CHEMISTRY

Revision guide
for A2 level

For CIE examination

Introduction
This book is for A2 level only and the practical work is not mentioned in this
book.

Each section starts with a list of learning objectives, which are directly related
to the CIE syllabus. Questions throughout the text reinforce students
understanding and offer excellent opportunities for independent study.

For CIE examinations

UNIT 6 IONIC COMPOUNDS AND ELECTROCHEMISTRY

UNIT 6 IONIC COMPOUNDS AND ELECTROCHEMISTRY

Section 1 Ionic compounds
Learning objectives:
1 explain and use the terms: (iii) lattice energy (H negative, i.e. gaseous ions to solid
lattice) explain, in qualitative terms, the effect of ionic charge and of ionic radius on the
numerical magnitude of a lattice energy apply Hess' Law to construct simple energy
cycles, and carry out calculations involving such cycles and relevant energy terms, with
particular reference to:
(iii) the formation of a simple ionic solid and of its aqueous solution
vv(iv) Born-Haber cycles (including ionisation energy and electron affinity) interpret and
explain qualitatively the trend in the thermal stability of the nitrates and carbonates in
terms of the charge density of the cation and the polarisability of the large anion
interpret and explain qualitatively the variation in solubility of the sulfates in terms of
relative magnitudes of the enthalpy change of hydration and the corresponding lattice
energy
2 explain, in qualitative terms, the effect of ionic charge and of ionic radius on the numerical
magnitude of a lattice energy
3 apply Hess' Law to construct simple energy cycles, and carry out calculations involving
such cycles and relevant energy terms, with particular reference to: (iii) the formation of a
simple ionic solid and of its aqueous solution (iv) Born-Haber cycles (including ionisation
energy and electron affinity)
4 interpret and explain qualitatively the trend in the thermal stability of the nitrates and
carbonates in terms of the charge density of the cation and the Polaris ability of the large
anion
5 interpret and explain qualitatively the variation in solubility of the sulfates in terms of
relative magnitudes of the enthalpy change of hydration and the corresponding lattice
energy

Key ideas
Lattice enthalpy (energy)
1 What is the lattice energy
Lattice enthalpy (energy) is a measure of the strength of the forces between the ions in an
ionic solid.
Na+(g)

Cl-(g)

Mg2+(g)

787 kJ mol-1

O2-(g)

3923 kJ mol-1

NaCl(s)

MgO(s)

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UNIT 6 IONIC COMPOUNDS AND ELECTROCHEMISTRY

Lattice enthalpy

Boiling point

Melting point

3923
3600
2852

1413
801

787

NaCl

MgO

The greater the lattice enthalpy, the stronger the forces and the higher the BP./MP.
2 Definitions
So lattice enthalpy could be described in either of two ways.
You could describe it as the enthalpy change when 1 mole of sodium chloride (or whatever)
was formed from its scattered gaseous ions. In other words, you are looking at a downward
arrow on the diagram.
In the sodium chloride case, that would be -787 kJ mol-1.
Or, you could describe it as the enthalpy change when 1 mole of sodium chloride (or
whatever) is broken up to form its scattered gaseous ions. In other words, you are looking
at an upward arrow on the diagram.
In the sodium chloride case, that would be +787 kJ mol-1.
The CIE definition
The enthalpy change when 1 mole of an ionic compound (solid lattice) is formed from its
gaseous ions under standard conditions (at 298K and 1 atm). (The downward arrow on the
diagram)
i.e.:
NaCl
Na+(g) +

Cl-(g)

NaCl(s)

= -787 kJ mol-1

Na2O,
2Na+(g) + O2- (g)

Na2O(s)

= -2590 kJ mol-1

Mg2+ (g) + O2- (g) MgO(s)

= -3923 kJ mol-1

MgO,

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UNIT 6 IONIC COMPOUNDS AND ELECTROCHEMISTRY

3 Factors affecting the Lattice enthalpy

(1)The charges on the ions
The greater the charges, the higher the lattice enthalpy
(2)The radius of the ions
The larger the ionic radius, the smaller the lattice enthalpy change
4 Calculate the lattice enthalpy
(1) Theoretical values for lattice energy (Not required by CIE)

