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Periodic Properties of Elements

I.

II.

Periodic Properties of Elements in the Periodic Table
A.

Periodic variation in physical properties of the elements H to Ar (First 18 elements)

B.

Variation in melting point and boiling point

Periodic relationship among the oxides, chlorides and simple hydrides of
the elements Li to Cl (Elements 3-17)
A.

B.

C.

Hydride
1.

Bonding

2.

Hydrolysis

Chloride
1.

Bonding

2.

Hydrolysis

Oxide
1.

Formation of acidic, amphoteric and basic oxides
a)

Amphoteric oxides

s-Block Elements
I.

Characteristic properties of the s-block elements
A.
B.
C.

II.

Variation in properties of the s-block elements and their compounds
A.

B.
C.

D.

III.

Metallic character and low electronegativity
Ionic bond formation and fixed oxidation state
Flame test
Reaction of the elements
1.
Reaction with hydrogen
2.
Reaction with oxygen
3.
Reaction with chlorine
4.
Reaction with water
Thermal stability of carbonates and hydroxides
1.
Thermal stability of carbonates
2.
Thermal stability of hydroxides
Solubility of sulphate and hydroxide
1.
Solvation energy
a)
Definition of solvation and solution processes
b)
Factors affecting the value of hydration energy
c)
Effect of lattice energy and hydration energy on solubility of ionic crystal
2.
Solubility of some ionic crystals
a)
Sulphate salt of group II metal
b)
Hydroxide of group II metal
c)
Solubility of salts of other group II metals
Abnormal behaviour of lithium

Uses of the compounds of the s-block elements
A.
B.
C.
D.
E.
F.

Manufacture of glass
Baking powder
Making of soap
Antacid
Slaked lime
Fireworks

p-Block Elements
I.

Halogens
A.
B.
C.
D.

E.

II.

Laboratory preparation of chlorine
Characteristic properties of the halogens
Properties of halogen
1.
Oxidizing power of halogen
2.
Disproportionation of halogen in alkalis
Properties of the halogen compound
1.
Reactions of halide
a)
with halogens
b)
with conc. sulphuric(VI) acid
c)
with conc. phosphoric(V) acid
d)
with silver ions
2.
Acidic properties of hydrogen halide
3.
Oxoacid
Uses of halogens and halogen containing compounds
1.
Fluoridation of water
2.
Use of chlorine
3.
Photographic films

Nitrogen and its compounds
A.
B.

Nitrogen
1.
Unreactive nature of nitrogen
2.
Direct combination of nitrogen and oxygen
Ammonia
1.
Haber process
2.
Chemical properties of ammonia
a)
Alkaline properties
(1)

b)

(1)
(2)
(3)
(4)
(5)

C.

D.
E.

Laboratory preparation of ammonia

Reducing properties
Combustion
Catalytic oxidation
With copper(II) oxide
With chlorine
Thermal decomposition of ammonia

Nitric(V) acid
1.
Ostwald Process
2.
Oxidizing properties of nitric(V) acid
a)
With copper
b)
With iron(II) ion
c)
With sulphur
Nitrate(V) salt
1.
Thermal decomposition of nitrate
2.
Brown ring test
Use of nitric(V) acid
a)
Fertilizers
b)
Explosives
c)
Nylon
d)
Dyestuffs

Oxidizing properties of sulphur dioxide a) With magnesium 3. Sulphur and its compounds A. Paints. C.III. B. Properties of concentrated sulphuric acid Sulphate(VI) salt 1. D. Test for sulphate(VI) ion Use of sulphuric(VI) acid 1. Pigments and dyestuffs . F. Allotrope of sulphur Burning of sulphur Sulphur dioxide / sulphate(IV) salt 1. Detergents 3. Distinguishing from carbon dioxide Concentrated sulphuric(VI) acid 1. Reducing properties of sulphur dioxide a) With manganate(VII) ion b) With dichromate(VI) ion c) With bromine 2. Fertilizers 2. Contact process 2. E.

II. D. Electronic configuration of d-block elements Electronic configuration of ions of d-block elements 1. B. Physical properties a) Ionization enthalpies and electronegativity b) Melting point and hardness c) Atomic radii of d-block elements d) Densities 2. Geometrical isomerism 5. Chemical properties a) Reaction with water Characteristic properties of the d-block elements and their compounds: A. Reaction between peroxodisulphate(VI) and iodide ions 3. General features of the d-block elements from Sc to Zn A. E. Stability of different ions Comparison of properties between d-block and s-block metals 1. Common oxidation states of vanadium and manganese compounds a) Vanadium compounds b) Manganese compounds Complex formation 1. Decomposition of hydrogen peroxide Magnetic properties of transition metal and ion . Stability constant 3. Relative stability of complex ion a) Basicity of the ligand b) Chelate effect 2. C. B. Nomenclature of complexes Coloured ions 1.d-Block Elements I. Variable oxidation states 1. Colours of different ions Catalytic properties of transition metals and their compounds 1. C. Haber process 2. Aquaton isomerism 4. Origin of the colour 2.

.

Variation in melting point and boiling point Periodic relationship among the oxides. Formation of acidic. Hydride 1. amphoteric and basic oxides a) Amphoteric oxides . chlorides and simple hydrides of the elements Li to Cl (Elements 3-17) A. Hydrolysis Oxide 1. II. Periodic Properties of Elements in the Periodic Table A. Periodic variation in physical properties of the elements H to Ar (First 18 elements) B. Hydrolysis Chloride 1.Periodic Properties of Elements I. Bonding 2. Bonding 2. B. C.

Furthermore. . chlorides hydrolyse faster in alkaline medium since OH-(aq) ion is a stronger nucleophile than water. the presence of alkali also shifts the equilibrium position to the right.Properties of compounds and bond energies Hydrolysis of Hyrides Hydride Reaction LiH(s) LiH(s) + H2O(l) → LiOH(aq) + H2(g) BeH2(s) BeH2(s) + 2H2O(l) → Be(OH)2(aq) + 2H2(g) B2H6(g) B2H6(g) + 6H2O(l) → 2H3BO3(aq) + 6H2(g) CH4(g) NH3(g) NH3(aq) + H2O(l) d NH4+(aq) + OH-(aq) H2O(l) H2O(l) + H2O(l) d H3O+(aq) + OH-(aq) HF(g) HF(l) + H2O(l) d H3O+(aq) + F-(aq) HF(l) + H+(aq) d H2F+(aq) NaH(s) NaH(s) + H2O(l) → NaOH(aq) + H2(g) MgH2(s) MgH2(s) + 2H2O(l) → Mg(OH)2(aq) + 2H2(g) AlH3(g) AlH3(g) + 3H2O(l) → Al(OH)3(aq) + 3H2(g) SiH4(g) SiH4(g) + 4H2O(l) → Si(OH)4(s) or SiO2·nH2O(s) + 4H2(g) PH3(g) H2S(g) H2S(aq) + 2H2O(l) d H3O+(aq) + HS-(aq) + H2O(l) d 2H3O+(aq) + S2-(aq) HCl(g) HCl(g) + H2O(l) → H3O+(aq) + Cl-(aq) Hydrolysis of Chlorides Chloride Reaction LiCl(s) BeCl(s) BeCl2(s) + 4H2O(l) → [Be(H2O)4]2+(aq) + 2Cl-(aq) [Be(H2O)4]2+(aq) + H2O(l) → [Be(H2O)3(OH)]+(aq) + H3O+(aq) BCl3(l) BCl3(l) + 3H2O(l) → H3BO3(aq) + 3HCl(aq) CCl4(l) NCl3(l) NCl3(l) + 3H2O(l) → NH3(aq) + 3HOCl(aq) Cl2O(g) Cl2O(g) + H2O(l) → 2HOCl(aq) ClO2(g) 2ClO2(g) + H2O(l) → HClO2(aq) + HClO3(aq) Cl2O6(l) Cl2O6(l) + H2O(l) → HClO3(aq) + HClO4(aq) Cl2O7(l) Cl2O7(l) + H2O(l) → 2HClO4(aq) ClF(g) ClF(g) + H2O(l) → HF(g) + HOCl(aq) NaCl(s) MgCl(s) MgCl(s) + warm H2O(l) → MgCl(OH)(s) + HCl(aq) AlCl3(s) AlCl3(s) + 6H2O(l) → [Al(H2O)6]3+(aq) + 3Cl-(aq) [Al(H2O)6]3+(aq) + H2O(l) → [Al(H2O)5OH]2+(aq) + H3O+(aq) SiCl4(l) SiCl4(l) + 4H2O(l) → Si(OH)4(aq) + 4HCl(aq) or SiCl4(l) + (x+2)H2O(l) → SiO2·xH2O(aq) + 4HCl(aq) PCl3(l) PCl3(l) + 3H2O(l) → H3PO3(aq) + 3HCl(aq) PCl5(s) or PCl5(s) + H2O(l) → POCl3(l) + 2HCl(g) POCl3(l) + 3H2O(l) → H3PO4(aq) + 3HCl(aq) SCl2(g) SCl2(g) + H2O(l) → HSCl(aq) + HOCl(aq) 2S2Cl2(g) + 2H2O(l) → 3S(s) + SO2(g) + 4HCl(aq) Cl2(g) Cl2(g) + H2O(l) → HCl(g) + HOCl(aq) Page 1 Remark Insoluble in water Slightly soluble in water Remark Soluble in water Dissolve and hydrolyse in water Immisicible with water Soluble in water Dissolve and hydrolyse in warm water In general.

The basic oxides could be neutralized by acid while the acidic oxides could be neutralized by alkali. Not reaction with water but it is amphoteric Not reaction with water but reacts with strong base P2O3(s) + 6H2O(l) → 4H3PO3(aq) P2O5(s) + 6H2O(l) → 4H3PO4(aq) SO2(g) + H2O(l) d H2SO3(aq) d H+(aq) + HSO3-(aq) d 2H+(aq) + SO32-(aq) SO3(g) + H2O(l) → H2SO4(aq) → H+(aq) + HSO4-(aq) d 2H+(aq) + SO42-(aq) Cl2O(g) + H2O(l) → 2HOCl(aq) 2ClO2(g) + H2O(l) → HClO2(aq) + HClO3(aq) Cl2O6(l) + H2O(l) → HClO3(aq) + HClO4(aq) Cl2O7(l) + H2O(l) → 2HClO4(aq) In general. Na(s) forms peroxide instead of oxide when burns in air. Insoluble in water neutral and insoluble but hydrolyses slowly. The exceptions are BeO(s) and Al2O3(s). They are called amphoteric because they react with both acid and alkali. MgO(s) only reacts with water very slowly due to high lattice energy.Properties of compounds and bond energies Hydrolysis of Oxides Oxide Reaction Li2O(s) Li2O(s) + H2O(l) → 2LiOH(aq) BeO(s) B2O3(s) B2O3(s) + 3H2O(l) → B(OH)3(aq) B(OH)3(aq) + 2H2O(l) e H3O+(aq) + [B(OH)4]-(aq) CO2(g) CO2(g) + H2O(l) d H2CO3(aq) CO(g) d H+(aq) + HCO3-(aq) d 2H+(aq) + CO32-(aq) N2O5(g) N2O5(s) + H2O(l) → 2HNO3(aq) N2O4(g) N2O4(g) [or 2NO2(g)] + H2O(l) → HNO2(aq) + HNO3(aq) N2O3(g) N2O3(g) + H2O(l) → 2HNO2(aq) NO(g) N2O(g) O2(g) F2O(g) F2O(g) + H2O(l) → 2HF(aq) + O2(g) Na2O2(s) Na2O2(s) + 2H2O(l) → 2NaOH(aq) + H2O2(aq) MgO(s) MgO(s) + H2O(l) e Mg(OH)2(s) e Mg2+(aq) + 2OH-(aq) Al2O3(s) SiO2(s) P2O3(s) P2O5(s) SO2(g) SO3(g) Cl2O(g) ClO2(g) Cl2O6(l) Cl2O7(l) Page 2 Remark No reaction with water but it is amphoteric Carbonic acid or carbonated water NO(g) and N2O(g) are neutral and insoluble in water. In Acid Oxide BeO(s) Al2O3(s) Reaction BeO(s) + 2H+(aq) → Be2+(aq) + H2O(l) Al2O3(s) + 6H+(aq) → 2Al3+(aq) + 3H2O(l) Remark Amphoteric oxide Amphoteric oxide In Alkali Oxide BeO(s) Al2O3(s) Reaction BeO(s) + 2OH-(aq) + H2O(l) → [Be(OH)4]2-(aq) Al2O3(s) + 2OH-(aq) + 3H2O(l) → 2[Al(OH)4]-(aq) Remark Amphoteric oxide Amphoteric oxide . metal oxides are basic and non-metal oxides are acidic in nature.

0 .0 H 435.9 435.3 in O=O) 464 F 158 568.9 Page 3 Bond energy E(X–O) in kJmol-1 (with oxygen) Bond energy E(X–Cl) in kJmol-1 (with chlorine) 358 214 144 346 466 469 464 432.0 Na 72 Mg Al Si 226 315 P 198 321 S 266 364 Cl 243.4 in N≡N) O 144 (498.Properties of compounds and bond energies Bond energy Bond energy Bond energy E(X–H) in kJmol-1 E(X–X) in kJmol-1 (with element) (with hydrogen) Li Be B C 347 413 N 391 158 (945.4 432.

In the periodic table.6 while the atomic mass of 53I is 126. Furthermore. elements with similar chemical properties are grouped in columns called groups.0 Chemistry in Context. For example.1. the atomic mass of 52Te is 127. not the atomic mass. Periodic Properties of Elements in the Periodic Table It is important to notice that the modern periodic table was developed by a Russian scientist Mendeléev in 1867 by comparing the physical and chemical properties of different elements. the periodic table aided the discovery of electronic configuration of atom and some new elements. the atomic mass of 18Ar is 39. However. elements can be classified into s-block. Glossary . the electronic configuration of atoms were only discovered by Bohr in 1913.Periodic Properties of Elements Unit 1 Topic Perioidic Properties of Elements Reference Reading 8. Indeed. 37–41 A-Level Chemistry.N. d-block and f-block elements depending on the orbital that the vacant electrons are filling.9.9 while the atomic mass of 19K is 39. p-block. 3rd Edition. elements are arranged according to the atomic number. Ramsden pg. 43–45 Page 1 Unit 1 Assignment Syllabus Notes I. 3rd Edition ELBS pg. E. With such arrangement.

Elements in same group have similar chemical properties.Periodic Properties of Elements Past Paper Question Unit 1 Page 2 91 2B 4 a i 94 1A 2 f 91 2B 4 a i 4a i Briefly explain what is meant by periodicity in the chemical properties of the elements. ½ mark K has one more proton than Ar does. of proton. In the Periodic Table. Properties recur after an interval (period). the elements are arranged in order of atomic number / no. also accept “element” properties are periodic functions of atomic number 2 1 mark 1 mark 94 1A 2 f 2f The relative atomic mass of potassium is less than that of argon. but not in order of atomic mass. State the reason why potassium follows argon in the Periodic Table. ½ mark 1 .

. 42–49. all varies periodically across the periodic table. Variation in electronegativity 1. 42–50.N. 5th Edition. the more regularly arranged particles are melted to randomly arranged liquid particles. 4th Edition. boiling point serves as a better indication of the strength of attraction than melting point does.Periodic Properties of Elements Unit 2 Topic Perioidic Properties of Elements Reference Reading 8. 176–177 Reading Syllabus Notes A.1 Chemistry in Context. melting point is also depending on the arrangement of particles in the structure. electronegativity. melting point and boiling points. 333–336 Page 1 Unit 2 Assignment Chemistry in Context. pg. However. E. For the details of variation in first ionization energy. 4–21 A-Level Chemistry. 169. T.M. in the melting point process. Besides the attraction. the randomly arranged liquid particles are vaporized to randomly arranged gaseous particles. In general. please refer to Atomic structure – Units 4 & 6. 3rd Edition. 191–201 Inorganic Chemistry. In the boiling process. atomic radius and electronegativity. Ramsden pg. 35–37. Periodic variation in physical properties of the elements H to Ar (First 18 elements) First ionization energy. 3rd Edition ELBS pg. Leung pg. atomic radius. Variation in melting points and boiling point Both melting point and boiling point reflects the strength of attraction among the particles. Thomas Nelson and Sons Ltd.

p.s.Periodic Properties of Elements Unit 2 Page 2 For example. are rather low. thus the m.s.p.m.p. thus all giant covalent structures have very high m. it forms an zig-zag line instead. Although melting point also shows a general increasing trend.c. Key - Glossary s.p.p.p. : Simple molecular structure The forces among the molecules are weak van der Waals' forces. of carbon (except methane) are more symmetrical than the ones with odd no. therefore S has a higher m. Giant metallic structure The m. of carbon. : g. and b. of a metal is depending on the strength of the metallic bond.s. : g. simple molecular structure giant metallic structure giant covalent structure . They are packed more regularly in the solid. and b. boiling point of unbranced alkane increases smoothly with increasing molecular size.p. than P.p. Giant covalent structure The attraction amount the atoms are strong covalent bond. and b.m. This is because the alkane with even no. P4 molecule is smaller than S8 molecule. and b. thus a little bit higher melting point.

3. and in white phosphorus. Explain the change in ionization energy between nitrogen and oxygen.Periodic Properties of Elements Past Paper Question 91 2B 4 a ii 92 2B 6 Aa ii Unit 2 Page 3 92 2B 6 Ba ii 91 2B 4 a ii 4a ii Draw diagrams showing the variations in melting point (or boiling point) and first ionization energy.3 pattern (not labelling each axis -½) Explanation: p3 for N (p4 for O not necessary) stability of half-filled subshell 92 2B 6 Aa ii 6Aa ii Describe the structure and the bonding in nitrogen. N2: N≡N structure: (linear) diatomic molecule bonding: intramolecular. E. Graph shows decrease in ionization energy down the group Graph shows 2. For melting point (or boiling point) Graph shows maxima for melting point at Group IV or for boiling point at either Group III or IV. for the elements from lithium to argon. Graph shows minima at Group V to Group 0 Graphs shows decreasing in melting point (or boiling point) down the group in Group III or IV (not labelling each axis -½) For I. P4. single covalent intermolecular. van der Waals 5 1 mark ½ mark ½ mark 1 mark 1 mark ½ mark ½ mark 2 ½ mark ½ mark ½ mark ½ mark P P white P4: structure: bonding: P P discrete tetrahedral intramolecular. and in rhombic sulphur. O2. N2. van der Waals 92 2B 6 Ba ii 6Ba ii Describe the structure and the bonding in oxygen. S8. covalent intermolecular. ½ mark ½ mark ½ mark ½ mark 4 .

covalent intermolecular. van der Waals Unit 2 Page 4 ½ ½ mark ½ mark ½ mark ½ mark ½ mark ½ mark ½ mark .Periodic Properties of Elements O2: O=O mark structure: (linear) diatomic molecule bonding: intramolecular. single covalent intermolecular. van der Waals S S S S S S S S S8: structure: bonding: molecular ring structure intramolecular.

This makes Li compound behave similarly as the Mg compound rather than other group I metal compounds. 338–340 Unit 3 Assignment Chemistry in Context. Consequently. E. i.Periodic Properties of Elements Unit 3 Page 1 Topic Periodic Properties of Elements Reference Reading 8.g. diagonal relationship does not apply to non-metals. the two ions share similar charge density( r ) and + polarizing power. pg. the electronegativity difference among the non-metals are larger than the difference among the metals. Consider lithium and magnesium.N. electronegativity of the element and charge density of the ion.g. e. some elements show similar chemical properties to another element in another group.M. → Li2O(s) + CO2(g) Li2CO3(s) heat MgCO3(s) heat → MgO(s) + CO2(g) However. 21–33 A-Level Chemistry. Be and Al. Periodic relationship among the oxides. Glossary diagonal relationship charge density polarizing power electronegativity . Leung pg. The chemical properties of a particle is depending on its ability to attract or donate electron. Li and Mg. Li+ ion is smaller than Mg2+ ion but Z+ Mg2+ ion carries higher charges than Li+ ion. 3rd Edition. T. All group I carbonates are stable to heat except lithium carbonate. 5th Edition. Lithium carbonate decomposes upon heating like magnesium carbonate.2. chlorides and simple hydrides of the elements Li to Cl (Elements 3-17) Besides similarity in chemical properties among the elements within the same group.0 Chemistry in Context. Thomas Nelson and Sons Ltd. This explains why CCl4 is stable in water but PCl3 hydrolyse in water readily.e. e. water → no reaction CCl4(l)  PCl3(l) + 3H2O(l) → H3PO3(aq) + 3HCl(aq) Furthermore. 3rd Edition ELBS pg. This relationship is called diagonal relationship. 177–178 Reading Syllabus Notes II. 4th Edition. This is because period 2 non-metals do not have low energy vacant d-orbital but period 3 non-metals can expand its octet and use the low energy vacant d-orbital to accept electrons from the others species. 200–208 Inorganic Chemistry. B and Si. Ramsden pg.

Reasons such as the different electronegativities of C and P. the different charge densities.Periodic Properties of Elements Past Paper Question Unit 3 Page 2 92 2B 5 a ii 92 2B 5 a ii 5a ii Explain why there is no apparent diagonal relationship in the properties of carbon and phosphorus. 1 mark C This question required application of knowledge to an unfamiliar situation.05) not similar Properties differ because of d-electron availability in P bonding. 1 . The question is difficult. Charge density Polarizing power Any one. and was poorly answered by most candidates. P (2.5). reasonable answer might cite: C electronegativity (2. or the availability of d orbitals for bonding in P were considered reasonable.

Hydride 1.N. 3rd Edition.M. For sure. the energetic stability of a compound is depending on the strength of the intramolecular forces.1 Inorganic Chemistry. Bonding s-block hydrides are ionic in nature. In general. period 2 hydrides are more stable than period 3 hydrides since the period 2 elements have smaller atomic sizes and form stronger bond with hydrogen. T. 339. 352–353 Page 1 Unit 4 Assignment Reading Syllabus Properties of hydrides Notes A. p-block hydrides are covalent in nature consisting of simple molecule. consisting of metal ion and hydride ions H-. . Ramsden pg. E. 4th Edition. Leung pg. 69–80 A-Level Chemistry.Perioidic Properties of Elements Unit 4 Topic Perioidic Properties of Elements Reference Reading 8.2.

δ+ H δ+ H N δ− H δ+ δ− δ− O H δ+ H δ+ δ− N H + H N H + O H H H H δ+ H δ+ δ+ H P H H Finally NH3 will hydrolyze in water but PH3 is insoluble and has no reaction with water at all. availability of low energy vacant d-orbital (SiH4 vs CH4) C is a period 2 element which has no low energy vacant 2d-orbital to accept electrons from water. Si is capable to use its low energy vacant 3d-orbital to accept electrons from water to form a stable intermediate. the lone pair of water would be attracted by the positive charge on the Si atom.) Furthermore. (It hydrolyses faster in alkali as OH. Consequently. Both HF and HCl are acidic in water but the acidity of HF is much lower. δ− δ− O H δ+ - H H δ+ - O H + H2 The properties of p-block hydrides are rather complicate. polarity of the molecule ii. Although both of them are pyramidal in shape. N is more electronegative than H but P has similar electronegativity as H. NH3 is alkaline but PH3 is neutral in water. H2S is acidic in water. the electronegativity of C is similar to that of H while Si is less electronegativity than H. NH3 is a much stronger Lewis base than PH3.g. Unit 4 Page 2 Hydrolysis s-block hydrides are highly reactive toward water and the hydride ion hydrolyses readily in water to form an alkaline solution and hydrogen. δ− H δ−H δ+Si H δ− H δ− δ− O H δ+ H δ+ . The reactivity of p-block hydrides towards water is depending on several factors : i. e. SiH4 hydrolyses very slowly in water.ion is a stronger nucleophile than water. CH4 is stable in water but SiH4 hydrolyses in water to give hydrogen. Therefore. Bond strength and difference in electronegativity (bond polarity) i.Perioidic Properties of Elements 2. polarity of the molecule (NH3 vs PH3) Comparatively. availability of low energy vacant d-orbital iii. PH3 is a less polar molecule. ii. Therefore. Even the hydrides of the elements in the same group do not show similar properties.

1 mark ½ mark HCl(g) does not undergo such reaction to release electron. H2O H2S HCl HF Difference in E. it is mainly depending on the relative strength of H–X and O–H bonds but it is also depending on the hydration energy of the ions formed.3 1. whereas CH4 is not. Glossary hydride Past Paper Question 91 1A 3 a 93 2B 4 b iii 95 1A 2 d i ii iii 99 2A 3 c ii iii 91 2B 5 b 93 2B 6 d 91 1A 3 a 3a Explain why NaH(s) is more reducing than HCl(g) whilst HCl(g) is more acidic than NaH(s). 1. Si has 3d (or accept C has no d orbitals) 1 mark ∴ Si can form activated complex (or Si accept lone pair/nucleophile) 1 mark Any one of the 3 reasons acceptable.g. X–H bond strengths 1 mark activation energy higher for breaking C-H 1 mark Reason C: C no 2d orbital. releasing electrons in an overall redox reaction. The acidity of HF is exceptionally low comparing with other hydrogen halide due to 2 factors : i.→ SiO32. Bond strength and difference in electronegativity (bond polarity) A low bond strength and high bond polarity favor the abstraction of proton from the molecule by water. sometimes. 1 mark ½ mark NaH(s) is not acidic because it is not a proton donor. the formation of hydrogen bond between HF(l) and H+(aq).+ H2O–H+ H–X + H–O–H d H2X+ + OH- NH3(aq) + H2O(l) d NH2-(aq) + H3O+(aq) NH3(aq) + H2O(l) d NH4+(aq) + OH-(aq) Indeed.+ 2H2O + H2) or SiH4 + 2H2O → SiO2 + 4H2 (SiH4 + H2O →Si(OH)4 + H2 (need not be balanced. If 2 facts from different reasons are mixed. then award only 1 mark Equation 1 mark SiH4 + (n+2)H2O → SiO2⋅nH2O + 4H2 (SiH4 + 2OH. ii. which does not favour the dissociation of the bond.5 0. e.only on Si 1 mark Reason B: state any one of the X–O.5 2. Answer must have the fact (1 mark) and then deduction (1 mark).→ ½H2 + e-. HCl(g) is acidic because it is a proton donor in the presence of a base. H.0 Bond energy (kJmol-1) + 463 + 364 + 432 + 568 Hydrolysis in water H2O(l) + H2O(l) d H3O+(aq) + OH-(aq) H2S(aq) + 2H2O(l) d 2H3O+(aq) + S2-(aq) HCl(aq) + H2O(l) → H3O+(aq) + Cl-(aq) HF(l) + H2O(l) d H3O+(aq) + F-(aq) HF(l) + H+(aq) d H2F+(aq) However. As an acid As a base H–X + H–O–H d X. strong H–F bond.e. it is difficult to predict whether a molecule will behave as a base or an acid. NaH(s) is an ionic compound and its reducing properties is due to the hydride anion which can undergo the reaction. this lowers the concentration of free H+(aq) in the solution. Miss out H2 -½) 3 3 . thus the acidity. i.N. 91 2B 5 b 5b Explain why SiH4 is hydrolysed by alkali. This makes the solution acidic. Reason A: electronegativity difference 1 mark ∴ nucleophilic attack by OH. and give an equation for the hydrolysis. Accept SiO32-. HCl(g) + H2O(l) → H3O+(aq) + Cl-(aq).Perioidic Properties of Elements Unit 4 Page 3 iii.

