Chapter 18 Lattice energy

18.1.1 Lattice energy, LE

18.1.2 Enthalpy change of atomisation Hөat
18.1.3 Enthalpy change of electron affinity, EA
Patterns of EA in the periodic table
Hөea Increases across the period (more exo)
Hөea Decreases down the grp (less exo)
Exception: for Grp 0/2/5 (Hөea less exothermic, not so likely to accept e-)
18.2 Born-Haber Cycle
18.3 Factors affecting the value of lattice energy
The ionic charge – the ↑ ion charge, the ↑ ΔH°latt
The ionic radius – the ↓ ion radii, the ↑ ΔH°latt
18.4 Ion polarisation – The ability of the cation to attract e- and distort the anion
– Thermal stability of Grp2 carbonates / nitrates increases down the group
18.5 Enthalpy changes in solution
Enthalpy change solution Hөsol
Enthalpy change hydration Hөhyd
ΔH°sol = ΔH°hyd – ΔH°latt
•Solubility of Grp II sulfates decreases down the group.
ΔH°hyd decreases more significantly than the decrease in ΔH°latt
•Solubility of Grp II hydroxides increase down the group.
ΔH°latt decreases more significantly than the decrease in ΔH°hyd
18.1.1 Lattice energy, LE, ΔH°latt
 Recall
 Ionic bonding – Strong force of attraction bet the oppositely
charge cation & anion.

 Ionic lattice – 3 dimensional arrangement of alternating

cation & anion.

 Ionic lattice are hard, brittle, high m.pt/b.pt, many are soluble
in water, it conducts electricity in molten/solution state.

 The enthalpy for bond forming is exo?endo?

 Formation of crystal lattice is depending on the attraction between
opposite charge ions in achieving the highest stability
◦ Higher attraction, higher stability

 The ions will tend to organised to reach the highest stability with
minimal repulsion forces

 How do we measure the strength of an ionic bond?

 Using lattice energy (LE) in gas phases. However LE does not
measure the strength of a single ionic bond between 2 ions, because
in a lattice structure, 1 Na+ is surrounded by 6 Cl- = 6 ionic bonds.
Nevertheless it still allows useful comparisons to be made.
 • Lattice energy, LE
• Defined as energy released when one mole of solid ionic
compound is form from its gaseous ions under standard
condition.
Mg2+(g) + 2Cl- (g) → MgCl2(s)

• Always exothermic; the larger the value the stronger the

ionic bond, the more stable the ionic compound formed, the
more energy required to break the strong electrostatic
forces between the 2 opposite charged ions.
• LE cannot be physically measured, it has to be calculated
using various experiment and an energy cycle called Born-
Haber cycle.

• Can ΔH°latt be measure for CO2, H2O, CH3CH2Br?

105Pa, 298K, in
normal physical
state.
 18.1.2 Enthalpy change of atomisation Hөat
 The standard enthalpy change of atomisation is the enthalpy
change when one mole of GASEOUS atom is formed from its
element in standard state under standard conditions.

 Formation of one mole of gaseous atom as PRODUCT

Li(s) → Li (g) ΔHatө [Li(s)] = + 159.4 kJ mol–1
½F2(g) → F (g) ΔHatө [F2(g)] = + 79 kJ mol–1
F2(g) → 2F (g) 2 X ΔHatө [F2(g)] = 2 (+79 )
= 158 kJ mol–1

 Always endothermic, due to bonds are being broken.

 In gas phase reactions, the energy required to completely
separate the atoms in one mole of covalent bonds is known
as the bond dissociation enthalpy /bond energy (given in data
booklet!).

 Ionic bond – LE
 Covalent bond – BE
18.1.3 Enthalpy change of electron affinity, EA
 First EA enthalpy is the change in energy (in kJ mol-1) is when 1 mole
of electron is added to the 1 mole gaseous atom to form a 1 mole of
gaseous -1 ions under standard condition.

 F (g) + e– → F–(g) EA1 = -328 kJ mol-1

 Cl (g) + e– → Cl–(g) EA1 = -348 kJ mol-1

 Electron affinity (EA) can be characterised as 1st EA, 2nd EA, 3rd EA….

 USUALLY, the 1st EA enthalpy is exothermic. This is because a more

stable anion is formed from the acceptance of e- by neutral atoms,
attracted by the nuclear charge.

 The easier the atom to receive the electron, the more energy is
release.
 What about the 1st EA enthalpy for metals (Grp1 and 2)? Endo/Exo?
 Endothermic, because they are less likely to gain e- , it is easier to lose
their e-.

• 2nd EA, 3rd EA… are ALWAYS endothermic reactions. This is

because energy is required to overcome the repulsive force
between the -1 anion and the (incoming) electron(s).