Z+ the relative charge of the cation

Z- the relative charge of the anion
r0 r+ + r(2) Experimental values Born Haber cycles
This method is based on the Hess law.
Hess law - The total enthalpy change for a chemical reaction is independent of the route by
which the reaction takes place, provided the initial and final conditions are the same.

a) Some enthalpy changes definitions

Standard enthalpy change of atomisation (
)
The enthalpy change when 1mol of gaseous atoms are formed from the element in its
standard conditions
i.e.
1/2 Br2(l) Br(g)
The first electron affinity: (

The enthalpy change when one electron is added to each gaseous atom in 1 mol, to form
1 mol of 1- gaseous ions.
i.e. Cl(g) + e- Cl-(g)
The second electron affinity: (

The enthalpy change when one electron is added to each 1- gaseous ion in 1 mol, to
form 1 mol of 2- gaseous ions.
i.e. Cl-(g) + e- Cl2-(g)
(b) Calculate the lattice enthalpy by drawing a Born Haber cycle
i.e. Calculate the lattice energy of the KClkJ/mol

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UNIT 6 IONIC COMPOUNDS AND ELECTROCHEMISTRY

-435.8 kJ mol-1
90.0 kJ mol-1
425.0 kJ mol-1
120.9 kJ mol-1
-349.0 kJ mol-1

Standard enthalpy change of formation of KCl

Standard enthalpy change of atomisation of K
The first ionisation energy of K
Standard enthalpy change of atomisation of Cl
The first electron affinity of Cl
How to draw a Born Haber cycle
High

K+(g)

(KCl)

Cl-(g)

Step 1
Construct the equation which

(K)

is

(Cl)

responsible

for

the

(KCl)

set

this

and

equation at the bottom of the

diagram.

enthalpy

K(g)

Construct another equation

Cl(g)

which is responsible for the

(KCl)

and

set

this

equation at the top of the

K(s)

diagram.

(Cl)

(K)

diagram.

(KCl)

1/2Cl2(g)

Low

NaCl(s)

Step 2

Step 3

List the enthalpy changes of

List the enthalpy changes of

the metal element in the order

the non - metal element in the

of atomisation and ionisation.

order

of

atomisation

and

electron affinity.

According to the Hess law, the relationship between these enthalpy changes is shown
below.
(KCl) =

(K) +

(KCl) =

(KCl) (

(K) +
(K) +

(Cl) +
(K) +

(Cl) +
(Cl) +

(KCl)
(Cl))

= - 435.8 (90.0 + 425.0 + 120.9 + (-349.0))

= - 725.4 kJ mol-1
Thermal stabilities of the carbonates and nitrates of Group II
1 The trends (Learned in AS)
The carbonates and nitrates of Group II become more stable to heat as you go down the
group.
4

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UNIT 6 IONIC COMPOUNDS AND ELECTROCHEMISTRY

2 Explanations

X2+
(1) The smaller the positive ion, the higher the charge density, and the greater polarising
ability it will have on the carbonate/nitrate ion.
(2) As the positive ions get bigger as you go down the Group, they have less effect on the
carbonate/nitrate ions near them.
(3) The distorted carbonate/nitrate breaks up into CO2 and O2- more readily
Solubility of the sulphate
1 The trend in solubility of the sulphate
The sulphates of Group II are less soluble in water as you go down the group.
2 Explanations
(1) Enthalpy changes during the dissolving

Lattice enthalpy
Enthalpy
change of solution

XSO4

Standard enthalpy change of hydration

dissolving

X2+(aq)

-91

MgSO4 (2959)

Mg2+ (-1890)

-18

CaSO4 (2704)

Ca 2+ (-1562)

-2

SrSO4 (2572)

Sr2+ (-1414)

SO42-(aq)

- 1160

+26
BaSO4 (2459)
Ba 2+ (-1273)
The enthalpy change of solution of the sulphate decreases down the Group, which
makes these sulphates less soluble.
Possible answers to explain the solubilities of the sulphates:
lattice energy decreases
solvation/hydration energy (of cation) decreases
but hydration energy decreases more than lattice energy/is not able to overcome LE
Hsolu becomes more endothermic/positive/less exothermic

