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Tata McGraw-Hill’s COURSE ane @ Tata McGraw-Hill Published by Tata McGraw Hill Education Private Limited, 7 West Patel Nagar, New Delhi 110 008 Course in Chemistry for IIT-JEE 2012 Copyright © 2011 by Tata McGraw Hill Education Private Limited, First reprint 2011 RQALCRAGDYLZX No part of this publication may be reproduced or distributed in any form or by any means, electronic, mechanical, photocopying, recording, or otherwise or stored in a database or retrieval system without the prior written permission of the Publishers. The program listings (if any) may be entered, stored and executed in a computer system, but they may not be reproduced for publication. ‘This edition can be exported from India only by the publishers, ‘Tata McGraw Hill Education Private Limited. Price: & 625.00 ISBN (13): 978-0-07-132927-9 ISBN (10): 0-07-132927-7 Vice President and Managing Director—MeGraw-Hill Education; Asia Pacific Region: Ajay Shukla Head—Test Prep and School: ¥. Biju Kumar Publishing Manager—Test Prep: K Prakash Manager (Sponsoring): Abhishek Sharma Editorial Executive: Pratibha Singh ‘Asst Manager (Developmental Editing): Amubha Srivastaver Junior Manager—Production: Media Arora Dy Marketing Manager: Niju Sreedharan General Manager—Production: Rajender P. Ghansela Asst General Manager—Production: B. L. Dogra Information contained in this work has been obtained by Tata McGraw-Hill, from sources believed to be reliable. However, neither Tata McGraw-Hill nor its authors guarantee the accuracy or completeness of any information published herein, and neither Tata MeGraw-Hill nor its authors shall be responsible for any errors, omissions, or damages arising out of use of this information. This work is published with the understanding that Tata McGraw-Hill and its authors are supplying information but are not attempting to render engincering or other professional services. If such services are required, the assistance of an appropriate professional should be sought. ‘Typeset at Script Makers, 19, A1-B, DDA Market, Paschim Vihar, New Delhi 110063 and text and cover printed st Gopsons, A-2 & 3, Sector-64, Noida, U.P. 201301 Cover Designer: K Anoop | =a! Tata McGraw-Hill Published by Tata McGraw Hill Education Private Limited, ‘7 West Patel Nagar, New Delhi 110 008 Course in Chemistry for IIT-JEE 2012 Copyright © 2011 by Tata McGraw Hill Education Private Limited. First reprint 2011 ROALCRAGDYLZX No part of this publication may be reproduced or distributed in any form or by any means, electronic, mechanical, photocopying, recording, or otherwise or stored in a database or retrieval system without the prior written permission of the publishers. The program listings (if any) may be entered, stored and executed in a computer system, but they may not be reproduced for publication. This edition can be exported from India only by the publishers, Tata McGraw Hill Education Private Limited. Price: € 625.00 ISBN (13): 978-0-07-132927-9 ISBN (10): 0-07-132927-7 Vice President and Managing Director—McGraw-Hill Education: Asia Pacific Region: Ajay Shukla Head—Test Prep and School: ¥. Biju Kumar Publishing Manager—Test Prep: K NV Prakash Manager (Sponsoring): Abhishek Sharma Editorial Executive: Pratibha Singh Asst Manager (Developmental Editing): Anubha Srivastava Junior Manager—Production: Medha Arora Dy Marketing Manager: Niju Sreedharan General Manager—Production: Rajender P. Ghansela ‘Asst General Manager—Production: 8. L. Dogra Information contained in this work has been obtained by Tata McGraw-Hill, from sources believed to be reliable. However, neither Tata McGraw-Hill nor its authors guarantee the accuracy or completeness of any information Published herein, and neither Tata McGraw-Hill nor its authors shall be responsible for any errors, omissions, or damages arising out of use of this information. This work is published with the understanding that Tata McGraw-Hill and its suthors are supplying information but are not attempting to render engineering or other professional services. If such services are required, the assistance of an appropriate professional should be sought. “Typeset at Script Makers, 19, A1-B, DDA Market, Paschim Vihar, New Dethi 110063 and text and cover printed at Gopsons, A-2.& 3, Sector-64, Noida, U.P. 201301 Cover Designer: K Anoop ‘Contents Syllabus PHYSICAL CHEMISTRY The Concept of Atoms and Molecules Gaseous, Liquid and Solid States Atomic Structure Periodicity of Properties of Elements Bonding and Molecular Structure Energetics Compounds of Metals }. Compounds of Nonmetals Transition E Ores/Minerals and Extractive Metallurgy Exercises in Inorganic Chemistry ORGANIC CHEMISTRY Hybridization, Isomerism and Nomenclature Inductive and Resonance Effects Alkanes: Alkenes Alkyoes Benzene Alkyl and Aryl Halides 13.1-13.24 14.1-14.31 15.1-15.59 16.1-16.33 171-1712 18.1-18.50 19.3-19.45 20.1-20.18 211-2117 22.1-22.32 23.1-23.18 24.1-24.34 25.1-25.16 Copyrighted material vi A Word to the Reader Organic and Inorganic ‘© Boron and its Compounds. Silicates and silicones. Oxoacids of P, $ and halogens. Intethalogens and compounds of noble gases. Transition elements, coordination compounds and lanthanides. Important compounds such as H,O,, NaHCOs, Na,CO,, KMnO, and K,CrO,. Quantitive analysis of salts. Isomerism including optical isomerism, Inductance and resonance effects on acidity and basicity of acids and bases. Factors affecting $1 and S,2 reactions. Reactions involving rearrangement. Bromination and hydrogenation of cis- and trans-alkenes, debromination of dibromobutane. * Characteristic reaction of aldehede, ketones and carboxylic acids derivatives. © Reactions with Grignard reagent and those of diazonium salt. ‘* Carbohydrates and polymers. ‘* Quantitative analysis of organic compounds. All the above topics are adequately covered in this edition, supported by plenty of practice problems. eee ee ee eens ‘We are hopeful that this comprehensive manual would be of great support to students preparing for the examination. We wish the aspirants all the best in their endeavours. ‘Tue Pusuisners Log on to http://www amhihe.com/igjee201 1sofutions for solutions to IT-JEE 2011 paper. A Word to the Reader Course in Chemistry for IIT-JEE is part of Tata McGraw-Hill’s series of books for IIT-JEE. Divided into 34 chapters that covers the entire gamut of the syllabus (Physical Chemistry, Inorganic Chemistry & ‘Organic Chemistry), each chapter begins with a revisit of the important list of definitions, formulae, theorems, etc. This is followed by MCQs, Linked-Comprehension Type, Assertion-Reason and Matrix match type questions, all of which reflect the latest pattern of the examination. All questions are fully solved and there is adequate coverage of more difficult concepts. Some key features * TUPAC recommendations and SI units used throughout. * Straight-Objective-type questions are enlarged and classified with their solutions ‘ Fully solved IIT-IEE papers of 2009 & 2010 * Practice Question Papers What's special? Over 3000 MCQs with one correct choice and completely solved Around 800 MCQs with more than one correct choice and fully solved More than 170 Linked comprehension type questions About 370 Assertion- Reason type questions & over 120 matrix-match questions Tips for preparation Systematic and early preparation is often the key to success in the ITT-JEE. Attempting questions with speed is a crucial factor. Also itis important to attempt all questions within the stipulated time. The three branches of Chemistry, viz., Physical, Inorganic and Organic are equally important. Physical Chemistry is less diverse compared to Organic and Inorganic. The applications to different problems in this are also straightforward. Given below are some important topics of Physical, Organic and Inorganic that require special attention: Physical: * Bobr’s theory of atomic structure, quantum numbers and orbitals. * MO approach to diatomic molecules, concepts of hybridization/VSEPR theory. * Van der Waals equation of state and its application to the behaviour of real gases. ‘* Crystal systems, packing of atoms, ionic solids, density of crystals and imperfection + Colligative properties of non-electrolytic and electrolytic solutions. * Electrolysis, conductance and galvanic cells + Rate laws, effect of catalyst and temperature on the rate of reaction. ‘+ PH of salt solutions and solubility product. + Le-Chatelier principle, relation between K, and K,. ‘* Thermochemical calculations and criterion of spontaneity. + Radioactive decay. Cuarrer 1 THE CONCEPT OF ATOMS AND MOLECULES Atomic AND Motecutar Masses The branch of chemistry which deals with mass relationships in chemical reactions is called stoichiometry. Before dealing with this branch, a brief review of the terms recommended by IUPAC in describing the atomic and molecular masses is in order. Relative Atomic Mass of an Element The ratio of the average mass per atom of the natural isotopic composition of the element to 1/12th of the mass of an atom of nuclide '*C is known as the relative atomic mass (formerly known as atomic weight) of the element. Relative Molecular Mass of a Compound The ratio of the average mass per molecule of the natural isotopic composition of the compound to 1/12th mass of an atom of nuclide '"C is known as relative molecular mass (formerly known as molecular weight) of the compound. Atomic Mass Unit The quantity 1/12th mass of an atom of nuclide '°C is known as the atomic mass unit. The value of atomic mass unit can be determined from the fact that 1 mol of °C has been assigned mass exactly to 0.012 kg. Hence, (0.012 kg mol™)/(6.022 x10” mot") 12 Atomic Mass The average mass per atom of natural isotopic composition of an element is known as atomic mass. It given.as Atomic mass = (Relative atomic mass) (atomic mass unit). Molecular Mass The average mass per molecule of natural isotopic composition of a compound is known as molecular mass. It is given as Molecular mass = (Relative molecular mass) (atomic mass unit). Mole of a Substance One mole (1 mol) of a substance contains as many objects (e.g. atoms, molecules, ions) as there are atoms in exactly 12 g of nuclide '*C, This number is approximately equal to 6.022 x 107. Amount of a Substance If a sample of a substance contians N specified entities, the amount of substance (formerly known as number of mole) is given as n = N/N,, where N, is Avogadro constant (= 6.022 x 10” mol”). The unit of amount of substance is ‘mol’, Molar Mass The average mass per unit amount of a substance (applicable to both elements and compounds) of naturally isotopic composition is known as molar mass. Its unit is g mol~? or kg mol”. ‘The molecular (or molar) mass of a compound is equal to the sum of atomic (or molar) masses of its constituent atoms. The atomic (or molecular) mass of an atom (or a compound) expressed in atomic mass unit and the molar mass expressed in g mol™' have the same numerical value. This value is also the same as that of relative atomic (or molecular) mass of the substance. 1 amu = 1.6606 1077" kg Laws of CHEMICAL COMBINATION ‘There are three laws of chemical combination. These are as follows. Law of Conservation of Masses (Lavoisier, 1774) The mass is conserved in a chemical reaction. 