate with hot water.4H 20 is obtained. A white flocculant precipitate of magnesium hydrogen phosphate. 8-Hydroxyquinoline or 'oxine' reagent (cp) when a solution of a magnesium salt. it will be seen to have acquired a violet-red colour. soluble in acetic acid and in mineral acids. The reagent is prepared by dissolving 0'2 g diphenylcarbazide in lO ml glacial acetic acid and diluting to 100 ml with ethanol.NH.C6HsJ The magnesium salt solution is treated with sodium hydroxide solution . reaction 3). except sodium and potassium.CO. Mg2+ +HPO~-+ MgHP0 4 ! 6.NH. 6H 20 in the presence of ammonium chloride (to prevent precipitation of magnesium hydroxide) and ammonia solutions: The precipitate is sparingly soluble in water.6H 20 is increased by its hydrolysis in water: Mg(NH 4)P04 + H 20 +z Mg2+ + HPO~. Metals of Groups 11 and III interfere and should therefore be absent. Diphenylcarbazidereagent (C 6Hs.

p-Nitrobenzene-azo-resorcinol (or magneson I) reagent this test depends upon the adsorption of the reagent. must be absent. introduce a drop of reagent and a drop of2M sodium hydroxide.1lI. which frequently yield a blue colouration.35 QUALITATIVE INORGANIC ANALYSIS 8. upon Mg(OHh in alkaline solution whereby a blue lake is produced. According to the concentration of magnesium a blue precipitate is formed or the reddish-violent reagent assumes a blue colour. The spot-test technique is as follows. Titan yellow reagent: titan yellow (also known as clayton yellow) is a watersoluble yellow dyestuff. A blue precipitate appears. An alternative technique is to treat 0'5 ml neutral or slightly acidic test solution with 0'2 ml 2M sodium hydroxide solution. All elements of Groups I to III should be removed before applying the test. and should therefore be eliminated. Two ml test solution. Place a drop of the test solution on a spot plate and add 1-2 drops of the reagent. but it is essential to perform a blank test with the reagents. is treated with I drop of the reagent and sufficient 2M sodium hydroxide solution to render the solution strongly alkaline (say 2-3 ml). A red precipitate or colouration is produced. Place a drop of the test solution on a spot plate. All metals. the addition of I drop of 2M sodium hydroxide may be advisable. Sensitivity: O' 5 ug Mg. The reagent (for macro analysis) consists of a 0'5 per cent solution of p-nitrobenzene-azo-resorcinol in 0'2M sodium hydroxide. 288 . An alternative agent is p-nitrobenzene-azo-IX-naphthol or magneson 11 It yields the same colour changes as magneson I. Filter or drop-reaction paper should not be used. It is essential that the solution be strongly alkaline. This is an excellent confirmatory test in macro analysis. Ammonium salts reduce the sensitivity of the test by preventing the precipitation of Mg(OHh. concentration limit: I in 250. Concentration limit: I in 100. Its mode of use and preparation are identical with that described above for Magneson 1. which is a dyestuff. A red colour or precipitate is produced. It is adsorbed by magnesium hydroxide producing a deep-red colour or precipitate.000. Barium and calcium do not react but intensify the red colour. but has the advantage that it is more sensitive (sensitivity: 0'2 ug Mg. 9. For this reason a blue precipitate should be looked for.000) and its tinctorial power is less so that the blank test is not so deeply coloured. acidified slightly with hydrochloric acid. except those of the alkalis. A comparative test on distilled water should be carried out.

the colour disappears (difference from beryllium). Concentration limit: I in 200. K 2Na[Co(N02)6] ' is formed. Alternatively.000. Quinalizarin reagent: blue precipitate or cornflower-blue colouration with magnesium salts. becoming covered with a blue film. The blank test has a blue-violet colour. Sodium hexanitritocobaltate(Ill) solution Na3[ CO(N0 2)6] : yellow precipitate of potassium hexanitritocobaltate(I1I): 3K+ + [CO(N0 2)6] 3. The metal decomposes water violently. can be used for these tests. Upon the addition of a little bromine water. it will be coloured yellowish-red by the reagent. 11. Iodides and other reducing agents interfere and should be removed before applying the test. In alkaline solutions a brown or black precipitate of cobalt(III) hydroxide Co(OHh is obtained.REACfIONS OF CAnONS m.-+ K 3[Co(N02)6] ! The precipitate is insoluble in dilute acetic acid. If larger amounts of sodium are present (or if the reagent is added in excess) a mixed salt. silver-white metal. 1. Phosphates and large amounts of ammonium salts decrease the sensitivity of the reaction. 10. KCl.36 Sensitivity: 1·5 ug Mg. A blue precipitate or colouration appears. Potassium melts at 63·5°C. a 0·05 per cent solution of O·IM sodium hydroxide may be used. The precipitate forms immediately in concentrated solutions and slowly in diluted solutions. Concentration limit: I in 33. The colouration can be readily distinguished from the blueviolet colour of the reagent.000. a pale-pink mass is obtained.36 POTASSIUM. Place a drop of the test solution and a drop of distilled water in adjacent cavities of a spot plate and add 2 drops of the reagent to each. unless the anion is coloured. K (Ar : 39·098) Potassium is a soft. but all elements of Groups I to III should be removed. Upon moistening with a drop or two of cobalt nitrate solution and reheating strongly. If the solution is acid.+H 2 l Potassium is usually kept under solvent naphtha. The reagent is prepared by dissolving 0·01-0·02 g quinalizarin in 100 ml alcohol. The alkaline earth metals and aluminium do not interfere under the conditions of the test. Potassium salts contain the monovalent cation K +. 111. 289 . The reagent consists of a 0·1 per cent aqueous solution of titan yellow. Reactions ofpotassium ions A Msolution of potassium chloride. precipitation may be accelerated by warming. Sensitivity: 0·25 ug Mg. evolving hydrogen and burning with a violet flame: 2K+ +2H 20 -+ 2K+ +20H. It remains unchanged in dry air. These salts are usually soluble and form colourless solutions. Ammonium salts give a similar precipitate and must be absent. but is rapidly oxidized in moist air. Dry test (blowpipe test) All magnesium compounds when ignited on charcoal in the presence of sodium carbonate are converted into white magnesium oxide. which glows brightly when hot. Add 2M sodium hydroxide until the colour changes to violet and a further excess to increase the volume by 25 to 50 per cent.

Tartaric acid solution (or sodium hydrogen tartrate solution): white crystalline precipitate of potassium hydrogen tartrate: K++H 2. only small quantities should be employed and all precipitates placed in the platinum residues bottle. . Sodium hexanitritocobaltate(III)-silver nitrate test This is a modification of reaction I and is applicable to halogen-free solutions. Lithium.C4H406 +:t KHC 4H406!+H+ and K+ +H. Owing to its expensive character. in dilute solutions.6H 20 in 10 ml water. K+ +CIO. The precipitate is slightly soluble in water (3·26 g rI. because the strong acid. The reagent is prepared by dissolving 2·6 g hydrated chloroplatinic acid H 2[PtCI6]. 4.36 QUALITATIVE INORGANIC ANALYSIS 2.C 4H40(j +:t KHC 4H406 (a) (b) If tartaric acid is used. Ammonium salts give a similar precipitate and must be absent.4).1 at 0° and lOOOC respectively). thallium.KCI0 4! The precipitate is slightly soluble in water (3·2 g r 1 and 198 g t. Precipitation of potassium salts with sodium hexanitritocobaltate(III) and silver nitrate solution gives the compound K 2Ag[Co(NH 2)6] ' which is less soluble than the corresponding sodium compound K 2Na[Co(N02)6] and hence the test is more sensitive. and ammonium salts must be absent for they give precipitates with sodium hexanitritocobaltate(III) solution. 5.Ill. 290 . and add a drop of O·IM silver nitrate solution and a small amount of finely powdered sodium hexanitritocobaltate(III). by scratching the sides of the vessel with a glass rod. Precipitation is accelerated by vigorous agitation of the solution. Hexachloroplatinic(IV) acid (H 2 [ PtCI 6 ] ) reagent: yellow precipitate of potassium hexachloroplatinate(lV): 2K+ + [PtCI 6 ] 2 - - K 2[PtCI6]! Precipitation is instantaneous from concentrated solutions. but quite insoluble in 50 per cent ethanol. formed in reaction (a) dissolves the precipitate. 3. Ammonium salts yield a similar precipitate and must be absent. but may be hastened by cooling and by rubbing the sides of the vessel with a glass rod. and practically insoluble in absolute alcohol. A yellow precipitate or turbidity appears. Perchloric acid solution (HClD 4): white crystalline precipitate of potassium perchlorate KCI0 4 from not too dilute solutions. the solution should be buffered with sodium acetate. Place a drop of the neutral or acetic acid test solution on a black spot plate. and by adding alcohol. This reaction is unaffected by the presence of ammonium salts. The precipitate is slightly soluble in water. Strong alkalis also dissolve the precipitate. The alcoholic solution should not be heated as a dangerous explosion may result. Kg = 3 x 10. precipitation takes place slowly on standing. but is almost insoluble in 75 per cent alcohol.

6. The yellow flame produced by small quantities of sodium obscures the violet colour. Dipicrylamine (or hexanitrodiphenylamine) reagent the hydrogen atom of the NH group is replaceable by metals. Sodium tetraphenylboron test Potassium forms a white precipitate in neutral solutions or in the presence of acetic acid: K+ + [B(C 6H s )4] - -+ K[B(C 6H s)4] ! The precipitate is almost insoluble in water (0'053 g t -1. and also in acetone. Magnesium does not interfere. This approximately O'IM solution keeps for 2 weeks. Kg = 2'25 x 10. Rubidium. Dry test (flame colouration) Potassium compounds. The reagent is prepared by dissolving 3-42 g sodium tetraphenylboron Na[B(C 6H s)4] (Mr : 342'2) in water and diluting it to 100 ml. which is unaffected by treatment with 1-2 drops of 2M hydrochloric acid. 8. and ammonium ions interfere.000.37 SODIUM. Sensitivity: 3 ug K. caesium. the sensitivity is 4 ug K. the sodium salt is soluble in water to yield a yellow solution. It oxidizes rapidly in moist air and is therefore kept under solvent 291 .37 Sensitivity: I ug K.000. Place a drop of the neutral test solution upon drop-reaction paper and immediately add a drop of the slightly alkaline reagent. it must be filtered.8). thallium(I).REACfIONS OF CAnONS Ill. the latter gives a crystalline orange-red precipitate of the potassium derivative. Concentration limit: I in 50. 3 cm thick. The test is applicable in the presence of 80 times as much sodium and 130 times as much lithium. If silver nitrate solution is not added. 7.1). Ammonium salts should be removed before applying the test. Na (Ar : 22'99) Sodium is a silver-white. potassium is precipitated quantitatively if a small excess of the reagent is applied (0'1-0'2 per cent). The precipitate is soluble in strong acids and alkalis. If the solution is not clear. preferably the chloride. the yellow sodium rays are absorbed and the reddish-violet potassium flame becomes visible. also makes a good filter. ° 111. Concentration limit: I in 10. colour the non-luminous Bunsen flame violet (lilac). An orange-red spot is obtained. but by viewing the flame through two thicknesses of cobalt blue glass. The reagent is prepared by dissolving 0'2 g dipicrylamine in 20 ml boiling 0'05M sodium carbonate and filtering the cooled liquid. soft metal. With solutions of potassium salts. A solution of chrome alum (31 g t . melting at 97·5°C.

NaZn(U0 2h (CH3COO)9. 292 . Dissolve 33 g magnesium acetate in lO g acetic acid and 100 ml water (solution b). barium. cobalt.000. Alternatively. a reagent of equivalent concentration may be prepared by dissolving uranyl zinc acetate in the appropriate volume of water or of M acetic acid. The sensitivity of the reaction is affected by copper. 3.+ H 2i In its salts sodium is present as the monovalent cation Na +. Alternatively. almost all sodium salts are soluble in water. aluminium. allow to stand for 24 hours. and filter. Place a drop of the neutral test solution on a black spot plate or upon a black watch glass. the uranyl zinc acetate reagent is sometimes preferred to that employing uranyl magnesium acetate. Reactions of sodium ions To study these reactions a chloride. Dissolve lO g uranyl acetate in 6 g glacial acetic acid and 100 ml water (solution a). The reaction is fairly selective for sodium. A yellow cloudiness or precipitate forms. and stir with a glass rod. Mix the two solutions a and b. These salts form colourless solutions unless the anion is coloured. manganese. and ammonium when present in concentrations exceeding 5 g t . 2. and filter from the precipitated sodium zinc uranyl acetate. is obtained. The reagent is prepared as follows. Sensitivity: 12'5 ug Na.37 QUALITATIVE INORGANIC ANALYSIS naphtha or xylene. Chloroplatinic acid. The metal reacts violently with water forming sodium hydroxide and hydrogen: 2Na + 2H 20 -+ 2Na+ + 20H.m. strontium. Na + + Mg2+ + 3UO~+ + 9CH 3COO- -+ NaMg(U0 2h(CH3COO)9! The reagent is prepared as follows. calcium. Concentration limit: I in 4. Mix the two solutions a and b. Allow to stand for 24 hours. and add a small quantity of sodium chloride.9H20. warming if necessary. can be used. cadmium. nickel. The yellow crystalline sodium zinc uranyl acetate. Uranyl magnesium acetate solution: yellow.1 respectively. crystalline precipitate of sodium magnesium uranyl acetate NaMg(U0 2h(CH3COO)9' 9H 20 from concentrated solutions. The addition of about one-third volume of alcohol helps the precipitation. add 8 drops of the reagent. tartaric acid or sodium hexanitritocobaltate(Ill) solution: no precipitate with solutions of sodium salts. zinc. Dissolve lO g uranyl acetate in 25 ml 30 per cent acetic acid. Uranyl zinc acetate reagent As a delicate test for sodium. M solution of sodium 1. a reagent of equivalent concentration may be prepared by dissolving uranyl magnesium acetate in the appropriate volume of water or of M acetic acid. NaCl. In a separate vessel stir 30 g zinc acetate with 25 ml 30 per cent acetic acid and dilute with water to 50 ml (solution b).1 .1 and I g t . mercury. potassium and lithium salts are precipitated if their concentration in solution exceeds 5 g t. and dilute with water to 50 ml (solution a).

Sodium hydroxide solution: ammonia gas is evolved on warming. Unless the acid is non-volatile. (b) by the formation of white fumes of ammonium chloride when a glass rod moistened with concentrated hydrochloric acid is held in the vapour. Dry test (flame colouration) The non-luminous Bunsen flame is coloured an intense yellow by vapours of sodium salts. and (e) filter paper moistened with a solution of manganese(II) chloride and hydrogen peroxide gives a brown colour. and must therefore be absent.Hg(NH 2)I! + 71. In test l(d) a mixture of mercury(II) amidonitrate (white precipitate) and mercury (black precipitate) is formed: 2NH3+Hg~++N03 -+ Hg(NH 2)N0 3!+Hg!+NH! In test I (e) hydrated manganese(IV) oxide is formed: 2NH 3+Mn2++H 20 2+H 20 -+ MnO(OHh!+2NHt 2. The reactions of ammonium ions are in general similar to those of potassium.REACTIONS OF CATIONS Ill. 111. Nessler's reagent (alkaline solution of potassium tetraiodomercurate( Il)): brown precipitate or brown or yellow colouration is produced according to the amount of ammonia or ammonium ions present.38 4. blackens mercury(I) nitrate paper. The characteristics of these ions are similar to those of alkali metal ions. however. NU! (M r : 18·038) Ammonium ions are derived from ammonia. The precipitate is a basic mercury(II) amido-iodide: NHt +2[HgI 4 ] 2 .+3H 20 The formula of the brown precipitate has also been given as 3HgO. NH! + OH- -+ NH 3i + H 20 This may be identified (a) by its odour (cautiously smell the vapour after removing the test-tube or small beaker from the flame). M solution of 1.+40H- -+ HgO. all ammonium salts decompose to ammonia and the appropriate acid. (c) by its turning moistened red litmus paper blue or turmeric paper brown. 293 . because the sizes of the two ions are almost identical.38 AMMONIUM ION. By electrolysis with a mercury cathode. forming colourless solutions (unless the anion is coloured). Reactions of ammonium ions To study these reactions a ammonium chloride NH 4 CI can be used. On heating. ammonium salts can be quantitatively removed from dry mixtures by heating. and the hydrogen ion H+. due to the oxidation of manganese by the alkaline solution thus formed. which has similar properties to the amalgams of sodium or potassium. (d) by its ability to turn filter paper moistened with mercury(I) nitrate solution black (this is a very trustworthy test*). Hg(NH3hI2 * Arsine. and it is only when the colour is intense and persistent that appreciable quantities of sodium are present. The colour is not visible when viewed through two thicknesses of cobalt blue glass. NH 3. ammonium amalgam can be prepared. Ammonium salts are generally water-soluble compounds. Minute quantities of sodium salts give this test.

and 2'5M in potassium hydroxide. from which it is distinguished by the evolution of ammonia gas on being heated with sodium hydroxide solution. 1934). Allow to stand for 24 hours. A drop of Nessler's solution is placed on the glass knob of the apparatus. until a slight. Saturated sodium hydrogen tartrate solution (NaH. tartaric acid solution. K 2[HgI4 ] .C4H40 6):* white precipitate of ammonium acid tartrate NH 4 • H. similar to but slightly more soluble than the corresponding potassium salt.1) in small quantities at a time.-+ (NH 4h[Co(N02)6] ! 4. Allow to stand overnight and decant the clear liquid. 0'09M in potassium tetraiodomercurate(II). A yellow or orange-red stain or ring is produced. 5. * Or. must be absent. Sensitivity: O' 3 ug NH 3 (in 0'002 ml). permanent precipitate is formed. Sensitivity: 0'25 ug NH 3 • 3. C 4H406 . but differ from it in being decomposed by warming with sodium hydroxide solution with the evolution of ammonia gas. Transfer a micro drop of the resulting solution or suspension to drop-reaction paper and add a drop of Nessler's reagent. (Na3[Co(NO)2)6]): yellow precipitate of ammonium hexanitritocobaltate(III).38 QUALITATIVE INORGANIC ANALYSIS (Britton and Wilson. All metals. The test is an extremely delicate one and will detect traces of ammonia present in drinking water. 1933) and as NH 2 • Hg 2I 3 (Nichols and Willits. An alternative method for the preparation of the reagent is as follows. A better procedure is to employ the technique described under the manganese(II) nitrate-silver nitrate reagent in reaction 9 below. Hexachloroplatinic[JV) acid (H2[PtCI 6]): yellow precipitate of ammonium hexachloroplatinate(lV) 2NHt + [PtCI 6 ] 2 .-+ (NH 4h[PtCI6 ] ! The characteristics of the precipitate are similar to that of the corresponding potassium salt. with shaking. Mix a drop of the test solution with a drop of concentrated sodium hydroxide solution on a watch glass. Sodium hexanitritocobaltate(III) . After the reaction is complete. Nessler's original reagent has been described as a solution which is c. (NH 4h[Co(N02)6] ' similar to that produced by potassium ions: 3NHt + [CO(N0 2)6] 3. The reagent is prepared by dissolving 109 potassium iodide in 10 ml ammoniafree water. adding saturated mercury(II) chloride solution (60 g t . . add 100 ml 6M sodium hydroxide. 294 less effectively. Dissolve 23 g mercury(II) iodide and 16 g potassium iodide in ammonia-free water and make up the volume to 100 ml. except sodium or potassium. then adding 80 ml 9M potassium hydroxide solution and diluting to 200 ml. The solution should be kept in the dark. The reagent thus consists of an alkaline solution of potassium tetraiodomercurate(II) K 2[HgI4 ].m. The spot-test technique is as follows. and decant the solution from any precipitate that may have formed. the drop of the reagent is touched with a piece of drop-reaction or quantitative filter paper when a yellow colouration will be apparent.

add 20 ml 2-5 per cent sodium nitrite solution with vigorous shaking. The apparatus is shown in Fig. followed by a drop of the reagent and a fine granule of calcium oxide between the two drops. 11. Mix 2 drops 5 per cent tannic acid (tannin) solution with 2 drops 20 per cent silver nitrate solution. A red zone forms round the calcium oxide. The reagent becomes turbid on keeping. A black stain is formed on the paper or upon the cotton wool. and add a drop of 2M sodium hydroxide solution. Place a drop of the test solution or a little of the solid in the micro test-tube. Continue the shaking until all dissolves. The test is a sensitive one. hr 8. The paper assumes a blue colour.000 Cyanides should be absent. A blank test should be carried out on a drop of water. for they give ammonia with alkalis: CN-+2H 2 0 -+ HCOO-+NH 3 i 295 .REACTIONS OF CATIONS 1lI. Cool. Tannic acid-silver nitrate test The basis of this test is the reducing action of tannic acid (a glucoside of digallic acid) upon the silver ammine complex to yield black silver: it therefore precipitates silver in the presence [Ag(NH 3 of ammonia but not from a slightly acid silver nitrate solution. Dissolve I g p-nitroaniline in 25 ml 2M hydrochloric acid (warming may be necessary) and dilute with 160 ml water. Ammonia-formation test This is a modification of reaction I as adapted to delicate analysis._ (1) --. 02 N-Q-N=NONH4+C1-+H20 (11) Place a drop of the neutral or slightly acid test solution on a spot plate. but can be employed again after filtering. 02 N-Q-N=N-CI+ N Hr+20H. which can be closed with a small ground-glass stopper carrying a small glass hook at the lower end. Hold the paper in the vapour produced by heating an ammonium salt with sodium hydroxide solution. The reagent (sometimes known as Riegler's solution) is prepared as follows.38 6. 7.55 and consists of a small glass tube of I ml capacity. Warm to 40°C for 5 minutes. Perchloric acid or sodium perchlorate solution: no precipitate (distinction from potassium). Concentration limit: I in 75. p-Nitrobenzene-diazonium chloride reagent The reagent (I) yields a red colouration (due to 11) with an ammonium salt in the presence of sodium hydroxide solution. and place the mixture upon drop-reaction paper or upon a little cotton wool.000. Sensitivity: 0' 7 ug NH 3 . Sensitivity: 0·0 I ug NH 3 • Concentration limit: I in 5. Fix a small piece of red litmus paper on the glass hook and insert the stopper into position.000. 9.

38 QUALITATIVE INORGANIC ANALYSIS If. Heat at 40°C for 5 minutes. ammonium chloride. e. also place a drop of the reagent on the glass knob of the stopper and close the apparatus. The manganese(lI) nitrate-silver nitrate reagent is prepared thus: dissolve 2·87 g manganese(lI) nitrate in 40 ml water. Neutralize the acid formed by hydrolysis by adding dilute alkali dropwise until a black precipitate is formed and filter. 296 . In some cases.53 or in Fig. Wash the drop of the reagent on to a piece of quantitative filter paper when a black or grey fleck will become transparent. Keep the reagent in a dark bottle. the alkalistable mercury(lI) cyanide Hg(CNh is formed and the interfering effect of cyanides is largely eliminated.000. the vapours recombine on cooling to form a sublimate of the salt. and dilute the mixture to 100 ml. (DANGER: THE REAGENT IS CARCINOGENIC).1lI.000. and filtering). Use the apparatus shown in Fig. however. An alternative method for carrying out the test is to employ the manganese(lI) nitrate-silver nitrate reagent. Upon treating a neutral solution of manganese(lI) and silver salts with ammonia.MnO(OHh!+2Ag!+4NHt The sensitivity can be increased by treating the resultant precipitate with an acetic acid solution of benzidine whereupon the manganese dioxide oxidizes the benzidine to a blue oxidation product. where the acid is volatile.54. 11. Sensitivity: 0·005 ug NH 3 • Concentration limit: I in 10. this turns blue upon treatment with a solution of'benzidine (the latter is prepared by dissolving 0·05 g benzidine or its hydrochloride in 10 ml glacial acetic acid. and filter. 11.g. Dry test All ammonium salts are either volatilized or decomposed when heated to just below red heat. diluting to 100 ml with water. Add a solution of 3·55 g silver nitrate in 40 ml water. a little mercury(lI) oxide or a mercury(lI) salt is added. a black precipitate is formed: 4NH 3+Mn 2+ +2Ag+ +3H 2 0 . 10. Place a drop of the test solution and a drop of2M sodium hydroxide in the micro test-tube.

can only be regarded as useful in giving an indication of the limitations of the method and for the confirmation of the results obtained by the simpler procedures to be described below. Class (B) is subdivided into (i) precipitation reactions. however. chlorate (DANGER).* hexacyanoferrate(II). and cyanate. these however. nitrite. and (ii) oxidation and reduction in solution. CLASS A (i) Gases evolved with dilute hydrochloric acid or dilute sulphuric acid: Carbonate. sulphide. nitrate. iodide.! SCHEME OF CLASSIFICATION The methods available for the detection of anions are not as systematic as those which have been described in the previous chapter for cations. hexafluorosilicate. * This is often included in Class B(i).* chloride. oxalate. It must. borate. acetate. thiocyanate. The following scheme of classification has been found to work well in practice. and. and of their zinc salts. and citrate. sulphite. These include those of (i) with the addition of the following: fluoride. and the subsequent unequivocal separation of each group into its independent constituents. permanganate (DANGER~ bromate. bromide. hypochlorite. (ii) Gases or acid vapours evolved with concentrated sulphuric acid. tartrate. thiosulphate. hexacyanoferrate(III). it has no theoretical basis. Essentially the processes employed may be divided into (A) those involving the identification by volatile products obtained on treatment with acids. No really satisfactory scheme has yet been proposed which permits of the separation of the common anions into major groups. perchlorate. and (ii) gases or vapours evolved with concentrated sulphuric acid. of their calcium or barium salts. and (B) those dependent upon reactions in solution.CHAPTER IV REACTIONS OF THE ANIONS IV. hydrogen carbonate. furthermore. it is not a rigid one since some of the anions belong to more than one of the subdivisions. Class (A) is subdivided into (i) gases evolved with dilute hydrochloric acid or dilute sulphuric acid. 297 . be mentioned that it is possible to separate the anions into major groups dependent upon the solubilities of their silver salts. cyanide. formate.

CO~. such as magnesite.Mg)C0 3. It must be remembered that. and succinates. arsenite. The hydrogen carbonates or bicarbonates of calcium. (i) Precipitation reactions. arsenate. The reactions of all these anions will be systematically studied in the following pages. barium. do not react appreciably in the cold. For convenience the reactions of certain organic acids are grouped together. magnesium. formates. chromate and dichromate.2 CARBONATES. salicylate. oxalates. with the exception of those of the alkali metals and of ammonium. Dilute hydrochloric acid: decomposition with effervescence. (Ca. chromate. all give a characteristic colouration or precipitate upon the addition of iron(III) chloride solution to a practically neutral solution. benzoates. hypophosphite. It may be pointed out that acetates. The solid substance is placed in the test-tube or small distilling flask (10-25 ml capacity). permanganate. and possibly of iron exist in aqueous solution. 298 . strontium. are insoluble in water. To study these reactions a O'5M solution of sodium carbonate Na2C03. dichromate. (ii) Oxidation and reduction in solution. The lime water or baryta water test is best carried out in the apparatus shown in Fig. they must be finely powdered and the reaction mixture warmed. and the cork immediately replaced. due to the evolution of carbon dioxide: CO~- + 2H+ -+ CO 2l + H 20 the gas can be identified by its property of rendering lime water (or baryta water) turbid: CO 2+Ca2++20HCO 2 + Ba2+ + 20H-+ -+ CaC0 3!+H20 BaC0 3! + H 20 Some natural carbonates. 1.1 OH20 can be used.Solubility All normal carbonates. IV. they are formed by the action of excess carbonic acid upon the normal carbonates either in aqueous solution or suspension and are decomposed on boiling the solutions. and succinates themselves form another group.2 QUALITATIVE INORGANIC ANALYSIS CLASS B Sulphate. phosphite. The gas which is evolved (warming may be necessary) is passed into lime water or baryta water contained in the test-tube. MgC0 3. citrates. salicylates. and succinate. salicylates. siderite. and dolomite. CaC0 3! +H 20+C02 -+ Ca2+ +2HC0 3 The hydrogen carbonates of the alkali metals are soluble in water. benzoates. but are best studied together with sulphates. * Strictly speaking peroxodisulphates should be grouped with Class B(ii).IV. dilute hydrochloric acid added. Manganate. tartrates. FeC0 3.l. IV. hexafluorosilicate. these include acetates. formates. benzoate. * phosphate. peroxodisulphate. silicate. the production of a turbidity indicates the presence of a carbonate. but are less soluble than the corresponding normal carbonates.

the weak boric acid (K I = 5'8 x 10.5 ) will decompose carbonates. The precipitate is soluble in mineral acids and carbonic acid: BaC0 3 + 2H+ BaC0 3+C02+H 20 -+ -+ Ba2+ + CO 2 i + H 20 Ba2++2HCO:.1 °) and hydrocyanic acid (K = 4'79 x 10. 3. Thus.1 °) will not. Fig. the same happens if the mixture is boiled: Ag 2C0 3! -+ Ag 20!+C0 2i 299 . which is stronger than carbonic acid (K I = 4'31 x 10.7 ) will displace it. the turbidity slowly disappears as a result of the formation of a soluble hydrogen carbonate: CaC0 3!+C02 +H 20 -+ Ca2+ +2HCO:.+Ba2+ -+ CO~. Any acid. even acetic acid (K = 1·76 x 10.! 2. Silver nitrate solution: white precipitate of silver carbonate: CO~.+2Ag+ -+ Ag 2C0 3! -+ -+ The precipitate is soluble in nitric acid and in ammonia: Ag 2C0 3+2H+ Ag 2C0 3 +4NH 3 2Ag+ +C0 2i+H 20 2[Ag(NH 3 +CO~- hr The precipitate becomes yellow or brown upon addition of excess reagent owing to the formation of silver oxide.REACTIONS OF ANIONS IV.2 with prolonged passage of carbon dioxide. IV. hydrogen carbonates do not. Barium chloride (or calcium chloride) solution: white precipitate of barium (or calcium) carbonate: CO~.+Ca2+ -+ BaC0 3! CaC0 3! Only normal carbonates react. especially on warming.

Section IV. IV. Cyanides are rendered innocuous by treating the test solution with 4 drops of a saturated solution of mercury(lI) chloride. followed by 2 drops sulphuric acid. Add 3-4 drops Msulphuric acid and insert the stopper into position. fluorides. 11. sulphites. Sensitivity: 4 ug CO 2 (in 2 drops of solution). can be used to study these reactions.. cyanates. cyanides. thiosulphates.3 HYDROGEN CARBONATES. 2. The sulphur-containing anions can be quantitatively oxidized to sulphates by hydrogen peroxide: S2. then to add 2 drops Msulphuric acid. Sulphides. -+ CO~. the slightly dissociated mercury(lI) cyanide is formed. and acetates interfere. and to continue as above. Concentration limit: I in 12. nitrites. 1. Sodium carbonate-phenolphthalein test This test depends upon the fact that phenolphthalein is turned pink by soluble carbonate and colourless by soluble bicarbonates.+3H 20+2H+ The modified procedure in the presence of these anions is therefore to stir a drop of the test solution with 4 drops 3 percent hydrogen peroxide. etc.+H 20+C02 i carbon dioxide. Hence if the carbon dioxide liberated by dilute acids from carbonates is allowed to come into contact with phenolphthalein solution coloured pink by sodium carbonate solution. The drop is decolourized either immediately or after a short time according to the quantity of carbon dioxide formed. Nitrites can be removed by treatment with aniline hydrochloride.500. Perform a blank test in a similar apparatus. Most of the reactions of hydrogen carbonates are similar to those of carbonates. formed in this way.2. The tests described here are suitable to distinguish hydrogen carbonates from carbonates.+4H 202 -+ 2S0i.+4H 202 -+ SOi. A freshly prepared 0'5M solution of sodium hydrogen carbonate. The reagent is prepared by mixing I ml 0'05M sodium carbonate with 2 ml 0'5 per cent solution of phenolphthalein.+4H 20 SO~. can be identified with lime water or baryta water (cf. NaHC0 3 .+H 202 -+ SOi. Magnesium sulphate 300 Adding magnesium sulphate to a cold solution of .3 QUALITATIVE INORGANIC ANALYSIS 4.IV. and lO ml water. Boiling When boiling. The concentration of the sodium carbonate solution must be such as not to be decolourized under the conditions of the experiment by the carbon dioxide in the atmosphere. it may be identified by the decolourization which takes place CO 2 +co~. KHC0 3 .+H 20 S20~. reaction I). Place 1-2 drops test solution (or a small quantity of the test solid) in the apparatus shown in Fig. hydrogen carbonates decompose: 2HCO:.+H 20 -+ 2HCO:. HCO:.53 and place I drop sodium carbonate-phenolphthalein reagent on the knob of the stopper. or potassium hydrogen carbonate.

2. reaction I).+2H+ -+ S02i+H20 301 . a white precipitate of magnesium carbonate is formed: Mg2+ + 2HC0 3 -+ MgC0 3 + H 20 + CO 2i The carbon dioxide gas. 3. Section IV. A freshly prepared O'5M solution of sodium sulphite Na2S03' 7H 20 can be used to study these reactions.4 SULPHITES. formed in the reaction. while in a solution of normal carbonates a reddish-brown precipitate of basic mercury(II) carbonate (3HgO. Solid test On heating some solid alkali hydrogen carbonate in a dry testtube carbon dioxide is evolved: 2NaHC0 3 -+ Na 2C03+H20+C02i The gas can be identified with lime water or baryta water (cf. The hydrogen sulphites of the alkali metals are soluble in water. Heating the mixture. can be detected with lime water or baryta water (cf.4 hydrogen carbonate no precipitation occurs. the hydrogen sulphites of the alkaline earth metals are known only in solution. The residue evolves carbon dioxide if dilute hydrochloric acid is poured on it after cooling: Na 2C03+2H+ -+ 2Na++C0 2i+H20 5. the sulphites of the other metals are either sparingly soluble or insoluble. MgC0 3. a white precipitate or cloudiness is obtained if hydrogen carbonates are present: 2HC0 3 +2Ca2+ +2NH 3 -+ 2CaC0 3! +2NHt IV. more rapidly on warming. SO~.Solubility Only the sulphites of the alkali metals and of ammonium are soluble in water. with the evolution of sulphur dioxide: SO~. Section IV. reaction I). reacting with the hydrogen ions formed in the reaction: CO~-+2H+ -+ C0 2i+H20 4. On adding ammonia to the filtrate. is formed with normal carbonates. while a white precipitate of magnesium carbonate. 1. Test for hydrogen carbonate in the presence of normal carbonate Adding an excess of calcium chloride to a mixture of carbonate and hydrogen carbonate the former is precipitated quantitatively: CO~- +Ca2+ -+ CaC0 3! On filtering the solution rapidly hydrogen carbonate ions pass into the filtrate. Mercury (II) chloride No precipitate is formed with hydrogen carbonate ions.2.HgC0 3 = Hg 40 3C03) is formed: CO~- +4Hg2+ +3H 20 -+ Hg 40 3C03!+6H+ the excess of carbonate acts as a buffer.REACfIONS OF ANIONS IV. Dilute hydrochloric acid (or dilute sulphuric acid): decomposition.

3S0 2 +Cr20~. and barium are respectively 1·25 g t. moistened with acidified potassium dichromate solution.1 . a white.+H 20 Another method of identification of the gas is (iii) to hold a filter paper. 0·033 g ri. in the vapour.+ 8H+ 2. when a blue colour. Silver nitrate solution: first. crystalline precipitate of silver sulphite is formed: [AgS0 3 +Ag+ -+ Ag 2S0 3! The precipitate dissolves if sulphite ions are added in excess: Ag 2S0 3! +SO~-+ r 2[AgS0 3 ] - On boiling the solution of the complex salt. Barium chloride or strontium chloride solution: white precipitate of barium or strontium) sulphite: SO~. or an aqueous suspension of the precipitate. is observable: 5S0 2 + 210 3 + 4H 20 -+ 12 + 5S0i. when sulphur dioxide evolves: BaS0 3! +2H+ -+ Ba2+ +S02 t +H 20 On standing. (ii) by the green colouration.+2H+ -+ 2Cr3+ +3S0i.4 QUALITATIVE INORGANIC ANALYSIS The gas may be identified (i) by its suffocating odour of burning sulphur.+S02i 2Ag!+SOi. due to the formation of chromium(lIl) ions.IV. is held over the mouth of the test-tube. 3.1 . the precipitate is slowly oxidized to the sulphate and is then insoluble in dilute mineral acids.+2H+ 3BaS0 3!+2HN03 -+ 3BaS0 4!+2NOi+H 20 BaS0 3! + H 20 2 -+ BaS04! + H 20 The solubilities at 18° of the sulphites of calcium. moistened with potassium iodate and starch solution. strontium. produced when a filter paper. 2BaS0 3! +0 2 -+ 2BaS04! BaS0 3!+Br 2+H20 -+ BaS04!+2Br.+ Ba2+ -+ BaS0 3! the precipitate dissolves in dilute hydrochloric acid. 0'022 g t. this change is rapidly effected by warming with bromine water or a little concentrated nitric acid or with hydrogen peroxide. owing to the formation of iodine. no visible change occurs because of the formation of sulphitoargentate ions: SO~- -i-Ag" -+ [AgS0 3 ] - on the addition of more reagent.+2H+ . grey metallic silver is precipitated: 2[AgS0 3 Ag 2S0 3!+H 20 302 r -+ -+ 2Ag!+SOi.