For CIE examinations

UNIT 6 IONIC COMPOUNDS AND ELECTROCHEMISTRY

Section 2 Electrochemistry
Learning objectives:
1 Define the terms:
(i) Standard electrode (redox) potential
(ii) Standard cell potential
2 Describe the standard hydrogen electrode
3 Describe methods used to measure the standard electrode potentials of:
(i) metals or non-metals in contact with their ions in aqueous solution
(ii) ions of the same element in different oxidation states
4 Calculate a standard cell potential by combining two standard electrode potentials
5 Use standard cell potentials to:
(i) Explain/deduce the direction of electron flow from a simple cell
(ii) Predict the feasibility of a reaction
6 Construct redox equations using the relevant half equations
7 Predict qualitatively how the value of an electrode potential varies with the concentration
of the aqueous ion
8 State the possible advantages of developing other types of cell, e.g. the H2/O2 fuel cell
and improved batteries (as in electric vehicles) in terms of smaller size, lower mass and
higher voltage
9 Predict the identity of the substance liberated during electrolysis from the state of
electrolyte (molten or aqueous), position in the redox series (electrode potential) and
concentration
10 State the relationship, F = Le, between the Faraday constant, the Avogadro constant
and the charge on the electron
11 Calculate:
(i) The quantity of charge passed during electrolysis
(ii) The mass and/or volume of substance liberated during electrolysis, including those in
the electrolysis of H2SO4 (aq); Na2SO4(aq)
12 Describe the determination of a value of the Avogadro constant by an electrolytic
method

Key ideas
Standard electrode (redox) potential
(1) What is the electrode potential
Copper bar

Cu2+(aq)

There is equilibrium present in the system shown above.

Cu2+(aq) + 2eCu(s)
The equation is called half cell.
1

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UNIT 6 IONIC COMPOUNDS AND ELECTROCHEMISTRY

Electrode potential is measured in volts (V) and is numerical indication of how favourable
(or easy) the reduction is. So that the half cell must be written in the reduction direction.
Cu2+(aq) + 2e-, is not acceptable because its an oxidation

The direction, Cu(s)

direction.

(2) Standard electrode potential

However, the value of the electrode potential is not measurable. We can only get the
differences in the electrode potential between two half cells.
If the other half cell consists of a 1.00 mol L-1 solution of H+ ions in contact with hydrogen
gas at 1 atm, all at temperature of 298K, then the voltage measured is called standard
electrode potential for the reaction.
Standard conditions: all concentrations are 1.00 mol dm-3
the temperature is 298K
the pressures of any gases used are 1 atm

Definition of the standard electrode potential:

The voltage measured under standard conditions when the half cell is incorporated into
an electrochemical cell with the other half cell being a standard hydrogen electrode.
(3) Standard hydrogen electrode potential (S.H.E.)

Platinum wire
Supply of hydrogen gas at a
pressure of 1 atmosphere

The half cell

+

2H + e

Platinum electrode
H

1 mol dm

-3

=0V
(4) Measuring a standard electrode potential
i.e. Measuring a metal ion/metal standard electrode potential, such as

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UNIT 6 IONIC COMPOUNDS AND ELECTROCHEMISTRY

The internal resistance of the standard hydrogen electrode is quite high due to the adsorbed
H2(g) so that we have to choose a high-resistance voltmeter to measure voltage accurately.
If the voltmeter has a high resistance, little current will flow through the cell, and so little
contamination from the ions in the salt bridge will occur.
The set can also be simply expressed as following:
(+) CuCu2+(1 mol dm-3 )H+(1 mol dm-3 )H2(g, 1atm),Pt ( )
means the boundary between two different phases and is the salt bridge.

i.e. Measuring a ion/ion standard electrode potential, such as

+ 0.77V

Platinum wire

Graphite electrode
Supply of hydrogen gas at a
pressure of 1 atmosphere
Salt bridge

H
1 mol dm-3 Fe2+(aq)
1 mol dm-3 Fe3+(aq)

1 mol dm

-3

Platinum electrode

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UNIT 6 IONIC COMPOUNDS AND ELECTROCHEMISTRY

This set can also be simply expressed as following:

(+) CFe2+(1 mol dm-3 ), Fe3+(1 mol dm-3 )H+(1 mol dm-3 )H2(g, 1atm),Pt ( )

i.e. Measuring a non metal /anion standard electrode potential, such as

+ 1.36V

Platinum wire

Supply of chlorine gas

at a pressure of 1
atmosphere

Platinum wire

Supply of hydrogen gas at

a pressure of 1
atmosphere

Salt bridge

Cl- 1 mol dm

-3

1 mol dm

-3

Platinum electrode

Platinum electrode
This set can also be simply expressed as following:

(+) Pt, Cl2(g, 1atm)Cl- (1 mol dm-3 )H+ (1 mol dm-3 )H2(g, 1atm),Pt ( )

(5) The meaning of the standard electrode potential

Stronger
agent

oxidising

Cl2(g) + 2e-

2Cl-(aq)

Ag+(aq) + eThe oxidising ability

of the ion/element on
the left increases as
the
increases

Ag(s)

Cu2+(aq) + 2eH+(aq) +

e-

= + 1.36V

Weaker
reducing agent

= + 0.80V

Cu(s)

= + 0.34V

1/2H2(s)

= + 0.00V

Zn2+(aq) + 2e-

Zn(s)

= - 0.76V

Mg2+(aq) + 2e-

Mg(s)

= - 2.38V

The reducing ability

of the ion/element on
the right increases
as the
gets more
negative.

Stronger
reducing agent

Weaker oxidising
agent

For CIE examinations

UNIT 6 IONIC COMPOUNDS AND ELECTROCHEMISTRY

Using the standard electrode potential

(1) Predict the cell voltage and electron flow
i.e. Label the electron flow on the graph and predict the cell voltage.
A

Platinum wire

Cu electrode
Supply of chlorine gas at
a pressure of 1 atm

Salt bridge

Cl (aq) 1 mol dm

-3

Platinum electrode

1 mol dm-3 Cu2+(aq)

How to answer this question?

Step 1 list the half cells in the electrochemical cell
Cu2+(aq) + 2eCl2(g) + 2e-

Cu(s)
2Cl-(aq)

= + 0.34V
= + 1.36V

Step 2 The electrons transfer from the electrode with a higher

with a lower

to the electrode

. So that in this cell the electrons move from the copper

electrode to the Cl2/ Cl- electrode.

Step 3 The cell voltage is the difference of the

between the two half cells.

Ecell = 1.36 0.34 = 1.02 V

(2) Predict the direction/possibility of a chemical reaction.

i.e. Predict feasibility of the chemical reaction below:
Cu + 2H+

Cu2+ + H2

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UNIT 6 IONIC COMPOUNDS AND ELECTROCHEMISTRY

Step 1 give out the half cells (reduction potential) included in the reaction.
Cu2+(aq)
H+(aq)

+ 2e-

Cu(s)

e-

1/2H2(s)

Step 2 reverse the sign of one of the

= + 0.34V
= + 0.00V

values

In the chemical reaction Cu is converted in Cu2+ which is an oxidation. The electrode

potential we used is the reduction potential so that reverse the sign of the
value,

(Cu2+/Cu)

(Cu2+/Cu).

value which has an opposite direction to the half cell.

Reverse the sign of the

Step 3 work out the standard cell potential

=

(H+/H2)

(Cu2+/Cu)

= 0 0.34 = 0.34V
<0
The chemical reaction (forward) is impossible.
>0
<0

forward reaction possible but backward impossible

forward reaction impossible but backward possible

(3) Concentrations affecting the direction of the chemical reactions

The

is measured under standard conditions only, but lots of reactions dont take

place under standard conditions.

i.e. Concentrated HCl is used to make chlorine gas by reacting with manganese(IV)
oxide.
4HCl(conc.) + MnO2(s) MnCl2(aq) + Cl2(g) + H2O(l)
However, the chlorine gas is not released by using a dilute HCl to instead the conc. HCl.
Give out an explanation in the terms of cell potential.

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UNIT 6 IONIC COMPOUNDS AND ELECTROCHEMISTRY