If 3 there is a reaction. Si=Si and Si≡Si cannot be formed easily.+ H2O → H2 + OH.pair in water will not attack CH4. It is an ionic compound. (Max. ½ mark OR ½ mark There is no empty / vacant low energy d-orbital in C ∴ lone e. It is covalent molecule where the intermolecular force is dipole-dipole attraction. because of its large size. 1½ mark. 3 points must not be in the same aspect) iii Explain the difference in reactivity with water between SiH4 and H2S. Carbon atom because of its small size (less shielding effect) forms stable covalent bond with other carbon atoms ∴ tends to catenate. H O H H Thermodynamic aspect C–H bond is strong when compared with Si–H bond ∴substitution of H in CH4 is energetically unfavourable.gas. there is low energy empty d-orbital. ∴ it can accept lone electron pair from water ½ mark H H δ+ Si Hδ− H H H Si OH + H2 etc. Compare the reaction between NaH and water with that between HCl and water. thus formation of C=C and C≡C are possible. 1½ Kinetic aspect ½ mark In CH4.solid.(result in alkaline solution) HCl: HCl + H2O → H3O+ + Cl. Si–H are weak compare with Si–O. C–H and C–O is small. For Si. In H2S. while C–C and C–H bond is not. Explain why they are different. a crystalline solid with the structure similar to NaCl.+ H3O+ OR (½ mark for correct product. there is almost no polarity in the C–H bonds ∴ CH4 is not affected by polar molecules of water In SiH4. 1 mark 93 2B 6 d 6d Give the states of NaH and HCl at room temperature and atmospheric pressure. while for Si. 1 mark Energy difference between C–C. Si–Si. ½ mark ½ mark ½ mark 1½ ½ mark ½ mark ½ mark . ½ mark fro balanced reaction) ½ mark HCl : HCl + H2O → H3O+ + Clii Explain the difference in reactivity with water between CH4 and SiH4. ∴ Si–Si and Si–H bond is easily oxidized to Si–O. NaH . 1½ mark HCl . whereas SiH4 gives an alkaline solution since the polarity is Siδ+–Hδ-. ∴ nucleophilic attack of H2O on H2S gives H3O+ and HS-.(result in acidic solution) 1 mark Page 4 3 4 95 1A 2 d i ii iii 2d i State whether the following hydrides would react with water under room temperature and atmospheric pressure. give the balanced equation. ½ mark fro balanced reaction) H2S + 2H2O d 2H3O+ + S2H2S : H2S + H2O d HS. the bond polarity is Siδ+–Hδ-. ½ mark OR ½ mark In Si. CH4 SiH4 H2S HCl CH4 : no reaction ½ mark SiH4 : SiH4 + 4H2O → Si(OH)4 + 4H2 (or SiO2·nH2O or SiO2) (½ mark for correct product. 1 mark C can also form π bond by sideway overlapping of p orbitals. the polarity is Hδ+–Sδ-. 1½ mark Reaction with water NaH: H.Perioidic Properties of Elements Unit 4 93 2B 4 b iii 4b Account for each of the following facts: iii Carbon forms stable hydrides with different structures whereas silicon forms only unstable hydrides.

1 2. with explanation.8 2. (9 marks) Page 5 . compare the reactions of these hydrides with water. PH3 and H2S ii With reference to the electronegativity values given below.5 iii State. Element H O Si P S Electronegativity (Pauling's scale) 2.1 3.Perioidic Properties of Elements Unit 4 99 2A 3 c ii iii 3c Consider the hydrides of three Period 3 elements : SiH4.5 1. whether SiH4 or H2S has a higher boiling point.

. However. T. Chlorides of phosphorus are very special comparing with the others.M. 3rd Edition ELBS pg. 3rd Edition.2. 4th Edition. PCl3(l) is a liquid possessing molecular structure where PCl5(s) is a solid possessing ionic structure. 50-68 A-Level Chemistry. + Cl P Cl Cl Cl P PCl3(l) Cl Cl Cl Cl - Cl Cl Cl Cl P Cl Cl Cl PCl5(s) P Cl Cl Cl PCl5(g) . s-block chlorides are ionic in nature and p-block chlorides are covalent in nature. 179–180 Assignment Advanced Practical Chemistry. 144–147 Reading Syllabus Notes B. 403–405 Chemistry in Context. Thomas Nelson and Sons Ltd.N.Perioidic Properties of Elements Unit 5 Page 1 Topic Perioidic Properties of Elements Unit 5 Reference Reading 8. Chloride 1. 5th Edition. Bonding The bonding of chlorides is similar to that of hydrides. E. Ramsden pg. pg. in gaseous state. 25–29. Leung pg. 202–203 Inorganic Chemistry.2 Chemistry in Context. John Murray (Publisher) Ltd. PCl5(g) also possesses a molecular structure.

sublimation. Whereas AlCl3 and PCl3 are hygroscopic and readily hydrolysed by water. and indicate the types of bonding in. etc. Physical properties e. Cl AlCl3 colourless covalent solid. P Cl Cl Al Cl Cl Al Cl Cl . Marking Scheme Overall presentation .Perioidic Properties of Elements 2. discuss their physical and chemical properties in terms of structure and bonding. ½ for structure and ½ for bonding) 4 marks Physical and chemical properties (1 mark each. [Be(H2O)4]2+(aq) + H2O(l) → [Be(H2O)3(OH)]+(aq) + H3O+(aq) BCl3(l) + 3H2O(l) → H3BO3(aq) + 3HCl(aq) AlCl3(s) + 6H2O(l) → [Al(H2O)6]3+(aq) + 3Cl-(aq) [Al(H2O)6]3+(aq) + H2O(l) d [Al(H2O)5OH]2+(aq) + H3O+(aq) [Al(H2O)5OH]2+(aq) + H2O(l) d [Al(H2O)4(OH)2]+(aq) + H3O+(aq) [Al(H2O)4(OH)2]+(aq) + H2O+(l) d [Al(H2O)3(OH)3](s) + H3O+(aq) N. the central atom will always carry the δ+ instead of δ-. undergoes sublimation. PCl3 and K2NiCl4. can be oxidized to POCl3. NiCl42-. Cl Cl 2- Ni Cl Cl . Cl PCl3 covalent colourless liquid. ½ for physical and ½ for chemical) 4 marks 10 . The main difference is that Cl is much more electronegative than H. For simplicity. owing to the high charge density of the metal ion. ease of oxidation.g. dimeric in structure.g. covalent Cl. etc. ionic chloride AlCl3. Cl-. BCl3 and AlCl3 hydrolyse readily in water.highlight on their differences (in table form -1) 2 marks Structure and bonding (1 mark each. the highly covalent BeCl2. LiCl. K2NiCl4 coloured ionic solid with complex anion. LiCl and K2NiCl4 do not react with water. solubility in water/organic solvent. Therefore. melting point/boiling point.B. colour of complex. Chemical properties e. LiCl and K2NiCl4 are ionic solids whereas AlCl3 and PCl3 are covalent molecules. Also. Glossary ligand Past Paper Question 90 2B 5 a 91 1A 3 b i 92 1A 3 e 93 1A 2 a iv 94 1C 2 96 1A 2 e i 91 2B 4 b 90 2B 5 a 5a Give the structures of. About the bonding: LiCl. Unit 5 Page 2 Hydrolysis s-block chlorides are basically ionic and only dissolve in water without going through hydrolysis. However. AlCl3. dative covalent bond. The reactivity of p-block chlorides towards water is similar to that of hydrides. hydrolysis. Cl . sometimes the ligand water will be omitted is the formula. LiCl colourless ionic solid with Li+.as ligand covalent bond between P and Cl PCl3. the formula [Al(H2O)3(OH)3](s) would be written as Al(OH)3(s) despite of the fact that Al3+ usually co-ordinates with 6 ligands. complex ion in equilibrium with water.

Draw the electronic structure of a molecule of each chloride and describe the molecular shape. [Fe(H2O)6]2+ + H2O → [Fe(H2O)5OH]+ + H3O+ (pKa = 9. SCl4 Cl S Cl Cl S Cl Cl Cl For S2Cl2 + H2O → S + SO2 (or SO3) don’t need HCl For SCl4. reasonable answer to give SO2 For SCl2 + H2O → HOCl + HSCl (or accept S + SO2 + HCl) 92 1A 3 e 3e Both FeCl2 and FeCl3 undergo hydrolysis in water.6 but not -1 or 7 for Cl. accept disproportionation reaction for oxidation states 2. formula 3 × ½ = 1½ mark equation 3 × ½ = 1½ mark (need not be balanced. must write + H2O) electronic structure 3 × ½ = 1½ mark (must show lone pair(s) on N. 3 .Perioidic Properties of Elements Unit 5 91 1A 3 b i 3b Write equation(s) to describe the reaction of i ZnCl2(s) with water. if either one is correct. Both aqueous solutions contain hydrated cations and Cl-(aq). O and S.2) 1 mark 1 mark Smaller size and greater charge of Fe3+ ion results in more acidic solution than that of Fe2+ ion.g. zigzag shape or SCl2. Write an equation for the reaction (if any) of each chloride with water. O and S) shape 3 × ½ = 1½ mark (draw and/or name. ZnCl(s) + 4H2O(l) → [Zn(OH2)4]2+(aq) + 2Cl-(aq) [Zn(OH2)4]2+(aq) + H2O(l) → [Zn(OH2)3(OH)]+(aq) + H3O+ or ZnCl2 + H2O → Zn(OH)Cl + HCl Page 3 1 1 mark 91 2B 4 b 4b Give the formula of one chloride for each of the elements N.5) 1 mark [Fe(H2O)6]3+ + H2O → [Fe(H2O)5OH]2+ + H3O+ (pKa = 2. Write equations for these reactions and explain why FeCl3 gives the more acidic solution. then ½ mark) Example: NCl3 NCl3(l) + 3H2O(l) → NH3(aq) + HOCl(aq) Cl 6 N Cl Cl pyramidal Example: Cl2O Cl2O(g) + H2O(l) → 2HOCl(aq) Cl O Cl V-shaped or 6ClO2 + 3H2O → 3HClO2 + 3HClO3 or Cl2O6 + H2O → HClO4 + HClO3 ClO3 is the same as Cl2O6. which is a solid ClO2+ClO4ClO2 + H2O → stable in dark sunlight 6ClO2(g) + 3H2O(l)  → HCl(aq) + 5HClO3(aq) Lewis and Waller give: ClO2(g) + 3H2O(l) → 2ClO-(aq) + 2H3O+(aq) 2ClO2(g) + 3H2O(l) → ClO2-(aq) + ClO3-(aq) + 2H3O+(aq) Cl2O6(l) + 3H2O(l) → ClO3-(aq) + ClO4-(aq) + 2H3O+(aq) Cl2O4(l) + 3H2O(l) → 2ClO4-(aq) + 2H3O+(aq) Cl2O7(l) + H2O(l) → 2HClO4(aq) For oxygen chlorides.4. For ClO2 accept eitherClO2 + H2O → HCl + HClO3 or ClO2 + H2O → stable (hydrate) ClO2 + H2O → HClO2 + HClO3 Example: S2Cl2(l) 2S2Cl2(l) + 2H2O(l) → 3S(s) + SO2(aq) + 4HCl(aq) Cl S S Cl any sensible description e.

P4O10(s). i [Fe(H2O)6]2+(aq) . Cu2+(aq). and hence the H develops larger partial +ve charge. ½ mark Fe3+ has a higher charge to radius ratio / charge density. S(s). Zn2+(aq) iv Which species fumes in moist air? AlCl3(s) + 3H2O(l) → Al(OH)3(s) + 3HCl(g) 1 mark AlCl3(s) 96 1A 2 e i 2e Which is the stronger acid in each of the following pairs of substances ? Briefly explain your choice. putting it in the box and giving the relevant equation(s).♣ ½ mark Page 4 2 2 . CO32-(aq). Al(s). S2O32-(aq).tends to stabilize the electron deficient Fe3+ more than Fe2+ / causes the eqm. AlCl3(s). AlO2-(aq). [Fe(H2O)6]3+(aq) [Fe(H2O)6]3+ ½ mark ½ mark The conjugate base [Fe(H2O)5OH]2+ is stabilized to a greater extent ½ mark because the anionic ligand OH. Na(s). ½ mark greater polarizing power. to lie towards the right / increase the ease of ionization of H ½ mark Or.Perioidic Properties of Elements Unit 5 93 1A 2 a iv 2a Answer the following questions by choosing in each case one of the species listed below.

4th Edition.Perioidic Properties of Elements Unit 6 Page 1 Topic Perioidic Properties of Elements Unit 6 Reference Reading 8. SO2(g). Leung pg. e.3 Chemistry in Context. T. 3rd Edition ELBS pg. 425–426 Assignment Advanced Practical Chemistry. Oxide 1. 204–208 Inorganic Chemistry. Ramsden pg.2. amphoteric and basic oxides Some oxides are acidic. 3rd Edition. 283–285 Reading Syllabus Notes C. 34–49 A-Level Chemistry. 180–184. 151–153 Chemistry in Context. Thomas Nelson and Sons Ltd.N. E. e. CO2(g).g.g. 27. When reacted with water. 29–31. CO2(aq) + H2O(l) d H2CO3(aq) SO2(aq) + H2O(l) d H2SO3(aq) H O H H O S H O H O O S O O H O S O . Formation of acidic.M. they form acids. pg. John Murray (Publisher) Ltd. 5th Edition..

e. Zn(OH)2(s) + 2H+(aq) → Zn2+(aq) + H2O(l) Zn(OH)2(s) + 2OH-(aq) → [Zn(OH)4]2-(aq) white colourless Pb(OH)2(s) + 2H+(aq) → Pb2+(aq) + H2O(l) Pb(OH)2(s) + 2OH-(aq) → [Pb(OH)4]2-(aq) white colourless Al(OH)3(s) + 3H+(aq) → Al3+(aq) + 3H2O(l) Al(OH)3(s) + OH-(aq) → [Al(OH)4]-(aq) white colourless Since Zn(OH)2(s). non-metal oxides are acidic and metal oxides are basic. If excess alkali is added. Al. Na2O(s) + H2O(l) → 2NaOH(aq) K2O(s) + H2O(l) → 2KOH(aq) O 2- H O 2 O H H In general. Amphoteric oxides There are a few oxides which reacts with both acid and alkali. This serves as a very good test for the three ions. e. 2Al(s) + 2OH-(aq) + 6H2O(l) → 2[Al(OH)4]-(aq) + 3H2(g) Zn(s) + 2OH-(aq) + 2H2O(l) → [Zn(OH)4]2-(aq) + H2(g) Pb(s) + 2OH-(aq) + 2H2O(l) → [Pb(OH)4]2-(aq) + H2(g) .g. e. If a little alkali (e. aluminium and lead are also amphoteric. Na2O(s). Zn2+(aq) + 2OH-(aq) → Zn(OH)2(s) colourless white Zn(OH)2(s) + 2OH-(aq) → [Zn(OH)4]2-(aq) white excess colourless For a similar result.g. K2O(s). ZnO(s) + 2H+(aq) → Zn2+(aq) + H2O(l) ZnO(s) + 2OH-(aq) + H2O(l) → [Zn(OH)4]2-(aq) white zincate ion (colourless) PbO(s) + 2H+(aq) → Pb2+(aq) + H2O(l) PbO(s) + 2OH-(aq) + H2O(l) → [Pb(OH)4]2-(aq) white plumbite ion (colourless) Al2O3(s) + 6H+(aq) → 2Al3+(aq) + 3H2O(l) Al2O3(s) + 2OH-(aq) + 3H2O(l) → 2[Al(OH)4]-(aq) (to be more accurate [Al(H2O)2(OH)4]-(aq)] white aluminate ion (colourless) The hydroxides of zinc. The hydroxides will be precipitated first.g.Perioidic Properties of Elements Unit 6 Page 2 Some oxides are basic. Pb(OH)2(s) and Al(OH)3(s) are insoluble in water. the hydroxide precipitate will redissolve to form a clear solution. PbO(s) and Al2O3(s. e. NaOH(aq)) is added into the Zn2+(aq). A.g. Pb and Zn metals also reacts directly with strong alkali besides strong acid. ZnO(s). When reacted with water. they forms alkalis. Pb2+(aq) or Al3+(aq) solution.g.

Cu2+(aq). Zn2+(aq) i Which species can react with excess dilute NaOH with effervescence. Greater stability of P(V) : P4O10 92 2B 6 Bc ii 6Bc ii Which is more reactive to oxidation.6 kJmol-1) 2 1 mark 1 mark 2 1 mark + 1 mark 2 1 mark 1 mark 93 1A 2 a i 2a Answer the following questions by choosing in each case one of the species listed below. Soluble in excess / Colour solution Cu2+(aq) Blue ppt. PbO(s) + 2HCl(aq) → PbCl2(s) + H2O(l) H2O(l) + PbO(s) + NaOH(aq) → NaPb(OH)3(aq) 92 2B 6 Ac ii 6Ac ii Which is more reactive to oxidation. (ii) sodium hydroxide solution Pb2+(aq) Cu2+(aq) (3 marks for 8 observations. PH3. AlCl3(s). putting it in the box and giving the relevant equation(s). until in excess.9 kJmol-1) but H2S only weakly so (∆Hf -20. CO32-(aq). P4O10(s).Perioidic Properties of Elements Unit 6 Glossary acidic oxides amphoteric oxides Past Paper Question 92 2B 5 b iii 93 1A 2 a i 95 1A 2 b ii 95 1B 4 g ii 92 2B 6 Ac ii Page 3 basic oxides 92 2B 6 Bc ii 92 2B 5 b iii 5b iii Write equations showing the amphoteric nature of lead(II) oxide. NH3 or PH3? Explain your answer. CaO + SiO2 → CaSiO3 This is an acid-base reaction. to aqueous solutions containing Pb2+ and Cu2+ ions respectively. Al(s). forming a solution which gives a white precipitate on addition of dilute HCl? 2Al(s) + 2OH-(aq) + 2H2O(l) → 2AlO2-(aq) + 3H2(g) Al(s) AlO2-(aq) + H+(aq) + H2O(l) → Al(OH)3(s) OR 2OH-(aq) + 2Al(s) + 6H2O(l) → 2[Al(OH)4]-(aq) + 3H2(g) 2[Al(OH)4]-(aq) + 2H+(aq) → Al(OH)3(s) + 2H2O(l) 3 marks 95 1A 2 b ii 2b ii Is the reaction below a "redox reaction" or an "acid-base reaction" ? Explain. AlO2-(aq). 3 2 ½ mark 1 mark ½ mark 95 1B 4 g ii 4g Give the observations when (ii) sodium hydroxide solution are added dropwise. such as more higher oxidation states available for S or enthalpy of formation of H2O is strongly exothermic (∆Hf -285. These experiments are carried out at room temperature. S2O32-(aq). CaO is a basic oxide and SiO2 is an acidic oxide The reaction does not involve a change in oxidation state. H2O or H2S? Explain your answer. S(s). H2S any reasonable answer. deduct ½ mark for each incorrect observation) (ii) sodium hydroxide solution 2+ Pb (aq) White ppt. Insoluble in excess 3 . Na(s).

II. Variation in properties of the s-block elements and their compounds A. C. C. Reaction with water Thermal stability of carbonates and hydroxides 1. Reaction with hydrogen 2. Thermal stability of carbonates 2. Reaction with oxygen 3. D. B. C. B. F. B. Metallic character and low electronegativity Ionic bond formation and fixed oxidation state Flame test Reaction of the elements 1. D.s-Block Elements I. III. Manufacture of glass Baking powder Making of soap Antacid Slaked lime Fireworks . Reaction with chlorine 4. Solubility of some ionic crystals a) Sulphate salt of group II metal b) Hydroxide of group II metal c) Solubility of salts of other group II metals Abnormal behaviour of lithium Uses of the compounds of the s-block elements A. Thermal stability of hydroxides Solubility of sulphate and hydroxide 1. Characteristic properties of the s-block elements A. E. Solvation energy a) Definition of solvation and solution processes b) Factors affecting the value of hydration energy c) Effect of lattice energy and hydration energy on solubility of ionic crystal 2.

HCl(aq) is also used to clean the nichrome or platinum wire to be used in the flame test. Furthermore. The colour of the flame can be used to identify the metal or metal ion that the sample contains. Since the outermost shell has been effectively shielded from the nuclear attraction. Flame test All s-block metal or compound containing s-block elements burning with characteristic colour due to the excitation of the electrons. chloride salt is lowest melting and boiling among different salts. Therefore. Leung pg. the difference between 1st and 2nd I.E. Similarly. the difference between the 1st I. 4th Edition. for group 2 elements. pg. is very large. and 3rd I. it order to obtain the best result. therefore group 1 elements only form ions with +1 oxidation state.E.E. a transition metal. This is done by dipping the wire in the acid and heating the wire with bunsen flame repeatedly until no colored flame is observed. Metallic character and low electronegativity All s-block elements are soft metals.0–9. is moderate. group II elements only form ions with +2 oxidation state. Fe is capable to form ions with oxidation state +2 and +3. 3rd Edition.E is very small but the difference between 2nd I.M. and 2nd I. 5th Edition. Inorganic Chemistry. Flame colour of some metals / metal salts Glossary Group I metals Lithium (Li) Sodium (Na) Potassium (K) Rubidium (Rb) Caesium (Cs) Deep red Yellow Lilac (a purple colour) Bluish Red Blue Other metals Copper (Cu) Bluish green nichrome wire flame test Group II metals Beryllium (Be) Magnesium (Mg) Calcium (Ca) Strontium (Sr) Barium (Ba) no special colour no special colour Brick red Blood red / Crimson red Apple green . conc. they only form ionic compound.e. 211–213.E. it would be better to heat the sample with the bunsen flame in the presence of conc. HCl(aq) so the sample would vaporize more readily. Ionic bond formation and fixed oxidation state s-block elements lose their outermost electron readily to form positive ions.N. 84–86 A-Level Chemistry.) B. Characteristic properties of the s-block elements A. 360–361 Assignment Chemistry in Context.E. 3rd Edition ELBS pg.1 Chemistry in Context. E. In general. C.s-Block Elements Unit 1 Page 1 Topic s-Block Elements Unit 1 Reference Reading 9. is very larger. the metallic bond would not be very strong and the electronegativity would also be very low (i. T. is small but the difference between 2nd I. 283 Reading Syllabus Notes I. Thomas Nelson and Sons Ltd.E.E. and 3rd I. Ramsden pg. the difference between 1st and 2nd I. For the group 1 elements. Generally speaking. very high electropositivity. Comparing with Fe.

s-Block Elements

Past Paper
Question

Unit 1

Page 2

94 1A 2 e
96 2B 4 b ii
99 1B 7 c i ii

94 1A 2 e
2e
Why is caesium, rather than sodium, used in a photo-electric cell?
(A photo-electric cell is a device which produces electrons when irradiated by photons.)
Cs, having a lower I.E., can be ionized easily by absorption of visible light ∴ it is more suitable to be used in
making photo-electric cell.
1 mark
96 2B 4 b ii
4b
For each of the following pairs of compounds, suggest a test to distinguish one compound from the other :
ii KCl(s) and MgCl2(s).
Carry out a flame test,
1 mark
½ mark
KCl(s) gives a lilac flame
½ mark
while MgCl2(s) gives no characteristic flame colour
Or
1 mark
Add NaOH(aq) / Na2CO3(aq) / Na2HPO4(aq) to aqueous solution of the substance.
½ mark
MgCl2 gives white precipitate
½ mark
while KCl does not.
(Accept any CORRECT test for the two compounds)
99 1B 7 c i ii
7c i
Describe the procedure for a flame test.
ii Describe how to distinguish between a sodium salt and a potassium salt of the same anion by flame test.

1

2

s-Block Elements

Unit 2

Topic

s-Block Elements

Reference
Reading

9.2.0–9.2.2
Chemistry in Context, 3rd Edition ELBS pg. 242–243
Inorganic Chemistry, 4th Edition, T.M. Leung pg. 94–98, 103–105
A-Level Chemistry, 3rd Edition, E.N. Ramsden pg. 363–367

Page 1

Unit 2

Assignment Chemistry in Context, 5th Edition, Thomas Nelson and Sons Ltd. pg. 213–214
Reading
Syllabus

Reactivities of s-block elements
Thermal stability of carbonates and hydroxide of s-block elements.

Notes

II. Variation in properties of the s-block elements and their compounds
A. Reaction of the elements
1.

Reaction with hydrogen

s-block elements are very electropositive, even more electropositive than hydrogen. When heated with hydrogen,
ionic hydride will be formed.
e.g. 2Na(s) + H2(g) → 2NaH(s)
2.

Reaction with oxygen

Ordinary s-block elements are very reactive towards oxygen. They almost tarnish immediately to form metal oxide
when exposed to air.
e.g. 4Na(s) + O2(g) → 2Na2O(s) (white powder)
2Ca(s) + O2(g) → CaO(s)
N.B.

Aluminium seems to be less reactive than the other metals in air because it is protective by a thin but
dense oxide layer. Once the oxide layer have been removed by dipping in mercury(II) chloride, aluminium
also reacts vigorously to form white powder of Al2O3(s) with air.

Besides the normal oxides, sodium forms peroxide, potassium and other more reactive group I metals form
superoxides when burn in air.
e.g. 2Na(s) + O2(g) → Na2O2(s ) (white when cold but yellow when hot)
K(s) + O2(g) → KO2(s) (yellow powder)
The hydrolysis of peroxide and superoxide is also different from that of normal oxide
Normal oxide
M2O(s) + H2O(l) → 2MOH(aq)
Peroxide
M2O2(s) + 2H2O(l) → 2MOH(aq) + H2O2(aq)
or 2M2O2(s) + 2H2O(l) → 4MOH(aq) + O2(g)
Superoxide
2MO2(s) + 2H2O(l) → 2MOH(aq) + H2O2(aq) + O2(g) or 4MO2(s) + 2H2O(l) → 4MOH(aq) + 3O2(g)
3.

Reaction with chlorine

Electropositive s-block elements also react with electronegative chlorine to form ionic chloride.
Group I
Group II

2M(s) + Cl2(g) → 2MCl(s)
M(s) + Cl2(g) → MCl2(s)

s-Block Elements

Unit 2
4.

Page 2

Reaction with water

s-block elements, especially group I elements, reacts readily with water with a reactivity increasing down the
group. They react with water to form an solution of metal hydroxide and hydrogen.
2M(s) + H2O(l) → 2MOH(aq)
B. Thermal stability of carbonates and hydroxides
1.

Thermal stability of carbonates

Generally speaking, carbonate is unstable to heat. Upon heating, most carbonates decompose into oxides and
carbon dioxide.
→ M2O(s) + CO2(g)
M2CO3(s) heat
heat
MCO3(s)  → MO(s) + CO2(g)

-

O

O C O

C O
-

+

O

2-

O

Depending on the polarizing power (i.e. charge density) of the cation, different carbonates have different stability
to heat.
A carbonate containing a more polarizing cation is less stable to heat. This is because the electron cloud of the
carbonate ion will be more distorted. Furthermore, upon decomposition, it will form a more stable oxide with
stronger ionic bond within the lattice. The evolution of CO2 gas will also increase the disorderness of the system
which is favourable in nature.
The temperature of a normal bunsen flame is about 1300 K. A subtance having a decomposition temperature higher
than this temperature is usually regarded as stable to heat.
Comparatively, group I ions are much bigger than group II ions, except Li2CO3(s), group I carbonate is regarded as
stable to heat.
→ Li2O(s) + CO2(g)
Li2CO3(s) heat

Among the group II carbonates, the decomposition temperature increases down the group as the polarizing power
of the cation decreases.
Group II carbonates
BeCO3(s)
MgCO3(s)
CaCO3(s)
SrCO3(s)
BaCO3(s)

Decomposition temperature / ºC
~ 100
540
900
1290
1360

The surface of the sodium becomes dull (less shiny. O 2M+ + - O C O - 2M+O2. Those of Group 2 and lithium are decomposed by heat to form oxides. Page 3 Thermal stability of hydroxides The decomposition of hydroxides is somehow similar to the decomposition of carbonates. → M2O(s) + H2O(l) 2MOH(s) heat M(OH)2(s) heat → MO(s) + H2O(l) - O H O H - H O H Glossa ry oxide peroxide Past Paper Question 90 1A 3 e ii 91 2B 5 d 92 1A 3 a 93 2B 4 b i 95 2B 5 a v 96 2B 4 b i 99 2A 1 a iii superoxide + O 2- thermal stability 90 1A 3 f 95 2B 5 b i ii 90 1A 3 e ii 3e Give observation. freshly-cut piece of sodium is exposed to air for a few minutes. 91 2B 5 d 5d Account for the observation that lithium carbonate decomposes at 700ºC whereas sodium carbonate is thermally stable at this temperature. the large hydroxide ion is converted to small oxide ion with liberation of water. 1 mark 1 mark When withdrawn from the solution.+ O C O Change of lattice energy from Li2CO3 to Li2O is greater than Na2CO3 to Na2O. 2Na(s) + 2H2O(l) → 2Na+(aq) + 2OH-(aq) + H2(g) 2H2(g) + O2(g) → 2H2O(l) 4 ½ mark 1 mark ½ mark 1 mark 1 mark 90 1A 3 f 3f Account for the observation that when a piece of aluminium foil is dipped into a solution of mercury(II) chloride and then withdrawn. The thermal stability of group II hydroxide is parallel to group II carbonates where the thermal stability increases down the group. The protective layer of Al2O3 is destroyed when the piece of Al is dipped in a solution of HgCl2. with same charge or higher charge density 1 mark The charge cloud of the oxy-anion is more distorted.s-Block Elements Unit 2 2. it becomes very hot and disintegrates into a white powder. and write balanced equations for the following: ii a small. more white) 4Na(s) + O2(g) → 4Na2O(s) The piece of sodium melts and burns with a yellow flame.and CO2. a similar piece of sodium is placed on filter paper on the surface of water in a glass trough. Li+ is more polarizing than Na+ 1 mark because it is smaller. causing the anion to break up to give O2. 1 mark 2 mark 3 3 . the fresh surface of Al reacts highly exothermically 1 mark with O2(air) to form white Al2O3 powder. Upon decomposition. Hydroxides of group 1 (except Li) are stable to heat.

