All Inorganic PDF

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
III.
Sulphur and its compounds

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

I.
II.

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.

a)
Amphoteric oxides
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 SiO2nH2O(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) SiO2xH2O(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, chlorides hydrolyse faster in alkaline medium since OH-(aq) ion is a stronger nucleophile than water. Furthermore, the
presence of alkali also shifts the equilibrium position to the right.

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.
Insoluble in water
neutral and insoluble but hydrolyses slowly.
Na(s) forms peroxide instead of oxide when burns in air.
MgO(s) only reacts with water very slowly due to high
lattice energy.
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)
2ClO2(g) + H2O(l) HClO2(aq) + HClO3(aq)
Cl2O6(l) + H2O(l) HClO3(aq) + HClO4(aq)
In general, metal oxides are basic and non-metal oxides are acidic in nature. The basic oxides could be neutralized by acid while the
acidic oxides could be neutralized by alkali. The exceptions are BeO(s) and Al2O3(s). They are called amphoteric because they react with
both acid and alkali.
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

Bond energy
Bond energy
Bond energy
E(XH) in kJmol-1
E(XX) in kJmol-1
(with element)
(with hydrogen)
Li
Be
B
C
347
413
N
391
158 (945.4 in NN)
O
144 (498.3 in O=O)
464
F
158
568.0
Na
72
Mg
Al
Si
226
315
P
198
321
S
266
364
Cl
243.4
432.0
H
435.9
435.9
Page 3
Bond energy
E(XO) in kJmol-1
(with oxygen)
Bond energy
E(XCl) in kJmol-1
(with chlorine)
358
214
144
346
466
469
464
432.0
Unit 1
Topic
Perioidic Properties of Elements
Reference
Reading
8.0
Chemistry in Context, 3rd Edition ELBS pg. 3741
A-Level Chemistry, 3rd Edition, E.N. Ramsden pg. 4345
Page 1
Unit 1
Assignment
Syllabus
Notes
I.
It is important to notice that the modern periodic table was developed by a Russian scientist Mendelev in 1867 by
comparing the physical and chemical properties of different elements. However, the electronic configuration of
atoms were only discovered by Bohr in 1913. Indeed, the periodic table aided the discovery of electronic
configuration of atom and some new elements.
In the periodic table, elements are arranged according to the atomic number, not the atomic mass. For example, the
atomic mass of 18Ar is 39.9 while the atomic mass of 19K is 39.1; the atomic mass of 52Te is 127.6 while the atomic
mass of 53I is 126.9. With such arrangement, elements with similar chemical properties are grouped in columns
called groups.
Furthermore, elements can be classified into s-block, p-block, d-block and f-block elements depending on the
orbital that the vacant electrons are filling.
Glossary
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.
Elements in same group have similar chemical properties.
Properties recur after an interval (period).
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. State the reason why potassium follows argon in
the Periodic Table.
In the Periodic Table, the elements are arranged in order of atomic number / no. of proton, but not in order of
atomic mass.
mark
K has one more proton than Ar does.
mark
Unit 2
Topic
Reference
Reading
8.1
Chemistry in Context, 3rd Edition ELBS pg. 4250, 191201
Inorganic Chemistry, 4th Edition, T.M. Leung pg. 421
Page 1
Unit 2
Assignment Chemistry in Context, 5th Edition, Thomas Nelson and Sons Ltd. pg. 3537, 4249, 169, 176177
Reading
Syllabus
Notes
A. Periodic variation in physical properties of the elements H to Ar (First 18 elements)

First ionization energy, atomic radius,
electronegativity, melting point and boiling points, all
varies periodically across the periodic table.
For the details of variation in first ionization energy,
atomic radius and electronegativity, please refer to
Atomic structure Units 4 & 6.
Variation in electronegativity
1.
Variation in melting points and boiling point
Both melting point and boiling point reflects the strength of attraction among the particles. In general, boiling point
serves as a better indication of the strength of attraction than melting point does. In the boiling process, the
randomly arranged liquid particles are vaporized to randomly arranged gaseous particles. However, in the melting
point process, the more regularly arranged particles are melted to randomly arranged liquid particles. Besides the
attraction, melting point is also depending on the arrangement of particles in the structure.
Unit 2
Page 2
For example, boiling point of unbranced alkane increases smoothly with increasing molecular size. Although
melting point also shows a general increasing trend, it forms an zig-zag line instead. This is because the alkane
with even no. of carbon (except methane) are more symmetrical than the ones with odd no. of carbon. They are
packed more regularly in the solid, thus a little bit higher melting point.
Key -
Glossary
s.m.s.
g.m.s.
g.c.s.
Simple molecular structure

The forces among the molecules are weak van der Waals' forces, thus the m.p. and b.p. are
rather low. P4 molecule is smaller than S8 molecule, therefore S has a higher m.p. and b.p.
than P.
Giant metallic structure
The m.p. and b.p. of a metal is depending on the strength of the metallic bond.
Giant covalent structure
The attraction amount the atoms are strong covalent bond, thus all giant covalent structures
have very high m.p. and b.p.
simple molecular structure
giant metallic structure
giant covalent structure
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, for the
elements from lithium to argon.
Explain the change in ionization energy between nitrogen and oxygen.
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.
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 -)
For I. E.
Graph shows decrease in ionization energy down the group
Graph shows 2,3,3 pattern
(not labelling each axis -)
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, and in white phosphorus, P4.
N2: NN
structure:
(linear) diatomic molecule
bonding:
intramolecular, covalent
intermolecular, van der Waals
1 mark
mark
mark
1 mark
1 mark
mark
mark
2
mark
mark
mark
mark
P
P
white P4:
structure:
bonding:
discrete tetrahedral
intramolecular, single covalent
92 2B 6 Ba ii
6Ba
ii Describe the structure and the bonding in oxygen, O2, and in rhombic sulphur, S8.
mark
mark
mark
mark

O2: O=O
mark
structure:
(linear) diatomic molecule
bonding:
intramolecular, covalent
S
S
S
S S S
S
S
S8:
structure:
bonding:
molecular ring structure

intramolecular, single covalent
Unit 2
Page 4
mark
mark
mark
mark
mark
mark
mark
Unit 3
Page 1
Topic
Reference
Reading
8.2.0
Unit 3
Assignment Chemistry in Context, 5th Edition, Thomas Nelson and Sons Ltd. pg. 177178
Reading
Syllabus
Notes
II. Periodic relationship among the oxides, 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, some elements show similar
chemical properties to another element in another group. e.g. Li and Mg; Be and Al, B and Si. This relationship is
called diagonal relationship.
The chemical properties of a particle is depending on its ability to attract or donate electron. i.e. electronegativity of
the element and charge density of the ion. Consider lithium and magnesium, Li+ ion is smaller than Mg2+ ion but
Z+
Mg2+ ion carries higher charges than Li+ ion. Consequently, the two ions share similar charge density( r ) and
+
polarizing power. This makes Li compound behave similarly as the Mg compound rather than other group I metal
compounds.
e.g. All group I carbonates are stable to heat except lithium carbonate.
Lithium carbonate decomposes upon heating like magnesium carbonate.
Li2O(s) + CO2(g)
Li2CO3(s) heat
MgCO3(s) heat
MgO(s) + CO2(g)
However, diagonal relationship does not apply to non-metals. 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.
This explains why CCl4 is stable in water but PCl3 hydrolyse in water readily.
water
no reaction
CCl4(l)
PCl3(l) + 3H2O(l) H3PO3(aq) + 3HCl(aq)
Furthermore, the electronegativity difference among the non-metals are larger than the difference among the
metals.
Glossary
diagonal relationship
charge density
polarizing power
electronegativity
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.
The question is difficult; reasonable answer might cite:
C electronegativity (2.5); P (2.05) not similar
Properties differ because of d-electron availability in P bonding.
Charge density
Polarizing power
Any one; 1 mark
C
This question required application of knowledge to an unfamiliar situation, and was poorly answered by most
candidates. Reasons such as the different electronegativities of C and P, the different charge densities, or the
availability of d orbitals for bonding in P were considered reasonable.
Unit 4
Topic
Reference
Reading
8.2.1
A-Level Chemistry, 3rd Edition, E.N. Ramsden pg. 339, 352353
Page 1
Unit 4
Assignment
Reading
Syllabus
Properties of hydrides
Notes
A. Hydride
1.
Bonding
s-block hydrides are ionic in nature, consisting of metal ion and hydride ions H-. p-block hydrides are covalent in
nature consisting of simple molecule.
For sure, the energetic stability of a compound is depending on the strength of the intramolecular forces. 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.

2.
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.
O H +
H
+
O H + H2
The properties of p-block hydrides are rather complicate. Even the hydrides of the elements in the same group do
not show similar properties. e.g. CH4 is stable in water but SiH4 hydrolyses in water to give hydrogen.
NH3 is alkaline but PH3 is neutral in water.
H2S is acidic in water.
Both HF and HCl are acidic in water but the acidity of HF is much lower.
The reactivity of p-block hydrides towards water is depending on several factors :
i. polarity of the molecule
ii. availability of low energy vacant d-orbital
iii. Bond strength and difference in electronegativity (bond polarity)
i.
polarity of the molecule (NH3 vs PH3)
Comparatively, N is more electronegative than H but P has similar electronegativity as H. Although both of them
are pyramidal in shape, PH3 is a less polar molecule. Consequently, NH3 is a much stronger Lewis base than PH3.
+
H
+ H N
H
+
O H +
H
+
+
H N H + O H
H
H
H
+ H +
+
P
H
Finally NH3 will hydrolyze in water but PH3 is insoluble and has no reaction with water at all.
ii. 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. Therefore, SiH4
hydrolyses very slowly in water. (It hydrolyses faster in alkali as OH- ion is a stronger nucleophile than water.)
Furthermore, the electronegativity of C is similar to that of H while Si is less electronegativity than H. Therefore,
the lone pair of water would be attracted by the positive charge on the Si atom.
H
H +Si H
H
O H +
H
+
Unit 4
Page 3
iii. 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. This
makes the solution acidic.
H2O
H2S
HCl
HF
Difference in E.N.
1.5
0.3
1.5
2.0
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, sometimes, it is difficult to predict whether a molecule will behave as a base or an acid.
As an acid
As a base
HX + HOH d X- + H2OH+
HX + HOH d H2X+ + OH-
NH3(aq) + H2O(l) d NH2-(aq) + H3O+(aq)

Indeed, it is mainly depending on the relative strength of HX and OH bonds but it is also depending on the
hydration energy of the ions formed.
The acidity of HF is exceptionally low comparing with other hydrogen halide due to 2 factors :
i. strong HF bond, which does not favour the dissociation of the bond.
ii. the formation of hydrogen bond between HF(l) and H+(aq), this lowers the concentration of free H+(aq) in the
solution, thus the acidity.
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).
NaH(s) is an ionic compound and its reducing properties is due to the hydride anion which can undergo the
reaction, H- H2 + e-, i.e. releasing electrons in an overall redox reaction.
1 mark
mark
HCl(g) does not undergo such reaction to release electron.
HCl(g) is acidic because it is a proton donor in the presence of a base.
e.g. HCl(g) + H2O(l) H3O+(aq) + Cl-(aq).
1 mark
mark
NaH(s) is not acidic because it is not a proton donor.
91 2B 5 b
5b
Explain why SiH4 is hydrolysed by alkali, whereas CH4 is not, and give an equation for the hydrolysis.
Reason A: electronegativity difference
1 mark
nucleophilic attack by OH- only on Si
1 mark
Reason B: state any one of the XO, XH bond strengths
1 mark
activation energy higher for breaking C-H
1 mark
Reason C: C no 2d orbital, 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. Answer must have the fact (1 mark) and then deduction (1 mark). If 2 facts
from different reasons are mixed, then award only 1 mark
Equation
1 mark
SiH4 + (n+2)H2O SiO2nH2O + 4H2 (SiH4 + 2OH- SiO32- + 2H2O + H2)
or SiH4 + 2H2O SiO2 + 4H2 (SiH4 + H2O Si(OH)4 + H2
(need not be balanced. Accept SiO32-. Miss out H2 -)

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.
Carbon atom because of its small size (less shielding effect) forms stable covalent bond with other carbon atoms
tends to catenate.
1 mark
Energy difference between CC, CH and CO is small, while for Si, SiSi, SiH are weak compare with SiO,
SiSi and SiH bond is easily oxidized to SiO, while CC and CH bond is not.
1 mark
C can also form bond by sideway overlapping of p orbitals, thus formation of C=C and CC are possible. For
Si, because of its large size, Si=Si and SiSi cannot be formed easily.
1 mark
93 2B 6 d
6d
Give the states of NaH and HCl at room temperature and atmospheric pressure. Explain why they are different.
Compare the reaction between NaH and water with that between HCl and water.
NaH - solid. It is an ionic compound, a crystalline solid with the structure similar to NaCl.
1 mark
HCl - gas. It is covalent molecule where the intermolecular force is dipole-dipole attraction.
1 mark
Reaction with water
NaH: H- + H2O H2 + OH- (result in alkaline solution)
HCl: HCl + H2O H3O+ + Cl- (result in acidic solution)
1 mark
Page 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. If 3
there is a reaction, give the balanced equation.
CH4
SiH4
H2S
HCl
CH4 : no reaction
mark
SiH4 : SiH4 + 4H2O Si(OH)4 + 4H2 (or SiO2nH2O or SiO2)
( mark for correct product, mark fro balanced reaction)
H2S + 2H2O d 2H3O+ + S2H2S : H2S + H2O d HS- + H3O+ OR
( mark for correct product, mark fro balanced reaction)
mark
HCl : HCl + H2O H3O+ + Clii Explain the difference in reactivity with water between CH4 and SiH4.
1
Kinetic aspect
mark
In CH4, there is almost no polarity in the CH bonds
CH4 is not affected by polar molecules of water
In SiH4, the bond polarity is Si+H-.
mark
OR
mark
There is no empty / vacant low energy d-orbital in C
lone e- pair in water will not attack CH4.
mark
OR
mark
In Si, there is low energy empty d-orbital.
it can accept lone electron pair from water
mark
H
H
+
Si H
H
H
Si OH + H2
etc.
H
O H
H
Thermodynamic aspect
CH bond is strong when compared with SiH bond
substitution of H in CH4 is energetically unfavourable.
(Max. 1 mark, 3 points must not be in the same aspect)
iii Explain the difference in reactivity with water between SiH4 and H2S.
In H2S, the polarity is H+S-.
nucleophilic attack of H2O on H2S gives H3O+ and HS-,
whereas SiH4 gives an alkaline solution since the polarity is Si+H-.
mark
mark
mark
1
mark
mark
mark

Unit 4
99 2A 3 c ii iii
3c
Consider the hydrides of three Period 3 elements : SiH4, PH3 and H2S
ii With reference to the electronegativity values given below, compare the reactions of these hydrides with water.
Element
H
O
Si
P
S
Electronegativity (Pauling's scale)
2.1
3.5
1.8
2.1
2.5
iii State, with explanation, whether SiH4 or H2S has a higher boiling point.
(9 marks)
Page 5
Unit 5
Page 1
Topic
Unit 5
Reference
Reading
8.2.2
Inorganic Chemistry, 4th Edition, T.M. Leung pg. 2529, 50-68
Chemistry in Context, 5th Edition, Thomas Nelson and Sons Ltd. pg. 179180
Assignment Advanced Practical Chemistry, John Murray (Publisher) Ltd., 144147

Reading
Syllabus
Notes
B. Chloride
1.
Bonding
The bonding of chlorides is similar to that of hydrides. s-block chlorides are ionic in nature and p-block chlorides
are covalent in nature.
Chlorides of phosphorus are very special comparing with the others. PCl3(l) is a liquid possessing molecular
structure where PCl5(s) is a solid possessing ionic structure. However, in gaseous state, PCl5(g) also possesses a
molecular structure.
+
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)

2.
Unit 5
Page 2
Hydrolysis
s-block chlorides are basically ionic and only dissolve in water without going through hydrolysis. However, owing
to the high charge density of the metal ion, the highly covalent BeCl2, BCl3 and AlCl3 hydrolyse readily in water.
[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.B.
For simplicity, sometimes the ligand water will be omitted is the formula, 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.
The reactivity of p-block chlorides towards water is similar to that of hydrides. The main difference is that Cl is
much more electronegative than H. Therefore, the central atom will always carry the + instead of -.
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, and indicate the types of bonding in, LiCl, AlCl3, PCl3 and K2NiCl4.
Also, discuss their physical and chemical properties in terms of structure and bonding.
LiCl
colourless ionic solid with Li+, Cl-.
Cl
AlCl3
colourless covalent solid, dimeric in structure,

Cl
PCl3
covalent colourless liquid,
P
Cl
Cl
Al
Cl
Cl
Al
Cl
Cl
, undergoes sublimation.
Cl
, can be oxidized to POCl3.

