Lattice Energy

19.1 defining lattice energy

The energy given out when ions of opposite charges come together to form
a crystalline lattice is called lattice energy,

NOTE:
1. 1 mole of ionic compound formed
2. from its gaseous ions
3. under standard conditions (298K, 101 kPa)
4. is always exothermic ( value is always negative)
5. the more negative the value, the stronger the ionic bonding
6. it is the enthalpy change
Questions ：
1. Write equations describing the lattice energy of:
a magnesium oxide
b potassium bromide
c sodium sulfide.
19.2 enthalpy change of atomization and
electronic affinity
Enthalpy change of atomisation
The standard enthalpy change of atomisation of lithium relates to the equation:
Li(s) → 1 Li(g) = +161 kJ mol−1

The standard enthalpy change of atomisation of chlorine relates to the equation:

Cl2 (g) → 1 Cl(g) = +122 kJ mol−1

NOTE:
1. is always positive (endothermic)
2. is under standard condition
Questions ：
2
a. The bond energy of the chlorine molecule is +244 kJ mol−1 . Why is the standard
enthalpy change of atomisation half this value?

b. Write equations, including state symbols, that represent the enthalpy change of
atomisation of:
i. oxygen
ii. barium
iii. bromine.

c. What is the numerical value of the enthalpy change of atomisation of helium? Explain
your answer.
Electron affinity
The energy change occurring when a gaseous non-metal atom accepts one electron is
called the electron affinity. The symbol for electron affinity is EA.

The first electron affinity, EA1, is the enthalpy change when 1 mole of electrons is added to
1 mole of gaseous atoms to form 1 mole of gaseous ions with a single negative charge
under standard conditions.

Equations representing the first electron affinity of chlorine and sulfur are:
1Cl(g) + 1e− → 1Cl−(g) EA1 = −348 kJ mol−1

1S(g) + 1e− → 1S −(g) EA1 = −200 kJ mol−1

Successive electron affinities

The first, second and third electron affinities have symbols EA1 , EA2 and EA3 .

The equations representing the first and second electron affinities of oxygen are:
1O(g) + 1e− → 1O−(g) EA1 = −141 kJ mol−1

1O−(g) + 1e− → 1O2−(g) EA2 = +798 kJ mol−1

NOTE:
The enthalpy change for the first electron affinity, EA1 is generally exothermic: EA1 is negative.
The second electron affinities are always endothermic (EA2 is positive),
and so are third electron affinities.
The overall enthalpy change in forming an oxide ion, O2−:

O(g) + 2e− → O2−(g)

EA1 + EA2 = (−141) + (+798) = + 657 kJ mol−1

Trends in electron affinities

Generally, electron affinities for non-metal atoms get more negative (more exothermic) across a
period with a maximum at Group 17, but the pattern is not always clear.

For Group 16 and 17, less negative (less exothermic) electron affinities as go down the group,
apart from the first member in the group. There is no clear pattern in electron affinities down many
groups apart from Groups 16 and 17.

The value of the EA1 depends on the attraction between

the added electron and the positively charged nucleus.
• The greater the nuclear charge, the greater the attractive force between the nucleus and the
outer electrons.

• The further away the outer shell electrons are from the positive nuclear charge, the less the
attractive force between the nucleus and the outer shell electrons is.

• The greater the number of electron shells, the greater the power of inner shell electrons to
shield the outer shell electrons from the nuclear charge.

• Fluorine does not fit the trend.

Questions ：
3.
a. Suggest why the second and third electron affinities are always endothermic.

b. The first electron affinity of sulfur is −200 kJ mol−1 . The second electron affinity of
sulfur is +640 kJ mol−1 .
Calculate a value for the enthalpy change: S(g) + 2e− → S2−(g)
c. Write equations representing:
i. the first electron affinity of iodine

ii. the second electron affinity of sulfur.

d. Explain the trend in the first electron affinities going from sulfur to tellurium.
19.3 Born-Haber cycles
Components of the Born-Haber cycle

The Born–Haber cycle is a particular type of energy cycle used to calculate lattice energy.
In simple terms it can be represented by below:

According to the Hess’s Law:

= +

So, = -
When constructing Born-Haber cycles

atomise metal: M(s) → 1M(g) ;

ionise metal: M(g) → M+(g) ; IE1

atomise non-metal: X2(g) → 1X(g) ;

ionise non-metal: X(g) → X-(g) ; EA1

Taking LiF as an example, the relevant enthalpy cycle can be written to show these steps.

