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) + O2-(g)
787 kJ mol-1

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) H latt = -787 kJ mol-1

Na2O,
2Na+(g) + O2- (g) Na2O(s) H latt = -2590 kJ mol-1
MgO,

Mg2+ (g) + O2- (g) MgO(s) H latt = -3923 kJ mol-1

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
2

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UNIT 6 IONIC COMPOUNDS AND ELECTROCHEMISTRY

4 Calculate the lattice enthalpy

(1) Theoretical values for lattice energy (Not required by CIE)
e
Z 2
1
M
(1 )
4 0 r0
n
N A
L=

Z r0

N A Me 2
1
L=[
1 ]
4 0
n
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 ( H at )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: ( H ef 1 )
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: ( H ef 2 )
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
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
3

-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

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UNIT 6 IONIC COMPOUNDS AND ELECTROCHEMISTRY

How to draw a Born Haber cycle

High

(KCl)
K+(g)

Cl-(g)

(K)

enthalpy

K(g)

Step 1
Construct the equation which is responsible for the (KCl) and se
Construct another equation which is responsible for the (KCl) an
diagram.
(Cl)

Cl(g)

(Cl)

(K)

(KCl)
Low

K(s)

1/2Cl2(g)

NaCl(s)

Step 2
Step 3
List the enthalpy changes of the metalList
element
the enthalpy
in the order
changes
of atomisation
of the non and
- metal
ionisation.
element in the order of atomisation and electron affinity.

According to the Hess law, the relationship between these enthalpy changes is shown
below.
H f (KCl) = H at (K) + H i 1 (K) + H at (Cl) + H ef 1 (Cl) + H latt (KCl)

H latt (KCl) = H f (KCl) ( H at (K) + H i 1 (K) + H at (Cl) + H ef 1 (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.
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.
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UNIT 6 IONIC COMPOUNDS AND ELECTROCHEMISTRY

(3) The distorted carbonate/nitrate breaks up into CO 2 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
-91
-18
-2

MgSO4 (2959)

CaSO4 (2704)

SrSO4 (2572)

Standard enthalpy change of hydration

dissolving

X2+(aq)

SO42-(aq)

2+

Mg (-1890)
Ca2+ (-1562)

Sr2+ (-1414)

- 1160

+26 BaSO4 (2459)

Ba2+ (-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

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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.
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.

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The direction, Cu(s)

UNIT 6 IONIC COMPOUNDS AND ELECTROCHEMISTRY

Cu

2+

(aq)

+ 2e-, is not acceptable because its an oxidation 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.)

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UNIT 6 IONIC COMPOUNDS AND ELECTROCHEMISTRY

Platinum electrode

The half cell

2H+ + e- H2

Supply of h

Plat

H+ 1 m

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UNIT 6 IONIC COMPOUNDS AND ELECTROCHEMISTRY

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

Cu
E

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

3+ /Fe
Fe
E

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UNIT 6 IONIC COMPOUNDS AND ELECTROCHEMISTRY

+ 0.77V

Salt bridge

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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

Cl2 /Cl
E

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UNIT 6 IONIC COMPOUNDS AND ELECTROCHEMISTRY

Supply of chlorine gas at a pressure of 1 atmosphere

Platinum electrode
Platinum wire

Cl- 1 mol dm-3

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UNIT 6 IONIC COMPOUNDS AND ELECTROCHEMISTRY

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) + 2eAg+(aq) + e-

The oxidising ability

of the ion/element
on the left increases

as
the
E
increases
Weaker oxidising
agent

Cu2+(aq)
H+(aq) +
Zn2+(aq)
Mg2+(aq)

+ 2ee+ 2e+ 2e-

2Cl-(aq)

= + 1.36V

Ag(s)

= + 0.80V

Cu(s) E = + 0.34V
1/2H2(s) E = + 0.00V
Zn(s) E = - 0.76V
Mg(s) E = - 2.38V

Weaker
reducing agent

The reducing ability

of the ion/element
on
the
right
increases as the

gets more
E
negative.
Stronger
reducing agent

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.

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UNIT 6 IONIC COMPOUNDS AND ELECTROCHEMISTRY

Salt bridge

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UNIT 6 IONIC COMPOUNDS AND ELECTROCHEMISTRY

How to answer this question?

Step 1 list the half cells in the electrochemical cell
Cu2+(aq) + 2eCu(s) E = + 0.34V
Cl2(g) + 2e2Cl-(aq) E = + 1.36V
Step 2 The electrons transfer from the electrode with a higher E to the
electrode with a lower E . 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 E 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
Step 1 give out the half cells (reduction potential) included in the reaction.
Cu2+(aq) + 2eCu(s) E = + 0.34V
H+(aq) + e1/2H2(s) E = + 0.00V
Step 2 reverse the sign of one of the E values
In the chemical reaction Cu is converted in Cu 2+ which is an oxidation. The electrode
potential we used is the reduction potential so that reverse the sign of the E

(Cu /Cu) value, E

(Cu /Cu).
2+

2+

Reverse the sign of the

E value which has an opposite direction to the half cell.

Step 3 work out the standard cell potential

Ecell = E (H /H ) E (Cu /Cu)
= 0 0.34 = 0.34V
<0
The chemical reaction (forward) is impossible.
+

Ecell
Ecell

2+

> 0 forward reaction possible but backward impossible

< 0 forward reaction impossible but backward possible

(3) Concentrations affecting the direction of the chemical reactions

The Ecell 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)
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UNIT 6 IONIC COMPOUNDS AND ELECTROCHEMISTRY

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.

11