Cl
Cl
2-
Ni
Cl
Cl
.
K2NiCl4 coloured ionic solid with complex anion,
LiCl and K2NiCl4 are ionic solids whereas AlCl3 and PCl3 are covalent molecules.
LiCl and K2NiCl4 do not react with water.
Whereas AlCl3 and PCl3 are hygroscopic and readily hydrolysed by water.
About the bonding: LiCl,
ionic chloride
AlCl3, covalent Cl- as ligand
covalent bond between P and Cl
PCl3,
NiCl42-, dative covalent bond.
Physical properties
e.g. melting point/boiling point; sublimation; solubility in water/organic solvent; colour of complex, etc.
Chemical properties
e.g. hydrolysis; ease of oxidation; complex ion in equilibrium with water, etc.
Marking Scheme
Overall presentation - highlight on their differences (in table form -1)
2 marks
Structure and bonding (1 mark each, for structure and for bonding)
4 marks
Physical and chemical properties (1 mark each, for physical and for chemical)
4 marks
10

Unit 5
91 1A 3 b i
3b
Write equation(s) to describe the reaction of
i
ZnCl2(s) with water.
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 mark
91 2B 4 b
4b
Give the formula of one chloride for each of the elements N, O and S.
Write an equation for the reaction (if any) of each chloride with water.
Draw the electronic structure of a molecule of each chloride and describe the molecular shape.
formula
3 = 1 mark
equation
3 = 1 mark (need not be balanced, must write + H2O)
electronic structure 3 = 1 mark (must show lone pair(s) on N, O and S)
shape
3 = 1 mark (draw and/or name, if either one is correct, then mark)
Example: NCl3
NCl3(l) + 3H2O(l) NH3(aq) + HOCl(aq)
Cl
N Cl
Cl
pyramidal
Example: Cl2O
Cl
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)
For oxygen chlorides, accept disproportionation reaction for oxidation states 2,4,6 but not -1 or 7 for Cl.
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
Cl
any sensible description e.g. zigzag shape

or SCl2, SCl4
Cl
S
Cl
Cl
S
Cl
Cl
Cl
For S2Cl2 + H2O S + SO2 (or SO3) dont 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. Write equations for these reactions and explain why FeCl3
gives the more acidic solution.
Both aqueous solutions contain hydrated cations and Cl-(aq).
[Fe(H2O)6]2+ + H2O [Fe(H2O)5OH]+ + H3O+ (pKa = 9.5)
1 mark
[Fe(H2O)6]3+ + H2O [Fe(H2O)5OH]2+ + H3O+ (pKa = 2.2)
1 mark
1 mark
Smaller size and greater charge of Fe3+ ion results in more acidic solution than that of Fe2+ ion.

Unit 5
93 1A 2 a iv
2a
Answer the following questions by choosing in each case one of the species listed below, putting it in the box and
giving the relevant equation(s).
Al(s), AlCl3(s), AlO2-(aq), Na(s), CO32-(aq), Cu2+(aq), P4O10(s), S(s), S2O32-(aq), 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.
i
[Fe(H2O)6]2+(aq) , [Fe(H2O)6]3+(aq)
[Fe(H2O)6]3+
mark
mark
The conjugate base [Fe(H2O)5OH]2+ is stabilized to a greater extent
mark
because the anionic ligand OH- tends to
stabilize the electron deficient Fe3+ more than Fe2+ / causes the eqm. to lie towards the right / increase the ease of
ionization of H
mark
Or,
mark
Fe3+ has a higher charge to radius ratio / charge density,
mark
greater polarizing power,
and hence the H develops larger partial +ve charge.
mark
Page 4
Unit 6
Page 1
Topic
Unit 6
Reference
Reading
8.2.3
Inorganic Chemistry, 4th Edition, T.M. Leung pg. 27, 2931, 3449
Assignment Advanced Practical Chemistry, John Murray (Publisher) Ltd., 151153

Chemistry in Context, 5th Edition, Thomas Nelson and Sons Ltd. pg. 180184, 283285
Reading
Syllabus
Notes
C. Oxide
1.
Some oxides are acidic. e.g. CO2(g), SO2(g). When reacted with water, they form acids.
e.g. CO2(aq) + H2O(l) d H2CO3(aq)
SO2(aq) + H2O(l) d H2SO3(aq)
H
O
H
O
S
O
O
S
O
O
H O
S
O
Unit 6
Page 2
Some oxides are basic. e.g. Na2O(s), K2O(s). When reacted with water, they forms alkalis.
e.g. Na2O(s) + H2O(l) 2NaOH(aq)
K2O(s) + H2O(l) 2KOH(aq)
2-
H
O
O H
H
In general, non-metal oxides are acidic and metal oxides are basic.
A. Amphoteric oxides
There are a few oxides which reacts with both acid and alkali. e.g. ZnO(s), PbO(s) and Al2O3(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, aluminium and lead are also amphoteric.
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), Pb(OH)2(s) and Al(OH)3(s) are insoluble in water. If a little alkali (e.g. NaOH(aq)) is added into the
Zn2+(aq), Pb2+(aq) or Al3+(aq) solution. The hydroxides will be precipitated first. If excess alkali is added, the
hydroxide precipitate will redissolve to form a clear solution. This serves as a very good test for the three ions.
e.g. 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, Al, Pb and Zn metals also reacts directly with strong alkali besides strong acid.
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)
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.
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, NH3 or PH3? Explain your answer.
PH3, Greater stability of P(V) : P4O10
92 2B 6 Bc ii
6Bc
ii Which is more reactive to oxidation, H2O or H2S? Explain your answer.
H2S
any reasonable answer, such as more higher oxidation states available for S
or enthalpy of formation of H2O is strongly exothermic (Hf -285.9 kJmol-1) but
H2S only weakly so (Hf -20.6 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, putting it in the box and
giving the relevant equation(s).
Al(s), AlCl3(s), AlO2-(aq), Na(s), CO32-(aq), Cu2+(aq), P4O10(s), S(s), S2O32-(aq), Zn2+(aq)
i
Which species can react with excess dilute NaOH with effervescence, 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.
CaO + SiO2 CaSiO3
This is an acid-base reaction.
CaO is a basic oxide and SiO2 is an acidic oxide
The reaction does not involve a change in oxidation state.
2
mark
1 mark
mark
95 1B 4 g ii
4g
Give the observations when (ii) sodium hydroxide solution are added dropwise, until in excess, to aqueous
solutions containing Pb2+ and Cu2+ ions respectively. These experiments are carried out at room temperature.
(ii) sodium hydroxide solution
Pb2+(aq)
Cu2+(aq)
(3 marks for 8 observations; deduct mark for each incorrect observation)
2+
Pb (aq)
White ppt.
Soluble in excess / Colour solution
Cu2+(aq)
Blue ppt.
Insoluble in excess
s-Block Elements
I.

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.
2.
3.
4.
Reaction with water
Thermal stability of carbonates and hydroxides
1.
2.
Solubility of sulphate and hydroxide
1.
Solvation energy
a)
Definition of solvation and solution processes
b)
Factors affecting the value of hydration energy
c)
2.
a)
Sulphate salt of group II metal
b)
Hydroxide of group II metal
c)
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
s-Block Elements
Unit 1
Page 1
Topic
s-Block Elements
Unit 1
Reference
Reading
9.09.1
Chemistry in Context, 3rd Edition ELBS pg.
Assignment Chemistry in Context, 5th Edition, Thomas Nelson and Sons Ltd. pg. 211213, 283
Reading
Syllabus
Notes
I.
A. Metallic character and low electronegativity

All s-block elements are soft metals. Since the outermost shell has been effectively shielded from the nuclear
attraction, the metallic bond would not be very strong and the electronegativity would also be very low (i.e. very
high electropositivity.)
B. Ionic bond formation and fixed oxidation state
s-block elements lose their outermost electron readily to form positive ions. In general, they only form ionic
compound. For the group 1 elements, the difference between the 1st I.E. and 2nd I.E. is very large, therefore group
1 elements only form ions with +1 oxidation state. Similarly, for group 2 elements, the difference between 1st and
2nd I.E is very small but the difference between 2nd I.E. and 3rd I.E. is very larger, group II elements only form
ions with +2 oxidation state. Comparing with Fe, a transition metal, the difference between 1st and 2nd I.E. is
small but the difference between 2nd I.E. and 3rd I.E. is moderate. Fe is capable to form ions with oxidation state
+2 and +3.
C. Flame test
All s-block metal or compound containing s-block elements burning with characteristic colour due to the excitation
of the electrons. The colour of the flame can be used to identify the metal or metal ion that the sample contains.
Generally speaking, chloride salt is lowest melting and boiling among different salts. Therefore, it order to obtain
the best result, 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. Furthermore, conc. HCl(aq) is also used to clean the nichrome or platinum
wire to be used in the flame test. This is done by dipping the wire in the acid and heating the wire with bunsen
flame repeatedly until no colored flame is observed.
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
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
mark
KCl(s) gives a lilac flame
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.
mark
MgCl2 gives white precipitate
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.
s-Block Elements
Unit 2
Topic
s-Block Elements
Reference
Reading
9.2.09.2.2
Inorganic Chemistry, 4th Edition, T.M. Leung pg. 9498, 103105
Page 1
Unit 2
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.
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.
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.
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.
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 C O
C O
-
2-
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 / C
~ 100
540
900
1290
1360
s-Block Elements
Unit 2
2.
Page 3
The decomposition of hydroxides is somehow similar to the decomposition of carbonates. Upon decomposition,
the large hydroxide ion is converted to small oxide ion with liberation of water.
Hydroxides of group 1 (except Li) are stable to heat. Those of Group 2 and lithium are decomposed by heat to form
oxides. The thermal stability of group II hydroxide is parallel to group II carbonates where the thermal stability
increases down the group.
M2O(s) + H2O(l)
2MOH(s) heat
M(OH)2(s) heat
MO(s) + H2O(l)
O H
O 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
2-
thermal stability
90 1A 3 f
95 2B 5 b i ii
90 1A 3 e ii
3e
Give observation, and write balanced equations for the following:
ii a small, freshly-cut piece of sodium is exposed to air for a few minutes;
a similar piece of sodium is placed on filter paper on the surface of water in a glass trough.
The surface of the sodium becomes dull (less shiny, more white)
4Na(s) + O2(g) 4Na2O(s)
The piece of sodium melts and burns with a yellow flame.
2Na(s) + 2H2O(l) 2Na+(aq) + 2OH-(aq) + H2(g)
2H2(g) + O2(g) 2H2O(l)
4
mark
1 mark
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, it becomes very hot and disintegrates into a white powder.
The protective layer of Al2O3 is destroyed when the piece of Al is dipped in a solution of HgCl2.
1 mark
1 mark
When withdrawn from the solution, the fresh surface of Al reacts highly exothermically
1 mark
with O2(air) to form white Al2O3 powder.
91 2B 5 d
5d
Account for the observation that lithium carbonate decomposes at 700C whereas sodium carbonate is thermally
stable at this temperature.
Li+ is more polarizing than Na+
1 mark
because it is smaller, with same charge or higher charge density
1 mark
The charge cloud of the oxy-anion is more distorted, causing the anion to break up to give O2- and CO2.
O
2M+ + -
2M+O2- + O C O
Change of lattice energy from Li2CO3 to Li2O is greater than Na2CO3 to Na2O.
1 mark
2 mark
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, sodium and
potassium. Use the symbol M for the elements.
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
i
The decomposition temperature of MgCO3 is lower than that of CaCO3.
3
charge
When compared with Ca2+, Mg2+ has higher radius ratio and is more polarizing,
1 mark
2 CO3 in MgCO3 is polarized to a greater extent than in CaCO3.
1 mark
1 mark
Hence MgCO3 undergoes thermal decomposition to form oxide (small anion) more readily than CaCO3.
95 2B 5 a v
5a
The table below lists some properties of the alkali metals.
Standard electrode
Melting point / C
Element
Atomic
Ionic radius / nm
First ionization
potential / V
radius / nm
energy / kJmol-1
Li
0.123
0.060
520
-3.04
180
Na
0.157
0.095
495
-2.71
98
K
0.203
0.133
418
-2.92
64
Rb
0.216
0.148
403
-2.93
39
Cs
0.235
0.169
374
-2.95
29
v With reference to the standard electrode potentials and the melting points of the elements, explain why the
reactivity of the alkali metals with water increases as the group is descended.
All group I elements react with cold water to give OH- and H2.
1 mark
OR M(s) + H2O(l) MOH(aq) + H(g)
The electrode potential of group I metal increases down the group with the exception of Li, therefore, the
reactivity increase.
1 mark
For Li, the relatively high melting point reduces the reactivity Q activation energy for the reaction is higher.
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.
Mg2+ is more polarizing than Na+ due to its smaller size and greater charge. The OH- is polarized to a greater
2 marks
extent in Mg(OH)2.
OR
Because of its high charge / radius ratio, Mg2+ forms more stable lattice with small anions e.g. O2-, Mg(OH)2 is
ready to decompose to give MgO.
2 marks
ii The thermal stability of the carbonates of the alkaline earth metals increases as the group is descended.
As the group is descended, the polarizing power of the cation decreases. Therefore, cations of the lighter elements
distort the anion electron clouds to a larger extend. Anions with highly distorted electron clouds are more readily
decomposed than those with little distortion. Hence the thermal stability increases as the group is descended.
3 marks
OR
The charge / radius ratio of cation increases as the group is ascended.
Cations with high charge/radius ratio tend to form stable lattice with small anions.
3 marks
Therefore, carbonates of Be, Mg tend to decompose to form the more stable oxides.
96 2B 4 b i
4b
For each of the following pairs of compounds, 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
+ mark
+ mark
which can turn lime water milky but Na2CO3 does not decompose.
Or
+ mark
dissolve the solid in water, add MgSO4(aq) to the solutions
+ mark
Na2CO3(aq) gives a white ppt.; but NaHCO3(aq) does not.
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
s-Block Elements
equation for the reaction.
Unit 2
Page 5
s-Block elements
Unit 3
Topic
s-Block Elements
Reference
Reading
9.2.3.0
Chemistry in Context, 3rd Edition ELBS pg. 142143, 183184, 243244
Page 1
Unit 3
Assignment Chemistry in Context, 5th Edition, Thomas Nelson and Sons Ltd. pg. 127128, 162163, 215, 284
Reading
Syllabus
Solvation process
Solubility of ionic crystal
Notes
C. Solubility of sulphate and hydroxide

The feasibility of a change is depending on the relative stability of the reactants and the products. Similarly,
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 - TS. Dissolution is a process accompanied with an increase in disorderness i.e. S is positive.
Therefore, an dissolution process is energetically feasible if H of solution is negative, zero or slightly positive.
The solute would be insoluble if H is highly positive. Or if we disregard the change in disorderness in the
dissolution process, G H. The solute would be soluble if the H of solution is negative.
According to Hess's law, the enthalpy change of a process is independent of the pathway of the process actually
taken. In the determination of H of solution of an ionic compound, the process can be imagined as vaporization of
the substance followed by solvation of the gaseous ion to form the solution.
1.
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.
The process in which a solute in any physical state is dissolved in a solvent to form a
solution.
Solvation energy (Hydration energy) Enthalpy change when 1 mole of formula units of gaseous particles are
solvated to form a infinitely diluted solution. If the solvent is water, then
the enthalpy change is called hydration energy.
s-Block elements
Unit 3
Page 2
Considering the process of solution of NaCl(s),
NaCl(s) Na+(aq) + Cl-(aq)
Hosoln = +5 kJmol-1
The process can be divided into two steps :

Ho = - Holat
i. NaCl(s) Na+(g) + Cl-(g)
For an ionic solid to dissolve, the crystal lattice must be broken up and the cations and anions have to be separated
from each other. If the ions are separated to infinite distance apart, the energy required is numerically equal to Holat.
Hohyd or Hosolv
ii. 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.
By Hesss Law, the heat of solution Hosoln = -Holat + Hohyd
Whether the heat of solution Hosoln is exothermic or endothermic depending on the relative magnitudes of Holat
and Hohyd.
Heat is always liberated in the hydration process. If the heat of hydration is high enough, the energy released will
be high enough to overcome the attractions between the ions. This makes the crystal soluble.
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
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. If an ion
has high 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.
Since the cation and anion are solvated independently, the total hydration energy can be expressed as :
1 1
Hydration energy ( r + r )
+
-
r +, r - :
radii of cation and anion
On top of charge density, 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 packing will be more efficient and
gives a higher lattice energy.
Furthermore, lattice energy is depending on the attraction between the cation and anion, therefore the lattice energy
can be expressed as :
1
Lattice energy r + r
+
-
c)
r +, r - :
radii of cation and anion
Solubility of a solute is depending on the interaction between the

solute and solvent particle. 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.
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, if the sizes of the ions in the crystal are different, the crystal will be soluble. And, if the sizes of the
ions in the crystal are similar, the crystal will be insoluble. This assumes that the crystal is purely ionic. e.g. This is
not applicable to the case of AgCl which is not purely ionic.
s-Block elements
Unit 3
2.
Page 4
a) Sulphate salt of group II metal

Compound
MgSO4
CaSO4
SrSO4
BaSO4
Relative solubility
Soluble
Sparingly soluble
Insoluble
Insoluble
1
+
-
Solubility mol/100g of water at 298 K

1.83 10-1
4.66 10-3
7.11 10-5
9.43 10-7
1 1
+
-
On descending the group, magnitudes of both hydration energy and lattice energy decrease as the size of the cation
increases.
SO42- ion is a polyatomic ion with a much larger size than group II ions. This makes the magnitude of lattice
energy rather constant and decreases slower than the magnitude of hydration energy on moving down the group.
Hosoln = -Holat + Hohyd
As a result, on moving down the group, Hosoln becomes less negative and the solubility decreases.
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
+
-
Solubility mol/100g of water at 298 K