SO~- +Ca2+ -+ CaS0 3! The precipitate dissolves on prolonged passage of the gas.5. Lime water This test is carried out by adding dilute hydrochloric acid to the solid sulphite.+Cr20~. Potassium permanganate solution. which may be detected by holding lead acetate paper to the mouth of the test-tube (cf.REACfIONS OF ANIONS IV. IV.+2MnO. owing to the formation of chromium(III) ions.+3H 20 5. Section IV. the latter produce a black precipitate (cf. the precipitate is oxidized by atmospheric oxygen and lead sulphate is formed: 2PbS0 3!+02 -+ 2PbS04! This reaction can be used to distinguish sulphites and thiosulphates. This may be effected by adding potassium dichromate solution to the test-tube before acidifying. is produced: 3S0~. Zinc and sulphuric acid: hydrogen sulphide gas is evolved. when sulphur dioxide gas is formed: PbS0 3!+2H+ -+ The gas may be identified by one of the methods listed under reaction I.6. +6H+ -+ 2Mn2+ +5S0i. Section IV. acidified with dilute sulphuric acid before the test: a green colouration.+4H 20 6. when the diammineargentate complex is formed: Ag 2S0 3!+4NH3 -+ 2[Ag(NH 3 hr +SO~- 4. On boiling. due to the formation of hydrogen sulphite ions: CaS0 3!+S02 +H 20 -+ Ca2+ +2HS0 3 A turbidity is also produced by carbonates. 7. Potassium dichromate solution. Lead acetate or lead nitrate solution: white precipitate of lead sulphite: SO~- + Pb2+ -+ PbS0 3! S02i+Pb2++H 20 The precipitate dissolves in dilute nitric acid. reaction 5) on boiling.l). a white precipitate of calcium sulphite CaS0 3 is formed. when sulphur dioxide gas is evolved: Ag 2S0 3!+2H+ -+ S02i+2Ag+ +H 20 The precipitate also dissolves in ammonia. acidified with dilute sulphuric acid before the test: decolourization owing to reduction to manganese(II) ions: 5S0~.+ 8H+ -+ 2Cr3+ + 3S0i. sulphur dioxide must therefore be first removed when testing for the latter. and bubbling the evolved sulphur dioxide through lime water (Fig. reaction I): SO~-+3Zn+8H+ -+ H 2Si+3Zn2++3H2i+3H20 8. The dichromate 303 .4 The precipitate is soluble in dilute nitric acid.

The fuchsin reagent is prepared by dissolving 0'015 g fuchsin in 100 ml water. Nickel(II) hydroxide test The auto-oxidation of sulphur dioxide (or sulphurous acid) induces the oxidation of green nickel(lI) hydroxide to the black nickel(III) hydroxide. The green hydroxide turns grey to black according to the amount of sulphite present.53 and place a little washed nickel(lI) hydroxide on the glass knob under the stopper. diluting to 100 ml with water and filtering. reaction 9) and malachite green. but nitrogen dioxide does. 304 . An alternative technique is to warm (water bath) the test solution in a semimicro test-tube with a little dilute hydrochloric acid. It should be freshly prepared. carbon dioxide does not interfere. but the reaction is not quite complete: nevertheless it is a very useful test for sulphur and acid sulphites. Place I drop of the fuchsin reagent on a spot plate and add I drop of the neutral test solution. are immediately decolourized by neutral sulphites. Thiosulphates do not interfere but sulphides.2).000. The stain acquires a black colour. lead. Place a drop of the test solution (or a little of the test solid) in the tube of the apparatus shown in Fig. The nickel(lI) hydroxide is prepared by precipitating nickel(lI) chloride solution with sodium hydroxide solution and washing thoroughly until free from alkali. 9. Zinc. Add 1-2 drops 6M hydrochloric acid.000. Sensitivity: I ug S02' Concentration limit: I in 50.IV. The colour change is quite distinct. Sodium nitroprusside-zinc sulphate test Sodium nitroprusside solution reacts with a solution of a zinc salt to yield a salmon-coloured precipitate of zinc nitroprusside Zn[Fe(CN)sNO]. sulphides also interfere. 11. it should preferably be just neutralized with sodium hydrogen carbonate. For small amounts of sulphites.) Thiosulphates give a similar reaction and must therefore be absent. 11. The reagent is decolourized. see Section IV. polysulphides. Sensitivity: 0'4 ug S02' Concentration limit: I in 125. but for very small amounts of sulphur dioxide use may be made of the conversion of benzidine acetate to 'benzidine blue' by the nickel(III) hydroxide. Fuchsin test Dilute solutions of triphenylmethane dyestuffs. transfer the nickel hydroxide to a quantitative filter paper and treat with a drop of the benzidine reagent: a blue colour is formed. the test is rendered more sensitive when the reaction product is held over ammonia vapour which decolourizes the unused zinc nitroprusside. (DANGER: THE REAGENT IS CARCINOGENIC. and expose the evolved gas to filter paper upon which a stain of nickel(lI) hydroxide has been made. such as fuchsin (for formula. Section IV.4 QUALITATIVE INORGANIC ANALYSIS oxidizes and destroys the sulphur dioxide without affecting the carbon dioxide (cf. and cadmium salts reduce the sensitivity of the test.I5. If the test solution is acid. Sulphur dioxide also decolourizes fuchsin solution. 10. The benzidine reagent is prepared by dissolving 0'05 g benzidine or its hydrochloride in 10 ml glacial acetic acid. The latter reacts with moist sulphur dioxide to give a red compound of unknown composition. close the apparatus and warm gently. hence the interference of sulphides cannot be obviated by the addition of these salts. and free alkali do.

Sensitivity: 3'5 ug S02' Concentration limit: I in 14. and kept in a dark glass bottle or tube.53 and coat the knob of the glass stopper with a thin layer of the zinc nitroprusside paste. sulphate ions are formed and the solution becomes neutral: SO. 11. the acidified liquid soon becomes turbid owing to the separation of sulphur.+2H+ Place a drop of the test solution and 2 drops of saturated mercury(lI) chloride solution in the same apparatus (Fig. 11. acidify with 2M hydrochloric or Msulphuric acid. It must be emphasized that these tests alone are not specific for sulphites or hydrogen sulphites. To study these reactions use a 0'5M solution of sodium thiosulphate Na 2S20 3·5H 20. 20 ug Na 2S0 3 can be detected in the presence of 900 ug Na2S203 and 1. IV. sulphur dioxide is evolved which is recognized by its odour and its action upon 305 . silver.+H 20 -+ -+ HgS! HgS!+SOi. Add a drop of 2M hydrochloric or sulphuric acid and close the apparatus.+ H 202 -+ SOi. Distinction between sulphites and hydrogen sulphites The solution of normal alkali sulphites shows an alkaline reaction against litmus paper.5 Place a drop of the test solution (or a grain of the solid test sample) in the tube of Fig.000. Adding a neutral solution of dilute hydrogen peroxide to the solution of normal sulphites.+H+ +H 20 and the solution shows a definite acid reaction. After the sulphur dioxide has been evolved. Dilute hydrochloric acid: no immediate change in the cold with a solution of a thiosulphate. and sulphurous acid is present in solution. +OH- while the solution of alkali hydrogen sulphites is neutral.53) and.+ H 20 with hydrogen sulphites the same test yields hydrogen ions: HSO:. The paste is coloured more or less deep red. On warming the solution. 12. The test is not applicable in the presence of sulphides and/or thiosulphates. S20~. Many of them dissolve in excess sodium thiosulphate solution forming complex salts. and barium are very sparingly soluble. those of lead. and proceed as above. These can be removed by the addition of mercury(lI) chloride which reacts forming the acid-stable mercury(lI) sulphide: Hg2+ +S2Hg2+ +S20~.REACTIONS OF ANIONS IV. 1.Solubility Most of the thiosulphates that have been prepared are soluble in water. hold the stopper for a short time in ammonia vapour.. after a minute. The zinc nitroprusside paste is prepared by precipitating sodium nitroprusside solution with an excess of zinc sulphate solution and boiling for a few minutes: the precipitate is filtered and washed.500 ug of Na 2S. +H 202 -+ SOi.S THIOSULPHATES. because of hydrolysis: SO~- +H 20 +:t HSO:. their presence must be confirmed first by other reactions.

Longman 1978.+2H+ -+ S! +S02i +H 20 2. including Elementary Instrumental Analysis. 5. 4. Barium chloride solution: white precipitate of barium thiosulphate. Side reactions also occur giving rise to thionic acids. turning dark on standing. The solubility is O' 5 g r 1 at 18°. 343 et f. Silver nitrate solution: white precipitate of silver thiosulphate: S20~.+2Ag+ -+ Ag 2S20 3! At first no precipitation occurs because the soluble dithiosulphatoargentate(l) complex is formed: 2S20~. but on further addition of the reagent a white precipitate of lead thiosulphate is formed: S20~. Section IV. Potassium cyanide solution (POISON): after alkalizing the test solution first * See A.--Ag" -+ [Ag(S203h]3- The precipitate is unstable. S20~. 6. which is gradually coagulated by the free acid present. * 3.+S40~This reaction has important practical applications in the iodiometric and iodimetric methods of titrimetric analysis. 306 . p. forming finally a black precipitate of lead sulphide: PbS 203! + H 20 -+ PbS! + 2H+ + SOi- This reaction can be applied to distinguish sulphite and thiosulphate ions (cf.5 QUALITATIVE INORGANIC ANALYSIS filter paper moistened with acidified potassium dichromate solution. On boiling the suspension the precipitate darkens.4. Lead acetate or lead nitrate solution: first no change. when silver sulphide is formed: Ag 2S20 3! + "20 -+ Ag 2S! + 2H+ + SOi- This hydrolytic decomposition can be accelerated by warming. 1. The sulphur first forms a colloidal solution. No precipitate is obtained with calcium chloride solution since calcium thiosulphate is fairly soluble in water. reaction 6). Vogel's A Textbook of Quantitative Inorganic Analysis. Iodine solution: decolourized when a colourless solution of tetrathionate ions is formed: 12 +2S20~. S20~.+ Ba2+ -+ BaS203! Precipitation is accelerated by agitation and by rubbing the sides of the vessel with a glass rod. for this reason no precipitation occurs first. BaS203' from moderately concentrated solutions.+Pb2+ -+ PbS 203! The precipitate is soluble in excess thiosulphate.IV.-+ 21. 4th ed..

and iodine (as 13") do not react. but hydrogen sulphide and ammonium sulphide decompose the reagent with the precipitation of nickel sulphide.+ Fe3+ -+ Fe(SCNh 7.000. cobalt. probably due to the formation of a dithiosulphatoiron(III) complex: 2S20~. in a well-ventilated fume cupboard. violet precipitate of the complex thiosulphate is obtained: [Ni(enh]2+ +S20~- -+ [Ni(enh]S203! Sulphites.5 with sodium hydroxide and adding potassium cyanide. with hydrochloric acid and adding iron(III) chloride. a blue ring is formed temporarily at the contact zone. a crystalline. Blue ring test When a solution of thiosulphate mixed with ammonium molybdate solution is poured slowly down the side of a test tube which contains concentrated sulphuric acid. 8. NH 2h](N03b abbreviated to [Ni(enh](N03h. thiocyanate ions are formed on boiling: S20~- +CN- -+ SCN.+2Fe3+ -+ S40~. The nickel ethylenediamine nitrate reagent is conveniently prepared when required by treating a little nickel chloride solution with ethylenediamine until a violet colour (due to the formation of the complex [Ni(enh]2+ ion) appears. the red colour of iron(III) thiocyanate can be observed: 3SCN. Concentration limit: I in 25. there is an immediate vigorous evolution of nitrogen: 2N3"+I3" -+ 31-+3N 2i Sulphides and thiocyanates act similarly and must therefore be absent. A vigorous evolution of bubbles (nitrogen) ensues. Mix a drop of the test solution and a drop of the iodine-azide reagent on a watch glass. 10.+2Fe2+ 9. Iron ( Ill) chloride solution: a dark-violet colouration appears. and chromium. tetrathionates. but on addition of a trace of thiosulphate. sulphates.REACTIONS OF ANIONS IV. Catalytic test Solutions of sodium azide. it is applicable in the presence of copper. By obvious modification the reaction may be used for the detection of nickel. NaN 3. which acts as a catalyst. Nickel ethylenediamine nitrate reagent [Ni(NH 2. while tetrathionate and iron(II) ions are formed: [Fe(S203hr +Fe3+ -+ 2Fe2+ +S40~- The overall reaction can be written as the reduction of iron(III) by thiosulphate: 2S20~. When a neutral or slightly alkaline solution of a thiosulphate is treated with the reagent. and thiocyanates do not interfere. 307 . The origin of this colour is as yet unexplained.+Fe3+ -+ [Fe(S203hr on standing the colour disappears rapidly. iron.+SO~- On acidifying the cold solution. CH 2. CH 2.

9H20 can be used.6 QUALITATIVE INORGANIC ANALYSIS Sensitivity: 0'15 ug Na 2S20 3 • Concentration limit: I in 330. and poly-sulphides of alkali metals are soluble in water. IV. extract the mass with water. The sulphides of iron.6 SULPHIDES. and by the blackening of filter paper moistened with lead acetate solution: S2. S2. Dilute hydrochloric or sulphuric acid: hydrogen sulphide gas is evolved. The presence of sulphide in insoluble sulphides may be detected by reduction with nascent hydrogen (derived from zinc or tin and hydrochloric acid) to the metal and hydrogen sulphide. and tin (IV) require concentrated hydrochloric acid for decomposition. which may be identified by its characteristic odour. chromium. cobalt. zinc. those of the alkaline earths are sparingly soluble. the sodium carbonate solution may also be treated with lead nitrate solution when black lead sulphide is precipitated. antimony.Solubility The acid. 1. a filter paper moistened with cadmium acetate solution turns yellow: H 2S+Cd2+ -+ CdS! A more sensitive test is attained by the use of sodium tetrahydroxo308 . their aqueous solutions react alkaline because of hydrolysis.+H 20 +=t H 2S+OHThe normal sulphides of most other metals are insoluble. those oflead. nickel. but dissolve in aqua regia with the separation of sulphur.+2H+ -+ H 2Sj H 2S+Pb2+ -+ PbS! Alternatively. as they are completely hydrolysed by water: Al 2S3 +6H 20 -+ 2Al(OHh! +3H 2Sj The characteristic colours and solubilities of many metallic sulphides have already been discussed in connection with the reactions of the cations in Chapter Ill. cadmium. S2. and magnesium can only be prepared in the dry.000. when a purple colour will be obtained.+H 20 +=t SH. are insoluble in concentrated hydrochloric acid. but are gradually changed by contact with water into soluble hydrogen sulphides: CaS+H 20 -+ Ca2+ +SH. For the study of these reactions a 2M solution of sodium sulphide Na 2S. An alternative method is to fuse the sulphide with anhydrous sodium carbonate.IV. the latter being identified with lead acetate paper (see reaction I below). and the alkali metals are decomposed by dilute hydrochloric acid with the evolution of hydrogen sulphide.+OH- The sulphides of aluminium. The sodium azide-iodine reagent consists of a solution of 3 g sodium azide in 100 ml 0'05M iodine. such as mercury(lI) sulphide. and to treat the filtered solution with freshly prepared sodium nitroprusside solution. others.+OHSH. manganese. normal.

+2Ag+ -+ Ag 2S! 3.000. a purple colouration is produced with free hydrogen sulphide. 6. Lead acetate solution: black precipitate of lead sulphide PbS (Section 111. 5. The result is obtained more expeditiously by the addition of a few drops of dilute hydrochloric acid.-+ Pb(OHh! Pb(OHh!+20H. Silver nitrate solution: black precipitate of silver sulphide Ag 2S. The stain may be removed by rubbing the coin with moist lime. Alternatively. reaction 2). + 5H 2S + 6H+ Cr20~-+3H2S+8H+ -+ -+ I. Mix on a spot plate a drop of the alkaline test solution with a drop of a I per cent solution of sodium nitroprusside. Small quantities of chlorine may be produced in (i) and (ii) if the hydrochloric acid is other than very dilute. S2.4. It reduces (i) acidified potassium permanganate. A violet colour appears.6 plumbate(II) solution. +H 2S -+ 2Mn2+ + 5S! + 8H 20 2Cr3++3S!+7H 20 31. Sensitivity: I ug Na 2 S. S2. 7. prepared by adding sodium hydroxide to lead acetate until the initial precipitate of lead hydroxide has just dissolved: Pb2+ +20H. however. Sodium nitroprusside solution (Na2[Fe(CN)sNO]): transient purple colour in the presence of solutions of alkalis. Concentration limit: I in 50. No reaction occurs with solutions of hydrogen sulphide or with the free gas: if. The spot-test technique is as follows.REACfIONS OF ANIONS IV.+2H+ +S! (i) (ii) (iii) in each case sulphur is precipitated. and (iii) potassium triiodide (iodine) solution: 2MnO. 2. insoluble in cold. Methylene blue test p-Aminodimethylaniline is converted by iron(III) 309 . filter paper is moistened with a solution of the reagent made alkaline with sodium hydroxide or ammonia solution.-+ [Pb(OH)4]2[Pb(OH)4]2-+H 2S -+ PbS!+20H-+2H 20 Hydrogen sulphide is a good reducing agent.+ [Fe(CN)sNO]2- -+ [Fe(CN)sNOS]4- The reagent must be freshly prepared by dissolving a crystal (about the size of a pea) of pure sodium nitroprusside in a little distilled water. but soluble in hot dilute nitric acid. Silver When a solution of a sulphide is brought into contact with a bright silver coin. filter paper impregnated with an ammoniacal (2M) solution of sodium nitroprusside may be employed. this is avoided by using dilute sulphuric acid. Barium chloride solution: no precipitate. (ii) acidified potassium dichromate. 4. a brown to black stain of silver sulphide is produced.

at the end of a platinum wire into a semimicro test-tube or centrifuge tube containing the iodine-azide reagent. [The test is rendered more sensitive (to 0'02 ug Na 2S) by employing a more concentrated reagent composed of I g sodium azide and a few crystals of iodine in 3 ml water. HN0 2 . The sulphide can.IV. there is an immediate evolution of nitrogen: 2N3"+I3" -+ 31-+3N 2 i Thiosulphates and thiocyanates act similarly and must therefore be absent. but on the addition of a trace of a sulphide. Mix a drop of the test solution and a drop of the reagent on a watch glass. N 20 3 ) and the evolution of brown fumes of nitrogen dioxide. 310 . KN0 2 . The precipitated sulphide may then be introduced. N0 2 Solubility Silver nitrite is sparingly soluble in water. which acts as a catalyst. Use freshly prepared O'IM solution of potassium nitrite. then dissolve a few grains of p-aminodimethylaniline in the mixture (or add I drop I per cent solution of the chloride or sulphate) and add a drop ofO'5Miron(III) chloride solution. the latter being largely produced by combination of nitric oxide with the oxygen of the air. mix.7 NITRITES. Sensitivity: I ug H 2S.000. say. Catalysis of iodine-azide reaction test Solutions of sodium azide. Sensitivity: 0'3 ug Na 2S. All other nitrites are soluble in water. and of iodine (as 13") do not react. NaN 3 . add a drop of concentrated hydrochloric acid. The sodium azide-iodine reagent is prepared by dissolving 3 g sodium azide in 100 ml 0'05M iodine. Similar results are obtained with the aqueous solution. pale-blue liquid (due to the presence of free nitrous acid. Concentration limit: I in 166. An immediate evolution of gas in the form of fine bubbles occurs. however. A clear blue colouration appears after a short time (2-3 minutes).000. Concentration limit: I in 50.7 QUALITATIVE INORGANIC ANALYSIS chloride and hydrogen sulphide in strongly acid solution into the water-soluble dyestuff. The solution is stable. 1. be separated by precipitation with zinc or cadmium carbonate. Place a drop of the test solution on a spot plate. 8. Dilute hydrochloric acid Cautious addition of the acid to a solid nitrite in the cold yields a transient. or its anhydride.] IV. when the evolution of nitrogen will be seen. methylene blue: This is a sensitive test for soluble sulphides and hydrogen sulphide. to study these reactions.

a brown colouration results. Urea CO(NH2 ) 2 When a solution ofa nitrite is treated with urea and the mixture acidified with dilute hydrochloric acid. An alternative method is to extract the liberated iodine with chloroform or carbon tetrachloride (see Section IV. followed by acidification with acetic acid or with dilute sulphuric acid. 5N02" +2MnO. reaction 4). If the addition has not been made cautiously.REACTIONS OF ANIONS IV. 2N02" +21. a brown ring. This reaction is similar to the brown ring test for nitrates (see Section IV. but no gas is evolved. Ammonium chloride By boiling a solution of a nitrite with excess of the solid reagent. +6H+ -+ 5N0 3 +2Mn2+ +3H 20 7.NO]S04' is formed at the junction of the two liquids. 3.16. due to the compound [Fe. Potassium iodide solution The addition of a nitrite solution to a solution of potassium iodide. Silver nitrate solution: white crystalline precipitate of silver nitrite from concentrated solutions. N02" +CH 3COOH 3HN0 2 Fe2+ +SOi.7 N02" + H+ (2HN0 2 3HN0 2 2NOi + O 2 t -+ -+ -+ -+ HN0 2 H 20+N 20 3 ) HN0 3 + 2NOi + H 20 2N0 2 t 2. N02"+NHt -+ N 2i+2H 20 8. and anions that give coloured compounds with iron(II) ions must be absent.+2CH 3COOH -+ 12 +2NOi +2CH 3COO. reaction 3). N02" + Ag" -+ AgN0 2 ! 5. and nitrogen and carbon dioxide are evolved. nitrogen is evolved and the nitrite is completely destroyed. Acidified potassium permanganate solution: decolourized by a solution of a nitrite. Barium chloride solution: no precipitate. A similar result is obtained by dipping potassium iodide-starch paper moistened with a little dilute acid into the solution. coloured ions. results in the liberation of iodine.NO]S04 Iodides.+2H 20 6. bromides. the nitrite is decomposed.+NOi -+ -+ -+ HN0 2 +CH 3COOH 20 + HN0 3 + 2NOi [Fe. Iron (II) sulphate solution When the nitrite solution is added carefully to a concentrated (25 %) solution of iron(II) sulphate acidified with dilute acetic acid or with dilute sulphuric acid. CO(NH 2h+2HN0 2 -+ 2N 2i+C02i+3H 20 311 .1S. 4. for which a stronger acid (concentrated sulphuric acid) must be employed. which may be identified by the blue colour produced with starch paste.

000. Sulphamic acid (HO. 12. must be removed either with excess of solid Ag 2S04 or with dilute AgN0 3 solution before adding the acetic acid and thiourea.7 QUALITATIVE INORGANIC ANALYSIS 9.. 10. and 9). CS(NH 2h + HN0 2 -+ N 2i + H+ + SCN. and mixing with 30 ml glacial acetic acid.S0 2·NH2+HN02 -+ N2i+2H++SO~-+H20 No nitrate is formed in this reaction. NH2.000. urea. Thiourea CS(NH2 ) 2 When a dilute acetic acid solution of a nitrite is treated with a little thiourea.0 I ug HN0 2. S03H NH 2 + CH 3COOH Iron(III) ions must be masked by tartaric acid.CH3 +2H + HN0 2 . nitrogen is evolved and thiocyanic acid is produced..NH2 ) When a solution of a nitrite is treated with sulphamic acid. followed by coupling with rx-naphthylamine to form a red azo dye: 11. and it is therefore an excellent method for the complete removal of nitrite. This test depends upon the diazotization of sulphanilic acid by nitrous acid. The rx-naphthylamine reagent is prepared by boiling 0'3 g «-naphthylamine with 70 ml water. Sulphanilic acid-a-naphthylamine reagent. filtering or decanting from the small residue.S0 2.+ 2H 20 Thiocyanates and iodides interfere and. 312 . Sensitivity: 0. The test solution must be very dilute. Traces of nitrates are formed with ammonium chloride. Place a drop of the neutral or acid test solution on a spot plate and mix it with a drop of the sulphanilic acid reagent. S~H S03 H ~N_OOCCH' ~ ~ Hso'-ON~N-8-NH' + .IV. Indole reagent (CO) a red-coloured nitroso-indole is formed. if present. The sulphanilic acid reagent is prepared by dissolving I g sulphanilic acid in 100 ml warm 30 per cent acetic acid. otherwise the reaction does not go beyond the diazotization stage: 0'2 mg N0 2 r 1 is the optimal concentration.8.' 20 I :::::. The latter may be identified by the red colour produced with dilute HCl and FeCl 3 solution.... followed by a drop of the «-naphthylamine reagent. (Griess-Ilosvay test) O :::::. A red colour is formed. it is completely decomposed: HO. Concentration limit: I in 5. and thiourea (reaction 7.CH3CO O H QN=IN-OOC.

HCN. Hg(CNh. due to the iron(III) thiocyanate complex. 3. A more satisfactory method for identifying hydrocyanic acid consists in converting it into ammonium thiocyanate by allowing the vapour to come into contact with a little ammonium polysulphide on filter paper. KCN. IV. or those in which cyanides are heated. but is practically a nonelectrolyte and therefore does not exhibit the ionic reactions of cyanides.34. reaction 7): CN.c).000. with an odour reminiscent of bitter almonds. Use a freshly prepared solution of O'IM potassium cyanide. the characteristic red colouration. CN. add lOdrops of the reagent and 5 drops of 8M sulphuric acid. is also soluble in water. HCN.8 CYANIDES. Many of the metallic cyanides dissolve in solutions of potassium cyanide to yield complex salts (cf.REACTIONS OF ANIONS IV. Silver nitrate solution: white precipitate of silver cyanide. carbon monoxide is evolved which may be ignited and burns with a blue flame. Note: All cyanides are highly poisonous. complex and simple. All cyanides. Mercury(II) cyanide is not decomposed by dilute acids. is volatile and is particularly dangerous so that all experiments in which the gas is likely to be evolved. CN. The reagen t consists of a 0'0 15per cent solution ofindole in 96 per cent alcohol. Concentration limit: I in 1. is obtained (see reaction 6 below). readily soluble in excess of the cyanide solution forming the complex ion.+H+ -+ HCNj 2. The paper may be conveniently placed over the test-tube or dish in which the substance is being treated with the dilute acid. It should be smelled with great caution. A purplish-red colouration appears. Upon adding a drop of iron(III) chloride solution and a drop of dilute hydrochloric acid to the filter paper. Fe(SCNh.+ H 2 0 -+ HCN + OH- Mercury(II) cyanide. is evolved in the cold. CN. Section 1.8 Place a drop of the test solution in a semimicro test-tube. are decomposed by this treatment. The free acid.000. 1. Dilute hydrochloric acid: hydrocyanic acid.(cf. AgCN.+Ag+ AgCN!+CN- -+ -+ AgCN! [Ag(CNh]- Silver cyanide is soluble in ammonia solution and in sodium thiosulphate solution.Solubility Only the cyanides of the alkali and alkaline earth metals are soluble in water. the solutions react alkaline owing to hydrolysis.6. Section 111. Concentrated sulphuric acid Heat a little of the solid salt with concentrated sulphuric acid. dicyanoargentate(I) [Ag(CNh]. should be carried out in the fume cupboard. but is insoluble in dilute nitric acid. to study these reactions. 313 .

and add 1-2 drops 3 per cent iron(III) chloride solution. A blood-red colouration. Section IV. 314 . Iron (Ill) thiocyanate test This is another excellent test for cyanides and depends upon the direct combination of alkali cyanides with sulphur (best derived from an alkali or ammonium polysulphide). is produced immediately: CN. this deposits Prussian blue on standing. other than on a water bath.+Hg~+ -+ Hg!+Hg(CNh Mercury(II) cyanide is very little ionized in solution. If the precipitate is filtered off.-+ SCN. reaction 6). Sensitivity: I ug CN-. If only a little cyanide was used. or is present. a green solution is obtained at first. Hexacyanoferrate(II) ions are thus formed. The latter is destroyed by the addition of a few drops of hydrochloric acid.8 QUALITATIVE INORGANIC ANALYSIS 4. To detect cyanide in the presence of mercury.tO. 6CN. and the whole evaporated to dryness on the water bath in the fume cupboard. A little ammonium polysulphide solution is added to the potassium cyanide solution contained in a porcelain dish. Mercury (I) nitrate solution: grey precipitate of metallic mercury (difference from chloride.+ Fe 3+ -+ Fe(SCNh (cf.53). bromide. The spot-test technique is as follows. which gives a precipitate of Prussian blue upon the addition of a little iron(III) chloride solution. Add 1-2 drops dilute hydrochloric acid. allow to cool. it is best to use a saturated (25 %) solution ofiron(II) sulphate) and the mixture boiled. = 4 x 10.+2CN- Mercury(II) cyanide is decomposed by hydrogen sulphide.IV. Stir a drop of the test solution with a drop of yellow ammonium sulphide on a watch glass and warm until a rim of sulphur is formed round the liquid (evaporation to dryness. A red colouration is obtained. due to the iron(lII) thiocyanate complex.000.+S~. when cyanide ions are liberated: Hg(CNh +4r -+ [HgI 4]2. cyanide ions can be tested for in the solution: Hg(CNh + H 2S -+ HgS! + 2HCN 6. a clear solution is obtained.+S2-. One or two drops of iron(III) chloride solution are then added. 3SCN. The solution of the cyanide is rendered strongly alkaline with sodium hydroxide solution. The residue contains alkali and ammonium thiocyanates together with any residual polysulphide. in the solution to be tested. and iodide): 2CN. an excess of potassium iodide should be added to the sample. Prussian blue test This is a delicate test and is carried out in the following manner.+ Fe2+ 3[Fe(CN)6]4. Concentration limit: I in 50. Upon acidifying with hydrochloric acid (in order to neutralize any free alkali which may be present). when mercury(II) sulphide is precipitated (K.+4Fe3+ -+ -+ [Fe(CN)6]4Fe 4[Fe(CN)6]3! 5. a few millilitres of a freshly prepared solution of iron(II) sulphate added (if only traces of cyanide are present. should be avoided).

7.8 The test is applicable in the presence of sulphide or sulphite. The benzidine reagent (solution 11) is a I per cent solution of benzidine in 2M acetic acid.000. place a drop of the test solution (or a few milligrams of the test solid) in the reaction bulb of Fig. 8. iodides. Copper acetate-benzidine acetate test (DANGER: THE REAGENT IS CARCINOGENIC. The test is best carried out on filter paper or drop-reaction paper and is applicable in the presence of chlorides.000. Mix a few drops of the test solution with a little dilute sulphuric acid in a micro test-tube and tie (or otherwise fix) a piece of drop-reaction paper which has been moistened with a mixture of equal parts of the copper acetate and benzidine reagents to the top of the tube. The copper(lI) acetate reagent (solution I) is a 3 per cent solution of copper(lI) acetate in water.+ 2S2 - + (CNh l Note that the oxidation number of copper in the solution is + I. Oxidizing and reducing gases interfere: it has been recommended that the hydrocyanic acid be liberated by heating with sodium hydrogen carbonate. Sensitivity: 2'5 ug CN-. Concentration limit: I in 50. if thiocyanate is originally present. Concentration limit: I in 200. Concentration limit: I in 20. hexacyanoferrate(lI) and (Ill) ions. adding a few drops of ammonia solution and rendering the solution cloudy with a little hydrogen sulphide. A blue colouration is produced.g.000. Sensitivity: 0'25 ug CN-. Copper sulphide test Solutions of cyanides readily dissolve copper(lI) sulphide forming the colourless tetracyanocuprate(l) ions: 2CuS! + IOCN- -+ 2[Cu(CN)4]3. Place a drop of the test solution upon this paper when a white ring will be obtained. These solutions are best kept apart in black well-stoppered bottles. 315 .000.56. The paper is coloured blue by the hydrocyanic acid carried over with the hydrogen. Immediately before the test a little hydrogen sulphide is blown on to the paper so that it acquires a uniform brown colour. Equal volumes of solutions I and 11 are mixed immediately before required. Concentration limit: I in 20. The brown colour of copper sulphide disappears at once. Place a drop of a freshly prepared copper sulphide suspension on a filter paper (or on a spot plate) and add a drop of the test solution. Sensitivity: 2' 5 ug CN-. The copper sulphide suspension is prepared by dissolving 0'12 g crystallized copper sulphate in 100 ml water. as zinc cyanide.) This reaction takes place because the oxidation-reduction potential of the copper(II)--copper(I) couple is increased if copper(l) ions are removed by cyanide ions. add 2 thin pieces zinc foil and 2-3 drops dilute sulphuric acid. 11. An alternative procedure is to employ quantitative filter paper or dropreaction paper which has been impregnated with an ammoniacal solution containing 0'1 g of copper sulphate per 100 ml and dried. bromides. the cyanide must be isolated first by precipitation. e. Place a small circle of quantitative filter paper (or dropreaction paper) moistened with acetate-benzidine acetate reagent across the funnel. Sensitivity: I ug CN-. Alternatively.REACTIONS OF ANIONS IV.

+H+ -+ HOCN HOCN + H+ + H 20 -+ CO 2i + NHt 2. 40CN. the reaction can therefore be applied to the detection of cyanates in alkaline solution. Concentration limit: I part cyanate in 20. Thiocyanates interfere.is produced. due to tetracyanatocobaltate(II) ions. The free cyanic acid. this is soluble in chloroform with the production of a sapphire-blue solution. Concentrated sulphuric acid The reaction is similar to that with the dilute acid. Shake the mixture briskly. and copper are insoluble. which is liberated initially.+Ag+ -+ AgOCN! 4. the latter combining with the sulphuric acid present to form ammonium sulphate. Barium chloride solution: no precipitate. is decomposed into carbon dioxide and ammonia. The blue complex is stable in the presence of a moderate excess of acetic acid.Solubility The cyanates of the alkalis and of the alkaline earths are soluble in water. 1.+Co2+ -+ [CO(OCN)4]26. but is somewhat more vigorous. HOCN. KOCN.IV. soluble in ammonia solution and in dilute nitric acid. Cobalt acetate solution When the reagent is added to a concentrated solution of potassium cyanate. As soon as the solution is neutral. Dilute sulphuric acid: vigorous effervescence. excess of copper solution should be avoided. Copper sulphate-pyridine test When a cyanate is added to a dilute solution of a copper salt to which a few drops of pyridine have been previously added. the chloroform will assume a blue colour.+Cu2+ +2C sH sN -+ [Cu(CsHsNh](OCNh Add a few drops of pyridine to 2-3 drops of a 0'25M solution of copper sulphate then introduce about 2 ml chloroform followed by a few drops of the neutral cyanate solution. The free acid is a colourless liquid with an unpleasant odour. 5. due largely to the evolution of carbon dioxide.OCN. a blue colouration. Silver nitrate solution: white. The colour is stabilized and intensified somewhat by the addition of ethanol. [CO(OCN)4]2. it is very unstable. without complex formation (difference from cyanide): OCN. A little cyanic acid. OCN. acetic acid added slowly and the solution shaken vigorously after each addition. 20CN. To study these reactions use a 0'2M solution of potassium cyanate. however. escapes decomposition and may be recognized in the evolved gas by its penetrating odour.9 CYANATES. 3. curdy precipitate of silver cyanate. 316 . mercury(I). Those of silver.9 QUALITATIVE INORGANIC ANALYSIS IV. If the resulting solution is warmed with sodium hydroxide.000. a lilac-blue precipitate is formed of the compound [Cu(CsHsNh](OCN)2. ammonia is evolved (test with mercury(I) nitrate paper). The precipitate appears instantaneously. the chloroform will acquire a blue colour. AgOCN. The solution to be tested is added to the copper-pyridine-chloroform mixture. lead.

3. in g r 1 at 20°. To study these reactions use a O'IM solution of potassium thiocyanate KSCN. carbonyl sulphide (bums with a blue flame) is formed. Silver nitrate solution: white. Mercury(Il) nitrate solution: white precipitate of mercury(II) thiocyanate Hg(SCNh. since a line assignable to the triple link and none for the double link was observed.IO THIOCYANATES.tO IV. In the solution some sulphur is precipitated.+SOi. Copper sulphate solution: first a green colouration. are 0'0003. After acidification with hydrochloric acid. sulphur dioxide and a little carbonyl sulphide are evolved. mercury(II) and lead thiocyanates are sparingly soluble. A similar but slower reaction takes place with Msulphuric acid. Salts will be written as. Silver thiocyanate also decomposes upon ignition or upon fusion with sodium carbonate.+Cu2+ -+ Cu(SCNh! Adding sulphurous acid (a saturated solution of sulphur dioxide) the precipitate turns into white copper(l) thiocyanate: 2Cu(SCNh+ S02 +2H 20 -+ 2CuSCN!+2SCN.0'7. The thiocyanates of most other metals are soluble. reaction 6). the solubilities. readily soluble in excess of the thiocyanate solution. 2.0'0005. soluble in ammonia solution but insoluble in dilute nitric acid. but on boiling a yellow solution is formed. SCN-* Solubility Silver and copper(I) thiocyanates are practically insoluble in water.g. thiocyanate ions can be detected with iron(III) chloride (cf.+ H 2S0 4 + H 20 -+ COSj + NHt + SOi- The reaction however is more complex than this. KSCN and the ion as SCN-.REACTIONS OF ANIONS IV. If the precipi*Raman spectra of thiocyanates appear to indicate that the ion is -S-C==N rather than S=C=N-. and 0'45 respectively. curdy precipitate of silver thiocyanate.+4H+ 4. and formic acid can also be detected. AgSCN. then a black precipitate of copper(II) thiocyanate is observed: 2SCN. the precipitate is converted into silver chloride: AgSCN! + CI-+ AgCl! + SCN- (distinction and method of separation from silver halides). e. With the 2'5M acid no reaction occurs in the cold. SCN. 317 . SCN.--Ag" AgSCN! + 2NH 3 -+ -+ AgSCN! [Ag(NH 3 h r + SCN- Upon boiling with M sodium chloride solution. 1. because sulphur dioxide (fuchsin solution decolourized) and carbon dioxide may be detected also in the gaseous decomposition products. Sulphuric acid With the concentrated acid a yellow colouration is produced in the cold: upon warming a violent reaction occurs.