1.4 Course in Chemistry for ITT-JEE Law of Constant Composition (Proust, 1799) All pure samples (drawn from different sources) of the same ‘compound contain the same elements combined in the same proportion by mass. Law of Multiple Proportion (Dalton, 1803) Two elements, A and B combine to form more than one compound, the masses of A which separately combine with a fixed mass of B (or vice versa) are in the ratio of small whole numbers. QwanTITATIVE INFORMATION FRoM A CHEMICAL EQUATION A balanced chemical equation provides quantitative information regarding the consumption of reactants and creation of products. The numbers which appear before the chemical symbols and which balance the equation (with the ‘understanding that if no number appears, it is equal to unity) are called the stoichiometric coefficients (or numbers) and are proportional to the number of molecules or the amount of the constituents that change during the progress of the reaction. For a general case vxA + ¥pB > VeC + vpD a where Va, Vy Ve and Vp are the stoichiometric coefficients of the species A, B, C and D, respectively. The progress of the reaction is described in terms of a physical parameter, known as extent of reaction (symbol; £, pronounced as xi). It is expressed as Any _ Amy _ Ane _ Arty “% Ve Yo where Ans represent the changes in the amount (i.e. number of moles) of the species. The negative and positive signs represent decrease and increase in the amount of the species, respectively. The unit of is mol. Equation (2) is often interpreted as follows. ~vaG of A= — vg E of B= ve G of C= vp E of D °) where the sign = is used for the term ‘equivalent to’. Equation (3) is often used for a unit extent of reaction where = 1 mol. In this case, we have =, mol of A = — vg mol of B® ve mol of C = Vp mol of D @) In other words v, mol of A on reacting with Vp mol of B gives Vc mol of C and vy mol of D. Since the amount of species is directly proportional to the number of species, Eq. (4) may also be expressed as. ~ Vq molecules of A = Vg molecules of B = Ve molecules of C = Vp molecules of D (5) indicating that v, molecules of A on reacting with vy molecules of B produces v, molecules of C and v,, molecules of D. ‘The relative changes in the masses of species are obtained by multiplying the terms in Eq. (4) by the respective molar masses, i.e. = 7) ~ VqM, mol of A =~ vyMy mol of B= voMc mol of C= vpMy mol of D (O} Equations (4) to (6) may be illustrated by taking the example of the reaction PO(NO,), + 2KI > Pl; + -2KNO, Molar mass: 3312g mol 166.0 gmol"! 4610 g mol” 101.1 g mol” Equation (4) tells that 1 mol of Pb(NO,), on reacting with 2 mol of KI produces 1 mol of Pbl, and 2 mol of KNO3. Equation (5) tells that 1 molecule of Pb(NO,)2 on reacting with 2 molecules of KI produces 1 molecule of PbI; and 2 molecules of KNO,. Equation (6) tells that 331.2 g of PDNO, on reacting with 2 x 166.0 g of KI produces 461.0 g of Pbl, and 2 101.1 g of KNOs. ExpressiNG CONCENTRATION OF A SUBSTANCE ‘The different ways of expressing the concentration of a substance are as follows. . fa Mass of substance A The defini M tage of A= —™ Mass Percentage lefining expression is ass percentage Of A a x 100 ‘The Concept of Atoms and Molecules 1.8 Mole Fraction The defining expression is Mole fraction of A= Ts In symbolic form, A= Males Molarity The defining expression is Molarity of A = —Amoust in mo of substance A Volume of solution expressed in dm In symbolic form, M= nV; (V expressed in dm’) ‘The unit of molarity is mol dm’. It is commonly abbreviated by the symbol M and is spelled as molar. The molarity of a substance is temperature-dependent property due to the variation of volume with temperature. Molality The defining expression is Molality of a = Amount (in mol) of substance A Mass of solvent expressed in kg In symbolic form, my = nim; (mm, expressed in kg) The unit of molality is mol kg“! and is spelled as molal. The molality of a substance is independent of temperature of solution. Conversion oF CONCENTRATION UNITS Representing solvent and solute in a binary solution by subscripts 1 and 2, respectively, the various conversion expressions are as follows. ic 2p a . MM, Mole fraction into molarity — M= —22__ Mobarits iaio woke - A fole fraction ity ai + mits folarity into fraction x, oral Mole fraction into molality m= i Molaity into mole fraction x= = ae Molality into molarity M= Tae Molarity into molality m= So where M, and M, are the molar masses of solvent and solute, respectively, and pis the density of solution (expressed in mass per dm’ of solution). Concert OF EQuIvALENT ‘One equivalent of a substance in a reaction is defined as the amount of substance which reacts or liberates | mol of electrons (or H* or OH” ions). In a reaction, a substance always reacts with another substance in equivalent amounts. ‘The equivalent mass of a substance in a reaction is defined as the molar mass divided by the number of equivalents in 1 mol of the substance. The concentration of a solution may be expressed in normality(Symbol: NV’) which is equal to the amount of solute in equivalents dissolved in 1 dm’ of the solution. It has the units of equivalent per dm’ and is abbreviated by the symbol N. The number of equivalents of the substance is given as Mass of solute Equivalent mass The equivalent mass of a solute (and also the normality of the solution) has to be determined with reference to a reaction since the solute may react in different ways in different reactions. For example, KMnO, oxidizes a reducing agent in different manners depending upon the medium as described in the following. Amount in equivalents = Acidic medium : MnOz + 8H" + Se” > Mn?* + 4H,0 Weakly acidic or neutral o weakly alkaline medium —: MnO + 3e” + 4H* + MnO, + 2H,0 Alkaline medium : MnO; +e + MnO} 1.6 Course in Chemistry for ITT-JEE Hence, Equivalent mass of KMnO, in acidic medium _ Meares ol NO mes Seqml Equivalent mass of KMnO, in weakly acidic, alkaline or neutral medium = youre na ene 4 Equivalent mass of KMnO, in alkaline medium = Molar mass of KMnO,/eq mol” In volumetric analysis, the expression N,V, = N,V; indicates the equality of substances being titrated in equival- ents at the equivalence point. Batancinc CHEMICAL EQuaTION Quite often one has to write a balanced chemical equation while dealing with the problem on stoichiometry. After writing reactants and products, the balancing can be carried out by hit and trial method. However, two systematic methods are available for balancing redox reactions. Before describing these methods, the rules governing the ‘computation of oxidation state of an element are described in the following. Rules to Compute Oxidation Number The oxidation number of an element is the number assigned to it by following the arbitrary rules given below. 1. A free element (regardless of whether it exists in monatomic or polyatomic form, e.g. Hg, H, P, and S,) is assigned an oxidation number of zero. 2. A free monatomic ion is assigned an oxidation number equal to the charge it carries. For example, the oxidation numbers of Al°*, S* and Cl” are +3, -2, and -1, respectively. 3. In their compounds, the alkali and alkaline earth metals are assigned oxidation numbers of +1 and +2, respectively. 4, The oxidation number of hydrogen in its compounds is generally +1 except the ionic hydrides such as LiH, LiAIH,, where its oxidation number is ~1. . The oxidation number of fluorine in all its compounds is ~1. The oxidation number of all other halogens is =1 in all compounds except those with oxygen (e.g. CIO,) and halogens having a lower atomic number (e.g. IC1;). The oxidation number of the latter is determined via oxygen and halogen of lower atomic number. 6. The oxidation numbers of both oxygen and sulphur in their normal oxides (e.g. Na ,O) and sulphides (e.g. CS,) is ~2. The exceptions are the peroxides (¢.g. HO, and Na ,O,), superoxides (e.g. KO,) and the compound OF. ‘Their oxidation numbers are determined by the rules 3, 4 and 5. 7. The algebraic sum of oxidation numbers of atoms in a chemical species (compound or ion) is equal to the net charge on the species. A few examples of the computation of oxidation number of atoms N in various compounds are as follows. If x is the oxidation number of N, we have NH, x+3(+1)=0 which gives x = ~3 HN, +1+3() =0 which gives x = -} NoHy 2e+4(+1)=0 which gives x = -2 NO, x+2(-2)=0 which gives = 4 N:0, 2x+4(-2)=0 which givesx= 4 NO; x+2(-2) =-1 which gives x= 3 NH,OH x+2(41)+1-2)+1=0 which gives x =-1 NO x41@2 which gives x = 2 HNO, which gives.x = 5 NO 2e+1-2) =0 which givesx=1 HCN which gives.x = —5 Balancing Redox Reactions via Oxidation Numbers The steps involved in this method are as follows. 1. Identify the elements in the unbalanced equation whose oxidation number are changed. 2. Balance the number of atoms of each element whose oxidation number is changed. 3. Find out the total change in oxidation number for each of oxidant and reductant and make them equal by multiplying by small coefficients. ‘The Concept of Atoms and Molecules 1.7 4, Balance the remainder of atoms by inspection and add, if necessary, H* (acidic medium) or OH™ (alkaline medium) or HO (to balance oxygen) as the case may be Taking the example of Cu +H* + NO; — Cu? +H,0+NO_ we have ° +5 #2 2 Step: Cut H™ +NO; Cu? +H,0+NO Step 2: Not required (G3) =~ 3) x2 EEE | 3Cu+ H+ 2NO,-93Cu + H,0 + 2NO Step 3: Step 4: 3Cu + 8H* + 2NO} -+ 3Cu** + 4H,0 + 2NO Teder ax Balancing Redox Reaction via lon-Electron (or Half-Equation) Method In this case, the steps involved are: 1, Write the two separate half equations involving the species oxidized along with its oxidation product and the species reduced along with its reduced product. 2, Balance the number of atoms oxidized (or reduced) on both sides of the equation, 3. Depending upon the medium (acidic or alkaline), add H” (0wo H” per O atom on the same side of oxygen) or OH™ (two OH™ per O atom on the opposite side of oxygen) so that the oxygen atoms in the equations are converted into water which are also included in the appropriate side of the equation, 4. Now add electrons in the right (or left) hand side of the oxidation (or reduction) reaction for balancing the charges on both sides. 5. Now multiply each resultant equation in step 4 by the smallest possible integer so as to have the same number of electrons in both oxidation and reduction reactions. 