Mg tend to decompose to form the more stable oxides.216 0.203 0. add MgSO4(aq) to the solutions ½ + ½ mark Na2CO3(aq) gives a white ppt. 1 mark 2M(s) + Cl2(g) → 2MCl(s) 2M(s) + 2H2O(l) → 2M+(aq) + 2OH-(aq) + H2(g) 1 mark Page 4 2 93 2B 4 b i 4b Account for each of the following facts: i The decomposition temperature of MgCO3 is lower than that of CaCO3.095 495 -2. cations of the lighter elements distort the anion electron clouds to a larger extend.060 520 -3. 1 mark For Li.is polarized to a greater 2 marks extent in Mg(OH)2. 3 charge When compared with Ca2+. As the group is descended. 2 marks 95 2B 5 b i ii 5b Explain the following facts : i The thermal stability of sodium hydroxide is higher than that of magnesium hydroxide. O2-. explain why the reactivity of the alkali metals with water increases as the group is descended.92 64 Rb 0. 3 marks OR The charge / radius ratio of cation increases as the group is ascended. the relatively high melting point reduces the reactivity Q activation energy for the reaction is higher.95 29 v With reference to the standard electrode potentials and the melting points of the elements. Cations with high charge/radius ratio tend to form stable lattice with small anions.s-Block Elements Unit 2 92 1A 3 a 3a Give balanced equations for two different reactions that are common to the three elements: lithium.. Use the symbol M for the elements.and H2.04 180 Na 0.148 403 -2.235 0.157 0. 1 mark 2∴ CO3 in MgCO3 is polarized to a greater extent than in CaCO3. Mg2+ has higher radius ratio and is more polarizing. OR Because of its high charge / radius ratio. sodium and potassium. ∴ Mg(OH)2 is ready to decompose to give MgO. carbonates of Be. 1 mark 1 mark Hence MgCO3 undergoes thermal decomposition to form oxide (small anion) more readily than CaCO3. 2 marks ii The thermal stability of the carbonates of the alkaline earth metals increases as the group is descended.123 0. therefore. 3 marks Therefore. suggest a test to distinguish one compound from the other : i Na2CO3(s) and NaHCO3(s) NaHCO3 decomposes on heating to give CO2 /a gas ½ + ½ mark ½ + ½ mark which can turn lime water milky but Na2CO3 does not decompose. Mg2+ is more polarizing than Na+ due to its smaller size and greater charge. Anions with highly distorted electron clouds are more readily decomposed than those with little distortion. the reactivity increase. Therefore.133 418 -2. 95 2B 5 a v 5a The table below lists some properties of the alkali metals. Standard electrode Melting point / ºC Element Atomic Ionic radius / nm First ionization potential / V radius / nm energy / kJmol-1 Li 0. 1 mark OR M(s) + H2O(l) → MOH(aq) + ½H(g) The electrode potential of group I metal increases down the group with the exception of Li.169 374 -2. The OH. 99 2A 1 a iii 1a iii What would be observed when a small piece of rubidium is added to 2-methylpropan-2-ol ? Write the balanced 4 2 3 2 . Or ½ + ½ mark dissolve the solid in water.93 39 Cs 0. but NaHCO3(aq) does not. Hence the thermal stability increases as the group is descended. the polarizing power of the cation decreases. All group I elements react with cold water to give OH. Mg2+ forms more stable lattice with small anions e.71 98 K 0.g. 96 2B 4 b i 4b For each of the following pairs of compounds.

Unit 2 Page 5 .s-Block Elements equation for the reaction.

243–244 Inorganic Chemistry.s-Block elements Unit 3 Topic s-Block Elements Reference Reading 9. an dissolution process is energetically feasible if ∆H of solution is negative. 215. the enthalpy change of a process is independent of the pathway of the process actually taken.T∆S. Solvation energy a) Definition of solvation and solution processes Solvation process – Solution process – The process in which the particle of the solute in gaseous state is dissolved in a solvent to form a solution. 127–128. then the enthalpy change is called hydration energy. 284 Reading Syllabus Solvation process Solubility of ionic crystal Notes C. Leung pg. The process in which a solute in any physical state is dissolved in a solvent to form a solution. . T. Therefore. In the determination of ∆H of solution of an ionic compound. The solute would be soluble if the ∆H of solution is negative. According to Hess's law. 3rd Edition. ∆S is positive. Ramsden pg. 183–184.2. 365–366 Page 1 Unit 3 Assignment Chemistry in Context. Solubility of sulphate and hydroxide The feasibility of a change is depending on the relative stability of the reactants and the products. the process can be imagined as vaporization of the substance followed by solvation of the gaseous ion to form the solution. zero or slightly positive. If the solvent is water.e. Dissolution is a process accompanied with an increase in disorderness i. E. 1. whether a substance would be soluble is depending on the stability of the solvent and solute comparing with the stability of the solution. The change in stability of a system is measured by standard change in Gibb's free energy ∆G which is defined as ∆G = ∆H . 142–143.3.N. 105–112 A-Level Chemistry. Similarly. 5th Edition. Solvation energy (Hydration energy) – Enthalpy change when 1 mole of formula units of gaseous particles are solvated to form a infinitely diluted solution. Thomas Nelson and Sons Ltd. The solute would be insoluble if ∆H is highly positive.0 Chemistry in Context. pg. Or if we disregard the change in disorderness in the dissolution process. ∆G ≈ ∆H.M. 4th Edition. 162–163. 3rd Edition ELBS pg.

By Hess’s Law. the crystal lattice must be broken up and the cations and anions have to be separated from each other.∆Holat i. ∆Hohyd or ∆Hosolv ii.s-Block elements Unit 3 Page 2 Considering the process of solution of NaCl(s). NaCl(s) → Na+(g) + Cl-(g) For an ionic solid to dissolve. the energy released will be high enough to overcome the attractions between the ions. This makes the crystal soluble. Heat is always liberated in the hydration process. the heat of solution ∆Hosol’n = -∆Holat + ∆Hohyd Whether the heat of solution ∆Hosol’n is exothermic or endothermic depending on the relative magnitudes of ∆Holat and ∆Hohyd. the energy required is numerically equal to ∆Holat. If the heat of hydration is high enough. NaCl(s) → Na+(aq) + Cl-(aq) ∆Hosol’n = +5 kJmol-1 The process can be divided into two steps : ∆Ho = . If the ions are separated to infinite distance apart. If ∆Hohyd is more negative than ∆Holat If ∆Hohyd is less negative than ∆Holat ⇒ the solute would be more soluble ⇒ the solute would be less insoluble . Na+(g) + Cl-(g) → Na+(aq) + Cl-(aq) This process is called either hydration or solvation and the energy involved is called hydration energy or solvation energy.

: radii of cation and anion On top of charge density. when it is solvated. the attraction forces developed between the solvent particles and the ion will be very large and the hydration energy with be very exothermic. If an ion has high charge density. r . the total hydration energy can be expressed as : 1 1 Hydration energy ∝ ( r + r ) + - r +. the packing will be more efficient and gives a higher lattice energy. e. This is not applicable to the case of AgCl which is not purely ionic. if the sizes of the ions in the crystal are different.: radii of cation and anion Effect of lattice energy and hydration energy on solubility of ionic crystal Solubility of a solute is depending on the interaction between the solute and solvent particle. r . Furthermore. A solute will only be soluble if the attraction between the solute and solvent particles is greater than the attractions between the solute-solute particles and solventsolvent particles.s-Block elements Unit 3 Page 3 b) Factors affecting the value of hydration energy The hydration energy is depending on the attraction between the gaseous ion and the solvent molecules. the magnitude of lattice energy is also depending on the packing efficiency of the ions in the crystal. If the cations and anions in the crystal lattice have similar size. the crystal will be soluble. if the sizes of the ions in the crystal are similar. .g. This assumes that the crystal is purely ionic. lattice energy is depending on the attraction between the cation and anion. the crystal will be insoluble. Since the cation and anion are solvated independently. therefore the lattice energy can be expressed as : 1 Lattice energy ∝ r + r + - c) r +. And. Sizes of the cations and anions Both of them are small Both of them are large They have different sizes Hydration energy 1 1 (∝ ( r + r )) + High Low High Lattice energy 1 (∝ r + r ) + High Low Low Solubility Low to moderate Low to moderate High to moderate In general.

In general. magnitudes of both hydration energy and lattice energy decrease as the size of the cation increases. OH.50 × 10-2 1 1 Hydration energy ∝ ( r + r ) + - Once again. magnitudes of both hydration energy and lattice energy decrease as the size of the cation increases. .53 × 10-3 3. The hydration energy is very large. ∆Hosol’n becomes less negative and the solubility decreases.43 × 10-7 1 1 Hydration energy ∝ ( r + r ) + - On descending the group. ∆Hosol’n becomes more negative and the solubility increases.37 × 10-3 1. on moving down the group.B. ∆Hosol’n = -∆Holat + ∆Hohyd As a result. N.ion is a polyatomic ion with a much larger size than group II ions. and rather constant on moving down the group since it is almost dominated by the small size of OH.66 × 10-3 7. on moving down the group. a substance with a solubility lower than 10-2 mol/100g of water is considered to be not very soluble.83 × 10-1 4.00 × 10-5 1. ∆Hosol’n = -∆Holat + ∆Hohyd As a result.ion.11 × 10-5 9. on moving down the group. SO42.s-Block elements Unit 3 2.ion is a small anion. Page 4 Solubility of some ionic crystals a) Sulphate salt of group II metal Compound MgSO4 CaSO4 SrSO4 BaSO4 Relative solubility Soluble Sparingly soluble Insoluble Insoluble 1 Lattice energy ∝ r + r + - Solubility mol/100g of water at 298 K 1. b) Hydroxide of group II metal Compound Mg(OH)2 Ca(OH)2 Sr(OH)2 Ba(OH)2 Relative solubility Insoluble Sparingly soluble Slightly soluble Slightly soluble 1 Lattice energy ∝ r + r + - Solubility mol/100g of water at 298 K 2. This makes the magnitude of lattice energy rather constant and decreases slower than the magnitude of hydration energy on moving down the group.

the lattice energy is larger than the enthalpy of hydration. N. Difference in solubility is a useful tool in qualitative analysis.s-Block elements Unit 3 c) Page 5 Solubility of salts of other group II metals Results obtained when 0. The first process requires an input of energy to break the lattice. the process is endothermic. 2 . Glossary solvation Past Paper Question 90 2B 4 e 91 2A 1 b iii 93 2B 4 b ii 96 2B 4 c 98 1A 3 b iii 99 1A 1 b ii hydration solution 91 2B 5 c 90 2B 4 e 4 Account for the following observations. there formation of Li(H2O)n+ involve high hydration energy. The enthalpy of solution is a measure of the difference between 2 marks these two processes. The dissolving of a salt in water is a case of an enthalpy change accompanying a chemical process. Although OH. 4e Lithium salts generally have high solubilities in water. For example Ca2+(aq) and Sr2+(aq) solutions can be distinguished by adding saturated CaSO4(aq) solution. 3 1 mark 1 mark 1 mark 91 2A 1 b iii iii When solid sodium chloride is dissolved in water. The second process involves the release of energy when new bonds are made between ions and water. Li salts . Li+ has very high charge density because of the small ionic radius. it is considered as a small ion.1M solution Mg2+.ion is a polyatomic ion. Sr2+ and Ba2+ are treated with various solutions.B. Explain this observation. In case of NaCl.lattice energy is low because of the crystal packing is not efficient. Ca2+.

CaSO4. magnitude of both hydration energy and lattice energy decrease. 1 ½ mark Lattice energy ∝ r+ + r− 1 1 Hydration energy ∝ ( + ) ½ mark r+ r− On descending the group.energy released in the formation of the solid crystal from the gaseous ions ∆HHE: Hydration enthalpy . 93 2B 4 b ii 4b Account for each of the following facts: ii MgCrO4 is more soluble in water than BaCrO4. 2 Hydration energy of Mg2+ is more exothermic than that of Ba2+ 1 mark due to the very small size of Mg2+ cation.s-Block elements Unit 3 Page 6 91 2B 5 c 5c Explain why the solubility of group(II) salts of large anions decreases on descending the group. the lattice of MgSO4 can easily be broken down by water. ½ mark For large anions. 1 mark 98 1A 3 b iii 3b Sketch the trends for the properties mentioned in (i). ∴ MgCrO4 is more soluble than 1 mark BaCrO4. SrSO4 and BaSO4 99 1A 1 b ii 1b Account for each of the following : ii The solubility in water of magnesium hydroxide is less than that of barium hydroxide. ½ mark ½ mark The ∆Hsoln becomes less negative on descending the group and solubilities decrease.energy released when the solute particles in gaseous state become associated with water molecule to form a solution. 3 2CrO4 is a large anion 1 mark The solubility of an ionic compound with large anion is affected more by the hydration energies of its ions than its lattice energy. the packing efficiency is high result in higher lattice energy. the lattice energy is rather constant. whereas the 4 solubility of group(II) salts of small anions shows the reverse trend. 1 mark ∆Hsoln = -∆HLE + ∆HHE ∆HLE: Lattice energy . MgSO4. and account for the trend in each case. ½ mark More negative the ∆Hsoln. Therefore. (ii). iii solubility in water of the Group II sulphates(VI). The magnitude of hydration energy decreases less than that of lattice energy as the size of the cation increases. For small anions with small cation. The ∆Hsoln becomes more negative on descending the group and solubilities increase. and (iii) below. 96 2B 4 c 4c Briefly explain why magnesium sulphate(VI) is soluble in water. more soluble would be the salt. whereas barium sulphate(VI) is almost insoluble. it has much higher hydration energy than Ba2+. The magnitude of hydration energy decreases more than that of lattice energy as the size of the cation increases. 1 mark Mg2+ is smaller than Ba2+. .

243 Inorganic Chemistry. fluoride and carbonate Do not form stable nitride. nitrogen dioxide and oxygen Do not form stable solid hydrogencarbonate Form organometallic compound e. E. This is an example of diagonal relationship. fluoride and carbonate Form stable nitride organometallic compound Sodium Formation of peroxide on top of normal oxide Stable to heat Stable to heat Decompose into nitrate(III) and oxygen only Form stable solid hydrogencarbonate Do not form any stable organometallic compound at all Soluble phosphate. Ramsden pg. 104 A-Level Chemistry. MgR2 Insoluble phosphate. Properties Burning in air Heating of carbonate Heating of hydroxide Heating of nitrate(V) Formation of hydrogencarbonate Formation of organometallic compound Solubility of salts Stability of compound Glossary anomaly Lithium Formation of normal oxide Decompose into oxide and carbon dioxide Decompose into oxide and water Decompose into oxide. nitrogen dioxide and oxygen Do not form stable solid hydrogencarbonate Form organometallic compound e.g. 3rd Edition ELBS pg. 374 Page 1 Unit 4 Assignment Reading Syllabus Anomaly of lithium Notes D. The properties of lithium resembles that of magnesium more than that of other group I metal. 4th Edition.g. fluoride and carbonate Form stable nitride Insoluble phosphate. Leung pg.M.s-Block elements Unit 4 Topic s-Block Elements Reference Reading 9.N. RLi Magnesium Formation of normal oxide Decompose into oxide and carbon dioxide Decompose into oxide and water Decompose into oxide. . T.4 Chemistry in Context. 3rd Edition.2. Abnormal behaviour of lithium Lithium exhibits anomalous behaviour comparing with other group I metal. The anomaly is mainly due to the exceptional high charge density and polarizing power of lithium ion comparing with other group I metal ions.

high charge density.forms more stable covalent bond with C when compare with other element in Group I.s-Block elements Past Paper Question Unit 4 Page 2 93 2B 4 a 96 2B 4 a 93 2B 4 a 4a The first member of a Group in Periodic Table usually exhibits anomalous behaviour. while carbonate of other Group I elements do not. hydroxide decomposes upon heating. For lithium in Group I. 3 Li2CO3  → Li2O + CO2 heat 4LiNO3  → 2Li2O + 4NO2 + O2 heat 2LiOH  → Li2O + H2O 2. nitrate. ½ mark nitrogen dioxide / a brown gas and oxygen.g. H-.is insoluble in H2O Q Li has a small size. Do not form solid hydrogencarbonate. give two examples of anomalous behaviour and explain how this behaviour arises. ½ + ½ mark Li2CO3 → Li2O + CO2 (1 mark) 1 mark But other alkali metal carbonates do not. 5. RLi 4. Lithium forms a number of organic compound e.forms more stable compounds with small anions e. ½ mark Lithium nitrate(V) decomposes on heating to give (lithium oxide). ∴ Li2CO3. Any two of the following examples: 1. 2 marks 6. Lithium do not form any superoxide and peroxide. O2-. Lithium carbonate. Slow reaction with water and not explosive with acid. LiNO3 tend to decompose on heating .g. high polarizing power and more electronegative(less stable in forming ionic compound) . Li+2S2.' Lithium carbonate decomposes on heating to give (lithium oxide) and carbon dioxide. 2LiNO3 → Li2O + 2NO2 + ½O2 (1 mark) 1 mark But other alkali metal nitrate(V) give nitrate(III) and oxygen.due to high lattice energy. 2MNO3 → 2MNO2 + O2 (1 mark) 4 . 3. N3. 1 mark heat 96 2B 4 a 4a Give TWO reactions to illustrate the following statement : 'Lithium compounds differ in their chemical properties from compounds of other Group I elements .

Baking powder The main ingredient of baking powder is sodium hydrogencarbonate which is not very stable to heat. Upon heating.M. Soda glass is a mixture of sodium silicate and calcium silicate. The carbon dioxide evolved will help to raise the bread in the baking process inside the oven. Ramsden pg. 4th Edition. 219–221 Reading Syllabus Notes III. Group II and other metal hydrogencarbonate do not exist at all. Na2CO3(s) + SiO2(s) → Na2SiO3(s) + CO2(g) CaCO3(s) + SiO2(s) → CaSiO3(s) + CO2(g) B.B. carbon dioxide and water. Manufacture of glass Sodium carbonate is used in the manufacture of glass.s-Block Elements Unit 5 Topic s-Block Elements Reference Reading 9. 2NaHCO3(s) → Na2CO3(s) + CO2(g) + H2O(l) N. which is made by fusing the carbonates with silica SiO2(s) (from sand) at 1500ºC. C. Making of soap Aqueous sodium hydroxide is used in the hydrolysis of fat (saponification) in the preparation of soap.is a large anion with high polarizability. Leung pg. Antacid Mg(OH)2(s) is commonly used as the antacid to neutralize the excess acid in the stomach. 5th Edition. . E.N. D. HCO3. 3rd Edition ELBS pg. 3rd Edition. 369 Page 1 Unit 5 Assignment Chemistry in Context. it decomposes into sodium carbonate. Inorganic Chemistry. T. Uses of the compounds of the s-block elements A. It only forms stable solid hydrogencarbonate with big group I metal ions. Thomas Nelson and Sons Ltd. pg.3 Chemistry in Context. 113–115 A-Level Chemistry.

with the aid of 3 chemical equation(s).s-Block Elements Unit 5 Page 2 E. Slaked lime Limestone (CaCO3(s)) is heated to give quicklime (CaO(s)) which is 'slaked' with water to give slaked lime (Ca(OH)2(s)). identify ONE inorganic compound which is an active ingredient: iv antacid 3 . Fireworks Salts of s-block metals are mixed with gunpowder in fireworks to give different colour to the fireworks. bleaching powder and manufacture of calcium hydrogensulphite which is used in paper industry. 97 1A 3 a iv 3a For each of the following materials. Sodium hydrogencarbonate in the self-raising flour undergoes thermal decomposition to give CO2 gas. F. the aqueous solution of slaked lime is called limewater. the role of sodium hydrogencarbonate in the baking process. Explain briefly. Glossary silica baking powder Past Paper Question 94 2B 6 a 97 1A 3 a iv slaked lime quicklime 94 2B 6 a 6a Self-raising flour for baking cakes and bread contains sodium hydrogencarbonate. making of mortar (slaked lime + sand + water). → CaO(s) + CO2(g) CaCO3(s) heat CaO(s) + H2O(l) → Ca(OH)2(s) Slaked lime (Ca(OH)2(s)) is used in the removal the acidity of the soil. 1 mark 2NaHCO3(s) → Na2CO3(s) + CO2(g) + H2O(g) 1 mark 1 mark The CO2 gas produced causes the cakes to rise. When dissolved in water.

Ostwald Process 2. Oxidizing properties of nitric(V) acid a) With copper b) With iron(II) ion c) With sulphur Nitrate(V) salt 1. E. E. Oxoacid Uses of halogens and halogen containing compounds 1. Reactions of halide a) with halogens b) with conc. II. Thermal decomposition of nitrate 2. B.p-Block Elements I. Acidic properties of hydrogen halide 3. Haber process 2. Direct combination of nitrogen and oxygen Ammonia 1. phosphoric(V) acid d) with silver ions 2. Chemical properties of ammonia a) Alkaline properties (1) b) (1) (2) (3) (4) (5) C. Fluoridation of water 2. Brown ring test Use of nitric(V) acid a) Fertilizers b) Explosives c) Nylon d) Dyestuffs . Halogens A. Unreactive nature of nitrogen 2. Disproportionation of halogen in alkalis Properties of the halogen compound 1. B. Laboratory preparation of ammonia Reducing properties Combustion Catalytic oxidation With copper(II) oxide With chlorine Thermal decomposition of ammonia Nitric(V) acid 1. sulphuric(VI) acid c) with conc. Use of chlorine 3. D. Laboratory preparation of chlorine Characteristic properties of the halogens Properties of halogen 1. Nitrogen 1. Photographic films Nitrogen and its compounds A. Oxidizing power of halogen 2. C. D.

Properties of concentrated sulphuric acid Sulphate(VI) salt 1. Fertilizers 2. F. E. B.III. Contact process 2. D. Paints. Sulphur and its compounds A. Distinguishing from carbon dioxide Concentrated sulphuric(VI) acid 1. Allotrope of sulphur Burning of sulphur Sulphur dioxide / sulphate(IV) salt 1. C. Test for sulphate(VI) ion Use of sulphuric(VI) acid 1. Reducing properties of sulphur dioxide a) With manganate(VII) ion b) With dichromate(VI) ion c) With bromine 2. Detergents 3. Oxidizing properties of sulphur dioxide a) With magnesium 3. Pigments and dyestuffs .

1. Halogens Unit 1 Reference Reading 10. heating is not essential. Since the oxidizing power of KMnO4(s) is very strong. T. 4th Edition. H2SO4(aq) must be added to provide the H+(aq) ions required in the reaction.2 Chemistry in Context.N. Laboratory preparation of chlorine Cl2(g) is a strong oxidizing agent. 265. 398–399 Assignment Chemistry in Context.I.1. 122–129 A-Level Chemistry.ion. The source of Cl. heating is mandatory. pg. KMnO4(s) and MnO2(s) are two commonly used oxidizing agents.ions may come from NaCl(s) or conc. Halogens A. 270–276 Inorganic Chemistry.M. Leung pg. If NaCl(s) is used. Ramsden pg. MnO2(s) + 4HCl(aq)  → MnCl2(aq) + 2H2O(l) + 2Cl2(g) heat 10HCl(aq) + 2MnO4-(aq) + 6H+(aq) → 5Cl2(g) + 8H2O(l) + 2Mn2+(aq) . 224–233 Reading Syllabus Notes I. 3rd Edition.0–10. 5th Edition. E. Halgoens Unit 1 Page 1 Topic I. an oxidizing agent stronger than Cl2(g) must be used. HCl(aq). 396. Thomas Nelson and Sons Ltd. In order to prepare Cl2(g) from Cl. 3rd Edition ELBS pg. if MnO2(s) is used. However.

They all accepts electron readily.d 2I-(aq) Br2(g) + 2e. Oxidizing power of halogen All halogens are strong oxidizing agents. Comparatively. Br. Characteristic properties of the halogens All halogens have high electronegative and accept electrons readily.d Mn2+(aq) + 4H2O(l) F2(g) + 2e. Properties of halogen 1. Cl. Cl. free halogen atom also has high electron affinity.07 V + 1. The word "halogen" means salt maker. Reduction half ionic equation I2(s) + 2e.I. Halgoens Unit 1 Page 2 B.36 V + 1. Furthermore.87 V Reaction with sodium Cl2(g) + 2Na(s) → 2NaCl(s) Br2(l) + 2Na(s) → 2NaBr(s) I2(s) + 2Na(s) → 2NaI(s) Reaction with iron(II) ion Cl2(g) + 2Fe2+(aq) → 2Cl-(aq) + 2Fe3+(aq) Br2(l) + 2Fe2+(aq) → 2Br-(aq) + 2Fe3+(aq) I2(l) + 2Fe2+(aq) → 2I-(aq) + 2Fe3+(aq) Reaction with phosphorus Most phosphorus form two kinds of halides PX3 (X = F.54 V + 1.d 2Cl-(aq) MnO4-(aq) + 8H+(aq) + 5e. I) and PX5 (X = F.d 2F-(aq) Standard reduction potential + 0. C.51 V + 2.d Mn2+(aq) + 2H2O(l) Cl2(g) + 2e.23 V + 1. It forms salt readilty with metal. the oxidizing power of fluorine is even stronger than potassium manganate(VII). P(s) + F2(g) → PF3(g) (colourless gas) P(s) + F2(g) → PF5(g) (colourless gas) P(s) + Cl2(g) → PCl3(l) (colourless liquid) P(s) + Cl2(g) → PCl5(s) (white solid) P(s) + Br2(l) → PBr3(l) (colourless liquid) P(s) + Br2(l) → PBr5(s) (yellow solid) P(s) + I2(s) → PI3(s) .d 2Br-(aq) MnO2(s) + 4H+(aq) + 2e. Br).

the element disproportionates and gets a more positive oxidation state more readily. The difference in mode of disproportionation can be explained by the difference in electronegativity of halogen atom. 3Cl2(g) + 6OH-(aq) → ClO3-(aq) + 5Cl-(aq) + 3H2O(l) 0 +5 -1 at about 70ºC This may be considered as thermal decomposition of ClO-(aq). Halgoens Unit 1 2. Disproportionation of chlorine in alkali Cl2(g) + 2OH-(aq) → ClO-(aq) + Cl-(aq) + H2O(l) 0 +1 -1 at room temp. (not a disproportionation reaction) 2F2(g) + 4OH-(aq) → O2(g) + 4F-(aq) + H2O(l) 0 -1 at about 70ºC F2(g) is extremely electronegative.I. it only behaves as an oxidizing agent but not a reducing agent. Glossary disproportionation Past Paper Question 90 1A 3 c 91 2B 4 c ii 92 1A 3 f iii 93 2B 6 a i 94 1A 2 a ii 96 1A 2 c d I ii 97 1B 7 a 98 2B 8 d i ii 93 2B 6 a ii 94 2B 4 a . Page 3 Disproportionation of halogen in alkalis Except fluorine. all halogens disproportionate in alkali. 3ClO-(aq) → 2Cl-(aq) + ClO3-(aq) +1 -1 +5 Disproportionation of bromine in alkali 3Br2(l) + 6OH-(aq) → BrO3-(aq) + 5Br-(aq) + 3H2O(l) 0 +5 -1 at room temp. As the most electronegative element. However. Disproportionation of iodine in alkali 3I2(s) + 6OH-(aq) → IO3-(aq) + 5I-(aq) + 3H2O(l) 0 +5 -1 at room temp. different halogens disproportionate differently in alkali medium at different temperature. Reaction of fluorine with alkali 2F2(g) + 2OH-(aq) → OF2(aq) + 2F-(aq) + H2O(l) 0 -1 -1 at room temp. With decreasing electronegativity on moving down the group. F tends to attain an oxidation state of -1 only.