+3SCN7. a polymerized cyanogen product. whether thiocyanate is present or not. Rinse the ammonia solution into a clean semimicro test-tube.+4Fe3+ Fe(SCNh +3(COO)~. more stable complexes are formed: Fe(SCNh + 6F. 1I. add a small fragment of broken porcelain and attach a gas absorption pipette (Fig.26. This test may be applied to separate thiocyanate from mixtures with ions which would interfere with reaction 6.+Hg2+ Hg(SCNh! +2SCN-+ -+ Hg(SCNh! [Hg(SCN)4]2- 5.29c) charged with a drop or two of ammonia solution. 2SCN. due to the formation of [CO(SCN)4]2. and oxalates.(Section 111. The (uncharged) complex can be extracted by shaking with ether. mercury(lI) ions.+ 3SCN4Fe(SCNh +3Hg2+ -+ 3[Hg(SCN)4Y. Boil the solution in the test-tube gently so as to distil any HSCN present into the ammonia solution. Mix a drop of the test solution in a micro crucible with a very small drop (0'02 ml) ofO'5M solution of cobalt nitrate and evaporate to dryness. can be liberated by hydrochloric acid. is 318 . a red colouration is produced. reaction 11). The red colour is discharged by fluorides. and nitrogen oxide and hydrogen cyanide (POISONOUS) are evolved: SCN.tO QUALITATIVE INORGANIC ANALYSIS tate is heated. The residue. when colourless. it swells up enormously forming 'Pharaoh's serpents'. due to the formation of a complex: 3SCN. Distillation test Free thiocyanic acid. acidify slightly with dilute hydrochloric acid and add a drop of iron(lIl) chloride solution. hexacyanoferrate(lI) and (Ill)]: 4SCN. A red colouration is obtained. HSCN. where it can be identified with iron(III) chloride (cf. Place a few drops of the test solution in a semimicro test-tube. with the formation of nitrogen oxide and carbon dioxide.-+ [Fe{(COOhhr. 9. Iron ( Ill) chloride solution: blood-red colouration. acidify with dilute hydrochloric acid. 8. but no precipitate [distinction from cyanide. reaction 6).IV. distilled into ammonia solution. Zinc and dilute hydrochloric acid: hydrogen sulphide and hydrogen cyanide (POISONOUS) are evolved: SCN-+Zn+3H+ -+ H 2Sj + HCNj +Zn2+ 6.+ H+ + 2N0 3 -+ 2NOj + HCNj + SOi- With concentrated nitric acid a more vigorous reaction takes place.-+ [FeF 6]3. Cobalt nitrate solution: blue colouration. reaction 6).+Co2+ -+ [CO(SCN)4]2- The spot-test technique is as follows.+Fe 3+ +:t Fe(SCNh In fact there are a series of complex cations and anions formed (see Section 111.22. Dilute nitric acid: decomposition upon warming.

5. Concentrated sulphuric acid: complete decomposition occurs on prolonged boiling with the evolution of carbon monoxide. Shake the mixture vigorously. Concentration limit: I in 30. which burns with a blue flame: [Fe(CN)6]4. [Fe(CN)6]4.+2H+ Considerable amounts of iodine retard the reaction. Catalysis ofiodine-azide reaction test Traces of thiocyanates act as powerful catalysts in the otherwise extremely slow reaction between triiodide (iodine) and sodium azide: I.n coloured violet and the colour slowly fades.ll HEXACYANOFERRATE(II) IONS. Nitrites yield a red colour due to nitrosyl thiocyanate and therefore interfere with the test. Bubbles of gas (nitrogen) are evolved. Mix a drop of the test solution with I drop of the iodine-azide reagent on a spot plate. to study these reactions. IV. K 4[Fe(CN)6]. which does not affect the catalysis.+Cu2+ +2C sH sN -+ [Cu(CsHsNh](SCNh! Add a few drops of pyridine to 3-4 drops of a 0'25M solution of copper sulphate.6. (often called potassium ferrocyanide). The chloroform will acquire a green colour.000. 11.+6H 2S04 +6H 20 -+ Fe2+ +6NHt +6COi +6S0i319 . then introduce about 2 ml chloroform.Solubility The alkali and alkaline earth hexacyanoferrate(II)s are soluble in water. Sensitivity: I ug SCN-.+H 20 -+ -+ HgS! HgS! +SOi. Copper(II) sulphate-pyridine reagent When a neutral solution of a thiocyanate is added to a dilute solution of a copper salt containing a few drops of pyridine.REACTIONS OF ANIONS IV.+2N. The reagent is prepared by dissolving 3 g sodium azide in 100 ml 0'05Miodine.3H20. 1. Concentration limit: I in 50. but are decomposed by alkalis. these may be removed by precipitation with mercury(II) nitrate solution: Hg2+ +S2Hg2+ +S20~. Concentration limit: I in 50. reaction 9) have a similar catalytic effect. Cyanates interfere with this reaction. Add a few drops of acetone. a yellowish-green precipitate ofthecomposition [Cu(CsH sN)2](SCN)2 is formed. Sensitivity: 1'5 ug KSCN. excess of pyridine should be avoided. the compound is soluble in chloroform to which it imparts an emeraldgreen colouration. iodine is therefore best largely removed by the addition of an excess of mercury(II) nitrate solution whereupon the complex [HgI 4]2.ion. 2SCN. followed by a few drops of the neutral thiocyanate solution.000. A bluegreen or green colouration is obtained. Use a 0'025M solution of potassium hexacyanoferrate(II). -+ 3I-+3N 2i Sulphides (see Section IV. is formed. reaction 8) and thiosulphates (see Section IV. 10. those of the other metals are insoluble in water and in cold dilute acids.000.

K 2Fe[Fe(CN)6]' which turns rapidly blue by oxidation (see reaction I and also Section 111.IV. little reaction occurs in the cold. the precipitate is converted to orange-red silver hexacyanoferrate(III).n QUALITATIVE INORGANIC ANALYSIS a little sulphur dioxide may also be produced. 2. react with some of the undecomposed hexacyanoferrate.+ 6H+ -+ 6HCNj + Fe2+ Iron(II) ions. Silver nitrate solution: white precipitate of silver hexacyanoferrate(II): [Fe(CN)6]4.+ [Fe(CN)6]4Upon warming with concentrated nitric acid. reaction 6). A blue precipitate or stain is formed.000. formed in this reaction. Section 111.21.+ 2Cu2+ 320 -+ Cu 2[Fe(CN)6]! . Mix a drop of the test solution on a spot plate with a drop of iron(III) chloride solution. reaction 6).+ Fe3+ -+ Fe4[Fe(CN)6]3! the precipitate is decomposed by solutions of alkali hydroxides.+ [Fe(CN)6]4Ag 4[Fe(CN)6]! + 8S20~. The spot-test technique is as follows. brown iron(lII) hydroxide being formed (cf. due to the oxidation of iron(II) with sulphuric acid: 2Fe2+ + 2H 2S04 -+ 2Fe3+ + S02 j + SOi. 5. but on boiling. when it becomes soluble in ammonia: 3Ag4[Fe(CN)6]! + HN0 3 + 3H+ -+ -+ 3Ag 3[Fe(CN)6]! + 3Ag+ + NOj +2H 20 Ag 3[Fe(CN)6]! + 6NH 3 -+ 3[Ag(NH 3hr + [Fe(CN)6r3. Concentration limit: I in 400. Sensitivity: I ug [Fe(CN)6]4-. a partial decomposition of hexacyanoferrate(II) occurs with the evolution of hydrogen cyanide (POISON): [Fe(CN)6]4.+4Ag+ -+ Ag 4[Fe(CN)6]! The precipitate is insoluble in ammonia [distinction from hexacyanoferrate(III)] and nitric acid.21. 4.+ 2H 20 With dilute sulphuric acid.+Fe2+ +2K+ -+ K 2Fe[Fe(CN)6]! This precipitate is gradually oxidized to Prussian blue by atmospheric oxygen (cf. Section 111. Copper sulphate solution: brown precipitate of copper hexacyanoferrate(II): [Fe(CN)6]4. but soluble in potassium cyanide and sodium thiosulphate: Ag 4[Fe(CN)6]! +8CN.-+ 4[Ag(CNh]. yielding initially a white precipitate of potassium iron(II) hexacyanoferrate(II) : [Fe(CN)6]4. reaction 6).-+ 4[Ag(S203h]3. Iron (Ill) chloride solution: precipitate of Prussian blue in neutral or acid solutions: 3[Fe(CN)6]4.22. Iron(ll) sulphate solution: white precipitate of potassium iron(II) hexacyanoferrate(II).

The drop test can be carried out as follows: place a drop of the test solution on a spot plate. The precipitate is insoluble in dilute acids. The test can be applied to differentiate hexacyanoferrate(II) ions from hexacyanoferrate(III) and thiocyanate. which do not react. Hexacyanoferrate(III) ions react only in concentrated solutions. a brown precipitate of molybdenyl hexacyanoferrate(II) is formed. as it tends to form a colloid. A reddish-brown precipitate is obtained in the presence of hexacyanoferrate(II) ions.+ Ti 4+ -+ Ti[Fe(CN)6]! The precipitate is insoluble in 6M hydrochloric acid. Cobalt nitrate solution: greyish-green precipitate of cobalt hexacyanoferrate. hydrogen hexacyanoferrate(II) is formed. after long standing or heating.+ 2Co2+ -+ Co 2[Fe(CN)6]! 11. which is insoluble in dilute hydrochloric or dilute acetic acid: [Fe(CN)6]4. just acidify with hydrochloric acid and introduce I drop of the reagent. which do not react. as these oxidize hexacyanoferrate(II) ions in acid medium. Oxidizing anions (like chromate. 8. 7.+ Th 4+ -+ Th[Fe(CN)6]! It is difficult to filter this precipitate. the substance is obtained as a white crystalline solid. 9. Uranyl acetate solution: brown precipitate of uranyl hexacyanoferrate(II): [Fe(CN)6]4.+ 4H+ +:t H 4[Fe(CN)6] By evaporating the ether. to give a dirtyyellow precipitate. The reaction can be used to distinguish hexacyanoferrate(II) ions from hexacyanoferrate(III) and thiocyanate. 6. Ammonium molybdate solution: from a solution of potassium hexacyanoferrate(II). but decomposes in solutions of alkali hydroxides. The reagent is prepared by adding 10 ml liquid titanium(IV) chloride to 90 ml of I : I hydrochloric acid. but soluble in solutions of alkali hydroxides. which can be extracted by ether: [Fe(CN)6]4. Thorium nitrate solution: white precipitate of thorium hexacyanoferrate: [Fe(CN)6]4. Hexacyanoferrate(III) ions do not react. arsenate or nitrite) should be absent.n The precipitate is insoluble in dilute acetic acid. acidified with dilute hydrochloric acid. The exact composition of the precipitate is not known.+2UO~+ -+ (U0 2h[Fe(CN)6]! Dilute acetic acid should be present as well. Filter paper may reduce some hexacyanoferrate(III) to 321 .REACTIONS OF ANIONS IV. 10. Hydrochloric acid If a concentrated solution of potassium hexacyanoferrate(II) is mixed with I : I hydrochloric acid. Titanium (IV) chloride solution: reddish-brown flocculent precipitate of titanium(lV) hexacyanoferrate(II): [Fe(CN)6]4.

Concentrated sulphuric acid On warming a solid hexacyanoferrate(III) with this acid. so is iron(III) hexacyanoferrate(III). Iron(lI) sulphate solution: dark-blue precipitate of Prussian blue (earlier termed Tumbull's blue). Sensitivity: I ug [Fe(CN)6]4-. 3.12 QUALITATIVE INORGANIC ANALYSIS hexacyanoferrate(II). The spot test is carried out as follows: place a drop of the test solution on a spot plate. but insoluble in nitric acid. To study these reactions use a 0·033M solution of potassium hexacyanoferrate(III) K 3[Fe(CN)6]. 4. Concentration limit: 1 in 50. lron(III) chloride solution: brown colouration. (Section 111. A brown precipitate or spot is obtained within 2 minutes. nitrogen and cyanogen being evolved: 3K 4[Fe(CN)6] -+ N 2t +2(CNh t + 12KCN +Fe3C+C IV. Concentrated hydrochloric acid: adding concentrated hydrochloric acid to a saturated solution of potassium hexacyanoferrate(III) in cold. it is decomposed completely.+ Fe3+ -+ Fe[Fe(CN)6] (cf. Dry test All hexacyanoferrate(II) compounds are decomposed on heating.+6H+ -+ Fe3+ +6HCNj This test must be carried out in a fume cupboard with good ventilation. a brown pre322 . and add a drop ofO·IM uranyl acetate solution. reaction 7). 2.IV. Silver nitrate solution: orange-red precipitate of silver hexacyanoferrate(III): [Fe(CN)6r. hence the test should not be carried out on filter paper.21. Those of most other metals are insoluble or sparingly soluble. in neutral or acid solution.22. Copper sulphate solution: green precipitate of copper(II) hexacyanoferrate(III) : 2[Fe(CN)6]3.000. owing to the formation of undissociated iron(III) hexacyanoferrate(III): [Fe(CN)6r.12 HEXACYANOFERRATE(III) IONS [Fe(CN)6]3.+3Cu2+ -+ Cu 3[Fe(CN)6]2! 6. but on boiling hydrocyanic acid (POISON) is evolved: [Fe(CN)6r. carbon monoxide gas being evolved: K 3[Fe(CN)6] +6H2S04 +6H 20 -+ 6COj +Fe3+ +3K+ +6NHt +6S0i- With dilute sulphuric acid. reaction 7).+3Ag+ -+ Ag 3[Fe(CN)6]! The precipitate is soluble in ammonia [distinction from hexacyanoferrate(II)]. Section 111. Metal hexacyanoferrate(III)s are in general more soluble than metal hexacyanoferrate(II)s.Solubility Alkali and alkaline earth hexacyanoferrate(III)s are soluble in water. no reaction occurs in the cold. 5. 12. 1.

11. etc.+H 20 +:t HOCl+OHIn solution hypochlorites disproportionate. By saturating 2M sodium hydroxide with chlorine gas.) must be absent. but soluble in ammonia: 2[Fe(CN)6]3.I3 HYPOCHLORITES. Potassium iodide solution: iodine is liberated in the presence of dilute hydrochloric acid. Cobalt nitrate solution: red precipitate of cobalt hexacyanoferrate(III). a drop of I per cent lead nitrate solution should be added before the reagent.+1 2 The reaction is reversible. a M solution of sodium hypochlorite is obtained: CI2+20H-+ ClO-+Cl-+H 20 Chloride ions are invariably present and these will interfere with some ionic reactions.OCl.+21- -+ 2[Fe(CN)6]4. 10. A blue precipitate or colouration appears. if these reactions are to be studied. 323 . Sensitivity: I ug [Fe(CN)6r-.Solubility All hypochlorites are soluble in water.REACTIONS OF ANIONS IV. Concentration limit: I in 50. reaction 12): 6K 3[Fe(CN)6] -+ 6N 2i+3(CN h t + 18KCN +2Fe 3C+ tOC IV. however. Mix a drop of the test solution on a spot plate with a drop of the benzidine reagent. They react alkaline because of hydrolysis: OCl. reduced and it is best to precipitate the hexacyanoferrate(II) first as the white. the hexacyanoferrate(III) remaining in solution. Benzidine reagent: (DANGER: THE REAGENT IS CARCINOGENIC) blue precipitate of oxidation product. when chlorate and chloride ions are formed: 30Cl-+ CIO:. Section IV.13 cipitate of free hydrogen hexacyanoferrate(III) (hexacyanoferric acid) is obtained: [Fe(CN)6]3. soluble lead hexacyanoferrate(II) by the addition of lead acetate. which is insoluble in hydrochloric acid. the solution should be freshly prepared. slowly in cold but fast in hot solution.+ 3HCl -+ H 3[Fe(CN)6]! + 3Cl- 7. 8. The test is applicable in the presence of hexacyanoferrate(II) for benzidine hexacyanoferrate(II) is white: the sensitivity is. Other oxidizing agents (molybdates.000. If hexacyanoferrate(II) is present. which may be identified by the blue colour produced with starch solution: 2[Fe(CN)6]3. in neutral solution iodine oxidizes hexacyanoferrate(II) ions. +2Cl- Thus. Action of heat Alkali hexacyanoferrate(III)s decompose similarly to hexacyanoferrate(II)s (cf. chromates.+3Co2+ -+ Co 3[Fe(CN)6]2! 9.

(b) by its bleaching a wet litmus paper. Lead acetate or lead nitrate solution: brown lead dioxide is produced on boiling: OCl. Potassium iodide-starch paper: a bluish-black colour is formed in neutral or weakly alkaline solution as the result of separation of iodine: 12+20H-+CIIf the solution is too alkaline the colour disappears because hypoiodite and iodide ions are formed: -+ OCl-+21-+H 20 12+20H- -+ 01. oxygen is liberated (identified by the rekindling of a glowing splint). a brown precipitate of basic mercury(II) chloride (HgClhO is formed: The precipitate is soluble in dilute hydrochloric acid.+Pb2+ +H 20 -+ Pb0 2! +2H+ +CI- 4.+5H 20 -+ 2Co(OHh! +CI.+ H+ HOCI+H+ +CI- Cl 2i + 21- -+ 2CI. Dilute hydrochloric acid: the solution first turns to yellow. which it turns blue-black: -+ -+ OCl. formed in the reaction are neutralized by the excess alkali present. the cobalt acting as a catalyst: 20CI-+ 2CI. and (c) by its action upon potassium iodide-starch paper.+02i 5. when undissociated mercury(lI) chloride is formed: 324 . Mercury On shaking a slightly acidified (use sulphuric acid) solution of a hypochlorite with mercury. On warming.13 QUALITATIVE INORGANIC ANALYSIS 1. a black precipitate of cobalt(llI) hydroxide is obtained: 2Co2+ +OCl. later effervescence occurs and chlorine is evolved: HOCl CI2i+H20 The gas may be identified (a) by its yellowish-green colour and irritating odour. Cobalt nitrate solution: adding a few drops of the reagent to a solution of the hypochlorite.IV.+4H+ Hydrogen ions.+r +H 20 3.+ 12 2.

Hg 20CI2 . bismuth oxychloride. and turning of potassium iodide-starch paper blue. Section 1. Hg 2C12 . Section 111.14 CHLORIDES. The hydrogen chloride first formed is oxidized to chlorine. Chlorine water. This may be used as a confirmatory test for a chloride.+Ag+ AgCl! +2NH 3 [Ag(NH 3 h r +CI. Manganese dioxide and concentrated sulphuric acid If the solid chloride is mixed with an equal quantity of precipitated manganese dioxide. Concentrated sulphuric acid: considerable decomposition of the chloride occurs in the cold. Section 111.-+ Ag 3As0 3!+3CI- * The commercial substance (pyrolusite) usually contains considerable quantities of chlorides. Mercury(l) chloride.8). under similar conditions. with the evolution of hydrogen chloride.+2H+ -+ -+ -+ AgCl! [Ag(NH 3h]+ +CIAgCl! +2NHt If the silver chloride precipitate is filtered off. CuCI. Mn0 2+2H 2S04+2CI- -+ Mn2++CI 2i+2S0i-+2H 20 3. also under Complex Ions. Silver nitrate solution: white. produces a white precipitate of mercury(II) chloride Hg 2C1 2 • IV. PbCl 2 (this is sparingly soluble in cold but readily soluble in boiling water). consisting of fine drops of hydrochloric acid. and (c) by its turning blue litmus paper red. AgCl. silver chloride. To study these reactions use a O'IM solution of sodium chloride. NaCl. curdy precipitate of silver chloride. lead chloride. antimony oxychloride.6. which are unaffected by this treatment).Solubility Most chlorides are soluble in water. washed with distilled water. (b) by the formation of white clouds of ammonium chloride when a glass rod moistened with ammonia solution is held near the mouth of the vessel.+H 2S04 -+ HCli+HSO. completely on warming. insoluble in water and in dilute nitric acid. reaction I. * concentrated sulphuric acid added and the mixture gently warmed. yellowish-green colour.14 If the precipitate is separated from the excess of mercury. chlorine is evolved which is identified by its suffocating odour. AgCl. on blowing across the mouth of the tube. 2. but soluble in dilute ammonia solution and in potassium cyanide and sodium thiosulphate solutions (see under Silver. and then shaken with sodium arsenite solution it is converted into yellow silver arsenite (distinction from silver bromide and silver iodide. The product is recognized (a) by its pungent odour and the production of white fumes. 1. and mercury(II) oxychloride. its bleaching of moistened litmus paper. copper(l) chloride. Cl.33): Cl. are insoluble in water.REACTIONS OF ANIONS IV. washed and dissolved in hydrochloric acid. mercury can be detected in the solution by passing hydrogen sulphide into it (cf. 325 . Cl. SbOCl. BiOCI. 3AgCl+AsO~.

+2H 20 3Cl 2l +2Cr3+ + 7H 20 Some chlorine may also be liberated. The chlorides of mercury. Lead acetate solution: white precipitate of lead chloride. reaction I): 2Cl. be absent. Section 111. Concentration limit: I in 30. which are evolved are passed into sodium hydroxide solution contained in a test-tube.33. the diphenylcarbazide reagent test (Section IV. less efficiently amyl acetate.+2Cl.14 QUALITATIVE INORGANIC ANALYSIS 4. Into the tube of Fig. Nitrites and nitrates interfere.+ 14H+ -+ and this decreases the sensitivity of the test. Potassium dichromate and sulphuric acid (chromyl chloride test) The solid chloride is intimately mixed with three times its weight of powdered potassium dichromate in a small distilling flask (Fig. Only partial conversion to Cr0 2Cl2 occurs with the chlorides of lead. it is preferable to employ amyl alcohol ir.p. Place a column about I mm long of a I per cent solution of diphenylcarbazide in alcohol into the capillary of the stopper and heat the apparatus for a few minutes. reaction 10) may be applied. 11. as nitrosyl chloride may be formed. Cr0 2F 2' which is decomposed by water. Chlorates must.57 place a few milligrams of the solid sample (or evaporate a drop or two of the test solution in it).l). 326 . Sensitivity: I' 5 ug Cl". This explains the failure to form chromyl chloride.000. regenerating iodide.+Cr20~. owing to the reaction: 6Cl.+Cr20~.19. adding 1-2 ml amyl alcoholr followed by a little hydrogen peroxide solution. but owing to its highly inflammable character and the possible presence of peroxides (unless previously removed by special treatment). owing to their slight ionization. 116·5°q. Cr0 2CI2. add a small quantity of powdered potassium dichromate and a drop of concentrated sulphuric acid. since chromyl chloride is a readily volatile liquid (b. Alternatively. PbCI 2. The spot-test technique is as follows. silver. which yield colourless solutions with sodium hydroxide: if the ratio of iodide to chloride exceeds I : 15. The formation of a chromate in the distillate indicates that a chloride was present in the solid substance. The resulting yellow solution in the test-tube contains sodium chromate. Bromides and iodides give rise to the free halogens. an equal bulk of concentrated sulphuric acid is added and the mixture gently warmed. t Diethyl ether may also be used. this is confirmed by acidifying with dilute sulphuric acid. and tin. the chromyl chloride formation is largely prevented and chlorine is evolved.IV.j Fluorides give rise to the volatilechromyl fluoride. The organic layer is coloured blue.4. from concentrated solutions (see under Lead. reaction I). * The deep-red vapours of chromyl chloride. * This test must not be carried out in the presence of chlorates because of the danger of forming explosive chlorine dioxide (Section IV. do not respond to this test. antimony. in the presence of concentrated sulphuric acid and especially on warming. The chromyl chloride evolved causes the reagent to assume a violet colour. of course.+Pb2+ -+ PbCI 2! 5.+6H+ Cr0 2Cl2t +40H-+ -+ 2Cr0 2Cl2t +3H 20 CrO~. IV. and hence should be absent or removed. liberates chlorine from chlorides. t The iodine reacts with the chromic acid yielding iodic acid: the latter. 4Cl.

53 and replace the diphenylcarbazide solution by a drop of dilute alkali on the glass knob. 1. Manganese dioxide and concentrated sulphuric acid When a mixture of a solid bromide. mercury(l). Nitrates interfere since nitrosyl chloride is formed. Concentrated sulphuric acid If concentrated sulphuric acid is poured on some solid potassium bromide. Br" Solubility Silver. +K+ The properties of hydrogen bromide are similar to those of hydrogen chloride. (b) by its bleaching of litmus paper. Small amounts of bromides (5 per cent) do not interfere. A violet colouration is obtained. and concentrated sulphuric acid is warmed.REACTIONS OF ANIONS IV. after cooling. pale-yellow precipitate of silver bromide. first a reddish-brown solution is formed.-+ [Ag(S203hr. Lead bromide is sparingly soluble in cold. If concentrated phosphoric acid is substituted for the sulphuric acid and the mixture is warmed. Concentration limit: I in 150. whereupon the bromine is removed as tribromophenol. Silver nitrate solution: curdy.IS BROMIDES. sparingly soluble in dilute. reddish-brown vapours of bromine are evolved. later reddish-brown vapours of bromine accompany the hydrogen bromide (fuming in moist air) which is evolved: HBri+HSO. but they may be reduced to ammonium salts. The precipitate is also soluble in potassium cyanide and sodium thiosulphate solutions. AgBr. but readily soluble in concentrated ammonia solution. It is therefore best to add a little phenol to the reagent solution. (d) by the red colouration produced upon filter paper impregnated with fluorescein (see reaction 8 below): 2KBr+Mn0 2+ 2H 2S04 -+ Br2i+2K+ +Mn2+ +2sOi. +K+ Br 2i+S02i+SOi-+2K++2H20 These reactions are accelerated by warming. precipitated manganese dioxide. employ the same quantities of materials in the apparatus of Fig. (c) by its staining of starch paper orange-red and. but insoluble in dilute nitric acid.-+ [Ag(CNhr +BrAgBr!+2S20~. IV. but large amounts of bromides give rise to sufficient bromine to oxidize the reagent. The interference of iodides is discussed above. only hydrogen bromide is formed: -+ -+ KBr+H 2S0 4 2KBr+2H 2S0 4 KBr+H 3P0 4 -+ HBri+H 2PO. and copper(l) are insoluble in water. All other bromides are soluble. bromine is recognized (a) by its powerful irritating odour. To study these reactions use a 0'1 M solution of potassium bromide KBr. dip the glass knob into a few drops of the alcoholic diphenylcarbazide solution which has been treated with a little dilute sulphuric acid and is contained on a spot plate.IS Alternatively.000. Br" +Ag+ -+ Agflr] Agflr] + 2NH 3 -+ [Ag(NH 3hr + Br" AgBr!+2CN.+2H 20 3.+Br327 . Warm for a few minutes and. 11. Sensitivity: 0'3 ug cr . 2. but more soluble in boiling water.

acidified with dilute hydrochloric acid. With excess chlorine water. it is more convenient to use dilute sodium hypochlorite solution. Fluorescein test Free bromine converts the yellow dyestuff fluorescein(l) into the red tetrabromofluorescein or eosin(II). Nitric acid Hot.+ 12H+ 6. 6KBr+K 2Cr20 7 + 7H 2S04 -+ 3Br 2 l +2Cr 3+ +4S0i. the bromine is converted into yellow bromine monochloride or into colourless hypobromous or bromic acid. 2Br.+Pb2+ -+ PbBr 2 ! The precipitate is soluble in boiling water.+2CI. 5. concentrated sulphuric acid.& ~C ° Br . Lead acetate solution: white crystalline precipitate of lead bromide: 2Br. reaction 5) and passing the evolved vapours into water. and potassium dichromate (see Chlorides. 328 . A colourless (or sometimes a pale-yellow) solution is obtained on treatment with sodium hydroxide solution this does not give the chromate reaction with dilute sulphuric acid. Section 1. and a pale-yellow or colourless solution results (difference from iodide). Chlorine water" The addition of this reagent dropwise to a solution of a bromide liberates free bromine.& ~ (11) ~COOH +4Br-+4H+ * In practice. a yellowish-brown solution. Section IV.45) and. the bromine dissolves in the solvent (see The Distribution Law. Potassium dichromate and concentrated sulphuric acid On gently warming a mixture of a solid bromide. if carbon disulphide.IV. fairly concentrated (l : I) nitric acid oxidizes bromides to bromine: 8. H°(XI°0° ~ HOhOOBr Br ~ (I) ~COOH +4Br 2 -+ C A. which colours the solution orange-red. is produced. or with the diphenyl carbazide reagent (distinction from chloride). chloroform or carbon tetrachloride (2 ml) is added and the liquid shaken.14. Filter paper impregnated with fluorescein solution is therefore a valuable reagent for bromine vapour since the paper acquires a red colour.IS QUALITATIVE INORGANIC ANALYSIS 4.+4H+ Br 2 l + 5Cl 2 l + 6H 20 -+ 2Br0 3 + IOCl. containing free bromine but no chromium.+ 7H 20 7. hydrogen peroxide and amyl alcohol.+C1 2i -+ Br2i+2CIBr2 t +C1 2 t +:t 2BrCI Br2 t +C1 2 t +2H 20 -+ 20Br. after allowing to stand. forms a reddish-brown solution below the colourless aqueous layer.

In a short time the liquid in the capillary assumes a violet colour.57 may be used. KI.57. add 2-4 drops 25 per cent chromic acid solution and close the apparatus with the 'head' which contains 1-2 drops of the reagent solution in the capillary. and lead iodides are the least soluble salts. 11. Sensitivity: 3 ug Br". violet vapours are evolved. is employed. Concentrated sulphuric acid With a solid iodide.16 Chlorine tends to bleach the reagent. Warm the apparatus gently (do not allow it to boil). Sensitivity: 2 ug Br 2 • Concentration limit: I in 25. Warm the apparatus gently.+2H 20 Place a drop of the test solution together with a few milligrams oflead dioxide and acetic acid in the apparatus of Fig. iodine is liberated. 9. Fuchsin (or Magenta) test The dyestuff fuchsin(l) forms a colourless (1) addition compound with hydrogen sulphite.000.16 IODIDES.this can be seen by blowing across the mouth of the 329 . The reagent consists of a 0·1 per cent fuchsin solution just decolourized by sodium hydrogen sulphite. 11. Some hydrogen iodide is formed . Silver. Concentration limit: I in 15. Alternatively. mercury(I).000. which turn starch paper blue. The fluorescein reagent consists of a saturated solution of fluorescein in 50 per cent alcohol. 1. r Solubility The solubilities of the iodides are similar to the chloride and bromides.+Pb0 2 +4CH 3COOH -+ Br 2 t +Pb2+ +4CH 3COO. practically no chlorine is simultaneously evolved from chlorides. hence the reaction may be employed for the detection of bromides in the presence of chlorides and iodides. 11. a column. Neither free chlorine nor free iodine affect the colourless fuchsin hydrogen sulphite compound.REACTIONS OF ANIONS IV. and hence the test may be conducted in the presence of chlorides. Iodine forms the red-violet coloured iodoeosin and hence must be absent. the apparatus of Fig. Free bromine converts the thus decolourized fuchsin into a blue or violet brominated dyestuff. IV. on warming. 2Br. If the bromide is oxidized to free bromine by heating with lead dioxide and acetic acid. copper(I). mercury(II). These reactions can be studied with a O'IM solution of potassium iodide. Place a drop of the test solution (or a few milligrams of the test solid) in the tube of the apparatus shown in Fig. A circular red spot is formed on the yellow test paper. about I mm long of the reagent.56 and close the tube with the funnel stopper carrying a piece of filter paper which has been impregnated with the reagent and dried.

chloroform or carbon tetrachloride (see Section 1. 61. it dissolves forming a violet solution.+ 4H 20 Pure hydrogen iodide is formed on warming with concentrated phosphoric acid: 1. hydrogen sulphide. readily soluble in potassium cyanide and in sodium thiosulphate solutions. + IOCl. and sulphur. which colours the solution brown. Pb12. when white fumes are produced .+ Pb2+ -+ Pb12! 4. If manganese dioxide is added to the mixture. only iodine is formed and the sulphuric acid does not get reduced: zr: + Mn0 2 +2H 2S0 4 -+ 12i+Mn2+ +2S0i.+7H 2S0 4 -+ 312i+2Cr3+ + 7S0i. very slightly soluble in concentrated ammonia solution.+7H 20 * In practice it is more convenient to use dilute sodium hypochlorite solution acidified with dilute hydrochloric acid. reaction 5) (difference from chloride). Section IV. 21. curdy precipitate of silver iodide AgI. and no chromate is present in the distillate (see Chlorides.+2H 20 2.-i-Ag" AgI!+2CN- -+ -+ AgI!+2S20~. 61-+4H 2S0 4 -+ 312i+S!+3S0i-+4H20 sr + 5H 2S0 4 -+ 412i + H 2Si + 4S0i. iodine is liberated. Silver nitrate solution: yellow. on shaking with 1-2 ml carbon disulphide.+ H 3P04 -+ Hl] + H 2PO.+ 12H+ 5. 330 . and yielding golden-yellow plates ('spangles') on cooling.IV. the relative proportions of which depend upon the concentrations of the reagents. The free iodine may also be identified by the characteristic blue colour it forms with starch solution.45).+H 2S0 4 -+ Hli+HSO. soluble in much hot water forming a colourless solution. Potassium dichromate and concentrated sulphuric acid: only iodine is liberated. and insoluble in dilute nitric acid.but most of it reduces the sulphuric acid to sulphur dioxide.14. the iodine is oxidized to colourless iodic acid.16 QUALITATIVE INORGANIC ANALYSIS vessel.+Cr20~.+2H 20 1.+C1 2i 12 + 5Cl 2i + 6H 20 -+ -+ 12+2Cl210:.-+ AgI [Ag(CNh]. 21.+2H 2S0 4 -+ 12 t +SOi. If excess chlorine water is added. Chlorine water" When this reagent is added dropwise to a solution of an iodide.+1[Ag(S203hr-+I- 3. which settles out below the aqueous layer. 21. 1. Lead acetate solution: yellow precipitate of lead iodide.

-+ 21-+S40~- 8. The best oxidizing agent to employ in the spot test reaction is acidified potassium nitrite solution (cf. Copper sulphate solution: brown precipitate consisting of a mixture of copper(l) iodide. reaction 6): 12 + 2NOj + 2H 20 Cyanides interfere because of the formation of cyanogen iodide: they are therefore removed before the test either by heating with sodium hydrogen carbonate solution or by acidifying and heating: -+ 2r + 2N0 2 + 4H+ 12 + CN.000. forming a tetraiodomercurate(lI) complex: Hg12! + 21-+ [HgI 4]2- 9. and a nearly white precipitate of copper(l) iodide obtained. zr +2N0 2 +4H+ -+ 12+2NOj+2H20 7. 10. or carbon tetrachloride violet. CuI.16 6.-+ 2Ce3+ + 12 reacting further according to (ii): AsO~.+ 12 + H 20 -+ AsOl. The iodine may be removed by the addition of sodium thiosulphate solution or sulphurous acid. the free iodine may then be identified by the deepblue colouration produced with starch solution. A blue colouration is obtained. Starch test Iodides are readily oxidized in acid solution to free iodine by a number of oxidizing agents. possibly owing to iodine liberated in the instantaneous reaction (i): (i) 2Ce 4+ + 21.+ 21. Mercury ( II) chloride solution: scarlet precipitate of mercury(lI) iodide: 2r + HgCl 2 -+ HgI 2!+2CI(note that mercury(lI) chloride is practically undissociated in solution). The iodine may be identified by colouring starch paste blue. Sensitivity: 2·5 ug 12 • Concentration limit: I in 20. Catalytic reduction of cerium (IV) salts test The reduction of cerium (IV) salts in acid solution by arsenites takes place very slowly: 2Ce4+ +AsO~.REACTIONS OF ANIONS IV. and iodine.+2H+ Iodides accelerate this change.+ 2H+ (ii) 331 .-+ ICNj + 1Mix a drop of the acid test solution on a spot plate with a drop of the reagent and add a drop of 50 per cent potassium nitrite solution. The precipitate dissolves in excess potassium iodide. Sodium nitrite solution Iodine is liberated when this reagent is added to an iodide solution acidified with dilute acetic or sulphuric acid (difference from bromide and chloride). 41.+ 2Cu2+ -+ 2Cul! + 12 12+2S20~.+H 20 -+ 2Ce3+ +AsOl.