= step 1 + step 2 + step 3 + step 4

Step 1: Li(s) → Li(g) ; = +161 kJ/mol

Step 2: Li(g) → Li+(g) + e- ; IE1 = +520 kJ/mol
Step 3: F2(g) → F(g) ; = +79 kJ/mol
Step 4: F(g) + e- → F-(g); EA1= -328 kJ/mol

= +432 kJ/mol
= -617 kJ/mol

So, = -
= -617 – (+432)
= -1049 kJ/mol
NOTE:
take care to account for the signs of the enthalpy changes. The values of the
enthalpy changes of formation and the overall electron affinity may be negative or
positive.
Questions ：
4
a. Write equations to represent:
i. the first ionisation energy of caesium
ii. the third ionisation energy of aluminium
iii. the enthalpy change of formation of calcium oxide
iv. the enthalpy change of formation of iron(III) chloride.
b. Calculate the lattice energy for sodium chloride, given that:
[NaCl] = −411 kJ mol−1
[Na] = +107 kJ mol−1
[Cl] = +122 kJ mol−1
IE1 [Na] = +496 kJ mol−1
EA1 [Cl] = −348 kJ mol−1
The Born-Haber cycle as an energy level diagram

NOTE ：
the arrows going upwards represent an
increase in energy (ΔH⦵ is positive) and the
arrows going downwards represent a decrease
in energy (ΔH⦵ is negative).
Questions ：
5.
a. Draw a fully labelled Born–Haber cycle for potassium bromide, naming each step
b. State the name of the enthalpy changes represented by the following equations:
i. I2 (s) → I(g)
ii. N(g) + e− → N−(g)
iii. Sr(s) + Cl2 (g) → SrCl2 (s)
iv. Cd2+(g) + 2Cl−(g) → CdCl2 (s)
The Born-Haber cycle for magnesium chloride
Some differences:

1. The magnesium ion is Mg 2+, so the first and the

second ionisation energies need to be taken into account:

2. There are two chloride ions in MgCl2 , so the values of

the enthalpy change of atomisation and the first electron
affinity of chlorine must be multiplied by 2.
Questions ：
6. Draw fully labelled Born–Haber cycles for:
a. MgO
b. Na2O
Constructing a Born-Haber cycle for aluminum oxide

In order to form 1 mole of gaseous Al3+ ions from 1 mole of Al(s), we apply the
following sequence of enthalpy changes:

In order to form 1 mole of gaseous O2− ions from oxygen molecules, we apply the
following sequence of enthalpy changes:
Questions ：
6.
a. Draw a Born–Haber cycle for aluminium oxide.
b. Calculate a value for the lattice energy of aluminium oxide using the data under the
arrows in the sequences above and given that [Al2O3 ] = −1676 kJ mol−1 .
Remember that there are 2 moles of Al3+ ions and 3 moles of O2− ions in 1 mole of Al2O3 .
 Factors affecting the value of lattice energy

Lattice energy arises from the electrostatic force of attraction of

oppositely charged ions when the crystalline lattice is formed.

The ion size and the charge on ions can affect the value of the lattice energy.
Lattice energy and ion size

As the ion size increases, the lattice energy becomes less exothermic.
This applies to both anions and cations.

• for any given anion, e.g. F−, the lattice energy gets less
exothermic as the size of the cation increases from Li + to Cs+

• for any given cation, e.g. Li+, the lattice energy gets less
exothermic as the size of the anion increases from F − to I−.
Lattice energy and the charge on ions
The lattice energy becomes more exothermic as the ionic charge increases.

Comparing LiF with MgO:

1. They have the same arrangement of ions in their lattice structure.
2. The cations Li+ and Mg2+ have similar sizes.
3. The anions F− and O2− are fairly similar in size (much larger than the cations).
4. The major physical difference between LiF and MgO is the ionic charge.

[LiF] = −1049 kJ mol−1

[MgO] = −3923 kJ mol−1

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. For ions of similar size, the greater the ionic charge, the higher the charge
density. This results in stronger ionic bonds.
The lattice energy is higher if the ionic charge
is and the ionic radius is
.
Questions ：
7.
a. For each pair of compounds, suggest which will have the most exothermic lattice
energy.
i. KCl and BaO (ionic radii are similar)
ii. MgI2 and SrI2
iii. CaO and NaCl (ionic radii are similar).

b. Place the following compounds in order of increasingly exothermic lattice energy.