2F2 + 2OH.→ OF2(g) + 2F.d XO3. 1 mark 2F2(g) + 2OH-(aq) → OF2(aq) + 2F-(aq) + H2O(l) Cl2(g) + 2OH-(aq) → OCl-(aq) + Cl-(aq) + H2O(l) 1 mark or 3Cl2(g) + 6OH-(aq) → ClO3-(aq) + 5Cl-(aq) + 3H2O(l) 3Br2(l) + 6OH-(aq) → BrO3-(aq) + 5Br-(aq) + 3H2O(l) 1 mark 91 2B 4 c ii 4c ii Explain what is meant by ‘disproportionation’. it will not disproportionate.ion.+ H2O ii at 350 K. involving the reaction of chlorine with KOH(aq). (no mark for atom/element -½) 1 mark H2O + Cl2 → HCl + HOCl 2NaOH + Cl2 → NaCl + NaOCl + H2O 4KClO3 → 3KClO4 + KCl 3HOCl + 3H2O → 3H3O+ + ClO3. or 6KOH(aq) + 3Cl2(g)   → 5KCl(aq) + KClO3(aq) + 3H2O(l) hot conc. Cl2. 6OH-(aq) + 3Cl2(g)   → 5Cl-(aq) + ClO3-(aq) + 3H2O(l) 3 1 2 temperature 2NaOH (aq. At 350 K. F2 + 4OH. Br2 and I2 all disproportionate as follows 3X2 + 6OH-(aq) → XO3-(aq) + 5X-(aq) + 3H2O(l) F2 oxidizes the alkali. At 295 K.→ O2(g) + 4F. X = Br or I 3OX. illustrate the reactions of the halogens F2(g). dilute) + Cl 2(g) room  → NaOCl(aq) + NaCl (aq) + H 2 O (l) Page 4 1 mark 1 . Halgoens Unit 1 90 1A 3 c 3c By means of balanced equations. hot conc.+ 2H2O 3 1 mark 1 mark 1 mark 2 1 mark 1 mark 2KOH(aq) + Cl2(g)  → KCl(aq) + KOCl(aq) + H2O(l) cold dil.are unstable and will undergo further disproportionation. chlorine. and write an equation involving a compound of chlorine to illustrate your answer. 2OH-(aq) + Cl2(g)  → Cl-(aq) + OCl-(aq) + H2O(l) cold dil.+ 2XF2 is the strongest [O] agent. Definition : Reaction in which a single species/ion/substance is simultaneously oxidized and reduced.+ 2Cl3Cl2 + 6NaOH → 5NaCl + NaClO3 + 3H2O 1 mark (½ mark for unbalanced equation. Cl2. 1 mark for balanced) 92 1A 3 f iii 3f Complete and balance the following equations: temperature iii dil NaOH + Cl room  → H O + + 2 93 2B 6 a i ii 6a Compare the reaction of aqueous alkali with each of fluorine. bromine and iodine i at 295 K. 2 1 mark 94 1A 2 a ii 2a ii Write a balance equation. to illustrate a disproportionation. instead.and OI. it will oxidize the OH. Cl2(g) and Br2(l) with OH-(aq) at room temperature. Br2 and I2 disproportionate according to the equation X2 + 2OH-(aq) → OX-(aq) + X-(aq) + H2O(l) OBr.I.

Heating conc. explain why a different reaction takes place.I. Would you expect the reaction of iodine with sodium hydroxide to be similar to the reaction of chlorine with sodium hydroxide at each temperature ? If not. The central atoms of the other three compounds are in their highest oxidation states whereas in HClO3. iodine solid instead of chlorine gas is added to the aqueous sodium hydroxide solution. Cl is in an intermediate oxidation state. HCl to solid KMnO4 10HCl(aq) + 2MnO4-(aq) + 6H+(aq) → 5Cl2(g) + 8H2O(l) + 2Mn2+(aq) heat Page 5 5 2 marks Pass the Cl2 produced through cold water to remove HCl. 3HClO3 → HClO4 + H2O + 2ClO2 2 4 × ½ mark 1 ½ mark ½ mark 1 1 mark 97 1B 7 a 7a Briefly describe how a sample of dry chlorine gas can be prepared in the laboratory. 5+) 2d i Explain why among the four compounds in (c). 1 mark 96 1A 2 c d i ii 2c What is the oxidation state of the central atom in each of the following compounds ? HClO4 HClO3 H2CrO4 HMnO4 HClO3 +5 or V HClO4 +7 or VII H2CrO4 +6 or VI HMnO4 +7 or VII (DO NOT accept a number preceding the charge e.g. Draw a labelled diagram of the laboratory set-up and state the safety precaution(s) that is/are required. H2SO4 and collect 2 marks by downward delivery. dry the gas by passing through conc. only HClO3 can undergo disproportionation. HCl in the presence of manganese(IV) oxide MnO2(s) + 4HCl(aq)  → MnCl2(aq) + 2H2O(l) + 2Cl2(g) OR Add conc. ii Write a balanced equation for the disproportionation of HClO3 to give HClO4 and ClO2. 6 4 . The experiment should be carried out in a fume cupboard. State the safety precaution(s) that is/are required. ii At each of the above temperatures. Halgoens Unit 1 94 2B 4 a 4a Describe how a sample of dry chlorine is prepared in the laboratory. 98 2B 8 d i ii 8d i Write the balanced equation for the reaction that occurs when chlorine gas is passed into an aqueous sodium hydroxide solution at (I) 298 K (II) 343 K.

H2SO4(l).g. Conc.ion is only capable to reduce conc. H2SO4(l) to H2S(g) while Br. H3PO4(l) (b. b) with conc. Moreover.ions.ion and I. H3PO4(l) is also a viscous liquid due to the formation of extensive hydrogen bonds among the molecules. Reactions of halide a) with halogens The oxidizing power of halogens show a decreasing trend on moving down the group. 3rd Edition ELBS pg.N. H2SO4(l) to SO2(g). Cl2 + 2Br. I.p.p. sulphuric(VI) acid (b. NaF(s) + H3PO4(l) → HF(g) + NaH2PO4(s) NaCl(s) + H3PO4(l) → HCl(g) + NaH2PO4(s) NaBr(s) + H3PO4(l) → HBr(g) + NaH2PO4(s) NaI(s) + H3PO4(l) → HI(g) + NaH2PO4(s) . orange to brown. Halogens Reference Reading 10.p. conc. 233–234 Reading Syllabus Notes D. A more reactive halogen is capable to displace a less reactive halogen from its salt. sulphuric(VI) acid Conc. 85ºC) from the salts since HF(g) and HCl(g) are very volatile. Therefore. Therefore. NaF(s) + H2SO4(l) → HF(g) + NaHSO4(s) NaCl(s) + H2SO4(l) → HCl(g) + NaHSO4(s) The oxidizing powers of Br2 and I2 are weaker than conc. Properties of the halogen compound 1. 276–278 Inorganic Chemistry. E. Leung pg. 20ºC) and HCl(g) (b. pg. its oxidizing power is not strong enough to oxidize F.I. Halogens Unit 2 Topic I.p. However.→ 2Cl. 5th Edition. It is capable to displace hydrogen halides form the solid halide salts without oxidizing the halide ion to halogen. 402–404 Page 1 Unit 2 Assignment Chemistry in Context. NaBr(s) + H2SO4(l) → HBr(g) + NaHSO4(s) 2HBr(g) + H2SO4(l) → SO2(g) + Br2(g) + 2H2O(l) NaI(s) + H2SO4(l) → HI(g) + NaHSO4(s) 8HI(g) + H2SO4(l) → 4I2(g) + H2S(g) + 4H2O(l) c) with conc.M. phosphoric(V) acid Similar to conc.ion is a stronger reducing agent than Br. e. F2 is the halogen with the strongest oxidizing power. I.p.1. conc.+ Br2 Aqueous halogens have similar colours with different intensity ranging from yellow.p.ion. 129–135 A-Level Chemistry. T.ion besides displacing HBr(g) (b. 3rd Edition. 338ºC) is an involatile acid and a strong oxidizing agent. Thomas Nelson and Sons Ltd. It can only displace HF(g) (b. -67ºC) and HI(g) (b. The halogen displaced could be identified more accurately by extracting with an organic solvent. Chlorine is pale green in organic layer while bromine is orange and iodine is purple. H2SO4(l). H2SO4(l) is capable to oxidze Br.3. Ramsden pg.1 Chemistry in Context.ion or Cl. -35ºC) from the salts. 4th Edition.ion is capable to reduce conc. 213ºC) is also involatile but it is non-oxidizing.

Ag2O(s) + 2NH3(aq) + H2O(l) d Ag(NH3)2+(aq) + OH-(aq) brown colourless (diamminesilver(I) ion) Cu(OH)2(s) + 4NH3(aq) d Cu(NH3)42+(aq) + 2OH-(aq) pale blue deep blue (tetraamminecopper(II) ion) Zn(OH)2(s) + 4NH3(aq) d Zn(NH3)42+(aq) + 2OH-(aq) white colourless (tetraamminezinc(II) ion) Glossary displace involatile tetraamminecopper(II) ion Past Paper Question 90 2B 6 c 92 1A 3 f i ii 93 2B 6 c 94 2B 4 d i ii 95 1B 4 a 96 2B 5 c i ii iii iv 98 2B 8 b ii 99 1A 3 d ii soluble complex redissolve tetraamminezinc(II) ion diamminesilver(I) ion . the three ions will form insoluble precipitate of oxide and hydroxides upon addition of a little aqueous ammonia since ammonia is a weak alkali. Silver nitrate must be used in acidic medium because silver(I) ion will form silver(I) oxide in the presence of hydroxide. Ag+(aq) + I-(aq) → AgI(s) yellow ppt. 2Ag+(aq) + 2OH-(aq) → Ag2O(s) + H2O(l) colourless brown Cu2+(aq) + 2OH-(aq) → Cu(OH)2(s) blue pale blue Zn2+(aq) + 2OH-(aq) → Zn(OH)2(s) colourless white If excess ammonia is added. At first. slightly soluble in NH3(aq) and decomposes under light to yellow grey ppt. 2Ag+(aq) + OH-(aq) → Ag2O(s) + H2O(l) Aqueous silver(I) ion forms silver halide precipitate with different colour and stability under light. AgCl(s) is soluble in aqueous ammonia because it has a larger share of ionic character and Ag+ ion is capable to form a soluble complex with NH3(aq) molecules. Ag+(aq) + Br-(aq) → AgBr(s) yellow ppt. soluble in NH3(aq) and deocmposes under light to purple grey ppt. AgCl(s) + 2NH3(aq) d Ag(NH3)2+(aq) + Cl-(aq) Besides Ag+(aq). the three precipitates will redissolve at high NH3(aq) concentration. Halogens Unit 2 Page 2 d) with silver ions The presence of halide ion in an aqueous solution can be identified by using acidified silver nitrate solution. Cu2+(aq) and Zn2+(aq) are also capable to form soluble complex with NH3(aq) molecules. Solubility and formation of ammonia complex AgBr(s) and AgI(s) are not very soluble in NH3(aq) solution because they are highly covalent. Ag+(aq) + Cl-(aq) → AgCl(s) white ppt.I. insoluble in NH3(aq) and stable to light N.B.

Cl is much more electronegative than I / the size of I. Prepare conc. NaCl gives similar reaction NaBr will react to give also Br2 and SO2. 2HBr + H2SO4 → 2H2O + SO2 + Br2 Q conc. will be oxidized by conc. 1 mark 3 1 mark 1 mark 1 mark 1 1 mark 2 1 mark 1 mark 95 1B 4 a 4a Devise an experiment to distinguish between KBr(s) and a mixture containing approximately 40% KCl(s) and 60% KBr(s) by mass.I.NH3 but soluble in conc. (Note : Br. and NaCl + H2SO4 → NaHSO4 + HCl ii concentrated H2SO4 and NaI.is larger than ClCl. being a stronger reducing agent than HCl. Will concentrate H2SO4 give a similar reaction in each case? Explain any difference(s) in reactivity between concentrated H3PO4 and concentrated H2SO4.to I2 or I. aqueous solutions by dissolving the solids in water. CuI2 → CuI + ½I2 92 1A 3 f i ii 3f Complete and balance the following equations: temperature i conc H 2 SO 4 + KBr room  → H 2 O + + ii conc H 3 PO 4 + KBr   → 3 1 mark 1 mark 1 mark 1 + temperature 2KBr(s) + 3H 2 SO 4 (conc) room  → 2KHSO 4(aq) + 2H 2 O (l) + SO 2(g) + Br2(g) heat Page 3 1 mark 1 + KBr(s) + H 3 PO 4(conc) heat  → HBr(g) + KH 2 PO 4(aq) 93 2B 6 c 6c Write the equation in each case.ion is polarized by Cu2+ CuI2 disproportionates. NaI + H2SO4 → HI + NaHSO4 8HI(g) + H2SO4(l) → 4I2(s) + H2S(g) + 4H2O(l) HI / I-. NH3) 3 . H2SO4 to give I2. H3PO4 is not.is insoluble in dil. decant the solution and compare the height of the precipitate. H2SO4 is an oxidizing agent while conc. 94 2B 4 d i ii 4d Write balanced equation(s) and comment on the difference for the reaction between i concentrated H2SO4 and NaCl.is more resistant to oxidation than Ior Cu2+ is an oxidizing agent strong enough to oxidize I.is a stronger reducing agent I. Reaction between NaX and H3PO4 (X = Cl or Br) H3PO4 + NaX → HX + NaH2PO4 With H2SO4. Halogens Unit 2 90 2B 6 c 6c Explain why copper(II) chloride is a stable compound whereas copper(II) iodide does not exist. 1 mark ½ mark Add AgNO3(aq) to solution in test tube ½ mark Add excess NH3(aq) to the precipitate 1 mark Let the precipitate settle. for the reaction of concentrated H3PO4 with NaCl and NaBr.

to a solution of copper(II) sulphate(VI). c. 1 mark for safety precaution.] marks for the diagram for the set-up 3 marks (½ mark for a tap funnel. Hydrogen chloride can be prepared by dropping (slow addition of) c. ii KBr(s) is heated with concentrated H2SO4. H2SO4 onto KCl ½ mark ½ mark and warming the reaction mixture. 1 1 mark KCl + H2SO4 → KHSO4 + HCl ii Briefly describe how a sample of dry hydrogen chloride can be prepared in the laboratory using the above 6 reaction. state the expected observation and write the relevant balanced equation(s). ½ The HCl produced is tried by passing through anhydrous CaCl2 /concentrated H2SO4 mark ½ mark and then collected by downward delivery / in a gas syringe. state the expected observation and write the relevant balanced equation(s). until in excess. Halogens Unit 2 Page 4 96 2B 5 c i ii iii iv 5c Hydrogen chloride can be prepared by the action of concentrated sulphuric(VI) acid on potassium chloride. 2 1 6 . 98 2B 8 b ii 8b For each of the following. Write a balanced equation to represent the reaction that occurs. H3PO4. 1 mark for the collection of HCl) (Deduct ½ mark for each minor mistake) iii Briefly explain why hydrogen bromide cannot be prepared by the action of concentrated sulphuric(VI) acid on potassium bromide. [2 marks for description of the expt. ii Ammonia solution is added dropwise. 99 1A 3 d ii 3d For each of the following.I. Draw a labelled diagram of the laboratory set-up and state the safety precaution(s) that is/are required. 1 mark Precaution: carry out experiment in fume cupboard. i Write a balanced equation for the reaction of concentrated sulphuric(VI) acid and potassium chloride. ½ marks for labelling the reactants 1 mark for correct set-up for the drying process. HBr can be prepared by heating KBr with cone. 1 mark Or (1 mark) Add Br2(l) to moist red phosphorus. H2SO4 can oxidize HBr produced to Br2 1 mark 2HBr + H2SO4 → 2H2O + SO2 + Br2 1 mark Or (1 2KBr + 3H2SO4 → 2KHSO4 + 2H2O + SO2 + Br2 mark) iv Suggest how a sample of hydrogen bromide can be prepared in the laboratory.

They have the forms HXO. Acidic properties of hydrogen halide All hydrogen halides are acidic in water. the oxoacid with more no. Oxoacid An acid containing oxygen is called an oxoacid. This reduces the amount of the hydroxonium ions in the solution and lowers the acidity of HF(aq). This will make the δ-O–Hδ+ bond more polar.2 568 3.1. e.M. 3rd Edition.3. Moreover. HF(aq) + H+(aq) d H2F+(aq) 3. 135–139 A-Level Chemistry. HXO3.1. This is because they are capable to form more identical resonance structures which imply a more evenly distributed electron cloud and more stable structure. of oxygen attaching to the atom X. of O atom would also be more acidic because the anions formed would be more stable. The attraction between the water molecules and Hδ+ will be strengthened and this favours the dissociation of the proton. Halogens Unit 3 Reference Reading 10.7 HI -10 298 0. HA(aq) + H2O(l) d A-(aq) + H3O+(aq) pKa E(H–X) ∆ EN HF 3.9 HCl -7 432 0.g. Ramsden pg. T. Therefore. Furthermore. Since O is an electronegative atom. it can be concluded that the solvation of the halide ion is not a determining factor affecting the strength of the acid. Leung pg. H2XO4 etc. The acidity of hydrogen halide decreases on moving down the group.3.I. The salts formed by them are called oxo-salts. the molecule will become more acidic. from the experimental data. it imposes a negative inductive effect on the central atom X.2–10.3 Inorganic Chemistry. Halogens Unit 3 Page 1 Topic I. E.9 HBr -9 366 0. H2XO3. O H O O O O S H O Cl O H chloric(I) acid (HOCl) O P H sulphuric(VI) acid (H2SO4) H O H phosphoric(V) acid (H3PO4) The acidity of an oxoacid is depending on the no. HF shows exceptionally low acidity because of the very strong H–F bond and the capability of the molecule to form hydrogen bond with the free proton in the aqueous medium. 4th Edition.N. 404–405 Assignment Reading Syllabus Notes 2. Glossary oxoacid oxo-salt .4 This can be explained the decrease in bond energy despite of the increase in bond polarity. HXO2.

I./ HBrO4 lowest oxidation state = -1 / -I ½ mark 1 mark example: Br. is highly polarizable. (H–F)n + H2O(l) d H3O+(aq) + F-(aq) the equilibrium lies to the L. state the expected observation and write the relevant balanced equation(s).ion. OR HX bond strength is greater in H–F than in H–Cl 1 mark 1 mark this outweighs the reduced hydration energy from F. so HCl is a strong acid.1 M HF(aq) is weaker than that of 0. 1 mark for order of acidity iv Explain why the acidity of 0. 3 . Mn O 2 1 - OO 2 O tetrahedral 1 mark 96 2B 5 b 5b What are the highest and lowest oxidation states of bromine ? Give one compound in which bromine is in its highest oxidation state and another compound in which bromine is in its lowest oxidation state. HOCl < HClO2 < HClO3 < HClO4 1 mark for 3 formulae. and arrange them in order of increasing acid strength. highest oxidation state = +7 / VII ½ mark 1 mark example: BrO4. having a larger size. i KIO3(aq) is added to acidified KI(aq).to ClOR 1 mark HF slightly ionizes in H2O & HCl completely ionizes in H2O 94 2B 5 a v 5a v Draw the three-dimensional structure of the manganate(VII) ion.S. 1 mark The Cl. Halogens Unit 3 Page 2 91 1A 3 c 94 1A 2 c iii iv 94 2B 5 a v 96 2B 5 b 99 1A 3 d i Past Paper Question 91 1A 3 c 3c Give the formulae of two chlorine-containing salts in which the oxidation number of Cl are +1 and +5 respectively.1 M HCl(aq) HF is extensively hydrogen-bonded in water. NaOCl and KClO3 ½ mark each 1 mark both are strong oxidizing agents 94 1A 2 c iii iv 2c iii Write the formulae of three oxoacids of chlorine./ HBr (Accept any correct example of Br containing compound) 99 1A 3 d i 3d For each of the following. it is stable in water.H. Suggest one common chemical properties shown by both compounds. Hence the equilibrium 1 mark HCl(aq) + H2O(l) d H3O+(aq) + Cl-(aq) lies to the right.

about half the people of the United States drink fluoridated water. 140–141 A-Level Chemistry. 3rd Edition ELBS pg. T. 2. Today. Many studies have shown that fluoridation reduces tooth decay substantially. However. Uses of halogens and halogen containing compounds 1. 4th Edition. risks.4 Chemistry in Context. 235–236 Reading Syllabus Notes E. 5th Edition. Local governments or the people of a community often must decide whether the water supply should be fluoridated.1. vinyl chloride is prepared by heating 1. as well as moral questions about its widespread use. Ramsden pg. perhaps chiefly because of the widespread use of fluoride toothpastes. 278–279 Inorganic Chemistry. Benefits. rates of tooth decay also have declined in areas without fluoridated water. Use of chlorine Manufacture of poly(chloroethene) Industrially.I. H H C C H H H H H C H H Cl2 Electrophilic addition H C C H Cl Cl H Heat 500 ° C C H H C Cl Cl Cl C H Eventually.N. H H H H C R Cl H H R C C Cl H R C C C Cl H H H H C Cl C H H H H H R C C C C Cl H Cl H . Thomas Nelson and Sons Ltd. and costs. and costs of fluoridation. This means balancing the benefits.2-dichloroethane at 500 ºC which is prepared from addition reaction between chlorine and ethene.M. In the 1930's. Halogens Unit 4 Reference Reading 10. The use of fluoride tablets and toothpastes and the application of strong fluoride solutions to the teeth by dentists can also help prevent tooth decay. poly(vinyl chloride) / poly(chloroethene) is prepared through a radical addition mechanism. People disagree over these issues. Halogens Unit 4 Page 1 Topic I. risks. 408–410 Assignment Chemistry in Context. E. Leung pg. pg. researchers discovered that people who grew up where water naturally contained fluoride had up to two-thirds fewer cavities than people living in areas without fluoride in the water. Fluoridation of water Fluoridation is the addition of a chemical called fluoride to water supplies to help teeth resist decay. and fluoridation has always been controversial. 3rd Edition.

In the developing process. the unexposed silver bromide will be washed away and a black image will be left behind to form a negative image. Photographic films Black and white film is made of emulation of silver bromide crystal in gelatin coated on a plastic base. Halogens Unit 4 Page 2 Manufacture of bleach and disinfectant Bleaching solution and bleaching powder are made by mixing chlorine with sodium hydroxide solution and calcium hydroxide respectively. silver bromide will decompose to black silver crystal. Glossary fluoridation Past Paper Question 96 1A 2 a 97 1A 3 a i iii bleach disinfectant photographic film 96 1A 2 a 2a State the method by which sodium hydroxide is produced industrially.I. chlorine bleach can also be used as a very effective disinfectant. NaOH(aq) is produced by electrolysis of brine / concentrated NaCl(aq) 1 mark (Deduct ½ mark for not mentioning ‘concentrated’. 3. In is also used in water and sewage treatment. Cl2(g) + 2NaOH(aq) → NaCl(aq) + NaClO(aq) + H2O(l) Cl2(g) + Ca(OH)2(s) → Ca(ClO)2(s) + CaCl2(s) + H2O(l) Besides using as a bleaching agent. Upon exposure to light. Give TWO other products obtained by this industrial process. identify ONE inorganic compound which is an active ingredient: i photographic film iii bleaching powder 2 3 .) ½ + ½ mark Other products: H2 / Cl2 / NaOCl solution (bleach solution) (any TWO) 97 1A 3 a i iii 3a For each of the following materials.

312–315 Syllabus Notes II. 3rd Edition. Unreactive nature of nitrogen Comparing with other p-block elements. the reaction with N2(g) involves a very high activation energy. When Mg(s) is burning in air. Nitrogen 1. T. 4th Edition. 443–448 Reading A-Level Chemistry.0–10. 3rd Edition ELBS pg.II. 5th Edition. E. Nitrogen and its compounds Reference Reading 10.M. Nitrogen and its compounds A. Therefore. Thomas Nelson and Sons Ltd. 362–365 Inorganic Chemistry. 142–159 Chemistry in Context. pg. This leads to formation of yellow magnesium nitride.2. Ramsden pg. A very high temperature is required to break the bond.N. nitrogen is quite unreactive because of the strong N≡N triple bond.2. the temperature is high enough to break the N≡N bond. Leung pg. Mg(s) + N2(g) → Mg3N2(s) N–N N=N N≡N N–H H–H Bond energy (kJmol-1) + 158 + 410 + 945 + 391 + 436 C–C C=C C≡C C–H Bond energy (kJmol-1) + 347 + 612 + 838 + 435 . Nitrogen and its compounds Unit 1 Topic II.2 Page 1 Unit 1 Assignment Chemistry in Context.

II. Nitrogen and its compounds
2.

Unit 1

Direct combination of nitrogen and oxygen

Normally, nitrogen doesn't react with oxygen.
But at a very high temperature, e.g. during lightning or
in the internal combustion engine, N2(g) combines with
O2(g) to produce colourless NO(g). In air, NO(g) is further
oxidized to NO2(g).
N2(g) + O2(g) → NO(g)
(involves high activation energy)
NO(g) + O2(g) → NO2(g)
(spontaneous at room temperature)
In laboratory, this can be done by passing a high tension
across an electric arc. The test tube of air will turn
brown gradually because of the formation of NO2(g).

NO2(g) is an acid anhydride which form nitric(V) and nitric(III) acid when dissolved in water.
NO2(g) + H2O(l) → HNO3(aq) + HNO2(aq)
HNO2(aq) is a weak acid which is vulnerable to air oxidation to strong HNO3(aq) acid.
2HNO2(aq) + O2(g) → 2HNO3(aq)
This is why the area with heavy traffic usually has more serious acid rain problem.
Overall equation

4NO2(g) + 2H2O(l) + O2(g) → 4HNO3(aq)

Page 2

II. Nitrogen and its compounds

Unit 1

Page 3

B. Ammonia
1.

Haber process

Haber Process – manufacturing of ammonia gas
N2(g) + 3H2(g) d 2NH3(g)

∆H = -92 kJ mol-1

Fe(s) catalyst, 200 atm, 500ºC

This method was invented by a German scientist called Haber.

Effect of temperature and pressure on the yield and rate of Haber
process
N2(g) + 3H2(g) d 2NH3(g)

∆H = -92 kJ mol-1

According to Le Chatelier’s principle, the reaction is favored by low
temperature and high pressure. On another hand, an increase in pressure
or temperature both increases the rate of reaction.
↑Pressure
↑Temperature

yield

rate of reaction

Therefore, a high pressure is ideal for achieving both high yield and
high rate of reaction.
However, manufacturing at high pressure requires the use of a strong
reacting vessel which is costly to build and operate. Therefore, only 200
atm was chosen.
500ºC is chosen because if the temperature is too high, the yield will be
too low. Moreover, if the temperature is too low, the rate of reaction
will be too slow and a very long time will be required for the reactants
to react.

The percentage of ammonia in the
equilibrium mixture obtained from a 1:1
mixture of N2 and H2 at different
temperature and pressure

The conditions chosen is actually a compromise between yield and rate of reaction. At such conditions, the
production of ammonia would be most economical.

II. Nitrogen and its compounds
2.

Unit 1

Page 4

Chemical properties of ammonia

a) Alkaline properties
Ammonia is a weak alkali in water. Kb of ammonia at 25ºC is 1.8 × 10-5 moldm-3.
NH3(aq) + H2O(l) d NH4+(aq) + OH-(aq)
(1) Laboratory preparation of ammonia
For this reason, ammonia gas is usually prepared by heating an
ammonium salt will a strong alkali in laboratory. e.g. soda lime (a
mixture of Ca(OH)2(s) and NaOH(s))
2NH4Cl(s) + Ca(OH)2(s) → NH3(g) + CaCl2(aq) + H2O(l)
Since water is produced, it has to be removed by a drying agent.
Anhydrous calcium oxide is the only suitable common drying agent.
This is because other common drying agents e.g conc. H2SO4(l) and
anhydrous CaCl2(s), react with ammonia.
Sulphuric acid neutralizes ammonia.
2NH3(g) + H2SO4(aq) → (NH4)2SO4(aq)
Anhydrous calcium chloride forms complex with ammonia.
4NH3(g) + CaCl2(s) → CaCl2·4NH3(s)
In the experimental setup, the reacting flask containing ammonium chloride and strong alkali have to be
inclined downwards to prevent the water condensed at the mouth from cracking the flask.
Moreover, ammonia is lighter than air and very soluble in water, it is collected by the method of upward
delivery (downward displacement of air) or using gas syringe.

b) Reducing properties
The nitrogen atom in ammonia has the lowest possible oxidation state of nitrogen, -3. Therefore, ammmonia can
only behave as a reducing agent in all kinds of redox reaction. Indeed, it is a fairly strong reducing agent.
(1) Combustion
Ammonia doesn’t burn in ordinary air but it burns with a yellow flame
in pure oxygen to give nitrogen.
4NH3(g) + 3O2(g) → 2N2(g) + 6H2O(l)

NH3(g) + HCl(g) → NH4Cl(s) . A red hot coil of platinum catalyst is then lowered into the flask. Pt catalyst → 4NO(g) + 6H2O(l) 4NH3(g) + 5O2(g)  ∆H = -907 kJmol-1 Since the reaction is highly exothermic. oxygen is bubbled through concentrated ammonia solution and mixed with ammonia vapour. e. 2NH3(g) + 3Cl2(g) → N2(g) + 6HCl(g) If ammonia is in excess. Nitrogen and its compounds Unit 1 Page 5 (2) Catalytic oxidation (Ostwald process in laboratory scale) In the presence of platinum catalyst. the platinum wire will continue to glow once the reaction has started. CuO(s) → Cu(s) 3CuO(s) + 2NH3(g) → 3Cu(s) + N2(g) + 3H2O(g) (4) With chlorine Chlorine is a strong oxidizing agent. (3) With copper(II) oxide Ammonia can also reduce oxides of unreactive metal to the metals with heating.g. a dense white fume of NH4Cl(s) will also be observed.II. NO(g) + O2(g) → NO2(g) Brown fume of NO2(g) will be observed at the mouth of the flask. ammonia can be oxidized further to NO(g) at high temperature. The initial product NO(g) is colourless which reacts with atmospheric oxygen to form brown NO2(g). Ammonia burns spontaneously in chlorine. In the experimental setup.

