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MODULE 4

ENERGETICS

Simple treatment (including calculations) of the Born-Haber cycle for

the halides of Group I and II.
(Lattice enthalpy will be regarded as the enthalpy of lattice breaking)

When you have finished this section you should be able to:
• Explain and use the term ‘lattice enthalpy’ as a measure of ionic bond strength.
• Construct Born-Haber cycles to calculate the lattice enthalpy of a simple ionic
solid e.g NaCl, MgCl2, using relevant energy terms (enthalpy changes of
formation, ionisation energy, enthalpy of atomisation and electron affinity.
• Explain, in qualitative terms, the effect of ionic charge and of ionic radius on the
numerical magnitude of a lattice energy.

Lattice Enthalpy
Bond enthalpies provide a measure of the strength of covalent bonds.
Ionic bonding is an electrostatic attraction between oppositely charged
ions. The attraction acts in all directions, resulting in a giant ionic lattice
containing many ions. For ionic compounds the corresponding enthalpy is
the lattice enthalpy (also called the lattice energy). Lattice enthalpy
indicates the strength of the ionic bonds in an ionic lattice.

The standard molar lattice enthalpy is the energy required to convert one
mole of a solid ionic compound into its constituent gaseous ions under
standard conditions.

e.g. NaCl (s) Na+ (g) + Cl- (g)

Born-Haber cycle
This is an application of Hess’s Law and can be used to calculate lattice
energies.
Lattice enthalpies cannot be determined directly by experiment and must
be calculated indirectly using Hess’s Law and other enthalpy changes that
can be found experimentally. The energy cycle used to calculate a lattice
enthalpy is the Born-Haber cycle.
The basis of a Born-Haber is the formation of an ionic lattice from its
elements.

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In general for an ionic compound a Born-Haber cycle can be written as:

M+ (g) + X- (g)

M+ (g) + X (g) ∆He.a.

∆Hdiss.
+
M (g) + ½ X2 (g)

∆HI.E. ∆Hlatt.
M (g) + ½ X2 (g)

∆Hsub.
M (s) + ½ X2 (g)

∆HFθ

M+X- (s)

According to Hess’s Law

∆Hlatt. = (-∆HFθ) + ∆Hsub. + ∆HI.E. + ∆Hdiss. + ∆He.a.

∆Hfθ = enthalpy of formation of MX (s)

∆Hsub. = enthalpy of sublimation of M (s)
∆HI.E. = ionisation energy
∆Hdiss. = dissociation energy of X2 (g)
∆He.a.= electron affinity of X (g)
∆Hlatt. = lattice energy

N.B. The actual figures may be positive or negative and are simply
substituted in the above equation.

2
Consider the reaction between sodium and chlorine to form sodium
chloride.
Na (s) + ½ Cl2 (g) NaCl (s)

The reaction can be considered to occur by means of the following steps:

• Vapourisation of sodium

Na (s) Na (g) ∆Hsub.

The standard enthalpy of sublimation or vaporisation is the enthalpy

change when one mole of sodium atoms are vaporised. This is an
endothermic process and can be determined experimentally.

• Ionisation of sodium

Na (g) Na+ (g) + e- ∆HI.E

The standard enthalpy of ionisation is the energy required to remove

one mole of electrons from one mole of gaseous atoms. This is
endothermic and can be determined by spectroscopy.

• Dissociation of chlorine molecules

Cl2 (g) 2Cl (g) ∆Hdiss.

The standard bond dissociation enthalpy is the energy required to

dissociate one mole of chlorine molecules into atoms (i.e. to break one
mole of bonds). This is also endothermic and can be determined by
spectroscopy.

• Ionisation of chlorine atoms

Cl (g) + e- Cl- (g) ∆He.a.

The electron affinity of chlorine is the energy released when one mole of
gaseous chlorine atoms accepts one mole of electrons forming one mole of
chloride ions.
• Reaction between the ions

Na+ (g) + Cl- (g) NaCl (s) -∆Hlatt.

This is the reverse of the lattice energy. The standard lattice enthalpy is
the energy absorbed when one mole of solid sodium chloride is separated
into its gaseous ions. It has a positive value and cannot be determined
experimentally.
3
A Born-Haber cycle can be drawn:

Na+ (g) + Cl- (g)

∆He.a.
+
Na (g) + Cl (g)

∆HI.E.
Na (g) + Cl (g) ∆Hlatt.

∆Hdiss.
Na (g) + ½ Cl2 (g)

∆Hsub. ∆HFθ
Na (s) + ½ Cl2 (g) NaCl (s)

Applying Hess’s Law

∆Hsub. + ∆HI.E. + ∆Hdiss. + ∆He.a. - ∆Hlatt. – ∆Hfθ =0

Calculate the lattice enthalpy of sodium chloride given

∆Hfθ (NaCl) = -411 kJ mol-1
∆Hsub. (Na) = 108.3 kJ mol-1
∆HI.E. (Na) = 500 kJ mol-1
∆Hdiss. (Cl) = 121 kJ mol-1
∆He.a. (Cl) = -364 kJ mol-1

Answer ∆Hlatt. = +776 kJ mol-1

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Exercise 1
Draw Born-Haber cycles for each of the following ionic compounds and
calculate their lattice enthalpies.
(Note : ∆Hat. of an element is the energy required to form one mole of
gaseous atoms from the element.)