2.00 10-5
1.53 10-3
3.37 10-3
1.50 10-2
1 1
+
-
Once again, on moving down the group, magnitudes of both hydration energy and lattice energy decrease as the
size of the cation increases.
OH- ion is a small anion. The hydration energy is very large, and rather constant on moving down the group since
it is almost dominated by the small size of OH- ion.
Hosoln = -Holat + Hohyd
As a result, on moving down the group, Hosoln becomes more negative and the solubility increases.
N.B.
In general, a substance with a solubility lower than 10-2 mol/100g of water is considered to be not very
soluble.
s-Block elements
Unit 3
c)
Page 5
Results obtained when 0.1M solution Mg2+, Ca2+, Sr2+ and Ba2+ are treated with various solutions.
Difference in solubility is a useful tool in qualitative analysis. For example Ca2+(aq) and Sr2+(aq) solutions can be
distinguished by adding saturated CaSO4(aq) solution.
N.B.
Although OH- ion is a polyatomic ion, it is considered as a small ion.
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.
4e
Lithium salts generally have high solubilities in water.
Li+ has very high charge density because of the small ionic radius.
there formation of Li(H2O)n+ involve high hydration energy.
Li salts - lattice energy is low because of the crystal packing is not efficient.
3
1 mark
1 mark
1 mark
91 2A 1 b iii
iii When solid sodium chloride is dissolved in water, the process is endothermic. Explain this observation.
The dissolving of a salt in water is a case of an enthalpy change accompanying a chemical process. The first
process requires an input of energy to break the lattice. The second process involves the release of energy when
new bonds are made between ions and water. The enthalpy of solution is a measure of the difference between
2 marks
these two processes. In case of NaCl, the lattice energy is larger than the enthalpy of hydration.
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, whereas the
4
solubility of group(II) salts of small anions shows the reverse trend.
1 mark
Hsoln = -HLE + HHE
HLE: Lattice energy - energy released in the formation of the solid crystal from the gaseous ions
HHE: Hydration enthalpy - energy released when the solute particles in gaseous state become associated with
water molecule to form a solution.
mark
More negative the Hsoln, more soluble would be the salt.
1
mark
Lattice energy
r+ + r
1 1
Hydration energy ( + )
mark
r+ r
On descending the group, magnitude of both hydration energy and lattice energy decrease.
mark
For large anions, the lattice energy is rather constant. The magnitude of hydration energy decreases more than
that of lattice energy as the size of the cation increases.
mark
mark
The Hsoln becomes less negative on descending the group and solubilities decrease.
For small anions with small cation, the packing efficiency is high result in higher lattice energy. The magnitude of
hydration energy decreases less than that of lattice energy as the size of the cation increases.
The Hsoln becomes more negative on descending the group and solubilities increase.
93 2B 4 b ii
4b
ii MgCrO4 is more soluble in water than BaCrO4.
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.
1 mark
Mg2+ is smaller than Ba2+, it has much higher hydration energy than Ba2+, MgCrO4 is more soluble than
1 mark
BaCrO4.
96 2B 4 c
4c
Briefly explain why magnesium sulphate(VI) is soluble in water, whereas barium sulphate(VI) is almost insoluble. 2
Hydration energy of Mg2+ is more exothermic than that of Ba2+
1 mark
due to the very small size of Mg2+ cation. Therefore, the lattice of MgSO4 can easily be broken down by water.
1 mark
98 1A 3 b iii
3b
Sketch the trends for the properties mentioned in (i), (ii), and (iii) below, and account for the trend in each case.
iii solubility in water of the Group II sulphates(VI), MgSO4, CaSO4, 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.
s-Block elements
Unit 4
Topic
s-Block Elements
Reference
Reading
9.2.4
Page 1
Unit 4
Assignment
Reading
Syllabus
Anomaly of lithium
Notes
D. Abnormal behaviour of lithium

Lithium exhibits anomalous behaviour comparing with other group I metal. The properties of lithium resembles
that of magnesium more than that of other group I metal. This is an example of diagonal relationship. The anomaly
is mainly due to the exceptional high charge density and polarizing power of lithium ion comparing with other
group I metal ions.
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
water
Decompose into oxide,
nitrogen dioxide and
oxygen
Do not form stable solid
hydrogencarbonate
Form organometallic
compound e.g. RLi
Magnesium
Formation of normal
oxide
carbon dioxide
water
Decompose into oxide,
nitrogen dioxide and
oxygen
Do not form stable solid
hydrogencarbonate
Form organometallic
compound e.g. MgR2
Insoluble phosphate,
fluoride and carbonate
Form stable nitride
Insoluble phosphate,
Form stable nitride
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
at all
Soluble phosphate,
Do not form stable nitride,
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. For lithium in Group I,
give two examples of anomalous behaviour and explain how this behaviour arises.
Any two of the following examples:
1. Lithium carbonate, nitrate, hydroxide decomposes upon heating, while carbonate of other Group I elements
do not.
Li2CO3 Li2O + CO2

heat
4LiNO3 2Li2O + 4NO2 + O2

heat
2LiOH Li2O + H2O

2. Lithium do not form any superoxide and peroxide.
3. Lithium forms a number of organic compound e.g. RLi
4. Slow reaction with water and not explosive with acid.
5. Do not form solid hydrogencarbonate.
2 marks
6. Li+2S2- is insoluble in H2O
Q Li has a small size, high charge density, high polarizing power and more electronegative(less stable in
forming ionic compound)
- forms more stable compounds with small anions e.g. O2-, H-, N3- due to high lattice energy.
Li2CO3, LiNO3 tend to decompose on heating
- forms more stable covalent bond with C when compare with other element in Group I.
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 .'
Lithium carbonate decomposes on heating to give (lithium oxide) and carbon dioxide.
+ mark
Li2CO3 Li2O + CO2
(1 mark)
1 mark
But other alkali metal carbonates do not.
mark
Lithium nitrate(V) decomposes on heating to give (lithium oxide),
mark
nitrogen dioxide / a brown gas and oxygen.
2LiNO3 Li2O + 2NO2 + O2
(1 mark)
1 mark
But other alkali metal nitrate(V) give nitrate(III) and oxygen.
2MNO3 2MNO2 + O2
(1 mark)
s-Block Elements
Unit 5
Topic
s-Block Elements
Reference
Reading
9.3
Page 1
Unit 5
Reading
Syllabus
Notes
III. Uses of the compounds of the s-block elements

A. Manufacture of glass
Sodium carbonate is used in the manufacture of glass. Soda glass is a mixture of sodium silicate and calcium
silicate, which is made by fusing the carbonates with silica SiO2(s) (from sand) at 1500C.
Na2CO3(s) + SiO2(s) Na2SiO3(s) + CO2(g)
CaCO3(s) + SiO2(s) CaSiO3(s) + CO2(g)
B. Baking powder
The main ingredient of baking powder is sodium hydrogencarbonate which is not very stable to heat. Upon
heating, it decomposes into sodium carbonate, carbon dioxide and water. The carbon dioxide evolved will help to
raise the bread in the baking process inside the oven.
2NaHCO3(s) Na2CO3(s) + CO2(g) + H2O(l)
N.B.
HCO3- is a large anion with high polarizability. It only forms stable solid hydrogencarbonate with big
group I metal ions. Group II and other metal hydrogencarbonate do not exist at all.
C. Making of soap
Aqueous sodium hydroxide is used in the hydrolysis of fat (saponification) in the preparation of soap.
D. Antacid
Mg(OH)2(s) is commonly used as the antacid to neutralize the excess acid in the stomach.
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)). When dissolved in water, the aqueous solution of slaked lime is called limewater.
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, making of mortar (slaked lime + sand +
water), bleaching powder and manufacture of calcium hydrogensulphite which is used in paper industry.
F. Fireworks
Salts of s-block metals are mixed with gunpowder in fireworks to give different colour to the fireworks.
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. Explain briefly, with the aid of 3
chemical equation(s), the role of sodium hydrogencarbonate in the baking process.
Sodium hydrogencarbonate in the self-raising flour undergoes thermal decomposition to give CO2 gas. 1 mark
2NaHCO3(s) Na2CO3(s) + CO2(g) + H2O(g)
1 mark
1 mark
The CO2 gas produced causes the cakes to rise.
97 1A 3 a iv
3a
For each of the following materials, identify ONE inorganic compound which is an active ingredient:
iv antacid
p-Block Elements
I.
Halogens
A.
B.
C.
D.
E.
II.
Laboratory preparation of chlorine

Characteristic properties of the halogens
Properties of halogen
1.
2.
Properties of the halogen compound
1.
Reactions of halide
a)
with halogens
b)
with conc. sulphuric(VI) acid
c)
d)
with silver ions
2.
3.
Oxoacid
Uses of halogens and halogen containing compounds
1.
2.
Use of chlorine
3.
Photographic films
Nitrogen and its compounds

A.
B.
Nitrogen
1.
2.
Ammonia
1.
Haber process
2.
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.
a)
With copper
b)
With iron(II) ion
c)
With sulphur
Nitrate(V) salt
1.
2.
Brown ring test
Use of nitric(V) acid
a)
Fertilizers
b)
Explosives
c)
Nylon
d)
Dyestuffs
III.
Sulphur and its compounds

A.
B.
C.
D.
E.
F.
Allotrope of sulphur
Burning of sulphur
Sulphur dioxide / sulphate(IV) salt
1.
a)
With manganate(VII) ion
b)
With dichromate(VI) ion
c)
With bromine
2.
a)
With magnesium
3.
1.
Contact process
2.
Sulphate(VI) salt
1.
1.
Fertilizers
2.
Detergents
3.
Paints, Pigments and dyestuffs
I. Halgoens
Unit 1
Page 1
Topic
I. Halogens
Unit 1
Reference
Reading
10.1.010.1.2
Chemistry in Context, 3rd Edition ELBS pg. 265, 270276
A-Level Chemistry, 3rd Edition, E.N. Ramsden pg. 396, 398399
Reading
Syllabus
Notes
I.
Halogens
A. Laboratory preparation of chlorine

Cl2(g) is a strong oxidizing agent. In order to prepare Cl2(g) from Cl- ion, an oxidizing agent stronger than Cl2(g) must
be used. KMnO4(s) and MnO2(s) are two commonly used oxidizing agents. Since the oxidizing power of KMnO4(s) is
very strong, heating is not essential. However, if MnO2(s) is used, heating is mandatory.
The source of Cl- ions may come from NaCl(s) or conc. HCl(aq). If NaCl(s) is used, H2SO4(aq) must be added to
provide the H+(aq) ions required in the reaction.
MnO2(s) + 4HCl(aq) MnCl2(aq) + 2H2O(l) + 2Cl2(g)
heat
10HCl(aq) + 2MnO4-(aq) + 6H+(aq) 5Cl2(g) + 8H2O(l) + 2Mn2+(aq)
I. Halgoens
Unit 1
Page 2
B. Characteristic properties of the halogens

All halogens have high electronegative and accept electrons readily. The word "halogen" means salt maker. It
forms salt readilty with metal.
C. Properties of halogen
1.
All halogens are strong oxidizing agents. Furthermore, free halogen atom also has high electron affinity. They all
accepts electron readily. Comparatively, the oxidizing power of fluorine is even stronger than potassium
manganate(VII).
Reduction half ionic equation
I2(s) + 2e- d 2I-(aq)
Br2(g) + 2e- d 2Br-(aq)
MnO2(s) + 4H+(aq) + 2e- d Mn2+(aq) + 2H2O(l)
Cl2(g) + 2e- d 2Cl-(aq)
MnO4-(aq) + 8H+(aq) + 5e- d Mn2+(aq) + 4H2O(l)
F2(g) + 2e- d 2F-(aq)
Standard reduction potential

+ 0.54 V
+ 1.07 V
+ 1.23 V
+ 1.36 V
+ 1.51 V
+ 2.87 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, Cl, Br, I) and PX5 (X = F, Cl, Br).
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)
I. Halgoens
Unit 1
2.
Page 3
Except fluorine, all halogens disproportionate in alkali. However, 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. (not a disproportionation reaction)
2F2(g) + 4OH-(aq) O2(g) + 4F-(aq) + H2O(l)

0
-1
at about 70C
F2(g) is extremely electronegative, it only behaves as an oxidizing agent but not a reducing agent.
Disproportionation of chlorine in alkali
Cl2(g) + 2OH-(aq) ClO-(aq) + Cl-(aq) + H2O(l)
0
+1
-1
at room temp.
3Cl2(g) + 6OH-(aq) ClO3-(aq) + 5Cl-(aq) + 3H2O(l)

0
+5
-1
at about 70C
This may be considered as thermal decomposition of ClO-(aq).

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.
Disproportionation of iodine in alkali

3I2(s) + 6OH-(aq) IO3-(aq) + 5I-(aq) + 3H2O(l)
0
+5
-1
at room temp.
The difference in mode of disproportionation can be explained by the difference in electronegativity of halogen
atom. As the most electronegative element, F tends to attain an oxidation state of -1 only.
With decreasing electronegativity on moving down the group, the element disproportionates and gets a more
positive oxidation state more readily.
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
I. Halgoens
Unit 1
90 1A 3 c
3c
By means of balanced equations, illustrate the reactions of the halogens F2(g), Cl2(g) and Br2(l) with OH-(aq) at room
temperature.
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, and write an equation involving a compound of chlorine to
illustrate your answer.
Definition : Reaction in which a single species/ion/substance is simultaneously oxidized and reduced.
(no mark for atom/element -)
1 mark
H2O + Cl2 HCl + HOCl
2NaOH + Cl2 NaCl + NaOCl + H2O
4KClO3 3KClO4 + KCl
3HOCl + 3H2O 3H3O+ + ClO3- + 2Cl3Cl2 + 6NaOH 5NaCl + NaClO3 + 3H2O
1 mark
( mark for unbalanced equation, 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, chlorine, bromine and iodine
i
at 295 K,
At 295 K, Cl2, Br2 and I2 disproportionate according to the equation
X2 + 2OH-(aq) OX-(aq) + X-(aq) + H2O(l)
OBr- and OI- are unstable and will undergo further disproportionation.
X = Br or I
3OX- d XO3- + 2XF2 is the strongest [O] agent, it will not disproportionate, instead, it will oxidize the OH- ion.
2F2 + 2OH- OF2(g) + 2F- + H2O
ii at 350 K.
At 350 K, Cl2, Br2 and I2 all disproportionate as follows
3X2 + 6OH-(aq) XO3-(aq) + 5X-(aq) + 3H2O(l)
F2 oxidizes the alkali,
F2 + 4OH- O2(g) + 4F- + 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.
2OH-(aq) + Cl2(g) Cl-(aq) + OCl-(aq) + H2O(l)

cold dil.
or 6KOH(aq) + 3Cl2(g)
5KCl(aq) + KClO3(aq) + 3H2O(l)
hot conc.
hot conc.
1 mark
94 1A 2 a ii
2a ii Write a balance equation, involving the reaction of chlorine with KOH(aq), to illustrate a disproportionation.
6OH-(aq) + 3Cl2(g)
5Cl-(aq) + ClO3-(aq) + 3H2O(l)
temperature
2NaOH (aq, dilute) + Cl 2(g) room
NaOCl(aq) + NaCl (aq) + H 2 O (l)
Page 4
1 mark
I. Halgoens
Unit 1
94 2B 4 a
4a
Describe how a sample of dry chlorine is prepared in the laboratory. State the safety precaution(s) that is/are
required.
Heating conc. HCl in the presence of manganese(IV) oxide
MnO2(s) + 4HCl(aq) MnCl2(aq) + 2H2O(l) + 2Cl2(g)
OR
Add conc. 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, dry the gas by passing through conc. H2SO4 and collect
2 marks
by downward delivery.
The experiment should be carried out in a fume cupboard.
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. 5+)
2d i
Explain why among the four compounds in (c), only HClO3 can undergo disproportionation.
The central atoms of the other three compounds are in their highest oxidation states
whereas in HClO3, Cl is in an intermediate oxidation state.
ii Write a balanced equation for the disproportionation of HClO3 to give HClO4 and ClO2.
3HClO3 HClO4 + H2O + 2ClO2
2
4 mark
1
mark
mark
1
1 mark
97 1B 7 a
7a
Briefly describe how a sample of dry chlorine gas can be prepared in the laboratory. Draw a labelled diagram of
the laboratory set-up and state the safety precaution(s) that is/are required.
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.
ii At each of the above temperatures, iodine solid instead of chlorine gas is added to the aqueous sodium hydroxide
solution. 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, explain why a different reaction takes place.
I. Halogens
Unit 2
Topic
I. Halogens
Reference
Reading
10.1.3.1
Page 1
Unit 2
Reading
Syllabus
Notes
D. Properties of the halogen compound

1.
Reactions of halide
a) with halogens
The oxidizing power of halogens show a decreasing trend on moving down the group. Therefore, F2 is the halogen
with the strongest oxidizing power.
A more reactive halogen is capable to displace a less reactive halogen from its salt.
e.g.
Cl2 + 2Br- 2Cl- + Br2
Aqueous halogens have similar colours with different intensity ranging from yellow, orange to brown. 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.
b) with conc. sulphuric(VI) acid
Conc. sulphuric(VI) acid (b.p. 338C) is an involatile acid and a strong oxidizing agent. However, its oxidizing
power is not strong enough to oxidize F- ion or Cl- ions. It can only displace HF(g) (b.p. 20C) and HCl(g) (b.p. 85C) from the salts since HF(g) and HCl(g) are very volatile.
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. H2SO4(l). Therefore, conc. H2SO4(l) is capable to oxidze
Br- ion and I- ion besides displacing HBr(g) (b.p. -67C) and HI(g) (b.p. -35C) from the salts.
Moreover, I- ion is a stronger reducing agent than Br- ion. I- ion is capable to reduce conc. H2SO4(l) to H2S(g) while
Br- ion is only capable to reduce conc. H2SO4(l) to SO2(g).
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)
Similar to conc. H2SO4(l), conc. H3PO4(l) (b.p. 213C) is also involatile but it is non-oxidizing. Conc. H3PO4(l) is also
a viscous liquid due to the formation of extensive hydrogen bonds among the molecules. It is capable to displace
hydrogen halides form the solid halide salts without oxidizing the halide ion to halogen.
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)
I. 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. Silver
nitrate must be used in acidic medium because silver(I) ion will form silver(I) oxide in the presence of hydroxide.
2Ag+(aq) + OH-(aq) Ag2O(s) + H2O(l)
Aqueous silver(I) ion forms silver halide precipitate with different colour and stability under light.
Ag+(aq) + Cl-(aq) AgCl(s) white ppt. soluble in NH3(aq) and deocmposes under light to purple grey ppt.
Ag+(aq) + Br-(aq) AgBr(s) yellow ppt. slightly soluble in NH3(aq) and decomposes under light to yellow grey ppt.
Ag+(aq) + I-(aq) AgI(s)
yellow ppt. insoluble in NH3(aq) and stable to light
N.B.
Solubility and formation of ammonia complex