The decomposition is almost complete at 1 atm in the presence of Fe catalyst with heating. Glossary high tension electric arc Haber process Le Chatelier’s principle catalytic oxidation (Ostwald process) thermal decomposition of ammonia . 2NH3(g) → N2(g) + 3H2(g) Because 2 moles of ammonia will decompose into 4 moles of gaseous products. The volume of the gas will be doubled if all ammonia is decomposed.II. Nitrogen and its compounds Unit 1 Page 6 (5) Thermal decomposition of ammonia Thermal decomposition of ammonia is only the reverse of Haber process. This is done by passing ammonia back and forth the heated iron wool.

Ammonia N2 + 3H2 d 2NH3 ∆H < 0 / exothermic 1 mark Conditions of reaction: 200 atm.50 mol dm-3 respectively. finely divided iron catalyst 1 mark Effect of temperature on the equilibrium constant 1 mark Effect of pressure 1 mark } any 2 1 mark 2 marks Effect of concentration of N2 and H2 1 mark Catalyst . discuss the major economic aspects of this process. For each test. ammonia is synthesized by the exothermic reaction of nitrogen and hydrogen at around 723K. N2(g) atmosphere fractional distillation H2(g) petroleum industry cracking /steam reforming locate near oil refinery to save transport costs recycle of raw material use of catalyst 1 mark each 97 2B 8 b ii iii 8b The synthesis of ammonia using the Haber Process involves the following: N2(g) + 3H2(g) d 2NH3(g) ∆Ho = -92 kJ mol-1 ii Name a catalyst for the process and state the effect of the catalyst on the reaction. When the equilibrium was attained at 723 K. iii (I) State. 97 2B 8 c i ii 8c The reaction of chlorine with excess ammonia in the gas phase to give ammonium chloride and nitrogen involves several steps.II. a mixture of nitrogen and hydrogen was placed in a closed container. the effect of temperature on Kc for the reaction.50 mol dm-3 and 1. The initial concentrations of nitrogen and hydrogen were 0. suggest a chemical test to distinguish one from the other. (II) Explain why the Haber process is not operated at temperatures much higher or much lower than 723 K. with explanation.0% of the original nitrogen was consumed. give the reagent(s) used and the expected observation. 25. Nitrogen and its compounds Past Paper Question 90 2B 5 b 92 2B 6 Ac iii 97 2B 8 b ii iii 99 2A 1 c i Unit 1 Page 7 97 2B 8 c i ii 99 2A 4 a iii 90 2B 5 b 5b Outline an industrial preparation of ammonia. N2(g) + 3H2(g) d 2NH3(g) In a simulation of the process. 7 4 7 4 . Your answer should include the physico-chemical principles involved and also the role of any catalyst. i Write a balanced equation for the overall reaction. i CsCl(s) and NH4Cl(s) 99 2A 4 a iii 4a In the Haber process.required because of the inertness of N2 and H2 molecules 1 mark NH3 is removed from the reaction mixture Overall presentation 1 mark 92 2B 6 Ac iii 6Ac iii Ammonia is synthesized by the Haber Process. 99 2A 1 c i 1c For each of the following pairs of substances. iii State how ammonia is isolated from unreacted nitrogen and hydrogen in the process. With reference to the availability and preparation of raw materials. 500ºC. ii Briefly explain how ammonia acts as a reducing agent and as a base in the reaction.

NH3(g) serves as an intermediate to break the whole process into steps with lower activation energies. pg. H2SO4(l) or P2O5(s). Ostwald Process Nitric(V) acid is manufactured from NH3(g) industrially through the NO(g) and NO2(g) intermediates. Nitrogen and its compounds Reference Reading 10. Thomas Nelson and Sons Ltd. Since the reaction is highly exothermic. . 315 Syllabus Notes C. It can further be concentrated to pure nitric(V) acid by distilling with conc. Leung pg. 365–366 Inorganic Chemistry. the heat generated is diverted to heat up the raw material in the heat exchanger. T. 5th Edition. Nitrogen and its compounds Unit 2 Topic II. b. 159–162 Reading A-Level Chemistry.. It can be concentrated to concentrated nitric(V) acid by distillation. 4th Edition. N2 → NH3(g) → NO2(g) → HNO3(aq) Ostwald process a. The process is called Ostwald process.950 kJmol-1 Similar to Haber process. E.2. 3rd Edition ELBS pg. 3rd Edition. Nitrogen dioxide is dissolved in water in the presence of O2(g) to form HNO3(aq) 4NO2(g) + O2(g) + 2H2O(l) → 4HNO3(aq) The final solution contains about 60% by mass of nitric(V) acid. NH3(g) is first oxidized by O2(g) in air to NO(g) in the presence of Pt(s) catalyst at 900 ºC and 8 atm. the conditions chosen in Ostwald process is also a compromise between yield and rate of reaction.N. this is not economical because the activation energy involved is very high. Nitric(V) acid 1. 453–457 Chemistry in Context.3 Page 1 Unit 2 Assignment Chemistry in Context. Pt 4NH3(g) + 5O2(g)  → 4NO(g) + 6H2O(l) ∆H = . Although NO(g) can be prepared by direct oxidation of N2(g) molecule.M.II. Ramsden pg. Cooled NO(g) is further oxidized by O2(g) to NO2(g) 2NO(g) + O2(g) → 2NO2(g) c. Concentrated nitric(V) acid is an azeotrope of 68% nitric(V) acid.

b) With iron(II) ion 3Fe2+(aq) + NO3-(aq) + 4H+(aq) → 3Fe3+(aq) + NO(g) + 2H2O(l) Concentrated nitric(V) acid oxidizes iron(II) salt to iron(III) salt. Thus.d 2½H2O + ½N2O NO3-(aq) + 8H+(aq) + 6e. +5.II.d NO(g) 2H+(aq) + 2e.d 3H2O + NH4+ a) With copper Concentrated nitric(V) acid is a very strong oxidizing. Furthermore. Nitrogen and its compounds 2. nitric(V) acid shows different degree of oxidizing power and gives different products.d NO2(g) NO3-(aq) + 4H+(aq) + 3e. Depending on the concentration. nitric(V) acid can also be reduced to other products with different oxidation states depending on the condition. Concentrated nitric(V) acid (16M) Dilute nitric(V) acid (2M) Very dilute nitric(V) acid (0. nitrogen in nitric(V) acid has the highest possible oxidation state. Indeed. NO3-(aq) + 5H+(aq) + 4e. The Fe2+(aq) solution may turn the solution brown eventually. with very dilute nitric(V) acid with dilute nitric(V) acid (with heating) with concentrated nitric(V) acid (cold) no reaction 3Cu(s) + 2NO3-(aq) + 8H+(aq) → 3Cu2+(aq) + 2NO(g) + 4H2O(l) Cu(s) + 2NO3-(aq) + 4H+(aq) → Cu2+(aq) + 2NO2(g) + 2H2O(l) Surprisingly. Therefore. The NO(g) produced will be further oxidized to brown NO2(g) in air. It has only very weak oxidizing power offered by the H+(aq) ions.1M) NO3-(aq) + 2H+(aq) + e. concentrated HNO3(aq) is usually stored in steel tanks. concentrated HNO3(aq) has no reaction with Fe(s) due to the formation of an impermeable oxide layer.d H2(g) Very dilute nitric(V) acid behaves similarly to other aqueous acids. . Fe(s) is said to be passive to concentrated HNO3(aq). Unit 2 Page 2 Oxidizing properties of nitric(V) acid In contrast to ammonia. It even oxidizes less reactive metal like copper. It can only behaves as an oxidizing agent.d 2H2O + H2NOH NO3-(aq) + 10H+(aq) + 8e. the NO molecule is capable to form a brown complex [Fe(H2O)5NO]2+(aq) with Fe2+(aq).

HNO3(aq).II. NO 6 6 . Pass purified N2 and H2 (ratio 1:3) over iron catalyst at 450ºC and 200 atm pressure. state the reactant(s) used and the reaction conditions. H2SO4(aq) formed 6Ab 1 1 mark 93 2B 5 Ia 5I For the industrial preparation of nitric(V) acid from nitrogen . conc. 1 mark 4NO2 + O2 + 2H2O → 4HNO3 97 2B 8 a ii 8a Suggest how the following nitrogen oxides can be prepared in the laboratory. In each case. 4NH3 + 5O2 → 4NO + 6H2O 2NO + O2 → 2NO2 3 marks Resulting gaseous mixture is passed through water. 2 marks N2 + 3H2 d 2NH3 Ammonia is mixed with O2 (excess air) and passed over a platinum catalyst at 900ºC at 8 atm. give the chemical reactions and the conditions a under which they take place. But upon heating. HNO3(aq) can oxidize S(s) to sulphuric acid. concentrated nitric(V) acid and hydrogen sulphide gas? H2S(g) + 2HNO3(conc.) → S(s) + 2H2O(l) + 2NO2(g) note: on boiling. and write balanced equation(s) for the reaction(s) involved. S(s) + 6HNO3(aq) → H2SO4(aq) + 6NO2(g) + 2H2O(l) Glossary Ostwald process Past Paper Question 92 2B 6 Ab ii 93 2B 5 Ia 97 2B 8 a ii passive 92 2B 6 Ab ii What are the products of the reactions between ii cold. ii nitrogen monoxide. Nitrogen and its compounds c) Unit 2 Page 3 With sulphur Sulphur has no reaction with cold conc.

2. Au i. it releases oxygen which supports the burning of gunpowder. For less reactive metal nitrate(V) e. from Ca(NO3)2(s) to Cu(NO3)2(s). Fe. 162–169 Reading A-Level Chemistry. 2NaNO3(s) → 2NaNO2(s) + O2(g) For this reason.g. Pb. Nitrogen and its compounds Reference Reading 10. Leung pg. Ramsden pg. LiNO3(s). Zn. Reactivity series of metal K. Nitrate(V) salt 1. For non-reactive metal nitrate(V) e. (N.g. For reactive metal nitrate(V) e. Nitrogen and its compounds Unit 3 Topic II.N.4 Page 1 Unit 3 Assignment Chemistry in Context.g 2Ca(NO3)2(s) → 2CaO(s) + 4NO2(g) + O2(g) iii. 457–458 Syllabus Notes D. thermal decomposition → Less reactive metal oxide + Nitrogen dioxide + Oxygen Less reactive metal nitrate(V)   e. KNO3(s) and NaNO3(s). Al. 2AgNO3(s) → 2Ag(s) + 2NO2(g) + O2(g) This may be considered as a 2 steps decomposition. different nitrate(V) salts will decompose to give different products depending on the reactivity of the metal in the salt. 3rd Edition ELBS pg. ii. Hg. 3rd Edition. 4AgNO3(s) → 2Ag2O(s) + 4NO2(g) + O2(g) 2Ag2O(s) → 4Ag(s) + O2(g) The stability of a nitrate(V) salt serves as an important clue of identifying the cation. nitrogen dioxide and oxygen. Cu. T. it will decompose into oxide. E. Ag. Mg.g. they will decompose into metal. Ca. .) thermal decomposition → Non-reactive metal + Nitrogen dioxide + Oxygen Non-reactive metal nitrate(V)   e. KNO3 is an ingredient of gunpowder. thermal decomposition → Reactive metal nitrate(III) + Oxygen Reactive metal nitrate(V)   e.II. Inorganic Chemistry. 4th Edition. HgNO3(s) and AgNO3(s). Upon heating.B. Na. nitrogen dioxide and oxygen.M.g. Thermal decomposition of nitrate Upon heating. Au does not form stable solid nitrate at all. they will decompose into nitrate(III) and oxygen.g.

the salt to be test is dissolved in a freshly prepared iron(II) sulphate solution. thermal decomposition NH4NO3(s)   → N2O(g) + 2H2O(l) In this reaction. Nitrogen and its compounds Unit 3 Page 2 iv. R–NH2 + HNO2(aq) → N2(g) + ROH NH4NO2(s) may be considered as a mixture of HNO2 and NH3 NH4NO2 d HNO2 + NH3 Therefore. Concentrated sulphuric acid is then added slowly and carefully into the resulting mixture without stirring it up. It should not be heated too strongly. thermal decomposition NH4NO2 (s)   → N2(g) + 2H2O(l) 2. NH4NO2(s) decomposes upon heating to give N2(g) and H2O(l) only.B. it will sink to the bottom. a solid reagent expands suddenly to gaseous products. In brown ring test. The reactions occurring at the interface are : NO3-(aq) + H2SO4(l) → HNO3(aq) + HSO4-(aq)f HNO3(aq) + 3Fe2+(aq) + 3H+(aq) → 2H2O(l) + NO(g) + 3Fe3+(aq) FeSO4(aq) + NO(g) → FeSO4·NO(aq) a simplified formula of the brown complex or [Fe(H2O)5NO]2+](aq) Glossary thermal decomposition of ntirate brown ring test . A brown ring will form at the interface between the concentrated sulphuric acid and the aqueous layer if nitrate(V) ion is present. 0 − 5° C Recall the action of nitric(III) acid on amino group. Because concentrated sulphuric acid is denser in water. NH4NO3(s) is potentially explosive. N. therefore.II. Ammonium nitrate(V) NH4NO3(s) will decompose to dinitrogen oxide and water leaving no residue behind. Brown ring test The presence of nitrate(V) ion can be detected by brown ring test.

or Add acidified AgNO3 solution to give pale yellow ppt which is slightly / partially / sparingly soluble in excess NH3 or which darkens in colour on exposure to sunlight. NH4NO3(s) is unstable and readily/easily decomposes to give large volumes of gaseous products (N2O and H2O) 1 mark and is therefore explosive. Outline laboratory tests to identify each anion positively. DANGEROUS GOODS . identify ONE inorganic compound which is an active ingredient: ii gun powder 97 2B 8 a i 8a Suggest how the following nitrogen oxides can be prepared in the laboratory. H2SO4 to give acid vapour of HBr which gives white fumes with NH3 and reddish brown vapours of Br2 which turns fluorescein impregnated paper red. Give chemical reasons why this is necessary. giving the reagents. state the reactant(s) used and the reaction conditions. Add freshly prepared FeSO4 and conc. N2O 3 6 . the vehicle must carry a sign clearly showing : AMMONIUM NITRATE . NO SMOKING.) For NaNO3(s). H2SO4 slowly / dropwise to give brown ring at the liquid junction. 1 mark No smoking because N2O is a supporter of combustion at elevated temperature 91 1B 4 a 4a You are give two solid samples. or Add HOCl solution to give orange-red colour of bromine. 2 4 For NaBr(s). H2SO4 + Cu and heat to give brown fumes of NO2 having no action on fluorescein (C20H12O5 yellowish to red in colour) impregnated paper. i dinitrogen oxide. H2SO4 and heat / add conc. Nitrogen and its compounds Past Paper Question 91 1A 3 h 97 1A 3 a ii Unit 3 Page 3 91 1B 4 a 97 2B 8 a i 91 1A 3 h 3h When solid ammonium nitrate(V) is transported. reaction conditions and the expected observations (Equations are not required.II. add conc. In each case. and write balanced equation(s) for the reaction(s) involved. add conc. 97 1A 3 a ii 3a For each of the following materials. ½ mark for each point the Br2 dissolves in the organic solvent leaving a colourless aqueous layer. one of which is sodium nitrate(V) and the other sodium bromide. When the solution is shaken with CS2 / CHCl3 / CCl4.

) H n cellulose nitrate (nitrocellulose. Dynamite. Thomas Nelson and Sons Ltd.).N. the yellow explosive). gun-cotton are also prepared by nitration using concentrated nitric acid. Although it retains its explosive properties. invented by the Swedish chemist.3-triyl trinitrate (nitroglycerine) CH2 O NO2 12 CO2(g) + 10 H2O(g) + 6 N2(g) + O2(g) CH O NO2 CH2 O NO2 propane-1. 154–155.T. Use of nitric(V) acid Majority of nitric acid produced is used to make fertilizers and explosives. a constituent of several explosives is manufactured by nitration of propane-1. Nobel. Besides nitroglycerin. 456 Chemistry in Context (4th ed.3-triol (glycerol) propane-1.. CH2 OH CH2 O NO2 CH OH + 3 HNO3 CH O NO2 CH2 OH CH2 O NO2 propane-1. They accounts for 75% and 15% of the total consumption. 5th Edition. 320 Chemistry in Context.4. CH3 O 2N CH2ONO2 NO2 O H H ONO2 H H ONO2 NO2 methyl-2.2. the nitroglycerin is less sensitive to shock. water vapour and nitrogen are liberated to produce a very large pressure. b) Explosives Nitroglycerin. gun cotton) . Bell & Hyman. Oxygen is present in the molecule. 355–357 Reading Modern Organic Chemistry (4th ed. pg.3-triyl trinitrate (nitroglycerine) Nitroglycerine is a colourless.II.5 Page 1 Unit 4 Assignment A-Level Chemistry.2. E.2. Thomas Nelson and Sons Ltd.N. is made by allowing kieselguhr (a kind of clay from seashell) to absorb nitroglycerin.T.2. Nitrogen and its compounds Reference Reading 10. and carbon dioxide. many other explosives like trinitrotoluene (T.N.2.. Ramsden pg.6-trinitrobenzene (trinitrotoluene.3-triol using concentrated nitric acid. 3rd Edition. 316–317 Syllabus Use of nitrc(V) acid Notes E. T. a) Fertilizers Nitric acid is used in making of fertilizer such as NH4NO3 by neutralization with ammonia.). Nitrogen and its compounds Unit 4 Topic II. oily liquid which is violently exploded on slight shock.

60 º C.6-diamine are then used to make nylon-6. + HOOC CH2CH2CH2CH2 COOH Part of the hexanedioic acid is converted to hexane-1.) For example.II. Hexanedioic acid and hexane-1. H2SO4 50 . + N N H N OH diazonium ion + H2O N OH OH + naphthalen-2-ol N - OH N H azo dye (an orange red ppt.55 蚓 + N N NH2 Sn HCl NaNO2 HCl. cat. OH O 60% HNO3. NO2 HNO3 . d) Dyestuffs Azo dye is prepared by coupling diazonium ion with phenolic compound. the food colour Orange II is made by diazotising the sodium salt of 4-aminobenzenesulphonic acid and coupling the product to naphthalen-2-ol : - + SO2O Na +- Na OO2S O + N N + - N N OH Orange II Nitric acid is used to prepare nitrobenzene through which diazonium ion is prepared.6-diamine through hexanedinitrile. Nitrogen and its compounds c) Unit 4 Page 2 Nylon In industrial production of nylon.6. 0-5 蚓 benzenamine (an aromatic primary amine) diazonium ion . hexanedioic acid is manufactured by oxidation of a mixture of cyclohexanol and cyclohexanone using moderately concentrated nitric acid and a copper salt as catalyst.

N.) 97 2B 8 b iv 8b iv Give TWO major uses of ammonia in industry. Page 3 dynamite azo dye diazonium ion .T. Nitrogen and its compounds Glossary nitroglycerine Past Paper Question 97 2B 8 b iv Unit 4 trinitrotoluene (T.II.

192–194 Assignment A-Level Chemistry (3rd ed.3.). Sulphur and its compounds Unit 1 Page 1 Topic III. It turns acidified K2Cr2O7(aq) from orange to green. The atomicity of sulphur is said to be 8.0–10. Acidity – SO2(g) forms sulphurous acid. Atomicity means the number of atoms in a molecule of an element. 3.g. sulphur molecule consists of 8 sulphur atoms joined together. Sulphur and its compounds A. . Sulphur crystal Different forms of the same element in the same physical state are called allotropes of the element. Rhombic sulphur can be prepared by evaporating a solution of sulphur in carbon disulphide at room temperature while monoclinic sulphur can be prepared by cooling molten sulphur slowly at an elevated temperature. e. 426–427 Chemistry in Context (4th ed.. rhombic sulphur is more energetically stable at room temperature while monoclinic sulphur is more stable at high temperature. 2. Reducing properties – SO2(g) is a reducing agent. Smell – SO2(g) has characteristic smell.. S8 molecule has the shape like a crown. e.g. H2SO3(aq) in water which turns blue litmus paper red. or simply S8(s) + 8 O2(g) → 8 SO2(g) S(s) + O2(g) → SO2(g) Heating of sulphur Characteristics of sulphur dioxide 1.. They melts at 113ºC and 119ºC respectively. Sulphur and its compounds Unit 1 Reference Reading 10.). Allotrope of sulphur Normally. diatomic oxygen O2(g) and ozone O3(g) are two allotropes of oxygen There are several different sulphur allotropes. sulphur exists in 2 forms of crystal called rhombic sulphur and monoclinic sulphur.III. Thomas Nelson and Sons Ltd. Stanley Thornes (Publisher) Ltd. Thermodynamically. 348–351 Reading Syllabus Notes III. rhombic sulphur. John Murray (Publisher) Ltd. S8. Sulphur burns in oxygen with a blue flame and sulphur dioxide is formed. 417–418.2 Advanced Practical Chemistry. monoclinic sulphur and plastic sulphur At room temperature.3.

It is stretchable like plastic (e → f). Upon heating. the liquid becomes dark red and viscous due to the large van der Waals’ forces. (c → d → e). On standing. if the boiling sulphur is cooled rapidly. It turns into a light yellow liquid (a → b).III. However. the long chain structure will be freezed and forming plastic sulphur. S8 molecules agitate and the solid starts to melt. Each chains has up to 106 atoms. the ring will open to form short chains (b → c). it changes back to rhombic sulphur gradually. If the sulphur is heated continuously. it will boil at 444ºC and the long chain will start to break up. At this stage. . If the heating is continued. Sulphur and its compounds Unit 1 Page 2 Both rhombic and monoclinic sulphur consists of S8 molecules. The short chains join to form long chains.

sulphuric(IV) acid would be displaced from the sulphate(IV) salt. a redox reaction or a displacment reaction may be used. S(s) + O2(g) → SO2(g) This can be used to prepared sulphur dioxide industrially for the contact process in the manufacturing of sulphuric(VI) acid. SO2(g) could be prepared. the weak acid. water is also produced which has to be removed by passing through a washing bottle conc. Eventually. Depending on the amount of sulphur dioxide to be prepared. Burning of sulphur Sulphur burns in air with a blue flame to form sulphur dioxide. the SO2(g) can be collected by downward delivery or a gas syringe because it is heavier than air and quite soluble in water. H2SO4(l) is capable to oxidize copper to copper(II) ion while the acid will be reduced to SO2(g). sulphur dioxide is seldom produced by burning of sulphur in laboratory due to the complicate experimental setup required. If only a small amount of SO2(g) is required.III. Upon the addition of a strong acid e. Sulphur dioxide / sulphate(IV) salt Laboratory preparation of sulphur dioxide However. Hot conc. Eventually. HCl(aq).g. H2SO4(l). a sulphate(IV) salt would be used instead. C. → CuSO4(aq) + SO2(g) + 2H2O(l) Cu(s) + 2H2SO4(l) heat Besides SO2(g). SO32-(aq) + 2H+(aq) → H2SO3(aq) → SO2(g) + H2O(l) . Sulphur and its compounds Unit 1 Page 3 B.

× 3 Cr2O72-(aq) + 14H+(aq) + 6e. In aqueous state.0.d H2SO3(aq) + H2O(l) Eo = + 0.17 V Eo = + 1. .17 V Eo = + 1.× 5 MnO4-(aq) + 8H+(aq) + 5e. c) With bromine H2SO3(aq) + H2O(l) d 4H+(aq) + SO42-(aq) + 2eBr2(aq) + 2e.33 V Eo = + 1.5 × 10-2 mol dm-3 HSO3-(aq) + H2O(l) d H3O+(aq) + SO32-(aq) Ka2 = 6. sulphur dioxide doesn’t behave as a oxidizing agent. SO2(g) can also be reduced to S(s). Mg(s).2 × 10-8 mol dm-3 Since the dissociation is rather weak.g.d Mn2+(aq) + 4H2O(l) × 2 Overall 5SO32-(aq) + 2MnO4-(aq) + 6H+(aq) d 5SO42-(aq) + 2Mn2+(aq) + 3H2O(l) Eo = . SO2(g) weakly dissociates to HSO3-(aq) or SO32-(aq).09 V Eo = + 0. e. Unit 1 Page 4 Reducing properties of sulphur dioxide Sulphur dioxide is a soluble gas.17 V Eo = + 1. 4H+(aq) + SO42-(aq) + 2e.16 V Orange Cr2O72-(aq) will be reduced to green Cr3+(aq) by sulphur dioxide.34 V The purple colour of MnO4-(aq) will be decolorized by sulphur dioxide. a) With manganate(VII) ion H2SO3(aq) + H2O(l) d 4H+(aq) + SO42-(aq) + 2e. Oxidizing properties of sulphur dioxide Normally. 2.51 V Eo = + 1. SO2(g) + H2O(l) d H3O+(aq) + HSO3-(aq) Ka1 = 1. a) With magnesium 2Mg(s) + SO2(g) → 2MgO(s) + S(s) Magnesium burns continuously in a gas jar of sulphur dioxide to from white magnesium oxide and yellow sulphur powder.0. Sulphur and its compounds 1. H2SO3(aq) can also be written as SO2(aq) and H2O(l).d 2Br-(aq) Overall SO32-(aq) + Br2(aq) + H2O(l) d SO42-(aq) + 2Br-(aq) + 2H+(aq) Eo = .d 2Cr3+(aq) + 7H2O(l) Overall 3SO32-(aq) + Cr2O72-(aq) + 8H+(aq) d 3SO42-(aq) + 2Cr3+(aq) + 4H2O(l) Eo = .17 V Because SO2(aq) is a mild reducing agent it reacts with strong oxidizing agent like MnO4-(aq) and Cr2O72-(aq). b) With dichromate(VI) ion H2SO3(aq) + H2O(l) d 4H+(aq) + SO42-(aq) + 2e.92 V The orange colour of Br2(aq) will be decolorized. And it is observed that the redox properties of SO2(aq) and SO32-(aq) are similar.0. But in the presence of a strong reducing agent. though not as soluble as HCl(g) or NH3(g).III.

the main difference between the two is that sulphur dioxide is reducing while carbon dioxide is non-reducing. Moreover. c SO2 as reducing agent : reaction with acidified K2Cr2O7 / KMnO4 Cr2O72. K2Cr2O7/H+(aq). Glossary atomicity Past Paper Question 93 2B 5 IIc rhombic sulphur monoclinic sulphur plastic sulphur 93 2B 5 IIc II SO2 can act as an oxidant or a reductant. Both form white precipitate with limewater.+ 3SO2 + 2H+ → 2Cr3+ + 3SO42. SO32-(aq) + Ca2+(aq) → CaSO3(s) CO32-(aq) + Ca2+(aq) → CaCO3(s) SO32-(aq) + 2Ag+(aq) → Ag2SO3(s) CO32-(aq) + 2Ag+(aq) → Ag2CO3(s) SO32-(aq) + Ba2+(aq) → BaSO3(s) CO32-(aq) + Ba2+(aq) → BaCO3(s) However.g. Therefore. sulphur dioxde and carbon dioxide are quite similar in chemical properties. Unit 1 Page 5 Distinguishing from carbon dioxide Comparatively. Sulphur dioxide is much more soluble in water and is pungent in smell.+ 5SO2 + 2H2O → 2Mn2+ + 5SO42. they are be distinguished by using an oxidizing agent e. Give one reaction in each case to illustrate this. they also show certain differences.+ 5H2O or MnO4.+ 5H2O + 4H+ SO2 as oxidising agent : H2S + SO2 → S(s) + H2O (any 2 appropriate examples) 2 2 marks .III. Sulphur and its compounds 3. KMnO4/H+(aq). silver nitrate and barium chloride solutions.