M X
Compound ∆HFθ ∆Hat. ∆HI.E. ∆Hat. ∆He.a.
kJmol-1 kJmol-1 kJmol-1 kJmol-1 kJmol-1
KBr -392 +89 +420 +112 -342
BaCl2 -860 +175 (1st) +500 +121 -364
(2nd) +1000

Use of Lattice Energies

• The melting points of ionic solids depend on their lattice enthalpies.

The greater the lattice energy the higher the melting point of the
compound.

NaF NaCl NaBr NaI

∆Hlatt. kJ 915 781 743 699
mol-1
m. pt. oC 995 808 750 662

• Solubility of ionic compounds is usually governed by its lattice energy.

In general the higher the lattice energy the lower the solubility.
(See enthalpy of solution below)
• A comparison of calculated and theoretical lattice energies gives an
indication of the degree of covalent character in an ionic compound.
The greater the difference between the two values the more covalent
the compound.

Compound Theoretical lattice Calculated lattice

energy energy (via Born-Haber
kJ mol-1 cycle) kJ mol-1
NaCl 766 776
NaBr 731 742
NaI 686 699
AgCl 768 890
AgBr 759 877
AgI 736 867

The close agreement between the theoretical and experimental values for
the alkali metal halides provides strong evidence that the simple ionic

5
model of a lattice, composed of discrete spherical ions with an even
charge distribution, is a very satisfactory one.
For the silver halides the theoretical values are about 15% less than the
experimental values based on the Born-Haber cycle. This indicates that
the simple ionic model is not very satisfactory.
When there is a large difference in electronegativity between the ions in
a crystal , as in the case of the alkali metal halides then the ionic model is
satisfactory. However as the difference in electronegativity gets smaller,
as in the case of the silver halides, the bonding is stronger than the ionic
model predicts. The bonding in this case is not purely ionic but
intermediate in character between ionic and covalent. The ionic bonds
have been polarised (Fajans rules) giving some covalent character.

Exercise 2
The figures below give a list of lattice energies in kJ mol-1. Try to find as
many patterns and trends in the figures as you can.

RbF 779 CaI2 2038

BeF2 3456 CaCl2 2197
BaI2 1841 MgCl2 2489
MgBr2 2416 KCl 710
CaBr2 2125 NaF 915
CsI 607 LiF 1029
KBr 671 MgI2 2314
BaF2 2289 LiBr 804
CsBr 644 RbI 624
LiI 753 SrBr2 2046
BeI2 2803 NaBr 742
LiCl 849 SrCl2 2109
NaI 699 BeBr2 2895
BeCl2 2983 KF 813
CsCl 676 BaBr2 1937
KI 643 CaF2 2583
MgF2 2883 NaCl 776
RbCl 685 SrF2 2427
SrI2 1954 RbBr 656
CsF 735 BaCl2 2049

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Trends in lattice enthalpy explained in terms of ionic radius and
charge.

Consider the ionisation of an ionic solid MX.

MX (s) Mn+ (g) + Xn- (g)

The ease of separation of the ions and hence the lattice energy is
determined by the size of the ions and their charge.

Group I Group II
Li Na K Rb Cs Be Mg Ca Sr Ba
F 1029 915 813 779 735 3456 2883 2583 2427 2289
Cl 849 776 710 685 676 2983 2489 2197 2109 2049
Br 804 742 671 656 644 2895 2416 2125 2046 1937
I 753 699 643 624 607 2803 2314 2038 1954 1841

Effect of ionic size

As the ionic radius of both Mn+ and Xn- the lattice energy decreases. The
attractive force between the ions decreases and they become easier to
separate.

e.g. LiBr 804 kJ mol-1 BeCl2 2983 kJ mol-1

NaBr 742 MgCl2 2489
KBr 671 CaCl2 2197
RbBr 656 SrCl2 2109
CsBr 644 BaCl2 2049

As we descend both Groups I and II the lattice energies become less

positive.
For any given metal the lattice energy also decreases in passing from the
fluoride to the iodide.

e.g. NaF 915 kJ mol-1 SrF2 2427 kJ mol-1

NaCl 776 SrCl2 2109
NaBr 742 SrBr2 2046
NaI 699 SrI2 1954

This is due to an increase in ionic size from F- to I- which increases the

internuclear distance. There is a corresponding decrease in attractive
force and hence lattice energy.
When the internuclear distances are about equal, as for RbF and LiI for
example, then the lattice energies are almost equal.