1. barium.+H 2S04 -+ H2F2i+SOiSi0 2 + 2H 2F2 -+ SiF 4i + 2H 20 3SiF 4t +3H 20 -+ 2[SiF 6]2. Concentration limit: I in 1. aluminium. Sensitivity: 0'03 ug 1-. hydrogen fluoride. bromides. and nickel are readily soluble in water. sulphates. unlike free molybdic acid. The latter. Pd12. NaF. F. H 2F 2' is evolved on warming. Moderate amounts of chlorides. the gas fumes in moist air. which liberates the gas. this is a product of the decomposition of the silicon tetrafluoride. Osmium and ruthenium salts have a similar catalytic effect. 11. Place a drop of the test solution together with a drop each of neutral or slightly acid O'IM sodium arsenite solution and O'IM cerium(IV) sulphate solution on a spot plate.+Pd2+ -+ Pd12! Mix a drop of the test solution on drop-reaction paper with a drop of a I per cent aqueous solution of palladium chloride. insoluble in mineral acids. iron(III).I7 FLUORIDES. and the test-tube acquires a greasy appearance as a result of the corrosive action of the vapour on the silica in the glass. silicon tetrafluoride is readily evolved. The spot-test technique of the reaction utilizes the conversion of the silicic and fluosilicic acids by means of ammonium molybdate into silicomolybdic acid H4[SiMo1204o]. a colourless. Concentration limit: 1 in 50. gelatinous silicic acid H 2Si0 3 is deposited on the rod. 21. (DANGER: THE REAGENT IS CARCINOGENIC.+H 2Si0 3 ! +4H+ Note that at room temperature hydrogen fluoride gas is almost completely dimerized.I7 QUALITATIVE INORGANIC ANALYSIS the iodide ion reacting again as in (i). SiF 4. 2F. mercury.000. The completion of the reduction is indicated by the disappearance of the yellow colour of the cerium(lV) solution. Sensitivity: I ug 1-.000. corrosive gas. silver. Concentrated sulphuric acid With the solid fluoride. IV. A brownish-black precipitate forms. those of lead. and lithium are slightly soluble.IV. The yellow colour soon disappears. making into a paste with concentrated sulphuric acid and warming gently.Solubility The fluorides of the common alkali metals and of silver. To study these reactions use a O·lM solution of sodium fluoride.) 332 . oxidizes benzidine in acetic acid solution to a blue dyestuff and 'molybdenum blue' is simultaneously produced.000. and manganese salts interfere. Palladium (II) chloride test Solutions of iodides react with palladium(II) chloride solution to yield a brownish-red precipitate of palladium(II) iodide. and nitrates have no influence. By holding a moistened glass rod in the vapour. and those of the other alkaline earth metals are insoluble in water. silicon tetrafluoride. therefore its formula has been written as H 2F 2' At elevated temperatures (say 90°C) it dissociates completely to monomer hydrogen fluoride: H 2F2 +:t 2HF The same result is more readily attained by mixing the solid fluoride with an equal bulk of silica. but cyanides and also mercury(II). copper.

After 5-10 minutes. and part of the glass is exposed by scratching a design on the wax with a nail or wire. and the latter immediately covered with watch glass. Iron( Ill) chloridesolution: white crystalline precipitate of sodium hexafluoroferrate(III) from concentrated solutions of fluorides. A blue colour is obtained.REACTIONS OF ANIONS IV. but slightly more soluble in dilute hydrochloric acid. and borates interfere and should therefore be absent.+Fe3+ +3Na+ -+ Na 3[FeF 6]! 6. reaction 8). 2F. 6F.53 and moisten the silica with 1-2 drops concentrated sulphuric acid. The precipitate does not give the reactions of iron (e. except upon acidification. with ammonium thiocyanate). and then breathing upon the surface of the glass. sparingly soluble in water. Zirconium-alizarin lake test Hydrochloric acid solutions of zirconium salts are coloured reddish-violet by alizarin-S or by alizarin (see under Aluminium. Remove the source of heat and allow to stand for 5 minutes. 2. provided with a closefitting lid made from lead foil. insert it in position and heat the apparatus gently for about I minute. Allow to cool. Calcium chloride solution: white. add 1-2 drops ammonium molybdate reagent and warm the mixture until bubbling just commences. silicates. Chlorates.23. Upon warming very gently (best on a water bath) it will be found that an etched spot appears on the glass where it covers the hole. 4. About 0'1 g suspected fluoride and a few drops concentrated sulphuric acid are placed in the clean capsule. The test may also be conducted in a small lead capsule. introduce a drop of a 0·05 per cent solution of benzidine in 2M acetic acid and a few drops of saturated sodium acetate solution. A mixture of about 0'3 g fluoride and I ml concentrated sulphuric acid is placed in a small lead or platinum crucible. CaF 2' sparingly soluble in acetic acid.g. Section 111. Sensitivity: I ug F.I7 Mix the solid test sample with a little pure silica powder in the tube of the apparatus shown in Fig. Wash the drop of water into a micro crucible. 3. Silver nitrate solution: no precipitate. since silver fluoride is soluble in water. The etching test A clean watch glass is coated on the convex side with paraffin wax. and a small piece of glass (e. a microscope slide) is placed over the hole in the lid. slimy precipitate of calcium fluoride.g. reactions 8 and 9 and under Zirconium. the hydrogen fluoride will have etched the glass. A little water should be poured in the upper (concave) side of the watch glass to prevent the wax from melting. This is readily seen after removing the paraffin wax by holding above a flame or with hot water. 11. Section VII.+Ca2+ -+ CaF 2 ! 5. A small hole of about 3 mm diameter is pierced in the lid. Place a drop of water on the glass knob of the stopper. The crucible is very gently warmed (best on a boiling water bath).IS. convex side down. upon adding a solution of a fluoride the colour of such solutions changes immediately to a pale yellow (that of the liberated alizarin sulphonic acid or alizarin) because of the formation of the colourless hexafluorozirconate(IV) ion 333 .

and oxalates interfere with the test. The zirconium-alizarin-S paper is prepared as follows. Impregnate some quantitative filter paper or drop-reaction paper with the zirconiumalizarin-S reagent. add a drop of dilute hydrochloric acid or of I : I (v/v) acetic acid. +2H 2S04 -+ 4N0 2 t +0 2 t +2S0i. the spot will turn yellow. dry it and moisten with a drop of 1: I (v/v) acetic acid. The nitrates of mercury and bismuth yield basic salts on treatment with water. mix 2 drops each of the alizarin-S and zirconyl chloride solutions in a semimicro test-tube. The pink colour will change to yellow.I8 QUALITATIVE INORGANIC ANALYSIS [ZrF 6]2-. Alternatively. NO:. The test may be performed on a spot plate. followed by 2 drops of the test solution. Concentrated sulphuric acid and bright copper turnings On heating these with the solid nitrate. IV. are formed on heating the solid nitrate with the reagent. Large amounts of sulphates. Concentrated sulphuric acid: reddish-brown vapours of nitrogen dioxide. drain and place in a 2 per cent aqueous solution of alizarin-So Wash the paper. +4H 2S04+3Cu 2NOj + O 2 t -+ -+ 3Cu2+ +2NOj+4S0i. arsenates. phosphates. accompanied by pungent acid vapours of nitric acid which fume in the air. nitrites. the sulphuric acid is then added very cautiously.IV. Mix together on a spot plate 2 drops each (equal volumes) of a 0'1 per cent aqueous solution of alizarin-S (sodium alizarin sulphonate) and zirconyl chloride solution (0'1 g solid zirconyl chloride dissolved in 20 ml concentrated hydrochloric acid and diluted to 100 ml with water): upon the addition of a drop or two of the fluoride solution the zirconium lake is decolourized to a clear yellow solution. Place a drop of the neutral test solution upon the moist red spot. These reactions can be studied with a O'IM solution of potassium nitrate KN0 3 • 1. these are soluble in dilute nitric acid.IS NITRATES. and the solution acquires a blue colour owing to the formation of copper(II) ions. until the washings are nearly colourless and then dry in air. A solution of the nitrate may also be used. and pour 3-5 ml concentrated sulphuric acid slowly down the side of the test-tube so that the acid forms a layer beneath the mixture. Solubility All nitrates are soluble in water. thiosulphates.+2H 20 2. which is coloured red-violet by the zirconium lake. reddish-brown fumes of nitrogen dioxide are evolved. Dilute sulphuric acid has no action (difference from nitrite): 4NO:. The most sensitive method of carrying out the spot test is as follows.000. Immerse quantitative filter paper (or drop-reaction paper) in a lO per cent solution of zirconium nitrate in 2M hydrochloric acid. Iron(II) sulphate solution and concentrated sulphuric acid (brown ring test) This test is carried out in either of two ways: (a) Add 3 ml freshly prepared saturated solution of iron(II) sulphate to 2 ml nitrate solution.+4H 20 2N0 2 t 3. Concentration limit: I in 50. A brown ring will form where the 334 . 2NO:. Sensitivity: 1 ug F-.

nitric oxide is evolved.I8 liquids meet. and 50 per cent Cu). All of these anions may be removed by adding excess of nitrate-free Ag 2S04 to an aqueous solution (or sodium carbonate extract). They are best removed by adding a little sulphamic acid (compare Section IV. Another. reaction 7) when a solution ofa nitrate is boiled with zinc dust or gently warmed. Pour a saturated solution iron(lI) sulphate slowly down the side of the tube so that it forms a layer on top of the liquid. Excellent results are obtained by the use of Devarda's alloy (45 per cent AI. Concentration limit: I in 25. or by the tannic acid-silver nitrate test. 5 per cent Zn.+ H+ + H 20 The spot-test technique is as follows.REACTIONS OF ANIONS IV. and filtering the insoluble silver salts. shaking vigorously for 3-4 minutes. reactions 3 and 4). The test is unreliable in the presence of bromide.7. sulphites.000. hexacyanoferrate(II) and (Ill) ions. and chromate (see Section IV. the solution is allowed to stand for a short time and then boiled in order to complete the reaction and to expel the readily volatile hydrogen azide: N02"+Ni+ 2H+ -+ N 2i+N20i+H10 Ni +H+ -+ HN 3 t 335 . Place a crystal of iron(II) sulphate about as large as a pin head on a spot plate. The brown ring is due to the formation of the [Fe(NO)]2+ . chlorate. evaporating almost to dryness) before the addition of the metal. thiocyanates. Section ill. thiosulphates. Sensitivity: 2'5 ug NOi. 4.with aluminium powder and sodium hydroxide solution.45. (b) Add 4 ml concentrated sulphuric acid slowly to 2 ml nitrate solution. Reduction ofnitrates in alkaline medium Ammonia is evolved (detected by its odour.38. be removed by boiling the solution with sodium hydroxide solution (and. the test is not trustworthy in the presence of chromates. and a yellow solution of iron(III) ions remains. Ammonium ions must. iodide.+ 18H20 -+ -+ NH 3 i+4[Zn(OH)4]23NH 3 l + 8[AI(OH)4]- Nitrites give a similar reaction and may be removed most simply with the aid of sulphamic acid (see reaction 3). A brown ring forms round the crystal of iron(II) sulphate. Nitrites react similarly to nitrates. A brown ring will form at the zone of contact of the two liquids. Add a drop of the test solution and allow a drop of concentrated sulphuric acid to run in at the side of the drop. but more expensive. NOi +4Zn+70H. preferably. by its action upon red litmus paper and upon mercury(l) nitrate paper. 2NOi + 4H 1S04 + 6Fe2+ Fe2+ +NOi -+ -+ 6Fe3+ + 2NOi + 4S0i. cyanides.+ 4H 10 [Fe(NO)]2+ Bromides and iodides interfere because of the liberated halogen. The following reaction takes place in the cold: H 2N-HS0 3 + N0Z" -+ N 2l + SO~. reaction 10). On shaking and warming the mixture the brown colour disappears.+6H 20 3NOi + 8AI + 50H. mix the liquids thoroughly and cool the mixture under a stream of cold water from the tap. nitrite. procedure involves the addition of sodium azide to the acid solution. etc. iodates. of course.

bromates. 5. Bromides. thiocyanates. reaction 8) on its underside upon the funnel stopper. Concentration limit: I in 5. hexacyanoferrate(lI) and (Ill) ions. Attention is directed to the fact that arsenites are reduced in alkaline solution by aluminium. which blackens mercury(l) nitrate paper and also gives a positive tannic acid-silver nitrate test.. The reagent is prepared by dissolving 5 g nitron in 100 ml2M acetic acid. perchlorates.NH. and picrates also yield insoluble compounds. to arsine. Nitron reagent (diphenyl-endo-anilo-dihydrotriazole C2oH16N4J CH . Section 111. thiocyanates. Add a tiny fragment of calcium oxide to the drop of the reagent: a red ring forms within 10-15 seconds. The nitrates of sodium and potassium evolve oxygen (test with glowing splint) and leave solid nitrites (brown fumes with dilute acid). oxalates. iodates.. The spot-test technique is carried out as follows. shaking vigorously for 3-4 minutes and filtering from the silver salts of the interfering anions and excess of precipitant. warming the mixture to about 60°. permanganates. The filtrate is concentrated and tested with zinc. Diphenylamine reagent (C 6Hs. 6. ammonium nitrate yields dinitrogen oxide and 336 . but unfortunately is also given by a number of oxidizing agents. iodides. 3). and iron(lIl) salts. 11. a blue ring is formed at the zone of contact of the two liquids. or Devarda's alloy.38.. Sensitivity: 10 ug NO:.N . chromates. and filtering from the precipitated silver oxide. 7. etc. aluminium.000. Hence neither the mercury (I) nitrate test nor the tannic acid-silver nitrate test for ammonia is applicable if arsenites are present.56. nitrites. Heat the apparatus gently for a short time. vanadates. see under Ammonium. chlorates.IV.HN03 with solutions of nitrates. Section IV. and hence the reaction is not very characteristic.C6HsJ Pour the nitrate solution carefully down the side of the test-tube so that it forms a layer above the solution of the reagent. The reagent is prepared by dissolving 0'5 g diphenylamine in 85 ml concentrated sulphuric acid diluted to 100 ml with water. The excess silver ions are removed from the filtrate by adding an excess of sodium hydroxide solution. Place a drop of the test solution in the tube of Fig. such as nitrites. Action ofheat The result varies with the metal. molybdates.I8 QUALITATIVE INORGANIC ANALYSIS Other nitrogen compounds which evolve ammonia under the above conditions are cyanides. chlorates. Devarda's alloy. The test is a very sensitive one.N o s I:!~II 'N/ HC C I CoH s white crystalline precipitate of nitron nitrate C2oH16N4. chromates. Place a watch glass with a drop of p-nitrobenzene-diazonium chloride reagent (for preparation. add 1-2 drops 20 per cent sodium hydroxide solution and a few milligrams of Devarda's alloy.45. These may be removed by treating the aqueous solution (or a sodium carbonate extract) with excess of nitrate-free silver sulphate (cf.

CIO:. the nitrates of the other metals. +3S0i.REACTIONS OF ANIONS IV. To study these reactions use a O'IM solution of potassium chlorate. The mixture of gases is sometimes known as 'euchlorine'. 2NaN0 3 NH 4N0 3 2AgN0 3 2Pb(N0 3 ) 2 -+ 2NaN0 2 + O 2 t -+ N 20i+2H 20 -+ 2Ag + 2N0 2 l + O 2 l -+ 2PbO+4N0 2 t +0 2 t 8.000. which may develop into a violent explosion..7. which dissolves in the sulphuric acid to give an orange-yellow solution. evolve oxygen and nitrogen dioxide.+4H+ +3K+ +H 20 2. the nitrates of the noble metals leave a residue of the metal. 1. Concentration limit: I in 1.1 at 18°).19 CHLORATES. and add a few milligrams of zinc dust. the nitrite can be readily detected by means of the sulphanilic acid-z-naphthylamine reagent (see under Nitrites. Solubility All chlorates are soluble in water. and leave a residue of the oxide. and its mouth should be directed away from the student. Section IV. In carrying out this test one or two small crystals of potassium chlorate (weighing not more than 0'1 g) are treated with I ml concentrated sulphuric acid in the cold. chlorine dioxide. and not more than 0'1 g potassium chlorate should be used. The experiment should be conducted on a very small scale. Reduction to nitrite test Nitrates are reduced to nitrites by metallic zinc in acetic acid solution. The nitrite must. IV. Nitrites. 3KCI0 3+3H2S04 -+ 2CI0 2i+CIO. together with varying quantities of the explosive chlorine dioxide. On warming gently (DANGER) an explosive crackling occurs. Sensitivity: 0'05 ug NO:. which may be identified by adding silver nitrate solution after acidification with dilute nitric acid. 337 . potassium chlorate is one of the least soluble (66 g t -1 at 18°) and lithium chlorate one of the most soluble (3150 g t . chlorine dioxide imparts a yellow colour to the acid. such as those of lead and copper. The test-tube should not be warmed. and chlorine. and a mixture of nitrogen dioxide and oxygen is evolved.19 steam. The following two chemical reactions probably occur simultaneously: 2KCI0 3+4HCl-+ 2CI0 2+CI 2i+2K++2Cl-+2H 20 KCI0 3 + 6HCl -+ 3Cl 2 i + K + + Cl. the latter is reduced to a chloride. Sodium nitrite solution On warming this reagent with a solution of the chlorate. Concentrated hydrochloric acid All chlorates are decomposed by this acid.000. reaction 11). CI0 2 . A red colouration develops. the yellow explosive chlorine dioxide can be seen on shaking the solution. interfere and are best removed with sulphamic acid (see reaction 3 above). Concentrated sulphuric acid (DANGER) All chlorates are decomposed with the formation of the greenish-yellow gas. of course. Mix on a spot plate a drop of the neutral or acetic acid test solution with a drop of the sulphanilic acid reagent and a drop of the «-naphthylamine reagent.+ 3H 20 3. is evolved.

+CI.IS. If acetic acid is used. 338 .19 QUALITATIVE INORGANIC ANALYSIS of course.+3H 20 -+ CI. 0·05 g) (DANGER) is mixed with I ml concentrated sulphuric acid. No precipitate is obtained with barium chloride solution. Excellent results are obtained with zinc. +6Fe2+ +6H+ -+ CI. + 61. a white precipitate of silver chloride is obtained because of the reduction of the chlorate to chloride (see reaction 3 above). +2AI+20H.+6Fe3+ +3H 20 7. and also periodates react simi- * It is best to filter off the excess metal before adding the silver nitrate solution. bromates.+6H+ -+ 6[Mn(P04 hr .+ 3[Zn(OH)4]4CI.+3HCOOH CI. +3HCHO -+ CIO:. nitrites. 8. Dilute sulphurous acid or sodium sulphite solution is then added drop by drop. iodates. aluminium or Devarda's alloy and sodium hydroxide solution (see under Nitrates. CIO:. Upon the addition of a little pure (chloride-free) sodium nitrite to the dilute nitric acid solution. +3N0 2 -+ CIO:. I part offormaline to 3 parts of water) acts similarly. +6Mn2+ + 12PO~.+ 3H 20 -+ CIO:. Potassium iodide solution: iodine is liberated if a mineral acid is present. a deep-blue colour is obtained (distinction from nitrate). Silver nitrate solution: no precipitate in neutral solution or in the presence of dilute nitric acid. the solution is acidified with dilute nitric acid after several minutes boiling* and silver nitrate solution added. CIO:.+3H 20 Peroxodisulphates. (C6Hs. 9.+6H+ CI. be free from chloride. and the latter bleaches the indigo. the blue colour is discharged. Indigo test A dilute solution of indigo in concentrated sulphuric acid is added to the chlorate solution until the latter has a pale-blue colour. Aniline sulphate test. CIO:. no iodine separates even on long standing (difference from iodate). Section IV.IV. +3H 2S0 3 -+ CIO:.NH2)2H2S04 A small quantity of the solid chlorate (say.+ 3H 20 6. CI.+ 6H+ -+ 312 + CI.+3S0i.+2[AI(OH)4r 4. and 2-3 ml aqueous aniline sulphate solution added. Iron (II) sulphate solution: reduction to chloride upon boiling in the presence of mineral acid (difference from perchlorate). Manganese(II) sulphate-phosphoric acid test: manganese(II) sulphate in concentrated phosphoric acid solution reacts with chlorates to form the violetcoloured diphosphatomanganate(III) ion: CIO:. The chlorate is reduced by the sulphurous acid to chlorine or to hypochlorite. 5.+3NO:. A solution of sulphurous acid or of formaldehyde (10 percent. reaction 4). + 3Zn + 60H.

lead acetate or mercury(I) nitrate to a concentrated solution of a bromate. BrO:. 7'0 g t.20 BROMATES. bromine and oxygen are evolved in the cold. BrO:. and lead bromates are slightly soluble in water. is produced with a concentrated solution of a bromate. 2BrO:. The precipitate is soluble in hot water. + Ag" -+ AgBr0 3 ! AgBr0 3 ! +2NH 3 -+ [Ag(NH 3 hr + BrO:. 2KCI0 3 2KCI0 3 -+ -+ 2KCl + 30 2l KCI0 4 +KCl+0 2t IV. the 339 . Ba(Br0 3 h! -+ Pb(Br0 3 h! -+ Hg 2(Br0 3 h! If the solution of silver bromate in dilute ammonia solution is treated dropwise with sulphurous acid solution.1 .000.. due to an oxidation product of the diphenylcarbazide.000. barium. Silver nitrate solution A white crystalline precipitate of silver bromate. Action of heat All chlorates are decomposed by heat into chlorides and oxygen. Solubility Silver. The reagent is prepared by mixing equal volumes of saturated manganese(II) sulphate solution and concentrated phosphoric acid. 1. Precipitates of the corresponding bromates are also produced by the addition of solutions of barium chloride. Place a drop of the test solution in a micro crucible and add a drop of the reagent. The first-named may be decomposed by evaporating the sulphuric acid solution with a little silver nitrate as catalyst. An insoluble chlorate should be mixed with sodium carbonate before ignition. Some perchlorate is usually formed as an intermediate product. AgBr0 3 .REACTIONS OF ANIONS IV. mercury(l) bromate is also sparingly soluble.1 at 20°. A violet colouration appears. and sparingly soluble in dilute nitric acid. Very pale colourations may be intensified by adding a drop of I per cent alcoholic diphenylcarbazide solution when a deep-violet colour. + Pb2+ 2BrO:. the solubilities being respectively 2'0 g t.1 and 13'5 g t. The chloride is identified in the residue by extracting with water and adding dilute nitric acid and silver nitrate solution. is obtained. Concentration limit: I in 1. readily soluble in dilute ammonia solution forming a complex salt. Sensitivity: 0'05 ug CIO:. Sulphur dioxide If the gas is bubbled through a solution of a bromate. To study these reactions use a O'IM solution of potassium bromate. 4KBr0 3 +2H 2S0 4 -+ 2Br2t +50 2t +4K + +2soi. +Hg~+ -+ 3. silver bromide separates: the latter dissolves in concentrated ammonia solution (difference from iodate). Most of the other metallic bromates are readily soluble in water. 10. +Ba2+ 2BrO:. Warm rapidly over a micro burner and allow to cool. Concentrated sulphuric acid Add 2 ml acid to O' 5 g solid bromate.+2H 20 2.20 larly.

A blue colouration results. brown. KI0 3 • 340 . and leave an oxide.+3H 20 6Mn0 2!+Br. Action of heat Potassium bromate on heating evolves oxygen and a bromide remains. a transient red colouration (due to manganese(III) ions) is observed. To study these reactions use a O'IM solution of potassium iodate. Sodium and calcium bromates behave similarly. 6.I at 200.+ 18H+ Mn2++2C0 2i+2H 20 In the spot-test technique. zinc. barium iodate 0'22. the reaction is combined with a sensitive test for manganese (oxidation of benzidine by manganese dioxide to 'benzidine blue'). Sensitivity: 30 ug Br0 3.+6"+ -+ 3Br2 t +3H 20 5. Section IV.330 g t . Br0 3 +6Mn2+ +6H+ Br0 3 +6Mn3+ +9H 20 -+ -+ MnO!+(COO)~-+4H+ -+ 6Mn3+ +Br. and sodium iodate 90'0. add a drop or two of 0'25M manganese(I1) sulphate solution acidified with dilute sulphuric acid and warm for 2-3 minutes in a boiling water bath. Some solubilities in g t. silver iodate 0'06. Section IV.+ 6H+ Br0 3 + 3H 2S -+ Br" + 3S! + 3H 20 Br0 3 + 3N0 2 -+ Br" + 3N0 3 4.) Place a drop of the test solution in a semimicro centrifuge tube.15).500. Hydrobromic acid Mix together solutions of potassium bromate and bromide. but dissolves in a mixture of dilute sulphuric and oxalic acids (difference from chlorates and iodates. in general. but cobalt. those of the other metals are sparingly soluble and.I at 200are: lead iodate 0·03 (25°). The latter is insoluble in dilute sulphuric acid.19. and has a solubility of 2. Br0 3 + 3H 2S0 3 -+ Br" + 3S0~. potassium iodate 81'3. The bromine may be extracted by adding a little chloroform or carbon tetrachloride. calcium iodate 3'7. 10 3 Solubility The iodates of the alkali metals are soluble in water. bromine is liberated as a result of interaction between the bromic and hydrobromic acids set free.21 IODATES. Cool. A similar result is obtained with hydrogen sulphide and with sodium nitrite solution (see under Chlorates. Iodic acid is a crystalline solid. and other similar metallic bromates evolve oxygen and bromine. IV. less soluble than the corresponding chlorates and bromates. Concentration limit: I in 2. reaction 3). Manganese (II) sulphate test If a bromate solution is treated with a little of a I: I mixture of saturated manganese(II) sulphate solution and Msulphuric acid. add a few drops of the benzidine reagent and a few small crystals of sodium acetate. Upon concentrating the solution rapidly. which neither give the colouration nor yield the brown precipitate).IV. (DANGER: THE REAGENT IS CARCINOGENIC.21 QUALITATIVE INORGANIC ANALYSIS latter is reduced to a bromide (see Bromides. and acidify with dilute sulphuric acid. hydrated manganese dioxide separates. Br0 3 +5Br.

REACTIONS OF ANIONS IV. but sparingly soluble in dilute nitric acid. the iodine is further reduced to iodide. 210 3 + Hg2+ 210 3 + Pb2+ -+ -+ Hg(10 3h! Pb(10 3h! 5. 210 3 +5H 2S0 3 -+ 12+H2S0 3+H 20 -+ 210 3 + 5H 2S + 2H+ -+ 12 + H 2S -+ 12 +5S0~. Sulphur dioxide or hydrogen sulphide Passage of sulphur dioxide or of hydrogen sulphide into a solution of an iodate.+2NHt +4H+ 3. which may be recognized by the addition of starch solution or chloroform or carbon tetrachloride.+6H+ -+ 312!+3H20 2. curdy precipitate of silver iodate. reaction 6): 10 3 +51. With an excess of either reagent. the latter is coloured violet by the liberated iodine.+8H+ +H 20 21.+6Fe3+ +3H 20 If the iodate is in excess.+SO~. Concentrated sulphuric acid: no action in the absence of reducing agents.+8H+ +H 20 4. Mercury(Il) nitrate solution: white precipitate ofmercury(I1) iodate (difference from chlorate and bromate). treated with a little sulphurous acid solution and 1-2 ml carbon tetrachloride. Potassium iodide solution Mix together solutions of potassium iodide and potassium iodate. and barium sulphate is precipitated: 210 3 + Ba2+ -+ Ba(10 3h! Ba(10 3)2!+5H 2S0 3 -+ 12 + BaS0 4! +4S0~. Silver nitrate solution: white. Barium chloride solution: white precipitate of barium iodate (difference from chlorate). liberates iodine. readily converted to iodide in the presence of iron(I1) sulphate: 10 3 +6Fe2+ +6H+ -+ 1. Lead acetate solution similarly gives a precipitate of lead iodate. but insoluble in alcohol (difference from iodide). acetic acid or with tartaric 341 . the latter is not dissolved by concentrated ammonia solution (difference from bromate).+4H+ 12 + 5S! + 6H 20 21. Mercury(I1) chloride solution. readily soluble in dilute ammonia solution. silver iodide is precipitated. 10 3 -i-Ag" -+ AgI0 3! AgI0 3! + 2NH 3 -+ [Ag(NH 3 h r + 10 3 If the ammoniacal solution of the precipitate is treated dropwise with sulphurous acid solution. acidified with dilute hydrochloric acid. which is practically un-ionized (as mercuric chloride is covalent) gives no precipitate. sparingly soluble in hot water and in dilute nitric acid. iodine is formed because of the interaction of iodate and iodide (cf. and acidify with hydrochloric acid. [Ag(NH 3 h r +10 3 +3H 2S0 3 -+ AgI!+3S0~.+2H+ + S! 6. If the precipitate of barium iodate is well washed.21 1.

hexoxoperiodate) : 2KI0 3 -+ 2KI + 30 2 l 2Pb(10 3h -+ 212 t + 50 2 t + 2PbO 5Ba(l03h -+ BaS(l06h +41 2 j +90 2 j 8.IV. The reaction takes place in three stages (with the transitional formation of phosphorous acid): 10 3 +3H 3P0 2 51.+ 10 3 + 6H+ 12 +H 3P03+H 20 -+ -+ -+ 1. exceptionally.1 at 25°).1 at 0° and 1000 respectively).16. Potassium thiocyanate test with the liberation of iodine: Iodates react with thiocyanates in acid solution -+ 610 3 + 5SCN. reaction 9) and a drop of a dilute solution of hypophosphorous acid.22 PERCHLORATES. Concentration limit: I in 12. A transitory blue colouration is produced. 9. Sensitivity: I ug 1° 3. Action of heat The alkali iodates decomposed into oxygen and an iodide. 10 3 + 51. Sensitivity: 3 ug 1° 3. A blue spot is obtained.H 20j+HSO. Most iodates of the bivalent metals yield iodine and oxygen and leave a residue of oxide. Concentration limit: I in 50. Chlorates and bromates do not react under these conditions. IV. The iodine can be readily identified by the starch reaction. Potassium perchlorate is one of the least soluble (7'5 g t. on strong heating white fumes of perchloric acid monohydrate are produced: NaCI0 4+H 2S04+H 20 342 -+ HCI0 4.+3H 3P03 312 + 3H 20 2r +H 3P0 4 +2H+ (i) (ii) (iii) The first two stages are rapid and the third stage is a slow reaction. Concentrated sulphuric acid: no visible action with the solid salt in cold. NaCI0 4 • 1.1 and 218 g t.+ 6H+ -+ 312 + 3H 20 7. CIO. iodine is immediately liberated (use the chloroform or carbon tetrachloride test). -i-Na" .000. barium iodate.096 g t . To study these reactions use a 2M solution of perchloric acid or solid sodium perchlorate. Hypophosphorous acid-starch solution test Iodates are reduced by hypophosphorous acid eventually to iodides. Place a drop of the neutral test solution on a spot plate and mix it with a drop of starch solution (for preparation. gives the periodate (more precisely. see under Iodides.000.22 QUALITATIVE INORGANIC ANALYSIS acid solution. and sodium perchlorate is one of the most soluble (2. Solubility The perchlorates are generally soluble in water.+ H+ + 2H 20 312 + 5HCNj + 5S0i- Treat a piece of starch paper successively with a drop of O'IM potassium thiocyanate solution and a drop of the acid test solution. Section IV.

insoluble in alcohol (see Section 111.B02" The boratesarederived from the three boric acids: orthoboric acid. +NH! -+ -+ KCI0 4! NH 4Cl04! 3.. BO~- B40~. at 140°pyroboric acid is produced.REACTIONS OF ANIONS IV. hydrogen sulphide. 5. per- chlorates are reduced to chlorides: CIO. or iron(1I) salts: no reduction (difference from chlorate). 343 Solubility . it is converted into metaboric acid. the soluble salts are hydrolysed in solution and therefore react alkaline. + [Cd(NH 3)4]2+ -+ [Cd(NH 3)4](CI04)2! Sulphides interfere by precipitating cadmium as cadmium sulphide. HB0 2 • Orthoboric acid is a white. +8Ti3+ +8H+ -+ Cl. 8.14): NaCI0 4 -+ NaCl+20 2 t IV. Sulphur dioxide. crystalline solid.BO~-. a white crystalline precipitate oftetramminecadmium perchlorate is obtained: 2CIO. H 2B 40 7 . H 3B0 3 . Barium chloride solution: no precipitate. Titanium(III) sulphate solution: in the presence of sulphuric acid. Potassium chloride solution: white precipitate of KCI0 4. On heating orthoboric acid at 100°. 4. very few salts of this acid are definitely known. A similar result is obtained with silver nitrate solution. and metaboric acid. Ammonium chloride solution gives a similar reaction: CIO. Indigo test: no decolourization even in the presence of acid (difference from hypochlorite and chlorate).23 2. 7. pyroboric acid. reaction 3).B40~:. Owing to the weakness of boric acid. +K+ CIO:.36.14). and in the residue chloride ions can be tested (see Section IV. Most of the salts are derived from the metaand pyro-acids. Action ofheat: oxygen is evolved from a solid perchlorate.23 BORATES. and should therefore be absent. Tetramminecadmium perchlorate test When a neutral solution of perchlorate is treated with a saturated solution of cadmium sulphate in concentrated ammonia solution. 6.+8Ti 4+ +4H 20 Chloride ions can be identified in the solution with the usual tests (see Section IV. sparingly soluble in cold but more soluble in hot water.+ + 3H 20 +:t H 3B0 3 + 30H7H 20 +:t 4H 3B0 3 +20HB0 2 + 2H 20 +:t H 3B0 3 + OHThe borates of the alkali metals are readily soluble in water.

and the alcohol ignited. The methyl borate is distilled off and passed into an aqueous solution containing potassium fluoride. manganese(lI) nitrate.-. reaction 9): Mn2+ + 2Ag+ + 40H. For very small amounts of borate it is best to add a few drops of benzidine acetate solution and thus to detect the traces of manganese dioxide by the . although orthoboric acid. and silver nitrate. these do not form volatile compounds under the experimental conditions given below. however. Concentrated sulphuric acid and alcohol (flame test) If a little borax is mixed with I ml concentrated sulphuric acid and 5 ml methanol or ethanol (the former is to be preferred owing to its greater volatility) in a small porcelain basin. 4H 3B0 3 i+2Na+ +SOiNa 2B407 +2HCI+5H 20 -. is set free.+ 7H 20 The reaction may be adapted as a spot test in the following manner. stopper the apparatus. 1. On heating. or upon the end of a glass rod. H 3B0 3 + 3CH 30H -. Thoroughly mix the borate with powdered calcium fluoride and a little concentrated sulphuric acid. Mn02! + 2Ag! + 2H 20 Place a drop of the alkaline test solution in the distillation apparatus of Fig. 11. Copper and barium salts may give a similar green flame. due to the formation of methyl borate B(OCH 3 h or of ethyl borate B(OC 2Hsh. Concentrated sulphuric acid: no visible action in the cold. but fairly soluble in acids and in ammonium chloride solution. Both these esters are poisonous. white fumes of boric acid are evolved. The ester is hydrolysed by the water to boric acid: B(OCH 3 h i + 3H 20 -. borax) Na2B407.38. If concentrated hydrochloric acid is added to a concentrated solution of borax.r 344 .23 QUALITATIVE INORGANIC ANALYSIS The borates of the other metals are. the latter will bum with a green-edge flame. Add 5 drops concentrated sulphuric acid and 5 drops pure methanol. Section 111. The following modification of the test. B(OCH 3 h i + 3H 20 Na2B407 +6CaF 2 + 7H 2S04 -.IOH20. boric acid is precipitated: Na 2B407+ H 2S0 4 +5H 20 -. H 3B0 3 . 4H 3B0 3! +2Na+ +2CI2.-. Collect the methyl borate which distils over in a micro porcelain crucible. H 3B0 3 + 3CH 30H The boric acid reacts with the alkali fluoride forming a borofluoride and liberating free caustic alkali: H 3B0 3 + 4F. and bring a little of the paste thus formed on the loop of a platinum wire. the free caustic alkali is identified by the formation of a black precipitate with manganese(lI) nitrate-silver nitrate solution (see under Ammonium. To study these reactions use a O'IM solution of sodium tetraborate (sodium pyroborate. A black precipitate forms.IV. very close to the edge of the base of a Bunsen flame without actually touching it. which depends upon the greater volatility of boron trifluoride.. waxed on the inside.59 and evaporate to dryness. BF 3' can be used in the presence of copper and barium compounds. in general. and heat to 80°C in a water bath. [BF + 30H. 4BF 3 l +6CaS04 +2Na+ + SOi. volatile boron trifluoride is formed and colours the flame green. sparingly soluble in water. and containing about I ml reagent.

a white precipitate will form which on heating becomes grey and black. 4. and other oxidizing agents interfere because of their bleaching action on the turmeric.2. it becomes bluish-black or greenish-black. Chromates. Action ofheat Powdered borax when heated in an ignition tube. Treat the filtrate with a solution of 3'5 g potassium fluoride in 50 ml water. This is the basis of the borax bead test for various metals (see Section 11. A brown precipitate of silver oxide is produced directly in very dilute solutions. and boiling the water for 2-3 minutes. B40~- +2Ba2+ + H 20 -+ 2Ba(B0 2h! +2H+ 6. and then subsides. Barium chloride solution: white precipitate of barium metaborate. nitrites. soluble in both dilute ammonia solution and in acetic acid. p-Nitrobenzene-azo-chromotropic acid" reagent 'N H03S~S03H = N (O-Q-N -AA ): * Alternative names are: p-nitrobenzene-azo-I : 8-dihydroxynaphthalene-3 : 6-disulphonic acid and 'Chromotrope 2B' (the latter is the sodium salt). reaction 5). The reagent (a manganese(II) nitrate-silver nitrate solution containing potassium fluoride) is prepared as follows. Solutions of calcium and strontium chloride behave similarly. it becomes reddish-brown. 7. formed in this reaction.000.REACTIONS OF ANIONS IV. (DANGER: THE REAGENT IS CARCINOGENIC. chlorates. Concentration limit: I in 5. 345 .23 resulting blue colour. Dissolve 2'87 g manganese(II) nitrate and 1'69 g silver nitrate in 100 ml water. The glass possesses the property of dissolving many oxides on heating. AgB0 2. 3. On moistening the paper with dilute sodium hydroxide solution. swells up considerably. which often have characteristic colours. leaving a colourless glass of the anhydrous salt. or upon a platinum wire. and use the clear solution as the reagent.) Sensitivity: 0'0 I ug B. it is completely hydrolysed and a brown precipitate of silver oxide is obtained. is practically undissociated. 2AgB0 2! + 3H 20 -+ B40~-+4Ag++H20 -+ 5. 4AgB0 2!+2H+ Ag 20! + 2H 3B0 3 The boric acid. in dilute acids. from fairly concentrated borax solution. Turmeric paper test If a piece of turmeric paper is dipped into a solution of a borate acidified with dilute hydrochloric acid and then dried at 100°. The drying of the paper is most simply carried out by winding it on the outside near the rim of a test-tube containing water. On boiling the precipitate with water. Silver nitrate solution: white precipitate of silver metaborate. the precipitate is soluble in excess reagent. iodides. Ba(B0 2b from fairly concentrated solutions. Boil.000. forming metaborates. add a drop of dilute alkali and filter the solution from the black precipitate. and in solutions of ammonium salts. filter.