This saves the fuel required to heat up the gas. H2SO4(l) to form oleum.. 2.3–10.). The gaseous mixture is directed through the catalytic converter and the heat exchanger for several times until the conversion reaches 98%. so the process is called contact process. Indeed. This will vaporize the sulphuric acid formed and cause difficulty in collection of acid. Burning sulphur S(s) + O2(g) → SO2(g) 2.4 Page 1 Unit 2 Assignment Chemistry in Context. Roasting sulphur containing ores in air 4FeS2(s) + 11O2(g) → 2Fe2O3(s) + 8SO2(g) 2ZnS(s) + 3O2(g) → 2ZnO(s) + 2SO2(g) 1. 3rd Edition ELBS pg.3. Contact process Sulphur dioxide used in contact process in obtained by 1. H2S2O7(l) is added to the correct amount of water to form conc. Concentrated sulphuric(VI) acid 1.). SO3(g) + H2SO4(l) → H2S2O7(l) 3. SO3(g) is dissolved in conc. H2S2O7(l) + H2O(l) → 2H2SO4(l) Note : SO3(g) is not added to the water directly because the reaction is highly exothermic. pg. Vanadium(V) oxide (V2O5(s)) catalyst..III. 428–434 Reading Chemistry in Context (4th ed.3. Sulphur and its compounds Reference Reading 10. 359–362 A-Level Chemistry (3rd ed. 1 atm SO2(g) + O2(g) d SO3(g) ∆H = -197 kJ mol-1 During the reaction. H2SO4(l). the conversion is done in several stages. . Thomas Nelson and Sons Ltd. Sulphur trioxide. H2S2O7(l) (also called fuming sulphuric acid). 310–311 Syllabus Notes D. Sulphur and its compounds Unit 2 Topic III. 5th Edition. Thomas Nelson and Sons Ltd. the gaseous reactant is in contact with the catalyst. Stanley Thornes (Publisher) Ltd. Because the reaction is exothermic. the hot emerging SO3(g) is diverted to the heat exchanger to heat up the incoming gas. 450 ºC. 348–350 Chemistry in Context.

Oxidation half equation Reduction half equation Cu(s) → Cu2+(aq) + 2eSO42-(aq) + 4H+(aq) + 2e. H2SO4(l) because of its strong oxidizing properties. Sulphur and its compounds Unit 2 Page 2 Effect of temperature and pressure on the yield 2SO2(g) + O2(g) d 2SO3(g) ∆H = -197 kJ mol-1 According to Le Chatelier’s principle the reaction is favored by a low temperature and a high pressure. Acid Effect of temperature on the equilibrium constant and percentage of conversion Conc. 2. the production of SO3(g) is most economical. 1 atm and 450ºC with the catalyst of V2O5(s) is a compromise between yield and rate of reaction. H2SO4(l) shows acidic properties when water is added. if the temperature is too low. ↑ Pressure ↑ Temperature yield ↑ ↓ rate of reaction ↑ ↑ Actually. It reacts with hot conc. the rate of reaction will also be lowered and a longer time will be required to reach the equilibrium. Properties of concentrated sulphuric acid i. ii. It is not worthy to use a pressure higher than 1 atm. . though a high pressure gives a higher yield. the yield at 1 atm is already 98% after several stages of conversion. However. the condition. Oxidizing properties with Cu(s) Normally. Furthermore. it turns blue because of the presence of Cu2+(aq) ion.→ SO2(g) + 2H2O(l) Ionic equation Cu(s) + SO42-(aq) + 4H+(aq) → Cu2+(aq) + SO2(g) + 2H2O(l) Full equation Cu(s) + 2H2SO4(l) → CuSO4(aq) + SO2(g) + 2H2O(l) When water is added into the reacting mixture. This requires the use of a stronger reacting vessel which is more costly to build. Cu(s) does not react will dilute sulphuric acid. At this condition.III.

Hygroscopic is the properties of absorbing water vapour from air. However. conc . It has the general formula Cx(H2O)y. H2SO4(l) can be used as a drying agent. H SO 2 4(l ) → xC(s) + yH2O(l) Cx(H2O)y(s)   According to this principle.III. H2SO4(aq) can be used as a magic ink. H2SO4(l) is also capable to oxidize the C(s) to CO2(g) and raise the spongy mass. with sugar Similarly. Conc. dil. conc. it cannot be used to dry alkaline or reducing gases. conc. H2SO4(l) is hygroscopic and dehydrating. This turns the blue crystal to white powder. Once the sulphuric acid is concentrated. Alkaline gas . H2SO4(l) is capable to extract the water from the structure of cellulose and char the paper. Hygroscopic properties Because of the hygroscopic properties.ethene C2H4(g) Dehydrating properties with copper(II) sulphate-5-water Conc. H2SO4(l) is also acidic and oxidizing. sugar is another carbohydrate. it is also charred by conc. it will char the paper and the word will appear.ammonia NH3(g) Reducing gas . By bubbling the wet gas through conc. H2SO4(l). H SO 2 4(l ) → CuSO4·5H2O(s)   blue crystal CuSO4(s) + 5H2O(l) white powder with paper The main composition of paper is cellulose which is a carbohydrate. Oxidation half equation Reduction half equation C(s) + 2H2O(l) → CO2(g) + 4H+(aq) + 4eSO42-(aq) + 4H+(aq) + 2e. conc . e. Sulphur and its compounds Unit 2 Page 3 iii. H2SO4(l).Hygroscopic and dehydrating properties Conc. the gas can be dried. Upon heating.g. The word written on the paper can be developed by heating the paper to evaporate the water. High affinity for water .→ SO2(g) + 2H2O(l) Ionic equation C(s) + 2H2O(l) + 2SO42-(aq) + 8H+(aq) → CO2(g) + 4H+(aq) + 2SO2(g) + 4H2O(l) C(s) + 2SO42-(aq) + 4H+(aq) → CO2(g) + 2SO2(g) + 2H2O(l) Full equation C(s) + 2H2SO4(l) → CO2(g) + 2SO2(g) + 2H2O(l) . H2SO4(l) removes the water of crystallization from CuSO4·5H2O(l). Dehydrating is the properties of removing water from a stable structure and this implies a structural change. since conc.

In the presence of BaCl2(aq). Ba2+(aq) + SO42-(aq) → BaSO4(s) However. H2SO4(l) is capable to displace HCl(g) from NaCl(s). Sulphate(VI) salt 1. This makes it capable to displace the more volatile. SO42-(aq) ion will be precipitated as insoluble BaSO4(s) and the solution will turn into a white suspension. H2SO4(l) is a non-volatile acid which boils at 380ºC. Non-volatile acid conc. H2SO4(l) : 380 ºC Boiling point of hydrogen chloride : -85 ºC Room temperature : 25 ºC H2SO4(l) + NaCl(s) → NaHSO4(s) + HCl(g) Even at room temperature. BaSO3(s) and BaCO3(s) will redissolve. pure HNO3(l) can be displaced from NaNO3(s). Test for sulphate(VI) ion SO42-(aq) is usually tested with BaCl2(aq) solution. Sulphur and its compounds Unit 2 Page 4 iv. They are distinguished from SO42-(aq) by addition of acid. Gentle heating is required. the boiling point of nitric acid is higher than room temperature. Displacement of hydrogen chloride Boiling point of conc. Conc. BaSO3(s) + 2HCl(aq) → BaCl2(aq) + H2O(l) + SO2(g) BaCO3(s) + 2HCl(aq) → BaCl2(aq) + H2O(l) + CO2(g) BaSO4(s) + HCl(aq) → no reaction (the ppt. Displacement of nitric acid Boiling point of nitric acid : 83 ºC Similarly. SO32-(aq) and CO32-(aq) also form white precipitate with Ba2+(aq). → NaHSO4(s) + HNO3(g) H2SO4(l) + NaNO3(s) heat E. However. hydrogen chloride is boiling. remains insoluble) Glossary contact process barium chloride vanadium(V) oxide oleum / fuming sulphuric acid hygroscopic dehydrating .III. In acidic medium.

with explanation.III. ∆H < 0 very slow in the absence of catalyst H O SO3 + H2SO4 → H2S2O7  → 2H2SO4 3 marks Steps involved: Production of SO2. 2 mark 2SO2 + O2 → 2SO3 1 mark SO3 gas is passed into conc. vanadium(V) oxide catalyst 1 mark 1 mark Effect of [O2]. give the reagent(s) used and the expected observation. For each test. 99 2A 1 c ii 1c For each of the following pairs of substances. Your answer should include the physico-chemical principles involved and also the role of any catalyst.) + H2S(g) → S(s) + 2H2O(l) + SO2(g) 1 1 mark 93 2B 5 IIa II For the industrial preparation of sulphuric(VI) acid from sulphur. removal of SO3 Conditions of conversion: 1 atm. give the chemical reactions and the conditions a under which they take place. 450ºC. S + O2 → SO2 1 mark A mixture of SO2 + O2 (slightly excess air) is passed over V2O5 catalyst at 450ºC and 1 atm. conversion to SO3. ii Na2SO3(aq) and Na2S2O3(aq) (4 marks) 6 1 5 . removal of SO3 Effect of pressure 1 mark } any 1 Effect of temperature on the equilibrium constant 1 mark 1 mark 1 mark Catalyst . Sulphur is burnt in air. Sulphur and its compounds Past Paper Question Unit 2 90 2B 5 b 92 2B 6 Bb ii 93 2B 5 IIa 98 1B 7 a iii 99 2A 1 c ii Page 5 98 2B 8 c i ii 90 2B 5 b 5b Outline an industrial preparation of sulphuric acid.lower the activation energy for the SO2 + O2 reaction as O2 is kinetically inert Overall presentation 1 mark 7 2 92 2B 6 Bb ii 6Bb What are the products of the reactions between ii concentrated sulphuric(VI) acid and hydrogen sulphide gas? H2SO4(conc. H2SO4 and then diluted with water SO3 + H2SO4 → H2S2O7 1 mark H2S2O7 + H2O → 2H2SO4 1 mark 98 1B 7 a iii 7a Briefly describe how you would test for the presence of the following chemical species in a sample of iron alum. Sulphuric acid S + O2 → SO2 2SO2 + O2 d 2SO3. (NH4)2SO4·Fe2(SO4)3·24H2O. pressure. the effect of each of the following changes on the position of the equilibrium. (I) increasing the total pressure (II) increasing the temperature ii Briefly describe how sulphur trioxide is converted to sulphuric(VI) acid in this process. iii sulphate(VI) ions 98 2B 8 c i ii 8c The conversion of sulphur dioxide to sulphur trioxide in the Contact Process involves the following : ∆Ho = -98 kJmol-1 SO2(g) + ½O2(g) d SO3(g) with V2O5(s) catalyst i State. suggest a chemical test to distinguish one from the other.

pg.. Thomas Nelson and Sons Ltd.). Sulphur and its compounds Reference Reading 10. Ca3(PO4)2(s) + 2H2SO4(l) → Ca(H2PO4)2(s) + 2CaSO4(s) (2) Ammonium sulphate(VI) is produced by the reaction of ammonia with sulphuric(VI) acid. in hot concentrated sulphuric(VI) acid. For example.5 Unit 3 Assignment Chemistry in Context (4th ed. 312 Reading Syllabus Use of sulphuric(VI) acid Notes F. the water-insoluble calcium phosphate(V) (found in phosphate ores) can be converted to the more soluble calcium dihydrogenphosphate(V) which can be used as a phosphorus fertilizer. (2) Concentrated sulphuric(VI) acid is used with concentrated nitric(V) acid in the preparation of nitrobenzene which is used for making azo dyes. TiOSO4.III. is produced by dissolving titanium(IV) oxide. sulphonic group –SO3H can be introduced to the dye molecule. . Use of sulphuric(VI) acid a) Fertilizers (1) By reacting with concentrated sulphuric(VI) acid. Pigments and Dyestuffs (1) The white pigment titanyl sulphate. Thomas Nelson and Sons Ltd. barium sulphate(VI) and calcium sulphate(VI) are used as paint additives. 2NH3(g) + H2SO4(aq) → (NH4)2SO4(aq) crystallization → (NH4)2SO4(s) (NH4)2SO4(aq)  b) Detergents Soapless detergents can be made by treating hydrocarbons from petroleum industry with concentrated sulphuric(VI) acid followed by sodium hydroxide. Sulphur and its compounds Unit 3 Page 1 Topic III. CH3(CH2)11 c) (i) conc. This group makes the dye more soluble in water and easily attached to fibre. (3) By reacting the dye with concentrated sulphuric(VI) acid. Besides.3. TiO2. 350–351 Chemistry in Context. H2SO4 (ii) NaOH CH3(CH2)11 - + SO3 Na Paints. 5th Edition.

Sulphur and its compounds Unit 3 Page 2 Uses of sulphuric acid Glossary fertilizer calcium phosphate(V) calcium dihydrogenphosphate(V) ammonium sulphate(VI) detergent paint pigment dyestuff titanyl sulphate titanium(IV) oxide barium sulphate(VI) calcium sulphate(VI) azo dye sulphonic group Past Paper Question 92 2B 6 Bc iii 92 2B 6 Bc iii iii Describe the part that H2SO4 plays in any TWO important industrial processes.III. not Contact Process Production of 'superphosphate' fertilizer 1 mark 2 marks Ca3(PO4)2 + H2SO4 → Ca(H2PO4)2 + 2CaSO4 acts as acid 1 mark or Production of fertilizer 1 mark 2 marks 2NH3(aq) + H2SO4(aq) → (NH4)2SO4(aq) acts as acid 1 mark or Manufacture of detergents or Manufacture of dyestuffs or Manufacture of drugs or Manufacture of explosives or Manufacture of rayon (artificial silk) 1 mark for function and 1 mark for process or Cleaning of metal before plating/galvanizing 2 processes required 6Bc 4 .

0 Modern Physical Chemistry ELBS pg. 3rd Edition ELBS pg. 450ºC. Your answer should include the physico-chemical principles involved and also the role of any catalyst. Chemistry in Context. removal of SO3 Conditions of conversion: 1 atm. Unit 1 Assignment Reading Syllabus Notes Glossary Past Paper Question 90 2B 5 b 81 2B 8 a i ii iii d 82 2B 10 b 84 2B 10 a i ii b 88 2B 6 d 89 2B 6 b 90 2B 5 b 5b Outline an industrial preparation of EITHER ammonia OR sulphuric acid. Fillans pg. vanadium(V) oxide catalyst 1 mark Effect of [O2].Topic Nitrogen and Sulphur Reference Reading 10.lower the activation energy for the SO2 + O2 reaction as O2 is kinetically inert Overall presentation 2 3 marks 1 mark 1 mark 1 mark 1 mark 7 . 500ºC.required because of the inertness of N2 and H2 molecules 1 mark NH3 is removed from the reaction mixture Overall presentation 1 mark Sulphuric acid S + O2 → SO2 2SO2 + O2 d 2SO3. ∆H < 0 very slow in the absence of catalyst H O → 2H2SO4 SO3 + H2SO4 → H2S2O7  Steps involved: Production of SO2. finely divided iron catalyst 1 mark Effect of temperature on the equilibrium constant 1 mark Effect of pressure 1 mark } any 2 1 mark 2 marks Effect of concentration of N2 and H2 1 mark Catalyst . removal of SO3 Effect of pressure 1 mark } any 1 Effect of temperature on the equilibrium constant 1 mark Catalyst . Ammonia N2 + 3H2 d 2NH3 ∆H < 0 / exothermic 1 mark Conditions of reaction: 200 atm. Physical Chemistry. conversion to SO3.

Give the conditions under which the various steps take place and briefly discuss which of the following will involve the highest costs: i energy. 1 mark (ii) The catalyst is expensive and it will lose and need to be refilled from time to time so it costs a lot. 1 mark each conc. 1 mark Concentrated sulphuric(VI) acid 1 mark SO2(g) is mixed with air 1 mark and the mixture is passed over a catalyst of Pt or V2O5. 1 mark The SO3(g) produced is then dissolved in 98% H2SO4 and fuming sulphuric acid (oleum) is formed.g. 1 mark Write on the present-day uses of EITHER concentrated nitric(V) acid. 1 mark 1 mark the reaction 4NH3(g) + 5O2(g) → 4NO(g) + 6H2O(g) 1 mark takes place with the evolution of heat. 1 mark 2NO2(g) + H2O(l) → 2HNO3(aq) + NO(g) the NO(g) is recycled. The operating temperature is about 450ºC at 1 atm.6-diamine which is a raw material for making nylon. 4 OR concentrated sulphuric(VI) acid. so special chemical resistant materials have to be chosen for handling. e. The gases must be pure and avoid poisoning the catalyst.T. 1 mark Absorption may be carried out up to 68%(conc. ( The lost of catalyst is due to the highly exothermic reaction produce energy which may vaporize the catalyst. SO3(g) + H2SO4(l) → H2S2O7(l) 1 mark 1 mark Oleum is then diluted with calculated amount of water so as to give back 98% H2SO4(l) SO3(g) is not dissolved directly in water to form sulphuric acid because the reaction between SO3(g) and water is violent and a mist of acid droplets forms instead of a solution. Concentrated nitric(V) acid 1 mark Ammonia(g) is mixed with air. 1 mark (ii) The catalyst is expensive and it will lose and need to be refilled from time to time so it costs a lot. Manufacture of fertilizers such as NH4NO3 Manufacture of dyestuffs Manufacture of hexane-1. . 1 mark (iii) Because SO2. 1 mark 1 mark 2SO2(g) + O2(g) → 2SO3(g) where the reaction is exothermic. Uses : 4 uses of conc. ( The lost of catalyst is due to the highly exothermic reaction produce energy which may vaporize the catalyst. 1 mark (iii) Because NO. ii capital investment in plant.81 2B 8 a i ii iii d 8a Describe I II 8d EITHER the process for the conversion of ammonia gas into (68%) nitric(V) acid. As2O3. NO2 and HNO3 are highly corrosive and toxic. passed over a Pt gauze or (Pt/Rh) 1 mark catalyst which is maintained at 800ºC and 8 atm. 1 mark Usually V2O5 is used because Pt is expensive and easily to be poisoned by impurities. Pt).) HNO3 which is the constant boiling mixture. H2SO4 Manufacture of fertilizers such as (NH4)2SO4 Manufacture of explosives Manufacture of pigments 84 2B 10 a i ii b 10a i Give the formulae of the oxides of EITHER nitrogen OR sulphur 2 . 1 mark (i) energy – the reaction condition of 450ºC is not difficult and expensive to maintain because the reaction is exothermic. 12 OR the process for the conversion of sulphur dioxide gas into (98%) sulphuric acid. HNO3 Manufacture of explosive such as T. 1 mark The NO(g) is then oxidised by further air to NO2(g) 2NO(g) + O2(g) → 2NO2(g) 1 mark which is then absorbed in water. so special chemical resistant materials have to be chosen for handling.N. and iii handling. H2SO4 and H2S2O7 are highly corrosive and toxic. (i) energy – the reaction condition of 800ºC is not difficult and expensive to maintain because the reaction is exothermic. Manufacture of soapless detergents conc. Pt). HNO3 or H2SO4.

upon oxidation. Nitrogen 1. platinium catalyst 3 marks 3. (C) with rain. 4NH3 + 5O2 d 4NO + 6H2O 600ºC. Conversion of sulphur to sulphur dioxide.N. 0(S). 1 atmosphere. Conversion of ammonia to nitrogen(II) oxide. excess oxygen or air.) of +2. 200-1000 atmosphere. -2(H2S). add water and air. 1 atmosphere.g. Conversion of nitrogen(II) oxide to nitric(V) acid. formed) 2 marks each Describe the industrial preparation of EITHER nitric(V) acid from nitrogen OR sulphuric(VI) acid from sulphur. Conversion of sulphur(IV) oxide to sulphur(VI) oxide.N. and (D) to form the element. Nitrogen (A) 5NO + 3MnO4. iron or iron oxide catalyst 3 marks 2. Redox chemistry of sulphur overall presentation 1 mark Principal oxidation states with examples 2 marks e. 4 marks O 3. 1 mark Intermediate oxidation states. give N2 or NH3. S2O32. 2 marks 2. give SO2 or SO42SO2 – through combustion of the sulphur compounds in air 1 mark SO42. +4(NO2). 4NO + 3O2 + 2H2O → 4HNO3 Room temperature. NO2/N2O4(+4). +4(SO2) and +6(SO3 or SO42-) Any sulphur containing compounds.+ 2Mn2+ + 4H+ (Purple colour decolourized / colourless solution) (B) 2Fe3+ + SO2 + 2H2O → 2Fe2+ + SO42. +4 and +6.is usually stable towards redox reactions in the absence of H+. 2NO2 + H2O → HNO3 + HNO2. 2H2SO3 + O2 → 2H2SO4 (no special observation) (D) Burning magnesium: SO2 + 2Mg → 2MgO + S (yellow / white ppt. formed) OR Mix with hydrogen sulphide: SO2 + 2H2S → 3S + 2H2O (yellow / white ppt.– oxidation in homogeneous solution. Conversion of nitrogen to ammonia. 8 atmosphere. -3(NH3).N. will undergo disproportionation in water. 2HNO2 + O2 → 2HNO3 (no special observation) (D) Electric: 2NO d N2 + O2 at 3000ºC (no special observation) OR Burning white phosphorus: 10NO + 4P → 2P2O5 + 5N2 (white fume) Sulphur (A) 5SO2 + 2MnO4. upon reduction. +4) (A) with acidified potassium manganate(VII) solution.is stable. and NO3. no catalyst required. 1 mark 6 .is usually the final product upon oxidation of any nitrogen containing compounds under drastic conditions. S or H2S are usually produced H2S is a mild reducing agent but SO42.+ 4H+ (Solution change from yellow brown to pale green / colourless) (C) SO2 + H2O → H2SO3. it is a strong oxidizing agent.+ 2H2O → 5SO42. no catalyst required. S + O2 → SO2 Burning sulphur. 3 marks Sulphur 1. N2 + 3H2 d 2NH3 450-500ºC. SO2(+4). SO3(+6) Describe what you would observe and give a balanced equation for the reaction the oxide of EITHER nitrogen (O.+ 4H+ → 5NO3. but in the presence of H+. Upon reduction. for example. Conversion of sulphur(VI) oxide to sulphuric(VI) acid. +5(NO3-) The highest oxidation state is +5. SO3 + H2SO4 → H2S2O7 H  → 2H2SO4 Add oxide to acid then dilute with water 3 marks 8 9 2 88 2B 6 d 6d Give examples of compounds of EITHER sulphur OR nitrogen to display the principal oxidation states and also give an account of their redox reactions. 1 mark Redox chemistry of nitrogen overall presentation 1 mark Principal oxidation states with examples 2 marks e. 2SO2 + O2 d 2SO3 450ºC. +2) OR sulphur (O. NO3(+6) 2 marks S: SO/S2O2(+2). 0(N2). 1 mark NO3. 1 atmosphere.g.ii 10b having oxidation numbers (O. N: NO(+2).or S4O62-.+ 3Mn2+ + 2H2O (Purple colour decolourized / colourless solution) (B) FeSO4 + NO → FeSO4·NO (Brown solution formed) (C) 2NO + O2 → NO2. (B) with an appropriate iron sulphate solution. platinium or vanadium(V) oxide catalyst.

or S4O62-.d H2S + 4H2O 1 mark 2SO42. illustrate using balanced half equations. NH3 – obtained by reduction of any nitrogen-containing compounds under drastic conditions.+ 4H+ + 2e.d NH3 + 3H2O 1 mark NO3. usually chemically insert in normal condition. Explain why an aqueous solution of either Na2SO4 or NaNO3 is not a strong oxidizing agent.+ 12H+ + 10e. having different oxidation states of N or S.d S + 4H2O 1 mark SO42.N2 is the most stable form. H2NNH2. how four possible reduction products. Depends on the nature of the reducing agents and the reaction conditions employed: Nitric(V) acid NO3.d N2 + 6H2O 1 mark NO3.d NO2 + H2O 1 mark 1 mark 2NO3.acts as an oxidizing agent 5 .+ 8H+ + 6e. For EITHER nitric(V) acid OR sulphuric(VI) acid.+ 2H+ + e.+ 4H+ + 3e.+ 9H+ + 8e. 1 mark H+ is required if SO42. may be obtained.d S2O32.d NO + 2H2O other possible product: N2O.acts as an oxidizing agent Sulphuric(VI) acid SO42.+ 10H+ + 8e. NO21 mark H+ is required if NO3. etc. Compounds in intermediate oxidation states such NO2 undergo disproportionation 2NO2 + H2O d HNO3 + HNO2 1 mark 1 mark 1 mark 89 2B 6 b 6b Nitric(V) acid and sulphuric(VI) acid can be reduced to form products having a variety of oxidation states of N or S.d SO2 + 2H2O 1 mark 1 mark SO42.

Nitrogen 10.required because of the inertness of N2 and H2 molecules 1 mark NH3 is removed from the reaction mixture Overall presentation 1 mark 7 .2. Your answer should include the physico-chemical principles involved and also the role of any catalyst. finely divided iron catalyst 1 mark Effect of temperature on the equilibrium constant 1 mark Effect of pressure 1 mark } any 2 1 mark 2 marks Effect of concentration of N2 and H2 1 mark Catalyst . 500ºC.1 90 2B 5 b 5b Outline an industrial preparation of ammonia. Ammonia N2 + 3H2 d 2NH3 ∆H < 0 / exothermic 1 mark Conditions of reaction: 200 atm.2.

1 84 2B 10 b 10b Describe the industrial preparation of nitric(V) acid from nitrogen. Nitrogen 1.2. HNO3 Manufacture of fertilizers such as NH4NO3 Manufacture of dyestuffs Manufacture of hexane-1. (C) with rain. so special chemical resistant materials have to be chosen for handling. 1 mark 1 mark the reaction 4NH3(g) + 5O2(g) → 4NO(g) + 6H2O(g) 1 mark takes place with the evolution of heat.2.6-diamine which is a raw material for making nylon. Pt).4. platinium catalyst 4 2 8 9 3 marks 3 marks .N. The gases must be pure and avoid poisoning the catalyst. 10.3. 1 mark The NO(g) is then oxidised by further air to NO2(g) 2NO(g) + O2(g) → 2NO2(g) 1 mark which is then absorbed in water. 8 atmosphere. Uses : 4 uses of conc. ( The lost of catalyst is due to the highly exothermic reaction produce energy which may vaporize the catalyst. passed over a Pt gauze or (Pt/Rh) 1 mark catalyst which is maintained at 800ºC and 8 atm. 2HNO2 + O2 → 2HNO3 (no special observation) (D) Electric: 2NO d N2 + O2 at 3000ºC (no special observation) OR Burning white phosphorus: 10NO + 4P → 2P2O5 + 5N2 (white fume) 2 marks each 10. 1 mark 2NO2(g) + H2O(l) → 2HNO3(aq) + NO(g) the NO(g) is recycled. (i) energy – the reaction condition of 800ºC is not difficult and expensive to maintain because the reaction is exothermic. NO3(+6) 2 marks ii Describe what you would observe and give a balanced equation for the reaction the oxide of nitrogen (O. +2) (A) with acidified potassium manganate(VII) solution. N: NO(+2). 2NO2 + H2O → HNO3 + HNO2. (B) with an appropriate iron sulphate solution.2.3.10. I Concentrated nitric(V) acid 1 mark Ammonia(g) is mixed with air. 1 mark Absorption may be carried out up to 68%(conc.0 84 2B 10 a i ii 10a i Give the formulae of the oxides of nitrogen having oxidation numbers (O.+ 3Mn2+ + 2H2O (Purple colour decolourized / colourless solution) (B) FeSO4 + NO → FeSO4·NO (Brown solution formed) (C) 2NO + O2 → NO2. Conversion of ammonia to nitrogen(II) oxide.+ 4H+ → 5NO3. and iii handling. 4NH3 + 5O2 d 4NO + 6H2O 600ºC. 1 mark each Manufacture of explosive such as T. NO2/N2O4(+4). HNO3. Conversion of nitrogen to ammonia.N.T.) HNO3 which is the constant boiling mixture.2. N2 + 3H2 d 2NH3 450-500ºC. iron or iron oxide catalyst 2. and (D) to form the element.5. 1 mark (ii) The catalyst is expensive and it will lose and need to be refilled from time to time so it costs a lot.) of +2. 12 Give the conditions under which the various steps take place and briefly discuss which of the following will involve the highest costs: i energy. Nitrogen (A) 5NO + 3MnO4. conc.N. 200-1000 atmosphere. ii capital investment in plant. +4 and +6.1 81 2B 8 a i ii iii 8a Describe the process for the conversion of ammonia gas into (68%) nitric(V) acid.0 81 2B 8 d 8d Write on the present-day uses of concentrated nitric(V) acid. 1 mark 10. 1 mark (iii) Because NO. NO2 and HNO3 are highly corrosive and toxic.