AgBr(s) and AgI(s) are not very soluble in NH3(aq) solution because they are highly covalent. 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.
AgCl(s) + 2NH3(aq) d Ag(NH3)2+(aq) + Cl-(aq)
Besides Ag+(aq), Cu2+(aq) and Zn2+(aq) are also capable to form soluble complex with NH3(aq) molecules. At
first, the three ions will form insoluble precipitate of oxide and hydroxides upon addition of a little
aqueous ammonia since ammonia is a weak alkali.
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, the three precipitates will redissolve at high NH3(aq) concentration.
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
I. Halogens
Unit 2
90 2B 6 c
6c
Explain why copper(II) chloride is a stable compound whereas copper(II) iodide does not exist.
Cl is much more electronegative than I / the size of I- is larger than ClCl- is more resistant to oxidation than Ior
Cu2+ is an oxidizing agent strong enough to oxidize I- to I2
or
I- is a stronger reducing agent
I- ion is polarized by Cu2+
CuI2 disproportionates, CuI2 CuI + I2
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
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, for the reaction of concentrated H3PO4 with NaCl and NaBr.
Will concentrate H2SO4 give a similar reaction in each case?
Explain any difference(s) in reactivity between concentrated H3PO4 and concentrated H2SO4.
Reaction between NaX and H3PO4 (X = Cl or Br)
H3PO4 + NaX HX + NaH2PO4
With H2SO4, NaCl gives similar reaction
NaBr will react to give also Br2 and SO2, 2HBr + H2SO4 2H2O + SO2 + Br2
Q conc. H2SO4 is an oxidizing agent while conc. H3PO4 is not.
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, and
NaCl + H2SO4 NaHSO4 + HCl
ii concentrated H2SO4 and NaI.
NaI + H2SO4 HI + NaHSO4
8HI(g) + H2SO4(l) 4I2(s) + H2S(g) + 4H2O(l)
HI / I-, being a stronger reducing agent than HCl, will be oxidized by conc. H2SO4 to give I2.
1 mark
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.
Prepare conc. aqueous solutions by dissolving the solids in water.
1 mark
mark
Add AgNO3(aq) to solution in test tube
mark
Add excess NH3(aq) to the precipitate
1 mark
Let the precipitate settle, decant the solution and compare the height of the precipitate.
(Note : Br- is insoluble in dil.NH3 but soluble in conc. NH3)
I. 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.
i
Write a balanced equation for the reaction of concentrated sulphuric(VI) acid and potassium chloride.
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.
Draw a labelled diagram of the laboratory set-up and state the safety precaution(s) that is/are required.
Hydrogen chloride can be prepared by dropping (slow addition of) c. H2SO4 onto KCl
mark
mark
and warming the reaction mixture.
The HCl produced is tried by passing through anhydrous CaCl2 /concentrated H2SO4
mark
mark
and then collected by downward delivery / in a gas syringe.
1 mark
Precaution: carry out experiment in fume cupboard.
[2 marks for description of the expt; 1 mark for safety precaution.]
marks for the diagram for the set-up

3 marks
( mark for a tap funnel; marks for labelling the reactants
1 mark for correct set-up for the drying process;
1 mark for the collection of HCl)
(Deduct 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.
Write a balanced equation to represent the reaction that occurs.
c. 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.
HBr can be prepared by heating KBr with cone. H3PO4.
1 mark
Or
(1 mark)
Add Br2(l) to moist red phosphorus.
98 2B 8 b ii
8b
For each of the following, state the expected observation and write the relevant balanced equation(s).
ii Ammonia solution is added dropwise, until in excess, to a solution of copper(II) sulphate(VI).
99 1A 3 d ii
3d
ii KBr(s) is heated with concentrated H2SO4.
I. Halogens
Unit 3
Page 1
Topic
I. Halogens
Unit 3
Reference
Reading
10.1.3.210.1.3.3
Assignment
Reading
Syllabus
Notes
2.
All hydrogen halides are acidic in water. The acidity of hydrogen halide decreases on moving down the group.
HA(aq) + H2O(l) d A-(aq) + H3O+(aq)
pKa
E(HX)
EN
HF
3.2
568
3.9
HCl
-7
432
0.9
HBr
-9
366
0.7
HI
-10
298
0.4
This can be explained the decrease in bond energy despite of the increase in bond polarity. Furthermore, from the
experimental data, it can be concluded that the solvation of the halide ion is not a determining factor affecting the
strength of the acid.
HF shows exceptionally low acidity because of the very strong HF bond and the capability of the molecule to
form hydrogen bond with the free proton in the aqueous medium. This reduces the amount of the hydroxonium
ions in the solution and lowers the acidity of HF(aq).
HF(aq) + H+(aq) d H2F+(aq)
3.
Oxoacid
An acid containing oxygen is called an oxoacid. They have the forms HXO, HXO2, HXO3, H2XO3, H2XO4 etc. The
salts formed by them are called oxo-salts.
e.g.
H O Cl
O
H
chloric(I) acid (HOCl)
O
P
sulphuric(VI) acid (H2SO4)
O
H
phosphoric(V) acid (H3PO4)
The acidity of an oxoacid is depending on the no. of oxygen attaching to the atom X. Since O is an electronegative
atom, it imposes a negative inductive effect on the central atom X. This will make the -OH+ bond more polar.
The attraction between the water molecules and H+ will be strengthened and this favours the dissociation of the
proton. Therefore, the molecule will become more acidic.
Moreover, the oxoacid with more no. of O atom would also be more acidic because the anions formed would be
more stable. This is because they are capable to form more identical resonance structures which imply a more
evenly distributed electron cloud and more stable structure.
Glossary
oxoacid
oxo-salt
I. 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.
Suggest one common chemical properties shown by both compounds.
NaOCl and KClO3
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, and arrange them in order of increasing acid strength.
HOCl < HClO2 < HClO3 < HClO4
1 mark for 3 formulae, 1 mark for order of acidity
iv Explain why the acidity of 0.1 M HF(aq) is weaker than that of 0.1 M HCl(aq)
HF is extensively hydrogen-bonded in water.
(HF)n + H2O(l) d H3O+(aq) + F-(aq)
the equilibrium lies to the L.H.S.
1 mark
The Cl- ion, having a larger size, is highly polarizable, it is stable in water.
Hence the equilibrium
1 mark
HCl(aq) + H2O(l) d H3O+(aq) + Cl-(aq) lies to the right, so HCl is a strong acid.
OR
HX bond strength is greater in HF than in HCl
1 mark
1 mark
this outweighs the reduced hydration energy from F- 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.
Mn
O
OO
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.
highest oxidation state = +7 / VII
mark
1 mark
example: BrO4- / HBrO4
lowest oxidation state = -1 / -I
mark
1 mark
example: Br- / HBr
(Accept any correct example of Br containing compound)
99 1A 3 d i
3d
i
KIO3(aq) is added to acidified KI(aq).
I. Halogens
Unit 4
Page 1
Topic
I. Halogens
Unit 4
Reference
Reading
10.1.4
Reading
Syllabus
Notes
E. Uses of halogens and halogen containing compounds

1.
Fluoridation is the addition of a chemical called fluoride to water supplies to help teeth resist decay. In the 1930's,
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.
Today, about half the people of the United States drink fluoridated water. 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.
Local governments or the people of a community often must decide whether the water supply should be
fluoridated. This means balancing the benefits, risks, and costs of fluoridation, as well as moral questions about its
widespread use. People disagree over these issues, and fluoridation has always been controversial.
Benefits, risks, and costs. Many studies have shown that fluoridation reduces tooth decay substantially. However,
rates of tooth decay also have declined in areas without fluoridated water, perhaps chiefly because of the
widespread use of fluoride toothpastes.
2.
Use of chlorine
Manufacture of poly(chloroethene)
Industrially, vinyl chloride is prepared by heating 1,2-dichloroethane at 500 C which is prepared from
addition reaction between chlorine and ethene.
H
H
C C
H H
H C
H H
Cl2
Electrophilic
addition
H C C H
Cl Cl
Heat 500 C
C H
H
C
Cl
Cl Cl
C
H
Eventually, poly(vinyl chloride) / poly(chloroethene) is prepared through a radical addition mechanism.

H H
H
H
C
Cl
H H
R C C
Cl H
R C C
Cl H
H
C
Cl
C
H
H H H H
R C C
Cl H Cl H
I. 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.
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, chlorine bleach can also be used as a very effective disinfectant. In is also
used in water and sewage treatment.
3.
Photographic films
Black and white film is made of emulation of silver bromide crystal in gelatin coated on a plastic base. Upon
exposure to light, silver bromide will decompose to black silver crystal. 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.
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. Give TWO other products obtained by this
industrial process.
NaOH(aq) is produced by electrolysis of brine / concentrated NaCl(aq)
1 mark
(Deduct mark for not mentioning concentrated.)
+ mark
Other products: H2 / Cl2 / NaOCl solution (bleach solution) (any TWO)
97 1A 3 a i iii
3a
i
photographic film
iii bleaching powder
II. Nitrogen and its compounds
Unit 1
Topic
Reference
Reading
10.2.010.2.2
Page 1
Unit 1
Assignment Chemistry in Context, 3rd Edition ELBS pg. 362365

Reading

Syllabus
Notes

A. Nitrogen
1.
Comparing with other p-block elements, nitrogen is quite unreactive because of the strong NN triple bond. A very
high temperature is required to break the bond. Therefore, the reaction with N2(g) involves a very high activation
energy.
When Mg(s) is burning in air, the temperature is high enough to break the NN bond. This leads to formation of
yellow magnesium nitride.
Mg(s) + N2(g) Mg3N2(s)
NN
N=N
NN
NH
HH

+ 158
+ 410
+ 945
+ 391
+ 436
CC
C=C
CC
CH

+ 347
+ 612
+ 838
+ 435

2.
Unit 1
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
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, 500C
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 Chateliers 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.
500C 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.

2.
Unit 1
Page 4
a) Alkaline properties
Ammonia is a weak alkali in water. Kb of ammonia at 25C is 1.8 10-5 moldm-3.
(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) CaCl24NH3(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 doesnt 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)
Unit 1
Page 5
(2) Catalytic oxidation (Ostwald process in laboratory scale)

In the presence of platinum catalyst, ammonia can be oxidized further to
NO(g) at high temperature.
In the experimental setup, oxygen is bubbled through concentrated
ammonia solution and mixed with ammonia vapour. 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, the platinum wire will continue to
glow once the reaction has started. The initial product NO(g) is colourless
which reacts with atmospheric oxygen to form brown NO2(g).
NO(g) + O2(g) NO2(g)
Brown fume of NO2(g) will be observed at the mouth of the flask.
(3) With copper(II) oxide
Ammonia can also reduce oxides of unreactive metal to the metals with heating. e.g. CuO(s) Cu(s)
3CuO(s) + 2NH3(g) 3Cu(s) + N2(g) + 3H2O(g)
(4) With chlorine

Chlorine is a strong oxidizing agent. Ammonia burns spontaneously in chlorine.
2NH3(g) + 3Cl2(g) N2(g) + 6HCl(g)
If ammonia is in excess, a dense white fume of NH4Cl(s) will also be observed.
NH3(g) + HCl(g) NH4Cl(s)
Unit 1
Page 6
(5) Thermal decomposition of ammonia

Thermal decomposition of ammonia is only the reverse of Haber process. The decomposition is almost
complete at 1 atm in the presence of Fe catalyst with heating. This is done by passing ammonia back and forth
the heated iron wool.
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.
Glossary
high tension
electric arc
Haber process
Le Chateliers principle
catalytic oxidation (Ostwald process)
thermal decomposition of ammonia
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.
Your answer should include the physico-chemical principles involved and also the role of any catalyst.
Ammonia
N2 + 3H2 d 2NH3
H < 0 / exothermic
1 mark
Conditions of reaction:
200 atm, 500C, 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 - 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. With reference to the availability and preparation of raw
materials, discuss the major economic aspects of this process.
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.
iii State how ammonia is isolated from unreacted nitrogen and hydrogen in the process.
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.
i
Write a balanced equation for the overall reaction.
ii Briefly explain how ammonia acts as a reducing agent and as a base in the reaction.
99 2A 1 c i
1c
For each of the following pairs of substances, suggest a chemical test to distinguish one from the other. For each
test, give the reagent(s) used and the expected observation.
i
CsCl(s) and NH4Cl(s)
99 2A 4 a iii
4a
In the Haber process, ammonia is synthesized by the exothermic reaction of nitrogen and hydrogen at around
723K.
N2(g) + 3H2(g) d 2NH3(g)
In a simulation of the process, a mixture of nitrogen and hydrogen was placed in a closed container. The initial
concentrations of nitrogen and hydrogen were 0.50 mol dm-3 and 1.50 mol dm-3 respectively. When the
equilibrium was attained at 723 K, 25.0% of the original nitrogen was consumed.
iii (I) State, with explanation, the effect of temperature on Kc for the reaction.
(II) Explain why the Haber process is not operated at temperatures much higher or much lower than 723 K.
Unit 2
Topic
Reference
Reading
10.2.3
Page 1
Unit 2

Reading

Syllabus
Notes
C. Nitric(V) acid
1.
Ostwald Process
Nitric(V) acid is manufactured from NH3(g) industrially through the NO(g) and NO2(g) intermediates. The process is
called Ostwald process. Although NO(g) can be prepared by direct oxidation of N2(g) molecule, this is not
economical because the activation energy involved is very high..
NH3(g) serves as an intermediate to break the whole process into steps with lower activation energies.
N2 NH3(g) NO2(g) HNO3(aq)
Ostwald process
a.
NH3(g) is first oxidized by O2(g) in air to NO(g) in the presence of Pt(s) catalyst at 900 C and 8 atm.
Pt
4NH3(g) + 5O2(g)
4NO(g) + 6H2O(l)
H = - 950 kJmol-1
Similar to Haber process, the conditions chosen in Ostwald process is also a compromise between yield and
rate of reaction.
Since the reaction is highly exothermic, the heat generated is diverted to heat up the raw material in the heat
exchanger.
b.
Cooled NO(g) is further oxidized by O2(g) to NO2(g)

2NO(g) + O2(g) 2NO2(g)
c.
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. It can be concentrated to concentrated
nitric(V) acid by distillation. Concentrated nitric(V) acid is an azeotrope of 68% nitric(V) acid. It can further
be concentrated to pure nitric(V) acid by distilling with conc. H2SO4(l) or P2O5(s).

2.
Unit 2
Page 2
In contrast to ammonia, nitrogen in nitric(V) acid has the highest possible oxidation state, +5. It can only behaves
as an oxidizing agent.
Depending on the concentration, nitric(V) acid shows different degree of oxidizing power and gives different
products.
Concentrated nitric(V) acid (16M)
Dilute nitric(V) acid (2M)
Very dilute nitric(V) acid (0.1M)
NO3-(aq) + 2H+(aq) + e- d NO2(g)

NO3-(aq) + 4H+(aq) + 3e- d NO(g)
2H+(aq) + 2e- d H2(g)
Very dilute nitric(V) acid behaves similarly to other aqueous acids. It has only very weak oxidizing power offered
by the H+(aq) ions.
Indeed, nitric(V) acid can also be reduced to other products with different oxidation states depending on the
condition.
NO3-(aq) + 5H+(aq) + 4e- d 2H2O + N2O
NO3-(aq) + 8H+(aq) + 6e- d 2H2O + H2NOH
NO3-(aq) + 10H+(aq) + 8e- d 3H2O + NH4+
a) With copper
Concentrated nitric(V) acid is a very strong oxidizing. It even oxidizes less reactive metal like copper.
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, concentrated HNO3(aq) has no reaction with Fe(s) due to the formation of an impermeable oxide
layer. Thus, Fe(s) is said to be passive to concentrated HNO3(aq). Therefore, concentrated HNO3(aq) is usually
stored in steel tanks.
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. The NO(g) produced will be further oxidized
to brown NO2(g) in air.
Furthermore, the NO molecule is capable to form a brown complex [Fe(H2O)5NO]2+(aq) with Fe2+(aq). The
Fe2+(aq) solution may turn the solution brown eventually.

c)
Unit 2
Page 3
With sulphur
Sulphur has no reaction with cold conc. HNO3(aq). But upon heating, conc. HNO3(aq) can oxidize S(s) to
sulphuric acid.
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, concentrated nitric(V) acid and hydrogen sulphide gas?
H2S(g) + 2HNO3(conc.) S(s) + 2H2O(l) + 2NO2(g)
note: on boiling, H2SO4(aq) formed
6Ab
1
1 mark
93 2B 5 Ia
5I
For the industrial preparation of nitric(V) acid from nitrogen , give the chemical reactions and the conditions
a
under which they take place.
Pass purified N2 and H2 (ratio 1:3) over iron catalyst at 450C and 200 atm pressure.
2 marks
N2 + 3H2 d 2NH3
Ammonia is mixed with O2 (excess air) and passed over a platinum catalyst at 900C at 8 atm.
4NH3 + 5O2 4NO + 6H2O
2NO + O2 2NO2
3 marks
Resulting gaseous mixture is passed through water.
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, state the reactant(s)
used and the reaction conditions, and write balanced equation(s) for the reaction(s) involved.
ii nitrogen monoxide, NO
Unit 3
Topic
Reference
Reading
10.2.4
Page 1
Unit 3
Assignment Chemistry in Context, 3rd Edition ELBS pg.