000. Concentration limit: I in 500. are rendered innocuous by evaporating with solid hydrazine sulphate. The reagent (a 10 per cent aqueous solution of mannitol) may also be neutralized with O'OIM potassium hydroxide solution. glycerol. bromothymol blue (green).1 °). Place a few drops of the test solution in a micro test-tube. SOi346 Solubility The sulphates of barium. = 5'8 x 10. it is transformed into a relatively strong acid. the latter because of the formation of borofluorides. Mannitol-bromothymol blue test Boric acid acts as a very weak monobasic aid (K. IV. 0'5 ug B in the presence of 2. A greenish-blue colouration is obtained on cooling. using bromothymol blue (a 0'04 per cent solution in 96 per cent ethanol) as indicator.000 times that amount of KCI0 3 or KN0 3 . Concentration limit: I in 30. such as mannitol (mannite). Evaporate a drop of the slightly alkaline solution to dryness in a semimicro crucible. Render the test solution almost neutral to bromothymol blue by treating it with dilute acid or alkali (as necessary) until the indicator turns green. whilst fluorides may be removed as silicon tetrafluoride by evaporation with silicic acid and sulphuric acid.500 times that amount of NaF. . A blank test should be performed simultaneously. Oxidizing agents and fluorides interfere. and heat cautiously until fumes of sulphuric acid appear. A yellow colouration is obtained in the presence of a borate.IV. including nitrates and chlorates. Sensitivity: 0'1 ug B. 8. Only periodate interferes with the test: it can be decomposed by heating on charcoal. then upon the addition of mannitol the colour becomes yellow. B-OH= + HO / The pH of the solution therefore decreases. and add a few drops of the reagent solution. but on the addition of certain organic polyhydroxy compounds. Treat 2 drops of the test solution in a small porcelain crucible either with a little solid hydrazine sulphate or with a few specks of precipitated silica and 1-2 drops concentrated sulphuric acid. Add 3-4 drops of the reagent whilst the residue is still warm and observe the colour on cooling.24 SULPHATES. strontium. probably of the type: -C-OH I HO -C-OH l I -. Oxidizing agents.24 QUALITATIVE INORGANIC ANALYSIS Borates cause the blue-violet reagent to assume a greenish-blue colour. It is advisable when testing for minute quantities of borates to recrystallize the mannitol from a solution neutralized to bromothymol blue. It is advisable to carry out a blank test with distilled water simultaneously. The reagent consists of a 0·005 per cent solution of Chromotrope 2B in concentrated sulphuric acid. Hence if the solution is initially almost neutral to. Stir the warm residue with 2-3 drops of the reagent. The experimental details are as follows. dextrose or invert sugar. say.000. wash with pure acetone and dry at 1000. Sensitivity: 0'25 ug B in the presence of 12.000. Sensitivity: 0'00 I ug B.

oily. consists of placing the fusion product on a silver coin and moistening with a little water. To study these reactions use a O'IM solution of sodium sulphate. as a precipitate of barium chloride or of barium nitrate may form.REACTIONS OF ANIONS IV. reactions 6 and 7). a black stain of lead sulphide is produced on the paper. are also insoluble in water.31).6. The so-called Hepar reaction. SO~- + Ba2+ -+ BaS04! The test is usually carried out by adding the reagent to the solution acidified with dilute hydrochloric acid. dissolving the melt in water. Section IV. 347 . concentrated hydrochloric acid.+4Ag+0 +2H 2S 2 20 -+ 2Ag 2S! +40HA more efficient method for decomposing most sulphur compounds is to heat them with sodium or potassium. BaS04 (see under Barium. the acid should always be poured in a thin stream into the water (if the water is poured into the heavier acid. carbonates. of specific gravity 1'838. a brownish-black stain of silver sulphide results. on mixing the two. An alternative method is to add a few drops of very dilute hydrochloric acid to the fused mass. but these dissolve in dilute hydrochloric or nitric acid. Na 2S04·lOH 20. It is miscible with water in all proportions with the evolution of considerable heat. that of strontium is the most soluble. Section IV. but moderately soluble in boiling. Sulphuric acid is a colourless. bismuth. when a transient. The reader is warned that the above tests (depending upon the formation of a sulphide) are not exclusive to sulphates but are given by most sulphur com- * Of these three sulphates. The pure. Barium chloride solution: white precipitate of barium sulphate. 1. commercial. Some basic sulphates such as those of mercury. sulphites. purple colouration is obtained (see under Sulphides. concentrated acid is a constant boiling point mixture. reaction 5). Concentrated hydrochloric acid or concentrated nitric acid should not be used. and to cover the latter with lead acetate paper. The latter may be extracted with water. when sodium sulphide will be formed. 98 per cent of acid. The test is rendered sensitive by heating the substance with potassium in an ignition tube. steam may be suddenly generated which willcarry with it some of the acid and may therefore cause considerable damage). and chromium. and most of the remaining metallic sulphates are soluble. and the extract filtered into a freshly prepared solution of sodium nitroprusside.24 and lead are practically insoluble in water: those of calcium and mercury(II) are slightly soluble. boiling point 3380 and containing c. these dissolve. BaS04 +4C+Na2C03 -+ Na 2S+BaC03+4COj Na 2S -+ 2Na+ +S22. which is less sensitive than the above two tests. insoluble in warm dilute hydrochloric acid and in dilute nitric acid. and testing for sulphide by the nitroprusside or methylene blue reactions (see under Sulphides. upon dilution with water.6. however. and phosphates are not precipitated under these conditions. and then test the solution of the product for sulphide. The barium sulphate precipitate may be filtered from the hot solution and fused on charcoal with sodium carbonate. and hygroscopic liquid. Section 111.

reaction 6). given even by suspensions of barium or lead sulphates. SO~- +2Ag+ -+ Ag 2S04! 4. Place a drop of barium chloride solution upon filter or drop-reaction paper. Lead acetate solution: white precipitate of lead sulphate.4. Section 111. reaction 5). thus rendering the pink barium sulphate clearly visible in the colourless solution.24 QUALITATIVE INORGANIC ANALYSIS pounds. yellow lead chromate is precipitated (see under Lead. 348 . If any of the aqueous solutions of the precipitate are acidified with acetic acid and potassium chromate solution added. from concentrated solutions. Sensitivity: 4 ug SO~-. however. Place 3 drops test solution in a semimicro centrifuge tube. Sulphates and sulphuric acid cause immediate decolourization because of the formation of insoluble barium sulphate. This test is specific for sulphates. Mercury (II) nitrate solution: yellow precipitate of basic mercury(II) sulphate: SO~- +3Hg2+ +2H 20 -+ HgS0 4.1 at 18°). 5. Potassium permanganate-barium sulphate test If barium sulphate is precipitated in a solution containing potassium permanganate. Sodium rhodizonate test Barium salts yield a reddish-brown precipitate with sodium rhodizonate (see under Barium. In the last case sodium tetrahydroxoplumbate(II) is formed.4. then the reaction may be employed as a confirmatory test for sulphates. Treat the reddish-brown spot with a drop of the acid or alkaline test solution. reaction 7). soluble in hot concentrated sulphuric acid. the barium sulphate precipitated in the presence of hydrochloric acid is employed. it is coloured pink (violet) by adsorption of some of the permanganate. Silver nitrate solution: white. Sensitivity: 2'5 ug SO~-. The coloured spot disappears.000. add 2 drops 0'02M potassium permanganate solution and I drop barium chloride solution. the excess of potassium permanganate in the mother liquor reacts readily with reducing agents. Section 111. and in sodium hydroxide solution. A pink precipitate is obtained. Add a few drops 3 per cent hydrogen peroxide solution or 0'5M oxalic acid solution (in the latter case it will be necessary to warm on a water bath until decolourization is complete). 6. Concentration limit: I in 20. the lead crystallizes out as the chloride. PbS0 4 . Ag 2S04 (solubility 5'8 g t. SO~- + Pb2+ -+ PbS0 4! 3. 2. Concentration limit: I in 10. The coloured precipitate is clearly visible.000. The permanganate which has been adsorbed on the precipitate cannot be reduced by the common reducing agents (including hydrogen peroxide). Centrifuge.2HgO!+4H+ This is a sensitive test. in solutions of ammonium acetate and of ammonium tartrate (see under Lead. Section 111. If.31. crystalline precipitate of silver sulphate.IV. and on acidification with hydrochloric acid. followed by a drop of a freshly prepared 0'5 per cent aqueous solution of sodium rhodizonate.

acts catalytically leading to the evolution of nitrogen and the liberation of considerable heat. A similar result is obtained with dilute sulphuric or nitric acid. which may be detected by its odour or by its property of turning starch-iodide paper blue. Barium chloride solution: no immediate precipitate in the cold with a solution of a pure peroxodisulphate.25 PEROXODISULPHATES. chlorine is evolved (see reaction 4 below). those of sodium. hexacyanoferrate(lI) and (Ill) ions interfere with the reaction. With dilute hydrochloric acid. on standing for some time or on boiling.Solubility The best known peroxodisulphates. Ag 202. 4.H2S04+2CI- Chromates. which liberate iodine immediately). ammonium. Potassium iodide solution: iodine is slowly liberated in the cold and rapidly on warming (test with starch solution) (distinction from perborate and percarbonate. 2S20~. Traces of copper catalyse the reaction. H 2SOS ' is formed in solution. (17'7 g t. oxalates. (DANGER: THE REAGENT IS CARCINOGENIC. free sulphuric acid. due to the decomposition of the peroxodisulphate. By dissolving the solid peroxodisulphate in concentrated sulphuric acid at 0°.+2H 20 -+ 4S0~. 1. S20~-+2Ag++2H20 I Ag202!+2S0~-+4H+ 3S20~-+8NH3 (Ag+) I N2i+6S0~-+6NH! 3. IV.REACTIONS OF ANIONS IV. the silver peroxide. S20~- + 21- -+ 12 + 2S0~349 .) --. Water All peroxodisulphates are decomposed on boiling with water into the sulphate.+4H+ +02i 2S20~. from concentrated solutions. Silver nitrate solution: black precipitate of silver peroxide.25 7. or the silver ion. this possesses strong oxidizing properties. and barium are soluble in water. H2ND--ONH2. the potassium salt being the least soluble. peroxomonosulphuric acid (Caro's acid). and oxygen. To study these reactions use a freshly prepared O'IM solution of ammonium peroxodisulphate (NH4hS20s. If only a little silver nitrate solution is added followed by dilute ammonia solution. The oxygen contains appreciable quantities of ozone.+3H 20 0 3t +2r +2H+ -+ 4S0~.+6H+ -+ +0 3i 12 +02i +H 20 2. S20~. potassium.1 at O°C). a precipitate of barium sulphate is obtained. Benzidine hydrochloride solution: white precipitate of benzidine sulphate.

+ 16H+ Silver ions act as catalysts (cf.000. particularly on boiling. reaction 6). and hydrogen peroxide do not react.The silicic acids may be represented by the general formula xSi0 2 . The metasilicates are sometimes designated simply as silicates. permanganate ions are formed on warming. Mix I drop of the test solution (neutral or faintly acid with acetic acid) with I drop of the benzidine acetate reagent. The reagent consists of a 0'05 per cent solution of benzidine in dilute acetic acid. Manganese (Il) sulphate solution: brown precipitate in neutral or preferably alkaline solution. no precipitation of silicic acid takes place. Na 2Si0 3 • Commercial (30 %) water-glass solutions should be diluted with a five-fold amount of water. Concentration limit: I in 100. The precipitate is manganese(lV) dioxide hydrate with a composition nearest to Mn02.26 QUALITATIVE INORGANIC ANALYSIS 5.H 20) are definitely known. 6. Sensitivity: I ug S20~-. hexacyanoferrate(III) ions. The freshly precipitated substance is appreciably soluble in water and in dilute acids. Peroxodisulphates are also unaffected by a solution of titanium(IV) sulphate. permanganates. 7.26 SILICATES.y H 20. Potassium permanganate solution: unaffected (distinction from hydrogen peroxide). a gelatinous precipitate of metasilicic acid is obtained. It is converted by repeated evaporation with concentrated hydrochloric acid on the water bath into a white insoluble powder (silica. Salts corresponding to orthosilicic acid. + lOSO~. (Si0 2. SiO~SiO~- +2H+ -+ H 2Si0 3! 350 . H 2Si0 3 (Si0 2.28.IV. Benzidine acetate test (DANGER: THE REAGENT IS CARCINOGENIC) A neutral or weakly acetic acid solution of a peroxodisulphate converts benzidine into a blue oxidation product. l-lO per cent) of water glass is quickly added to moderately concentrated hydrochloric acid. SiO~. Section 111. The precipitate is insoluble in concentrated acids. percarbonates. Solubility Only the silicates of the alkali metals are soluble in water.H20!+2SO~-+H20 In the presence of nitric or sulphuric acid and small amounts of silver nitrate. A blue colouration is produced. H 4Si04 . S20~-+Mn2++40H--+ Mn02. Perborates. Chromates.2H 20) metasilicic acid.H 20). Si0 2).H20. and hypohalites react similarly to peroxodisulphates. If a dilute solution (say. and the solution turns to violet: 5S20~- +2Mn2+ +8H 20 -+ 2MnO. 1. +2H 20 +:t H 2Si0 3+20HTo study these reactions use a M solution of sodium silicate. Dilute hydrochloric acid Add dilute hydrochloric acid to the solution of the silicate. it remains in colloidal solution (sol). and disilicic acid H 2Si20s (2Si0 2. IV. they are hydrolysed in aqueous solution and therefore react alkaline.

Si0 2 + Na 2C03 -+ CO 2i + Na2Si03 SiO~. Barium chloride solution: white precipitate of barium silicate. A simpler. This reaction is important in routine qualitative analysis since silicates. Na(NH 4)HP04. 3. will be precipitated by ammonium chloride solution in Group IlIA. SiO~. SiO~- 5. and also silica. white. 351 . unless previously removed. when a minute quantity of the solid silicate or even of the solution is introduced into the bead (best by dipping the hot bead into the substance) and the whole again heated. Ammonium chloride or ammonium carbonate solution: gelatinous precipitate of silicic acid. the silica produced will not dissolve in the bead. amorphous silica. ultimately.26 2. and is visible as white opaque masses or 'skeletons' in both the fused and the cold bead. Silver nitrate solution: yellow precipitate of silver silicate. but not quantitative. method is to extract the fusion mixture melt with boiling water: sufficient sodium or potassium silicate passes into solution to give any of the reactions referred to above. 6). whilst the metallic oxides derived from the insoluble silicate are converted into chlorides.REACTIONS OF ANIONS IV. the alkali carbonates react with the silicate yielding an alkali silicate. soluble in dilute acids and in ammonia solution: SiO~- +2Ag+ -+ Ag 2Si0 3! 4. This reaction is essentially an acid-base process.+2NHt -+ H 2Si0 3! +2NH 3 Base! + Acid. in a loop of platinum wire give this test. The cold mass is then evaporated to dryness on the water bath with excess dilute hydrochloric acid. The residue is extracted with boiling dilute hydrochloric acid.23).2. when fused in a bead of microcosmic salt. the alkali silicate is thereby decomposed yielding first gelatinous silicic acid and.+ 2H+ -+ Si0 2! + H 20 * A nickel or iron crucible should be used if metals of Group I or II are likely to be present. but will swim about in the fused mass. Microcosmic salt bead test Most silicates. which is most conveniently explained in terms of the Brensted-Lowry theory of acids and bases (see Section 1. The microcosmic salt first fuses to a transparent bead consisting largely of sodium metaphosphate (see Section 11. mixed with six times its weight of fusion mixture. -+ Acid! + Base. CaSi0 3 + NaP0 3 -+ CaNaP04 + Si0 2 Insoluble silicates are best brought into solution by fusing the powdered solid. + Ba2+ -+ BaSi0 3! Calcium chloride solution gives a similar precipitate of calcium silicate. in a platinum crucible* or upon platinum foil. soluble in dilute nitric acid. this removes the metals as chlorides and insoluble silica remains behind.4H 20.

Silicon tetrafluoride test This test depends upon the fact that when silica (isolated from a silicate by treatment with ammonium chloride solution or with hydrochloric acid. Concentration limit: I in SO. add a drop of the benzidine reagent followed by a drop of saturated sodium acetate solution. warm gently. Concentration limit: I in SOO. The test depends upon the reaction between silicomolybdic acid and benzidine in acetic acid solution whereby 'molybdenum blue' and a blue quinonoid oxidation compound of benzidine are produced. Add a drop ofO'OS per cent benzidine acetate and hold the paper over ammonia vapour. Sensitivity: I ug Si0 2. A better method for conducting the test is the following. Place a drop of the slightly acid test solution (the acidity should not exceed O'SM) in a small porcelain crucible of good quality. Warm cautiously over a wire gauze (or upon a sheet of asbestos resting upon a hot plate) until bubbles escape. due to the hydrolysis of the silicon tetrafluoride absorbed. is soluble in water and acids to give a yellow solution. silicic acid isolated by treatment of the silicate with ammonium chloride solution) with one-third of its weight of calcium fluoride in a small lead (or platinum) capsule.) is heated with less than an equivalent amount of calcium fluoride and some concentrated sulphuric acid. Mix the solid substance (or. In the presence of phosphoric acid. It is essential to carry out a blank test with a drop of water and a drop of the molybdate reagent in another crucible of similar quality. Phosphoric and arsenic acids form compounds analogous to silicomolybdic acid which also react with benzidine with colour formation hence these acids should be removed before applying the test. Cool. preferably. Warm gently (FUME CUPBOARD) and hold close above the mixture a loop of platinum wire supporting a drop of water. A blue colour is obtained. then introduce a drop 352 .26 QUALITATIVE INORGANIC ANALYSIS 6. etc. A blue colouration results. the test is carried out as follows. Ammonium molybdate-benzidine test (DANGER: THE REAGENT IS CARCINOGENIC. Mix a drop of the test solution with 2 drops of the molybdate reagent in a micro centrifuge tube and centrifuge the mixture. The latter is identified by its action upon a drop of water held in a loop of platinum wire. Sensitivity: 0'1 ug Si0 2. unlike the analogous phosphoric acid and arsenic acid compounds.IV.OOO. silicon tetrafluoride is evolved. The ammonium salt. when a turbidity (due to silica) is produced. Place a drop of the test solution and of the molybdate reagent upon dropreaction paper.) Silicates react with molybdates in acid solution to form the complex silicomolybdic acid H4[SiMo1204o]. Transfer the supematant liquid to a micro crucible by means of a capillary tube. cool and add 2 drops O'SM oxalic acid solution (the latter decomposes the small quantity of residual phosphomolybdate (NH4h[PMo1204o] but has little action on the silicomolybdic acid complex).OOO. Si0 2+2CaF2+2H2S04 -+ 2CaS0 4+SiF4i+2H20. 3SiF 4i+2H20 -+ Si0 2!+2[SiF 6]2.+4H+ Excess of calcium fluoride should be avoided since a mixture of H 2F2 and SiF 4 will be formed and interfere with the test. and add a drop of the molybdate reagent. 7. The drop of water will become turbid. and warm gently over a wire gauze. and add sufficient concentrated sulphuric acid to form a thin paste: mix the contents of the capsule with a stout platinum wire.

H 2[SiF 6 ] +2H 20 To study these reactions use a freshly prepared O'IM solution of sodium hexafluorosilicate. add a little sodium fluoride and a few drops of concentrated sulphuric acid. Then add a few drops 0'25M tin(II) chloride followed by sufficient sodium hydroxide solution to dissolve the tin(II) hydroxide. 8. the escaping gas will etch glass and will cause a drop of water to become turbid (see under Silicates. A solution of the acid (hydrofluosilicic acid H 2[SiF 6]) is one of the products of the action of water upon silicon tetrafluoride. IV.REACTIONS OF ANIONS IV. but phosphates and arsenates must be absent. reaction 6).R.26. and is also formed by dissolving silica in hydrofluoric acid. add 2 drops ammonium molybdate reagent and then 2M acetic acid until feebly acidic. are soluble in water. Na2[SiF 6] + H 2S04 -+ SiF 4l + H 2F 2l + 2Na + + SO~2.27 HEXAFLUOROSILICATES (SILICOFLUORIDES). A blue colour forms. Cover the crucible with a small sheet of cellophane from which is suspended a drop of 2M sodium hydroxide solution (freshly prepared from the A.27 of the benzidine reagent and 2-3 drops of saturated sodium acetate solution. solid). Concentration limit: I in 10. crystalline precipitate of barium hexafluorosilicate. The reaction may be applied to aqueous solutions of silicates. but may be removed by warming with methanol and sulphuric acid. A blue colouration is obtained. Sensitivity: 6 ug Si0 2 in the presence of 250 times that amount of P 205' Concentration limit: I in 8. -+ Si0 2 +6HF 1.000. Phosphates and arsenates give the same reaction. Ba[SiF 6]' sparingly soluble in water (0'25 g r 1 at 25°) and insoluble in dilute hydrochloric acid. Ammonium molybdate-tin (II) chloride test The silicate is separated by volatilization as silicon tetrafluoride and the latter collected in a little sodium hydroxide solution. but do not interfere under the conditions of the test: large amounts of borates should be absent. H4[SiMo1204o]. Section IV. The resulting silicate is treated with ammonium molybdate solution and the ammonium salt of silicomolybdic acid. Place a little of the solid silicate in a small lead or platinum crucible. Transfer the drop of sodium hydroxide solution to a porcelain micro crucible. If the reaction is carried out in a platinum or lead capsule or crucible. Barium chloride solution: white. [SiF 6]2Solubility Most metallic hexafluorosilicates (with the exception of the barium and potassium salts which are sparingly soluble). Tin(II) chloride does not reduce ammonium molybdate solution. is reduced by tin(II) chloride solution to 'molybdenum blue'. Concentrated sulphuric acid: silicon tetrafluoride and hydrogen fluoride are evolved on warming the reagent with the solid salt.000. Warm gently for 3-5 minutes over a micro burner with the crucible about 8 cm from the flame. The precipitate is distinguished from 353 .

IV. with the exception of lithium.12H 20. the primary phosphates of the alkaline earth metals are also soluble. The precipitate is slightly soluble in water (1'77 g t. secondary orthophosphates.+2K+ -+ K 2[SiF 6]! 4. Na 2HP04 is neutral to phenolphthalein and alkaline to methyl orange. pyrophosphoric. e.g. which can be tested for in the usual manner (see under Fluorides.28 QUALITATIVE INORGANIC ANALYSIS barium sulphate by the evolution of hydrogen fluoride and silicon fluoride.* solutions of pyro. Na 2[SiF 6 ] -+ SiF 4t +2Na+ +2F- IV.28 ORTHOPHOSPHATES. from concentrated solutions. on heating with concentrated sulphuric acid in a lead crucible. and tertiary orthophosphates.12H20. NaH 2P04. and the metallic fluoride.+4NHt 5.+Ba2+ -+ Ba[SiF 6]! 3. Na 3P04 is alkaline to most indicators because of its extended hydrolysis. e.+4NH 3 +3H 20 -+ H 2Si0 3!+6F.and metaphosphates pass into orthophosphates slowly at the ordinary temperature. Metaphosphates. and more rapidly on boiling. K 2[SiF 6 ] . To study these reactions use a 0·033M solution of disodium hydrogen phosphate Na2HP04. Potassium chloride solution: white. gelatinous precipitate of potassium hexafluorosilicate. * They are often referred 354 to simply as phosphates. unless prepared by special methods. Ammonia solution: decomposition occurs with the separation of gelatinous silicic acid. Action of heat: decomposition occurs into silicon tetrafluoride. Le. H 3P0 4. the solution will react neutral when the secondary phosphate is formed. and of ammonium are soluble in water. with phenolphthalein as indicator.1 at 25°). and metaphosphoric acid. H 4P20 7 . and also the secondary and tertiary phosphates of the alkaline earth metals are sparingly soluble or insoluble in water. which renders a drop of water turbid. NaH 2P04 is neutral to methyl orange and acid to phenolphthalein. are usually polymeric. Na 2HP04. e. [SiF 6]2. HP0 3 • Salts of the three acids exist: the orthophosphates are the most stable and the most important. [SiF 6]2. Solubility The phosphates of the alkali metals. are derived from (HP0 3 )n' Orthophosphoric acid is a tribasic acid giving rise to three series of salts: primary orthophosphates. the tertiary or normal phosphate is formed. Section IV. with 3 moles of alkali. . Ordinary 'sodium phosphate' is disodium hydrogen phosphate.g.Three phosphoric acids are known: orthophosphoric. [SiF 6]2. All the phosphates of the other metals. which etch glass. If a solution of orthophosphoric acid is neutralized with sodium hydroxide solution using methyl orange as indicator. less soluble in excess of the reagent and in 50 per cent alcohol). Na 3P0 4. POl.I7). the neutral point is reached when the acid is converted into the primary phosphate.g. Na 2HP04.

Precipitation is accelerated by warming to a temperature not exceeding 40°. amorphous precipitate of secondary barium phosphate.+3Ba2+ +2NH 3 -+ Ba 3(P04h! +2NHt 3. In the presence of dilute ammonia solution. They are most simply distinguished from one another by treating the washed precipitate with silver nitrate solution containing a few drops of dilute acetic acid: the phosphate turns yellow (Ag 3P04) whilst the arsenate assumes a brownish-red colour (Ag 3As04). The precipitate is soluble in ammonia solution and in solutions of caustic alkalis. and a little aqueous NH 3 . The magnesium nitrate reagent is generally preferred since it may be employed in any subsequent test with silver nitrate solution. reaction 5.REACTIONS OF ANIONS IV. BaHP0 4.+ Ba2+ -+ BaHP0 4! 2HPOi. Mg(NH 4)P04. Silver nitrate solution: yellow precipitate of normal silver orthophosphate. Reducing agents. HPOi. Ba 3(P04h.+3Ag+ Ag 3P04!+2H+ Ag 3P04! +6NH 3 -+ -+ -+ Ag 3P0 4!+H+ H 2PO.28 1. Section 111.6H20.+Mg2+ +NH 3 -+ MgNH 4P04! Arsenates give a similar precipitate Mg(NH 4)As04. 4. reaction 3). crystalline precipitate of ammonium phosphomolybdate.13. crystalline precipitate of magnesium ammonium phosphate. Section 111. 6H 20 with either reagent. The correct formula is (NH4h[PMoI2040] or (NH 4h[P(M0 30 10)4]' the M0 30 lO group replacing each oxygen atom in phosphate.NH4CI.13. Ammonium molybdate reagent The addition of a large excess (2-3 ml) of this reagent to a small volume (0'5 ml) of a phosphate solution produces a yellow. is produced: this precipitate is soluble in acetic acid and in mineral acids. Section 111. hexacyanoferrate(II)s. and tartrates. also under Arsenic(V). to which the formula (NH 4hP04. seriously affect the reaction. soluble in dilute mineral acids and in acetic acid. Large quantities of hydrochloric acid interfere with the test and should preferably be removed by evaporation to a small volume with excess concentrated nitric acid. Magnesium nitrate reagent or magnesia mixture The former is a solution containing Mg(N0 3 b NH 4N0 3 . and should be destroyed before carrying out the test. HPOi. 12Mo0 3 was formerly assigned. is precipitated. and a little aqueous NH 3 . Both ammonium phosphomolybdate and ammonium 355 . from neutral solutions.35. sulphites. soluble in dilute ammonia solution and in dilute nitric acid. such as sulphides. +3Ag+ 3[Ag(NH 3 h r +POl- 2. The resulting solution should be strongly acid with nitric acid. Barium chloride solution: white. and by the addition of ammonium nitrate solution. Ag 3P04 (distinction from meta. reaction 4). but practically insoluble in 2'5 per cent ammonia solution (see under Magnesium. Arsenates give a similar reaction on boiling (see under Arsenic. the less soluble tertiary phosphate. With either reagent a white. the latter is usually present in the reagent and addition is therefore unnecessary. and the latter is a solution containing MgCI 2.and pyrophosphate). HPOi.

7. Species like ZrO(H 2P04h and ZrP0 4 may also be formed. Moisten the cold mass with water and observe the unpleasant odour of phosphine. such as ammonium or sodium acetate. but only the latter yields a white precipitate on cooling.23). phosphate. This reaction forms the basis of a simple method for the removal of phosphate prior to the precipitation of Group IlIA (cf. precipitation is almost complete. Na 3P04+4Mg Na 3P + 3H 20 -+ -+ 4MgO+Na 3P. Na(NH)4 HP0 4 -+ NaP0 3 + NH 3 l + H 20. but the ion MoOi. depending on the concentrations of zirconium. and hydrogen ions.28 QUALITATIVE INORGANIC ANALYSIS arsenomolybdate dissolve on boiling with ammonium acetate solution.I3. 5. soluble in dilute mineral acids. Intimately mix a small quantity of sodium phosphate with magnesium powder and heat in an ignition tube. HPOi. 6. NaP0 3+CoO -+ NaCoP0 4 8. The latter is readily identified by the odour and the inflammability of the phosphine formed on the addition of water. 4). Zirconium nitrate reagent When the reagent is added to a solution of a phosphate containing hydrochloric acid not exceeding M in concentration. Cobalt nitrate test Phosphates when heated on charcoal and then moistened with a few drops of cobalt nitrate solution.+23H+ -+ (NH 4h[P(Mo 30 lO)4]! + 12H 20 Note: Commercial ammonium molybdate has the formula (NH4)6Mo7024' 4H 20 (a paramolybdate) and not (NH 4hMo04. This must not be confused with the blue mass produced with aluminium compounds (see Section 111. whereby a phosphide is produced. PH 3 i + 3Na+ + 30H(DANGER: THE REAGENT IS 9. Iron(IIl) chloride solution: yellowish-white precipitate of iron(I1I) phosphate. are removed by the addition of the salt of a weak acid. HPOi. arising from the complete ionization of the mineral acid. in qualitative analysis. Section V. which interfere with the precipitation of Group IlIA metals. If the hydrogen ions. Ammonium molybdate-benzidine test 356 .is employed in the equations for purposes of simplicity.+3NHt + 12MoOi.IV. FeP04.+Zr0 2+ -+ ZrO(HP0 4)! In fact the precipitate is of variable composition.+ Fe3+ -+ FeP0 4! + H+ Precipitation is incomplete owing to the free mineral acid produced. These ions may exist under the experimental conditions of the reaction. This is the basis of one of the methods for the removal of phosphates. Magnesium The only simple method for reducing the stable phosphates consists in heating with magnesium powder. NaCoP0 4. HPOi. give a blue mass of the phosphate. a white gelatinous precipitate of zirconyl phosphate ZrO(HP0 4) is obtained. but insoluble in dilute acetic acid.

Sensitivity: 1'5 ug P 205 in the presence of 500 times that amount of Si0 2. add a drop of the ammonium molybdate reagent. All should be removed before applying the test. followed by a drop of the tartaric acid-ammonium molybdate reagent. Hydrogen peroxide. Then add a drop of the benzidine reagent and develop over ammonia vapour.000. chromates. and silicates give a similar reaction with some variation in the colour of the precipitate. tartrates. the blue reduction product of molybdenum compounds ('molybdenum blue') and the blue oxidation product of benzidine ('benzidine blue'). Arsenates (warming is usually required).000. Place a drop of the test solution upon quantitative filter paper. A yellow precipitate is produced within a few minutes. etc. The tartaric acid-ammonium molybdate reagent is prepared by dissolving 15 g crystallized tartaric acid in 100 ml ammonium molybdate reagent. gentle warming (water bath) is sometimes necessary. However. which is unaffected by normal molybdates and by free molybdic acid. oxalates. The reagent is prepared by dissolving 4'0 g finely powdered ammonium molybdate. wire gauze (or over a sheet of asbestos heated on a hot plate) to accelerate the reaction. solutions of phosphates which are too dilute to show a visible precipitate with the ammonium molybdate reagent will react with the molybdate reagent and benzidine to give a blue colouration. Place a drop of the acid solution under test upon quantitative filter paper. with stirring. Sensitivity: 1'25 ug P 205' Concentration limit: 1 in 40. arsenites. 10. viz. H4[SiMoI2040] or H 4[Si(Mo30 1o)4]' acids respectively.28 CARCINOGENIC. This reaction is extremely sensitive. Moreover. phosphates may be detected in the presence of arsenates and silicates by preventing the formation of the corresponding molybdo-acids by the use of a tartaric acidammonium molybdate reagent which does not react with arsenic and silicic acids but does react with phosphoric acid when the reaction is carried out on filter paper. Ammonium molybdate-quinine sulphate reagent Phosphates give a yellow precipitate with this reagent: the exact composition appears to be unknown. proceed as follows.) interfere since they yield 'molybdenum blue' . Concentration limit: I in 20. A blue stain is formed when most of the mineral acid has been neutralized. hexacyanoferrate(II) ions give a red colouration. Reducing agents (sulphides. a solution of 0'1 g quinine sulphate in 80 ml concentrated nitric acid.4H20 in 20 ml water and adding. Hold the paper over ammonia vapour. H3[AsMoI2040] or H 3[As(Mo30 IO)4]' and silicomolybdic. two coloured products are formed.REACTIONS OF ANIONS IV.000. In the presence of silicates and/ or arsenates.) In this test use is made of the fact that benzidine. oxalates. Place I ml test solution in a semimicro test-tube and add I ml reagent. (NH4)6Mo7024. Concentration limit: I in 50. is oxidized in acetic acid solution by phosphomolybdic acid or by its insoluble ammonium salt (see reaction 4 above). Hold the paper over a hot. followed by a drop of 0'05 per cent benzidine acetate. and fluorides interfere with the precipitation of the phosphomolybdate and should therefore be absent. 357 . Arsenates and silicates with ammonium molybdate yield the ammonium salts of arsenomolybdic. A blue colouration results. thiosulphates. these complex acids and their salts react similarly with benzidine.

. IV. all other metallic phosphites are insoluble in water. Calgon. (HP0 3 )n. HPO~. insoluble in dilute acetic acid. is probably (NaP0 3)6 or Na 2[Na4(P03)6]. White ppt.. Table IV. e. pyro. No ppt.30 PHOSPHITES. 3. soluble in dilute acetic acid. PO:. AND METAPHOSPHATES. used for water softening.g. Cadmium acetate solution and dilute acetic acid. this is doubtless due to their initial conversion in solution into orthophosphates.. Zinc sulphate solution. No ppt. even on boiling. Reactions of ortho-. Na 2H 2P20 7 . White ppt. Metaphosphate White ppt. p 2 ot-. To study these reactions use freshly prepared solutions of sodium pyrophosphate and sodium metaphosphate. No ppt. Sodium metaphosphate (polymeric) may be prepared by heating microcosmic salt or sodium dihydrogen phosphate: Na(NH 4)HP04 NaH 2P04 -+ -+ NaP0 3 + NH 3 j + H 20j NaP0 3 + H 20j A number of metaphosphates are known and these may be regarded as derived from the polymeric acid.. on warming.IV. i.and metaphosphates give the ammonium molybdate test on warming for some time. White ppt..29 PYROPHOSPHATES. polymetaphosphoric acid. The student should carry out all the tests. No coagulation. 358 . soluble in dilute HN0 3 and in dilute NH 3 solution: sparingly soluble in dilute acetic acid.e..and metaphosphates Orthophosphate Yellow ppt. Copper sulphate solution. pyro. soluble in dilute NH 3 solution. Pyrophosphate White ppt. White ppt. 4. 6. soluble in dilute acetic acid. are known. Very pale blue ppt. Silver nitrate solution. soluble in excess of reagent. soluble in dilute HN0 3 . yielding a white ppt. but reprecipitated on boiling. To study these reactions use a freshly prepared O'IM solution of sodium phosphite Na 2HP0 3. 5.. (separates slowly). Sodium pyrophosphate is prepared by heating disodium hydrogen phosphate: 2Na 2HP04 -+ Na 4P20 7+H 20j This is the normal salt. Acid salts. Pyro. Noppt. 2. White ppt. insoluble in excess of the reagent.Solubility The phosphites of the alkali metals are soluble in water. Coagulation. White ppt.5H20.I Reagent I. Pale blue ppt. soluble in dilute HN0 3 and in dilute NH 3 solution. Albumin and dilute acetic acid. No coagulation.and metaphosphates are incorporated in the following table. in dilute NH 3 solution and in dilute acetic acid.. Magnesia mixture or Mg(N0 3 h reagent. The chief differences between ortho-.29/30 QUALATIVE INORGANIC ANALYSIS IV. on boiling.

insoluble in acetic acid. Upon adding the reagent to a warm solution of a phosphite. 4.+ H 20 -+ 2Hg! + H 3P04 + 2CINote that HgCl 2 and H 3P04 are practically undissociated. the silver nitrate paper is stained first yellow and then black. on warming with excess of the phosphite solution. Hypophosphites. which soon passes in the cold into black metallic silver.30 1. Action of heat: inflammable phosphine is evolved. 5. Ag 2HP03.3AgN03!(yellow)+3H+ Ag 3P.REACTIONS OF ANIONS IV.14). HPO~-+3Zn+8H+ -+ PH 3i+3Zn2++3H20 PH 3l +6Ag+ +3N0 3 -+ Ag 3P. Mercury (II) chloride solution: white precipitate of calomel in the cold. 8Na 2HP03 -+ 2PH 3l + 4Na 3P04 + Na4P207 + H 20 359 . Lead acetate solution: white precipitate. HPO~- +Pb2+ -+ 9. CuHP0 3. HPO~- +Cu2+ -+ CuHP0 3! PbHP0 3! 8. Potassium permanganate solution: no action in the cold with a solution acidified with acetic acid. a black precipitate of metallic silver is obtained immediately. Warming is necessary with dilute solutions.+2Ag+ +H 20 HPO~- -+ -+ -+ Ag 2HP03! 2Ag! + H 3P04 2Ag!+ H 3P04 2. BaHP0 3. but on warming sulphur dioxide is evolved. Copper sulphate solution: light-blue precipitate of copper phosphite. Zinc and dilute sulphuric acid Phosphites are reduced by the nascent hydrogen to phosphine.3AgN03! +3H 20 -+ 6Ag!(black)+H 3P03+3H+ +3N0 3 7. metallic mercury is produced.31). PH 3. Section IV. Silver nitrate solution: white precipitate of silver phosphite.+H 20 H 3P03+H2S0 4 -+ S02i+H 3P04+H20 6. Barium chloride solution: white precipitate of barium phosphite. but decolourized on warming. Na2HP03+H2S04 -+ S02i+2Na+ +HPO~. grey. HPO~- + Ba2+ -+ BaHP0 3! 3. HPO~-+2HgCI2+H20 -+ Hg 2CI2!+H 3P04+2CIHg 2C12! + HPO~. the precipitate merely dissolves when it is boiled with acetic acid (cf. Concentrated sulphuric acid: no reaction in the cold with the solid salt. which may be identified as described in the Gutzeit test under Arsenic (Section 111. soluble in dilute acids. and a mixture of phosphates is produced. + 2Ag+ Ag 2HP03+ H 20 HPO~.