2.+ 4H+ + 3e. no catalyst required. upon reduction.is usually the final product upon oxidation of any nitrogen containing compounds under drastic conditions.d NO2 + H2O 1 mark + + 12H + 10e d N + 6H O 1 mark 2NO3 2 2 + 1 mark NO3 + 9H + 8e d NH3 + 3H2O 1 mark NO3. Conversion of nitrogen(II) oxide to nitric(V) acid.g. 3 marks 10. and NO3. Redox chemistry of nitrogen overall presentation 1 mark Principal oxidation states with examples 2 marks e. it is a strong oxidizing agent. +5(NO3-) The highest oxidation state is +5. how four possible reduction products. H2NNH2. add water and air.3. having different oxidation states of N.3.is stable. NO21 mark H+ is required if NO3.2 89 2B 6 b 6b Nitric(V) acid can be reduced to form products having a variety of oxidation states of N. 0(N2). but in the presence of H+. -3(NH3).+ 2H+ + e. Explain why an aqueous solution of NaNO3 is not a strong oxidizing agent.acts as an oxidizing agent 5 . usually chemically insert in normal condition.d NO + 2H2O other possible product: N2O.0 88 2B 6 d 6d Give examples of compounds of nitrogen to display the principal oxidation states and also give an account of their 6 redox reactions. give N2 or NH3. 1 mark 1 mark N2 is the most stable form. +4(NO2). 1 mark NO3. illustrate using balanced half equations. may be obtained. 1 atmosphere. Depends on the nature of the reducing agents and the reaction conditions employed: Nitric(V) acid NO3.2.4. Compounds in intermediate oxidation states such NO2 undergo disproportionation 1 mark 2NO2 + H2O d HNO3 + HNO2 10. For nitric(V) acid. 4NO + 3O2 + 2H2O → 4HNO3 Room temperature. 1 mark NH3 – obtained by reduction of any nitrogen-containing compounds under drastic conditions.

1 90 2B 5 b 5b Outline an industrial preparation of sulphuric acid. 450ºC.lower the activation energy for the SO2 + O2 reaction as O2 is kinetically inert Overall presentation 1 mark 2 7 .3. removal of SO3 Conditions of conversion: 1 atm. Your answer should include the physico-chemical principles involved and also the role of any catalyst. conversion to SO3. vanadium(V) oxide catalyst 1 mark 1 mark Effect of [O2]. ∆H < 0 very slow in the absence of catalyst H O SO3 + H2SO4 → H2S2O7  → 2H2SO4 3 marks Steps involved: Production of SO2.Sulphur 10. Sulphuric acid S + O2 → SO2 2SO2 + O2 d 2SO3.3. removal of SO3 Effect of pressure 1 mark } any 1 Effect of temperature on the equilibrium constant 1 mark 1 mark 1 mark Catalyst .

2. Sulphur 1. 1 mark The SO3(g) produced is then dissolved in 98% H2SO4 and fuming sulphuric acid (oleum) is formed. e.+ 2Mn2+ + 4H+ (Purple colour decolourized / colourless solution) (B) 2Fe3+ + SO2 + 2H2O → 2Fe2+ + SO42. H2SO4 and H2S2O7 are highly corrosive and toxic. (B) with an appropriate iron sulphate solution.+ 4H+ (Solution change from yellow brown to pale green / colourless) (C) SO2 + H2O → H2SO3.3. SO3(+6) 2 marks ii Describe what you would observe and give a balanced equation for the reaction the oxide of sulphur (O. Pt).g. and iii handling. Conversion of sulphur to sulphur dioxide. no catalyst required. H2SO4. Conversion of sulphur(IV) oxide to sulphur(VI) oxide. 1 atmosphere. SO2(+4). Manufacture of soapless detergents conc.1 81 2B 8 a i ii iii 8a Describe the process for the conversion of sulphur dioxide gas into (98%) sulphuric acid. formed) OR Mix with hydrogen sulphide: SO2 + 2H2S → 3S + 2H2O (yellow / white ppt.5. +4) (A) with acidified potassium manganate(VII) solution. 2SO2 + O2 d 2SO3 450ºC. ( The lost of catalyst is due to the highly exothermic reaction produce energy which may vaporize the catalyst. H2SO4 Manufacture of fertilizers such as (NH4)2SO4 Manufacture of explosives Manufacture of pigments 4 1 mark each 10. As2O3. 1 atmosphere. 2H2SO3 + O2 → 2H2SO4 (no special observation) (D) Burning magnesium: SO2 + 2Mg → 2MgO + S (yellow / white ppt. S + O2 → SO2 Burning sulphur. 1 mark (i) energy – the reaction condition of 450ºC is not difficult and expensive to maintain because the reaction is exothermic. 1 mark Usually V2O5 is used because Pt is expensive and easily to be poisoned by impurities. 1 mark (iii) Because SO2. The operating temperature is about 450ºC at 1 atm.) of +2.10. +4 and +6.+ 2H2O → 5SO42. S: SO/S2O2(+2).3. (C) with rain.0 84 2B 10 a i ii 10a i Give the formulae of the oxides of sulphur having oxidation numbers (O.N. 1 mark 10.N.1 84 2B 10 b 10b Describe the industrial preparation of sulphuric(VI) acid from sulphur. excess oxygen or air. 12 2 8 9 2 marks 4 marks . 1 mark 1 mark 2SO2(g) + O2(g) → 2SO3(g) where the reaction is exothermic. Sulphur (A) 5SO2 + 2MnO4.0 81 2B 8 d 8d Write on the present-day uses of concentrated sulphuric(VI) acid. platinium or vanadium(V) oxide catalyst.3. Concentrated sulphuric(VI) acid 1 mark SO2(g) is mixed with air 1 mark and the mixture is passed over a catalyst of Pt or V2O5.2.3. 1 mark (ii) The catalyst is expensive and it will lose and need to be refilled from time to time so it costs a lot.3. so special chemical resistant materials have to be chosen for handling. ii capital investment in plant.3. Give the conditions under which the various steps take place and briefly discuss which of the following will involve the highest costs: i energy. formed) 2 marks each 10. SO3(g) + H2SO4(l) → H2S2O7(l) 1 mark 1 mark Oleum is then diluted with calculated amount of water so as to give back 98% H2SO4(l) SO3(g) is not dissolved directly in water to form sulphuric acid because the reaction between SO3(g) and water is violent and a mist of acid droplets forms instead of a solution. and (D) to form the element. Uses : 4 uses of conc.

having different oxidation states of S.3.+ 4H+ + 2e. etc.or S4O62-.d S + 4H2O 1 mark SO42.is usually stable towards redox reactions in the absence of H+. 1 mark H+ is required if SO42. Redox chemistry of sulphur overall presentation 1 mark Principal oxidation states with examples 2 marks e.or S4O62-. S or H2S are usually produced H2S is a mild reducing agent but SO42. 1 mark Intermediate oxidation states. illustrate using balanced half equations.g. Depends on the nature of the reducing agents and the reaction conditions employed: Sulphuric(VI) acid SO42. -2(H2S). SO3 + H2SO4 → H2S2O7 H Add oxide to acid then dilute with water marks 2 3 10. For Sulphuric(VI) acid. Upon reduction. O  → 2H2SO4 Conversion of sulphur(VI) oxide to sulphuric(VI) acid. upon oxidation.d S2O32. S2O32. give SO2 or SO42SO2 – through combustion of the sulphur compounds in air 1 mark SO42.d SO2 + 2H2O 1 mark 1 mark SO42.3.3.d H2S + 4H2O 1 mark 2SO42. 1 mark 10.2 88 2B 6 d 6d Give examples of compounds of sulphur to display the principal oxidation states and also give an account of their redox reactions.3.– oxidation in homogeneous solution. 0(S). how four possible reduction products. Explain why an aqueous solution of either Na2SO4 is not a strong oxidizing agent.3. for example.+ 10H+ + 8e. may be obtained.+ 8H+ + 6e. +4(SO2) and +6(SO3 or SO42-) Any sulphur containing compounds. will undergo disproportionation in water.acts as an oxidizing agent 6 5 .2 89 2B 6 b 6b Sulphuric(VI) acid can be reduced to form products having a variety of oxidation states of S.

d-Block Elements
I.

General features of the d-block elements from Sc to Zn
A.
B.
C.

II.

Electronic configuration of d-block elements
Electronic configuration of ions of d-block elements
1.
Stability of different ions
Comparison of properties between d-block and s-block metals
1.
Physical properties
a)
Ionization enthalpies and electronegativity
b)
Melting point and hardness
c)
Atomic radii of d-block elements
d)
Densities
2.
Chemical properties
a)
Reaction with water

Characteristic properties of the d-block elements and their compounds:
A.

B.

C.
D.

E.

Variable oxidation states
1.
Common oxidation states of vanadium and manganese compounds
a)
Vanadium compounds
b)
Manganese compounds
Complex formation
1.
Relative stability of complex ion
a)
Basicity of the ligand
b)
Chelate effect
2.
Stability constant
3.
Aquaton isomerism
4.
Geometrical isomerism
5.
Nomenclature of complexes
Coloured ions
1.
Origin of the colour
2.
Colours of different ions
Catalytic properties of transition metals and their compounds
1.
Haber process
2.
Reaction between peroxodisulphate(VI) and iodide ions
3.
Decomposition of hydrogen peroxide
Magnetic properties of transition metal and ion

d-Block Elements

Unit 1

Page 1

Topic

d-block Elements

Unit 1

Reference
Reading

11.1.0–11.1.1
Chemistry in Context, 3rd Edition ELBS pg. 292–295
Inorganic Chemistry, 4th Edition, T.M. Leung pg. 192–196
A-Level Chemistry, 3rd Edition, E.N. Ramsden pg. 490

Assignment Chemistry in Context, 5th Edition, Thomas Nelson and Sons Ltd. pg. 249–251
Reading
Syllabus
Notes

I.

General features of the d-block elements from Sc to Zn

A. Electronic configuration of d-block elements
d-block elements are usually defined as those with partially filled d-orbitals or forms compound with partially filled
d-orbitals. Or they may be defined as those situated between s-block and p-block elements. However, according to
the first definition, Sc and Zn would be excluded since they only form Sc3+ and Zn2+ ions which do not have
partially filled d-orbitals. In certain extent, Sc and Zn resemble the properties of s-block metals more than other dblock metals.
3d
4s
21Sc

[Ar] 3d14s2

[Ar]

2

2

[Ar]

23V

3

[Ar] 3d 4s

2

[Ar]

24Cr

[Ar] 3d54s1

[Ar]

22Ti

[Ar] 3d 4s

5

25Mn

[Ar] 3d 4s

2

[Ar]

26Fe

[Ar] 3d64s2

[Ar]

7

27Co

[Ar] 3d 4s

2

[Ar]

28Ni

[Ar] 3d84s2

[Ar]

10

29Cu

[Ar] 3d 4s

1

[Ar]

30Zn

[Ar] 3d104s2

[Ar]

10000
11000
11100
11111
11111
21111
22111
22211
22222
22222

2
2
2
1
2
2
2
2
1
2

half-filled 3d and 4s orbitals

full-filled 3d and half-filled 4s orbitals

B. Electronic configuration of ions of d-block elements
When 3d orbital is empty, the energy of 4s orbital is lower than that of 3d orbital due to the penetration effect of 4s
orbital despite of the further position of 4s orbital from the nucleus. However, if 3d orbital is occupied, the electron
in the 3d orbital will offer a primary shielding effect on the 4s electrons and makes them more energetic. Therefore,
when an atom from Sc to Zn is going to lose its electron, 4s electrons will be lost first instead of the 3d electron.

Element
[Ar] 3d14s2
21Sc
[Ar] 3d24s2
22Ti
[Ar] 3d34s2
23V
[Ar] 3d54s1
24Cr
[Ar] 3d54s2
25Mn
[Ar] 3d64s2
26Fe
[Ar] 3d74s2
27Co
[Ar] 3d84s2
28Ni
[Ar] 3d104s1
29Cu
[Ar] 3d104s2
30Zn

Oxidation State
+2

+1

3+

Cu+

[Ar] 3d10

Mn2+
Fe2+
Co2+
Ni2+
Cu2+
Zn2+

[Ar] 3d5
[Ar] 3d6
[Ar] 3d7
[Ar] 3d8
[Ar] 3d9
[Ar] 3d10

Sc
Ti3+
V3+
Cr3+
Mn3+
Fe3+
Co3+

+3
[Ar]
[Ar] 3d1
[Ar] 3d2
[Ar] 3d3
[Ar] 3d4
[Ar] 3d5
[Ar] 3d6

d-Block Elements

Unit 1

Page 2

Except Sc and Zn, other transition
metals are capable to form compounds
with more than 1 oxidation state. The
ions listed above are only common
ones. For an oxidation state higher
than 3, metals never exist as simple
ions due to the high charge density.
Probably, they will form complex with
ligands or covalently bonded to other
atoms.

1.

Stability of different ions

Comparing Mn2+ [Ar] 3d5 and Mn3+ [Ar] 3d4, it is found that Mn2+ is the more stable one in natural environment.
This can be explained by the presence of half filled d-orbital of Mn2+. The same logical also applies to Fe2+ and
Fe3+ where Fe3+ is the more stable one.
However, considering Cu+ [Ar] 3d10 and Cu2+ [Ar] 3d9, Cu2+ is the more abundant one in nature despite of the fullfilled d-orbital of Cu+. This seems to be contradictory.
When we discussed the stability of ion, we only considered the stability of the electronic configuration of an
isolated ion only. In the nature, ions are not isolated. They may be solvated or forming compounds with the other
ions.
In aqueous state, two Cu+(aq) ions are capable to undergo disproportionation to give a Cu(s) atom and a Cu2+(aq) ion.
Cu+(aq) + e- d Cu(s)
Cu2+(aq) + e- d Cu+(aq)

Eo = +0.52 V
Eo = +0.15 V

2Cu+(aq) d Cu2+(aq) + Cu(s)

Eo = (+0.52V) + (-0.15V) = +0.37V (energetically feasible)

Therefore, aqueous Cu+(aq) does not exist. Cu(I) compound only exists in solid state or if complexed.

Glossary

d-block elements

Past Paper
Question

91 2B 6 a i
92 2B 4 a i ii iii
94 2B 5 a i ii iii
95 1A 2 f i ii iii
96 2B 6 a
99 1A 3 a

half-filled orbital

full-filled orbital

91 2B 6 a i
6a i
What is the meaning of ‘d-block element’?
Element which has incompletely filled d orbital when combined in compounds
(or complete in case of Zn)
between s and p block

1
1 mark
½ mark

but Mn2+ ions are not readily oxidized to Mn3+ ions. Mn2+ [Ar] 11111 1 mark 2+ 1 mark Fe [Ar] 21111 iii Explain briefly why Fe2+ ions are easily oxidized to Fe3+ ions.d-Block Elements Unit 1 92 2B 4 a i ii iii 4a i Using the ‘electrons-in-boxes’ representation./ Cr2O72. CrO42. Removing e. 3 Mn2+ with half-filled 3d orbitals is relatively stable.from the outermost shell will attain the relatively stable e. Therefore. or name (any chromium(VI) compound) 1 mark ii 1 1 1 mark 96 2B 6 a 6a Using the "electrons-in-boxes" representation. write the electronic structure outside the argon core for Mn2+ and Fe2+ respectively. Fe2+ with an electronic configuration of d6. 3d 1 mark [Ar] 11100 V2+ + Cu [Ar] 22222 1 mark 99 1A 3 a 3a Deduce the number of unpaired electrons for Fe3+(g) at its ground state.disturbs this stable configuration. 1 mark iii Why is the copper(I) ion unstable in aqueous solution? 29Cu 22222 1 0 24Cr 2Cu 2+ ( aq )   → Cu disproportionation 2 3+ ii + ( aq ) Page 3 + Cu( s ) 1 1 ½ mark for disproportionation and ½ mark for correct product 94 2B 5 a i ii iii 5a Manganese and iron are d-block elements. 1s 2s 2p 3s 3p 3d 4s 4p 4d 1 0 0 000 0 000 00000 0 000 00000 1s 2s 2p 3s 3p 3d 4s 4p 4d 2 2 222 2 222 11110 0 000 00000 What is the highest possible oxidation state of chromium ? +6 / VI iii Give a chromium compound in which chromium is in its highest oxidation state. Cu+ d10 is expected to be more stable than Cu2+ d9 since it has completely filled d-orbital. give the electronic structure outside the argon core of Cu and Cr3+./ HCrO4./ CrO2Cl2 / CrO3 etc.configuration with half-filled 3d orbitals. 1 mark 95 1A 2 f i ii iii 2f i Show the electronic configuration of a ground state Cr2+ ion by filling in the appropriate boxes below. . 3d 4s 3d 4s 11100 0 1 mark each Which of the two ions. relatively high 2 marks energy is required. the Fe2+ ions are easily oxidized to Fe3+. after removal of an e. has the more stable electronic structure? Give an explanation. 1 mark 2 ii Using the “electron-in-boxes” representation. i What do you understand by the term “d-block element”? 1 Elements with partially filled d-orbitals. write the ground state electronic structure outside the argon core for 2 V2+ and Cu+ respectively. Therefore. Mn2+ is not readily oxidized to Mn2+. copper(I) or copper(II).

from metallic properties to non-metallic properties. the increase in nuclear charge has been effectively shielded and the attraction between the nucleus and the 4s electrons (valence electrons) would remain rather constant on moving across the period. This is different from the situation in the main group. Physical properties Main group elements (s-block and p-block) show a considerable change in properties on moving across a period. As a result. unlike the change from Ne to Na.e. the 1st I.E. Comparing with main group elements. . comparing with the main group elements. of d-block elements are rather constant. all elements in the first transition period share similar properties.g. where the shielding effect is primary in nature. the ionization energies do not raise sharply across the transition period. from Sc to Cu).1.2 Modern Physical Chemistry ELBS pg. This can be interpreted as a rather constant effective nuclear charge experienced by the outermost electron. doesn't drop sharply either. Comparison of properties between d-block and s-block metals 1. They are all hard. pg. The weak shielding effect can be explained by the diffuse nature of d-electrons.E. Fillans pg. The primary shielding effect of the d-electrons must not be very strong. 5th Edition. Physical Chemistry. Page 1 Unit 2 Assignment Chemistry in Context. 3rd Edition ELBS pg. These properties can be explained by the weak shielding effect of diffuse d-electrons and a rather constant effective nuclear charge experienced by the valence electron on moving across the period. On moving across the first transition period. However.d-Block Elements Unit 2 Topic d-Block Elements Reference Reading 11. As a result of the stronger primary shielding effect. 251–254 Reading Syllabus Notes C. i. the I. where an electron is added to s or p orbital on moving across the period and the shielding effect is only secondary in nature. Thomas Nelson and Sons Ltd. a) Ionization enthalpies and electronegativity On moving across a transition period (e. dense and comparatively less reactive. electrons are added to the 3d oribitals which will impose a primary shielding effect on the 4s electrons (valence electron). Chemistry in Context.

The difference in strength of a metallic bond can be explained by the effective nuclear charge and the no. of s-block elements (419-516 kJmol-1). the availability of the delocalized electrons are also higher. For the same reason. Nevertheless. thus less metallic. First of all. the availability of the delocalized electrons will be lowered. Furthermore. i. d-block elements are more electronegative. Therefore. the melting point increases gradually and drops when approaching the end of the period with a depression in the middle. Since Mn has a half-filled 3d orbital and full-filled 4s orbital. comparing with s-block element. Any further increase in effective nuclear charge will lower the availability of delocalized electron and make the melting point drop. b) Melting point and hardness Both melting point and hardness are indications of the strength of the metallic bond. It is observed that on moving across the first transition period. It is found that the melting point and hardness of dblock elements are much higher than that of s-block elements. the effective nuclear charge experienced by the valence electrons of d-block metal is higher than that of s-block metal because of the poor shielding effect of diffuse d-electrons. The increase is due to the general increase in effective nuclear charge experienced by the valence electrons and availability of delocalized electron. the primary shielding effect of the diffuse d-electrons must be not as effective as the primary shielding effect found in s-block elements. less electropositive. of delocalized electrons available. 3d 21Sc 1 2 2 2 [Ar] 3d 4s 22Ti [Ar] 3d 4s 23V [Ar] 3d34s2 24Cr [Ar] 3d54s1 5 2 25Mn [Ar] 3d 4s 26Fe [Ar] 3d64s2 27Co [Ar] 3d74s2 28Ni [Ar] 3d84s2 29Cu [Ar] 3d104s1 30Zn [Ar] 3d104s2 4s 10000 [Ar] 11000 [Ar] 11100 [Ar] 11111 [Ar] 11111 [Ar] 21111 [Ar] 22111 [Ar] 22211 [Ar] 22222 [Ar] 22222 2 [Ar] 2 2 2 1 2 2 2 2 1 half-filled 3d and 4s orbitals full-filled 3d and half-filled 4s orbitals . d-block metals can use its 3d electrons on top of the 4s electrons in the formation of metallic bond. the electronegativities of the d-block elements are rather constant and only shows a gradual increase across the period. When we look at the electronic configuration of Mn.E of d-block elements (631-906 kJmol-1) comparing with the lower 1st I. the weak shielding effect also accounts for the high I.d-Block Elements Unit 2 Page 2 Furthermore.e.E. it will not be surprised that it has a melting point much lower than the expected.

86 FCC 1. d) Densities Owing to the small atomic sizes.1 BCC : body centered cubic (not a close packing) FCC : face centered cubic (a close packing) HCP : hexagonal close packing (a close packing) .9 HCP 7. However. of electrons becomes significant.9 FCC 8. the d-block metals are much denser than the s-block metals. the size of the atom gets larger as the repulsion among the larger no.0 HCP 4.9 FCC 8. structure density g/cm3 19K 20Ca 21Sc 22Ti 23V 24Cr 25Mn 26Fe 27Co 28Ni 29Cu 30Zn BCC 0. comparing with the s-block metals. strong metallic bond and close crystal packing. the atomic radii of d-block elements are quite small and rather constant across the period.9 FCC 8. the atomic size decreases gradually due to the small increase in effective nuclear change and remain constant thereafter.d-Block Elements c) Unit 2 Page 3 Atomic radii of d-block elements For similar reasons.1 BCC 7.5 BCC 6. On moving across the period.2 BCC 7. a small variation is observed.55 HCP 3.4 BCC 7. On reaching the end of the transition period.

Glossary Past Paper Question Page 4 . d-block metals are much less reactive towards water than s-block metals do.d-Block Elements 2. This is parallel to low electropositivity of d-block elements. Unit 2 Chemical properties a) Reaction with water In general.

K only forms +1 but not +2 ion. Variable oxidation states Unlike s-block metals.g. the no. Concerning the energetic of formation of ion. One of the explanations to this phenomenon is the small difference in energy between the (n-1)d and ns electrons. 5th Edition. of possible oxidation states increases from Sc and reaches the maximum at Mn due to the increase in the number of d-electrons. this will cause a moderate increase in successive ionization energies. the formation of the highest oxidation state would be preferable. many transition metals are capable to form compounds with more than one oxidation state. the formation of the lowest oxidation state would be preferable. e. 254–257 Reading Syllabus Variable oxidation states Notes II. The no. Consequently. e. Thereafter. If the difference in successive ionization energy is large. Ca only forms +2 ion but not +1 ion. Physical Chemistry.g. 3rd Edition ELBS pg. the energy of (n-1)d electron will decrease moderately as the p to e. Characteristic properties of the d-block elements and their compounds: A. As the energy of (n-1)d and ns electrons are similar. Chemistry in Context. Therefore.2. formation of compounds with variable oxidation state must be due to a moderate and gradual increase in successive ionization energies.1 Modern Physical Chemistry ELBS pg.ratio increase.d-Block Elements Unit 3 Topic d-Block Elements Reference Reading 11. once a ns electron is removed. Fillans pg. of possible oxidation states decreases from Fe to Zn as the nuclear charge and ionization energies increase. Thomas Nelson and Sons Ltd. if the difference in successive ionization energy is small. pg. Page 1 Unit 3 Assignment Chemistry in Context. .

(∆ I.g. As a result. Their existence can be demonstrated by shaking a solution of ammonium vanadate(V) (NH4VO3) with zinc power in dilute sulphuric acid. green and eventually violet since zinc is a very strong reducing agent which is capable to reduce V(V) to V(II) stepwise.→ V2+(aq) this is not a redox reaction. ions with more than 3+ charge do not exist freely at all due to the high charge density of the ion. blue.g. 1.E.→ V3+(aq) + H2O(l) V3+(aq) + e. are rather constant while the gap between second I.→ VO2+(aq) + H2O(l) VO2+(aq) + 2H+(aq) + e.g. . This reflects the increasing difficulty of removing a 3d electron as the nuclear charge increases. and third I. When approaching the end of the transition period. VO3-(aq) + 2H+(aq) → VO2+(aq) + H2O(l) VO2+(aq) + 2H+(aq) + e.E. Mn(VII). +3.) 7975 (2088) 8144 (1670) 6985 (2045) First 5 successive ionization energies On moving across the transition period. widens. (∆ I. the elements at the beginning of the transition period favours the formation of +3 oxidation state. the gap between first I.) 4412 (1361) 4912 (3767) 3249 (1740) 4th I.E.E. and second I.E.) 3051 (2632) 1145 (555) 1509 (792) Page 2 3rd I.E.d-Block Elements Unit 3 kJmol-1 K Ca Mn 1st I.E. MnO4-). 419 590 717 2nd I.E. V(V) white → V(V) yellow V(V) yellow → V(IV) blue V(IV) blue → V(III) green V(III) green → V(II) violet Upon shaking. the formation of +2 oxidation state is more favorable.E. (∆ I. They are either covalently bonded (e.E.) 5887 (1475) 6474 (1562) 4940 (1691) 5th I. +4 and +5 are the common oxidation states of vanadium compound. Common oxidation states of vanadium and manganese compounds a) Vanadium compound +2. Although many transition metals are capable to form compounds with high oxidation state e.E.E.E. (∆ I. the solution will turn from yellow. Mn2O7) or complexed (e.

Please note that the scales of both x and y axes are reversed so that the half-equations will be in line with the definition of reduction potential and the order of the electrochemical series. . the combination with an anticlockwise direction as shown on the diagram on the right would be energetically feasible. For any two half-equations.00V) = +0.d-Block Elements Unit 3 Page 3 The following is an electrode potential .oxidation state chart Regarding the use of the chart.23V Since the overall Eo is positive. Electrode potential . Similarly.g. I-(aq) is capable to reduce VO2+(aq) to VO2+(aq) but neither Fe2+(aq) nor I-(aq) is capable to reduce VO2+(aq) further to V3+(aq) according to the chart. e.77V) + (1.oxidation state chart which can be used to predict the energetic feasibility of a redox reaction. Zn(s) + Fe2+(aq) → Zn2+(aq) + Fe(s) Zn2+(aq) + Fe(s) → Zn(s) + Fe2+(aq) energetically feasible energetically not feasible Example Fe2+(aq) can be used to reduce VO2+(aq) to VO2+(aq) Fe2+(aq) + VO2+(aq) + H2O(l) → Fe3+(aq) + VO2+(aq) + 2H+(aq) Eo = (-0. there is a rule called anticlockwise rule. the value of Eo doesn't tell anything about the kinetic feasibility of the reaction. the change is energetically feasible. However.