6. Add the two equations and cance! the common species appearing on both sides of the equation, ‘Taking again the example Cu +H* + NOZ~> Cu"? +H,0+NO we bave oxidation Step: Ca —Ssidation_, yz No; —SHo2, No Step2: Not required Step3: Cu+Cu* NO} + 4H* + NO+2H,0 Step4: Cu Cu** +2" NO; + 4H* + 3e° -+NO+2H,0 StepS: [Cu>Cu* + 20] x3 INO; + 4H* + 3e~-» NO + 2H,0)} x2 Step6: —3Cu+2NO; +8H* + 3Cu** + 2NO + 44,0 _—_____s—E Atomic and Molar Masses 1, The atomic mass of an element is measured relative to the mass of (a) hydrogen atom (b) oxygen atom (©) carbon-12 (d) isotopic mixture of °C, 8 and “Cc. 2. One atomic mass unit is equivalent to (a) 1.66 x 10°" g (b) 1.66 x 10°” kg (©) 1.66 x 10°? mg @) 1.66 x 10° eg 3. The numerical value of atomic mass of an element is equal to its relative atomic mass when the former is expressed in (a) g mol! (b) kg mol (©) mg mol (4) eg mot? 4, The numerical values of molecular mass and molar mass of a substance are identical when (a) molecular mass is expressed in grams and molar mass in atomic mass unit (b) both molecular mass and molar mass are expressed in atomic mass unit (©) molecular mass is expressed in atomic mass unit and molar mass in grams (@) both molecular mass and molar mass are expressed in grams 1.8 - Course in Chemistry for IIT-JEE. 5. The value of Avogadro constant is (a) 6.022 x 10 (b) 6,022 x 10 mor (c) 6.022 x 10” atoms (d) 6.022 x 10'* molecules mot! 6. The amount of electrons in one kg is 23 1 , 6.022 1 (a) 6.022 x 10% (b) aoa!" © oi08 * 10 @ Si0exeon * 10° 7. Which of the following has maximum number of atoms? (a) 24g of C (M = 12 g mol") (b) 23 g of Na (M = 23 g mol) (e) 48 g of S (M = 32 ¢ mot") d) 108 g of Ag (M = 108 g mot!) (2003) 8. Given that the abundances of isotopes “Fe, “Fe and *'Fe are 5%, 90% and 5%, respectively, the relative atomic mass df Fe is (a) 55.85 (b) 55.95 (©) 55.15 (a) 56.05 (2009) 9. The largest number of molecules is in (a) 36 g of water (b) 28 g of carbon monoxii (©) 46 g of ethyl alcohol (@) 54 g of nitrogen pentoxide (1979) 10. A gaseous mixture contains oxygen ans nitrogen in the ratio of 1: 4 by mass. The ratio of their number of molecules is (a) 4 () 1: 8 (© 732 @) 3:16 (1979) 11. Which of the following has highest mass? (a) 20 g phosphorus (b) 5 mol of water (©) 2 equivalent of Na,CO, (@) 12 x 10* atoms of hydrogen (1978) 12. The volume of H, evolved at STP when 0.9 g of Al (molar mass: 27 g mot) is dissolved in excess of dilute H,S0, is (a) 0.58 L (b) 112 L (©) 240 L @) 29 Concentrations 13. 40.25 g of Glauber's salt is dissolved in water to obtain 500 mL. of solution of density 1077.5 g dm”. The molality of Na,SO, in solution is about (a) 0.25 mol kg™ (b) 0.24 mol kg (©) 0.26 mol kg"! (@) 0.27 mol kgt 14. The mass of NaBrO, required to prepare 150 mL of 0.75 N of a solution based on the reaction BrO; + 6H* + 6e° > Br + 3H,0 is (a) 1428 (b) 2.83 g (c) 3.85 g (d) 4.25 g 15. Which of the following expressions correctly represent the conversion expression of molality m of a solution in terms of mole fraction 1 of the solute in the solution? (a) x, = mM ~ mMf,) (b) x, = mM (1 + mM) (C) x, = (1 + mM, imi, (4) x, = (1 ~ mynd, where M, is the molar mass of solvent. 16. Which of the following expressions correctly represent the conversion of molality m into molarity M of a solution? (a) M = mp/(1 + mM;) (b) M = mpl(1 + mBf;) (©) M= (1 + mp\/mM, (d) M = (1 = mp)imM; where p and M, are the density of solution and molar mass of solute, respectively. 17, The mole fraction of ethanol in water is 0.08, Its molality will be (a) 241 mol kg (b) 4.83 mol kg"! (c) 3.33 mol kg (@) 6.41 mol kg! 18. The expression converting mole fraction of a solute into molarity of solution is (a) M =x My / (4 M, +) M) (b) M = (% My + xy My) Jr, My (©) M =x p/ (i M, + %) My) (d) M = x, pi (x My + My) where the various symbols have their usual meanings. 19. The expression converting molarity (M) into mole fraction x, of the solute in the solution is MM, MM, mM) p+M(M, p+M (My, @) y= a) 2 b) y= mL ‘The Concept of Atoms and Molecules 1.9 © m= — 4h @ 5-H _ 2 pe M (=) p+ (My ~M,) where the various symbols have their usual meanings. The normality of 0.3 M phosphorous acid (H,PO,) is, fa) 1 (b) 0.9 (©) 0.3 @) 06 An aqueous solution of acetic acid has density 1.1 g mol and molality 4.6 mol kg”. The molarity of acetic acid would be (a) 32M (b) 35M (© 397M @ 46M The volume of 82.5 mass percent of H;SO, (density 1.6 g em) to prepare 200 cm’ of 15 mass per cent of H,SO, (density 1.1 g cm™) is (a) 162 em* (b) 173 cm* (©) 180 cm* (d) 193. em? 115 ml of ethanol (density = 0.8 g mI) on mixing with 99 mL of water gives 200 mL of solution. The numerical values molarity, molality and mole fraction of ethanol, respectively, are» (@) 10, 20.2, 0.267 (b) 20.2, 10, 0.267 (©) 10, 20.2, 0.733 (@) 202, 10, 0.733 Oxidation Number 2. 8 2, 8 a. 32, a 37. ‘One mole of N;H, loses 10 mol of electrons to form a new compound Y. Assuming that all the nitrogen ‘appears in the new compound, what is the oxidation state of nitrogen in Y? (There is no change in the oxidation state of hydrogen.) @) -1 (b) -3 © +3 @ +5 (1981) ‘The oxidation number of carbon in CHO is (a) -2 (b) +2 0 @ +4 (1982) The brown ring complex compound is formulated as [Fe (H,0),(NO)* }SO,. The oxidation state of iron is 1 (b) 2 3 @o (1984) The equivalent mass of MnSO, is half its molar mass when it is converted to (a) Mn0, (b) MnO, (©) Mn0; @) Mnod (1988) ‘The oxidation number of phosphorus in Ba(H,PO;), is (a) 43 (b) +2 ©) +1 @ -1 (1990) ‘The oxidation states of the most electronegative element in the products of the reaction, BaO, with dil. H,SO, are (a) 0 and -1 (b) =1 and -2 (©) -2 and 0 (@) -2and +1 (1992) For the redox reaction MnO; + C,0} + H*—> Mn™* + CO, + HO the correct coefficients of the reactants for the balanced reaction are MnO; = C,07 Ht MnO; coy Ht @ 2 5 16 ) 16 5 2 © 5 16 2 (a) 2 16 s (1993) White phosphorus reacts with caustic soda, The products are PH, and NaH,PO;. This reaction is an example of (a) oxidation (b) reduction (©) oxidation and reduction (4) neutralization (1980) Oxidation state of oxygen atom in potassium superoxide is (@ -12 (b) -1 © -2 @ 0 . The compound having the lowest oxidation state of iron is (a) K,Fe(CN), (b) K,Fe0, © FeO (@) Fe(CO), ‘The oxidation state of nickel in Ni(CO), is @ 0 (b) +2 © +4 @ -4 The oxidation state of nitrogen in N3H is (a) -173 (b) -1 +R @ +2 Which of the following reactions is a redox reaction? (a) Cr,0, + 6HCI > 2CrCl, + 3H,0 (b) CrO, + 2N2OH + Na,CrO, + H,0 (©) 2Cro} + H* == Cr,0} + OH” (d) Cr,0F + 6 + 14H* == 2Cr** + 31, + 7H,0 ‘The compound having +2 as the oxidation state of oxygen is (a) HO, (b) CO; © F,0 (6) MnO; 1.40 Course in Chemistry for IT-JEE a1. 42. 43. 48. 47. ‘The oxidation state of oxygen in O, is (a) +1 and -1 (b) +2 and -2 (©) 0.5 and -0.5 (d) zero The anion nitrate can be converted into ammonium ion. The equivalent mass of NO; ion in this reaction would be (a) 6.20 g eq? (b) 7.75 g eq! (©) 10.5 g eq? (d) 21.0 g eq" The equivalent mass of Na,S,O; in its reaction with Ip is equal to (a) molar mass (b) molar mass/2 (©) molar mass/3 (@) molar mass/4 The oxidation numbers of sulphur in Ss, S,F;, H,S respectively, are (a) 0, +1 and -2 (b) +2, +1 and-2 (©) 0, +1 and +2 (@) -2, +1 and -2 (1999) Amongst the following, identifies the species with an atom in +6 oxidation state (a) Mn03 (b) CCNY (© NiFE @ Cr0,Cl, (2000) The correct order of compounds with increasing oxidation number of Ni is (a) Ni(CO), < K,{NiF,] < K,[Ni(CN)) (b) Ni(CO), < K,[Ni(CN),] < K,{NiF] (©) Ky{Ni(CN),) < K,INiFe] < Ni(CO), (@) KyINi(CN),] < Ni(CO), < K,{NiF,] Which of the iilowing acids has more than one oxidation state of sulphur atoms? (a) HS,05 (b) H,S;0, (©) H,8,0, (@) H,S;05 ‘The correct order of compounds with increasing oxidation number of phosphorus is (a) Py< PH; < PO; (0) Py< P,0,< PH, (c) P,0,< P< PH; (4) PH, < P, < P,0, ‘The oxidation numbers of P in P,, PH; and NaH,PO,, respectively, are (a) 0, -3, +1 (b) 0, ~3, -1 (c) 0, +3, -1 (@) 0, +3, +1 In the reaction KSbO; + 2KOH + 2H,O + 2CIO, + KSb(OH); + KCIO,, the species undergone (a) oxidation is Cl (b) oxidation is Sb (c) oxidation is O (d) reduction is Sb ‘The pair of the compounds in which both the metals are in the highest possible oxidation state is (@) [Fe(CN)gI*, [Co(CN) I> () [Co(CN)_]*, Ni(CO)* (©) TiO,, MnO? (@) CrO,Cl;, MnO; (2004) Balancing Chemical Equation 49. 50. SL. 52, 53, The stoichiometric numbers of species from left to right in the chemical equation Cu,0 + NO; + H* = Cu** + NO + HO when balanced respectively are (@) 1,1, 6,2, 1,3 OM AWWA (2212426 — d) 3,2, 146,27 The stoichiometric numbers of species from left to right in the chemical equation ‘Mn** + PbO, + H* -» MnO; + Pb** + HO when balanced respectively are @) 14,8 14,4 (b) 13,4, 1, 3,2 © 2,5,4,2,5,2 @) 2,7, 12, 2, 7,6 The stoichiometric numbers of species from left to right in the chemical equation 103 + I + H* + I, + H,O when balanced respectively are (@) 2,4, 12, 3,6 (b) 1,3, 6,2,3 © 1,5,6,3,3 @ 1,1,6,1,3 The stoichiometric numbers of species from left to right in the chemical equation Br; + NaOH — NaBr + NaBrO; + HO when balanced respectively are (@) 3,4, 3,1, 2 () 1,2, 1,1,2 (c) 2, 4,3, 1,2 (d@) 3, 6, 5, 1,3 The stoichiometric number of species from left to right in the chemical equation P, + NaOH + H,O — PH, + NaH,PO, when balanced respectively are (@ 1,2, 2,1,2 () 1,3,3,1,3 ©2644 @) 2,6,6,3,1 Chemical Reactions 54, 55, If 0.5 mol of BaCl, is mixed with 0.20 mol of Na;PO,, the maximum amount of Ba;(PO,); that can be formed is (a) 0.70 mol (b) 0.50 mol (©) 0.20 mol (@) 0.10 mol asst) ‘A certain compound has the molecular formula X,Q¢, If 10.0 g of compound contains 6.06 g of X, the atomic mass of X is (@) 32 amu (b) 37 amu (©) 42 amu (@ 48 amu 61, 62. 70. nL. ‘The Concept of Atoms and Molecules 1.L1 ‘The extent of reaction {a) is unitless (b) has the unit of g (c) has the unit of mol (4) has the unit of mol”! ‘The number of moles of KMnO, that will be needed to react with one mole of sulphite ion in acidic solution is (a) (2/5) mal (b) /5) mal (©) (4/5) mal (@) 1 mal (1997) HBr and HI can reduce sulphuric acid, HCI can reduce KMnO, and HF can reduce (a) H,SO, () KMn0, (©) K,Cr,0, (@) none of these A solution of sodium metal in liquid ammonia is strongly reducing agent due to the presence of (a) sodium atoms (b) sodium hydride (©) sodium amide (d) solvated electrons ‘The reaction which proceeds in the forward direction is (a) Fe,0, + 6HCI = 2FeCl, + 3H,0 (b) NH, + H,0 + NaCl = NH,CI + NaOH (c) SnCl, + Hg,Cl, = SnCl, + 2HgCl, (d) 2Cul + 1; + 4K* = 2Cu** + 4KL (1991) The masses of PO, and P,O,o that will be produced by the combustion of 2.0 g of P, in 2.0 g of oxygen eaving no P, and O, respectively are (a) 30g, 10g (b) 15,25 © 25g15¢8 @) 202,208 Mixing of $0 ml. of 0.25 M lead nitrate solution with 25 ml, of 0.10 M chromic sulphate solution causes the precipitation of lead sulphate. The molarity of Pb°* and Cr’* ions in the solution respectively are (a) 0.0667 M, 0.0667 M_ (b) 0.1 M, 0.2 M (©) 0.125 M, 0.05 M4) 0.05 M, 0.125 M A mixture weighing 4.08 g of BaO (molar mass of Ba = 138 g mol) and unknown carbonate XCO, was heated strongly. The residue weighed 3.64 g. This was dissolved in 100 mL of 1 M HCl. The excess acid required 16 mL of 2.5 M NaOH solution for complete neutralization. The molar mass of M is about (a) 20 g mor (b) 30 g mol! (©) 40 g mol @) $0.g mol ‘A solid mixture (5.0 g) consisting of lead nitrate and sodium nitrate was heated below 600 °C until the mass of residue was constant. If the loss in mass is 28 per cent, the masses of lead nitrate and sodium nitrate in the mixture respectively were (a) 3.32 g, 1.68 g _ (b) 1.68 g, 3.32 g (c) 2.50 g, 2.50 g (@) 3.50 g, 1.50 g ‘A compound Pb(NO,); on strong heating loses 32.6 per cent of its mass. The molar mass of Pb is about (a) 200 g mol! (b) 207 g mol (©) 214 g mol (d) 221 g mol ‘The per cent loss in mass of K,Cr,0, (molar mass Cr = $2 ¢ mol”) on heating will be about (a) 25% (b) 16% ©) 8% @) 4% . Five millilitre of 0.1 M Pb (NO;), is mixed with 10 mL of 0,02 M KI. The amount of PbI, precipitated will be about (a) 10° mol (b) 10% mol (c) 2x 10+ mol (a) 4x 10% mol A solution containing NajCO, and NaHCO, is titrated against 0.1 M HCI solution using methyl orange indicator. At the equivalence point, (a) both Na,CO, and NaHCO, are completely neutralized (b) only Na,CO, is wholly neutralized (c) Only NaHCO; is wholly neutralized (4) Na,CO, is neutralized upto the stage of NaHCO, A solution containing NaC, and NaHCO, is titrated against 0.1 M HC! solution using phenolphthalein indicator. At the equivalence point, (a) both Na,CO; and NaHCO, are completely neutralized (b) only Na,CO; is wholly neutralized (©) only NaHCO, is wholly neutralized * (d) Na,CO, is neutralized upto the stage of NaHCO; A solution containing NaOH and Na;CO, is titrated against 0.1 M HCI solution using phenolphthalein indicator. At the equivalence point, (a) both NaOH and Na,CO, are completely neutralized (b) only NaOH is completely neutralized (©) only Na;CO, is completely neutralized (a) NaOH completely and NaCO, upto the stage of NaHCO, are neutralized. A solution containing NaOH and Na,CO, is titrated against 0.1 M HCI solution using methyl orange indicator. ‘At the equivalence point, 1.12 Course in Chemistry for ITT-JEE {a) both NaOH and NaxCO, are completely neutralized (b) only NaOH is completely neutralized (©) only NaCO, is completely neutralized (@) NaOH completely and NaCO, upto the stage of NaHCO, are neutralized. 