IV. To study these reactions use a freshly prepared O'IM solution of sodium hypophosphite NaH 2P02. Potassium permanganate solution: reduced to colourless immediately in the cold.-+ 2H2i+PO~- 8. AgH 2P02. Concentrated sulphuric acid: reduced to sulphur dioxide by the solid salt on warming. Silver nitrate solution: white precipitate of silver hypophosphite. hydrogen being simultaneously evolved. copper(l) hydride is precipitated. but on warming red. Ammonium molybdate solution: reduced to 'molybdenum blue' in solution acidified with dilute sulphuric acid (difference from phosphite). H 2P0 2 +4HgC1 2 +2H 20 -+ 2Hg 2C12! +H 3P04 +3H+ +4CIH 2P0 2 +2Hg 2CI2!+2H20 -+ 4Hg!+ H 3P04 +3H+ +4CI4.3! HYPOPHOSPHITES. 3. H 2P0 2 + Ag" -+ AgH 2P02! 2AgH 2P02!+4H20 -+ 2Ag!+2H 3P04+3H 2i 2. H 2P0 2+20H. which is slowly reduced to silver at the ordinary temperature. 9. metallic mercury . Zinc and dilute sulphuric acid: inflammable phosphine is evolved (see under Phosphites.31 QUALITATIVE INORGANIC ANALYSIS IV. CuH!+HCI-+ CuCI!+H 2 5. Barium chloride solution: no precipitate. reaction 6). + 17H+ -+ 5H 3P04 +4Mn2+ +6H 20 6. 4NaH 2P02 -+ Na 4P 207 + 2PH 3 t + H 20 360 . 7. 10. 1. H 2P0 2 Solubility All hypophosphites are soluble in water.30. Concentrated sodium hydroxide solution: hydrogen gas is evolved and phosphate ions formed on warming. Section IV. 3H 2P0 2 + 4Cu2+ + 6H 20 -+ 4CuH! + 3H 3P04 + 5H+ When heated with concentrated hydrochloric acid. converted by warming into grey. the precipitate decomposes to white copper(I) chloride precipitate and hydrogen gas. Copper sulphate solution: no precipitate in the cold. NaH 2P02+4H2S0 4 -+ 2S0 2i+H 3P04+3H+ +Na+ +2S0i. Action ofheat: phosphine is evolved. but more rapidly on warming. Mercury (1I) chloride solution: white precipitate of calomel in the cold. and a pyrophosphate is produced.+2H 20 Some elementary sulphur may also be formed during the process. 5H 2P0 2 +4MnO. H 20.

see Section 1.13. hr Cr20~. on boiling with water.+2H+ 361 .. precipitation becomes quantitative. 2CrOi. +:t Cr20~. AsO~. AsO~ Section 111. K 2Cr20 7 • 1. the latter yield orange-red aqueous solutions. 2. Le. with a solution of a chromate. i.+H 20 The reactions may also be expressed as: 2CrOi. See under Arsenic.32 ARSENITES.+2Ag+ -+ Ag2Cr20~. Most other metallic chromates are insoluble in water. chromates are converted into dichromates. this passes.33 CHROMATES.28). CrOi. or potassium dichromate. strontium chromate is sparingly soluble. yielding yellow solutions when soluble in water.12 and 111. but is insoluble in acetic acid.e.Themetallic chromates are usually coloured solids. and ammonium dichromates are soluble in water.+H 20 -+ Ag 2Cr20 7! Ag 2Cr04!+CrOi.Cr20~. is formed with a concentrated solution of a dichromate. by hydroxyl ions.+2H+ +:t Cr20~. CrOi. K 2Cr0 4 . precipitation is only partial: Cr20~-+2Ba2++H20 +:t 2BaCr0 4!+2H+ If sodium hydroxide or sodium acetate is added.AND ARSENATES.+ Ba2+ -+ BaCr04! Dichromate ions produce the same precipitate.+H 20 Ag 2Cr04!+4NH 3 -+ 2[Ag(NH 3 +CrOiAg 2Cr04!+2CI.+H 20 or Cr20~- +20H.+:t 2CrOi.. potassium. but as a strong acid is formed. CrOi. Hydrochloric acid converts the precipitate into silver chloride (white). The change is reversed by alkalis. Ag 2Cr20 7 . into the less soluble silver chromate. of hydrogen ions. Silver nitrate solution: brownish-red precipitate of silver chromate. The precipitate is soluble in dilute nitric acid and in ammonia solution. but soluble in dilute mineral acids (for explanation. In the presence of dilute mineral acids. To study these reactions use a O'IM solution of potassium chromate. Barium chloride solution: pale-yellow precipitate of barium chromate. insoluble in water and in acetic acid.REACTIONS OF ANIONS IV.+H 20 Solubility The chromates of the alkali metals and of calcium and magnesium are soluble in water.+2Ag+ -+ Ag 2Cr04! 2Ag 2Cr0 4! +2H+ -+ 4Ag+ +Cr20~.-+ 2AgCI!+CrOiA reddish-brown precipitate of silver dichromate.32/33 IV. BaCr0 4 .ANDDICHROMATES. Sodium. Ag2Cr04 .+2H+ +:t 2HCrO. IV.

With potassium dichromate the reaction is as follows: K 2Cr207 + 14HCI . The blue solution is very unstable and soon decomposes. Section 1. acetic acid reprecipitates lead chromate from such solutions. chromates can be reduced by heating the solid substance with concentrated hydrochloric acid. Section 111.28).. On adding a few strips of filter paper to the mixture and boiling.+CrOi4. and consequently the latter dissolves (cf. PbCr0 4..+ Pb2+ -+ PbCr0 4! 2PbCr04! +2H+ +::t 2Pb2+ +Cr20~. Lead acetate solution: yellow precipitate of lead chromate. a deep-blue solution of chromium pentoxide is obtained (cf.24.. The solubility in sodium hydroxide solution is due to the formation of the soluble complex tetrahydroxoplumbate(II) ion. The chromium pentoxide is more stable below OOC than at laboratory temperature. PbCr04! +40H. then I ml of lO-volume (3 per cent) hydrogen peroxide solution dropwise and with shaking after each addition: the organic layer is coloured blue. is due to the formation of complexes with these oxygen-eontaining compounds. The blue colouration is attributed to the presence of chromium pent oxide. and can be extracted from aqueous solutions by these solvents to yield somewhat more stable solutions..+:t [Pb(OH)4]2. c-o. add 1-2 ml amyl alcohol. crOi.+2H+ +2H 202 -+ e-o. Hydrogen peroxide If an acid solution of a chromate is treated with hydrogen peroxide. ether.+H 20 The precipitate is soluble in sodium hydroxide solution.. The blue compound is soluble in amyl alcohol and also in amyl acetate and in diethyl ether. etc. Hydrogen sulphide An acid solution of a chromate is reduced by this reagent to a green solution of chromium(III) ions. CrOi. 5. Peroxides may be removed from diethyl ether by shaking with a concentrated solution of iron(II) salt or with sodium sulphite. which suppresses the Pb 2+ ion concentration to such an extent that the solubility product of lead chromate is no longer exceeded. reaction 8b).. +3H 20 The enhanced stability in solutions of amyl alcohol.+ 7H 20 Chlorine gas must be removed from the mixture.33 QUALITATIVE INORGANIC ANALYSIS 3. evaporating most of the acid and then diluting with water. the precipitate coagulates and can be filtered easily. insoluble in acetic acid. Chromium.IV. accompanied by the separation of sulphur" 2CrOi. 362 . but soluble in dilute nitric acid. 2Cr 3+ + 3CI2 t +2K+ + 8C1. this is done during evaporation. Amyl alcohol is recommended. Just acidify a cold solution of a chromate with dilute sulphuric acid or dilute nitric acid. before the use of hydrogen sulphide. because the precipitate is almost colloidal and can hardly be filtered.+3H 2S+ lOH+ -+ 2Cr3+ +3S!+8H 20 * In qualitative analysis the production of sulphur in the reduction ofchromates may be troublesome. Alternatively. Diethyl ether is not recommended for general student use owing to its highly inflammable character and also because it frequently contains peroxides after storage for comparatively short periods: which may interfere. yielding oxygen and a green solution of a chromium(III) salt.

when warming with hydrochloric acid and alcohol (a) or hydrochloric acid and 10 per cent formaldehyde solution (b) the reduction is achieved: 2CrO~- +3C 2H sOH+ 10H+ -+ 2CrO~-+3HCHO+IOH+ -+ 2Cr 3+ +3CH 3CHO+8H 2 0 2Cr 3++3HCOOH+5H 2 0 (a) (b) In reaction (a) the acetaldehyde. Reduction of chromates and dichromates (a) Sulphur dioxide. Diphenylcarbazide reagent The solution is acidified with dilute sulphuric acid or with dilute acetic acid. chlorine is evolved. reduces chromates or dichromates : 2CrOi. may reduce some chromate and form acetic acid.REACTIONS OF ANIONS IV. in the presence of dilute mineral acid. The colour of the solution becomes brown or bluish. strontium.+ 7H 20 If the solution is evaporated almost to dryness (to remove chlorine). and 1-2 ml of the reagent added.33 6. Thus. (b) Potassium iodide. A deep-red colouration is produced.+ 16H+ -+ 2Cr3+ + 312 + SH 20 (c) Iron(II) sulphate. can be used as a reductant. Full details of the use of the reagent as a spot test are given under Chromium. after dilution chromium(I1I) ions can be tested in the solution (cf. also Section IV. and this will precipitate lead. and barium if these metals are present.+3Fe2+ +SH+ -+ Cr3+ +3Fe3+ +4H 20 (d) Ethanol.+3S0 2 +4H+ -+ 2Cr3+ +3S0i. The reaction is analogous to (b). Section 111.14. Section m. 9. the solution is coloured violet. 7.+ 61. With small quantities of chromates. reaction Se. but rapidly if the solution is heated: 2CrOi. 8.45. reduces chromates or dichromates slowly in cold.24. Easier ways to reduce chromates are also available.+SH 20 2Cr3+ +3C1 2 t +2K+ +SC1. reaction 5. in the presence of dilute mineral acid. 363 . which are formed in the reaction: 2CrOi.+ 3C 2H sOH + IOH+ -+ 2Cr3+ + 3CH 3CHOj + SH 20 The smell of acetaldehyde (CH 3CHO) is easily observed if the mixture is heated. Section IV. according to the amounts of iodine and chromium(III) ions. and a solution containing chromium(III) ions is produced: 2K 2Cr04 + 16HCl K 2Cr20 7+ 14HCl -+ -+ 2Cr3+ +3C1 2 t +4K+ + IOCl.24). as sulphuric acid is formed. again in the presence of mineral acid. Concentrated sulphuric acid and a chloride See chromyl chloride test under Chlorides.+2H 20 The solution becomes green owing to the formation of chromium(III) ions. which is formed. Reduction of solid chromates or dichromates with concentrated hydrochloric acid On heating a solid chromate or dichromate with concentrated hydrochloric acid. in the presence of mineral acid. 5. reduces chromates or dichromates smoothly: CrOi. The use of sulphur dioxide is not recommended.

KMn0 4 • 1. reaction 8d.34 PERMANGANATES. Reduction ofpermanganates In acid solutions the reduction proceeds to the formation of colourless manganese(II) ions. the quantity being dependent upon the experimental conditions: 2MnO. reduces permanganate instantaneously: 2MnO. the solution may be reduced with formaldehyde solution. The use of sulphur dioxide is not recommended (see footnote in connection with Chromates. best seen by transmitted light. MnO. in the presence of sulphuric acid. Hydrogen peroxide The addition of this reagent to a solution of potassium permanganate. Section 111. +5N0 2 +6"+ -+ 2Mn2+ +5N0 3 +3H 20 * To avoid the production of sulphur by the reduction of potassium permanganate by hydrogen sulphide in systematic qualitative analysis.+4S0i. For details.33. +5S0 2 +2H 20 -+ 5S0i. (d) Potassium iodide. The following reducing agents may be used: (a) Hydrogen sulphide: in the presence of dilute sulphuric acid the solution decolourizes and sulphur is precipitated" 2MnO. To study these reactions use a O'02M solution of potassium permanganate. reduces permanganate with formation of nitrate ions: -+ 2MnO.+2Mn2+ +4H+ Some dithionate (S20~-) may also be formed in this reaction. The solution becomes yellow because of the formation of iron(III) ions.+4H+ (c) Iron(II) sulphate. Chromotropic acid test A red colouration. forming purple (reddish-violet) solutions. 2MnO. 2MnOi +5HCHO+6H+ -+ 2Mn2+ +5HCOOH+3H 20 364 . MoO. IV. reduces permanganate to manganese(II). is given by chromates. see under Chromium. in the presence of sulphuric acid. in the presence of sulphuric acid.+ 16H+ 2MnO. + 101. acidified with dilute sulphuric acid. Solubility All permanganates are soluble in water.24. reaction 5). in the presence of sulphuric acid. +6S0 2 +2H 20 -+ 2Mn2+ +S20~. +5H 2S+6H+ -+ 5S!+2Mn2+ +8H 20 (b) Sulphur dioxide. results in decolourization and the evolution of pure but moist oxygen. they form colourless complexes with iron(III). reduces permanganate with the formation of iodine: 512 +2Mn2+ +8H 20 (e) Sodium nitrite.IV. +5H 202 +6H+ -+ 50 2t +2Mn2+ +8H 20 2. +5Fe2+ +8H+ -+ 5Fe3+ +Mn2+ +4H 20 The yellow colour disappears if phosphoric acid or potassium fluoride is added. or the solid substance may be boiled with concentrated hydrochloric acid. Section IV.34 QUALITATIVE INORGANIC ANALYSIS 10.

Mn 20 7 . (f) Oxalic acid. + 16HCl -+ 5Cl 2 t +2Mn2+ +6Cl. the reaction is autocatalytic. the permanganate is decolourized. but manganese dioxide is precipitated. When the manganate solution is poured into a large volume of water or is acidified with dilute sulphuric acid.+ H 20 -+ -+ 2Mn0 2 ! + 10:.+SH 20 4. once manganese(lI) ions are formed. and a very vigorous explosion may result on warming. 3. The experiment is best omitted. it becomes faster and faster. + 20H2Mn0 2 ! + 3S0i. +40H3MnOi. 2KMn0 4 + H 2S04 -+ Mn 20 7 + 2K + + SOi. produces carbon dioxide gas: 2MnO.28. which contains manganese heptoxide (permanganic anhydride). + Mn0 2 ! +40H- The latter reaction is in fact a disproportionation. Dry tests). 4MnO. the solution is liable to explode spontaneously at the ordinary temperature. and sodium sulphite solution into sodium sulphate on boiling. Action ofheat When potassium permanganate is heated in a test-tube. 2MnO. Table LIS).+ H 20 5. when manganese(VI) is partly oxidized to manganese(VII) and partly reduced to manganese(IV). a green solution of potassium manganate is produced and oxygen is evolved. in the presence of sulphuric acid. 6. In the presence of sodium hydroxide solution. but becomes fast at 60°C. A manganate is produced when a manganese compound is fused with potassium nitrate and sodium carbonate (see Section 111. 2MnO. In alkaline solution. The student is therefore warned not to carry out this experiment except with minute quantities of materials (not more than 0'05 g) and then only under the direct supervision of the teacher. Sodium hydroxide solution Upon warming a concentrated solution of potassium permanganate with concentrated sodium hydroxide solution. Concentrated hydrochloric acid All permanganates on boiling with concentrated hydrochloric acid evolve chlorine.+ H 20 2MnO.REACTIONS OF ANIONS IV.34 Some side reactions also take place. and manganese dioxide is precipitated. Manganese(lI) ions catalyse the reaction. + 1. and the mixture has the smell of nitrogen oxide gas. thus. and a black residue of potassium manganate K 2Mn04 and 365 .+2H 20 -+ -+ 4MnOi.+5(COO)~-+16H+ -+ IOC0 2i+2Mn2++SH 20 This reaction is slow at room temperature.+0 2 t +2H 20 2MnO. pure oxygen is evolved. the purple colour of the potassium permanganate is restored. + 3S0~.potassium iodide is converted into potassium iodate.+ 20H- These reactions indicate that permanganate oxidizes more strongly in alkaline medium than in acidic solutions (cf. Concentrated sulphuric acid (GREAT DANGER) Permanganates dissolve in this reagent to yield a green solution.

1 at 300 and 25'2 g t. The precipitate is more soluble in boiling water (l0-4 g t.35 ACETATES. The free acid. is therefore to be preferred as a test for an acetate. 1. those of iron. Dilute sulphuric acid: acetic acid. easily recognized by its vinegar-like odour. On cooling and dilution with water on a clock glass. in which the acetic acid vapour is diluted with steam.+ H+ -+ CH 3COOHi 2. the fragrant odour will be more readily detected.1 at 80°) and readily soluble in dilute ammonia solution. Some basic acetates. melting point 17°and is miscible with water in all proportions. Barium chloride. e.C2Hs is formed. the precipitate redissolves without the formation of black precipitate of silver metal (distinction from formate ions).IV.g. 366 . The test with dilute sulphuric acid.+Ag+ +:t CH 3COOAg! When heating the mixture. boiling point 117°.3H 20. CH 2COOH. CH 3COO. and chromium. calcium chloride or mercury (1I) chloride solution: no change in the presence of acetates (distinction from oxalates and formates). CH 3COOH+C 2H sOH -+ CH 3COO.C 2H si+H 20 (In the second reaction the sulphuric acid acts as a dehydrating agent. 2KMn04 -+ K 2Mn04 + Mn0 2 + 02 t IV. CH 3COO. which is recognized by its pleasant. 5. CH 3COO.) It is preferable to use iso-amyl alcohol because the odour of the resulting iso-amyl acetate is more readily distinguished from the alcohol itself than is the case with ethanol. aluminium. Concentrated sulphuric acid: acetic acid is evolved on heating. 3. CH 3COONa+H 2S04 -+ CH 3COOH+Na+ + HSO. with the exception of silver and mercury(I) acetates which are sparingly soluble. the latter tending to mask the penetrating odour of the concentrated acetic acid vapour. it has a corrosive action on the skin. To study these reactions use a 2M solution of sodium acetate CH 3COONa.35 QUALITATIVE INORGANIC ANALYSIS manganese dioxide remains behind.Solubility All normal acetates. a green solution of potassium manganate is obtained. It is as well to run a parallel test with a known acetate and to compare the odours of the two products. 4. is a colourless liquid with a pungent odour. Silver nitrate solution: a white. and the whole gently warmed for several minutes. are readily soluble in water. Upon extracting with a little water and filtering. is evolved on warming. crystalline precipitate of silver acetate is produced in concentrated solutions in the cold. are insoluble in water. Ethanol and concentrated sulphuric acid 1 g of the solid acetate is treated with I ml concentrated sulphuric acid and 2-3 ml rectified spirit in a test-tube. fruity odour. ethyl acetate CH 3COO. together with sulphur dioxide.

Propionates give a similar reaction. and heat slowly to the boiling point. Sulphates and phosphates interfere. but can be removed by precipitation with barium nitrate solution before applying the test. Add a drop of Mammonia solution. formed by the dry distillation of acetates (see reaction 10). Cacodyl oxide reaction If a dry acetate. but the sensitivity is reduced in their presence. Iron (Ill) chloride solution: deep-red colouration. Within a few minutes a blue to bluebrown ring will develop round the drop of ammonia solution.58. both operations may be carried out in the hard glass tube of Fig. preferably that of sodium or potassium.35 6. Concentration limit: I in 2000. and preferably in the fume chamber. into indigo. 8. Insert the tube into a hole in an asbestos or 'uralite' sheet and heat the tube gently. Lanthanum nitrate test Treat 0'5 ml of the acetate solution with 0'5 ml O'IM lanthanum nitrate solution. it is best to remove the filter paper after the reaction and treat it with a drop of dilute hydrochloric acid. Sensitivity: 60 ug CH 3COO-. No other fatty acids give this test. the experiment must therefore be performed on a very small scale. alternatively. Mix a drop of the test solution on a spot plate with a drop of O'IM lanthanum nitrate solution and a drop of 0'OO5M iodine.+ 3Fe3+ + 2H 2 0 -+ [Fe 3(OH 2(CH 3COO)6r + 2H+ [Fe 3(OHh(CH 3COO)6r +4H 2 0 -+ -+ 3Fe(OHhCH 3COO!+3CH 3COOH+H+ 7. owing to the formation of a complex ion. evaporate a drop of the test solution to dryness with calcium carbonate. 9. For minute amounts of acetates. Mix not more than 0'2 g sodium acetate with 0'2 g arsenic(III) oxide in an ignition tube and warm. an extremely nauseating odour of cacodyl oxide is produced. the original yellow colour of the paper is thus bleached and the blue colour of the indigo is more readily apparent. add 0'5 ml iodine solution and a few drops of dilute ammonia solution. is heated in an ignition tube or test-tube with a small quantity of arsenic(III) oxide. this is probably due to the adsorption of the iodine by the basic lanthanum acetate. Mix the solid test sample with calcium carbonate or. A blue colour is produced. On boiling the red solution it decomposes and a brownish-red precipitate of basic iron(III) is formed: 6CH 3COO. Acetone is evolved which colours the paper blue or bluish-green. and hold the paper in position with a small glass cap or a small watch glass. 367 . All cacodyl compounds are extremely POISONOUS. Sensitivity: 50 ug CH 3COO-.REACTIONS OF ANIONS IV. The spot-test technique is as follows. Cover the open end of the tube with a strip of quantitative filter paper moistened with a freshly prepared solution of o-nitrobenzaldehyde in 2M sodium hydroxide. This reaction provides an extremely sensitive test for an acetate. [Fe 3(OHh(CH 3COO)6r. observe the extremely unpleasant odour that is produced. Formation of indigo test The test depends upon the conversion of acetone. 11.

owing to ethyl formate. most formates are soluble in water. Ethanol and concentrated sulphuric acid: a pleasant odour. is apparent on warming (for details. melting point 8°). To study these reactions use a M solution of sodium formate. +H 20 3.CH3. 2CH 3COONa -+ CIi3·CO. 6HCOO. the gas should be ignited and the characteristic blue flame obtained.+ H+ -+ HCOOHi 2.+3Fe3+ -+ [Fe 3(HCOO)6]3+ [Fe 3(HCOO)6]3+ + 4H 20 -+ 2Fe(OHhHCOO! + 4HCOOHi + Fe 3+ 368 . Concentrated sulphuric acid: carbon monoxide (HIGHLY POISONOUS) is evolved on warming. see under Acetates. 1. the colour is discharged by hydrochloric acid. HCOONa+H 2S0 4 -+ COi+Na+ + HSO. Silver nitrate solution: white precipitate of silver formate in neutral solutions. and producing blisters when allowed to come into contact with the skin. a black precipitate of silver being formed (distinction from acetate). HCOOH+C 2HsOH -+ HCOO.35. Carry out the experiment in an ignition tube with sodium acetate and lead acetate. silver. Section IV. reaction 3).Solubility With the exception of the lead. and a residue which consists of the carbonates for the alkali acetates. is produced in practically neutral solutions. slowly reduced at room temperature and more rapidly on warming. HCOONa. HCOO. Dilute sulphuric acid: formic acid is liberated. HCOONa+H 2S0 4 -+ HCOOH+Na++HSO. yielding the highly inflammable acetone. 6. HCOO.36 FORMATES. HCOO. due to the complex [Fe 3(HCOO)6]3+. a brown precipitate of basic iron(III) formate is formed. The test can be successfully carried out with solid sodium formate. the pungent odour of which can be detected on warming the mixture.IV. is a pungent smelling liquid (boiling point 100'5°. the silver may be deposited in the form of a mirror on the walls of the tube. CH 3. The free acid HCOOH. and mercury(I) salts which are sparingly soluble. With very dilute solutions. of the oxides for the acetates of the alkaline earth and heavy metals. and of the metal for the acetates of silver and the noble metals. miscible with water in all proportions. Iron ( Ill) chloride: a red colouration.C 2Hsi+H20 4. If the red solution is diluted and boiled.CO. Action ofheat All acetates decompose upon strong ignition.CH3i+Na2C03 IV.+ Ag" -+ HCOOAg! 2HCOOAg! -+ 2Ag! + HCOOH + CO 2i 5. Barium chloride or calcium chloride solution: no change (distinction from oxalates).36 QUALITATIVE INORGANIC ANALYSIS 10.

gives momentarily a white precipitate of mercury(l) formate. H.REACTIONS OF ANIONS IV. (COONah. Action of heat Cautious ignition of the formates of the alkali metals yields the corresponding oxalates (for tests. To study these reactions a O'IM solution of sodium oxalate. (COO)~. Oxalic acid (a dibasic acid) is a colourless. (HCOOhHg+H20 -+ (HCOOhHg 2!+HCOOH+C02i -+ 2Hg! + HCOOH + CO 2i Formic acid and mercury(II) formate are almost completely undissociated under these circumstances. metallic mercury. crystalline solid. should be used. .H 20.37 OXALATES. Some of the oxalates dissolve in a concentrated solution of oxalic acid by virtue of the formation of soluble acid or complex oxalates. 10. Concentration limit: I in 20. and becomes anhydrous on heating to 1100. is reduced to formaldehyde H. add a drop or two of dilute hydrochloric acid. (COONH 4h. A violet-pink colouration appears within a few minutes. this passes into grey.000. it is readily soluble in water (Ill g r 1 at 2(0). Sensitivity: 1'5 ug H. all other oxalates are either insoluble or sparingly soluble in water.37) and hydrogen. which rapidly changes to a grey precipitate of metallic mercury. The formaldehyde is identified by its reaction with chromotropic acid (see Section 111.COOH. Mercury(II) formate test Free formic acid is necessary for this test. 1.24. 2HCOONa -+ (COOhNa2 + H 2l IV. (COOHh . in the presence of excess formate solution (distinction from acetate). followed by magnesium powder until the evolution of gas ceases. water) and a little solid chromotropic acid. Formaldehyde-chromotropic acid test Formic acid. Place a drop or two of the test solution in a semimicro test-tube. The solution must be then filtered. acid + 2 vol. the latter can be detected by passing the escaping gases through lime water (distinction from formate) and 369 . 2HCOO. Other aliphatic aldehydes do not give the violet colouration.+COi+C0 2i+H20 8. Concentrated sulphuric acid: decomposition of all solid oxalates occurs with the evolution of carbon monoxide and carbon dioxide.Solubility The oxalates of the alkali metals and of iron(II) are soluble in water. The filtrate.+ Hg 2C12! -+ 2Hg!+2Cl. Mercury(II) chloride solution: white precipitate of mercury(I) chloride (calomel) is produced on warming.+COi +C0 2i +H 20 2HCOO.CHO by magnesium and hydrochloric acid. see Section IV. Introduce 3 ml sulphuric acid (3 vol.COOH. and warm to 600C. reaction 9d) in strong sulphuric acid when a violet-pink colouration appears. or ammonium oxalate.+2HgC1 2 -+ Hg 2C12! +2Cl. when boiled. The solution of sodium formate must be acidified with dilute sulphuric acid and shaken vigorously with a little mercury(II) oxide.37 7.2H 20. They are all soluble in dilute acids. -+ 2HCOOH+HgO 2(HCOOhHg (HCOO)2 Hg2! 9.

but soluble in dilute hydrochloric acid and in dilute nitric acid.28. Resorcinol test Place a few drops of the test solution in a test-tube: add several drops of dilute sulphuric acid and a speck or two of magnesium powder. the blue colour spreads downwards from the interface and eventually colours the whole of the sulphuric acid layer. reaction I). oxalic acid. Barium chloride solution similarly gives a white precipitate of barium oxalate sparingly soluble in water (0'016 g t -1 at SO). and in ammonium oxalate solution. made 370 . and shake until dissolved. 5(COO)~- +2MnO. there is no visible action.IV. but soluble in solutions of acetic and of oxalic acids.+ 2Ag+ -+ (COOAgh! (COOAgh!+4NH 3 -+ 2[Ag(NH 3 h r +(COO)~(COOAgh! + 2H+ -+ Ag" + (COO)~. in the presence of manganese dioxide. 6. carbon dioxide is evolved.+ +Ca2+ -+ (COO)2Ca! Ba2+ -+ (COOhBa! 4.2. reaction I). the solution of the oxalate. Upon warming the sulphuric acid layer at the bottom of the tube very gently (CAUTION). insoluble in dilute acetic acid. Citrates do not interfere. When the metal has dissolved.1 at 13°)and is even precipitated by calcium sulphate solution and acetic acid. Section 111. (COOHh -+ (COO)~-+Mn02+4H+ -+ H 20+COi+C02i Mn2++2C0 2i+2H20 (the concentrated sulphuric acid acts as a dehydrating agent). The bleaching of permanganate solution is also effected by many other organic compounds but if the evolved carbon dioxide is tested for by the lime water reaction (Section IV. Calcium chloride solution: white. It is the most insoluble of all oxalates (0'0067 g t . In the presence of tartrates. soluble in ammonia solution and in dilute nitric acid. Manganese (Il) sulphate test A solution of manganese(II) sulphate is treated with sodium hydroxide and the resulting mixture warmed gently to oxidize the precipitate by atmospheric oxygen to hydrated manganese dioxide (cf. Carefully pour down the side of the tube 3-4 ml concentrated sulphuric acid. (COO)~. however. Cool. + 16H+ -+ IOC0 2t +2Mn2+ +SH 20 5.+ 2H+ 3. After cooling. add about 0·1 g resorcinol. Potassium permanganate solution: decolourized when warmed in acid solution to 60°-70°. Silver nitrate solution: white.37 QUALITATIVE INORGANIC ANALYSIS the former by burning it at the mouth of the tube. a blue ring is obtained in the cold or upon very gently warming (compare similar test under Tartrates in the following section). 2. (COO)~(COO)~. curdy precipitate of silver oxalate sparingly soluble in water. A blue ring will form at the junction of the two liquids. With dilute sulphuric acid. the test becomes specific for oxalates. crystalline precipitate of calcium oxalate from neutral solutions.

The dye may be extracted from aqueous solution by ether. and fluoride. Action of heat All oxalates decompose upon ignition. Place a few milligrams of the test sample (or. The colour disappears on cooling. Mix a small amount of the precipitate with diphenylamine in a dry micro test-tube. is added. a little carbon is also formed.000. When cold. benzoates. tartrates. Remove the water from the precipitate either by drying or by washing with alcohol and ether. citrates. 2Ag+2C0 2j (COOHh -.38 TARTRATES.REACTIONS OF ANIONS IV. succinates. Solubility Tartaric acid. it is best to heat the precipitate formed by calcium chloride with phosphoric acid as detailed below. Dissolve the melt in alcohol. proceed as follows. which is extremely soluble in water. In the presence of anions which are precipitated by calcium chloride solution. are converted into carbon monoxide. BaC0 3+ COj (COOhMg -. Potassium and ammonium hydrogen 371 . magnesium and zinc oxalates. acetates. Sensitivity: 5 ug (COOHh. tartrate. which is coloured light blue by the adsorption of the dyestuff. Silver oxalate yields silver and carbon dioxide. COj + H 20j 8. is a crystalline solid. HCOOH + CO 2l HCOOH -. when a blue colouration appears. the latter being further partially decomposed into carbon monoxide and water.+ 2MnO(OH)2! + 8H+ -. The precipitate dissolves and a red colour is produced.g. and collect the precipitate on a filter or in a centrifuge tube.38 acid with dilute sulphuric acid. alternatively. C4H40~[CH(OH)]2COOH or H 2.+ 2C02j + 6H 20 7. MgO+COj+C0 2j (COOAgh -. carbon dioxide. Concentration limit: I in 10. Formation of aniline blue test Upon heating insoluble oxalates with concentrated phosphoric acid and diphenylamine or upon heating together oxalic acid and diphenylamine. use the residue obtained by evaporating 2 drops of the test solution to dryness) in a micro testtube. Oxalic acid decomposes into carbon dioxide and formic acid. Pour the alcoholic solution into water thus precipitating the excess of diphenylamine. Formates. Precipitate the acetic acid test solution with calcium chloride solution. and heat gently over a free flame. which is probably due to the formation of trioxalatomanganate(III) complex ion: 7(COO)~. and salts of other organic acids do not react under these experimental conditions. and the oxide.C4H40 6 . Those of the alkali metals and of the alkaline earths yield chiefly the carbonates and carbon monoxide. phosphate. HOOC. 7Na2C03 + 3COj + 2C02j + 2C (COOhBa -. e. the dyestuff aniline blue (or diphenylamine blue) is formed. 2{Mn[(COO)2]3P. sulphate. 7(COONah -. In the presence of other anions which are precipitated by calcium chloride solution. e. add a little concentrated phosphoric acid. The oxalates of the metals whose carbonates are easily decomposed into stable oxides. add a little pure diphenylamine and melt over a free flame. and the latter condenses with the diphenylamine to aniline blue and colours the hot phosphoric acid blue.g. silver oxide decomposes on heating. sulphite. IV. Calcium phosphate and free oxalic acid are formed. it is a dibasic acid. take up the melt in a drop or two ofalcohol when the latter will be coloured blue.

C4H40 6 -+ COi+C0 2i2C+3H 20i C+2H 2S04 -+ 2S0 2i+C0 2i+2H 20i 2. Silver nitrate solution : white.C 4H40 6. together with some sulphur dioxide. those of the other alkali metals are readily soluble. this can be deposited in the form of a mirror under suitable conditions. excess of silver nitrate solution added and any precipitate present filtered off. reminiscent of burnt sugar. Introduce about 0·5 ml neutral tartrate solution. Immediately discard all the solution which remains after the test. the lastnamed probably arises from the reduction of the sulphuric acid by the carbon. in dilute ammonia solution and in dilute nitric acid.38 QUALITATIVE INORGANIC ANALYSIS tartrates are sparingly soluble in water. A silver mirror is formed in a few minutes. The reaction is interfered with by other acids. A brilliant mirror is formed on the sides of the tube after a few minutes. 372 .C 4H40 6 • To study these reactions use a O'IM solution of tartaric acid. C4H40~. which often do not give the typical reactions of the metals present. the solution is filtered. to a minimum).C 4H40 6 ! +4NH 3 -+ 2[Ag(NH 3h]+ +C4H40~The silver mirror test is best performed as follows. KNa. carbon dioxide and carbon monoxide are evolved. It is best to isolate the potassium hydrogen tartrate. The latter solution is neutral.IV.C4H40 6 . and 'cream of tartar'. the latter is then placed in a beaker of boiling water.4H 20. or a O'IM solution of Rochelle salt.+2Ag+ -+ Ag 2. from neutral solutions of tartrates. 1.C 4H40 6. The most important commercial salts are 'tartar emetic'. The test-tube may be cleaned either by boiling with chromic acid mixture or by boiling it with a little sodium hydroxide solution. AgN 3 . An empyreumatic odour. but dissolve in solutions of alkali tartrates forming complex salts. Concentrated sulphuric acid When a solid tartrate is heated with concentrated sulphuric acid. Prepare ammoniacal silver nitrate solution by placing 5 ml silver nitrate solution in a thoroughly clean test-tube and add 2-3 drops of dilute sodium hydroxide solution. An alternative method for carrying out the silver mirror test is the following.curdy precipitate of silver tartrate. and the filtrate collected in a clean test-tube. KNa. before carrying out the test. The solution of the tartrate is acidified with dilute nitric acid.C 4H40 6 • 0'5H 20. can be detected in the evolved gases. Very dilute ammonia solution (approximately 0'02M) is then added to the solution until the precipitate at first formed is nearly redissolved. Charring occurs almost immediately (owing to the separation of carbon). those of the other metals being sparingly soluble in water. soluble in excess of the tartrate solution.4H 20. as in reaction 4 below. K(SbO). Ag 2 . 'Rochelle salt'. Place the tube in warm water. it is decomposed in a complex manner. The normal tartrates of the alkali metals are easily soluble. H 2.C 4H40 6 ! Ag 2. and then rinsing it well with distilled water. add dilute ammonia solution dropwise until the precipitated silver oxide is almost redissolved (this procedure reduces the danger of the formation of the explosive silver azide. On warming the ammoniacal solution.C 4H406 . Dilute sulphuric acid has no visible action. KH. metallic silver is precipitated. H 2.