Reading
Syllabus
Notes
D. Nitrate(V) salt
1.
Upon heating, different nitrate(V) salts will decompose to give different products depending on the reactivity of the
metal in the salt.
Reactivity series of metal
K, Na, Ca, Mg, Al, Zn, Fe, Pb, Cu, Hg, Ag, Au
i.
For reactive metal nitrate(V) e.g. KNO3(s) and NaNO3(s), they will decompose into nitrate(III) and oxygen.
thermal decomposition
Reactive metal nitrate(III) + Oxygen

Reactive metal nitrate(V)
e.g. 2NaNO3(s) 2NaNO2(s) + O2(g)
For this reason, KNO3 is an ingredient of gunpowder. Upon heating, it releases oxygen which supports the
burning of gunpowder.
ii. For less reactive metal nitrate(V) e.g. LiNO3(s), from Ca(NO3)2(s) to Cu(NO3)2(s), it will decompose into oxide,
nitrogen dioxide and oxygen.
Less reactive metal oxide + Nitrogen dioxide + Oxygen

Less reactive metal nitrate(V)
e.g 2Ca(NO3)2(s) 2CaO(s) + 4NO2(g) + O2(g)
iii. For non-reactive metal nitrate(V) e.g. HgNO3(s) and AgNO3(s), they will decompose into metal, nitrogen
dioxide and oxygen. (N.B. Au does not form stable solid nitrate at all.)
Non-reactive metal + Nitrogen dioxide + Oxygen

Non-reactive metal nitrate(V)
e.g. 2AgNO3(s) 2Ag(s) + 2NO2(g) + O2(g)
This may be considered as a 2 steps decomposition.
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.
Unit 3
Page 2
iv. Ammonium nitrate(V) NH4NO3(s) will decompose to dinitrogen oxide and water leaving no residue behind.
NH4NO3(s)
N2O(g) + 2H2O(l)
In this reaction, a solid reagent expands suddenly to gaseous products, therefore, NH4NO3(s) is potentially
explosive. It should not be heated too strongly.
N.B.
0 5 C
Recall the action of nitric(III) acid on amino group, RNH2 + HNO2(aq) N2(g) + ROH
NH4NO2(s) may be considered as a mixture of HNO2 and NH3 NH4NO2 d HNO2 + NH3
Therefore, NH4NO2(s) decomposes upon heating to give N2(g) and H2O(l) only.
NH4NO2 (s)
N2(g) + 2H2O(l)
2.
Brown ring test
The presence of nitrate(V) ion can be detected by brown ring test.

In brown ring test, the salt to be test is dissolved in a
freshly prepared iron(II) sulphate solution.
Concentrated sulphuric acid is then added slowly and
carefully into the resulting mixture without stirring it
up. Because concentrated sulphuric acid is denser in
water, it will sink to the bottom. A brown ring will form
at the interface between the concentrated sulphuric acid
and the aqueous layer if nitrate(V) ion is present.
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) FeSO4NO(aq) a simplified formula of the brown complex or [Fe(H2O)5NO]2+](aq)
Glossary
thermal decomposition of ntirate
brown ring test
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, the vehicle must carry a sign clearly showing :
AMMONIUM NITRATE ; DANGEROUS GOODS ; NO SMOKING.
Give chemical reasons why this is necessary.
NH4NO3(s) is unstable and readily/easily decomposes to give large volumes of gaseous products (N2O and H2O)
1 mark
and is therefore explosive.
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, one of which is sodium nitrate(V) and the other sodium bromide. Outline
laboratory tests to identify each anion positively, giving the reagents, reaction conditions and the expected
observations (Equations are not required.)
For NaNO3(s),
add conc. H2SO4 and heat / add conc. H2SO4 + Cu and heat
to give brown fumes of NO2 having no action on fluorescein (C20H12O5 yellowish to red in colour) impregnated
paper.
Add freshly prepared FeSO4 and conc. H2SO4 slowly / dropwise to give brown ring at the liquid junction.
For NaBr(s),
add conc. 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.
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.
or
Add HOCl solution to give orange-red colour of bromine. When the solution is shaken with CS2 / CHCl3 / CCl4,
mark for each point
the Br2 dissolves in the organic solvent leaving a colourless aqueous layer.
97 1A 3 a ii
3a
ii gun powder
97 2B 8 a i
8a
Suggest how the following nitrogen oxides can be prepared in the laboratory. In each case, state the reactant(s)
used and the reaction conditions, and write balanced equation(s) for the reaction(s) involved.
i
dinitrogen oxide, N2O
Unit 4
Topic
Reference
Reading
10.2.5
Page 1
Unit 4
Assignment A-Level Chemistry, 3rd Edition, E.N. Ramsden pg. 456

Chemistry in Context (4th ed.), Thomas Nelson and Sons Ltd., 355357
Reading
Modern Organic Chemistry (4th ed.), Bell & Hyman, 154155, 320
Syllabus
Use of nitrc(V) acid
Notes
E. Use of nitric(V) acid

Majority of nitric acid produced is used to make fertilizers and explosives. They accounts for 75% and 15% of the
total consumption.
a) Fertilizers
Nitric acid is used in making of fertilizer such as NH4NO3 by neutralization with ammonia.
b) Explosives
Nitroglycerin, a constituent of several explosives is manufactured by nitration of propane-1,2,3-triol using
concentrated nitric acid.
CH2 OH
CH2 O NO2
CH OH + 3 HNO3
CH O NO2
CH2 OH
CH2 O NO2
propane-1,2,3-triol
(glycerol)
propane-1,2,3-triyl trinitrate
(nitroglycerine)
CH2 O NO2
12 CO2(g) + 10 H2O(g) + 6 N2(g) + O2(g)
CH O NO2
CH2 O NO2
propane-1,2,3-triyl trinitrate
(nitroglycerine)
Nitroglycerine is a colourless, oily liquid which is violently exploded on slight shock. Oxygen is present in the
molecule, and carbon dioxide, water vapour and nitrogen are liberated to produce a very large pressure.
Dynamite, invented by the Swedish chemist, Nobel, is made by allowing kieselguhr (a kind of clay from seashell)
to absorb nitroglycerin. Although it retains its explosive properties, the nitroglycerin is less sensitive to shock.
Besides nitroglycerin, many other explosives like trinitrotoluene (T.N.T., the yellow explosive), gun-cotton are also
prepared by nitration using concentrated nitric acid.
CH3
O 2N
CH2ONO2
NO2
H
H
ONO2
ONO2
NO2
methyl-2,4,6-trinitrobenzene
(trinitrotoluene, T.N.T.)
n
cellulose nitrate (nitrocellulose, gun cotton)

c)
Unit 4
Page 2
Nylon
In industrial production of nylon, hexanedioic acid is manufactured by oxidation of a mixture of cyclohexanol and
cyclohexanone using moderately concentrated nitric acid and a copper salt as catalyst.
OH
O
60% HNO3, 60 C, cat.
HOOC
CH2CH2CH2CH2 COOH
Part of the hexanedioic acid is converted to hexane-1,6-diamine through hexanedinitrile. Hexanedioic acid and
hexane-1,6-diamine are then used to make nylon-6.6.
d) Dyestuffs
Azo dye is prepared by coupling diazonium ion with phenolic compound.
+
N N
H
N
OH
diazonium ion
+ H2O
OH
OH
naphthalen-2-ol
OH
N H
azo dye
(an orange red ppt.)
For example, 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
+
N N +
N N
OH
Orange II
Nitric acid is used to prepare nitrobenzene through which diazonium ion is prepared.
NO2
HNO3 , H2SO4
50 - 55
+
N N
NH2
Sn
HCl
NaNO2
HCl, 0-5
benzenamine
(an aromatic
primary amine)
diazonium ion
Glossary
nitroglycerine
Past Paper
Question
97 2B 8 b iv
Unit 4
trinitrotoluene (T.N.T.)
97 2B 8 b iv
8b iv Give TWO major uses of ammonia in industry.
Page 3
dynamite
azo dye
diazonium ion
III. Sulphur and its compounds
Unit 1
Page 1
Topic
Unit 1
Reference
Reading
10.3.010.3.2
Advanced Practical Chemistry, John Murray (Publisher) Ltd., 192194
Assignment A-Level Chemistry (3rd ed.), Stanley Thornes (Publisher) Ltd., 417418, 426427
Reading
Syllabus
Notes

A. Allotrope of sulphur
Normally, sulphur molecule consists of 8 sulphur atoms joined together, S8. S8 molecule has the shape like a
crown. The atomicity of sulphur is said to be 8. Atomicity means the number of atoms in a molecule of an
element.
Sulphur burns in oxygen with a blue flame and sulphur

dioxide is formed.
or simply
S8(s) + 8 O2(g) 8 SO2(g)

S(s) + O2(g) SO2(g)
Heating of sulphur
Characteristics of sulphur dioxide

1. Smell SO2(g) has characteristic smell.
2. Acidity SO2(g) forms sulphurous acid, H2SO3(aq) in
water which turns blue litmus paper red.
3. Reducing properties SO2(g) is a reducing agent. It
turns acidified K2Cr2O7(aq) from orange to green.
Sulphur crystal
Different forms of the same element in the same physical state are called allotropes of the element. e.g. diatomic
oxygen O2(g) and ozone O3(g) are two allotropes of oxygen
There are several different sulphur allotropes. e.g. rhombic sulphur, monoclinic sulphur and plastic sulphur
At room temperature, sulphur exists in 2 forms of crystal called rhombic sulphur and monoclinic sulphur. They
melts at 113C and 119C respectively. Thermodynamically, rhombic sulphur is more energetically stable at room
temperature while monoclinic sulphur is more stable at high temperature.
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.
Unit 1
Page 2
Both rhombic and monoclinic sulphur consists of S8 molecules.

Upon heating, S8 molecules agitate and the solid starts to melt. It turns into a light yellow liquid (a b).
If the heating is continued, the ring will open to form short chains (b c).
The short chains join to form long chains. Each chains has up to 106 atoms. At this stage, the liquid becomes dark
red and viscous due to the large van der Waals forces. (c d e).
If the sulphur is heated continuously, it will boil at 444C and the long chain will start to break up. However, if the
boiling sulphur is cooled rapidly, the long chain structure will be freezed and forming plastic sulphur. It is
stretchable like plastic (e f). On standing, it changes back to rhombic sulphur gradually.
Unit 1
Page 3
B. Burning of sulphur
Sulphur burns in air with a blue flame to form sulphur dioxide.
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.
C. Sulphur dioxide / sulphate(IV) salt

Laboratory preparation of sulphur dioxide
However, sulphur dioxide is seldom produced by burning of sulphur in laboratory due to the complicate
experimental setup required.
Depending on the amount of sulphur dioxide to be prepared, a redox reaction or a displacment reaction may be
used.
Hot conc. H2SO4(l) is capable to oxidize copper to
copper(II) ion while the acid will be reduced to SO2(g).
CuSO4(aq) + SO2(g) + 2H2O(l)
Cu(s) + 2H2SO4(l) heat
Besides SO2(g), water is also produced which has to be

removed by passing through a washing bottle conc.
H2SO4(l).
Eventually, the SO2(g) can be collected by downward
delivery or a gas syringe because it is heavier than air
and quite soluble in water.
If only a small amount of SO2(g) is required, a
sulphate(IV) salt would be used instead.
Upon the addition of a strong acid e.g. HCl(aq), the weak
acid, sulphuric(IV) acid would be displaced from the
sulphate(IV) salt. Eventually, SO2(g) could be prepared.
SO32-(aq) + 2H+(aq) H2SO3(aq) SO2(g) + H2O(l)

1.
Unit 1
Page 4
Sulphur dioxide is a soluble gas, though not as soluble as HCl(g) or NH3(g). In aqueous state, SO2(g) weakly
dissociates to HSO3-(aq) or SO32-(aq).
SO2(g) + H2O(l) d H3O+(aq) + HSO3-(aq)
Ka1 = 1.5 10-2 mol dm-3
HSO3-(aq) + H2O(l) d H3O+(aq) + SO32-(aq)
Ka2 = 6.2 10-8 mol dm-3
Since the dissociation is rather weak, H2SO3(aq) can also be written as SO2(aq) and H2O(l). And it is observed that the
redox properties of SO2(aq) and SO32-(aq) are similar.
4H+(aq) + SO42-(aq) + 2e- d H2SO3(aq) + H2O(l)
Eo = + 0.17 V
Because SO2(aq) is a mild reducing agent it reacts with strong oxidizing agent like MnO4-(aq) and Cr2O72-(aq).
a) With manganate(VII) ion
H2SO3(aq) + H2O(l) d 4H+(aq) + SO42-(aq) + 2e- 5
MnO4-(aq) + 8H+(aq) + 5e- d Mn2+(aq) + 4H2O(l) 2
Overall 5SO32-(aq) + 2MnO4-(aq) + 6H+(aq) d 5SO42-(aq) + 2Mn2+(aq) + 3H2O(l)
Eo = - 0.17 V
Eo = + 1.51 V
Eo = + 1.34 V
The purple colour of MnO4-(aq) will be decolorized by sulphur dioxide.

b) With dichromate(VI) ion
H2SO3(aq) + H2O(l) d 4H+(aq) + SO42-(aq) + 2e- 3
Cr2O72-(aq) + 14H+(aq) + 6e- d 2Cr3+(aq) + 7H2O(l)
Overall 3SO32-(aq) + Cr2O72-(aq) + 8H+(aq) d 3SO42-(aq) + 2Cr3+(aq) + 4H2O(l)
Eo = - 0.17 V
Eo = + 1.33 V
Eo = + 1.16 V
Orange Cr2O72-(aq) will be reduced to green Cr3+(aq) by sulphur dioxide.

c)
With bromine
H2SO3(aq) + H2O(l) d 4H+(aq) + SO42-(aq) + 2eBr2(aq) + 2e- d 2Br-(aq)
Overall SO32-(aq) + Br2(aq) + H2O(l) d SO42-(aq) + 2Br-(aq) + 2H+(aq)
Eo = - 0.17 V
Eo = + 1.09 V
Eo = + 0.92 V
The orange colour of Br2(aq) will be decolorized.

2.
Normally, sulphur dioxide doesnt behave as a oxidizing agent. But in the presence of a strong reducing agent. e.g.
Mg(s), SO2(g) can also be reduced to S(s).
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.

3.
Unit 1
Page 5
Comparatively, sulphur dioxde and carbon dioxide are quite similar in chemical properties. Both form white
precipitate with limewater, silver nitrate and barium chloride solutions.
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, they also show certain differences. Sulphur dioxide is much more soluble in water and is pungent in
smell. Moreover, the main difference between the two is that sulphur dioxide is reducing while carbon dioxide is
non-reducing. Therefore, they are be distinguished by using an oxidizing agent e.g. KMnO4/H+(aq), 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. Give one reaction in each case to illustrate this.
c
SO2 as reducing agent :
reaction with acidified K2Cr2O7 / KMnO4
Cr2O72- + 3SO2 + 2H+ 2Cr3+ + 3SO42- + 5H2O
or MnO4- + 5SO2 + 2H2O 2Mn2+ + 5SO42- + 5H2O + 4H+
SO2 as oxidising agent :
H2S + SO2 S(s) + H2O
(any 2 appropriate examples)
2 marks
Unit 2
Topic
Reference
Reading
10.3.310.3.4
Page 1
Unit 2

A-Level Chemistry (3rd ed.), Stanley Thornes (Publisher) Ltd., 428434
Reading
Syllabus
Notes
D. Concentrated sulphuric(VI) acid

1.
Contact process
Sulphur dioxide used in contact process in obtained by

1. Burning sulphur S(s) + O2(g) SO2(g)
2. Roasting sulphur containing ores in air 4FeS2(s) + 11O2(g) 2Fe2O3(s) + 8SO2(g)
2ZnS(s) + 3O2(g) 2ZnO(s) + 2SO2(g)
1.
Vanadium(V) oxide (V2O5(s)) catalyst, 450 C, 1 atm

SO2(g) + O2(g) d SO3(g) H = -197 kJ mol-1
During the reaction, the gaseous reactant is in contact with the catalyst, so the process is called contact
process.
Because the reaction is exothermic, the hot emerging SO3(g) is diverted to the heat exchanger to heat up the
incoming gas. This saves the fuel required to heat up the gas.
Indeed, the conversion is done in several stages. The gaseous mixture is directed through the catalytic
converter and the heat exchanger for several times until the conversion reaches 98%.
2.
Sulphur trioxide, SO3(g) is dissolved in conc. H2SO4(l) to form oleum, H2S2O7(l) (also called fuming sulphuric
acid).
SO3(g) + H2SO4(l) H2S2O7(l)
3.
H2S2O7(l) is added to the correct amount of water to form conc. H2SO4(l).