O(g) + e– → O–(g) EA1 = –141 kJ mol-1

O–(g) + e– → O2–(g) EA2 = +798 kJ mol-1
O(g) + 2e– → O2–(g) EAtotal = +657 kJ mol-1
 Patterns of EA in the periodic table
• Across the period
• EA increases, become more negative.
1. nuclear charge increases, stronger the attraction between the nucleus &
incoming electron into the same shell.
2. The distance is relatively the across the same period.
3. Shielding effect of the outer electrons from the nuclear charge is relatively
constant
 Therefore more energy is released when an electron is added
to the valence orbital across the period due to more
attraction between nucleus and incoming electrons.
Relative Grp 6 (S) Grp 7 (Cl)
Nuclear charge lower Higher
The ease of accepting electrons Easy Very easy
Energy release when an electron was Less energy More energy
accepted released released
EA1 -200 kJ mol-1 -348 kJ mol-1
• Down a group (Group 16 & Group 17)
• EA decreases, becomes less negative
1. nuclear charge increases, stronger the attraction between the nucleus
& incoming electron.
2. The distance of the outer electrons to the nucleus/nuclear charge
increases because there is an increase in electron shells descending a
group / atomic radii increases.
3. Shielding effect of the outer electrons from the nuclear charge is
increases due to increase in electron shells.
 Therefore lesser energy is released when an electron is
added to the valence orbital descending a group due to
lesser attraction between nucleus and incoming electrons.
• EA going down a grp;
• EA decreases (becomes less exothermic), shielding effect inc,
repulsion occurs between the e-.

• Group VII: highest EA;

• Exception:
• Group II and 0: fully occupied
atomic orbitals;
• Group V: half-filled atomic
orbitals;
• Reason: have a very stable
electronic configuration, hard to
accept electron.
18.2 Born-Haber Cycle
 Born-Haber cycle is an energy level diagram use to
calculate lattice energy, ΔH°latt of ionic compounds which
cannot be measured directly from experiments.

 An application of Hess’ Law to ionic compounds.

 To determine the lattice energy, we need:

a) ∆ Hөf
b) and the enthalpy changes that changes the elements in
their std states to gaseous ions.

 To convert elements in their std states to its gaseous ions,

atomisation of the elements to gaseous is done follow by the
conversion of gaseous atoms to its ions.
18.2 Born-Haber Cycle
 Born-Haber cycle is an energy level diagram use to calculate
lattice energy, ΔH°latt of ionic compounds which cannot be
measured directly from experiments.

 f
An application of Hess’ Law to ionic compounds

 To determine the lattice energy, we need:

a) enthalpy changes that changes the elements in their std
states to gaseous ions
b) and the ∆ Hөf
 Step 1: atoms from their constituent element → gaseous state
 Step 2: gaseous atoms → gaseous ions
 Step 3: Draw Born-Haber cycle / Draw energy level diagram
 Step 4: Calculate lattice energy

 Example 1:
1. Calculate the lattice energy of Lithium Fluoride (LiF) from
the following data.
ΔH°at Li(s): +161 kJ mol-1
ΔH°IE Li(g): +520 kJ mol-1
ΔH°at F2(g): +159 kJ mol-1
EA1 F (g): -328 kJ mol-1
ΔH°f LiF(s): -617 kJ mol-1

ΔH°latt = -1129 kJ mol-1

Example 2:
Calculate the lattice energy of calcium oxide from the following
data and draw the energy level diagram.

ΔH°at Ca(s): 178 kJ mol-1

ΔH°IE1Ca(g): 590 kJ mol-1
ΔH°IE2 Ca(g): 1150 kJ mol-1
ΔH°at O2(g): 124.5 kJ mol-1
EA1 O(g): -141 kJ mol-1
EA2 O(g): 844 kJ mol-1
ΔH°f CaO(s): -635 kJ mol-1

ΔH°latt = -2745 – 635 = -3380.5 kJ/mol

 Example 3:
 Calculate the lattice energy of magnesium chloride from the
following data.

ΔH°at Mg(s): 148 kJ mol-1

ΔH°IE1 Mg(g): 736 kJ mol-1
ΔH°IE2 Mg(g): 1450 kJ mol-1
ΔH°at Cl2(g): 122 kJ mol-1
EA1 Cl(g): -349 kJ mol-1
ΔH°f MgCl2(s): -641 kJ mol-1

ΔH°latt = -2521 kJ mol-1

 18.3 Factors affecting the value of lattice
energy
 In order to form a lattice ionic compound with the highest
stability, large amount of energy need to be released.

 The more energy release (more exothermic) in forming the

ionic compound, the higher the stability.

 The magnitude of the lattice energy depends on:

a) The ionic charge – the ↑ ion charge, the ↑ ΔH°latt

b) The ionic radius – the ↓ ion radii, the ↑ ΔH°latt

 The higher the LE, the higher the melting point.