373 . 6. If only small quantities of tartrate are present. malates or succinates. The formula of the condensation product is CH 20H. and in cold alkali solutions.C 4H406 . and then 2-3 drops of hydrogen peroxide solution (10 volume).38 3. add several drops of dilute sulphuric acid and a speck or two of magnesium powder. the latter arising from the action of the sulphuric acid upon the tartaric acid. The colour becomes more intense upon the addition of a drop of iron(III) chloride solution.C 4H40 6 .REACTIONS OF ANIONS IV. The precipitate is soluble in dilute acetic acid (difference from oxalate). Carefully pour down the side of the tube 3-4 ml concentrated sulphuric acid. with a concentrated neutral solution. crystalline precipitate of calcium tartrate. In the presence of oxalate. [Cu(C 4H406hJ 2-. Precipitation is slow in dilute solutions. C4H40~- +K+ +CH 3COOH -+ KH. and shake until dissolved. a blue ring is formed in the cold and on gentle warming of the sulphuric acid layer at the bottom of the tube the blue colouration spreads downwards into the concentrated acid layer and a red ring forms at the interface. which is best detected by filtering the solution. Potassium chloride solution When a concentrated neutral solution of a tartrate is treated with a solution ofa potassium salt (e.C(OH)=C(OH). Resorcinol test Place a few drops of the test solution in a test-tube.CHO. An excess of the reagent must be added because calcium tartrate dissolves in an excess of an alkali tartrate solution forming a complex tartrate ion. The colour is due to the formation of a condensation product of resorcinol. Cool. A deep-violet or blue colouration is developed on adding excess sodium hydroxide solution. The precipitate forms slowly in dilute solutions. CH 20H. is obtained. the red colour spreads downwards from the interface and eventually colours the whole of the sulphuric acid layer. Copper hydroxide test Tartrates dissolve copper hydroxide in the presence of excess alkali hydroxide solution to form the dark-blue ditartratocuprate(II) ion. in dilute mineral acids. Citrates do not interfere. C 6H 4(OHh. the filtrate should be acidified with acetic acid and tested for copper by the potassium hexacyanoferrate(II) test. add about 0'1 g resorcinol. but may be accelerated by vigorous shaking or by rubbing the walls of the test-tube with a glass rod. With continued gentle heating. The violet colour is due to the formation of a salt or dihydroxymaleic acid. Calcium chloride solution: white. C0 2H. a colourless crystalline precipitate of potassium hydrogen tartrate. potassium chloride or potassium acetate) and then acidified with acetic acid.C02H. The test is not given by citrates. Fenton's test Add I drop of a 25 per cent solution of iron(II) sulphate to about 5 ml of the neutral or acid solution of the tartrate. Ca. and glycollic aldehyde. KH.CH[C 6H 3(OHhJ2' 7. crystallization is induced by vigorous shaking or by rubbing the walls of the vessel with a glass rod. [Ca(C4H40 6hJ 2-. C4H40~- +Ca2+ -+ Ca.g.C 4H406! 4. a red layer (or ring) forms at the junction of the two liquids.C 4H40 6!+CH 3COO- 5. When the metal has dissolved. Upon warming the sulphuric acid layer at the bottom of the tube very gently (CAUTION).

shake the mixture vigorously for 5 minutes.H20 is a crystalline solid which is very soluble in water. warm to coagulate the colloidal copper hydroxide and filter again. the solution slowly darkens owing to the separation of carbon. a green colouration is obtained. charring takes place. it is perhaps better to acidify with 2M acetic acid and add potassium hexacyanoferrate(II) solution to the clear solution whereupon a reddish-brown precipitate or (with a trace of a tartrate) a red colouration is obtained.IV. it intensifies on cooling. 9. The experimental details are as follows.COOH. and filter. A luminous green fluorescence appears during the heating. a smell of burnt sugar is apparent and inflammable vapours are evolved. Sensitivity: lO ug tartaric acid.CH 2. and organic compounds convertible into tartaric acid also give a blue colouration. 8. If a pale colouration is obtained.000.38.H20 or H3.e. To study these reactions use a 0'5M solution of sodium citrate. Oxalic. 374 . A distinct blue colouration indicates the presence of a tartrate. it is advisable to add concentrated ammonia solution dropwise when the blue colour intensifies. C6HsO~.C6Hs07. just sufficient to yield a visible precipitate of copper(II) hydroxide). and cinnamic acids do not interfere. It is a tribasic acid. Concentrated sulphuric acid When a solid citrate is heated with concentrated sulphuric acid. The normal citrates of the alkali metals dissolve readily in water. which char almost immediately). it becomes anhydrous at 55° and melts at 160°. pp' -Dinaphthol test ( HO~OH ) : ~~ when a solution of pp'-dinaphthol in concentrated sulphuric acid is heated with tartaric acid. Na 3. add a few drops of 0'25Mcopper sulphate solution (i.CH2. and therefore gives rise to three series of salts. citric. Action ofheat The tartrates and also tartaric acid decompose in a complex manner on heating. 2H 20.Solubility Citric acid.C 6Hs07. Treat the test solution with an equal volume of 2M sodium or potassium hydroxide (or treat the test solid directly with a few ml of the alkali hydroxide solution. carbon monoxide and carbon dioxide are evolved. succinic. If the filtrate is not clear. The acid citrates are more soluble than the acid tartrates.39 CITRATES. IV. The reagent consists of a solution of 0·05 g pp' -dinaphthol in 100 ml concentrated sulphuric acid. HOOC. Section IV. Concentration limit: I in 5. 1. and at the same time the violet fluorescence of the reagent disappears. and should therefore be absent or be removed. other metallic citrates are sparingly soluble.C(OH)C0 2H.39 QUALITATIVE INORGANIC ANALYSIS Arsenites. Heat a few milligrams of the solid test sample or a drop of the test solution with 1-2 ml of the dinaphthol reagent in a water bath at 85°C for 30 minutes. warm for a few minutes with stirring and then cool). and sulphur dioxide is evolved (compare Tartrates. ammonium salts.

C6Hs07!+6NH3 -+ -+ Ag 3. but soluble in ammonium chloride solution.C6Hs07.2[CO(CH 2. somewhat suddenly. gelatinous precipitate of cadmium citrate Cd 3(C6Hs07h. insoluble in solutions of caustic alkalis. Cadmium acetate solution: white. heat to boiling and then add a few drops of a 0'02M solution of potassium permanganate. The precipitate is soluble in dilute ammonia solution. which is now insoluble in ammonium chloride. an intense red colouration results. If sodium hydroxide solution is added to the cold solution containing excess calcium chloride. Decolourization of the permanganate will take place rapidly and then. Salts of the halogen acids interfere and must therefore be removed before carrying out the test. 2C6HsO~. CH 2. on boiling the ammonium chloride solution. rendered alkaline with sodium hydroxide solution and then a few millilitres of a freshly prepared solution of sodium nitroprusside added. Deniges's test Add 0·5 ml acid mercury(II) sulphate solution to 3 ml citrate solution. crystalline calcium citrate is precipitated. 375 . HOOC. is produced. the latter undergoes further partial decomposition into acetone(II) and carbon dioxide.39 The first products of the reaction are carbon monoxide and acetone dicarboxylic acid(I). COOH -+ -+ CH 3. Ca3(C6Hs07h. and this solution undergoes only very slight reduction to silver on boiling (distinction from tartrate). When about 0'5 g of a citrate or of citric acid is treated with I ml concentrated sulphuric acid for I minute. CH 3j(II) + 2C02l Use may be made of the intermediate formation of acetone dicarboxylic acid and of the interaction of the latter with sodium nitroprusside solution to yield a red colouration as a test for citrates.CH2·COOH -+ -+ COi+H 20i+HOOC. but on boiling for several minutes a crystalline precipitate of calcium citrate. the mixture cooled. HOOC.4H20. CH 2CO. Ag 3.CO.C02hHg]! is formed.+3Ag+ Ag3. from neutral solutions.CH2·CO.CH2·COOH(I). 2. 2C6HsO~- +3Ca2+ -+ Ca 3(C6H s07h! 4. curdy precipitate of silver citrate. but readily 'soluble in warm acetic acid (tartrate gives no precipitate).REACTIONS OF ANIONS IV. Calcium chloride solution: no precipitate with neutral solutions in the cold (difference from tartrate).CH 2.CH 3. a heavy white precipitate.C(OH)C02H.+ 3Cd2+ -+ Cd 3(C6Hs07h! 5.CO. C6HsO~. consisting of the double salt of basic mercury(II) sulphate with mercury(II) acetone dicarboxylate HgS0 4·2HgO.C6Hs07! 3[Ag(NH 3h]+ +C6HsO~- 3. there results an immediate precipitation of amorphous calcium citrate. practically insoluble in boiling water. cautiously diluted with water. Silver nitrate solution: white.

With the exception of the lead. Concentrated sulphuric acid and methanol ('oil of wintergreen' test) When 0·5 g of a salicylate or of salicylic acid is treated with a mixture of 1·5 ml concentrated sulphuric acid and 3 ml methanol and the whole gently warmed. and dissolving 2·2 g inercury(II) oxide in the hot solution. Action of heat Citrates and citric acid char on heating.OR C 7H sO:. Dilute hydrochloric acid:* crystalline precipitate of salicylic acid from solutions of the salts. and acrid-smelling vapours are evolved. it is soluble in boiling water and crystallizes from the solution on cooling. IV. Concentrated sulphuric acid: solid sodium salicylate dissolves on warming. C 6H 4(OH)COOH + CH 30H -+ C 6H 4(OH)COO. The odour is readily detected by pouring the mixture into dilute sodium carbonate solution contained in a porcelain dish. from which it crystallizes on cooling. C 6H4(OH)COONa or Na. carbon dioxide. carbon monoxide. the monobasic salts. from which it can be recrystallized. *Or any other mineral acid. crystalline precipitate of silver salicylate. Ag. C 6H4(OH)COO. forms colourless needles.these are the most commonly occurring salts . fragrant odour of the ester. and citric) prevents the development of the colour. but more soluble in hot water. C 6H4(OH)COOM . It is readily soluble in alcohol and ether. The precipitate is moderately soluble in hot water. tartaric.) 3. silver. the characteristic. the colour disappears upon the addition of dilute mineral acids. To study these reactions use a 0·5M solution of sodium salicylate. but the addition of a few drops of dilute ammonia solution will cause it to appear. The acid is sparingly soluble in cold water. Silver nitrate solution: heavy. but not of a little acetic acid. Iron(III) chloride solution: intense violet-red colouration with neutral solutions of salicylates or with free salicylic acid. methyl salicylate(I) ('oil of wintergreen'). charring occurs slowly. 6.C 7H s0 3 . mercury. accompanied by the evolution of carbon monoxide and sulphur dioxide. Solubility Salicylic acid.are readily soluble in cold water. C 6H4(OH)COO. 2.40 SALICYLATES.IV. 376 . The presence of a large excess of many organic acids (acetic. C 6H4(OH)COOH (o-hydroxybenzoic acid). which melt at 155°. from neutral solutions.C 7H s0 3 • 1. is obtained.40 QUALITATIVE INORGANIC ANALYSIS The reagent (an acid solution ofmercury(II) sulphate) is prepared by adding lO ml concentrated sulphuric acid slowly to 50 ml water. CH 3 to) + H 20 (The sulphuric acid acts as a dehydrating agent. and barium salts. 4.+ Ag" -+ C 6H4(OH)COOAg! 5.

All the benzoates. If the latter is somewhat low. it has a melting point of 121°. is a white crystalline solid. C 6H4(OH)COONa + NaOH -+ C 6H sOHj + Na 2C0 3 8. Salicylates char on heating and phenol is evolved. are readily soluble in cold water. when gradually heated above its melting point. The acid is sparingly soluble in cold water. C6"sCOO. Soda lime When salicylic acid or one of its salts is heated with excess of soda lime in an ignition tube.OR C 7 " S 2 Solubility Benzoic acid. To study these reactions use a 0'5M solution of potassium benzoate. 2. it is decomposed into carbon dioxide and phenol. It must be emphasized that nitrosalicylic acids may explode on strong heating. is evolved. C 6H4(OH)COOH -+ C 6H sOHj +C0 2 j IV. If it is rapidly heated. it is probably best to remove it by acidifying the concentrated solution with dilute hydrochloric acid: most of the salicylic acid will separate out upon cooling. C6H4(OH)COOH + HN0 3 -+ C6H3(N02 ) (OH)COOH! + H20 Polynitro salicylic acids are formed when the concentration of nitric acid exceeds 2-3M. it may be recrystallized from hot water. the acid. after drying. Concentrated sulphuric acid and ethanol Heat 0'5 g of a benzoate or of benzoic acid with a mixture of 1-5 ml concentrated sulphuric acid and 3 ml • Or any other mineral acid.41 BENZOATES. has a melting point of 226°. the acid forms a sublimate on the sides of the test-tube and irritating fumes are evolved. Dilute nitric acid When a salicylate or the free acid is boiled with dilute nitric acid (2M) and the mixture poured into 4 times its volume of cold water. 7.REACTIONS OF ANIONS IV. sublimes. dried between filter paper or upon a porous tile and identified by means of its melting point (l21 0). C 6H sCOOK or K. phenol. which may be recognized by its characteristic odour. a crystalline precipitate of 5-nitrosalicylic acid is obtained.C 7H s0 2 • 1. from which it crystallizes out on cooling. Action ofheat Salicylic acid. crystalline precipitate of benzoic acid from cold solutions of benzoates.C 7H s0 2 . Concentrated sulphuric acid: no charring occurs on heating solid benzoic acid with this reagent. 0 C 6H sCOOH or H. with the exception of the silver and basic iron(I1I) salts. C 6H sCOO. and this must be borne in mind when removing salicylates by oxidation with nitric acid and evaporating to dryness prior to the precipitation of Group IlIA. 377 . The acid may be filtered off. If salicylate is suspected.+ H+ -+ C 6H sCOOH! 3. it is soluble in alcohol and in ether. but more soluble in hot water. Dilute sulphuric acid:* white.41 6. C 6H s(OH). The precipitate is filtered off and recrystallized from boiling water.

and sparingly soluble in chloroform. CH 2. ethyl benzoate. and condenses in the cool parts of the tube. it melts. 1. oily drops of ethyl benzoate will separate out. Action of heat When benzoic acid is heated in an ignition tube. but no charring occurs. Ag. from neutral solutions. Silver nitrate solution: white precipitate of silver succinate.1 at 2(0). and note the pleasant and characteristic aromatic odour of the ester. C 6H6. The precipitate is soluble in hot water and crystallizes from the solution on cooling. and basic iron(III) salts are sparingly soluble. smoky flame (distinction from succinate). Allow the mixture to cool. C 6Hs. by the loss of one molecule of water.6H20 or Na2. Dilute sulphuric acid has no visible action.C 7H s02.C4H404. Ag 2. it boils at 2350 with the formation of succinic anhydride. are decomposed into benzene. slight charring takes place and sulphur dioxide is evolved. crystalline solid with a melting point of 1820 .COOAg! [Ag(NH 3h]+ +C 6Hs·COO- 5. 2. Soda lime -+ (C6HsCOOhFe. slightly soluble in ether. C 2H4(COONah.Solubility Succinic acid. but more soluble in hot water. Silver nitrate solution: white precipitate of silver benzoate. concentrated sulphuric acid without charring. The precipitate is soluble in hydrochloric acid. Most normal succinates are soluble in cold water.42 QUALITATIVE INORGANIC ANALYSIS ethanol for a few minutes. C 4H40 3 . barium.C4H404 (a dibasic acid).-l-Ag" C 6Hs. when heated in an ignition tube with excesssoda lime.COOAg!+2NH 3 -+ -+ C 6Hs. To study these reactions use a O'5M solution of sodium succinate.6H20.CH 2. calcium.IV. the silver.COOH or H 2. IV.Fe(OHh! +3H+ Benzoic acid and benzoates. Iron(III) chloride solution: buff-eoloured precipitate of basic iron(III) benzoate from neutral solutions.42 SUCCINATES.C4H404. C 6Hs·COOH+C2HsOH -+ C6Hs·COOC2Hsi+H20 4. from neutral solutions.+2Ag+ C 2H4(COOAgh! +4NH 3 -+ -+ C 2H4(COOAgh! 2[Ag(NH 3 h r +C2H4(COO)~- 378 . HOOC. The acid is fairly soluble in water (68-4 g t. evaporates. 3C6HsCOO. it is moderately soluble in alcohol and in acetone.COO. which burns with a smoky flame. If a little of the acid or of one of its salts is heated upon platinum foil or broken porcelain it burns with a blue.COOH + 2NaOH -+ C 6H6i + Na 2C0 3 + H 20i 7. C4"40i. readily soluble in dilute ammonia solution. if the solution is strongly heated. C2H4(COO)~. An irritating vapour is simultaneously evolved. C 6Hs . with the simultaneous separation of benzoic acid (see reaction 2). and carbon dioxide. Concentrated sulphuric acid The acid or its salts dissolve in warm. is a white. The odour is more apparent if the mixture is poured into dilute sodium carbonate solution contained in an evaporating basin.+2Fe3+ +3H 20 6. it is also soluble in dilute ammonia solution. the latter combining with the alkali present.

IV. blue flame. Action of heat When succinic acid or its salts are strongly heated in an ignition tube. which exhibits an intense green fluorescence. succinic anhydride(I) is first formed. and the colour of the solution changes to bright red. and lOO-volume' solutions. but may be accelerated by vigorous shaking or by rubbing the inner wall of the test-tube with a glass rod. 40-. 0 +2 HO~OH (11) ~ -2"2° I The quinoid structure (IV) is predominant in alkaline solutions. C2H4(COO)~. Barium chloride solution: white precipitate of barium succinate from neutral or slightly ammoniacal solutions (distinction from benzoate). 7. Under the influence of concentrated sulphuric acid. Iron(Ill) chloride solution: light-brown precipitate of basic iron(III) succinate with a neutral solution. Precipitation is slow from dilute solutions... a deep-red solution is formed. is formed and irritating vapours are evolved. C2H4(COO)~- + Ba2+ -+ C 2H4(COOhBa! 5. CH 2 . CH 2-CO (1) I .+Ca2+ -+ C 2H4(COOhCa! 6. It is formed upon adding 379 . and this condenses with the resorcinol(II) to yield succinylfluorescein(III). H 20 2 This substance is marketed in the form of '10-. 3C2H4(COO)~- +2Fe3+ +2H 20 -+ -+ 2C 2H4(COOhFe(OH)! + C 2H4(COOHh 4.43 3. leaving a residue of carbon (distinction from benzoate). Calcium chloride solution: a precipitate of calcium succinate is very slowly produced from concentrated neutral solutions. On pouring the latter into a large volume of water. 20-.REACTIONS OF ANIONS IV. and the mixture gently heated. and the solution becomes slightly acidic.C O . C 4H40 3 . The addition of excess sodium hydroxide solution intensifies the fluorescence. a white sublimate of succinic anhydride. an orange-yellow solution is obtained.43 HYDROGEN PEROXIDE. a few drops of concentrated sulphuric acid added. some free succinic acid is simultaneously produced. Fluorescein test About 0'5 g of the acid or one of its salts is mixed with I g resorcinol. the vapour burns with a non-luminous. If the ignition is carried out on platinum foil or upon broken porcelain.

reaction 8b. Potassium hexacyanoferrate( Ill) and iron(Ill) chloride To a nearly neutral solution of iron(III) chloride add some potassium hexacyanoferrate(I1I) solution. to be preferred. p. A yellow solution is obtained. The peroxides may be removed by shaking I t of ether with a solution containing 60 g FeS04. Potassium permanganate solution: decolourized in acid solution and oxygen is evolved: 2MnO. Chromium pentoxide test If an acidified solution of hydrogen peroxide is mixed with a little diethyl ether (highly inflammable). followed by washing with alkali and redistilling. Melior's Modern Inorganic Chemistry. reaction 4. * Cf. acidified previously by dilute sulphuric acid. 323.33. . Section VII.24. 380 6th edn. -+ H 202 +2H+ +21- 3.43 QUALITATIVE INORGANIC ANALYSIS sodium peroxide in small portions to ice water: Na 202 +2H 20 = H 202 +2Na+ +20HOwing to the heat liberated in the reaction.. The use of amyl alcohol is.IV. Longman 1967. To this. reaction 6). the upper organic layer is coloured a beautiful blue. and 110 ml water. NaB0 3 AH 30. 6 ml concentrated H 2S04. a blank test must always be carried out with the ether alone because after standing it may contain organic peroxides which give the test. + H 20 -+ H 202 + B0 2 1. amyl alcohol or amyl acetate and a few drops of potassium dichromate solution added and the mixture gently shaken. If ether is employed. add a nearly neutral solution of hydrogen peroxide. part of the hydrogen peroxide is decomposed: 28 202 -+ 2H 20+02t Hydrogen peroxide is prepared in industrial scale by an electrochemical method. iodine is formed slowly and the solution turns gradually to deeper and deeper blue: 12 +2H 20 Molybdate ions accelerate this reaction. In the presence of I drop of 0'025M (0'4 per cent) ammonium molybdate solution the reaction is instantaneous. and Section 111. This is a very delicate test. The test will detect 0'1 mg of hydrogen perodide. Potassium iodide and starch If potassium iodide and starch are added to hydrogen peroxide.7H20. this yields hydrogen peroxide when its aqueous solution is heated: BO:. however. The peroxides may also be removed by treatment with aqueous sodium sulphite. see Section IV. The solution turns to green and Prussian blue separates slowly. * A convenient source is the inexpensive sodium perborate. + 5H 202 + 6H+ -+ 2Mn2+ + 50 2i + 8H 20 4. then with chromic acid solution (to oxidize any acetaldehyde produced). 5. Titanium (IV) chloride solution: orange-red colouration (see under Titanium. 2. For further details.I7.

p. e.+ H 20 2 4Fe3+ +3[Fe(CN)6]4-+ 2[Fe(CN)6]4. Add a drop of the reagent (equal volumes ofO'5M iron(III) chloride solution and 0'033M potassium hexacyanoferrate(III) solution) to each. To 20 ml 2M sodium hydroxide add 5 ml I per cent aqueous solution of lucigenine (dimethyl diacridylium dinitrate).000. gold chloride solution in a micro crucible and warm. sodium thiosulphate.250. Lead sulphate test white lead sulphate: PbS! + 4H 20 2 -+ Hydrogen peroxide converts black lead sulphide into PbS0 4! + 4H 20 Place a drop of the neutral or slightly acid test solution upon drop-reaction paper impregnated with lead sulphide. In adjacent depressions of a spot plate place a drop of distilled water and a drop of the test solution. sodium sulphite. To one-half of the solution add I drop of 1 per cent osmium tetroxide solution and mix. For the explanation of these phenomena consult the literature. Gold chloride solution: reduced to finely divided metallic gold. the solution is coloured red or blue with colloidal gold.+ 2H+ + O 2 l Fe4[Fe(CN)6]3! Prussian blue is then produced from iron(III) and hexacyanoferrate(II) ions: -+ (cf. 2Au3+ + 3H 20 2 -+ 2Au! + 30 2 i + 6H+ The spot-test technique is as follows. which appears greenish-blue by transmitted light and brown by reflected light. Mix a drop of the neutral test solution with a drop ofO·33M. etc. A white spot is formed on the brown paper. Switch off the light.43 Hydrogen peroxide reduces hexacyanoferrate(III) ions to hexacyanoferrate(II) : 2[Fe(CN)6]3. Indicators. 8. Chemiluminescence test This test has to be carried out in a dark room. turns to bluish-violet. exposing it to a little hydrogen sulphide gas and then drying in a vacuum desiccator. 381 .g.000. Erdey in E. Other reducing agents. tin(II) chloride. Add 5 ml 3 per cent hydrogen peroxide solution and mix. The light flares up. reaction 6 and Section 111. Section 111. then quickly fades away. After a short time.22. Sensitivity: 0'1 ug H 20 2 • Concentration limit: I in 600." * See L. reaction 5). Sensitivity: 0'07 ug H 20 2 • Concentration limit: I in 700. The lead sulphide paper is prepared by soaking drop-reaction paper in a 0'OO25M solution of lead acetate. 7. so that this reaction is not always a reliable test. will reduce hexacyanoferrate(III) ions to hexacyanoferrate(II). the phenomenon lasts for about 15 minutes. Bishop (ed. Pergamon Press 1972. A steady greenish-yellow light is emitted. The paper will keep in a stoppered bottle.REACTIONS OF ANIONS IV. The spot-test technique is as follows. 713 et f.). 6.21.000. Sensitivity: 0'04 ug H 202 • Concentration limit: I in 1. A blue colouration or precipitate is formed.

which soon disappears. Sodium dithionite is a powerful reducing agent. S20~- +Cu2+ +2H 20 -+ CU!+2S0~. Na2S204' 1. S20~- + HgCl 2 +2H 20 -+ Hg!+2S0~. which are produced in both processes can be removed from the solution with sodium carbonate.+Zn 2.+2CI- +4H+ 6. accompanied by the evolution of sulphur dioxide and the precipitation of sulphur: 2S20~. Concentrated sulphuric acid: immediate evolution of sulphur dioxide and the precipitation of pale-yellow sulphur. A solution of the salt. is precipitated. containing an excess of sodium hydroxide. To study these reactions use a freshly prepared O'5M solution of sodium dithionite. 4.+C16HI002N2 +2H 20 -+ C16H1202N2 +2S0~. S20~. Methylene blue solution: immediate decolourization in the cold. sodium dithionite. 7. known as indigo white.+2H+ (indigo) (indigo white) 382 . Na2S204.44 QUALITATIVE INORGANIC ANALYSIS IV.Dithionites are obtained by the action of reducing agents.4. Mercury(II) chloride solution: grey precipitate of metallic mercury.44 DITHIONITES. when zinc carbonate is precipitated.IV.+2H 20 Sulphur dioxide may also be passed into a cooled suspension of zinc dust in water: Zn+2S0 2 -+ Zn2+ +S20~Zinc ions. Silver nitrate solution: black precipitate of metallic silver.+4H+ -+ 3S0 2i+S!+2H20 2. is used as an absorbent for oxygen in gas analysis.+ 2H 2S04 -+ 3S0 2l + S! + 2S0~. Copper sulphate solution: red precipitate of metallic copper. Section IV.2H20. reaction 3). upon hydrogen sulphites 4HS0 3 +Zn -+ S20~. The methylene blue is reduced to the colourless leuco compound. S20~.+4H+ 5. Indigo solution: reduced to the colourless leuco compound. By saturating the solution with sodium chloride. Dilute sulphuric acid: orange colouration. S20~- +2Ag+ +2H 20 -+ 2Ag! +2S0~.+ 2820 3. 2S20~. such as zinc. white silver sulphite is also precipitated (cf.+2S0~.+4H+ If the reagent is added in excess.

like carbondioxide. of course. liberate sulphur dioxide which. The nitrate cannot.45 SPECIAL TESTS FOR MIXTURES OF ANIONS When the reactions of individual anions have been studied. not influenced by the presence of carbonates. The residue has lost its reducing power to indigo and methylene blue solution. To detect carbonates in the presence of sulphites. treat the solid mixture with dilute sulphuric acid and pass the evolved gases through a small wash-bottle or boiling tube containing potassium dichromate solution and dilute sulphuric acid.REACTIONS OF ANIONS IV. as samples often contain mixtures of ions which might interfere with each other's tests. Potassium hexacyanoferrate(II) and iron(II) sulphate If potassium hexacyanoferrate(II) and iron(II) sulphate are mixed. be completely removed. on treatment with dilute sulphuric acid. produces a turbidity with lime or baryta water. because of oxidation caused by dissolved and atmospheric oxygen. Action of heat Upon heating solid sodium dithionite it suddenly evolves sulphur dioxide at about 1900 (exothermic reaction). at the same time. white precipitate of dipotassium iron(II) hexacyanoferrate(II) turns quite rapidly into Prussian blue (cf. All of these are of great practical importance. The nitrite is therefore completely decomposed first by one of the following methods: (i) Boil with ammonium chloride solution until effervescence ceases.21. Reference will be made to the 'soda extract' and to the 'neutralized soda extract' (see 20 below) as these are normally used in systematic analysis.4S 8. 383 . 2. however. Section 111. 2Na 2S20 4 -+ Na 2S03+ Na2S203 + S02 i IV. be used when trying out these procedures. being a mixture of sodium sulphite and sodium thiosulphate. and starch paste (or potassium iodide-starch paper). reaction 6). reaction takes place in * Traces of nitrate are always formed in this reaction. Nitrate in the presence of nitrite The nitrite is readily identified in the presence of a nitrate by treatment with dilute mineral acid. In the presence of dithionite the precipitate remains durably white. An alternative procedure is to add a little solid potassium dichromate or a small volume of 3 per cent hydrogen peroxide solution to the mixture and then to warm with dilute sulphuric acid. Full experimental details of the various tests referred to in this section will be found under the reactions of the anions.* (ii) Warm with urea and dilute sulphuric acid until evolution ofgasceases. the student should try his skill in carrying out these special tests. The solution will be turned green and the sulphur dioxide will. however. the residual gas is then tested with lime or baryta water in the usual manner.* (iii) Add the solution to solid hydrazine sulphate. potassium iodide. A solution of the sodium salts of the various anions may. The dichromate test for sulphites is. 9. be detected in the presence of a nitrite since the latter gives the brown ring test with iron(II) sulphate solution and dilute sulphuric acid. the evolved gas is then passed through lime or baryta water. Carbonate in the presence of sulphite Sulphites. 1.

(Discard the ammoniacal silver reagent immediately after use. cf. Chloride in the presence ofbromide and/or iodide Method A This procedure involves the removal of the bromide and iodide (but not chloride) by oxidation with potassium or ammonium peroxodisulphate in the presence of dilute sulphuric acid. Since silver sulphate is only slightly soluble in water. The nitrate can then be tested for by the brown ring test. powdered Devarda's alloy or aluminium powder (or wire) is then added and the solution gently warmed. Nitrate in the presence ofbromide and iodide The brown ring test for nitrates cannot be applied in the presence of bromides and iodides since the liberation of the free halogen with concentrated sulphuric acid will obscure the brown ring due to the nitrate. and the danger of slight oxidation of nitrite to nitrate is thereby avoided.IV. 5. the chlorate is at the same time reduced to chloride. if present. detected by its smell and its action upon mercury(I) nitrate paper (see Section 111.45 QUALITATIVE INORGANIC ANALYSIS the cold. it may be removed first by the addition of silver sulphate solution or ammoniacal silver sulphate solution. a portion of the filtrate is carefully mixed with a five-fold excess of concentrated sulphuric acid. Section 111. The nitrate is reduced to ammonia as described under 3. 2r+S20~. it is better to use ammoniacal silver sulphate solution. The free halogens are thus liberated. 4. and may be removed either by simple evaporation (addition of water may be necessary to maintain the original volume) or by evaporation at about 80° in a stream of air. and the iron(II) sulphate solution cautiously introduced down the side of the tube.6. 3.-+ I 2i+2S0i- 2Br. Nitrate in the presence of chlorate The chlorate obscures the brown ring test. This reagent contains [Ag(NH3hJ2S04 and provides a high concentration of silver ions: it is prepared by dissolving 7'8 g pure silver sulphate in 50 ml of 2M ammonia solution and diluting to 100 ml with water. reaction 3). An alternative method is to remove the halides by adding saturated silver sulphate solution. the silver halides are filtered off. which may be tested for with silver nitrate solution and dilute nitric acid. The solution is therefore boiled with sodium hydroxide solution until ammonium salts.38. The test solution is treated with sufficient of the reagent to precipitate all the halides. reaction 1) and upon red litmus paper. are completely decomposed. The evolution of ammonia. If a chloride is originally present.+S20~384 -+ Br 2i+2S0i- . 2N0 2 +N 2H4 +2H+ N0 2 +N 2H4+2H+ -+ -+ N 2i+N20i+3H20 NHt +N 20i+H20 (iv) Add some sulphamic acid to the solution: N0 2+HO.S0 2·NH2 -+ N 2i+SOi-+H++H20 The sulphamic acid procedure is probably the simplest and most efficientmethod for the removal of nitrite in aqueous solution. indicates the presence of a nitrate.

2 tube). add excess silver nitrate solution. Add more potassium peroxodisulphate or water as may be found necessary. and aspirate a current of air through the solution with the aid of a filter pump until the solution is colourless (Fig. but not silver bromide or silver iodide. The addition of bromide ions to the solution of silver chloride in ammonia results in the solubility product of silver bromide being exceeded.REACfIONS OF ANIONS IV.2. is appreciably soluble. freshly prepared solution containing 4 per cent formaldehyde in 0'05M sodium carbonate solution: pour a little of the latter reagent through the filter several times. Add solid potassium peroxodisulphate and dilute sulphuric acid to the 'neutralized soda extract' of the mixed halides contained in a conical flask. silver iodide is unaffected. Alternatively. and precipitation occurs.45 It must be emphasized that these reactions take place only in acid media. Test the filtrate for chloride with silver nitrate solution and dilute nitric acid. Do not mistake precipitated silver sulphate for silver chloride. Acidify the solution with acetic acid. In a modification of this method. T is a drawn out capillary Fig. Silver bromide reacts slightly with the reagent yielding a faint opalescence. 385 . and then treat the precipitate with a cold. and test the filtrate. IV. add lead dioxide. wash the precipitated halides until free from excess silver nitrate solution. and wash until the washings no longer give the reactions of silver ions. which should be colourless. lead dioxide issubstituted for potassium peroxodisulphate. filter. filter. Shake the precipitate with ammonium carbonate solution. and boil the mixture until bromine and iodine are no longer evolved. Filter. with silver nitrate solution and dilute nitric acid. and add a few drops of potassium bromide solution to the filtrate. Method B Acidify the neutralized soda extract (see 20 below) of the halides with dilute nitric acid. IV. a yellowish-white precipitate of silver bromide is obtained if a chloride is present. Test the residual colourless liquid for chloride with silver nitrate solution and dilute nitric acid. The hydrolysis of the ammonium carbonate in aqueous solution gives rise to free dilute ammonia solution in which silver chloride. heat the flask to about 80°.

