CHAPTER 19

LATTICE ENERGY
1
 DEFINING LATTICE ENERGY

• When ions combine to form an ionic solid there is a huge release of

energy. The reaction is highly exothermic. The energy given out when
ions of opposite charges come together to form a crystalline lattice is
called the lattice energy, ΔHᶱ latt.

2
 DEFINING LATTICE ENERGY

Note that:
1) Gaseous ions that combine to form the ionic solid
2) Lattice energy is always exothermic
3) Larger exothermic value shows that ionic lattice is stable & the
stronger the ionic bonding in the lattice
3
ENTHALPY CHANGE OF ATOMISATION

Li (s) → Li (g) ∆Hᶱat = +161 kJ mol-1

1
2
Cl2 (g) → Cl (g) ∆Hᶱat = +122 kJ mol-1

* Value of ∆Hᶱat always positive (endothermic).

4
 ELECTRON AFFINITY
• The energy change occurring when a gaseous non-metal atom
accepts one electron is called the electron affinity (∆Hᶱea).

Cl (g) + e– → Cl–(g) ΔHᶱea1 = –348 kJ mol–1

S (g) + e– → S–(g) ΔHᶱea1 = –200 kJ mol–1
5
 ELECTRON AFFINITY

1st electron affinity:

O(g) + e– → O–(g) ΔHᶱea1 = –141 kJ mol–1
2nd electron affinity:
O–(g) + e– → O2–(g) ΔHᶱea2 = +798 kJ mol–1
6
 ELECTRON AFFINITY

• The overall enthalpy change in forming an oxide ion, O2–,

from an oxygen atom is found by adding together the 1st and
2nd electron affinities:

O(g) + 2e– → O2–(g)

ΔHᶱea1 + ΔHᶱea2 = (–141) + (+798)
= +657 kJ mol–1

7
 BORN-HABER CYCLES

A simple enthalpy cycle that can be used to calculate 8

lattice energy
 BORN-HABER CYCLES

• According to Hess’s law:

∆Hᶱ1 + ∆Hᶱlatt = ∆Hᶱf

• The enthalpy change ΔHᶱ1 involves several steps.

9
 BORN-HABER CYCLES
For example: Lithium fluoride

An enthalpy cycle that can be used to calculate the lattice energy 10

of lithium fluoride
 Step 1:Convert solid lithium to gaseous lithium atoms:
the enthalpy change required is the enthalpy change of
atomisation of lithium, ΔHᶱat.

Li(s) → Li(g) ΔHᶱat = +161 kJ mol–1

11
Step 2: Convert gaseous lithium atoms to gaseous lithium
ions: the enthalpy change required is the 1st ionisation
energy of lithium, ΔHᶱi1

Li(g) → Li+(g) + e– ΔHᶱi1 = +520 kJ mol–1

12
 Step 3: Convert fluorine molecules to fluorine atoms:
the enthalpy change required is the enthalpy change of
atomisation of fluorine, ΔHᶱat.
1
F (g) → F(g)
2 2
ΔHᶱat = +79 kJ mol–1
13
 Step 4: Convert gaseous fluorine atoms to gaseous
fluoride ions: the enthalpy change required is the 1st
electron affinity of fluorine, ΔHᶱea1.

F(g) + e– → F–(g) ΔHᶱea1 = –328 kJ mol–1

14
 BORN-HABER CYCLES
Step 5: By adding all these values together, we get a value for ∆Hᶱ1

15
 QUESTION
1) Calculate the lattice energy for sodium chloride, given that:
∆Hᶱf [NaCl] = -411 kJ mol-1
∆Hᶱat[N] = +107 kJ mol-1
∆Hᶱat[Cl] = +122 kJ mol-1
∆Hᶱi1[Na] = +496 kJ mol-1
∆Hᶱea1[Cl] = -348 kJ mol-1

16
 QUESTION
2) Use the following data, together with relevant data from the Data Booklet, to construct
a Born-Haber cycle and calculate a value for the lattice energy of zinc chloride.

17
THE BORN-HABER CYCLE AS
AN ENERGY LEVEL DIAGRAM

Born-Haber cycle for lithium

fluoride

• Arrows going upwards:

increase in energy (∆Hᶱ is
positive).
• Arrows going downwards:
decrease in energy (∆Hᶱ is
negative).
18
 THE BORN-HABER CYCLE AS AN ENERGY
LEVEL DIAGRAM

Question:
1) Draw a Born-Haber cycle for magnesium chloride.

19
 FACTORS AFFECTING THE VALUE OF
LATTICE ENERGY

1)Ion size
2)Charge on the ions

20
 21

Lattice enthalpies of the Group 1 halides

 1) ION SIZE

Ions with same ionic charge have a lower charge density

if their radius is larger

Lower charge density results in weaker electrostatic

forces of attraction in the ionic lattice.

Example: sodium fluoride (NaF) has a less exothermic

lattice energy than lithium fluoride (LiF).

22
 2) CHARGE ON THE IONS
• Lattice energy becomes more exothermic as the ionic
charge increases.
• Compare LiF & MgO
• The cations Li+ and Mg2+ have similar sizes. The anions F –
and O2– are fairly similar in size.
• The doubly charged Mg2+ and O2– ions in magnesium
oxide attract each other more strongly than the singly
charged ions of the same size in LiF.
23
 ION POLARISATION
• The electron cloud of an anion may be distorted by a cation
with high charge density (small size but large charge, like
Mg2+, Al3+ and Fe3+).
• This distortion is called the polarisation of the anion.