LE ∝ melting point.

a) Ionic Charge
 The higher the charge on the cation and anion, the stronger
the attraction, the stronger the lattice energy (more
exothermic). This is due to more heat energy is released as
stronger bond are formed between the ions.
b) Ionic radius
 The smaller the cation and anion radius, the more
exothermic the lattice energy.
18.4 Ion polarisation
 Very few bonds are purely ionic.

 This is because when ionic compound is formed, the anion

tends to be attracted by the cation in a lattice structure.

 This will cause the distortion of electron density (cloud) of

the ionic bond = Ion polarisation
◦ The larger the distortion, it will lead to compounds that
are more covalent than ionic character.

 The ability of a cation to attract electrons and distort and

anion is called the polarising power of the cation.
 The degree of polarisation is determined by:
a) the charge density of the cation (hence high polarising
power)
b) ease of polarisability of the anion

 Cation: ↑charge, ↓size, ↑charge density, ↑polarising power

 Anion: ↑size, more easily to be polarised
 Factor of size and charge of cation
Thermal stability of Grp2 carbonates /
nitrates
 Thermal stability (TS) describes the stability of the
compounds upon heating.

 Also referred as the decomposition of the compound on

heating.

 Usually endothermic: required to break chemical bonds.

 Higher TS means higher T needed to decompose the

compound; compound is more stable.

 Higher temperature is needed to decompose the Group II

compound as descending the group.
• Going down group 2, cation size increases.
• Small cations: more charge packed into a small volume of
space; high charge density.

• Bigger cations: charges spread over a larger volume of space;

low charge density, cause less distortion to nearby negative
anions.

• Single charge cation polarises lesser than the doubly charge

cation.
 Thermal decomposition (produced oxide + gas)

Grp II carbonate
MgCO3(s) → MgO(s) + CO2(g)
Δ Grp II nitrates
2Ca(NO3)2(s) → 2CaO(s) + 4NO2(g) + O2(g)
Δ
The group II carbonates/nitrates become more stable to thermal
decomposition going down the group

MgCO3/ Mg(NO3)2
CaCO3 / Ca(NO3)2
SrCO3 / Sr(NO3)2
BaCO3/ Ba(NO3)2
 Group 2 carbonates/nitrates thermal decomposition

↓ Size (with the same Decomposition

charge) temperature ↓

Lesser thermal
↑ charge density
stability

The easier the

↑ polarising power
covalent bond to be
towards anion
broken
 18.5 Enthalpy changes in solution
 ΔH°sol = enthalpy change when one mole of substance (ionic solid)
completely dissolves in water to form a very dilute solution / aqueous
solution under 298 K and 100 kPa.

 Example:
NaCl(s) + aq → Na+(aq) + Cl-(aq) ΔH°sol = +4 kJ mol-1
MgCl2(s) + aq → Mg2+(aq) + 2Cl-(aq) ΔH°sol = -125 kJ mol-1

 Can be exothermic/endothermic.
Enthalpy change of solution ΔH°sol
Always Exothermic

Is this exo / endo?

 Ways of writing the equation:

 MgCl2(s) + aq → MgCl2 (aq) ΔH°sol = -55 kJ mol-1
 MgCl2(s) + aq → Mg2+(aq)+ 2Cl- (aq) ΔH°sol = -55 kJ mol-1

 The more negative, the more soluble the substance.

ΔH°sol = ΔH°hyd – LE
Enthalpy changes of hydration ΔH°hyd
 Involves GASEOUS ion dissolving in water to produce an
aqueous solution.

 The ions were separated from their ionic lattice structure

through the strong attraction forces (Ion-dipole interaction)
of the ions and the water molecules.
 Enthalpy change of hydration is exothermic.
 A larger charge density ion will exert a stronger ion-dipole
attraction and hence, produce a larger magnitude of ΔH°hyd,
more energy is given out.
 Factors affecting ΔH°hyd
1. Ionic charge
 Li+ and Mg2+ have similar sizes (76 pm and 72pm
respectively).
 For the same ionic radii but smaller ionic charge, the smaller
ionic charge ion will have a greater charge density, hence the
ion-dipole interaction of the smaller ions with water will be
greater. ΔH°hyd is more exothermic.
Example: Ionic charge Li+ < Mg2+

2. Ionic radius
 For the same charge but smaller ionic radii, the smaller ionic
radii ion will have a greater charge density, hence the ion-
dipole interaction of the smaller ions with water will be
greater. ΔH°hyd is more exothermic.
Example: Ionic radii Li+ < Na+
 Always Exothermic

Always Exothermic

ΔH°sol = ΔH°hyd – LE

 ΔH°hyd = energy change when one mole of gaseous ion dissolves

in water to form a very dilute solution / aqueous solution under
standard conditions.