Explain your answer.
LiF MgO RbCl
Questions ：
Questions ：
Ion polarisation

The positive charge on the cation in an ionic lattice may attract the electrons in the
anion towards it, this results in a distortion of the electron cloud of the anion.
This distortion is ion polarization.

The ability of a cation to attract electrons and distort an anion is called the
polarizing power of the cation.
Factors affecting ion polarisation

The degree of polarization of an anion depends on:

1. the charge density of the cation
2. the ease with which the anion can be polarised: its polarisability.

An anion is more likely to be polarised if:

1. the cation is small
2. the cation has a charge of 2+ or 3+
3. the anion is large
4. the anion has a charge of 2− or 3−.
A small highly charged cation such as Fe3+ can attract electrons and distort a larger
anion to such an extent that the bond formed has a considerable amount of covalent
character.

Pure ionic bonding and pure covalent bonding are extremes.

Many ionic compounds have some covalent character due to ion polarisation. Many
covalent compounds have some degree of charge separation, i.e. they are polar, due to
bond polarization.
Questions ：
11.
a. Explain why a cation with a smaller ionic radius has a higher charge density.

b. Which one of the following ions will be the best polariser of the large nitrate ion?
Explain your answer.
Cs+ Li+ Na+ K+

c. Which one of these ions will be most polarised by a Mg2+ ion?

Explain your answer.
Br− Cl− F− I−
The thermal stability of Group 2 carbonates and nitrates

MCO3 → MO + CO2
Relative ease of thermal decomposition can be shown by:

Enthalpy change:
down the group, the enthalpy change value is more positive, so the more
stable the carbonate relative to its oxide and carbon dioxide.

Decomposition temperature:
down the group, the higher the temperature required to decompose the
carbonate
So, the relative stabilities of these carbonates increase down the group in the order:
BaCO3 > SrCO3 > CaCO3 > MgCO3.

Explain this trend using ideas about ion polarisation:

1. the carbonate ion has a relatively large ionic radius, so it is easily polarised by a small
highly charged cation
2. the Group 2 cations increase in ionic radius down the group: Mg 2+ < Ca2+ < Sr2+ < Ba2+
3. the smaller the ionic radius of the cation, the better it is at polarising the carbonate ion, so
the degree of polarisation of the carbonate ion by the Group 2 cation follows the order
Mg2+ > Ca2+ > Sr2+ > Ba2+
4. the greater the polarisation of the carbonate ion, the easier it is to weaken a carbon–oxygen
bond in the carbonate and form carbon dioxide and the oxide on heating
 2M(NO3)2 → 2MO + 4NO2 + O2

The order of stability with respect to the products is in the

order: Ba(NO3 )2 > Sr(NO3 )2 > Ca(NO3 )2 > Mg(NO3 )2
Questions ：
12. Use ideas about ion polarisation to explain why magnesium nitrate undergoes
thermal decomposition at a much lower temperature than barium nitrate.
19.4 Enthalpy changes in solution

Enthalpy change of solution

The standard enthalpy change of solution, , is the energy absorbed or released when 1
mole of an ionic solid dissolves in sufficient water to form a very dilute solution.

MgCl2 (s) + aq → MgCl2 (aq) = −55 kJ mol−1

or
MgCl2 (s) + aq → Mg 2+(aq) + 2Cl−(aq) = −55 kJ mol−1
 NaCl(s) + aq → NaCl (aq) = +3.9 kJ mol−1
or
NaCl(s) + aq → Na+(aq) + Cl−(aq) = +3.9 kJ mol−1

NOTE:
1. the symbol for enthalpy change of solution is
2. the symbol ‘aq’ represents the very large amount of water used
3. enthalpy changes of solution can be positive (endothermic) or negative (exothermic)
4. a compound is likely to be soluble in water only if is negative or has a small positive
value; substances with large positive values of are relatively insoluble.
Questions ：
13
a. Write equations to represent the enthalpy change of solution of:
i. potassium sulfate
ii. zinc chloride

b. The enthalpies of solution of some metal halides are given below. What do these
values tell you about the relative solubilities of these four compounds?
sodium chloride, = +3.9 kJ mol−1
silver chloride, = +65.7 kJ mol−1
sodium bromide, = −0.6 kJ mol−1
silver bromide, = +84.5 kJ mol−1
Enthalpy change of hydration
For NaCl:
= -788 kJ/mol = +3.9 kJ/mol

When an ionic solid dissolves in water,

bonds are formed between water
molecules and the ions. These bonds are
called ion–dipole bonds.
The energy released in forming ion–dipole bonds is sufficient to compensate for the
energy that must be put in to separate the anions and cations that are bonded together in
the crystal lattice.
The standard enthalpy change of hydration, , is the enthalpy change
when 1 mole of a specified gaseous ion dissolves in sufficient water to
form a very dilute solution.