H2S2O7(l) + H2O(l) 2H2SO4(l)
Note :
SO3(g) is not added to the water directly because the reaction is highly exothermic. This will vaporize the
sulphuric acid formed and cause difficulty in collection of acid.
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 Chateliers principle the reaction is favored by a low

temperature and a high pressure.
However, if the temperature is too low, the rate of reaction will also be
lowered and a longer time will be required to reach the equilibrium.
Furthermore, though a high pressure gives a higher yield, the yield at 1 atm
is already 98% after several stages of conversion. It is not worthy to use a
pressure higher than 1 atm. This requires the use of a stronger reacting
vessel which is more costly to build.
Pressure
Temperature
yield
rate of reaction
Actually, the condition, 1 atm and 450C with the catalyst of V2O5(s) is a
compromise between yield and rate of reaction. At this condition, the
production of SO3(g) is most economical.
2.
i.
Acid
Effect of temperature on the

equilibrium constant and percentage
of conversion
Conc. H2SO4(l) shows acidic properties when water is added.

ii. Oxidizing properties
with Cu(s)
Normally, Cu(s) does not react will dilute sulphuric acid. It reacts with hot conc. H2SO4(l) because of its strong
oxidizing properties.
Oxidation half equation
Reduction half equation
Cu(s) Cu2+(aq) + 2eSO42-(aq) + 4H+(aq) + 2e- 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, it turns blue because of the presence of Cu2+(aq) ion.
Unit 2
Page 3
iii. High affinity for water - Hygroscopic and dehydrating properties

Conc. H2SO4(l) is hygroscopic and dehydrating.
Hygroscopic is the properties of absorbing water vapour from air.
Dehydrating is the properties of removing water from a stable structure and this implies a structural change.
Hygroscopic properties
Because of the hygroscopic properties, conc. H2SO4(l) can be
used as a drying agent. By bubbling the wet gas through conc.
H2SO4(l), the gas can be dried.
However, since conc. H2SO4(l) is also acidic and oxidizing, it
cannot be used to dry alkaline or reducing gases.
e.g. Alkaline gas - ammonia NH3(g)
Reducing gas - ethene C2H4(g)
Dehydrating properties
with copper(II) sulphate-5-water
Conc. H2SO4(l) removes the water of crystallization from CuSO45H2O(l). This turns the blue crystal to white
powder.
conc . H SO
2
4(l )
CuSO45H2O(s)
blue crystal
CuSO4(s) + 5H2O(l)
white powder
with paper
The main composition of paper is cellulose which is a carbohydrate. It has the general formula Cx(H2O)y.
Conc. H2SO4(l) is capable to extract the water from the structure of cellulose and char the paper.
conc . H SO
2
4(l )
xC(s) + yH2O(l)
Cx(H2O)y(s)
According to this principle, dil. H2SO4(aq) can be used as a magic ink. The word written on the paper can be
developed by heating the paper to evaporate the water. Once the sulphuric acid is concentrated, it will char the
paper and the word will appear.
with sugar
Similarly, sugar is another carbohydrate, it is also charred by conc. H2SO4(l).
Upon heating, conc. H2SO4(l) is also capable to oxidize the C(s) to CO2(g) and raise the spongy mass.
Oxidation half equation
Reduction half equation
C(s) + 2H2O(l) CO2(g) + 4H+(aq) + 4eSO42-(aq) + 4H+(aq) + 2e- 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)
Unit 2
Page 4
iv. Non-volatile acid

conc. H2SO4(l) is a non-volatile acid which boils at 380C. This makes it capable to displace the more volatile.
Displacement of hydrogen chloride
Boiling point of conc. H2SO4(l) : 380 C
Boiling point of hydrogen chloride : -85 C
Room temperature : 25 C
H2SO4(l) + NaCl(s) NaHSO4(s) + HCl(g)
Even at room temperature, hydrogen chloride is boiling. Conc. H2SO4(l) is capable to displace HCl(g) from
NaCl(s).
Displacement of nitric acid
Boiling point of nitric acid : 83 C
Similarly, pure HNO3(l) can be displaced from NaNO3(s). However, the boiling point of nitric acid is higher
than room temperature. Gentle heating is required.
NaHSO4(s) + HNO3(g)
H2SO4(l) + NaNO3(s) heat
E. Sulphate(VI) salt
1.
SO42-(aq) is usually tested with BaCl2(aq) solution. In the presence of BaCl2(aq), SO42-(aq) ion will be precipitated as
insoluble BaSO4(s) and the solution will turn into a white suspension.
Ba2+(aq) + SO42-(aq) BaSO4(s)
However, SO32-(aq) and CO32-(aq) also form white precipitate with Ba2+(aq). They are distinguished from SO42-(aq) by
addition of acid. In acidic medium, BaSO3(s) and BaCO3(s) will redissolve.
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. remains insoluble)
Glossary
contact process
barium chloride
vanadium(V) oxide
oleum / fuming sulphuric acid
hygroscopic
dehydrating
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.
Sulphuric acid
S + O2 SO2
2SO2 + O2 d 2SO3;
H < 0 very slow in the absence of catalyst
H O
SO3 + H2SO4 H2S2O7
2H2SO4
3 marks
Steps involved: Production of SO2, conversion to SO3, removal of SO3
Conditions of conversion: 1 atm, 450C, vanadium(V) oxide catalyst
1 mark
1 mark
Effect of [O2], removal of SO3
Effect of pressure
1 mark } any 1
1 mark
1 mark
1 mark
Catalyst - lower the activation energy for the SO2 + O2 reaction as O2 is kinetically inert
1 mark
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.) + 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, give the chemical reactions and the conditions
a
under which they take place.
Sulphur is burnt in air.
S + O2 SO2
1 mark
A mixture of SO2 + O2 (slightly excess air) is passed over V2O5 catalyst at 450C and 1 atm. pressure. 2 mark
2SO2 + O2 2SO3
1 mark
SO3 gas is passed into 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,
(NH4)2SO4Fe2(SO4)324H2O.
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) + O2(g) d SO3(g) with V2O5(s) catalyst
i
State, with explanation, 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.
99 2A 1 c ii
1c
For each of the following pairs of substances, suggest a chemical test to distinguish one from the other. For each
test, give the reagent(s) used and the expected observation.
ii Na2SO3(aq) and Na2S2O3(aq)
(4 marks)
Unit 3
Page 1
Topic
Reference
Reading
10.3.5
Unit 3
Assignment Chemistry in Context (4th ed.), Thomas Nelson and Sons Ltd., 350351
Reading
Syllabus
Notes
F. Use of sulphuric(VI) acid
a) Fertilizers
(1) By reacting with concentrated sulphuric(VI) acid, 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.
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.
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. For example,
CH3(CH2)11
c)
(i) conc. H2SO4

(ii) NaOH
CH3(CH2)11
SO3 Na
Paints, Pigments and Dyestuffs

(1) The white pigment titanyl sulphate, TiOSO4, is produced by dissolving titanium(IV) oxide, TiO2, in hot
concentrated sulphuric(VI) acid. Besides, barium sulphate(VI) and calcium sulphate(VI) are used as paint
additives.
(2) Concentrated sulphuric(VI) acid is used with concentrated nitric(V) acid in the preparation of
nitrobenzene which is used for making azo dyes.
(3) By reacting the dye with concentrated sulphuric(VI) acid, sulphonic group SO3H can be introduced to
the dye molecule. This group makes the dye more soluble in water and easily attached to fibre.
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.
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
Topic
Nitrogen and Sulphur
Reference
Reading
10.0
Modern Physical Chemistry ELBS pg.
Physical Chemistry, Fillans pg.
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.
Ammonia
N2 + 3H2 d 2NH3
H < 0 / exothermic
1 mark
1 mark
1 mark
Effect of pressure
1 mark } any 2
1 mark
2 marks
1 mark
1 mark
1 mark
Sulphuric acid
S + O2 SO2
2SO2 + O2 d 2SO3;
H O
2H2SO4
SO3 + H2SO4 H2S2O7
1 mark
Effect of pressure
1 mark } any 1
1 mark
2
3 marks
1 mark
1 mark
1 mark
1 mark
81 2B 8 a i ii iii d
8a
Describe
II
8d
EITHER
the process for the conversion of ammonia gas into (68%) nitric(V) acid,
12
OR
the process for the conversion of sulphur dioxide gas into (98%) sulphuric acid.
Give the conditions under which the various steps take place and briefly discuss which of the following will
involve the highest costs:
i
energy,
ii capital investment in plant, and
iii handling.
Concentrated nitric(V) acid
1 mark
Ammonia(g) is mixed with air.
passed over a Pt gauze or (Pt/Rh)
1 mark
catalyst which is maintained at 800C and 8 atm.
1 mark
1 mark
the reaction 4NH3(g) + 5O2(g) 4NO(g) + 6H2O(g)
1 mark
takes place with the evolution of heat.
The gases must be pure and avoid poisoning the catalyst.
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.
1 mark
2NO2(g) + H2O(l) 2HNO3(aq) + NO(g)
the NO(g) is recycled.
1 mark
Absorption may be carried out up to 68%(conc.) HNO3 which is the constant boiling mixture.
(i) energy the reaction condition of 800C is not difficult and expensive to maintain because the reaction is
exothermic.
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. ( The lost
of catalyst is due to the highly exothermic reaction produce energy which may vaporize the catalyst, Pt).
1 mark
(iii) Because NO, NO2 and HNO3 are highly corrosive and toxic, so special chemical resistant materials have to be
chosen for handling.
1 mark
1 mark
SO2(g) is mixed with air
1 mark
and the mixture is passed over a catalyst of Pt or V2O5.
1 mark
Usually V2O5 is used because Pt is expensive and easily to be poisoned by impurities. e.g. As2O3.
The operating temperature is about 450C at 1 atm.
1 mark
1 mark
2SO2(g) + O2(g) 2SO3(g) where the reaction is exothermic.
1 mark
The SO3(g) produced is then dissolved in 98% H2SO4 and fuming sulphuric acid (oleum) is formed.
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.
1 mark
exothermic.
1 mark
1 mark
(iii) Because SO2, H2SO4 and H2S2O7 are highly corrosive and toxic, so special chemical resistant materials have
to be chosen for handling.
.
1 mark
Write on the present-day uses of EITHER
concentrated nitric(V) acid,
4
OR
concentrated sulphuric(VI) acid.
Uses : 4 uses of conc. HNO3 or H2SO4.
1 mark each
conc. HNO3
Manufacture of explosive such as T.N.T.
Manufacture of fertilizers such as NH4NO3
Manufacture of dyestuffs
Manufacture of hexane-1,6-diamine which is a raw material for making nylon.
Manufacture of soapless detergents
conc. 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
ii
10b
having oxidation numbers (O.N.) of +2, +4 and +6.

N: NO(+2), NO2/N2O4(+4), NO3(+6)
2 marks
S: SO/S2O2(+2), SO2(+4), SO3(+6)
Describe what you would observe and give a balanced equation for the reaction the oxide of
EITHER
nitrogen (O.N. +2)
OR
sulphur (O.N. +4)
(A) with acidified potassium manganate(VII) solution,
(B) with an appropriate iron sulphate solution,
(C) with rain, and
(D) to form the element.
Nitrogen
(A) 5NO + 3MnO4- + 4H+ 5NO3- + 3Mn2+ + 2H2O (Purple colour decolourized / colourless solution)
(B) FeSO4 + NO FeSO4NO (Brown solution formed)
(C) 2NO + O2 NO2; 2NO2 + H2O HNO3 + HNO2; 2HNO2 + O2 2HNO3 (no special observation)
(D) Electric: 2NO d N2 + O2 at 3000C (no special observation)
OR Burning white phosphorus: 10NO + 4P 2P2O5 + 5N2 (white fume)
Sulphur
(A) 5SO2 + 2MnO4- + 2H2O 5SO42- + 2Mn2+ + 4H+ (Purple colour decolourized / colourless solution)
(B) 2Fe3+ + SO2 + 2H2O 2Fe2+ + SO42- + 4H+ (Solution change from yellow brown to pale green / colourless)
(C) SO2 + H2O H2SO3; 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. formed)
2 marks each
Describe the industrial preparation of
EITHER
nitric(V) acid from nitrogen
OR
sulphuric(VI) acid from sulphur.
Nitrogen
1. Conversion of nitrogen to ammonia, N2 + 3H2 d 2NH3
450-500C; 200-1000 atmosphere; iron or iron oxide catalyst
3 marks
2. Conversion of ammonia to nitrogen(II) oxide, 4NH3 + 5O2 d 4NO + 6H2O
600C; 8 atmosphere; platinium catalyst
3 marks
3. Conversion of nitrogen(II) oxide to nitric(V) acid, 4NO + 3O2 + 2H2O 4HNO3
Room temperature; 1 atmosphere; add water and air; no catalyst required.
3 marks
Sulphur
1. Conversion of sulphur to sulphur dioxide, S + O2 SO2
Burning sulphur, 1 atmosphere, no catalyst required.
2 marks
2. Conversion of sulphur(IV) oxide to sulphur(VI) oxide, 2SO2 + O2 d 2SO3
450C; 1 atmosphere; excess oxygen or air; platinium or vanadium(V) oxide catalyst.
4 marks
O
3. Conversion of sulphur(VI) oxide to sulphuric(VI) acid, SO3 + H2SO4 H2S2O7 H
2H2SO4
Add oxide to acid then dilute with water
3
marks
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.
Redox chemistry of sulphur
overall presentation
1 mark
Principal oxidation states with examples
2 marks
e.g. -2(H2S), 0(S), +4(SO2) and +6(SO3 or SO42-)
Any sulphur containing compounds, upon oxidation, give SO2 or SO42SO2 through combustion of the sulphur compounds in air
1 mark
SO42- oxidation in homogeneous solution.
Upon reduction, S or H2S are usually produced
H2S is a mild reducing agent but SO42- is usually stable towards redox reactions in the absence of H+. 1 mark
Intermediate oxidation states, for example, S2O32- or S4O62-, will undergo disproportionation in water. 1 mark
Redox chemistry of nitrogen
1 mark
2 marks
e.g. 0(N2), -3(NH3), +4(NO2), +5(NO3-)
The highest oxidation state is +5, and NO3- is usually the final product upon oxidation of any nitrogen containing
compounds under drastic conditions.
1 mark
NO3- is stable, but in the presence of H+, it is a strong oxidizing agent, upon reduction, give N2 or NH3. 1 mark
N2 is the most stable form, usually chemically insert in normal condition.

NH3 obtained by reduction of any nitrogen-containing compounds under drastic conditions.
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.
For EITHER nitric(V) acid OR sulphuric(VI) acid, illustrate using balanced half equations, how four possible
reduction products, having different oxidation states of N or S, may be obtained.
Explain why an aqueous solution of either Na2SO4 or NaNO3 is not a strong oxidizing agent.
Depends on the nature of the reducing agents and the reaction conditions employed:
Nitric(V) acid
NO3- + 2H+ + e- d NO2 + H2O
1 mark
1 mark
2NO3- + 12H+ + 10e- d N2 + 6H2O
1 mark
NO3- + 9H+ + 8e- d NH3 + 3H2O
1 mark
NO3- + 4H+ + 3e- d NO + 2H2O
other possible product: N2O, H2NNH2, NO21 mark
H+ is required if NO3- acts as an oxidizing agent
Sulphuric(VI) acid
SO42- + 4H+ + 2e- d SO2 + 2H2O
1 mark
1 mark
SO42- + 8H+ + 6e- d S + 4H2O
1 mark
SO42- + 10H+ + 8e- d H2S + 4H2O
1 mark
2SO42- d S2O32- or S4O62-, etc.
1 mark
H+ is required if SO42- acts as an oxidizing agent
Nitrogen
10.2.2.1
90 2B 5 b
5b
Outline an industrial preparation of ammonia.
Ammonia
N2 + 3H2 d 2NH3
H < 0 / exothermic
1 mark
1 mark
1 mark
Effect of pressure
1 mark } any 2
1 mark
2 marks
1 mark
1 mark
1 mark
10.2.3.1
81 2B 8 a i ii iii
8a
Describe the process for the conversion of ammonia gas into (68%) nitric(V) acid.
12
i
energy,
iii handling.
I Concentrated nitric(V) acid
1 mark
Ammonia(g) is mixed with air.
passed over a Pt gauze or (Pt/Rh)
1 mark
catalyst which is maintained at 800C and 8 atm.
1 mark
1 mark
the reaction 4NH3(g) + 5O2(g) 4NO(g) + 6H2O(g)
1 mark
takes place with the evolution of heat.
The gases must be pure and avoid poisoning the catalyst.
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.
1 mark
2NO2(g) + H2O(l) 2HNO3(aq) + NO(g)
the NO(g) is recycled.
1 mark
Absorption may be carried out up to 68%(conc.) HNO3 which is the constant boiling mixture.
exothermic.
1 mark
1 mark
(iii) Because NO, NO2 and HNO3 are highly corrosive and toxic, so special chemical resistant materials have to be
chosen for handling.
1 mark
10.2.5.0
81 2B 8 d
8d
Write on the present-day uses of concentrated nitric(V) acid.
Uses : 4 uses of conc. HNO3.
1 mark each
Manufacture of explosive such as T.N.T.
conc. HNO3
Manufacture of fertilizers such as NH4NO3
Manufacture of dyestuffs
Manufacture of hexane-1,6-diamine which is a raw material for making nylon.
10.2.4.0
84 2B 10 a i ii
10a i
Give the formulae of the oxides of nitrogen having oxidation numbers (O.N.) of +2, +4 and +6.
N: NO(+2), NO2/N2O4(+4), NO3(+6)
2 marks
ii Describe what you would observe and give a balanced equation for the reaction the oxide of nitrogen (O.N. +2)
(C) with rain, and
Nitrogen
(A) 5NO + 3MnO4- + 4H+ 5NO3- + 3Mn2+ + 2H2O (Purple colour decolourized / colourless solution)
(B) FeSO4 + NO FeSO4NO (Brown solution formed)
(C) 2NO + O2 NO2; 2NO2 + H2O HNO3 + HNO2; 2HNO2 + O2 2HNO3 (no special observation)
(D) Electric: 2NO d N2 + O2 at 3000C (no special observation)
OR Burning white phosphorus: 10NO + 4P 2P2O5 + 5N2 (white fume)
2 marks each
10.2.3.1
84 2B 10 b
10b
Describe the industrial preparation of nitric(V) acid from nitrogen.
Nitrogen
1. Conversion of nitrogen to ammonia, N2 + 3H2 d 2NH3
450-500C; 200-1000 atmosphere; iron or iron oxide catalyst
2. Conversion of ammonia to nitrogen(II) oxide, 4NH3 + 5O2 d 4NO + 6H2O
600C; 8 atmosphere; platinium catalyst
2
8
3 marks
3 marks
3.
Conversion of nitrogen(II) oxide to nitric(V) acid, 4NO + 3O2 + 2H2O 4HNO3