24

A small highly charged cation can distort the shape of the anion
 ION POLARISATION

• The ability of a cation to attract electrons and distort

an anion is called the polarising power of the cation.

25
 FACTORS AFFECTING ION POLARISATION

The degree of polarization of an anion depends on:

• The charge density of the cation
• The ease with which the anion can be polarized (polarisability)
An anion is more likely to be polarized if:
• The cation is small
• The cation has a charge of 2+ or 3+
• The anion is large
• The anion has a charge of 2- or 3-
26
 THE THERMAL STABILITY OF GROUP 2
CARBONATES & NITRATES
• The Group 2 carbonates decompose to their oxides and carbon
dioxide on heating;
CaCO3(s) → CaO(s) + CO2(g)

27
Group 2 carbonates @ nitrates are more stable going down the group 28
29
 THE THERMAL STABILITY OF GROUP 2
CARBONATES & NITRATES
• The Group 2 nitrates decompose to their oxides, nitrogen dioxide and
carbon dioxide.
2Mg(NO3)2(s) → 2MgO(s) + 4NO2(g) + O2(g)

A similar pattern is observed with thermal

decomposition of Group 2 nitrates

30
 ENTHALPY CHANGES IN SOLUTION

The enthalpy change of solution, ΔHᶱsol, is the energy

absorbed or released when 1 mole of an ionic solid
dissolves in sufficient water to form a very dilute solution.

For example:
MgCl2(s) + aq → MgCl2(aq) ΔHᶱsol = –55 kJ mol–1

or
MgCl2(s) + aq → Mg2+(aq) + 2Cl–(aq) ∆Hᶱsol = –55 kJ mol–1

31
ENERGY NEEDED TO BREAK THE LATTICE

32
ENERGY RELEASED FROM HYDRATION OF
IONS

33
 ENTHALPY CHANGE OF HYDRATION

• Lattice energy for NaCl is -788 kJ mol-1;

• but ∆Hᶱsol for NaCl is only +3.9 kJ mol-1;

Where does the energy come from???

• Dissolving process can be taken as two-step process:
• first, energy is needed to break the lattice (reverse of lattice
energy),
• then solvation (hydration) of the ions which release energy. 34
 ENTHALPY CHANGE OF HYDRATION

The enthalpy change of hydration, ΔHᶱhyd, is the enthalpy

change when 1 mole of a specified gaseous ion dissolves
in sufficient water to form a very dilute solution.

For example:
Ca2+(g) + aq → Ca2+(aq) ΔHᶱhyd = –1650 kJ mol–1
Cl–(g) + aq → Cl–(aq) ΔHᶱhyd = –364 kJ mol–1

35
 ENTHALPY CHANGE OF HYDRATION

• The value of ∆Hᶱhyd is more exothermic for ions with the

same charge but smaller ionic radii.
- ∆Hᶱhyd is more exothermic for Li+ than for Na+

• The value of ∆Hᶱhyd is more exothermic for ions with the

same radii but a larger charge.
- ∆Hᶱhyd is more exothermic for Mg2+ than for Li+.
36
CALCULATING ENTHALPY CHANGES IN
SOLUTION

ΔHᶱlatt + ΔHᶱsol = ΔHᶱhyd 37

 EXAMPLE

Determine the enthalpy change of solution of sodium

fluoride using the following data:

 lattice energy = –902 kJ mol–1

 enthalpy change of hydration of sodium ions = –406 kJ mol-1
 enthalpy change of hydration of fluoride ions = –506 kJ mol–1

38
 39
An energy level diagram to determine ∆Hᶱsol of NaF
 QUESTION
1.

(a)Draw an enthalpy cycle to calculate the enthalpy of

hydration of magnesium ions when magnesium chloride
dissolves in water.
(b)Calculate the enthalpy of hydration of magnesium ions
given that:
∆Hᶱlatt [MgCl2] = -2582 kJmol-1
∆Hᶱsol [MgCl2] = -55 kJ mol-1
∆Hᶱhyd [Cl-] = -364 kJ mol-1
40
THE SOLUBILITY OF GROUP 2 SULFATES

Solubility
decreases
Solubilities in water of some Group 2 sulfates down the41
group
 CHANGE IN HYDRATION ENTHALPY DOWN
THE GROUP

• Smaller ions (with the same charge) have greater enthalpy

changes of hydration
• So the enthalpy change of hydration decreases (gets less
exothermic) in the order Mg2+ > Ca2+ > Sr2+ > Ba2+
• This decrease is relatively large down the group and it
depends entirely on the increase in the size of the cation, as
the anion is unchanged (it is the sulfate ion in every case)
42
 CHANGE IN LATTICE ENERGY DOWN THE
GROUP

• Lattice energy is greater if the ions (with the same charge)

forming the lattice are small
• So the lattice energy decreases in the order Mg2+ > Ca2+ >
Sr2+ > Ba2+
• the lattice energy is also inversely proportional to the sum of
the radii of the anion and cation

43
 CHANGE IN LATTICE ENERGY DOWN THE
GROUP

• The sulfate ion is much larger than the group 2 cations

• so the sulfate ion contributes a relatively greater part to the
change in the lattice energy down the group
• so the decrease in lattice energy is relatively smaller down
the group and it is determined more by the size of the large
sulfate ion than the size of the cations.

44