 Mg2+(g) + aq → Mg2+(aq) ΔH°hyd = -1926 kJ mol-1

 Cl-(g) + aq → Cl- (aq) ΔH°hyd = -364 kJ mol-1
minus
Example
1. Dissolving NaCl in water, draw the energy level diagram
◦ Lattice energy: -776 kJ mol–1
◦ Enthalpy change of hydration: -771 kJ mol–1
  Worksheet 18.3
a) Draw an enthalpy cycle to show the dissolving of magnesium
chloride (MgCl2) in water. [5]
b) The table below shows the values of all but one of the
enthalpy changes relevant to this cycle.

Enthalpy change Value / kJ mol –1

enthalpy change of solution –155
lattice energy –2493
enthalpy change of hydration of Cl– ion –364

i. Define the enthalpy change of hydration for the magnesium

ion. [3]
ii. Use the values given to calculate the value of the enthalpy
change of hydration for magnesium ions. [5]
c) Draw a diagram to show how water molecules are
arranged around a magnesium ion in a solution of
magnesium chloride. [2]

d) Explain why the enthalpy change of hydration for a

magnesium ion is more exothermic than for a sodium ion.
[3]

e) The enthalpy change of solution of magnesium chloride is

exothermic whilst that of potassium chloride is
endothermic. Explain this difference. [4]
a. Solubility of Grp II sulfates
 Solubility of Grp II sulfates decreases. Magnesium sulphate is
soluble in water, calcium sulphate is slightly soluble and
barium sulphate is insoluble.

ΔH°sol = ΔH°hyd – ΔH°latt

ΔH°sol = ΔH°hyd (M2+) + ΔH°hyd (SO42+) – ΔH°latt (MSO4)

◦ When solubility dec, the ΔH°sol is more endothermic.

 The hydration energy going down Grp 2 ions decreases much
more (less exothermic) because the ionic radii increases, resulting
in a lower charge density.

 Due to the large sulfate ions, the overall (r+ + r –) does not show
any signifcant increase down the group. The LE does not decrease
very much from magnesium sulphate to barium sulphate.
Q+. Q−
Lattice energy 
r+ + r−
 The LE of Grp 2 sulfates decrease because the charge density of
Grp 2 ions decreases. LE dec is relatively small, which remains
almost unchanged due to the large size of the sulfate ions. Hence
the decrease in hydration energy is more significant.
 ΔH°sol = ΔH°hyd (M2+) + ΔH°hyd (SO42+) – ΔH°latt (MSO4)

 Going down Grp II sulfates

 Solubility of Grp II sulfates decreases
 ΔH°sol gets more endothermic
 ΔH°latt (MSO4) becomes less exothermic down Grp 2
 ΔH°hyd (M2+) becomes less exothermic with greater degree down Grp 2
(more endo)

 Solubility of Grp II sulfates decreases

 ΔH°sol gets more endothermic
 ΔH°latt (MSO4) and ΔH°hyd (M2+) becomes less exothermic down Grp 2
 The change in ΔH°hyd (M2+) is greater / more significant.
b. Solubility of Grp II hydroxides
 The solubility of Grp II hydroxides increases.

 Magnesium oxide is insoluble but reacts slowly with water to form

Mg(OH)2; likewise CaO reacts with water to form the partially
soluble Ca(OH)2.

 The oxides of Sr and Ba, SrO and BaO, dissolve in water to form
the strongly basic hydroxide solutions:
BaO(s) + H2O (l) → Ba2+ (aq) + 2OH- (aq)

ΔH°sol = ΔH°hyd – ΔH°latt

ΔH°sol = ΔH°hyd (M2+) + 2 ΔH°hyd (OH-) – ΔH°latt M(OH)2

When solubility inc, the ΔH°sol is more exothermic.

 ΔH°sol = ΔH°hyd (M2+) + 2 ΔH°hyd (OH-) – ΔH°latt M(OH)2

 The hydration energy going down Grp 2 ions decreases

because the ionic radii increases, resulting in a lower charge
density.

 The LE decreases since the ionic radii of Grp 2 increases. The

decrease in LE is greater than the hydration energy because
the OH- anion size is smaller. Therefore the LE decreases as
the cation size increases.
 ΔH°sol = ΔH°hyd (M2+) + 2 ΔH°hyd (OH-) – ΔH°latt M(OH)2

 Going down Grp II hydroxides

 Solubility of Grp II hydroxide increases
 ΔH°sol is more exothermic.
 ΔH°hyd (M2+) becomes less exothermic Grp 2 (more endo)
 ΔH°latt M(OH)2 less exothermic with greater degree down Grp 2

 Solubility of Grp II hydroxides decreases

 ΔH°sol gets more endothermic
 ΔH°latt (MSO4) and ΔH°hyd (M2+) becomes less exothermic down Grp 2
 The change in latt M(OH)2 is greater / more significant.