Room temperature; 1 atmosphere; add water and air; no catalyst required.
3 marks
10.2.4.0
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.
Redox chemistry of nitrogen
1 mark
2 marks
e.g. 0(N2), -3(NH3), +4(NO2), +5(NO3-)
The highest oxidation state is +5, and NO3- is usually the final product upon oxidation of any nitrogen containing
compounds under drastic conditions.
1 mark
NO3- is stable, but in the presence of H+, it is a strong oxidizing agent, upon reduction, give N2 or NH3. 1 mark
1 mark
N2 is the most stable form, usually chemically insert in normal condition.
1 mark
NH3 obtained by reduction of any nitrogen-containing compounds under drastic conditions.
Compounds in intermediate oxidation states such NO2 undergo disproportionation
1 mark
2NO2 + H2O d HNO3 + HNO2
10.2.3.2
89 2B 6 b
6b
Nitric(V) acid can be reduced to form products having a variety of oxidation states of N.
For nitric(V) acid, illustrate using balanced half equations, how four possible reduction products, having different
oxidation states of N, may be obtained.
Explain why an aqueous solution of NaNO3 is not a strong oxidizing agent.
Nitric(V) acid
NO3- + 2H+ + e- 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- + 4H+ + 3e- d NO + 2H2O
other possible product: N2O, H2NNH2, NO21 mark
H+ is required if NO3- acts as an oxidizing agent
Sulphur
10.3.3.1
90 2B 5 b
5b
Outline an industrial preparation of sulphuric acid.
Sulphuric acid
S + O2 SO2
2SO2 + O2 d 2SO3;
H O
SO3 + H2SO4 H2S2O7
2H2SO4
3 marks
1 mark
1 mark
Effect of pressure
1 mark } any 1
1 mark
1 mark
1 mark
1 mark
2
10.3.3.1
81 2B 8 a i ii iii
8a
Describe the process for the conversion of sulphur dioxide gas into (98%) sulphuric acid.
i
energy,
iii handling.
1 mark
SO2(g) is mixed with air
1 mark
and the mixture is passed over a catalyst of Pt or V2O5.
1 mark
Usually V2O5 is used because Pt is expensive and easily to be poisoned by impurities. e.g. As2O3.
The operating temperature is about 450C at 1 atm.
1 mark
1 mark
2SO2(g) + O2(g) 2SO3(g) where the reaction is exothermic.
1 mark
The SO3(g) produced is then dissolved in 98% H2SO4 and fuming sulphuric acid (oleum) is formed.
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.
1 mark
exothermic.
1 mark
1 mark
(iii) Because SO2, H2SO4 and H2S2O7 are highly corrosive and toxic, so special chemical resistant materials have
to be chosen for handling.
1 mark
10.3.5.0
81 2B 8 d
8d
Write on the present-day uses of concentrated sulphuric(VI) acid.
Uses : 4 uses of conc. H2SO4.
Manufacture of soapless detergents
conc. H2SO4
Manufacture of fertilizers such as (NH4)2SO4
Manufacture of explosives
Manufacture of pigments
4
1 mark each
10.3.2.0
84 2B 10 a i ii
10a i
Give the formulae of the oxides of sulphur
having oxidation numbers (O.N.) of +2, +4 and +6.
S: SO/S2O2(+2), SO2(+4), SO3(+6)
2 marks
ii Describe what you would observe and give a balanced equation for the reaction the oxide of sulphur (O.N. +4)
(C) with rain, and
Sulphur
(A) 5SO2 + 2MnO4- + 2H2O 5SO42- + 2Mn2+ + 4H+ (Purple colour decolourized / colourless solution)
(B) 2Fe3+ + SO2 + 2H2O 2Fe2+ + SO42- + 4H+ (Solution change from yellow brown to pale green / colourless)
(C) SO2 + H2O H2SO3; 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. formed)
2 marks each
10.3.3.1
84 2B 10 b
10b
Describe the industrial preparation of sulphuric(VI) acid from sulphur.
Sulphur
1. Conversion of sulphur to sulphur dioxide, S + O2 SO2
Burning sulphur, 1 atmosphere, no catalyst required.
2. Conversion of sulphur(IV) oxide to sulphur(VI) oxide, 2SO2 + O2 d 2SO3
450C; 1 atmosphere; excess oxygen or air; platinium or vanadium(V) oxide catalyst.
12
2 marks
4 marks
3.
2H2SO4
Conversion of sulphur(VI) oxide to sulphuric(VI) acid, SO3 + H2SO4 H2S2O7 H
Add oxide to acid then dilute with water
marks
2
10.3.3.2
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.
Redox chemistry of sulphur
1 mark
2 marks
e.g. -2(H2S), 0(S), +4(SO2) and +6(SO3 or SO42-)
Any sulphur containing compounds, upon oxidation, give SO2 or SO42SO2 through combustion of the sulphur compounds in air
1 mark
SO42- oxidation in homogeneous solution.
Upon reduction, S or H2S are usually produced
H2S is a mild reducing agent but SO42- is usually stable towards redox reactions in the absence of H+. 1 mark
Intermediate oxidation states, for example, S2O32- or S4O62-, will undergo disproportionation in water. 1 mark
10.3.3.2
89 2B 6 b
6b
Sulphuric(VI) acid can be reduced to form products having a variety of oxidation states of S.
For Sulphuric(VI) acid, illustrate using balanced half equations, how four possible reduction products, having
different oxidation states of S, may be obtained.
Explain why an aqueous solution of either Na2SO4 is not a strong oxidizing agent.
Sulphuric(VI) acid
SO42- + 4H+ + 2e- d SO2 + 2H2O
1 mark
1 mark
SO42- + 8H+ + 6e- d S + 4H2O
1 mark
SO42- + 10H+ + 8e- d H2S + 4H2O
1 mark
2SO42- d S2O32- or S4O62-, etc.
1 mark
H+ is required if SO42- acts as an oxidizing agent
d-Block Elements
I.

A.
B.
C.
II.
Electronic configuration of d-block elements

Electronic configuration of ions of d-block elements
1.
Comparison of properties between d-block and s-block metals
1.
Physical properties
a)
Ionization enthalpies and electronegativity
b)
Melting point and hardness
c)
d)
Densities
2.
Chemical properties
a)
Reaction with water
Characteristic properties of the d-block elements and their compounds:

A.
B.
C.
D.
E.

1.
a)
Vanadium compounds
b)
Manganese compounds
Complex formation
1.
a)
Basicity of the ligand
b)
Chelate effect
2.
Stability constant
3.
Aquaton isomerism
4.
5.
Coloured ions
1.
2.
Catalytic properties of transition metals and their compounds
1.
Haber process
2.
3.
Magnetic properties of transition metal and ion
d-Block Elements
Unit 1
Page 1
Topic
d-block Elements
Unit 1
Reference
Reading
11.1.011.1.1
Reading
Syllabus
Notes
I.
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]
[Ar]
23V
[Ar] 3d 4s
[Ar]
24Cr
[Ar] 3d54s1
[Ar]
22Ti
[Ar] 3d 4s
25Mn
[Ar] 3d 4s
[Ar]
26Fe
[Ar] 3d64s2
[Ar]
27Co
[Ar] 3d 4s
[Ar]
28Ni
[Ar] 3d84s2
[Ar]
10
29Cu
[Ar] 3d 4s
[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.
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
mark
d-Block Elements
Unit 1
92 2B 4 a i ii iii
4a i
Using the electrons-in-boxes representation, give the electronic structure outside the argon core of Cu and Cr3+.
3d
4s
3d
4s
11100 0
1 mark each
Which of the two ions, copper(I) or copper(II), has the more stable electronic structure? Give an explanation.
Cu+ d10 is expected to be more stable than Cu2+ d9 since it has completely filled d-orbital.
1 mark
iii Why is the copper(I) ion unstable in aqueous solution?
29Cu
22222 1
24Cr
2Cu
2+
( aq )

Cu
disproportionation
3+
ii
+
( aq )
Page 3
+ Cu( s )
1
1
mark for disproportionation and mark for correct product
94 2B 5 a i ii iii
5a
Manganese and iron are d-block elements.
i
What do you understand by the term d-block element?
1
Elements with partially filled d-orbitals.
1 mark
2
ii Using the electron-in-boxes representation, write the electronic structure outside the argon core for Mn2+ and
Fe2+ respectively.
Mn2+ [Ar] 11111
1 mark
2+
1 mark
Fe [Ar] 21111
iii Explain briefly why Fe2+ ions are easily oxidized to Fe3+ ions, but Mn2+ ions are not readily oxidized to Mn3+ ions. 3
Mn2+ with half-filled 3d orbitals is relatively stable. Removing e- disturbs this stable configuration; relatively high
2 marks
energy is required. Therefore, Mn2+ is not readily oxidized to Mn2+.
Fe2+ with an electronic configuration of d6, after removal of an e- from the outermost shell will attain the relatively
stable e- configuration with half-filled 3d orbitals. Therefore, the Fe2+ ions are easily oxidized to Fe3+.
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.
1s 2s
2p
3s
3p
3d
4s
4p
4d
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.
CrO42- / Cr2O72- / HCrO4- / CrO2Cl2 / CrO3 etc. 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 ground state electronic structure outside the argon core for 2
V2+ and Cu+ respectively.
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.
d-Block Elements
Unit 2
Topic
d-Block Elements
Reference
Reading
11.1.2
Page 1
Unit 2
Reading
Syllabus
Notes
C. Comparison of properties between d-block and s-block metals

1.
Physical properties
Main group elements (s-block and p-block) show a considerable change in properties on moving across a period.
i.e. from metallic properties to non-metallic properties. Comparing with main group elements, all elements in the
first transition period share similar properties. They are all hard, dense and comparatively less reactive. 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.
a) Ionization enthalpies and electronegativity
On moving across a transition period (e.g. from Sc to Cu), comparing with the main group elements, the 1st I.E. of
d-block elements are rather constant. This can be interpreted as a rather constant effective nuclear charge
experienced by the outermost electron.
On moving across the first transition period, electrons are added to the 3d oribitals which will impose a primary
shielding effect on the 4s electrons (valence electron). This is different from the situation in the main group, where
an electron is added to s or p orbital on moving across the period and the shielding effect is only secondary in
nature. As a result of the stronger primary shielding effect, the ionization energies do not raise sharply across the
transition period.
However, unlike the change from Ne to Na, where the shielding effect is primary in nature, the I.E. doesn't drop
sharply either. The primary shielding effect of the d-electrons must not be very strong. The weak shielding effect
can be explained by the diffuse nature of d-electrons.
As a result, 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.
d-Block Elements
Unit 2
Page 2
Furthermore, the weak shielding effect also accounts for the high I.E of d-block elements (631-906 kJmol-1)
comparing with the lower 1st I.E. of s-block elements (419-516 kJmol-1). Therefore, the primary shielding effect of
the diffuse d-electrons must be not as effective as the primary shielding effect found in s-block elements.
For the same reason, the electronegativities of the d-block elements are rather constant and only shows a gradual
increase across the period. Nevertheless, comparing with s-block element, d-block elements are more
electronegative, i.e. less electropositive, thus less metallic.
b) Melting point and hardness

Both melting point and hardness are indications of the
strength of the metallic bond.
It is found that the melting point and hardness of dblock elements are much higher than that of s-block
elements.
The difference in strength of a metallic bond can be
explained by the effective nuclear charge and the no. of
delocalized electrons available.
First of all, 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. Furthermore, the
availability of the delocalized electrons are also higher.
d-block metals can use its 3d electrons on top of the 4s
electrons in the formation of metallic bond.
It is observed that on moving across the first transition period, the melting point increases gradually and drops
when approaching the end of the period with a depression in the middle. The increase is due to the general increase
in effective nuclear charge experienced by the valence electrons and availability of delocalized electron. Any
further increase in effective nuclear charge will lower the availability of delocalized electron and make the melting
point drop.
When we look at the electronic configuration of Mn, it will not be surprised that it has a melting point much lower
than the expected. Since Mn has a half-filled 3d orbital and full-filled 4s orbital, the availability of the delocalized
electrons will be lowered.
3d
21Sc
[Ar] 3d 4s
22Ti
[Ar] 3d 4s
23V
[Ar] 3d34s2
24Cr
[Ar] 3d54s1
5
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 Elements
c)
Unit 2
Page 3
For similar reasons, the atomic radii of d-block elements are quite small and rather constant across the period,
comparing with the s-block metals. However, a small variation is observed. On moving across the period, the
atomic size decreases gradually due to the small increase in effective nuclear change and remain constant
thereafter. On reaching the end of the transition period, the size of the atom gets larger as the repulsion among the
larger no. of electrons becomes significant.
d) Densities
Owing to the small atomic sizes, strong metallic bond and close crystal packing, the d-block metals are much
denser than the s-block metals.
structure
density
g/cm3
19K
20Ca
21Sc
22Ti
23V
24Cr
25Mn
26Fe
27Co
28Ni
29Cu
30Zn
BCC
0.86
FCC
1.55
HCP
3.0
HCP
4.5
BCC
6.1
BCC
7.2
BCC
7.4
BCC
7.9
FCC
8.9
FCC
8.9
FCC
8.9
HCP
7.1
BCC
: body centered cubic

(not a close packing)
FCC
: face centered cubic

(a close packing)
HCP
: hexagonal close packing

(a close packing)
d-Block Elements
2.
Unit 2
Chemical properties
a) Reaction with water

In general, d-block metals are much less reactive towards water than s-block metals do. This is parallel to low
electropositivity of d-block elements.
Glossary
Past Paper
Question
Page 4
d-Block Elements
Unit 3
Topic
d-Block Elements
Reference
Reading
11.2.1
Page 1
Unit 3
Reading
Syllabus
Notes
II. Characteristic properties of the d-block elements and their compounds:

A. Variable oxidation states
Unlike s-block metals, many transition metals are capable to form compounds with more than one oxidation state.
The no. of possible oxidation states increases from Sc and reaches the maximum at Mn due to the increase in the
number of d-electrons. Thereafter, the no. of possible oxidation states decreases from Fe to Zn as the nuclear
charge and ionization energies increase.
Concerning the energetic of formation of ion, if the difference in successive ionization energy is small, the
formation of the highest oxidation state would be preferable. e.g. Ca only forms +2 ion but not +1 ion. If the
difference in successive ionization energy is large, the formation of the lowest oxidation state would be preferable.
e.g. K only forms +1 but not +2 ion.
Therefore, formation of compounds with variable oxidation state must be due to a moderate and gradual increase in
successive ionization energies. One of the explanations to this phenomenon is the small difference in energy
between the (n-1)d and ns electrons. As the energy of (n-1)d and ns electrons are similar, once a ns electron is
removed, the energy of (n-1)d electron will decrease moderately as the p to e- ratio increase. Consequently, this
will cause a moderate increase in successive ionization energies.
d-Block Elements
Unit 3
kJmol-1
K
Ca
Mn
1st I.E.
419
590
717
2nd I.E. ( I.E.)

3051 (2632)
1145 (555)
1509 (792)
Page 2
3rd I.E. ( I.E.)
4412 (1361)
4912 (3767)
3249 (1740)
4th I.E. ( I.E.)

5887 (1475)
6474 (1562)
4940 (1691)
5th I.E. ( I.E.)

7975 (2088)
8144 (1670)
6985 (2045)
First 5 successive ionization energies

On moving across the transition period, the gap between first I.E. and second I.E. are rather constant while the gap
between second I.E. and third I.E. widens. As a result, the elements at the beginning of the transition period
favours the formation of +3 oxidation state. When approaching the end of the transition period, the formation of +2
oxidation state is more favorable. This reflects the increasing difficulty of removing a 3d electron as the nuclear
charge increases.
Although many transition metals are capable to form compounds with high oxidation state e.g. Mn(VII), ions with
more than 3+ charge do not exist freely at all due to the high charge density of the ion. They are either covalently
bonded (e.g. Mn2O7) or complexed (e.g. MnO4-).
1.
a) Vanadium compound
+2, +3, +4 and +5 are the common oxidation states of vanadium compound. Their existence can be demonstrated
by shaking a solution of ammonium vanadate(V) (NH4VO3) with zinc power in dilute sulphuric acid.
VO3-(aq) + 2H+(aq) VO2+(aq) + H2O(l)
VO2+(aq) + 2H+(aq) + e- VO2+(aq) + H2O(l)
VO2+(aq) + 2H+(aq) + e- V3+(aq) + H2O(l)
V3+(aq) + e- V2+(aq)
this is not a redox reaction, 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 solution will turn from yellow, blue, green and eventually violet since zinc is a very strong
reducing agent which is capable to reduce V(V) to V(II) stepwise.
d-Block Elements
Unit 3
Page 3
The following is an electrode potential - oxidation state chart which can be used to predict the energetic feasibility
of a redox reaction. 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.
Electrode potential - oxidation state chart

Regarding the use of the chart, there is a rule called anticlockwise rule. For
any two half-equations, the combination with an anticlockwise direction as
shown on the diagram on the right would be energetically feasible.
e.g. 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 = (-0.77V) + (1.00V) = +0.23V
Since the overall Eo is positive, the change is energetically feasible. However, the value of Eo doesn't tell anything
about the kinetic feasibility of the reaction.
Similarly, 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.
d-Block Elements
Unit 3
Page 4
2) Manganese compounds
+2, +4 and +7 are the three most common oxidation states of manganese compound.
Common manganese containing species
+2
+3
+4
+6
+7
Mn2+(aq) colourless (or very pale pink)