72. A solution containing 2.68 x 10° mol of A'* ions requires 1.61 x 10 mol of MnO; for the oxidation of A to AO} in acidic medium, The value of @1 (b) 2 3 @4 73. 20 mL of an acidified solution of ferrous sulphate requires 15 mL. of 0.1 M solution of KMnO, for complete oxidation. For the same solution, the volume of 0.1 M K;Cr,0, for complete oxidation would be (a) 24 mL (b) 18.0 mL (©) 16.67 mL (@) 125 mL. 74, Twenty milliitre of a solution is 0.1 M in each of Na,CO, and NaHCO,, It is titrated against 0.1 M HCI using phenolphthalein as the indicator. The volume of HCI used at the end point will be (a) 10 mL. (b) 20 mL. (©) 30 mL (@) 60 mb 78. Twenty millitre of a solution is 0.1 M in each of Na,CO, and NaHCO, It is titrated against 0.1 M HCI using methyl orange as the indicator. The volume of HCI used at the end point will be (a) 10 mL (b) 20 ml. (©) 30 mL (@) 60 mL 76. Ten millilitre of 0.01 M iodine solution is titrated against 0.01 M sodium thiosulphate solution using starch solution. The volume of sodium thiosulphate consumed upto the end point is (a) 10 mL. (b) 15 mL (©) 20 mL (d) 30 mL 77. An aqueous solution of 6.3 g oxalic acid dibydrate is made up to 250 mL. The volume of 0.1 N NaOH required to completely neutralize 10 mL. of this solution is (a) 40 mL (b) 20 mL (c) 10 mL (d) 4mL (2001) 78. The reaction, 3CIO5 (aq) > CIO3 (aq) + 2CI- (aq), is an example of (a) oxidation reaction (b) reduction reaction (©) disproportionation reaction (@) decomoposition reaction (2001) 79. In the standardization of Na,S,O; using K;Cr,0; by iodometry, the equivalent mass of K;Cr,0, is (a) (molar mass)/2 (b) (molar mass (¢) (molar mass. (@) same as molar mass 80. Which of the following is not oxidized by 0,? (a) Ki (b) KMnO, (©) KMn0, (d) FeSO, 81. Consider a titration of potassium dichromate solution with acidified Mohr’s salt solution using diphenylamine as indicator. The number of moles of Mohr's salt required per mole of dichromate is (@) 3 (b) 4 Ss @ 6 82. 2.76 g of silver carbonate, on heating strongly yields a residue of (@) 2.32 8 (b) 2.48 g (©) 2.32 8 (d) 264 g 83. One gram of CaCO,(s) and Na,CO,(s) when heated strongly left a residue weighing 0.56 g. The mass per ‘cent of CaCO, in the mixture is {a) 50% (b) 60% (©) 75% (d) 80% 84, 6.0 g of C reacts completely with 12 g of O; producing a mixture of CO(g) and CO,(g). The mass percent ‘of CO(g) in the gaseous mixture will be about (a) 45% (b) 57% (©) 64% () 16% 85. A mixture of CO(g), CH,(g) and He gases has a volume of 20 cm’, When exploded in the presence of excess ‘of O,, a net decrease of 13.0 cm’ in volume is observed at room temperature. When the remaining mixture is passed through NaOH solution, a further decrease of 14.0 cm’ in volume is observed. The volume percentages of CO, CH, and He in the original mixture, respectively, are (a) 50, 30, 20 (b) 50, 20, 30 (©) 20, 50, 30 (a) 20, 30, 50 86. A compound M-xH,O contains 45.5 mass per cent of water. If the molar mass M is 152 g mol", the value of x will be @ 4 (b) 5 © 6 @7 87. 0.5 g of fuming H,SO, is diluted with water. This solution requires 22 mL of 0.5 M NaOH for complete neutralization. The mass per cent of SO, in the fuming H,SO, is fa) 25.1 () 30.2 (©) 35.2 @) 40.1 88. 90 mL of 10 mass percent solution of KI (density: 1.132 g mL) is mixed with 90 mL of 20 mass per cent ‘of Pb(NO,), (density : 1.1 g mL, M(Pb) = 208 g mol') The amount of Pbl; precipitated will be (a) 0.04 mol (b) 0.05 mol (©) 0.06 mot (d) 0.1 mot ‘The Concept of Atoms and Molecules 1.13 89. A mass of 0.355 g of the compound M,CO,-xH,0 (molar mass of M: 23 g mol) is dissolved in 100 mL water and titrated against 0.05 M HCI using methyl orange indicator. If the volume of HCl consumed is 100 mL, the value of x is (@ 2 b) 5 ©7 @ 10 90. 20 mL of a solution containing 0.34 g of an impure sample of H;O, reacts with 0.465 g of KMnO, (molar mass: 155 g mol) in acidic medium. The per cent purity of HO, is about (@) 60% (b) 70% (©) 75% @) 80% 91. A mixture of Na;CO, and NaOH in a solution requires 20 mL of 0.1M HCI solution for neutralization when phenolphthalein indicator is used. The volume consumed is 25 mL when methyl orange indicator is used. The mass per cent of Na;CO, in the given mixture is about (a) 47% {b) 57% (c) 67% @) 75% 92. The mass of AgCl precipitated when 4.68 g of NaCI is added to a solution containing 6.8 g of AgNO, is (@) 452g (b) 5.74 g (©) 7.18 g @ 82g _______—s ee 1. Which of the following statements are correct? (a) The reaction 2H,0, > 2H,0 + O, is not an example of redox reaction. (b) The reaction 28,0% + 2H,O -> 480°; + O, + 2H” is an example of a redox reaction, (©) The oxidation number of an oxidant is increased in a redox reaction. (@) The oxidation number of a reductant is increased in a redox reaction, 2. Which of the following statements are not correct? (a) The increase in oxidation number of an element implies that the element has undergone oxidation. (b) The increase in oxidation number of an element implies that the elements has undergone reduction. (©) The oxidation number can never be a fraction. It is always a positive or negative integer. (@) In a reaction H;MoO, is changed to MoO}, In this case, H)MoO, acts as a reducing agent. 3. Which of the following statements are correct? (a) The oxidation state of Mo when it undergoes transition from HjMoO, to MoO}* is increased by one. (b) The disproportionation reaction 2Mn’* + 2H,0 — MnO, + Mn”* + 4H" is an example of a redox reaction. (c) The equivalent mass of KMnO, in alkaline medium is molar mass divided by five. (d) The equivalent mass of KMnO, in weakly acidic or neutral or weakly alkaline medium is molar mass divided. 4. Which of the fotlowing statements are correct? (a) The equivalent mass of KMnO, in strongly alkaline medium is equal to its molar mass. (b) The equivalent mass of $,0}" in its reaction with 1, is molar mass divided by two. (©) A solution of cerium(IV) in sulphuric acid acts as an oxidizing reagent. (d) The equivalent mass of K,Cr,0, in acidic medium is molar mass divided by five. 5. Which of the following statements are correct? (a) Potassium bromate, KBrOs, acts as a strong oxidizing agent. It accepts 6 electrons to give KBr. (b) Potassium bromate can quantitatively convert Br to Bry. (©) Potassium iodate solution can be kept for a long time without decomposition. (@) In 3N HCI solution, iodate can oxidize I, according to the reaction 10} + 2h, + 10CI> + 6H > SICH; + 3H,0 In this reaction, the equivalent mass of 103 is molar mass divided by four. 6. Which of the following statements are correct? (a) The equivalent mass of a substance can be calculated with out considering the reaction it undergoes. (b) One mole of K,Fe(CN), produces 17 mol of total species in solution. (©) The molar mass of N, is 28 g mol", Its molecular mass will be 28 u. (@) Hydrogen peroxide can act both as oxidizing as well reducing agent, 7. The reaction between peroxydisulphate ion (S,07;) and chromium in acidic medium produces sulphate and dichromate ions. In this reaction (Choose only the correct ones) (a) the oxidation state of S changes from +7 to +6. (b) the oxidation state of Cr changes from 0 to +3. 1.14 Course in Chemistry for ITT-JEE (©) The equivalent mass of $,07, would be molar mass divided by two. (a) The equivalent mass of Cr would be molar mass divided by three. 8 In 2N HEN solution, iodate 1, according to the reaction 105 + 21, + 10CN™ + 6H — SCN) 3 + 3H,0 In this reaction (choose only the correct ones), (a) the oxidation state of I in 105 is changed from +5 to +1. (b) the oxidation state of I in Ip is changed from +1 to 0. {c) the equivalent mass of 10; is molar mass divided by four. (d) the equivalent mass of 1, is molar mass divided by two. (e) 10; acts a a/an reducing reagent. (8) 1, acts ag a/an oxidizing reagent, 9. Which of the following statements are correct? (a) The oxidation number of iodine in periodic acid (H.10,) is +7 (b) Hydraziné (NjH,) is a reducing agent. In its reaction with I, nitrogen is evolved. The equivalent mass of hydrazine in this reaction is molar mass divided by two. (©) In the reaction 10; + ST + 6H* —> 31, + 3H,O the equivalent mass of 10; is molar mass divided by five. (d) The iodinje produced in the reaction 10; + SI” + 6H* —» 31; + 3H,O is titrated against $0") ions. Knowing the normality of $,07;, normality of iodine and hence normality of 103 is determined. To get the strength of 105 in gL“, the equivalent mass employed for 103 in g L”', would be molar mass divided by four, 10. Which of the following statements are not correct? (a) 10; is a strong oxidizing agent in acidic medium. In its oxidizing action, it is reduced to 1,. The equivalent mass of 10% will be molar mass divided by seven (b) In a oxidation reaction, bromate (BrO3) is converted into Br°. The equivalent mass of BrO} will be molar mass divided by five, (c) The oxidation state of $ in CNS” is +1. (@) In a reaction between 103 and CNS", the latter is converted into SOF and HCN. The equivalent mass of CNS” would be molar mass divided by six. 11. Which of the following statements are correct? (a) One mole of potash alum contains a total 32 mol of the independent species. (b) One of mole of K3Fe(CN), contains # total 10 mol of the independent species. (©) 0.1 M sulphuric acid has a normality of 2 N. (d) The oxidation number of alkali metal is always taken equal to +1. 