CI0 3 +3H. The violet colour will disappear. into sodium hydroxide solution. reject the filtrate. filter off the precipitated silver chloride.45 QUALITATIVE INORGANIC ANALYSIS 6. the reduction may be effected by heating the filtrate with a few ml of 10 per cent formaldehyde solution: a white precipitate of silver chloride forms if a chlorate is present. Chloride Acidify with dilute nitric acid and boil to expel carbon dioxide. and perchlorate in the presence ofeach other Each anion must be tested for separately. shake. which contain chromyl chloride. 386 . The separation is based upon the solubility of silver chloride in dilute ammonia solution and the practical insolubility of silver iodide in this reagent. will be obtained if a bromide is present. the solution will be colourless after the violet colour has disappeared. Continue the addition of chlorine water or of acidified sodium hypochlorite solution drop by drop to oxidize the iodine to iodate and shake after each addition. due to dissolved bromine (and/or bromine monochloride.+3H. a white. b. a white precipitate of silver chloride indicates the presence of chloride. 9. chlorate. Add silver nitrate solution. a violet colour indicates iodide. 7. To the soda extract. be absent. Chlorates must. of course. Test for chromate. Alternatively. and pass the vapours.COOH * If a solution is being analysed. it should be evaporated to dryness before applying the test. Wash the precipitate with dilute ammonia solution and filter again. Chloride in the presence of bromide Warm the solid mixture* with a little potassium dichromate and concentrated sulphuric acid in a small distilling flask (Fig. Add dilute nitric acid to the washings. Now introduce a little chloride-free sodium nitrite (which reduces the chlorate to chloride) and more silver nitrate solution into the filtrate. a. Chloride in the presence of iodide Add excess silver nitrate solution to the neutralized soda extract (see 20) and filter. IV. Silver chlorate and perchlorate are soluble in water.IV. (a) Acidify with dilute nitric acid and add excess silver nitrate solution.CHO -+ Cl. strongly acidified with dilute hydrochloric acid add 1-2 drops of chlorine water (the solution obtained by carefully acidifying a dilute solution of sodium hypochlorite with dilute hydrochloric acid may also be used) and 2-3 ml chloroform or carbon tetrachloride. and a reddish-brown colouration of the chloroform or carbon tetrachloride. 8. a white precipitate of silver chloride indicates the presence of chloride. Ifiodide alone is present. which proves the presence of a chloride. Chloride. curdy precipitate of silver chloride indicates the presence of chlorate. Bromide and iodide in the presence ofeach other and ofchloride The presence of a chloride does not interfere with the reactions described below. Divide the soda extract into 3 parts. Chlorate Any of the following methods may be used. BrCI).I). with hydrogen peroxide and amyl alcohol or with the diphenylcarbazide reagent.

and test for chloride with silver nitrate solution and dilute nitric acid. Iodate and iodide in the presence ofeach other The addition of dilute acid to a mixture of iodate and iodide results in the separation offree iodine. add a little indigo solution followed by sulphurous acid solution: the indigo is bleached if a chlorate is present. boil off the excess sulphur dioxide. pass in sulphur dioxide to reduce the arsenate to arsenite. and add silver nitrate solution and dilute nitric acid. Pass sulphur dioxide into the filtrate to reduce iodate to iodide. due to the interaction between these ions: 103 + 51. the latter on gently warming and the former on boiling. A white precipitate indicates the presence of a phosphate. and pass hydrogen sulphide into the solution to precipitate the arsenic as arsenic(III) sulphide. AsO~-+21-+8H+ -+ 2As H +3H 2S 12+H 2S -+ -+ As H+1 2+4H20 As 2S3!+6H+ S!+21-+2H+ 387 . c. afterwards removing the excess silver with a solution of sodium carbonate. heat to boiling.REACTIONS OF ANIONS IV. boil off the excess sulphur dioxide. the latter is coloured violet. Add excess silver sulphate solution to another portion of the neutral solution and filter off the silver iodide. and boil off the hydrogen sulphide from the filtrate. Test for iodide in the neutralized soda extract or in a solution of the sodium salts by the addition of a few drops of chlorine water (or acidified sodium hypochlorite solution) and 2-3 ml chloroform or carbon tetrachloride. Add ammonia solution until alkaline. boil off the excess sulphur dioxide (test with potassium dichromate paper). An alternative method for the elimination of arsenate is the following. and excess of the magnesium nitrate reagent. sulphuric or acetic acids in the cold. Evaporate the resulting solution to dryness and heat to dull redness (better in the presence of a little halide-free lime) to convert the perchlorate into chloride. Acidify the soda extract with dilute hydrochloric acid. 11. Filter off the arsenic(III) sulphide.45 (b) Acidify with dilute sulphuric acid. A yellow precipitate of silver iodide confirms the presence of iodate in the original substance. Acidify the soda extract with dilute hydrochloric acid and then add about onequarter of the volume of concentrated hydrochloric acid (the total volume should be about 10 ml). remove the excess silver sulphate with sodium carbonate solution. Extract the residue with water.+ 6H+ -+ 312 + 3H 20 Neither iodates nor iodides alone do this when acidified with dilute hydrochloric. Filter. boil off the hydrogen sulphide. continue the passage of hydrogen sulphide until no more precipitate forms. Phosphate in the presence ofarsenate Both arsenate and phosphate give a yellow precipitate on warming with ammonium molybdate solution and nitric acid. 10. and test the filtrate for phosphate by the ammonium molybdate test or with the magnesium nitrate reagent. and precipitate the chloride with silver sulphate solution. and pass hydrogen sulphide into the boiling solution until precipitation is complete (5-10 minutes). Add O· 5 ml of 10 per cent ammonium iodide solution. Perch/orate Pass excess sulphur dioxide into the solution to reduce chlorate to chloride.

the sulphate is precipitated as barium sulphate 388 . and sulphate in the presence of each other Upon the addition of dilute acid to the mixture. Phosphate. Test for arsenite in the filtrate (B) by acidifying with dilute hydrochloric acid and passing hydrogen sulphide. Render the filtrate (C) slightly ammoniacal and add a little magnesium nitrate reagent: white. render just alkaline with dilute ammonia solution and filter. Treat the residue on the filter with a little silver nitrate solution containing a few drops of dilute acetic acid: a brownish-red residue (due to Ag 3As04 ) indicates arsenate present. and then adding a further excess: Zn2+ + 8NH 3 + 2H 2 0 -+ [Zn(NH 3)6]2+ + 20H. Filter off the precipitate.IV. and keep the filtrate (B). Wash the precipitate (A) with 2M ammonia solution. liberated from the sulphide. liberated from the sulphite and thiosulphate. Filter off the white.45 QUALITATIVE INORGANIC ANALYSIS 12. A mixture of the sodium salts or soda extract is employed for this separation. when a black precipitate of copper(II) sulphide will indicate sulphide. arsenate. or it may be tested for sulphide in the usual manner. and pour a little silver nitrate solution (containing a few drops of dilute acetic acid) over it: yellow silver phosphate will be formed.+ 2NHt when zinc sulphide will be precipitated and is filtered off. crystalline precipitate ofmagnesium ammonium phosphate andj or magnesium ammonium arsenate(A). if necessary. the hydrogen sulphide. wash with a little water. shake or stir from time to time. and remove half of it to a small beaker with the aid of a clean spatula. warm to expel carbon dioxide. A simple method for separating sulphite and sulphate consists in acidifying the neutral solution of the alkali salts with dilute hydrochloric acid and adding excess barium chloride solution. Treat the solution of the sodium salts with an alkaline solution of hexamminezincate hydroxide [Zn(NH 3)6](OHh prepared by adding ammonia solution to zinc nitrate solution until the initial precipitate of zinc hydroxide has redissolved. Alternatively. if the organic layer acquires a purple colour. this complication necessitates the use of a special procedure for their separation (see Table IV. If the residue is yellow (largely Ag3P04 ) . react and sulphur is precipitated.2). pour 6M hydrochloric acid through the filter a number of times. precipitate the arsenic as arsenic(III) sulphide with hydrogen sulphide and boil off the hydrogen sulphide in the filtrate. and arsenite in the presence of each other Treat the soda extract with dilute sulphuric acid until acidic. Sulphide. sulphite. and add a little potassium iodide solution and 1-2 rnl chloroform or carbon tetrachloride to the extract and shake. with ammonium iodide solution (as described under 11). when a yellow precipitate of arsenic(III) sulphide is immediately produced if arsenite is present. The precipitate may be treated with dilute hydrochloric acid and a few drops of copper sulphate solution. An alternative procedure for the removal of the sulphide is the following. Add a few millilitres of the magnesium nitrate reagent and allow to stand for 5-10 minutes. better. and the sulphur dioxide. the ammonium molybdate test may be applied to the filtrate (C) after evaporating to a small volume. thiosulphate. reduce the arsenate (if present) with sulphur dioxide or. Dissolve the white precipitate in the beaker in dilute hydrochloric acid. 13. an-arsenate is present. crystalline magnesium ammonium phosphate will be precipitated if a phosphate is present.

and warming. Thiosulphate present. treat the remainder ofthe filtrate with a drop ofphenolphthalein solution and pass in carbon dioxide until the solution is decolourized by it. SrS04· White. When no sulphide is present. a thiosulphate is indicated. SrS03 and SrS04' Wash.REACfIONS OF ANIONS IV. allow to stand overnight and filter.g. If sulphur separates. Test a portion of the filtrate with sodium nitroprusside solution to see that all the sulphide has been removed. 15. t Sulphite present. and filter. proves the presence of sulphite. Residue CdS and excess ofCdC0 3. sulphite. Wash and reject washings. and sulphate Shake the solution with excess offreshly precipitated CdC0 3 . the latter is decolourized.23. Acidify with dilute HCl and boil. Digest residue with dilute acetic acid to remove excess carbonate. e. Alternatively. treat with dilute HCl and filter.2 Separation of sulphide. The formation of a purple colouration indicates the presence of a sulphide. Sulphide. and is removed by filtration. SrS0 3. Test 2-3 ml of the colourless solution with 0'5-1 ml of the fuchsin reagent. the presence of sulphite is indicated. Residue Filtrate Contains sulphurous acid. u. reaction 2). If the reagent is decolourized. . if it is decolourized. remove it by shaking with freshly precipitated cadmium carbonate and filter. it must be remembered that copper and barium salts may also impart a green colour to the alcohol 389 • Solubility in g £ -1: SrS203' 250 at 13°. The production of a further precipitate of barium sulphate upon the addition to the filtrate of a little concentrated nitric acid or bromine water. A yellow residue indicates sulphide. Sulphate present. S02 is evolved and S is slowly precipitated. Confirm by fusion with Na2C03 and apply sodium nitroprusside test. and thiosulphate in the presence of each other It is assumed that the solution is slightly alkaline and contains the sodium salts of the anions. (i) Test a portion of the solution for sulphide with sodium nitroprusside solution. sulphite. Confirm by warming with dilute HCl and test the evolved H 2S with lead acetate paper. (iii) Treat the remainder of the colourless solution with dilute hydrochloric acid and boil for a few minutes. the soda extract is used. Borate in the presence of copper and barium salts When carrying out the ethyl borate test for borates (Section IV. sulphite is present. thiosulphate. shake. add a few drops offuchsin reagent. reaction 9) may be applied. t Alternatively. Add a few drops of a dilute solution of iodine.5. (ii) If sulphide is present. Filtrate Contains SrS203. the nickel ethylenediamine nitrate test (Section IV. 0'033 at 17°.4S Table IV. Residue Filtrate Add Sr(N0 3h solution" in slight excess.

390 . fitted with a glass jet and surmounted by a wide glass tube. Table IV. 16. The residue is soluble in ammonium acetate solution. and the vapours ignited at the top of the wide glass tube.3 flame. and sulphate in the presence ofeach other The following differences in solubilities ofthe lead salts are utilized in this separation: lead hexafluorosilicate is soluble in water. test 10. lead sulphate is insoluble in water and in boiling dilute acetic acid. An alternative procedure is given in Section V. (ii) Larger portion.2. White residue indicates sulphate. but soluble in concentrated ammonium acetate solution.3 Detection of fluoride. White crystalline precipitate indicates hexafluorosilicate. concentrated sulphuric acid. and ethanol is placed in a small round-bottomed flask. Milkiness of the water and etching of the tube indicate fluoride.3). Filtrate Add Ba(N0 2 h solution and warm gently. Add excess dilute acetic acid and boil (this will dissolve any lead fluoride). Fluoride. IV. (i) Smaller portion.IV.45 QUALITATIVE INORGANIC ANALYSIS o Fig. A green flame confirms the presence of a borate. which acts as a 'chimney' (Fig. The test may be carried out in the following way when salts of either or both of these metals are present. hexajluorosi/icate. lead fluoride is insoluble in water but soluble in dilute acetic acid. Treat cautiously with concentrated sulphuric acid and test with a moist glass rod. and sulphate in the presence of each other Add excess lead acetate solution to the solution of the alkali metal salts. Divide into two parts. The mixture of the borate.IV. hexafluorosilicate. The mixture is gently warmed. and filter cold. Residue Wash well with cold water.

a white precipitate of silver cyanide is obtained. 391 . The calcium salts are precipitated in neutral or faintly basic solution. the mixture warmed.I7. For the detection of cyanide. curdy precipitate of silver chloride confirms the presence of chloride. reaction 6). hexacyanoferrate(III). and the evolved hydrogen cyanide passed into silver nitrate solution acidified with dilute nitric acid. The residue is then tested for fluoride by the zirconiumalizarin-S test. chloride. ammonia is evolved. (i) The concentrated solution. and the separation of chloride.45 17.REACfIONS OF ANIONS IV. and iodide carried out as detailed under 8. The cyanide can also be detected by the usual Prussian blue test or 'iron(III) thiocyanate' test (Section IV.I7. Use may be made of the fact that even solid calcium fluoride reacts with the zirconium-alizarin-S reagent (compare Section IV. bromide. and iodide in the presence of one another the cyanide is first completely removed. the whole is filtered and the excessnickel sulphate removed by boiling with sodium hydroxide solution and filtering off the precipitate of nickel hydroxide. and thiocyanate ions. This method can be employed in the presence of hexacyanoferrate(II). or preferably the solid mixture of sodium salts is treated with about 5 times its weight of' I ()() volume' hydrogen peroxide and the mixture gently warmed. which interfere in aqueous solution. reactions 4 and 6).I). bromide. which is recognized by its action upon mercury(I) nitrate paper. + NH 3 (ii) The cyanide is precipitated as the pale-green nickel cyanide by the addition of excess of a solution of nickel sulphate to the neutral solution. IV. and then tested for chloride with silver nitrate solution and dilute nitric acid. CN. HCO.+H 2 0 2 OCN.S. The oxalate is most simply detected by dissolving a portion of the precipitate in hot dilute sulphuric acid and then adding a few drops of a very dilute solution of potassium permanganate. The solution is then boiled to decompose all the hydrogen peroxide. The filtrate is acidified with dilute nitric acid and excess silver nitrate solution added. The precipitate is ignited and digested with dilute acid. A white. reaction 6) and. The fluoride may be identified in the usual manner with concentrated sulphuric acid or as described below. 18 Chloride and cyanide in the presence ofeach other Both silver chloride and silver cyanide are insoluble in water. the red hue of the reagent disappears and a yellow colouration results (see Section IV. Three methods are available for the detection of cyanide in the presence of chloride. in consequence. but soluble in dilute ammonia solution. the fluoride test may be carried out in the presence of oxalate and phosphate.+ 2H 20 -+ -+ OCN. The latter will be decolourized if an oxalate is present.+H 2 0 . Oxalate in the presence of fluoride Both calcium fluoride and calcium oxalate are precipitated by ammonium oxalate solution in the presence of dilute acetic acid. (iii) The solution of the mixed sodium salts is treated with excess solid sodium hydrogen carbonate (see Fig.

Detection of organic acids (oxalate. acidify extract wit dilute HCI. It is advisable to boil gently for a minute or two to remove any appreciable excess of ammonia. boil gently to expel carbon dioxide and allow to cool. in the form of a Whatman filtration accelerator) cannot be used as the organic matter may cause appreciable reduction of the hexacyanoferrate(III). add excess of a solution ofthorium nitrate and a little Gooch asbestos and shake well. 392 . hexacyanoferrate(III). formate. acidify the alkaline extract with dilute HCl and add a few drops of FeCl 3 solution. Cd 3[Fe(CN)6]2 and asbestos. Note: With Fenton's reagent and a neutral solution of a citrate. when benzoic acid will separate out on cooling. Red colouration of ether proves presence of thiocyanate. filter. Filtrate Add CdS04 solution and a little Gooch asbestos. a yellow or brown colour is obtained. citrate. It can be identified by its melting point. on the filter paper with dilute NaOH solution.5). Extract with NaOH solution. Treat the ppt. benzoate. filter off the precipitated iron(III) hydroxide and discard the precipitate. Residue Th[Fe(CN)6] and asbestos (the latter is added to facilitate filtration of the gelatinous precipitate). and salicylate) in the presence of each other Intimately mix the mixture of acids and/or their salts with 3-4 times the bulk of anhydrous sodium carbonate. the iron is precipitated as the hydroxide. with an oxalate. The resulting solution will be free from heavy metals and almost neutral. succinate. I l) . • Filter paper pulp (e. acetate. A precipitate of Prussian blue indicates hexacyanoferrate(lI). boil offthe excessammonia from the filtrate. Procedure A Separation of benzoate and succinate Boil the precipitated iron(III) salts with a little dilute ammonia solution. It will be referred to as the neutralized soda extract (see Table IV.4 Separation of hexacyanoferratetlf). 20.g. filter. if not clear. but there is no precipitation ofiron . and thiocyanate in the Table IV. Wash and neglect the residue. add freshly prepared FeS04 solution. Acidify the second portion of the filtrate with dilute hydrochloric acid. and thiocyanate Acidify the neutralized soda extract of the sodium salts with acetic acid. h e x a c y a n o f e r r a t e t I l l) . The filtrate will be termed the soda extract. Precipitate of Prussian blue indicates hexacyanoferrate(lII). Residue Orange. Filtrate Add FeCl 3 solution and ether. Filter. add just sufficient water to dissolve the sodium carbonate. Confirm the succinate by the fluorescein test. Treat the combined filtrate and washings with dilute nitric acid a little at a time with stirring until acid (use litmus paper test). Add dilute ammonia solution portionwise and with stirring until just alkaline. tartrate.45 QUALITATIVE INORGANIC ANALYSIS Hexacyanoferratet presence ofeach other 19.IV. Divide the filtrate into two parts. and filter. shake.· Wash with a little cold water. heat under reflux for 15 minutes. The residue consists of barium succinate. Treat one portion with barium chloride solution and filter off the precipitate formed.

(a) Violetsalicylate. boil and filter. Separate by procedure B. It must be remembered that phosphates. or by decolourization of a dilute solution of acidified KMn04 at 60-700.REACTIONS OF ANIONS IV. (b) Deep blue or greenish black .5 Separation and detection of organic acids" Add CaCl 2 solution to the cold neutralized soda extract. Residue Filtrate Add more CaCl 2 solution. filter. which is converted into a black deposit of silver on boiling. Boil under reflux with an equal volume of potassium dichromate solution and dilute sulphuric 393 . Test neutral solution with Fenton's reagent. (ii) In the presence of tartrates. proceed with solution.t Basic iron(III) formate and basic iron(III) acetate. Divide into 2 parts. A solution of formic and acetic acids will pass over. fluorides.. may form gradually. Residue Filtrate May contain Ca tartrate. Neutralize the distillate with dilute ammonia solution. violet colouration (see Note).4S Table IV. If citrate absent. citrates. citrates. Oxalate present. Separate by procedure A. Ca citrate. filter.. or by silver mirror test for tartrate. Filtrate Coloured. convert into neutral solution with NH 3 solution. Confirm by resorcinol test. evaporate to dryness on water bath. etc. Residue Filtrate If citrate present. Table V. etc. use the neutralized soda extract. and filter from any residue of Ca citrate. and add CdCl 2 solution. Add FeCl 3 solution. Filtrate Coloured. Acetate If other organic acids are present. otherwise. are precipitated by calcium chloride solution. t Gallates and tannates are of rare occurrence in general qualitative analysis. a white precipitate. when carbon monoxide (burns with blue flame) will be evolved in the cold. Citrate present. t Procedure B Formates and acetates in the presence of each other Formate. Acidify the mixture with dilute sulphuric acid and distil. Residue May be Ca oxalate (formed immediately) or Ca tartrate (formed on standing). Dilute. Add silver nitrate solution to the neutralized soda extract. Confirm by copper hydroxide test. Residue Iron (Ill) benzoate and/or iron(III) succinate. and reducing agents. (i) Confirm by Deniges's test. • See Section V. filter (if necessary). Boil with dilute acetic acid and filter. (ii) Dissolve in dilute HCl.29 for a slightly modified procedure. indicates formate. A ppt. boil off excess ammonia (if necessary) and test as in (i).'] Wash. Confirm by 'oil of wintergreen' test. White. (i) In the absence of tartrates. obtain the solution of mixed acids as in (ii). rub sides of vessel with a glass rod. A little of the solid substance may be treated with concentrated sulphuric acid. add a little cold water. sulphates.IS. insoluble in dilute acetic acid. boil under reflux for at least 5 minutes. White gelatinous precipitate. add NH 3 solution in slight excess White ppt.gallate or rannate. and reducing agents. CaC 2 0 4 • Dissolve in a little dilute HCl. allow to stand for 10 minutes with occasional shaking.

see Section VI. 394 .45 QUALITATIVE INORGANIC ANALYSIS acid. the cacodyl test may be employed. For other methods of separation and detection of selected anions. If the solid is available. this will decompose the formic acid. Distil off the acetic acid. neutralize and test with iron(III) chloride solution.IV.7.

iron(III) chloride and nitrate. The examination for metal ions (cations) in solution. i. the relative magnitudes of the various precipitates will provide a rough guide as to the proportions of the constituents present. Some of the commonly occurring coloured compounds are listed below: Red: Pb 304 . it is assumed that the student is already familiar with the tests and operations described in the preceding chapters. For this purpose 0'5-1 g of the substance is usually employed for the analysis. AS2 S3 . Cr(OHh. to liquids. dichromates are orange-red. permanganates and chrome alum are reddishpurple. It must be emphasized that the object of qualitative analysis is not simply to detect the constituents of a given mixture. chromates. PbI 2 .I INTRODUCTION In the scheme of analysis to be described in the following pages. examination of the volatile products with sodium hydroxide solution (for ammonium). V.2 PRELIMINARY TESTS ON NON-METALLIC SOLID SAMPLES 1. to alloys. Pink: hydrated salts of manganese and of cobalt. Cu 20. but also to mixtures of solid substances. The examination for anions in solution. SnS2 . substances which are insoluble in aqua regia and acid solvents. 2.3H20. HgS. HgI 2 . It will be shown how these isolated facts are incorporated in the systematic methods of qualitative analysis. FeS04. iron(II) salts. Cr0 3 . This includes preliminary examination by dry tests.e. whether it is magnetic and whether it possesses any characteristic odour or colour.g. AS 2 S2 . Appearance The appearance of the substance should be carefully noted. a lens or microscope should be used ifnecessary. Sb2S3 . e. and (D) an 'insoluble' substance. 3. K 4[Fe(CN)6]. applicable not only to simple solid substances. The preliminary examination. an equally important aim is to ascertain the approximate relative amounts of each component. (B) a liquid (solution). HgO. K 3[Fe(CN)6]. Observe whether it is crystalline' or amorphous. Hg 2I 2 . Yellow: CdS. and to 'insoluble' substances. and with dilute and concentrated sulphuric acid (for acid radicals or anions). The substance to be analysed may be: (A) solid and non-metallic. Green: Cr 20 3 .7H 20. HgO (precipitated). Every analysis is divided into three parts: 1. Each of these will be discussed separately. (C) a metal or an alloy. 395 .CHAPTER V SYSTEMATIC QUALITATIVE INORGANIC ANALYSIS V.

Brown when hot. White sublimate. orange-red: dichromates. e. Prussian blue. CdO and many Cd salts.2 QUALITATIVE INORGANIC ANALYSIS FeS04. heat with 4 times the bulk of anhydrous sodium carbonate and a little potassium cyanide in an ignition tube. violet vapour. CuO. tartrates and citrates. iron(II). FeS. Organic substances. HgI 2 (red when rubbed with a glass rod). Brown: Pb0 2. CoS. The following colours are shown by the ions (the cations are usually hydrated) present in the dilute solution: Blue: copper(II). hydrated copper(II) salts. CuC12. 4. 396 . Table V. and any changes which take place carefully noted. often accompanied by burning. Mn0 2. 3. a brownish-black mirror. HgBr 2. purple: permanganates. green: nickel. Fe203' HgCI 2. they are quickly performed (l0-15 minutes) and should never be omitted. The temperature is gradually raised.6H20. HgS. CuS. brown when cold. K 2Mn04· Blue: anhydrous cobalt salts. Yellow sublimate. as this may often give valuable information. Black: PbS. • If a white sublimate forms. AS202. CrC13. S (melts on heating). Grey sublimates. ammonia evolved (test with mercury(l) nitrate paper) indicates ammonium salts.6H20. yielding a white sublimate and an odour of garlic when heated in a wide tube. Yellow when hot. 6. 2. yellow when cold. As. Heating in a test tube Place a small quantity (4-5 mg) of the substance in a dry test-tube so that none of it remains adhering to the sides." 2. ZnO and many Zn salts.Fe 304. The colour of the solution obtained when the substance is dissolved in water or in dilute acids should be noted. CuC0 3. Ag3As04.4H20. A grey mirror. 5: Blue-black sublimate. Blackening. Hg. Steel-grey sublimate. Fe203 and Fe(OHh (reddishbrown). halides. Yellow when hot. indicates Hg. 7. 5. yellow when cold. chromium(III). manganates. Ni 203. Black. I. and Ni salts at a very high temperature.(NH4)2S04. Hg 2C1 ammonium 2. The substance should be reduced to a fine powder in a suitable mortar before proceeding with the following tests. Cu. Yellowish-brown when hot. (b) A sublimate is formed. C0 304. benzoic acid). Blackening from separation of carbon. 2. PbO and some Pb salts. Sn02 or Bi202. CdO. easily rubbed to globules. white when cold. Sb 203. manganese(II). SnS.g. NiS. garlic odour. brown when cold. AS2S3. 3. These tests usually give a great deal of useful information. 4. Heating test Inference I. convertible into globules on rubbing with a glass rod. iron(II). nickel salts. Red to black when hot.I Observation (0) The substance changes colour. C. hexacyanoferrate(II). the tube should be held in an almost horizontal position. red on trituration. certain volatile organic compounds (oxalic acid. and heat cautiously. Mn. Ag2S.V. not accompanied by burning or odour. \. FeC12.2H20. indicates As. pink: cobalt. 6. HgS. yellow: chromates.

also acids. inflammable). and permanganates. 397 .4). e. hydrated sulphides. oxy-acids. bleaches litmus paper. Dinitrogen oxide (rekindles glowing splint) and steam are evolved. turns red litmus paper blue. e. Phosphites and hypophosphites. 4. Free iodine and certain iodides. and introduce a little of the substance on a clean platinum wire into the base of the nonluminous Bunsen flame (Table V. Acetates. Ammonium salts. Sources similar to chlorine. 5. turns potassium dichromate paper green. ammonium salts. The water is acid 2. Oxalates. Nitrates or nitrites of heavy metals. A less delicate method is to view the flame through two thicknesses of cobalt blue glass. Au and Pt. Iodine is evolved (violet vapours condensing to black crystals). 8.) Inference Compounds with water of crystal1ization (often accompanied by change of colour). Oxygen is evolved (rekindles glowing splint). chlorides in presence of oxidizing agents. The water is alkaline. Ammonium nitrate or nitrate mixed with an ammonium salt. Readily decomposed salts of strong acids. sufficient will adhere to the platinum wire for the test to be carried out. Chlorine is evolved (yel1owish-green gas. Phosphine is evolved (odour of fish . Ammonia is evolved (odour. brornates. Hydrogen sulphide is evolved (odour of rotten eggs. Acetone is evolved (burns with luminous flame). Dark-brown or reddish fumes (oxides of nitrogen). acidic in reaction. iodates. 6. of Cu. oxalates. Nitrates. 13. Cyanogen is evolved (burns with violet flame and characteristic odour). Ammonium salts. e. 3.I Observation (c) A gas or vapour is evolved. test with litmus paper. per-salts. poisonous gas. 11. Acid sulphides. certain complex ammines. turns lead acetate paper black or cadmium acetate paper yel1ow). and organic compounds. turns fluorescein paper red). Cyanides of heavy metals. Carbonates. 10. hydroxides. thiosulphates. IS. decolourizes fuchsin solution). K 3[Fe(CN)6].2). 9.g.3. moisten with a little concentrated hydrochloric acid. turns potassium iodide-starch paper blue).SYSTEMATIC ANALYSIS V. acid salts. of Hg and Ag. Mixtures can be readily detected with the direct vision spectroscope (see Fig. that of potassium. and the other colours are modified as listed in Table V. chlorates. whereby the yellow colour due to sodium is masked or absorbed. hydrogen carbonates. 3. An alternative method is to dip the platinum wire into concentrated hydrochloric acid contained in a watch glass and then into the substance. perchlorates. very poisonous. I\. Carbon monoxide is evolved (burns with a blue flame forming carbon dioxide). The sodium flame masks that of other elements. Bromine is evolved (reddish-brown vapour. 7. Water is evolved. very poisonous gas.g. Sulphur dioxide is evolved (odour of burning sulphur. certain sulphates. choking odour. Normal and acid sulphites. Carbon dioxide is evolved (lime water rendered turbid). very poisonous. Flame eolourations Place a small quantity (3-4 mg) of the substance on a watch glass. 12. turns mercury(l) nitrate paper black). peroxides. Heating test (contd.2 Table V. Unstable chlorides. \.g. 14.

Yellow incrustation. yellow when hot. or forms a liquid bead. The substance is infusible and incandescent. Inferences Sodium. The substance deflagrates. Barium (molybdenum). A1203 . Brick-red. Calcium. Flame colouration through cobalt glass Nil. Pb. Potassium. e. Calcium. Ag and Sn (white). 4. brittle metal. MgO (residue alkaline to litmus paper). Carmine-red flame. Sb. NaCI. Livid blue flame (wire slowly corroded). nitrites. iodates. ZnO. Co. Green flame. Apply test (b) below. 3. Table V. garlic odour. perchlorates. or forms an incrustation upon the charcoal. Brick-red (yellowish-red) flame. Borates.3 Flame test with cobalt glass Flame colouration Golden-yellow Violet. Crimson flame. Incrustation with metal: White incrustation. Inference Sodium. marks paper. Table V. Table V. Bluish-green. Incrustation without metal: White. antimony. Crimson. Strontium. White. Barium.5 Ignition with Na 2C03 on charcoal Observation I. The substance decrepitates. Bi. Yellowish-green flame. 2. Nitrates. Inference Crystalline salts. SrO. CaO.V.4 Charcoal block reduction test Observation 1. chlorates. 2. Potassium.2 QUALITATIVE INORGANIC ANALYSIS Table V. malleable metal. 3. Si0 2 (residue not alkaline to litmus paper). permanganates. Strontium. copper (thallium). Ni. attracted by magnet. Brown. copper. brittle metal. Light-green.g. Yellow incrustation. Fe. Lead. Inference BaO. White. Violet (lilac) flame. Malleable beads. Yellowish-green. KCI. Crimson. Lithium. arsenic. bismuth. infusible and incandescent when hot. Purple. 398 . Metal without incrustation: Grey metallic particles. Salts of the alkalis and some salts of the alkaline earths. 4. Cu (red flakes) Au. The substance fuses and is absorbed by the charcoal.2 Flame test Observation Persistent golden-yellow flame.

borates. and nickel (see however. and thus reduction occurs more rapidly than with the charcoal alone.SYSTEMATIC ANALYSIS V.6 Ignition with Co-salts Observation 1. the sodium carbonate acts as a flux and. 3. Blue. Table V. or it may be extracted with a little water and filtered into a freshly prepared sodium nitroprusside solution. Further. chromium. Dark yellow when hot. Yellowish-brown or red when hot. hot and cold. hot and cold. Blue residue. Table V. ZnO. opaque-red. Green residue. 4.25. Reducing flame Colourless when hot. Reddish-brown when cold. Observe the colour when the bead is hot and also when it is cold. yellow when cold. Section VII. Pink residue. Cobalt. 2. when an unstable purple colouration will indicate the presence of sulphur (see Section IV.7. phosphates. when cold.) Prepare a borax beadinaloop ofplatinum wire by dipping the hot wire into borax and heating until colourless and transparent. hot and cold. hot and cold. protects any metallic globules. blue when cold. Colourless. Heat the bead in the inner or reducing flame and observe the colours in the hot and cold states. Green when hot. in the fused state. Table VII. silicates. Blue. 5. place the mixture in a cavity of a piece of charcoal and heat in the reducing flame of the blowpipe.6. 2. Coloured beads are obtained with compounds ofcopper. Charcoal block reductions (a) Heat a little of the substance (3-4 mg) in a small cavity scooped in a charcoal block in a blowpipe flame (Table V. (b) Mix the substance (3-4 mg) with twice its bulk of anhydrous sodium carbonate. which may have formed beneath it. cobalt. The sodium carbonate converts a metallic salt into a carbonate or oxide on heating. the residue may be moistened with water and placed in contact with a silver coin when a brown to black stain of silver sulphide is obtained (Hepar reaction). MgO.2 4. The presence of manganese and of chromium is confirmed by fusing the substance with sodium carbonate and potassium nitrate on platinum foil or 399 . manganese. 6. 3. green when cold. Iron. Chromium. Sulphur compounds are reduced to sulphide by this treatment. from oxidation. Green. hot and cold.6). Violet (amethyst). arsenates. hot and cold. Grey or black and opaque when cold. iron. as in (a). reaction 5) (Table V. Manganese. Bring a minute quantity of the substance into contact with the hot bead and heat in the outer or oxidizing flame. Borax bead reactions (Table V. 5. Green. Metal Copper. Inference A120 3 . (c) Moisten the substance or the infusible residue of test (b) with one or two drops of cobalt nitrate solution and ignite strongly (Table V.8). Nickel.5).7 Borax bead test Oxidizing flame 1.4).

A useful reaction which may be carried out at this stage is the microcosmic bead test (Section 11. 6. If ammonia is present. Under no circumstances should one attempt to smell the vapour whilst heating the mixture. the test paper is supported on the upper end of the wide glass tube. These mixtures tend to bump and should preferably be heated in the fume cupboard.2.2. The following experimental details in testing for ammonia are of value for other gases (with suitable modification of reagents). * indicates the presence of an ammonium salt. The evolution of ammonia. scattered blue spots indicate that droplets of the alkaline solution have come into contact with the paper. may also be used.l may be employed.) in the vapour. the apparatus shown in Fig. detected by its odour and its action upon red litmus paper and upon filter paper soaked in mercury(I) nitrate solution. reaction 7).V. if desired. v. V. The spray may be trapped. 0'1 g) of the substance with sodium hydroxide solution.r • Drop-reaction paper. Note. dissolves slowly in the bead may be mistaken for silica. etc. Fig. Tin(IV) oxide.2 QUALITATIVE INORGANIC ANALYSIS broken porcelain. 400 . by a loosely fitting plug ofcotton wool inserted in the upper part of the test-tube. chromium. Test for ammonium ions Boil a little (c. Great care must be exercised when heating mixtures containing solutions of alkali hydroxides because of their destructive effects upon the eyes. test 7) may also be employed.38. The presence of a white skeleton (of silica) in the coloured glass indicates silicate. Sn0 2 . a yellow mass. The sodium carbonate bead test (Section 11. treated with tannic acid and silver nitrate solution (see Section 111. This test is carried out in a loop of platinum wire exactly as for the borax bead test. test 6). A green mass on cooling indicates manganese. In order to avoid holding the test paper (litmus. the litmus paper should show a gradual development of colour from the bottom upwards and should eventually become uniformly blue.

Colourless gas is evolved with effervescence. and add a drop or two of 6M HC\. see Section IV. CI2 from hypochlorite. recognized by reddishbrown colour. 2. 7. blackens filter paper moistened with lead acetate solution.S. cadmium acetate paper turned yellow. Odour of acetylene. N0 2 from nitrite. produces turbidity when passed into lime water.the second method of preparation is recommended). warm. :\: If cyanide is suspected. dolomite. place a filter paper moistened at the centre with I drop of NaOH solution over the mouth of the tube. IV. an orange or brown precipitate confirms ammonia. and a few other native carbonates give little or no CO 2 in the cold. 8. Colourless gas is evolved. gives above tests for S02. odourless and produces turbidity when passed into lime water. 12. etc. O 2 from peroxides and peroxo-salts of alkali and alkaline earth metals. pungent odour. S02 and S from thiosulphate. from thiocyanate. turns filter paper moistened with acidified potassium dichromate solution green. sulphur is deposited in the solution. sulphur is deposited. and turning starch-potassium iodide paper bluish-black. very poisonous. reminiscent of S02 . 10. CO 2 and a little HCNO from cyanate. some H 2S is evolved upon warming with concentrated HO alone or with a little tin. Table V. reddens and then bleaches litmus paper. Colourless gas is evolved. After 2 minutes." (C) Nitrous fumes evolved. burns with luminous. especially native ones. reaction 2 . rekindles glowing splint. 5. are not affected by dilute H 2S0 4. Colourless gas is evolved. gives above tests for H 2S. 11.2 If the evolved gas is soluble in water and a solution is required for further testing. reaction I. Colourless gas is evolved. Colourless gas is evolved. A blue colour indicates the presence of a cyanide. decolourizes fuschsin soln. 13. S02.l (with the delivery tube of fairly wide tubing and about twice the length of the test-tube or distilling flask in order to avoid the danger of 'sucking back') may be employed. Colourless gas is evolved. Odour of vinegar. (C) Yellowish-green gas evolved. 401 . 3. Upon boiling. CO 2 is readily evolved upon warming. etc. gently warm (water bath) 5 mg of the mixture in a small test-tube (e. S02 from sulphite. CH 3COOH from acetate.) evolved. odour of bitter almond r] highly poisonous. suffocating odour. smoky flame. 6. • Magnesite. turns starch-Kl paper blue.g. the apparatus shown in Fig. 75 x 10 mm) with 5-10 drops of M H 2S0 4. t Many sulphides. 4. gas is Inference CO 2 from carbonate or hydrogen carbonate. H 2S from sulphide.38. Upon adding Nessler's reagent (Section 111. In the present case the ammonia may be absorbed in 3-4 ml of distilled water..SYSTEMATIC ANALYSIS V.] H 2S and S from polysulphide. (C) Colourless gas is evolved with suffocating odour. HCN from cyanide or from soluble hexacyanoferrate(III)s and hexacyanoferrate(ll)s. 9. treat the drop of the paper with I drop of FeS04 solution. Mercury(II) cyanide is attacked slowly. odour of rotten eggs. For another test.8 Test with dilute "28°4 Observation I. This test is an extremely sensitive one and in order to establish the presence of ammonia evolved in the reaction a precipitate and not a colouration must be obtained. yellow solution formed and S02 (fuchsin solution decolourized.

pungent gas evolved which corrodes the glass. and warm the mixture gently. gelatinous ppt. incline the mouth of the test tube away from the observer. In such a case. it is best to add dilute sulphuric acid dropwise to another portion of the substance until reaction ceases. burns with blue flame. 0'1 g) of the substance with 1-2 ml concentrated sulphuric acid. on passing into water. obtain chromic and hydrochloric acids. lead acetate solution. and note whether any reaction takes place in the cold (indicated by C).· 402 . Yellow gas evolved in the cold with characteristic odour. 6. and fumes in moist air. Gas evolved with pungent odour. 9. Mn207 from permanganate. Action of concentrated sulphuric acid Treat a small quantity (say. 5. both readily identified (yellow ppt. turns Kl-starch paper blue). (If chlorates or permanganates are suspected from the preliminary charcoal reduction tests to be present. Pungent acid fumes evolved. Purple fumes evolved with explosion (GREAT DANGER). Inference HCl from chloride. and often S02 and even H 2S.2 QUALITATIVE INORGANIC ANALYSIS 7. Action of dilute sulphuric acid Treat 0'1 g of the substance in a small test tube with 2 ml M sulphuric acid. HN0 2 and N0 2 from nitrate. 8. often coloured brown by N0 2.) If the substance reacted with dilute sulphuric acid. increased amount of red fumes with odour of bromine (fumes colour moist starch paper orange-red or fluorescein paper red). Cl 2 evolved on addition of precipitated Mn02 (bleaches litmus paper. The following results may be obtained (Table V. 7. irritating odour. very small quantities must be used (about 0·02 g) as a dangerous explosion may occur on warming.8). Cr0 2Cl2 from chloride in presence of chromate. HBr and Br2 from bromide. CI2 from chloride in presence of oxidizing agent. 8. Table V. HF from fluoride or silicofluoride. 2. Colourless gas evolved with pungent odour and which fumes in the air. turns KI-starch paper blue.9 Test with concentrated "28°4 Observation 1. Warm gently and observe the effect produced (Table V. if moistened glass rod introduced into the vapour. the add