Mn2O3(s) brown, 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.
O2(g) + 2H2O(l) + 2e- d 4OH-(aq)
Cu+(aq) + e- d Cu(s)
I2(aq) + 2e- d 2I-(aq)
MnO42-(aq) + 2H2O(l) + 2e- d MnO2(s) + 4OH-(aq)
2H+(aq) + O2(g) + 2e- d H2O2(aq)
MnO2(s) + 4H+(aq) + 2e- d Mn2+(aq) + 2H2O(l)
Mn3+(aq) + e- d Mn2+(aq)
MnO4-(aq) + 4H+(aq) + 3e- d MnO2(s) + 2H2O(l)
H2O2(aq) + 2H+(aq) + 2e- d 2H2O(l)
Eo / V
+ 0.40
+ 0.52
+ 0.54
+ 0.59
+ 0.68
+ 1.23
+ 1.49
+ 1.51
+ 1.70
+ 1.77
KMnO4(s) is one of the most popular strong oxidizing used in the laboratory. The oxidizing power of MnO4-(aq) is so
strong that it is capable to oxidize water and give O2(g) and MnO2(s) slowly. This reaction can be accelerated by
light therefore KMnO4(aq) have to be stored in a brown bottle.
4MnO4-(aq) + 4H+(aq) 4MnO2(s) + 3O2(g) + 2H2O(l)
In acidic medium, when MnO4-(aq) is reduced. It will be converted to colourless Mn2+(aq).
Eo = + 1.51 V
In less acidic or alkaline medium, MnO4-(aq) will be converted to MnO2(s) instead. From the value of Eo, MnO4-(aq)
shows a even stronger oxidizing power in less acidic medium with the formation of the brown MnO2(s) ppt.
Eo = + 1.70 V
MnO4-(aq) + 4H+(aq) + 3e- d MnO2(s) + 2H2O(l)
Therefore, when MnO4-(aq) is used as a testing agent or an ordinary oxidizing agent, acidic medium will be used. If
MnO4-(aq) is used as a very strong oxidizing agent, alkaline medium may be used.
Glossary
variable oxidation state
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, NH4VO3, and give the colours of the
products.
(I) by mild reductants e.g. H2S, SO2, Fe2+, oxalate, Sn2+, I1 mark
Blue
mark
(II) by Zn or Zn/HCl
1 mark
Violet
mark
94 2B 5 b i
5b
Account for each of the following:
i
KMnO4 solutions are best stored in brown bottles.
MnO4- is unstable in the presence of sunlight.
it will decompose to form brown MnO2
2
1 mark
1 mark
d-Block Elements
Unit 4
Topic
d-Block Elements
Reference
Reading
11.2.2
Page 1
Unit 4
Assignment Chemistry in Context, 5th Edition, Thomas Nelson and Sons Ltd. pg. 201207, 257258, 269270
Reading
Syllabus
Notes
B. Complex formation
When an ion is placed in a polar solvent e.g. water, it will be hydrated due to the electrostatic attraction between
the ion and water molecules. Moreover, if the ion possesses a very high charge density and a low lying energy
vacant orbital, the ion may be capable to form a dative covalent bond with the lone pair from the solvent molecule.
The dative covalent bond formed in this way would be much strong than the ordinary ion-dipole attraction.
For example, when anhydrous NaCl(s) and anhydrous CoCl2(s) are dissolved in water, both of them will dissolve and
the ions will be hydrated. However, upon crystallization, 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.
Furthermore, the comparatively higher electronegativity of d-block elements also favours the formation of dative
covalent bond.
The molecules which form dative covalent bond with the ion (or an atom) are called ligands. The species with the
ion (or the atom) joining together with the ligands is called a complex. Because the ion is coordinated with ligands,
a complex is also called a coordinated compound and the dative covalent bond formed is called coordinate bond.
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
d-Block Elements
1.
Unit 4
Page 2
a) Basicity of the ligand

Basically, stability of a complex ion is depending on the strength of the dative bond. For a given central ion, the
strength of the coordinate bond is depending on the electron donating ability of the ligand i.e. basicity (or
nucleophilicity) of the ligand.
Consider the ligands Cl-, H2O, NH3 and CNparent acid
pKa
conjugate base
H3O+
-1.74
H2O
HCl
-7
Cl-
NH4+
9.2
NH3
HCN
9.3
CN-
basicity of the conjugate base increase
NH3 molecule is a strong base than H2O molecule, NH3 molecule is also a stronger ligand than H2O molecule.
At the same concentration, the strong ligand is capable to displace the weak ligand from a complex. If the
concentrations are not the same, the equilibrium position may be shifted back.
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.B.
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), Fe2+(aq) and Fe3+(aq) do not form soluble complex with ammonia
molecules. Indeed, they will form insoluble ppt. of Fe(OH)2(s) and Fe(OH)3(s) with the hydroxide ions in
the ammonia solution and remain undissolved.
Sometimes, 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). This is because the two water molecule ligands at axial positions are only loosely
held. The complexes are sometimes regarded as square planar instead of octahedral.
b) Chelate effect
Besides the basicity, the strength of a ligand is also depending on the no. of dative covalent bond that the ligand
can form. A ligand which is capable to form 1 dative covalent bond is called a monodentate ligand; a ligand which
is capable to form 2 dative covalent bonds is called a bidentative ligand etc.
In general, the larger the no. of bond a ligands can form, the stronger will be the ligand.
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
H2O
OH2
OH2
+ bi
H2O
H2O
H2O
OH2
H2N
n+
CH2 CH2 NH2
+ 2H2O
H2O
a bidentate ligand
bi : a bidentate ligand
In the above reaction, one bidentate ligand e.g. ethane-1,2-diamine (H2NCH2CH2NH2 or ethylenediamine or en)
displaces two water molecules from the complex. There is an overall change in the no. of particles in this reaction.
At the reactant side, there are only 2 particles but at the product side, there are 3 particles. Besides the displacement
of ligand, there is an overall increase in the no. of molecules and disorderness of the system. i.e. S increase. The
extra strength of a polydentate ligand due to increase in disorderness is called chelate effect.
2.
Stability constant
The strength of a ligand can be expressed as an equilibrium constant called stability constant, Kst.
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, the stronger would be the complexing ability of the ligand.
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
d-Block Elements
Unit 4
3.
Page 4
Aquation isomerism
Some coordinated compounds share the same empirical formula but when dissolved in water, they give different
number of ions. This phenomenon is called aquation isomerism. Cr(H2O)6Cl3 is one of the examples.
Structural formula
[Cr(H2O)6]Cl3
[CrCl(H2O)5]Cl2H2O
[CrCl2(H2O)4]Cl2H2O
4.
Ions present in aqueous solution

[Cr(H2O)6]3+(aq), 3Cl-(aq)
[CrCl(H2O)5]2+(aq), 2Cl-(aq)
[CrCl2(H2O)4]+(aq), Cl-(aq)
Colour
Violet
Blue-green
Green
Tetra-coordinated complex
Square planar complex
[MA2B2]n+
n+
B
n+
M
A
B
M
B
cis-isomer
trans-isomer
Hexa-coordinated complex
Octahedral complex
[MA2B4]n+
n+
A
B
[MA3B3]n+
M
B
N.B.
5.
cis-isomer
n+
B
B
M
A
n+
M
B
trans-isomer
n+
A
M
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.
Naming of a complex is based on the name of the ligand, the no. of ligands and overall charge of the complex.
1.
Like all ionic compounds, cations are named first and anions second.
2.
Ligand name of a negative ligand will end with -o, e.g. CN- cyano, Cl- chloro.
Ligand name of a neutral ligand is not changed
e.g. H2NCH2CH2NH2 is just called ethane-1,2-diamine
Exceptions : H2O is called aqua and NH3 is called ammine.
3.
The number of each ligand in the complex is indicated by the prefixes di, tri, tetra etc.
4.
The oxidation state of the metal is indicated in parentheses.

Furthermore, If the complex is cationic or neutral, the name of the metal is used.
e.g. [Fe(H2O)6]3+ hexaaquairon(III) ion
If the complex is anionic, the ending -ate is added to the name of the metal, in certain cases, Latin name will be
used. e.g. [Fe(CN)6]3- hexacyanoferrate(III) ion
5.
The negative ligands are placed before the neutral ligands in the name. (Not in alphabetical order.)
e.g. [CoCl3(NH3)3] trichlorotriamminecobalt(III)
6.
Geometrical isomers are designated by cis- or trans- and mer- or fac-.
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. Explain, in each case, why this is so.
iv [NaI4]3Because there is no low energy vacant orbitals for bonding / Na+ has too low charge density for complex ion
formation.
1 mark
90 2B 6 b
6b
Account for the following observations.
An aqueous solution of FeSO4 readily gives a rusty brown precipitate on standing in air, whereas an aqueous
solution of K4[Fe(CN)6] under similar conditions does not.
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 stable because CN- is a better ligand than H2O / CN- ligands stabilize Fe2+
(no mark for Fe(CN)64- is a stable complex)
The redox potential of Fe(CN)64- is different from Fe(H2O)n2+
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. Describe what changes you
would observe during these reactions.
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, at first insoluble pale blue basic salt or hydroxide is formed, but these dissolve
1 mark
readily in excess NH3(aq) to give deep blue solution containing tetraaminecopper(II) ion.
d-Block Elements
Unit 4
91 2B 6 a ii iii
6a ii Give the name and formula, and draw the 3-dimensional structure of a hexa-coordinated complex of a d-block
element.
Name (must be named correctly) e.g. hexaamminecobalt(III) ion
mark
mark
Formula e.g. [Co(NH3)6)]3+
Shape e.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
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.
2
Atoms lose electrons to form ions, whose polarizing power increases with number of electrons lost.
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.
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.
The addition of an aqueous solution of KSCN to a solution containing Fe(III) ions gives a complex with a deep
red colour. The deep red colour fades when excess NaF solution is added. On the addition of dilute alkali to the
resulting solution, a brown precipitate forms.
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.] + 6F-(aq)
1 mark
94 1A 2 b i
2
2b i
Explain why Ni2+ forms more complexes than K+ does.
2+
+
Ni has higher charge density / more polarizing than K / greater ability to form covalent bond (dative bond) with
ligand
Any 2, 1 mark each
Ni2+ has low lying , vacant d orbital.
94 2B 5 b iii
5b
iii The addition of 2M NaOH to an aqueous solution of Fe3+ ions gives a brown precipitate, whereas the addition of
2M NaOH to an aqueous solution of Fe3+ ions in the presence of excess CN- ions gives no precipitate.
In aqueous solution, Fe3+ exists as aquo-complex.
Addition of OH- causes the formation of a brown ppt.
[Fe(H2O)6]3+(aq) + 3OH-(aq) Fe(OH)3(s) + 6H2O(l)
1 mark
brown ppt.
In the presence of excess CN-, Fe3+ forms a very stable complex [Fe(CN)6]3-, concentration of free Fe3+ ions is
lowered addition of 2M NaOH cannot cause [Fe3+][OH-] to exceed the Ksp of Fe(OH)3.
2
marks
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, until in 3
excess, to aqueous solutions containing Pb2+ and Cu2+ ions respectively. These experiments are carried out at room
temperature.
(i) ammonia solution
Pb2+(aq)
Cu2+(aq)
(3 marks for 8 observations; deduct mark for each incorrect observation)
(i) ammonia solution
Pb2+(aq)
White ppt.
White ppt.
Insoluble in excess
Soluble in excess / Colour solution
Cu2+(aq)
Blue ppt.
Blue ppt.
Soluble in excess / Deep blue solution
Insoluble in excess
96 1A 2 f i
2f
The complex ion [Co(H2NCH2CH2NH2)2Cl2]+ has THREE isomers. These isomers belong to TWO types of
isomerism.
i
Draw a three-dimensional structure for each isomer.
Cl
en
Co
Cl
en
en
Co
Cl
Cl
en
Cl
Cl
en
Co
en
1 + + mark
(en represents H2NCH2CH2NH2)

(1 mark for the trans-isomer; mark for each cis-isomer )
96 2B 6 b i ii
6b
What do you understand by the following terms ?
In each case, illustrate your answer with an example involving copper(II).
i
complex ion
A complex ion is formed by combination of a central metal ion
mark
mark
with ligands / complexing agents.
The ligands/complexing agents are either neutral molecules / negatively charged ions carrying lone pair(s) of
electrons
1 mark
mark
which can be donated to the metal ion / can form dative bond with the metal ion.
mark
e.g. [Cu(NH3)4]2+ (accept any complex of Cu(II)
ii stability constant
Stability constant Kst : e.g. [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.e. 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 0.40 g of a complex salt Cr(NH3)5Cl3. The free chloride ions present in the
solution required 21.90 cm3 of 0.150 M silver nitrate(V) solution for complete precipitation. Deduce the structural
formula of the complex ion present in the salt.
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.
d-Block Elements
Unit 5
Topic
d-Block Elements
Reference
Reading
11.2.3
Page 1
Unit 5
Reading
Syllabus
Coloured ions
Notes
C. Coloured ions
1.
The origin of the colour of an transition metal ion is similar to that of emission spectrum. Instead of emitting
radiation while the excited atom is falling back to the lower energy state, radiation is absorbed from the
illuminating radiation. The energy absorbed is eventually dissipated in form of heat. The atom returns to the lower
energy state. The colour of hydrated ion (e.g. Cu2+(aq)) is the result of absorption of light.
Most pure substances in nature are colourless or white because they do no absorb light from the visible region.
However, most substances in nature are coloured because most of them are mixtures containing a very small
percentage of coloured substance. Whether a substance would be coloured or not is solely a coincidence.
Many transition metal complexes, including aqueous
complex, are coloured because under the influence of
the ligands, the 5 degenerate d-orbitals will be split into
different levels with small gaps between them. The
degenerate energy levels split because the five 5 dorbitals are not equally arranged in space and are
affected by the ligands differently.
Eventually, if the d-orbitals are partially filled (not completely filled nor completely empty), the electron transition
will produce a colour. The electron transition is called d-d transition.
This explains why anhydrous copper(II) sulphate is white while hydrated copper(II) sulphate is blue. Sc(III) and
Zn(II) compounds are not coloured while the other transition metal compounds are usually coloured.
d-Block Elements
2.
Unit 5
Page 2
[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, in terms of electronic arrangement, why most transition metal ions are coloured.
1. Absorption of photon in the visible region
2. Unpaired electron or partly filled orbital
3. Small energy difference between d orbitals under the influence of the ligands
4. Transition of electron
94 1B 4 d iii
4d
This question refers to reactions which occur between the following pairs of substances.
boxes in the following table.
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
pale blue precipitate,
deep blue solution
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,
(1)
deep blue solution
94 2B 5 b ii
5b
ii Cobalt(II) chloride can be used to test for the presence of water.
Cobalt(II) chloride, in anhydrous state is blue in colour.
After absorption of water / forming complex ion with H2O,
it changes colour to pink.
2 marks
Complete the empty
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, state the expected observation and write the relevant balanced equation(s).
i
Concentrated hydrochloric acid is added dropwise to an aqueous solution of copper(II) sulphate(VI) until no
further change is observed.
ii Aqueous ammonia is added dropwise, until in excess, to the resulting solution in (i).
d-Block Elements
Unit 6
Topic
d-Block Elements
Reference
Reading
11.2.411.2.5 11.2.0
Page 1
Unit 6
Reading
Syllabus
Catalytic properties
Magnetic properties
Notes
D. Catalytic properties of transition metals and their compounds

Many transition metals or compounds of transition metal exhibit catalytic behavior. This is because, basically, all
chemical reactions involve electron transfer or redistribution of electron. 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.
1.
2.
3.
Haber process
For details please refer to Rate of reaction Catalysis

E. Magnetic properties of transition metal and ion
When an electron spins, a magnetic moment will be induced. Normally, electrons will pair up in an atom and the
magnetic moments will be canceled out. Therefore, most substance are non-magnetic i.e. diamagnetic.
In certain substance containing unpaired electrons, e.g. Mn2+ [Ar] 3d5, the magnetic moments are not canceled out
completely and they are weakly magnetic i.e. paramagnetic.
A very few no. of substances are strongly magnetic e.g. Fe, due to the spinning of the protons. They are
ferromagnetic.
Glossary
diamagnetic
paramagnetic
ferromagnetic
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, with examples using nickel, two characteristic properties of transition metals.
Catalytic properties. e.g. the use of a nickel catalyst in the hydrogenation of oils to make margarine
Complex ion formation. e.g. [Ni(H2O)6]2+
Accept also colours, paramagnetic or other properties which can be illustrated.
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; full orbitals can act as electron donors to
reactant species and weak bonds (chemisorption) are formed between catalyst and reactant particles.
1 mark, either
II Variable oxidation states enable oxidation-reduction cycle of transition metal catalyst.
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.
Give one example of such a catalytic reaction.
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.
Any one example of transition metal or its compound as catalyst
V O
2 5
SO3 (redox reaction)
e.g. 2SO2 + O2
1 mark
96 2B 6 c
6c
State THREE characteristic properties of d-block elements, apart from complex ion formation. In each case,
illustrate your answer with an example involving copper or vanadium.
Any THREE of the following:
+
exhibition of variable oxidation states e.g. Cu(I) & Cu(II) / V2+, V3+, VO2+ and VO2+
mark
+ mark
formation of coloured compounds e.g. Cu2+(aq) is blue / VO2+ is yellow
+ mark
exhibition of catalytic properties e.g. V2O5 in contact process
+ mark
exhibition of paramagnetic properties e.g. Cu2+ / V2+ are paramagnetic
+ mark
formation of non-stoichiometric compounds e.g. sulphide of vanadium
( marks for each properties; marks for a correct example)

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Periodic Properties of Elements

Periodic Properties of Elements in the Periodic Table

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

Variation in melting point and boiling point

Periodic relationship among the oxides, chlorides and simple hydrides of

Formation of acidic, amphoteric and basic oxides

Characteristic properties of the s-block elements

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

Metallic character and low electronegativity

Uses of the compounds of the s-block elements

Laboratory preparation of chlorine

Nitrogen and its compounds

Laboratory preparation of ammonia

Sulphur and its compounds

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

Electronic configuration of d-block elements

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

Variable oxidation states

Periodic Properties of Elements

Periodic Properties of Elements in the Periodic Table

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

Variation in melting point and boiling point

Periodic relationship among the oxides, chlorides and simple hydrides of

Formation of acidic, amphoteric and basic oxides

Properties of compounds and bond energies

Slightly soluble in water

Immisicible with water

Properties of compounds and bond energies

Carbonic acid or carbonated water

NO(g) and N2O(g) are neutral and insoluble in water.

P2O3(s) + 6H2O(l) 4H3PO3(aq)

Properties of compounds and bond energies

Periodic Properties of Elements

Perioidic Properties of Elements

Periodic Properties of Elements in the Periodic Table

Periodic Properties of Elements

Periodic Properties of Elements

Perioidic Properties of Elements

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

Variation in melting points and boiling point

Periodic Properties of Elements

Simple molecular structure

simple molecular structure

giant metallic structure

giant covalent structure

Periodic Properties of Elements

For melting point (or boiling point)

Periodic Properties of Elements

molecular ring structure

Periodic Properties of Elements

Periodic Properties of Elements

Periodic Properties of Elements

Perioidic Properties of Elements

Perioidic Properties of Elements

Perioidic Properties of Elements

polarity of the molecule (NH3 vs PH3)

ii. availability of low energy vacant d-orbital (SiH4 vs CH4)

Perioidic Properties of Elements

iii. Bond strength and difference in electronegativity (bond polarity)

Bond energy (kJmol-1)

NH3(aq) + H2O(l) d NH2-(aq) + H3O+(aq)

Perioidic Properties of Elements

Perioidic Properties of Elements