12, In the reaction 60CI” + 2NH, — 6Cl, + N, + GOH’, the species undergone (a) oxidation is N (b) reduction is N (©) oxidation is Cl_ (4) reduction is C1 13, Which of the following concentrations are correct for 13 mass percent of sulphuric acid (dendity : 1.09 g mL”)? (a) 1.443 M (b) 1.625 M (©) 1.625 mol kg? (d) 1.525 mol kg 14, 18 g of Mg in burt in a closed vessel which contains 0.8 g of oxygen. Which of the following facts are correct for the resultant system? (a) Amount of MgO formed is 0.05 mol (b) Mass of Mg left in excess is 0.8 g (©) Amount of oxygen left is zero. (d) Volume of 0.25 M H,SO, to dissolve the formed MgO is 200 mL. EERE 1, 250 mL of a solution contains 0,42 g of oxalic acid. This solution is used in determining molarity of sodium hydroxide solution which, in turn, is used to determine the molarity of sulphuric acid solution. This acid solution is furthur used in determining the masses of Na;CO, and NaHCO, present in a solution. Based on these experiments, answer correctly the following three questions. Gi) In determining the molarity of sodium hydroxide solution, 9.6 mL. of this solution required 10 mL. of ‘oxalic acid solution to locate end point with the help of phenolphthalein indicator. For sulphuric acid ‘The Concept of Atoms and Molecules 1.15 solution, 9.0 mL of NaOH solution is used in neutralizing 10 mL of sulphuric acis solution while using phenolphthalein indicator. The molarity of sulphuric acid solution is (a) 0.01 M (b) 0.0125 M (©) 0.02 M (@) 0.025 M (ii) 10.0 mL of the solution containing Na;CO, and NaHCO, requires 4.0 mL of sulphuric acid with Phenolphthalein indicator. The mass of Na,CO, present per litre of the solution is (a) 1.06 g Lt (b) 2.12 gL? © 252 gL @ 318 gL" Gii) 10.0 mL of the solution containing Na,CO, and NaHCO, requires 14.0 mL of suphuric acid with methyl orange indicator. The mass of NaHCO, present per lite of the solution is (@) 0.63 gL (b) 1.06 g L- (©) 126 gL! (@) 252 gL 2. 250 mL of a solution contains 0.63 g of oxalic acid. This solution is used in determining molarity of sodium hydroxide solution, which, in turn, is used to determine the molarity of sulphuric acid solution. This acid solution is furthur used in determining the masses of Na;CO, and NaOH present in a solution. Based on these experiments, answer correctly the following three questions. () In determining the molarity of sodium hydroxide solution, 9.6 mL of this solution required 10 mL of oxalic acid solution to locate end point with the help of phenolphthalein indicator. For sulphuric acid solution, 8.4 mL of NaOH solution is used in neutralizing 10 mL. of sulphuric. acid solution while using phenolphthalein indicator. The mass of sulphuric acid present per litre of the solution is (@) 151g (b) L72.g (©) 192g (d) 2.21 g Gi) 10.0 mL of the solution containing Na,CO and NaOH requires 12.0 mL of sulphuric acid with phenolphthalein indicator and 16.0 mL with methyl orange indicator. The mass of NajCO, present per litre of the solution is (@) 148g (b) 1.88 g (©) 2.28 g (@) 268 g (iii) From the part (ii), the mass of NaOH present per litre of the solution is (a) 0.56 g () 0.92 g ©) 1.128 @) 1528 3. 250 mL of a solution contains 0.63 g of oxalic acid. This solution is used to determine molarities of NaQH solution and KMnO, solution. These solutions, in turn, are used separately to determine the masses of oxalic acid and sodium oxalate present together in a solution. Based on these experiments, answer correctly the following three questions (i) In determining the molarty of sodium hydroxide solution, 9.6 mL of this solution is used to locate the end point for 10 mL of oxalic acid solution with phenolphthalein indicator. For KMnO, solution, 9.8 mL. of KMnO, solution is used to locate the end point for acidified 10 mL. of oxalic acid. The molarities of NaOH and KMnO, solutions, respectively, are (a) M24, M243 (b) M/24, M/122.5_——(c) M/24.5, M/24 (@) M/122.5, M/24 Gi) 10.0 mL of the solution containing oxalic acid and sodium oxalate together requires 8.5 mL of sodium hydroxide to get end point with phenolphthalein indicator. The mass of oxalic acid present per litre of the solution is (a) 2.23 g (b) 1.58 g © 2588 @ 328 (ii) 10.0 mL of the acidified solution containing oxalic acid and sodium oxalate required 20.7 mL of KMnO, solution. The mass of sodium oxalate present per litre of the given solution is (a) 2.86 g (b) 3.08 g (©) 358 g (6) 4.18 g 4. 10 mL of a given hydrogen peroxide sample (density 1.2 g/mL) is titrated with M/50 solution of KMnO, in acidic medium. The volume of KMnO, solution used is found to be 28.4 mL. Based on this information, answer the following three questions. (@) The molatity of HO; in the given hydrogen peroxide sample is (a) 0284 M (b) 0.142 M (©) 0.426 M (@) 0071 M (ii) The molality of H,0, in the given hydrogen peroxide sample is (a) 0.119 mol kg!” (b) 0.238 mol kg” (©) 0.056 mol kg (@) 0.36 mol kg (iii) The volume strength at STP of the given hydrogen peroxide sample is (@) 2.59 (b) 2.09 ©) 1.59 (@ 0.99 i Asscion Ran Ty Below are given a STATEMENT (S) in the left hand columa and an EXPLANATION (E) in the right hand column. Ascertain the relationship between S and E and select the correct code among a, b, c and d which are, defined below. 1.16 Course in Chemistry for UT-JEE Code @ ) © qd) 10. 13. 14, 15. Both S and E are true, and E is the correct explanation of S. Both S and E are true but E is not the correct explanation of S. S is true but E is false. S is false but B is true STATEMENT(S) 1, In the titration of Na,CO, with HCI using methyl orange indicator, the volume of acid required at the equivalence point is twice that Of the acid required using phenolphthalein as the indicator. 2, In the titration of Na;CO, with HCI using methyl orange indicator, the equivalent mass ‘of Na,COy is the molar mass divided by 2. 3. In the titration of Na;CO, with HCl using phenolphthalein indicator, the equivalent mass of Na;CO, is the molar mass divided by 2. 4, The equivalent mass of KMnO, in a redox reaction depends on the medium whether it is acidic, basic or neutral. 5. The Cr,0%; is reduced to CrO?; when the medium is made alkaline. 6. The atomic mass of an element expressed in amu (atomic mass unit) and its molar mass expressed in g mol” have the same numerical value, 7. The density of a substance expressed in g cm™> kg dm” have the same numerical value. 8. The atomic mass of most elements have non- integral values. 9. Amount of a substance is defined as n = NN, where N is the number specified entities of the substance and N, is Avogadro constant. If the amount x of A in the reaction 2A + B is converted into B, then the extent of reaction is 11. The extent of reaction has the unit of ‘mol’. 12, Molarity of a solution is a temperature depen- dent physical property. In the volumetric analysis, molarity of unknown solution may be determined by using the molarity expression M,V, = M,V3 1 mol (5 Fe** ions) = 5 mol of Fe** ions. Mole fraction of a constituent in a solution is an intensive quantity. EXPLANATION) Two moles of HCl are required for the complete neutralization of one mole of Na,CO, Two moles of HCI are required for the complete neutralization of one mole of Na;CO}. Two moles of HCI are required for the ‘complete neutralization of one mole of Na,CO}. The oxidation reaction of MnO; is MnO; + 8H’ + Se” = Mn** + 4H,O. This reaction occurs irrespective of the nature of medium ‘The oxidation states of Cr in Cr,0% and CrO¥ are identical. ‘The numerical value of product of amu in SI unit Avogadro constant is equal to 1 The numerical value of density is same because 1 kg = 10° g and 1 cm = 10" dm. The atomic mass of an element is the mass of protons and neutrons contained in its nucleus. ‘The amount of a substance may be expressed in various ways such as parts per million and grams. ‘The extent of reaction is defined as Any'Vy where An, is the amount of substance under- gone a change and vj is its stoichiometric number. ‘The unit of amount of substance is ‘mol’. Volume of a solution changes with change in temperature, The molarity expression M,V, = MV; can- not be written like the normality expression MY, = NV. A grouping of five Fe** ions together as a single unit decreases the amount of Fe’* ion to one fifth of the original amount. Mole fraction of a constituent is independant of the volume of the solution. ‘The Concept of Atoms and Molecules 1.17 esi T—CS 1, Column I lists some of the concentration terms and Column II includes some of their characteristics. Match each entry of Column I with those listed in Column Il. Column 1 Column 1 (a) Molarity (p) eq dm? (b) Molality (q) mol dm (©) Mole fraction (8) unit less (d) Normality (s) mol kg! (®) Temperature dependent (u) Temperature independent 2. Column I lists equivalent masses and Column I lists some of the typical titrations. ’Match each entry of Column I with those given in Column Ii. Column 1 Column 1 & (a) Molar mass/ (5 eq mol) (p) KMnO, in Fe** versus MnO; titration in alkaline medium (b) Molar mass/ (2 eq mol) (q) KMn0, in oxalic acid vesut! "MnO; titration in acidic medium (©) Molar mass/ (6 eq mol”) (x) Na,S,0; in I; versus 8,05 titration (d) Molar mass/ (1 eq mol”) (8) K,Cr,0, in Fe?* versus cpr titration (W) Oxalie acid in oxalic acid $prsus MnO; titration in acidic medium. 3. Column I includes some of the concentration terms and their defining/ equivalent expressions are listed in Column Il. In the expressions, the symbols stand for the various physical fquantities as described in the following x, Mole fraction of solvent p density of solution 2% Mole fraction of solute ‘m Molality of solute in solution M, Molar mass of solvent M Molarity of solute in solution M, Molar mass of solute Match each entry in Column I with those given in Column II. ‘Column I Column I @ x (p) xyaltyM, + x) ) (@) 2M, mM (8) mM yl. + mit) (a) m (3) MM\/Ip + M(M, ~ M,)) (0) mrl(1 + mM) (u) Mitr ~ MM) (v) 1 + mM) ANSWERS = 1 © 3. (@) 4 © 5. (b) 6. (d) 7. @ 8. (b) 10. (c) 1. ©) 12. b) 13. (b) 14. (b) 15, (b) 17. (b) 18, (c) 19. (b) 20. (d) 21. (©) 22. (d) 24. ©) 25. (c) 26. (a) 27. (b) 28. (c) 29. (b) 31. (©) 32. (a) 33. @) 34. (a) 35. (a) 36. (d) 38. (d) 39. (b) 40. (a) 41. @) 42. @) 43. (b) 45. (a) 46. (a) 47. (b) 48. (d) 49. (d) 50. (c) 52. (a) 53. (b) 54. (d) 55. (b) 56. (©) 57. (a) 59. (a) 60. (a) 61. (d) 62. (a) 63. (©) 64. (a) 66. (c) 67. (b) 68. (a) 69, (d) 70. (a) 1.18 Course in Chemistry for ITT-JEE TL (a) 72. (b) 73. (d) 74. (b) 75. (d) 76. (c) ‘77. (a) 78. (©) 79. (b) 80. (b) 81. (@) 82. (a) 83. (0) 84. (©) 85. (b) 86, (d) 87. (c) 88. (b) 89. (a) 90. (c) OL. (a) 1. (b), @) 2. (b), (©), @) 3. (b), (@) 4 (a), (0) 5. (a), (b). (©), @) 6. (c). (@) 7. @). ©) 8. @), ©). @ 9 {a), (c) 10. (b), (c) 11. (a), (c), (d) 12. (a), (d) 13. (a), @) 14. (@), (©), @ 1 @ ©) Gi) (@ dit) (©) 2H) Gi) (@) dit) © 3.) GG) Git (a) 4.0) i) (a) Gi) (@) 1. () 2. (a) 3. @) 40 5. @) 6 ©) 7. @) 8 (c) % © 10. (d) I. (bo) 12. (a) 13. (d) 14. (a) 15. (6) 1. @) - @, (b) = (8), (ws (©) - ©, (a); @ -@). © 2 (@)- Qi ) -@: © - ©): @ - 0 3. (a) - (Wy; 0b) =). (©) ~ (P). (0; @ -@, @ iE OE Atomic and Molar Ma: 1. The atomic mass of an element is measured relative to the atomic mass of carbon-12. (1/12)(12g mot) ' 1 2. One stomic mass unit w {/12)thof masact (C = 1.66 x 10g = 1.66 x 1077 kg Avogadro constant 6.023 x10" mol 5 ° 6. Mass of a single electron = 9.108 x 10° g; Number of electrons in | kg = —s 9.108 x10 g . . Amount of electrons in 1 kg = 8 __ iy (9.108 x10 g) (6.022 x10 mmol") 9.108 6.022 7. Amount of C= —™48 = 2 mol Amount of Na = —238__ = 1 mol e 23g mol” Amount of S Amount of Ag = —088 1 mol 108g inol™ Larger the amount of substance, larger the number of molecules. 8. Relative atomic mass Fe is (0.05 x 54 + 0.9 x 56 + 0.05 x 57) = 55.95 ‘The Concept of Atoms and Molecules 1.19 9. Amount of water, “= 268 —- 2 mot; Amount of carbon monoxide = —*8__ = 1 mot M18 ¢mol 28 gmol ‘Amount of ethyl alcohol = Tat = 1 mol; Amount of nitrogen pentoxide = meet = 0.5 mol Larger the amount of substance, larger the number of molecules. 