77 KMnO4(s) is one of the most popular strong oxidizing used in the laboratory.51 V MnO4-(aq) + 8H+(aq) + 5e.68 + 1.d Mn2+(aq) + 4H2O(l) MnO4-(aq) + 4H+(aq) + 3e. If MnO4-(aq) is used as a very strong oxidizing agent.d H2O2(aq) MnO2(s) + 4H+(aq) + 2e.d-Block Elements Unit 3 Page 4 2) Manganese compounds +2. acidic medium will be used. MnO4-(aq) will be converted to MnO2(s) instead.d MnO2(s) + 2H2O(l) H2O2(aq) + 2H+(aq) + 2e. Eo = + 1.d 2H2O(l) Eo / V + 0.51 + 1. when MnO4-(aq) is reduced.d 4OH-(aq) Cu+(aq) + e.70 V MnO4-(aq) + 4H+(aq) + 3e.d MnO2(s) + 4OH-(aq) 2H+(aq) + O2(g) + 2e.54 + 0.70 + 1. From the value of Eo. It will be converted to colourless Mn2+(aq). MnO4-(aq) shows a even stronger oxidizing power in less acidic medium with the formation of the brown MnO2(s) ppt. 4MnO4-(aq) + 4H+(aq) → 4MnO2(s) + 3O2(g) + 2H2O(l) In acidic medium.49 + 1.d Mn2+(aq) + 2H2O(l) Mn3+(aq) + e.52 + 0.59 + 0. O2(g) + 2H2O(l) + 2e. Eo = + 1.40 + 0.d Mn2+(aq) MnO4-(aq) + 8H+(aq) + 5e.d MnO2(s) + 2H2O(l) Therefore. +4 and +7 are the three most common oxidation states of manganese compound. alkaline medium may be used.d Cu(s) I2(aq) + 2e. Glossary variable oxidation state . The oxidizing power of MnO4-(aq) is so strong that it is capable to oxidize water and give O2(g) and MnO2(s) slowly. Common manganese containing species +2 +3 +4 +6 +7 Mn2+(aq) colourless (or very pale pink) Mn2O3(s) brown. This reaction can be accelerated by light therefore KMnO4(aq) have to be stored in a brown bottle.d 2I-(aq) MnO42-(aq) + 2H2O(l) + 2e.d Mn2+(aq) + 4H2O(l) In less acidic or alkaline medium. when MnO4-(aq) is used as a testing agent or an ordinary oxidizing agent.23 + 1. Mn3+(aq) red MnO2(s) brown MnO42-(aq) green MnO4-(aq) purple The energetic feasibility of redox reaction involving manganese can also be predicted by using the standard electrode potential as mentioned above.

MnO4. it will decompose to form brown MnO2 3 2 1 mark 1 mark . NH4VO3. Sn2+. I1 mark Blue ½ mark (II) by Zn or Zn/HCl 1 mark Violet ½ mark 94 2B 5 b i 5b Account for each of the following: i KMnO4 solutions are best stored in brown bottles. (I) by mild reductants e.is unstable in the presence of sunlight. oxalate. and give the colours of the products. Fe2+.d-Block Elements Past Paper Question Unit 3 Page 5 91 2B 6 a iv 94 2B 5 b i 91 2B 6 a iv 6a iv State the reagents you would employ to obtain (I) vanadium(IV) and (II) vanadium (II) from vanadium(V) in an acidic solution of ammonium metavanadate. H2S.g. SO2.

The dative covalent bond formed in this way would be much strong than the ordinary ion-dipole attraction.g. NC Ag CN + NC Cu 2+ 3- CN H3N CN H3N Pt NH3 NH3 CN 2+ H2O H2O H2O Co OH2 OH2 H2O linear complex tetrahedral complex square planar complex octahedral complex . anhydrous NaCl(s) crystal will be obtained from the NaCl(aq) solution while only [Co(H2O)6]Cl2(s) will be obtained from the CoCl2(aq) solution.d-Block Elements Unit 4 Topic d-Block Elements Reference Reading 11. water. if the ion possesses a very high charge density and a low lying energy vacant orbital. Complex formation When an ion is placed in a polar solvent e. the ion may be capable to form a dative covalent bond with the lone pair from the solvent molecule. 269–270 Reading Syllabus Notes B.2. Fillans pg. The molecules which form dative covalent bond with the ion (or an atom) are called ligands. a complex is also called a coordinated compound and the dative covalent bond formed is called coordinate bond.2 Modern Physical Chemistry ELBS pg. 201–207. Thomas Nelson and Sons Ltd. both of them will dissolve and the ions will be hydrated. it will be hydrated due to the electrostatic attraction between the ion and water molecules. Furthermore. 257–258. Page 1 Unit 4 Assignment Chemistry in Context. Moreover. However. For example. The species with the ion (or the atom) joining together with the ligands is called a complex. when anhydrous NaCl(s) and anhydrous CoCl2(s) are dissolved in water. 5th Edition. 3rd Edition ELBS pg. the comparatively higher electronegativity of d-block elements also favours the formation of dative covalent bond. Chemistry in Context. upon crystallization. Physical Chemistry. Because the ion is coordinated with ligands. pg.

they will form insoluble ppt. Sometimes. At the same concentration. NH3 molecule is also a stronger ligand than H2O molecule.2 NH3 HCN 9. the strength of a ligand is also depending on the no. Fe2+(aq) and Fe3+(aq) do not form soluble complex with ammonia molecules. b) Chelate effect Besides the basicity. the strong ligand is capable to displace the weak ligand from a complex.e. This is because the two water molecule ligands at axial positions are only loosely held. A ligand which is capable to form 1 dative covalent bond is called a monodentate ligand. Iron(II) [Fe(Cl)4]2-(aq) Iron(III) [Fe(Cl)4]-(aq) yellow Cobalt(II) H2O CN[Fe(CN)6]3-(aq) [Fe(H2O)6]3+(aq) d d colourless/yellow red [Co(Cl)4]2-(aq) blue Copper(II) [Cu(Cl)4]2-(aq) yellow N. Indeed.74 H2O HCl -7 Cl- NH4+ 9. NH3 and CNparent acid pKa conjugate base H3O+ -1. . stability of a complex ion is depending on the strength of the dative bond. of dative covalent bond that the ligand can form. a ligand which is capable to form 2 dative covalent bonds is called a bidentative ligand etc. If the concentrations are not the same. of Fe(OH)2(s) and Fe(OH)3(s) with the hydroxide ions in the ammonia solution and remain undissolved. Unit 4 Page 2 Relative stability of complex ion a) Basicity of the ligand Basically. The complexes are sometimes regarded as square planar instead of octahedral. For a given central ion. the strength of the coordinate bond is depending on the electron donating ability of the ligand i. basicity (or nucleophilicity) of the ligand. H2O. the stronger will be the ligand.d-Block Elements 1. Consider the ligands Cl-. H2O CN[Fe(CN)6]4-(aq) [Fe(H2O)6]2+(aq) d d green yellow H2O NH3 CN[Co(NH3)6]2+(aq) [Co(CN)6]4-(aq) [Co(H2O)6]2+(aq) d d d pink deep red H2O NH3 CN[Cu(NH3)4(H2O)2]2+(aq) [Cu(CN)4]2-(aq) [Cu(H2O)6]2+(aq) d d d blue deep blue Upon addition of aqueous NH3(aq). the larger the no. the equilibrium position may be shifted back. of bond a ligands can form. the complexes of Cu2+ are written as [Cu(H2O)4]2+(aq) instead of [Cu(H2O)6]2+(aq) and [Cu(NH3)4]2+(aq) instead of [Cu(NH3)4(H2O)2]2+(aq). In general.B.3 CN- basicity of the conjugate base increase → NH3 molecule is a strong base than H2O molecule.

one bidentate ligand e. Besides the displacement of ligand. Kst. The displacement of the ligands may also be expressed in consecutive steps Cu2+(aq) + NH3(aq) d [Cu(NH3)]2+(aq) [[Cu(NH3)]2+(aq)] K1 = [Cu2+ ][NH ] (aq) 3(aq) [Cu(NH3)]2+(aq) + NH3(aq) d [Cu(NH3)2]2+(aq) [[Cu(NH3)2]2+(aq)] K2 = [Cu(NH )]2+ ][NH ] (aq) 3 3(aq) [Cu(NH3)2]2+(aq) + NH3(aq) d [Cu(NH3)3]2+(aq) [[Cu(NH3)3]2+(aq)] K3 = [Cu(NH ) ]2+ ][NH ] (aq) 3 2 3(aq) [Cu(NH3)3]2+(aq) + NH3(aq) d [Cu(NH3)4]2+(aq) [[Cu(NH3)4]2+(aq)] K4 = [Cu(NH ) ]2+ ][NH ] (aq) 3 3 3(aq) K 1 × K2 × K3 × K4 = [[Cu(NH3)2]2+(aq)] [[Cu(NH3)3]2+(aq)] [[Cu(NH3)4]2+(aq)] [[Cu(NH3)]2+(aq)] × × × 2+ 2+ 2+ [Cu (aq)][NH3(aq)] [Cu(NH3)] (aq)][NH3(aq)] [Cu(NH3)2] (aq)][NH3(aq)] [Cu(NH3)3]2+(aq)][NH3(aq)] = [[Cu(NH3)4]2+(aq)] [Cu2+(aq)][NH3(aq)]4 = Kst . There is an overall change in the no. there are 3 particles.e. the stronger would be the complexing ability of the ligand. At the reactant side. of molecules and disorderness of the system.g.2-diamine (H2NCH2CH2NH2 or ethylenediamine or en) displaces two water molecules from the complex. Stability constant The strength of a ligand can be expressed as an equilibrium constant called stability constant. there are only 2 particles but at the product side. of particles in this reaction. i. there is an overall increase in the no.d-Block Elements Unit 4 Page 3 Consider the following example [M(H2O)6]2+(aq) + bi → [M(bi)(H2O)4]2+(aq) + 2H2O(l) n+ bi H2O H2O M H2O OH2 OH2 + bi H2O H2O M H2O OH2 H2N n+ CH2 CH2 NH2 + 2H2O H2O a bidentate ligand bi : a bidentate ligand In the above reaction. The extra strength of a polydentate ligand due to increase in disorderness is called chelate effect. ∆S increase. Consider the formation of a complex in aqueous medium Cu2+(aq) + 4NH3(aq) d [Cu(NH3)4]2+(aq) Cu2+(aq) ≡ [Cu(H2O)6]2+(aq) ≡ [Cu(H2O)4]2+(aq) [Cu(NH3)4]2+(aq) ≡ [Cu(NH3)4(H2O)2]2+(aq) [[Cu(NH3)4]2+(aq)] Kst = [Cu2+ ][NH ]4 (aq) 3(aq) The larger the value of Kst. 2. ethane-1.

the no. e. 4. [Fe(CN)6]3.g. 3. Cr(H2O)6Cl3 is one of the examples. CN. Page 4 Aquation isomerism Some coordinated compounds share the same empirical formula but when dissolved in water. in certain cases. cations are named first and anions second. .) e. Cl. Latin name will be used.or trans.B. Structural formula [Cr(H2O)6]Cl3 [CrCl(H2O)5]Cl2·H2O [CrCl2(H2O)4]Cl·2H2O 4. Cl-(aq) Colour Violet Blue-green Green Geometrical isomerism Tetra-coordinated complex Square planar complex [MA2B2]n+ n+ B n+ A A B A M A B M B cis-isomer trans-isomer Hexa-coordinated complex Octahedral complex [MA2B4]n+ n+ A B [MA3B3]n+ B B M B B A N. H2NCH2CH2NH2 is just called ethane-1.hexacyanoferrate(III) ion 5. 2. e. B B cis-isomer B B n+ B B M A B n+ A M B trans-isomer n+ A A M A B A meridional isomer A A facial isomer The exact geometry of a complex cannot be predicted by the Valence Shell Electron Pair Repulsion Theory that have been studied. The oxidation state of the metal is indicated in parentheses. Like all ionic compounds.2-diamine Exceptions : H2O is called aqua and NH3 is called ammine.g. 5. Ions present in aqueous solution [Cr(H2O)6]3+(aq). The negative ligands are placed before the neutral ligands in the name. Nomenclature of complexes Naming of a complex is based on the name of the ligand. tetra etc. 3Cl-(aq) [CrCl(H2O)5]2+(aq). of ligands and overall charge of the complex. e.and mer. the name of the metal is used. Furthermore.g. [CoCl3(NH3)3] trichlorotriamminecobalt(III) 6.chloro. This phenomenon is called aquation isomerism. The number of each ligand in the complex is indicated by the prefixes di.or fac-. tri. Ligand name of a negative ligand will end with -o.d-Block Elements Unit 4 3. If the complex is cationic or neutral. (Not in alphabetical order. the ending -ate is added to the name of the metal. they give different number of ions. 2Cl-(aq) [CrCl2(H2O)4]+(aq).cyano.g. 1. Ligand name of a neutral ligand is not changed e. [Fe(H2O)6]3+ hexaaquairon(III) ion If the complex is anionic. Geometrical isomers are designated by cis.g.

whereas an aqueous solution of K4[Fe(CN)6] under similar conditions does not. Explain.ligands stabilize Fe2+ (no mark for Fe(CN)64. but these dissolve 1 mark readily in excess NH3(aq) to give deep blue solution containing tetraaminecopper(II) ion. “An aqueous solution of FeSO4 readily gives a rusty brown precipitate on standing in air.is different from Fe(H2O)n2+ 1½ 5 1 mark 1 mark 1 mark 1 mark 1 mark 91 1A 3 f 3 3f Write equations for stepwise reactions of [Cu(H2O)4]2+(aq) with aqueous ammonia.is stable because CN. iv [NaI4]3Because there is no low energy vacant orbitals for bonding / Na+ has too low charge density for complex ion formation. 1½ mark 90 2B 6 b 6b Account for the following observations.” nH 2 O linear detail explanation FeSO4 → Fe(H2O)n2+/Fe2+(aq) Fe(H2O)n2+ + O2 → Fe(H2O)n3+ air oxidation Fe(H2O)n3+ → Fe2O3 or Fe(OH)3 + H+ product Fe(CN)64.is a better ligand than H2O / CN. in each case. . 1 mark [Cu(H2O)6]2+(aq) + 2NH3(aq) → [Cu(H2O)4]2+·Cu(OH)2(s) + 2NH4+(aq) or Cu(OH)2(s) [Cu(H2O)4]2+·Cu(OH)2(s) + excess NH3(aq) → [Cu(NH3)4]2+ 1 mark When NH3(aq) is added slowly.is a stable complex) The redox potential of Fe(CN)64. why this is so. at first insoluble pale blue basic salt or hydroxide is formed.d-Block Elements Unit 4 Other examples K4[Fe(CN)6] [Fe(Cl)4][Cr(Cl)4][Fe(H2O)6]3+ [Co(Cl)4]2[Cu(CN)4]2Ligand Cl- Fe2+ [Fe(Cl)4]2tetrachloroferrate(II) ion H2O potassium hexacyanoferrate(II) tetrachloroferrate(III) ion tetrachlorochromate(III) ion hexaaquairon(III) ion tetrachlorocobaltate(II) ion tetracyanocuprate(II) ion Fe3+ [Fe(Cl)4]tetrachloroferrate(III) ion [Fe(H2O)6]3+ hexaaquairon(III) ion Co2+ [Co(Cl)4]2tetrachlorocobaltate(II) ion Cu2+ Cr3+ [Cr(Cl)4]tetrachlorochromate(III) ion [Cu(NH3)4]2+ tetraamminecopper(II) ion [Cu(CN)4]2tetracyanocuprate(II) ion NH3 CN- Page 5 [Fe(CN)6]2+ hexacyanoferrate(II) ion Glossary Complex ligand ion-dipole attraction coordinated compound coordinate bond tetrahedral square planar octahedral chelate effect monodentate ligand bidentate ligand polydentate ligand stability constant aquation isomerism meridional isomer facial isomer Past Paper Question 90 2B 6 a iv 91 1A 3 b i 92 1A 3 e 93 1A 2 b iv 94 1A 2 b i 95 1B 4 g 96 1A 2 e i 97 1B 7 b 99 1A 3 c 90 2B 6 b 91 1A 3 f 92 2B 4 a vi vii 91 2B 6 a ii iii 94 2B 5 b iii 96 1A 2 f i 96 2B 6 b i ii 90 2B 6 a iv 6a The following species are either impossible to prepare or very unstable. Describe what changes you would observe during these reactions.

whose polarizing power increases with number of electrons lost. In aqueous solution. and draw the 3-dimensional structure of a hexa-coordinated complex of a d-block element. 1 mark Fe3+(aq) + SCN-(aq) → Fe(SCN)2+(aq) [deep red] Fe(SCN)2+(aq) + 6F-(aq) → [FeF6]3-(aq) + SCN-(aq) 1 mark [FeF6]3-(aq) + 3OH-(aq) → Fe(OH)3(s) [brown ppt. On the addition of dilute alkali to the resulting solution.causes the formation of a brown ppt. vacant d orbital.ions gives no precipitate. [Fe(H2O)6]3+(aq) + 3OH-(aq) → Fe(OH)3(s) + 6H2O(l) 1 mark brown ppt. Fe3+ forms a very stable complex [Fe(CN)6]3-. 1 mark each Ni2+ has low lying . Addition of OH. [Co(NH3)6)]3+ Shape e. The addition of an aqueous solution of KSCN to a solution containing Fe(III) ions gives a complex with a deep red colour. a brown precipitate forms. concentration of free Fe3+ ions is lowered ∴ addition of 2M NaOH cannot cause [Fe3+][OH-] to exceed the Ksp of Fe(OH)3.g. Co NH3 NH3 NH3 1 mark iii Why do V4+ ions react to give VO2+ ions in aqueous solution? V4+ is small and highly charged (or has high charge density) V4+ ion polarizes H2O molecule so strongly that it attracts the electrons shared between H and O V4+ + O 2 3+ NH3 NH3 NH3 Page 6 2 1 mark 1 mark H 2H+ + VO2+ H 92 2B 4 a vi vii 4a vi State two reasons why transition metal ions readily form complexes whereas Group I metal ions do not.d-Block Elements Unit 4 91 2B 6 a ii iii 6a ii Give the name and formula. The deep red colour fades when excess NaF solution is added. 94 2B 5 b iii 5b Account for each of the following: iii The addition of 2M NaOH to an aqueous solution of Fe3+ ions gives a brown precipitate. Cu(H2O)42+ + 4NH3 d Cu(NH3)42+ + 4H2O 1 mark 93 1A 2 b iv 2b iv Write equations for the reactions described below. 2 marks 3 .] + 6F-(aq) 1 mark 3 94 1A 2 b i 2 2b i Explain why Ni2+ forms more complexes than K+ does.g. Name (must be named correctly) e. 2+ + Ni has higher charge density / more polarizing than K / greater ability to form covalent bond (dative bond) with ligand Any 2. hexaamminecobalt(III) ion ½ mark ½ mark Formula e. In the presence of excess CN-. whereas the addition of 2M NaOH to an aqueous solution of Fe3+ ions in the presence of excess CN.g. Atoms have partially-filled d-orbitals that can interact with ligand orbitals by transfer of electron density Complex ion formation is favoured by high charge density on cation High electronegativity of cation Available orbitals of right energy to interact with ligand orbitals 1 mark each vii Write the chemical equation on which the overall stability constant for the reaction between the cation Cu(H2O)42+ 1 and the ligand NH3 in aqueous medium can be based. Fe3+ exists as aquo-complex. 2 Atoms lose electrons to form ions.

These isomers belong to TWO types of isomerism. Kst = [Cu2+][NH ]4 1 mark 3 (Accept expressions for stability constant of other copper(II) complexes and answers for stepwise and overall stability constants) 97 1B 7 b 7b An aqueous solution contained 0. These experiments are carried out at room temperature.e. Soluble in excess / Deep blue solution Insoluble in excess 96 1A 2 f i 2f The complex ion [Co(H2NCH2CH2NH2)2Cl2]+ has THREE isomers.90 cm3 of 0. ½ mark for each cis-isomer ) 96 2B 6 b i ii 6b What do you understand by the following terms ? In each case. to aqueous solutions containing Pb2+ and Cu2+ ions respectively. Insoluble in excess Soluble in excess / Colour solution Cu2+(aq) Blue ppt. illustrate your answer with an example involving copper(II).g. until in 3 excess. White ppt. 99 1A 3 c 3c Draw the structures of all isomers of the complex [Co(NH3)4Cl2]Cl and give the systematic name of each isomer.40 g of a complex salt Cr(NH3)5Cl3. Deduce the structural formula of the complex ion present in the salt. The free chloride ions present in the solution required 21. 3 2 .g.150 M silver nitrate(V) solution for complete precipitation. The ligands/complexing agents are either neutral molecules / negatively charged ions carrying lone pair(s) of electrons 1 mark ½ mark which can be donated to the metal ion / can form dative bond with the metal ion. deduct ½ mark for each incorrect observation) (i) ammonia solution (ii) sodium hydroxide solution Pb2+(aq) White ppt. [Cu(NH3)4]2+ (accept any complex of Cu(II) ii stability constant Stability constant Kst : e. [Cu(NH3)4]2+ Kst is the equilibrium constant for the following process 1 or 0 mark Cu2+(aq) + 4NH3(aq) d [Cu(NH3)4]2+ [Cu(NH3)42+] i. ½ mark e. + Cl en Co Cl + en en Co Cl Cl en Cl Cl en 2 + Co en 1 + ½ + ½ mark (en represents H2NCH2CH2NH2) (1 mark for the trans-isomer. Blue ppt. (i) ammonia solution (ii) sodium hydroxide solution Pb2+(aq) Cu2+(aq) (3 marks for 8 observations. i complex ion A complex ion is formed by combination of a central metal ion ½ mark ½ mark with ligands / complexing agents. i Draw a three-dimensional structure for each isomer.d-Block Elements Unit 4 Page 7 95 1B 4 g 4g Give the observations when (i) ammonia solution and (ii) sodium hydroxide solution are added dropwise.

the electron transition will produce a colour. . However. The electron transition is called d-d transition. Eventually. Cu2+(aq)) is the result of absorption of light. This explains why anhydrous copper(II) sulphate is white while hydrated copper(II) sulphate is blue. The atom returns to the lower energy state. 5th Edition. Whether a substance would be coloured or not is solely a coincidence. Thomas Nelson and Sons Ltd. Origin of the colour The origin of the colour of an transition metal ion is similar to that of emission spectrum. radiation is absorbed from the illuminating radiation. Page 1 Unit 5 Assignment Chemistry in Context. The degenerate energy levels split because the five 5 dorbitals are not equally arranged in space and are affected by the ligands differently. most substances in nature are coloured because most of them are mixtures containing a very small percentage of coloured substance. Fillans pg. the 5 degenerate d-orbitals will be split into different levels with small gaps between them. pg.d-Block Elements Unit 5 Topic d-Block Elements Reference Reading 11. Chemistry in Context. Most pure substances in nature are colourless or white because they do no absorb light from the visible region. 3rd Edition ELBS pg.3 Modern Physical Chemistry ELBS pg.g. 259–261 Reading Syllabus Coloured ions Notes C.2. are coloured because under the influence of the ligands. The colour of hydrated ion (e. Coloured ions 1. Instead of emitting radiation while the excited atom is falling back to the lower energy state. including aqueous complex. Physical Chemistry. if the d-orbitals are partially filled (not completely filled nor completely empty). Sc(III) and Zn(II) compounds are not coloured while the other transition metal compounds are usually coloured. The energy absorbed is eventually dissipated in form of heat. Many transition metal complexes.

until in excess. deep blue solution Substances Reaction method Expected observation(s) Example: CH3COOH(l) and Warm / reflux with miscible. Small energy difference between d orbitals under the influence of the ligands 4. Absorption of photon in the visible region 2. state the expected observation and write the relevant balanced equation(s). in terms of electronic arrangement. i Concentrated hydrochloric acid is added dropwise to an aqueous solution of copper(II) sulphate(VI) until no further change is observed. fruity odour C2H5OH(l) conc H2SO4 (iii) CuSO4(aq) and 2M NH3 pale blue precipitate. 1. ii Aqueous ammonia is added dropwise. Cobalt(II) chloride. . Substances Reaction method Expected observation(s) Example: CH3COOH(l) and Warm / reflux with miscible. fruity odour C2H5OH(l) conc H2SO4 (iii) CuSO4(aq) and 2M NH3 Add NH3(aq) dropwise pale blue precipitate.d-Block Elements 2. why most transition metal ions are coloured. After absorption of water / forming complex ion with H2O. it changes colour to pink. in anhydrous state is blue in colour. boxes in the following table. Unit 5 Page 2 Colours of different ions [Fe(Cl)4]2-(aq) [Fe(Cl)4]-(aq) yellow H2O CN[Fe(CN)6]4-(aq) [Fe(H2O)6]2+(aq) d d green yellow H2O CN[Fe(CN)6]3-(aq) [Fe(H2O)6]3+(aq) d d colourless/yellow red [Co(Cl)4]4-(aq) blue [Cu(Cl)4]4-(aq) yellow Glossary d-d transition Past Paper Question 93 1A 2 b i 94 1B 4 d iii 99 2A 2 d i ii H2O NH3 CN[Co(NH3)6]2+(aq) [Co(CN)6]4-(aq) [Co(H2O)6]2+(aq) d d d pink deep red H2O NH3 CN[Cu(NH3)4(H2O)2]2+(aq) [Cu(CN)4]2-(aq) [Cu(H2O)6]2+(aq) d d d blue deep blue 94 2B 5 b ii 93 1A 2 b i 2b i Explain. Unpaired electron or partly filled orbital 3. (1) deep blue solution 94 2B 5 b ii 5b Account for each of the following: ii Cobalt(II) chloride can be used to test for the presence of water. Transition of electron 94 1B 4 d iii 4d This question refers to reactions which occur between the following pairs of substances. to the resulting solution in (i). 2 2 marks Complete the empty 6 Main product(s) CH3COOC2H5(l) Cu(OH)2(s) [Cu(NH3)4]2+(aq) Main product(s) CH3COOC2H5(l) Cu(OH)2(s) [Cu(NH3)4]2+(aq) 2 1 mark 1 mark 99 2A 2 d i ii 2d For each of the following experiments.

A very few no. 1. 3.2. Magnetic properties of transition metal and ion When an electron spins. Mn2+ [Ar] 3d5. all chemical reactions involve electron transfer or redistribution of electron.e. 3rd Edition ELBS pg. Many transition metal has low lying energy vacant d-orbital to accept the electron and possesses variable oxidation state which aids the electron transfer process and lowers the activation energy of redox reaction. This is because.g. most substance are non-magnetic i.g.d-Block Elements Unit 6 Topic d-Block Elements Reference Reading 11. 5th Edition.2.5 11. Glossary diamagnetic paramagnetic ferromagnetic . e.0 Modern Physical Chemistry ELBS pg. Fe.2. of substances are strongly magnetic e. Physical Chemistry. Normally. 261–262 Reading Syllabus Catalytic properties Magnetic properties Notes D. the magnetic moments are not canceled out completely and they are weakly magnetic i. a magnetic moment will be induced. Therefore. Fillans pg. electrons will pair up in an atom and the magnetic moments will be canceled out. basically. Page 1 Unit 6 Assignment Chemistry in Context. diamagnetic. Thomas Nelson and Sons Ltd. They are ferromagnetic. Haber process Reaction between peroxodisulphate(VI) and iodide ions Decomposition of hydrogen peroxide For details please refer to Rate of reaction – Catalysis E.4–11. paramagnetic.e. Chemistry in Context. pg. Catalytic properties of transition metals and their compounds Many transition metals or compounds of transition metal exhibit catalytic behavior. In certain substance containing unpaired electrons. 2. due to the spinning of the protons.

In each case. the use of a nickel catalyst in the hydrogenation of oils to make margarine Complex ion formation. 1 mark.g. with examples using nickel. Cu(I) & Cu(II) / V2+. apart from complex ion formation.g. Catalytic properties. two characteristic properties of transition metals. [Ni(H2O)6]2+ Accept also ‘colours’. illustrate your answer with an example involving copper or vanadium.g. Any THREE of the following: ½+½ exhibition of variable oxidation states e. Cu2+(aq) is blue / VO2+ is yellow ½ + ½ mark exhibition of catalytic properties e. e.g. V2O5 in contact process ½ + ½ mark exhibition of paramagnetic properties e.d-Block Elements Past Paper Question Unit 6 Page 2 90 1A 3 d 92 1A 3 h 94 2B 5 a iv 96 2B 6 c 90 1A 3 d 3d Illustrate.g. ½ marks for a correct example) 3 . Variable oxidation states of d-block elements allow electron transfer between reactants and products by means of 2 marks catalyst changing between two oxidation states. Cu2+ / V2+ are paramagnetic ½ + ½ mark formation of non-stoichiometric compounds e. Give one example of such a catalytic reaction.g. sulphide of vanadium (½ marks for each properties. VO2+ and VO2+ mark ½ + ½ mark formation of coloured compounds e. e.g. full orbitals can act as electron donors to reactant species and weak bonds (chemisorption) are formed between catalyst and reactant particles. ‘paramagnetic’ or other properties which can be illustrated. 1 mark 94 2B 5 a iv 5a iv Explain briefly why d-block elements and their compounds are frequently used as catalysts in redox reactions. either II Variable oxidation states enable oxidation-reduction cycle of transition metal catalyst.g. 2SO2 + O2   2 3 1 mark 96 2B 6 c 6c State THREE characteristic properties of d-block elements. 2 1 mark 1 mark 92 1A 3 h 3h Which two properties of transition metal ions make them suitable for use as catalyst? I Vacant orbitals may act as electron acceptors from reactant species. V3+. Any one example of transition metal or its compound as catalyst V O 2 5 → SO3 (redox reaction) e.