Ca2+(g) + aq → Ca2+(aq) = −1650 kJ mol−1

Cl−(g) + aq → Cl−(aq) = −364 kJ mol−1

NOTE:
1. the symbol for enthalpy change of hydration is
2. the enthalpy change of hydration is always exothermic
3. the value of is more exothermic for ions with the same charge but smaller ionic radii, e.g.
is more exothermic for Li+ than for Na+. The charge density is greater for lithium than for
sodium because the ionic radius of Li+ is smaller and there is less shielding than for Na+.
This effect is greater than the effect of increased nuclear charge present in Na+. Water is a
polar molecule. So ion–dipole attractions between water and Li+ are stronger than ion–
dipole attractions between water and Na+.
4. the value of is more exothermic for ions with the same radii but a larger charge, e.g. is
more exothermic for Mg2+ than for Li+. The charge density is greater for magnesium than
for lithium because the charge on Mg 2+ is greater for the same size of atom. There are also
a greater number of positive charges in the nucleus. So ion–dipole attractions between water
and Mg 2+ are stronger than ion–dipole attractions between water and Li+.
Questions ：
14
a. Why is the enthalpy change of hydration always exothermic?

b. Write equations to represent:

i. the hydration of a sodium ion

ii. the hydration of a chloride ion

c. Draw diagrams to show:
i. four water molecules hydrating a magnesium ion
ii. two water molecules hydrating a bromide ion.
Show the dipole on each water molecule.
d. Explain why the value of for magnesium ions is much more exothermic than for
potassium ions.

15. Name the changes associated with the equations below:

a. KBr(s) + aq → KBr(aq) (for 1 mole of KBr)
b. K +(g) + aq → K +(aq) (for 1 mole of K + ions)
c. K +(g) + Br−(g) → KBr(s) (for 1 mole of KBr)
d. Br−(g) + aq → Br−(aq) (for 1 mole of Br− ions)
Calculating enthalpy changes in solution
By constructing an energy cycle using Hess’s law

According to the Hess’s Law:

+ =

NOTE:
value for both anions and cations
are added together to get total value
of .
WORKED EXAMPLE

1. 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
2. Determine the enthalpy change of hydration of the chloride ion using the following data.
• lattice energy of lithium chloride = −846 kJ mol−1
• enthalpy change of solution of lithium chloride = −37 kJ mol−1
• enthalpy change of hydration of lithium ion = −519 kJ mol−1
Questions ：
16.
a. Draw an energy 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:
The solubility of Group 2 sulfates

The solubility decreases as the radius of the metal ion increases.

This variation in solubility can be explained in terms of the relative values of

enthalpy change of hydration and the corresponding lattice energy
Change in hydration enthalpy down the group

1. Smaller ions (with the same charge) have greater enthalpy changes of hydration
2. so the enthalpy change of hydration decreases (gets less exothermic) in the order:
Mg 2+ > Ca 2+ > Sr2+ > Ba2+
3. 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).
Change in lattice energy down the group

1. Lattice energy is greater if the ions (with the same charge) forming the lattice are
small
2. so the lattice energy decreases in the order: Mg 2+ > Ca 2+ > Sr2+ > Ba 2+
3. the lattice energy is also inversely proportional to the sum of the radii of the anion
and cation
4. the sulfate ion is much larger than the Group 2 cations
5. so the sulfate ion contributes a relatively greater part to the change in the lattice
energy down the group
6. 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.
 Difference in enthalpy change of solution of Group 2 sulfates

the higher the positive value of , the less soluble the salt.

We have seen that:

1. the lattice energy of the sulfates decreases (gets less exothermic) by relatively smaller values down
the group
2. the enthalpy change of hydration decreases (gets less exothermic) by relatively larger values down
the group
3. so applying Hess’s law, the value of gets more endothermic down the group, so the solubility of the
Group 2 sulfates decreases down the group.
Questions ：
17.
a. Draw an enthalpy cycle as an energy level diagram showing the relationship
between lattice energy, enthalpy change of solution and enthalpy change of
hydration for barium sulfate. [BaSO4 ] is very endothermic.
b. Explain why magnesium sulfate is more soluble than barium sulfate by referring to
the relative values of the lattice energies and enthalpy changes of hydration.