11. Mass of water = (5 mol) (18g mot") = 90 g; Mass of Na,CO, = (2 eq) (53 g eq!) = 106 g 12x10 Mass of hydrogen = [ } @emory = 08 6.022 x10” mol" 12. The reaction is 2Al + 3H,SO, > Al{SO,) + 3H, 3y1 1 aw (Syl, a sel Amount of H, evolved Gy mal) mol Volume of H, evolved = ($m) 224 .L mot") = 1.12 L 13. Molar mass of Glauber’s salt, Na,SO,10H,0 = 322 g mol! Molar mass of Na,SO, = 142 g mot" = 17.752 gem) 322g mol Mass of solution = (S00 mL) (1.0775 g mot!) = 538.75 g Mass of water = (538.75 — 17.75) g = 521 g Mass of Na;SO, in solution = (40.25 g) ( ‘Amount of Na,SO, = ese = 0.125 mol 142g mol — Molality of Na,SO, = 21250! _ 0.94 mot kg 0.521 kg 14, Amount of NaBrO, in the solution = (0.75 eq dm”) (0.150 dm’) = 0.1125 eq Mass of NaBrO, required = (0.1125 eq) (151 / 6) g eq”! = 2.83 g 15, Since m = n;/ (1 kg of solvent), we have m, = 1 kg / M, yee fy = —_imtke) mM, a many kgs My) +m ~ C/M,)+nj/kg 1+mM, 16, Since m = ny/(1 kg of solvent), we have m, = 1 kg/M, m milks) p mp. it ion i =%=.—_"%__.._ The molarity of solution is M= T= Tena /p ~ itm like) My T+m My 17. We have nz = 0.08 mol, my = 0.92 mol; m = ————2.98 mol__ 4.83 mol kg"? ~ (0.92 mol)(0.018 kg mol”) 18. We have m= —2 nytny Mass of solution = mM; + M3; Volume of solution, V = (nM, + mM,)/p * Hence, we & ee —_%__ 5 —_BP _ % Vo" (My +m M2) nMy+m MxM. +m My 1.20 Course in Chemistry for IIT-JEE 20. Phosphorous acid is a dibasic acid. Hence 0.3 M will be 0.6 N. 21. Let m, = 1000 g. Then ny = 4.6 mol; m, = nM, = (4.6 mol) (60 g mol”) = 276 g Mass of solution = 100g + 276g = 1276g; Volume of solution = m/p = (1276g)(1.1g mL!) M, = ng/V = (4.6 mol)(1.16 L) = 3.97 M 22. Mass of 200 cm* of 15 mass percent of H,SO,; im = pV = (I.1g cm™\200 cm’) = 220 g 1160 mL. Mass of H,SOy in this solution = a x 208) = 33g: Mass of water in this solution = 220g ~ 33g = 187g Mass of 82.5% H,SO, containing 33 g H,SO,, M = aa x33g=40¢ Mass of water in this solution = 40 g - 33 g = 7 g; Volume of water in this solution = 7 cm? Thus 7 cm® of 84 % H,S0, should be diluted to get 200 cm? of 15% H,SO,. The volume of water required with be 200 cm? — 7 cm?® = 193 cm’, 23. Mass of ethanol, my = Vzp = (115 mL) (08 g mL~) 2.0 g Amount of ethanol, n; = 72 = 2208 2.9 mol; Mass of water, m; = 99 g (since p= 1 g mL“) M, ~ 46 emol ML Amount of water, nm; = "tL = —°8— = 5.5 mot M, 18g mol" Molality of ethanol, m = 22 = —200l_ 2 90 mot kg” m, (99x11 ) m . __2.0:mol V (20010 L) Mass fraction of ethanol, x, = —"2— = —2 mtn, 2453 ‘Molarity of ethanol, M = = 10 mol L™ = 0.267 Oxidation Number GN) i =Wer, (oN) _ ‘ 24, (2N) in NH, =" (2N) in ¥. Oxidation state of Nin ¥ is +3 25. We have x + 2(+1) + (-2) = 0. This gives x = 0. 26. The oxidation state of iron in (Fe(H,0).(NO)"]** is +1. 27. The oxidation states of Mn?* are Mn$O,; Mn,O, ; MnO,; MnO, ; MnOz ‘When MnSO, is changed to MnO,, the change in oxidation state is +2. Hence, equivalent mass of MnSO, will be half of its molar mass. 28, For the species H,PO;, we have 2(+1) +x +2(-2)=-1 = x= +1 29. The reaction is BaO, + H;S0, —+ BaSO, + H,0, ‘The oxidation states of most electronegative atom in the products (which is oxygen) are -2 and —1. 30. The balanced equation can be obtained as follows. MnO; + 8H* + Se” Mn** + 4H,0) x 2 OF -+ 2CO, + 2] x 5 2MnOj + SC,0F + 16H* — 2Mn** + 10CO, + 8) 31. Oxidation and reduction reactions take place simultaneously. 32. Potassium superoxide is KO. The oxidation state of oxygen is -1/2. 37. 39. 41. 4. 48. 49, 50, Si. 52. 53. ‘The Concept of Atoms and Molecules 1.21 The oxidation states of Fe are K,Pe(CN),; K, FeO, ; Fez 0; Fe(CO), The oxidation state of Ni is zero as the CO ligand is a neutral species. ’. The oxidation of N in N3H may be computed from the expression 3x + 1 = 0. This gives x = -1/3. Only in the reaction d, oxidation states of Cr and I change. In the other reactions, no change in oxidation state of any of the species occurs. 41 2 a 2 The oxidation states of oxygen are H,O,; CO,; F,0 ; MnO, ‘The oxidation state of oxygen in O, is zero. ws “ We have NO; — NH}. The change in oxidation state is -8. The equivalent mass of NO; would be molar masy/8, i.e., 62 g mol/8 eq mol = 7.75 g eq! The reactions are 28,07 — $07 + 26° 1, + 2e° > 2 28,0} + 1, > S,0F + 20 For 2 mol of Na,S,03, 2 mol of electrons are involved. Hence, its equivalent mass will be equal to molar mass. o 2 The oxidation numbers are S,; $,F, ; H,S ws Pa The oxidation states are MnO;; Cr(CN)>; NiF?-; CrO,Cl, 0 + att The oxidation number of Ni are as follows, Ni(CO), ; K,(NiF,) ; Kz[Ni(CN),] rf The structure of H,S,03 is HO—S—S—OH. The oxidation states of $ are +V and +IIl oO The oxidation number of phosphorus in PH, P, and P,Q, are ~3, 0 and +3, respectively. Oxidation implies increase in oxidation number. The oxidation number of Sb in KSbO3 and KSb(OH), are +2 and +4, respectively. The oxidation states are as follows. (a) #2, +3 (6) #3,0. (©) +4, +4 (Ad) 46, 47 The balanced chemical equation is 3Cu,0 + 2NO3 + 14H* > 6 Cu** + 2NO + 7H,O Not only atoms but also the charges should be balanced on both sides of a balanced chemical equation. The balanced chemical equation is 2Mn** + 5PbO, + 4H* > 2MnOj + SPb** + 2H,0. The balanced chemical equation is 103 + SI” + 6H* — 31, + 3H,0 The balanced chemical equation is 3Br, + 6NaOH -+ SNaBr + NaBrO, + 3H,0 The balanced chemical equation is Py + 3NaOQH + 3H,0 — PH, + 3NaH,PO, Chemical Reactions 54. 55. ‘The reaction is 3BaCl, + 2NaPO, —> Bay(PO,); + 6NaCl. Hence 3 mol BaCl; = 2 mol NasPO, and thus 0.5 mol BaCl, = (2/3) (0.5 mol Na,PO,) = 0.33 mol Na,PO, 2mol Na,PO, =3 mol BaCl, and thus 0.2 mol Na;PO, = (3/2) (0.2 mol BaCl,) = 0.1 mol BaCl, Obviously, Na,PO, is the limiting reagent. Hence 2 mol Na,PO, = 1 mol BaPO,); and thus 0.2 mot Na;PO, = 0.1 mol Bay(PO,), 4M __ 6.06 4M+96amu 10 Solving for M, we get M = 36.9 amu If M is the atomic mass of X, we have 1.22 56, 57. 58. 39, 61. 62. ‘Course in Chemistry for ITT-JEE ‘The unit of extent of reaction is mol. ‘The reactions are MnO; + 8H* + Se” Mn?* + 4H,O ] x 2 SO} + H,O > SO} + 2H’ + 2e1 x 5 2MnO; + SSO} + 6H* > 2Mn** + SSO} + 3H,O 2 mol MnO; = 5 mol S,0} and hence (2/5) mol MnO; = | mol S,0; Fis most stable species amongst CI’, Br” and I". It does not reduce none of the three species H,SO,, KMnO, and K;Cr,0;. Sodium in liquid ammonia is strongly reducing agent due to the presence of solvated electrons. ‘The reactions b to d have tendencies to proceed from right side to left side. The reaction a proceeds in the forward direction. ‘The reactions are. Py + 30; > P\Og_ and Py + 50; > PQ ~ ym me St 2 Given: my my = — 28 = 41 mol and 3n, + 5m) = —28 — = | mot 24g mort ~ 62 124g mol! ~ 16 Solving for n and my, we get m, = 0.009 mol and n; = 0.007 mol m, = (0.009 mol) (124 + 96) g mot! = 1,98 g and m; = (0.007 mol) (124 + 160) g mol" = 1.99 g, ‘The reaction is 3PR(NO4), + Cr(SO,), > 3PbSO, + 2C(NO)s Amount of Pb(NOs), = (0.25 mol dm“) (0.05 dm’) = 0.0125 mol Amount of Cr,(SO4)s = (0.10 mol dm™) (0.025 dm*) = 0.0025 mot Here, Cr,(SO,), acts as a limiting reagent. (0.0125 ~ 30,0025) mot 5 Molarity of Pb®* ions = K ee ) mol 0.066 mol dm? (0.075 dm Molarity of C2* ions = 2%00025 mol «9965 mot dm? 0.075 dm’ Loss in mass on heating is due to the reaction XCO, ~» XO + COs. Hence Amount of XCO, = Amount of XO = Amount of CO, = 4988-3648 _ 9.61 mot 44gmol"! The dissolution of BaO and XO consumes HCI due to the processes BaO + 2HCI > BaCl; + HO and XO + 2HCL > XCI, + H,0 Amount of excess acid = Amount of NaOH consumed = (2.5 M) (0.016 L) = 0.04 mol Amount of HCI used in the dissolution processes = (1.0 M) (0.1 L) ~ 0.04 mol = 0.06 mol Hence m,(BaO) + n,(XO) = 0.06 mol / 2 = 0.03 mol Amount of BaO in the mixture is n(BaO) = 0.03 mol ~ 0.01 mo} = 0.02 mot Hence (0.02 mol) (Myo) + (0.01 mol) Myco, = 4.08 ¢ that is, (0.02 mol) (154 g mol) + (0.01 mol) (My + 60 g mol!) = 4.08 g ‘This gives My = 40 g mol! Heating of the mixture results into the reactions: 2PO(NO,). > 2PbO + 4NO, + 0, and 2NaNO, ~ 2NaNO, + ‘We have M(Pb(NO,),) = 331 g mol M(NaNO;) = 85 g mol M(PbO) = 223 g mol M(NaNO,) = 69 g mol 23 If.x is the mass of Pb(NO,),, then Solving for x, we get x= 3.32 g + © (50-9 = 0.72) 608) + G5 608-0) = 0.72) 5.0 8) 67. 14. 75. 76. ‘The Concept of Atoms and Molecules 1.23 The reaction to be considered is 2Pb(NO,), +2PbO + 4NO, + O, Mp, +16g mol! 67.4 = Solving for My, we Mp, = 207 g mor My, +124g mol ~ 100° ge Maa AEE Mes = OTE & The reaction to be considered is 4K,Cr,0, -> 4K,Cr0, + 2Cr,0; + 30, ‘The loss in mass is due to escape of O;. For 1 mol of K;Cr,0;, (3/4) mol of O, is released. Hence mass of (3/4) mol of O, 24g * 100 = —= x 100 = 8% mass of I mol of K; Cr, 0; 249g ‘The reaction to be considered is Pb(NO,), + 2KI > Pbl, + 2KNO, Amount of Pb(NO;), = (0.1 M) (5 x 10° L) = 5 x 10°* mol Amount of KI = (0.02 M) (10 x 10 L) = 2 x 10° mol Limiting reagent is KI. The amount of Pbl; will be 1 x 10 mol, With methyl orange indicator, both Na,CO, and NaHCO, are neutralized. With phenolphthalene indicator, Na,CO, is neutralized upto the stage of NsHCO;. With phenoiphthalene, NaOH and Na;CO, upto the stage of NaHCO; are neutralized, With methyl orange, both NaOH and Na,CO, are completely neutralized. ‘The reactions are MnO + 8H* + Se” > Mn* + 41,0 AM + 3H,0 + AO} + 6H’ + (5 — mer Hence, we will have (5)(1.61 a mol) = (5 - 1)(2.68 x 10° mol) which’ gives Volume of KxCr,0; required will be (15 mL) (3) = 125 mL ‘here, is the number of electrons involved in the oxidation reaction with MnO and 6 is those involved with Cr,03; The above expression follows from the normality expression, (15 mL) (0.1 x $ N MnO§) = (V) (0.1 x 6 N Cr,0F) The reaction occurring is Na;CO, + H* — NaHCO, + Na’ Since molarity of Na,CO, and HCi are identical, the volume of HCl required in the above reaction will be the same as that of Na,CO,. The reactions occurring are Na,CO, +2H* -» 2Na* + H,O + CO, NaHCO, + H* + Na* + H,0 + CO, Since molarity of Na,COs, NaHCO, and HCI are identical, the volume of HCI consumed will be 2 x 20 mL +20 mL (= 60 mL). The reaction to be considered is 28,0F + 1, 3 8,0% + 2 Amount of 1, = (0.01 mot L~) (10 x 10% L) = (1 x 10-4 mot Amount of $,03° consumed = 2 x 10™ mol e Votune of 0% consumed = 2220S 9 51g? a 20 mt 0.01 mol 04 eq Lt Normality of oxalic acid = (ts stoq) 63 ¢ eq” (250x107 ¥% (10 mL) (0.4 N) Noo (O.1N) 40 mL. 1.24 8. 81. Course in Chemistry for IIT-JEE o 4 a 4 ‘The changes in oxidation numbers are C10; +2CI0, > ClO, +C- Chlorine undergoes increase as well decrease in oxidation states, Hence, the reaction is disproportionation reaction. ‘The reaction of Cr,0}- involving the release of I, from I” is Cr0F + 14H* + 6€ > 2Cr?