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Effect of ionic charge
As the charge on Mn+ increases there is a greater attractive force
between the ions and lattice energies increase. In addition, the decrease
in size of Mn+ with increasing charge increases the attractive force
between the ions and also increases the lattice energy.
The ionic radius of the Na+ and Ca2+ ions are very similar. However the
lattice energy of CaCl2 is about 3 times that of NaCl.

NaCl 776 kJ mol-1 CaCl2 2197 kJ mol-1

This is due to the increased charge on the metal ion giving greater
electrostatic attraction.
In general Group II halides have a lattice energy about three times that
of the equivalent Group I halide.
Beryllium halides have considerable covalent character and the lattice
energies are bigger than expected.

Exercise 3
What would be the effect on lattice energy of increasing the charge on
Xn- ? (i.e. forming a Group VI compound rather than a Group VII
compound).
Describe and explain the trends.

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Enthalpy of solution related to lattice enthalpy and enthalpy of
solvation of simple ionic salts.

When an ionic solid dissolves two enthalpy changes are involved:

1 The ionc lattice must be broken down and the ions separated.
The energy required is the lattice enthalpy.

NaCl (s) Na+ (g) + Cl- (g) ∆Hlattice

This is an endothermic process.

2 The separate ions interact with the solvent molecules. If the

solvent is polar, the charged ions can be attracted to one end of
the polar solvent molecules. The energy released is called the
enthalpy of solvation.
When the solvent is water the enthalpy change is called the
enthalpy of hydration. This process is exothermic.

Na+ (g) + Cl- (g) + solvent Na+ (aq) + Cl- (aq) ∆Hsolvation

The difference between the two is called the enthalpy of solution.

∆Hlattice
NaCl (s) + (aq) Na+ (g) + Cl- (g

∆Hsolution ∆Hhydration

Na+ (aq) + Cl- (aq)

Applying Hess’s Law

∆Hsolution = ∆Hlattice + ∆Hhydration

The enthalpy of solution can be exothermic or endothermic depending on

the size of the lattice energy (∆H +ve) and the solvation (hydration)
energy (∆H -ve).

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e.g. for NaCl
∆Hlattice = +776 kJ mol-1
∆Hhydration = -772 kJ mol-1

Therefore ∆Hsolution = +4 kJ mol-1

The enthalpy of solution is the energy change when one mole of solute is
dissolved in a solvent to form an infinitely dilute solution.
Some values for enthalpies of hydration are given below.

H+ Li+ Na+ K+ Rb+ Cs+

-1075 -449 -390 -306 -281 -248
Be2+ Mg2+ Ca2+ Sr2+ Ba2+
-2425 -1891 -1562 -1414 -1273
Al3+
-4613

Exercise 4
Describe and explain the trends in hydration energy.

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Energetics
QUESTIONS
Section A
1 The Born-Haber cycle for sodium chloride is represented below:

Na+(g) + Cl(g)

z Na+(g) + Cl-(g)
y Na+(g) + ½ Cl2(g)

x Na(g) + ½ Cl2(g) u

w Na(s) + ½ Cl2(g)
v NaCl(s)

Which one of the following statements is correct?

A The bond dissociation energy of chlorine is y.

B The electron affinity of chlorine is z.
C The first ionisation energy of sodium is w.
D The lattice energy of sodium chloride is v.

2 The reactions represented by the following equations are part of

the Born-Haber cycle for sodium bromide. Which one of the
reactions is exothermic?

A Na (s) Na (g)
B Na (g) Na+ (g) + e-
C Br (g) + e- Br- (g)
D Br2(g) 2Br(g)

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 Section B
1. Lithium chloride is formed from lithium (atomic number 3) and
chlorine (atomic number 17). Its lattice energy may be calculated
from a Born-Haber cycle using the following experimental data.
ΔH/kJ mol-1
First ionisation energy of lithium = +520
Heat of atomisation of lithium = +159
Heat of formation of lithium chloride = -409
Heat of atomisation of chlorine per mole of chlorine atoms = +122
Electron affinity of chlorine atoms = -349

(a) Using the usual chemical symbols, the state symbols (s), (1), (g)
and the symbol for an electron, e-, write an equation in each case to
define the following terms.

(i) The first ionisation energy of lithium

(ii) The second ionisation energy of lithium.

(iii) The heat of formation of lithium chloride.

(iv) The electron affinity of chlorine.

(v) The lattice energy of lithium chloride.

[5]

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 (b)
(i) Construct a labelled Born-Haber cycle for the formation of
lithium chloride.

[6]

(ii) Using the constructed Born-Haber cycle, or any other

method, calculate the lattice energy of lithium chloride.

kJmol-1

[2]
(c) The lattice enthalpies for sodium chloride, potassium chloride and potassium
bromide are + 780, +710 and +680 kJ mol-1 respectively. Comment on these
results and that for lithium chloride.

[4]

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