* + 7H{O. Hence, Equivalent mass of K,Cr,0, = Molar mass Mn in KMnO, is already present in the highest oxidation state. ‘The reaction is CO} +14H* +6Fe* + 2Cr** +7 H,0 +6Fe* Inal mel Ag,CO, > Ag,0 + COx: ( 2108 +16 2768] 232 e108 +12 + 48 © ~7°8) = (Fex27*) 28 Only CaCO, on heating undergoes the reaction CaCO,(s) > CaO(s) + CO,(g) Loss of mass is due to escape of CO,(g) 3 2 = x 107 mol z m Amount of CaCO,(s) in mixture will be equal to the amount of CO, evolved. Hence, mass of CaCO, will be aaaia (3xio? nol) (00g mot") = 0.75g ‘Mass percent of CaCO, = ‘Tic reactions are CW+}0, (2)+C0(G) and C(6)+ O:(8)-+C04 (8) " na " " Total mass of C in CO and CO, = (n, + n3) (12g mol") Total mass of oxygen in CO and CO, = (n, + 2ny) (16g mol”) Hence (n, + n;) (12g mot!) = 6.0g and (m+ 2n3) (16g mol) = 12.0 or ny +m, = 0.5 mol and m, + 2n) = 0.75 mol Solving for n, and ns, we get 0.25 mol and n, = 0.25 mol; (0.25 mol) (28g mol) = 7g mol!; my, ny my (0.25 mol) (44g mol) = 11g mol Mass percent of CO = z X 100 = 63.6 On explosion, CO and CH, is converted to CO, CO(g) + Fo) > COAXg) and CHy(g) + 20,(g) + COAg) + H,O(1) Let V,, Vz and V, be the partial volumes of CO, CH, and He in the original 20 cm? of the mixture, From the chemical equations given above, we have vy VCO) = 1 (OY = VKCO;) and VICH, = 2V{0}) = V{CO, The decrease in volume is due to consumption of , since V,(CO) and V,(CH,) are replaced by equal volumes of V\(CO;) and V;(CO,), respectively. Hence ‘The Concept of Atoms and Molecules 1.25 4 + 2V, = 13 cm* On passing through NaOH(aq), CO,(g) will be absorbed. Hence V, + Vy = 14 em? ‘These two equations give V, = 10 cm’ and V, = 4 cm* Thus, V,(He) = (20 - 10 - 4) em’ = 6 em® Volume percent of CO = (10/20) x 100 = 50%; Volume percent of CH, = (4/20) x 100 = 20% Volume percent of He = (6/20) x 100 = 30% 18x 45.5 a = 95. ais - ix+152 ~ Too" B® Let m; and nz be the amounts of $O, and H,SO, in the given solution of fuming HSO,. The neutralization reactions are We have SO, + 20H — SO} + H,O and H,SO, + 20H > SO} + 2H,0 We will have (1) nyM, + mM, = 0.5 83 (Given mass of mixture) (2) 2m, + my) = (22 x 10 L) (0.5 mol L“) = 0.011 mol (Equivalent H,SO, is consumed) or ny +n; = 0.0055 mol; Eliminating n, from Eqs (1) and (2), we get n,(80 g mot”) + (0.0055 mol ~ n;) (8 g mot") = 0.5 g or (80-98) g mol! = 0.5 g ~ 0.0055 x 98 g = 0.5 g - 0.539 g 0.039 ny = SF mol-= 0.0022 mol; _m, = (0.0022 mol) (80 g mot) = 0.176 g Mass percent of SO; = oe x 100 = 35.2 Mass of KI in solution = (i) (1.132 g mL) (90 mL) = 16.30 g Amount of KI= 16:38 9,10 mol (39 +127)g mol Mass of Pb(NO,)> in solution = () (1 g mL“) (90 mL) = 19.8 g 19.88 {208 + 2(14 +48)} g mol”! ‘The precipitation reactionis Pb(NOs); + 2KI > Pbl, + 2KNO; 0.06 mol 0.1 mol Here KI is the limiting reagent. Thus amount of Pbl, precipitated will be 0.05 mol ‘The neutralization reaction is M,CO, + 2HCI — 2MCI + CO, + H,0 Amount of H* in 100 mL, of 0.05 M HCI solution, n = VM = (100 x 10% L) (0.05 mol L“') = 0,005 mol (HCl) _ 0.005 mol 2 2 Hence (0.0025 mol) [{106 + x(18)} g mol] = 0.355 g ‘This gives x = 2 Amount of Pb(NO,), = 0.06 mol Amount of M,CO, = = 0,0025 mol ‘The reaction between MnO; and HO, is 2MnOj + 5H,O, + 6H* — 2Mn"* + 8H,O + 50, 1.26 Course in Chemistry for IIT-JEE Amount of HO, in the given solution = z x 0,003 mol = 0.0075 mol Mass of H,0, = (0,0075 mol) (34 g mol") = 0.255 g¢ Mass percent purity of H,O, = oe x 100 = 75 91. The neutralization reactions are Phenolphthalein OH” + H* + H,O Methyl orange OH” + H* — H,0 CO} + HY + HCO; CO} + 2H* + CO, + H,0 The extra S mL of HCI used in the methyl orange indicator corresponds to the neutralization reaction HCO} + H* > H,0 + CO, ‘Therefore, for the complete neutralization of Na;CO,, the volume of HCI used will be 10 mL. The vol used for neutralizing NaOH will be 25 mL - 10 mL = 15 mL. Amount of HCI in 10 mL HCI solution = (10 x 10° L) (0.1 mo! L“!) = 10° mol Amount of HCI in 15 mL HC! solution = 1.5 x 10 mot Amount of NaOH in the mixture = amount of HCI = 1.5 x 10% mol Amount of Na,COs in the mixture = 3 (amount of HCI) = 0 x 10° mol | | ‘Mass of NaOH in the mixture = (1.5 x 10° mol) (40 g mot) = 0.06 g ‘Mass of Na,CO; in the mixture = (0.5 x 10° mol) (106 g mol”) = 0.053 g 0.053 M t of Ni in the mixture = ——————- x 100 = 47 iiiinthdiimiaaiiias 0053+0.06 * 68g 58.5 g mol Since the amount of AgNO, is less than that of NaCl, the whole of AgNO, is precipitated. Mass of AgCl precipitated = (0.04 mol) (143.5 g mot") = 5.74 g oC 1. (a) The oxidation state of oxygen in HO, is ~1. It is changed to ~2 in water and to zero in O;. (b) The oxidation state of S is changed from +7 to +6 whereas that of O is changed from 0 to ~2. (©) An oxidant absorbs electron(s), its oxidation number is decreased. @ A reductant releases electron(s), its oxidation number is increased. 2. (a) The element undergoing oxidation causes the release of electron(s). Hence, its oxidation number i increased. (b) The element undergoing reduction absorbs electron(s). Hence, its oxidation number is decreased. (@) The oxidation state of Mo is changed from +6 to +5. Thus, H»MoO, is an oxidizing agent. 3. (a) Itisdecreased by one. (b) In this case, Mn°* is changed to Mn‘* and another Mn** is changed to Mn**. (©) In alkaline medium, the reaction is MnO; + & — MnO (@) In neutral medium (or weakly acidic or alkaline), the reaction is MnO; + 4H* + 3e” > MnO, + 2H,0 4. (a) In strongly alkaline medium, MnO; undergoes the reaction MnO] + e” > MnO". Hence, its equivalen mass is equal to its molar mass. (b) The reaction is 28,0} ~» $,Q? + 267 Hence, Equivalent mass = 2a Molar mass = molar mass 92. Amount of NaCl = = 0.08 mol; Amount of AgNO, = ‘The Concept of Atoms and Molecules 1.27 (©) The reaction is Ce** + & > Ce** (d) The reaction is Cr,0?” + 14H* + 6e” + 2Cr** + 7H,O Equivalent mass = molar mass/6 eq mol! $. (a) The reaction is BrO; + 6H* + 6c Br + 3H,0. 9% 10. i. 13. 14. (d) The change in oxidation state of iodine in 10; is from +5 to +1. (a) The equivalent mass of a substance may have different values in different reactions. Thus, the reaction hhas to be considered before determining its equivalent mass. (b) One mole of K,Fe(CN), produces 4 mol of K* and ! mol of Fe(CN){ ions. (d) As an oxidizing reagent, the reaction is 2H* + H,O, + 2e° + 2H,0. As a reducing reagent, the reaction is HO, + 0, + 2H* + 2e (b) The oxidation state changes from 0 to +6. (a) The equivalent mass is molar mass divided by six (b) The oxidation state changes from 0 to +1 (c) 103 is oxidizing agent. (A) I; is reducing agent, (b) The equivalent mass is molar mass divided by four. (d) The equivalent mass is molar mass divided by five. (b) The equivalent mass is molar mass divided by six. (c) The oxidation state of S is zero. (b) There are four species. The mass of 1000 mL solution will be (1000 ml.) (1.09 g mL“) = 1090 g. The mass of sulphuric acid in the solutionis (13/100) (1090 g) = 141.7 g. Amount of sulphuric is 141.7 g/98 g mol = 1.446 mol. Hence, 1.446 mol Molarity of H,SO, = = 1.446 mol L* Molality of H,S0, = ——!H#6mol____ 595 mol kg"! (1090 = 141.7) x10" kg The burning reaction is 2 Mg + 0; > 2MgO Initial amount of Mg = (1.8 g/24g mol") = 0.075 mol Initial amount of O, = (0.8 g/32 g mol) = 0.025 mol In the combustion reaction, whole of O, will be used Amount of MgO formed = 2 x 0.025 mol = 0.050 mol Amount of O, left = 0 Mass of Mg left = [(0.075 ~ 0.050) mol} (24 ¢ mol") From the reaction MgO + H;SO, -+ MgSO, + H,0, we write 0.05 <= L = 0.2 L or 200 mL 0.25 V(0.25 M) = 0.05 mol or V Link Comprehension Type 1. Normality of oxalic acid solution is Ny = my! Mog _ (0.42 8) (63 g ea") _ Ys (250x107 L) 5 (2N/75) (10 mL) _ 1 0.6 mL) i i uti Ny = 2 N Normality of sulphuric acid solution is Ny = “> iéeb Molarity of sulphuric acid solution = (1/2) (1/40) M = M/80 1.28 Course in Chemistry for ITT-JEE (ii) With phenolphthalene, the reaction occurring is Na,CO, + H* —> NaHCO, + Na* ‘To neutralize whole of Na;COs, volume of H,SO, solution will be twice of the given volume of 4,0 mL. (2x40) (N40) _N (0 mL) Hence, the normality of Na;CO, in the solution is Ny Mass of Na,CO, in IL of solution ism = (N/S0) (53 g eq) = 1.06 g L* (iii) Volume of sulphuric acid solution used in neutralizing NaHCO, will be (14.0 - 2 x 4.0) mL = 6.0 mL. Hence, the normality of NaHCO, in the solution is N, = (COMLIN/40) | 3 (10 mL) 200 = 1.26 gL? Mass of NaHCO, in | L of solution is m = (3 N/200) (84 g eq”! m/Moy _ 0.63 81063 geq7* 2, Normality of oxalic acid solution is Ny = vy (250x107 L) 24 (Normality of sodium hydroxide solution is N, = MM, (N/25) Om) 1 ay Vy (8.6 mL) Normality of sulphuric acid solution is Ny = N2¥z _(N/2)GAmL) 74, Vy @omL) 200 ‘Mass of sulphuric acid present in 1 L of solution m = L715 gL eq") (2 ge? (ii) The reaction occurring are Phenolphthalein: CO} + H* > COx; OH + H* + H,O Methyl orange: CO} + 2H* + CO, + H,0; OH + H* + H,0 Volume of sulphuric acid used to neutralize Na,CO, will be 2(16.0 mL - 12.0 mL) = 8.0 mL. BODO NZD 7. 0 mL) ‘Mass of Na,CO, in IL of solution is _m = (7N/250) (53 g eq”) = 1.484 g L™ (iii) Volume of sulphuric acid used to neutralize NaOH will be 16.0 mL ~ 8.0 mL = 8.0 mL BO mL)CTNI20) 7 0 mL) 250 112 gL? Hence, normality of Na;CO, in solution is Ny = N Hence, Normality of NaHCO; in solution is Ny = Mass of NaOH in 1 L of solution is _m = (7 N/250) (40g eq my! Meg _ (0.63 8) (63 8 €4 N y (250x107 mL) 25 3. Normality of oxalic acid solution is Ny = @) Normality of NaOH solution is Ny = MW’. (N25)Q0mL) _ 1 Vy @.8mL) Since normality of NaOH is its molarity, the molartiy of NaOH is (1/24) M. ‘The Concept of Atoms and Molecules 1.29 NM _ (N25) (10 mL) 1 Vy @8mL) 245 In the reaction of MnO with oxalic acid, it undergoes the reaction MnO; + 8H* + Se” -> Mn’* + 4H,0 Normality of KmnO, solution is Ns = “1 ar26syeql! 1 yy (Seqmor!) 122.5 Gi) Normality of oxalic acid in the solution containing both oxalic acid and sodium oxalate is x Mo'srity of KMnO, solution = —"MO._ Seq mot Mass of oxalic acid per litre of solution ism $y) (3 geq') = 2.23 g Ges Gii) Normality of sodium oxalate in the solution containing both oxalic acid and sodium oxalate is Ne Mass of sodium oxalate present per litre of solution is m = (0.0498 N) (84 g eq!) = 4.18 L 4, (i) The reactions between H,0, and MnO} are as follows MnO; +8H* +5e” > Mn™* +4H,0]x2 H,O, 90, +2H* +2e"]x5 +5H,0, > 2Mn** +50, +4H,0 2Mn0, + 6H Normality of KMnO, solution = (5 eq mol”) (mol L“'/50) = 0.1 eq L* . fe Ne (O-LN)(28.4 mL) Nommality of HO, is N= OTS 0.284 N 0.142 mol Lt Molarity of H,O, = (sana) (0.284 eq L Gi). Mass of 1000 mL of HO; sample = (1000 mL) (1.2 g mL") = 1200 g Mass of H,O, in this solution = (0,142 mol) (34 g mot) = 4.83 g Mass of solvent in this solution = (1200 g - 4.83 g) = 1195.17 g = 1.195 kg Molality of H,O, = ————— = 0.119 mol kg ii) The volume strength of HO, is based on the reaction 2H,0, + 2H,0 + 0, 2 mol of H,O; gives 1 mol of O, or 22.414 L of O, at STP Hence, 0.142 mol L~ solution of H,0, will liberate = (0.142 M) = 1.59 130 Course in Chemistry for IT-JEE ANNEXURE ____t—C—OWRE ee Balancing Chemical Equations 1. Balance the following equations. (@ Cu,0 + H* + NO; > Cu** + NO + H,0 (ii) K,Fe(CN),+H,S0,+ H,0 + K,S0,+ FeSO,+ (NH,),80,+CO (iii) CJH,OH + 1, + OH” + CHI, + HCO; + F + HO Solution ‘The above equations may be balanced following either oxidation-state change method or ion-electron method. Steps listed in each case are those mentioned earlier in the text. i) Cu,0 + H* + NO; > Cu** + NO + H,0 Step: Cu, —2eidation_, Cy?+ No; —Sduction_, No Step2: Cu,0 > 2Cu* NO; > NO Step3: Cu,O + 2H" + 2Cu?* + H,0 NO; + 4H* + NO + 2H,0 Step 4: Cu,0 + 2H* + 2Cu** + H,0 +20" NO} + 4H* + 3e" > NO + 2H,0. Step5: [Cu,0 + 2H* + 2Cu”* +H,0 + 2e-] x3. UNO} + 4H? + 3e° 9 NO + 2H,0] x2 Step6: —3Cu,0 + 2NO; + 14H* > 6Cu** + 2NO +7H,0 (ii) K,Fe(CN),+ H,S0,+ 1,0 + K,S0, + FeSO,+ tl) 50,+00 44-5 Step 1: KFeCCN e+ H,80y+ H40— K,S0,+ FeSO,+ (NH,),50,+ 6O Step 2: KFe(CN),+H,S0,+H,0 + K,S0,+ FeSO, + 3(NH,4),S0,+ 6CO 622412 nn 7 Step 3: K,Fe(CN),+H,SO, + HO + K,S0, + FeSO, + 3(NH,);S0, + 6CO ca a A O-2=-12 Step 4: K,Fe(CN)g+ 6H ,S0,+ 6H0 + 2K,SO,+ FeSO,+ 0NH,),80, +6CO (ii), C,H,OH +1, + OH” > CHI, + HCO; + I + 4,0 2 Guba n@oce ils Ons Ty + OH ~ CHI, + HCO; +I C,H.OH +21, + OH” > CHI, + HCO; +1 +H Step 1: Step. 4345248 ¥ y Step3: C3HjOH +41, + OH” CHI, + HCO; + S1-+H,0 C44eD= Step 4: C,HjOH +41, + 6OH” > CHI, + HCOO™ + SI” + SHO. 2. Complete and balance the following equations, @ Zn + NO; > Zn** + NH} (ii) CO} + CJH,O > C,H,0, + Cr** (iii) HNO, + HCl -» NO + Cl, fiv) Ce** + $,03° + SO?” + Ce** (¥) Cl, + OH” > Cl + C10 ‘The Concept of Atoms and Molecules 1.31 lution ‘The above equations may be balanced following either oxidation-state change method or ion-electron method. Steps in each case are those mentioned earlier in the text. @ Zn + NO} Zn?* + NH} Za oxidation Zn* NO reduction NHY Not required ep: Zn—>Zn"* NO; + 10H* +NHj + 3H,0 jteps 4and 5 : [Zn > Zn?* + 2e7] x4 INO; + 10H* + Se" NH} + 3H,0) x1 ep 6: 4Zn+NO; + 10H* + 4Zn** +NHj +3H,0 (i) Cr,0}" + C,H, > C,H, + Cr+ CH,0 —S2ae, o.11,0, Cr,0} Bie, c+ C,H,0 > C)H,0, Cr,0} > 2¢r* tep3: C,H,O+H,0>C,H,O, + 2H” Cr,0} + 14H* > 2Cr** + 7H,0 eps 4 and 5 : (C;H,O +H,0 > CH,O, + 2H? + 2c") x3 Cr,0} + 14H* + 6" > 2Cr** + 7H,0 Btep6: 3C,H,O+Cr,07-+8H* 43C,H,0,+ 2Cr** + 4H,0 Gi) HNO, + HCl > NO + Cl; pi: ci —Sxiation_, cy, No; —Btuction_, NO p2: 2+; NO; + NO ep3: 2CI > C, NO; + 4H* > NO +2H;0 teps 4 and 5 : (2CI”—> Cl, + 2e) x3 (NO; + 4H* + 3e”-+ NO +2H,0] x2 Step6: 2NO;+6CI"+8H* -+3C1,+2NO+4H,0 or HNO, + 6HC1 + 3Cl, + 2NO + 4H,0 (iv) Ce** + 8,07" > SOP + Ce Step: Cod —98idation_, Cgt+ s,03- —Sustion_, s02- ‘Step Ce¥* + Ce S,0;~ + 280} Step 3: Not required Steps 4and 5 : (Ce** + Ce** + e"] x2 S,0}" + 2c" > 2807" Step6: 2Ce** + S,03° + 280} + 2Ce** () Cl, + OH” > Cl" + ClO™ ci, —22iation, 10" cl, Ee ca Cl; > 2C10~ ci, 2cr Cl, + 40H > 2C10- + 2H,0 cl, > 2c1" Steps 4 and 5 : Cl, + 40H” — 2C10" + 2H,0 + 2e7 Cl, + 26° 9 20r- Step6: 2Cl, + 40H" 2CI" + 2C10 + 2H,0 or Cl, +20H" + CI"+ ClO“ +H,0 3. Complete and balance the following equations. (i) Mn?* + PbO, > MnO; + Pb** + H,0 (ii) S + OH + S*- + 8,07 Git) C1OS + 1 + HyS0, > C1" + HSOZ +1, (iv) Ag’ + ASH, > HAsO, +H" + Ag (1986) Solution ‘The above equations may be balanced following either oxidation-state change method or ion-electron method. Listed steps are those mentioned earlier in the text. @) Mn?* + PbO, MnO; + Pb?* + H,0 1.32 Course in Chemistry for IT-JEE, Step 1: Mn?* “oxidation MnO; PbO; reduction Pp?* Step2: Not required. Step3: Mn®* + 4H,0 MnO; + 8H* PbO; + 4H’ > Pb?* + 2H,0 Steps 4.and 5: [Mn?* + 4H, MnO; + 8H* + Se™] x2 [PbO, + 4H* + 2c” Pb** + 2H,0] x5 Step6: — 2Mn** + SPbO, + 4H* — 2MnOj + SPb™* + 2H,0 (i) S + OH” S* + $,07 Steps1 and 2 : 25 —Seidation_, §,.92- 9 mats, og? Stwep3: 28 +3H,0- 8,0?" + 6H* Sas* Steps 4 and 5 : 28 + 3H,0 + 8,0} + 6H* + 4e~ [S +26 9S] x2 Step6: 48 +3H,0 - 2S” + $07" + 6H* or 48 +6OH~ 28> +8,0? + 3H,0 (il) ClOs + F + HS0, + Cr + HSO, + 1, - Steps | and 2 : 21> —2xation_, clos — auction, cy- Sup3: Wk C10; + 3H,S0, > Cl + 3HS0; + 3H,0 Steps 4 and 5 : 21° 9 1; + 2e (ClO; + 3H,S0, +e” > Cl” + 3HSO; + 3H,0] x2 Step 6: 21° + 2C10; + 6H,S0, >I, + 2Cl- + 6HSO; + 6H, (iv) Ag* + ASH, > H3AsO, + HY + Ag Steps | and 2: AsH, —*siition_, 1,480, Agh —fetuction_, ag Step3: ASH + 3H,0 > HAsO; + 6H* Ag > Ag Steps 4 and 5: ASH, + 3H,0 + HAsO, + 6H* + 6e™ (Ag* +9 Ag) x6 Step 6: AsHl + 6Ag* + 3H;0 > HAsO, + 6Ag + 6H* 4. Balance the following equations, (i) As;8, + OH” + HO, > AsO} + SO} + H,O. (ii) Crl, + H,0, + OH” CrO} + 310; + H,0. (ii) Py + OH” + HO, HPO; + PH (iv) As:S; + NO +H" + H,0 > HAs, + NO +S Solution ‘We may arrive at the balanced equations as shown in the following. (i) As)S, + OH” + H,O, + AsO}” + SOF + H,O. Steps | and 2: As,S, —S=idation_, 2as0}° + 3803 H,0, —Eaustion_, 20H- Step3: As,S, + 400H™ — 2AsO} + 380)" + 20H,0 H,0, + 20H™ Steps 4 and 5: As,S, + 400H™ - 2AsO}- + 3SO}° + 20H,0 + 28 (H,0, + 2e° > 20H7] x 14 Step: 8,5, + 10H” + 14,0, ~» 2480)" + 3803" + 20H,0 (i) Cri, + H,0, + OH” > Cro} + 310; + H,0 Steps 1 and 2: Cr, “#2, Cro?" 4 310; H,0, —2ietion_, 20H- Step3: Cel +320H™ + CrOF" + 310; + 16H,0 H,0, + 20H" Steps 4 and 5 : [Cry +320H” > CrO} + 310; + 16H,0 + 277] x2 {H,0, + 26" > 2087] x27 Step 6: 2Crly+ OOH” + 27H,0, > 2CrO} + 610; + 32H,0 (iii) P, + OH” + H,0, + HPO; + PH, Steps | and 2: +P, —=sation_, POS 4p, duction, pH, Step3: +P,+ 20H” HPO; 4P,+3H,0 ~ PH, + 30H) ‘The Concept of Atoms and Motecules 1.33 Steps 4 and 5 : ({P, + 20H” + H,PO; +e] x3 4P,+3H,0 +3¢ — PH, + 30H” Step6: P,+30H™ + 3H,0 > 3H,PO; + PH, (iv) As,S, + NOy + H* + H,0 > Hj AsO, + NO +S Steps 1 and 2: As,S, —=iation_, 211,450, + 38 No; —Raction_, No Step3: As,S, + 8H,O ~ 2H, AsO, + 3S + 10H* NO; + 4H* > NO +2H,0 Steps 4 and 5 : (As,S, + 8H,0 > 2H,AsO, + 3S + 1OH* + 1027] <3 INO; + 4H* + 3” 9 NO + 2H,0] x 10 Step 6: 3As,S,+4H,0+ 10NO}+ 10H” —+ 6H,As0, + 9S + 10NO 5, Balance the following equations. @ 0, + Cr —kaline medium, (OH); (ii) MnO} + H* -» MnO, + MnO; Gil) Ag, + AsH, “line medium , ge 4 HAsO; (iv) IOs + Cl 9 1, + Cl Solution alkaline mediums @ 0, + Cr —talnemedion CHO); Steps and 2: Cr —SHation_, COM); 20, auction, CrOH); Step3: Cr+ 40H~ > Cr(OH); 20; + Cr+ 4H,0— Cr(OH); + 40H" Steps 4 and 5 : [Cr+ 40H” Cr(OH); + 3€°] x5 [20, + Cr + 4H,0 + Se” > C(OH); + 4OH™] x3 Step 6: 8Cr-+ 60; + 8OH™ + 12H,0 > 8Cr(OH); or 4Cr+30, + 40H” + 6H,0 4CxOH); (ii) MnO} + H* — MnO, + MnOz Steps 1 and 2 : Mno}- —2=idation_, Mnoy ‘Mnoj- —auction_, Mino, Step3: MnO} > MnO; MnO} + 4H* + MnO, + 2H,0 Steps 4 and 5 : [MnO > MnO; + e&°] x2 MnO} + 4H* + 2e° > MnO, + 2H,O Step: 3MnO} + 4H* + 2MnO; + MnO, + 2H,0 Gili) Ag,0 + AsH, —tktline medium ay 4 11,4805 Steps 1 and 2: AsH, —dation_, 11, ASOT Ag,0 —Sauction_, rag Step: AsHy + 70H” + HAsO; + 4H,0 Ag,0 +H, ~» 2Ag + 20H” Steps 4 and 5: ASH; + TOH~ -+ HAsO; + 41,0 + 6e- Step6: (Ag,O + H,0 + 2c” 2Ag+ 20H"] x3 AsH, + 3Ag,0 + OH” > HAsO; + 6Ag + H,0 (iy) 105+ Cr > + Ch Steps 1 and 2: 2c1- —2idation_, cy, 210; —eevstion_, 1, Sep: 2+ Cy 210; + 12H* > 1, + 6H,0. Steps 4 and 5 : (2C\” > Cl; + 20") x5 210; + 12H* + 10e-— 1, + 6H;,0 Step6: CI + 2105 + 12H* SCI, +1, + 6H,0 6. Arrange the following in order of increasing oxidation number of (@) Iodine : 15, HI, HIO,, ICl ii) Manganese : MnCl, MnO;, KMnO, (iii) Nickel : K,[Ni(CN),}, Kp [NiFg], Ni(CO), (iv) Sulphur : S,, $,0}°, 8,03", S,03-. (i) The oxidation numbers of iodine are shown below alongwith the compounds, L.HI.HTO,, Yel 1,34 Course in Chemistry for ITT-JEE Hence, the increasing order of oxidation number of iodine in the compounds is HI Fe** + U** (d) Cu,0 + NO; + Cu?* + NO (©) P, + HNO; + HPO, + NO, ( Pb,0, + HO, > PSO, + 0, @) 105+ oh (h) HNO, + 1, > NO, + HIO, @_P,O,, + HNO, + HPO; + N,0, @ 10s + HAsO, + CI” = ICIS + HAsO, (k) Cr?" + MnO; > Cr07° + Mn?* @ Mg + HNO, -» Mg(NO,), + NH,NO (m) SnS, + NaOH + Na,SnS, + Na,Sn0, (n) CrOH); + HO; > CrO} + OHT + HO (0) Cu+HNO, + Cu(NO,), + NO (p) Ag +0, + CN” Ag(CN); + OH” (q@) Zn +NaNO, + NaOH NH, + Na,Zn0, (©) Au+HNO, + HCI ~ HAuCl, + NO (9) BrOs + Br” + Br, () MnO; + As;0, > Mn?* + HAsO, (u) Cu+HNO, > Cu** + NO, + NO; {v) S+OH™ + S87 + 8,07 (w) 1,+ OH” oI +10; (x) P, + OH” + H,PO; + PH, (y) KCIO, + H,SO, + HCIO, + KHSO, + ClO, (@) 1 + ClO; + H,SO, > Cl” + HSO; + I, ANSWERS (a) 2CrO}" + 3Cu,0 + 2H" + 9H,0 > 2Cr(OH); + 6Cu(OH), (b) 6Cu,P + 11Cr,0}7 + 124H* — 18Cu?* + 6HAPO, + 22Cr** +53H,0 (©) 2Fe?* + UO}* + 4H* = 2Fe** + Ut* + 2H,0 (@) 3Cu,0 + 2NO; + 14H* + 6Cu?* + 2NO + 7H,0 (©) Py + 20HNO, > 4H,PO, + 20NO, + 4H,0 (0) 2Pb,0, + 6H,SO, -> 6PbSO, + 6H,0 + 0, (g) 10; + ST + 6H* ~ 31, + 3H,0 (h) 10HNO, + I, > 10NO, + 2HIO, + 44,0 (@ 2P,0,; + 2HNO, + 3H,0 — SHPO, + N,Os @ 10; + 2CI” + 2H* + 2H,AsO, — ICI, + 2H,ASO, + HO (kK) 10Cr3* + 6MnO; + 220H~ — SCr,07" + 11H,0 + 6Mn** “The Concept of Atoms and Molecules 1.35 () 4Mg + 10HNO, — 4Mg(NO,), + NH,NO, + 3H,0 (im) 3SnS, + 6NaOH —+ 2Na,SnS, + Na,SnO, + 34,0 (a) 2Cr(OH); + 3HOS > 2CrO}P + OH” + SHO. (0) 3Cu + 8HNO, + 3Cu(NO,), + 2NO + 4H,O (p) 4Ag + O, + 8CN” + 2H,O — 4[Ag(CN),]) + 40H™ (q) 4Zn + NaNO, + 7NaOQH — NH, + 4Na;Zn0, + 2H, (r) 2Au + 2HNO, + 8HCI > 2HAuCL, + 2NO + 4H,O (s) BrOy + SBr~ + 6H* — 3Br, + 3H,O (t) 4MnO; + SAs,0, + 12H* + 9H,0 > 4Mn** + 10H,AsO, (u) Cu + 4HNO, + Cu?* + 2NO; + 2NO, + 2H,0 (¥) 4S + 6OH™ — 28** + $0} + 3H,0 (w) 61, + 120H” 101> + 210; + 64,0 (x) 2P, + 30H” + 9 H,O + 3H,PO; + SPH, (y) 3 KCIO, + 31,80, > HCIO, + 3KHSO, + H,0 + 2C10, (2) 61” + ClO; + 6 H,SO, > Cl” + 6 HSO; + 31, + 3H,0 Solved Problems 1, A LO g sample of H,0, solution containing X% HO, by mass requires X cm? of a KMnO, solution for complete oxidation under acidic conditions. Calculate the normality of KMnO, solution. agg) Solution The equations involved are MnO; + 8H* + Se — Mn’* + 4H,0] x 2 H,0, + 0, + 2H’ + 26] x5 2 MnO; + SHO, + 6 H* + 2Mn"* + SO, + 8H,0 From this equation, we find that Molar mass of H. 34g mor! 2eq mol! 2eq mol" Equivalent mass of H,0,, M,, = = IT geq' Mass of HO, in the given 1.0 g sample, —mgy = os x 10g ‘Amount (in equivalents) of HO, in the given 1.0 g sample is m_ _ (X/100) x My I geq' 17x100 eq ) If Nyngan, 38 the normality of KMnO,, the amount (in equivalents) of KMnO, consumed is Nea = Vaasa, Nawno, = (54) New, (2) Equating Eqs (1) and (2), we get or Mew, = * eq L™! = 0.588 eq L™! 2. Hydroxylamine reduces iron(1I1) according to the equation 2NH,OH + 4Fe** — N,O(g) + H,O + 4Fe** + 4H" Iron (It) thus produced is estimated by titration with a standard permanganate solution. The reaction is ‘MnO; + SFe** + 8H* — Mn’? + SFe** + 44,0 1.36 Course in Chemistry for IIT-JEE A 10 mL sample of hydroxylamine solution was diluted to 1 litre. 50 mL of this diluted solution was boiled with excess of iron (III) solution. The resulting solution required 12 mL of 0.02 M KMaO, solution for complete oxidation of iron(I). Calculate the mass of hydroxylamine in one litre of the original solution, (1982) Solution From the given chemical equations, we find that 2 mol NH,OH = 4 mol Fe?* and 1 mol MnO; Amount of MnO,” consumed in the oxidation of iron(II) mol Fe?* 2 iy _ 2x 002 = VM = (12 mL) (0.02 M) = (5#) oar mate >= F009 Since 1 mol MnO; = 5 mol Fe?*, we have ‘Amount of Fe?* forme bythe rtucton of Fe by NH,OH =() (275902) mot Now since 2 mol NH,OH = 4 mol Fe?*, we have Amount of NH,OH present in 50 mL of dtd station = (3) ts (2x08 v2) . con = (1000) (2 12002 Amount of NHOH present in I L of diluted solution = ( a \(3) o ( od ) mol ‘Amount of NH,OH present in 1 L of undiluted solution = (e\AS 2 ] 6) (32) mol = 1.2 mol Mass of NH,OH present in 1 L of undiluted solution = (1.2 mol) (33 g mol”) = 39.6 g. 3. A mixture weighing 4.08 g of BaO and unknown carbonate XCO, was heated strongly. The residue weighed 3.64 g. This was dissolved in 100 mL of 1 N HCL The excess acid required 16 mL of 2.5 N NaOH solution for complete neutralization. Identify the metal M. (1983) Solution On heating, we have XCO, > XO +CO; ‘The loss of mass (= 4.08 g -3.64 g = 0.44 g) is due to the removal of CO,. Thus Amount of CO, released = = 107 mol Hence, Amount of XO = 107? mol Now ‘Mass of BaO in the mixture after heating = 3,64 ~ (10? m0) (My) 3.64 g ~ (10? mol) (Mx + 16 g mot) = 3.48 g - (10? mol) (My) From the dissolution reactions BaO + 2HCi -> BaCl, +H,0 and XO + 2HCI + XCl, + H,0 we conclude that 3.48 g - (10~* mol 22 apa | Amount of HCI consumed for the dissolution process = 2 [tse ts X410 * mot ao Amount of HCl taken for the dissolution process = (100 mL) (0.1 M) (= 1} (1 mol LE“) = 0.1 mol Amount of remaining HCl = 1 mot — 2 [2888407 0 Ma 167 mot 154g mol! 16 Too *25 wa for complete neutralization, we would Since the remaining HCI required 16 mL of 2.5 M NaQH ( have 348g - (10°? mol) M, 16x25 nai -2[ = (10? mod My =O. +107 mol 1009 M0! = 0.1 154g mol |