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Energetics

Definition: A Born-Haber cycle is an energy cycle used to determine the lattice energy of
an ionic compound.
Characteristic features of a Born-Haber cycle:
- A BHC always begins with the elements in their standard states under standard conditions.
- Mass and charge is always balanced through out the cycle
- Only one mole of an ionic compound is formed in the BHC.
- Endothermic processes have arrows pointing upward
- Exothermic processes have arrows pointing downward
- Overall charge at each step is zero
- The state of a species at any given moment must be indicated.
-
The energy diagram below represents the Born-Haber cycle for the formation of NaCl.
Na+(g) + é + Cl(g)
∆H5
∆H4
Na +
(g) + Cl-(g) ∆H1 = H [NaCl(s)] = - 411 kJmol–1.
Na+(g) + é + 1/2Cl2(g)
∆H2 = H [Na] = +108 kJmol–1.
∆H3
∆H3 = H [Na] = +498 kJmol–1.
Na(g) + 1/2Cl2(g) ∆H6
∆H4 = H [Cl] = +121 kJmol–1.
∆H2
∆H5 = 1st electron affinity of Cl = -351 kJmol–1.
Na(s) + 1/2Cl2(g) ∆H6 = lattice energy of NaCl = ……. kJmol–1.
∆H1 ∆H1 = H = ∆H2 + ∆H3 + ∆H4 + ∆H5 + ∆H6.
NaCl(s)

1st ionisation energy of Na; = H [Na], 1st electron affinity of Cl; = H [Cl],
For the ionic compound to be formed, lattice energy (exothermic process) must be large
enough to compensate for the endothermic processes (∆H2 + ∆H3 + ∆H4).
Act:
Use the data above to calculate ∆H6 which is the lattice energy of sodium chloride; H
[NaCl(s)]
The energy diagram below represents the born Haber cycle for the formation of MgO.
Mg2+(g) + 2é + O(g) Mg2+(g) + O2-(g)
∆H1 = standard enthalpy of formation of
∆H5 ∆H6 ∆H7
MgO; H [MgO(s)]
Mg2+(g) + 2é + ½O2(g) Mg2+(g) + é + O-(g)
∆H2 = standard enthalpy of atomisation
∆H4 of Mg; H [Mg]
Mg +
(g) + é + ½O2(g) ∆H3 = 1st ionisation energy of Mg
∆H4 = 2nd ionisation energy of Mg
∆H3 ∆H8
∆H5 = standard enthalpy of atomisation
Mg(g) + ½O2(g)
of oxygen; H [O]
∆H2 ∆H6 = 1st electron affinity of oxygen
Mg(s) + ½O2(g) ∆H7 = 2nd electron affinity of oxygen
∆H1 ∆H8 = lattice energy of MgO(s).
MgO(s)

Lattice energies can be used to compare the stability of ionic compounds. The larger the
exothermic value of lattice energy, the stronger the ionic bond and the more stable the ionic
compound. Lattice energy is an exothermic process because energy is release when
oppositely charged ions come together to form an ionic bond. The Born-Haber cycle is
similar in applicant to Hess’s and is therefore an extension of Hess’s law.

THE NEN SERIES A-Level chemistry notes 2023-2024 school year prepared by Nkemzi E.N
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Energetics

Factors affecting lattice energy:

Charge on the ion: The bigger the charge on the ion, the greater (more exothermic) the
lattice energy.
Size of ion: The smaller the ionic size, the higher the lattice energy.
The packing arrangement of ions in crystal structure also affects the lattice energy but the
effect is negligible.
ACT01: Compare with an explanation the lattice energies of:
(i) LiF and LiCl (ii) LiCl and NaCl (iii) NaCl and MgCl2 (iv) NaCl and MgO.

Act02:Given the following enthalpy change data.

Enthalpy change Value/kJmol–1
Standard enthalpy change of formation of sodium oxide - 414
Standard enthalpy change of atomisation of sodium + 108
First ionisation energy of sodium + 496
Standard enthalpy change of atomisation of oxygen + 249
First electron affinity of oxygen - 141
Second electron affinity of oxygen + 791
Lattice energy of sodium oxide
(a) Draw a Born-Haber cycle for sodium oxide.
(b) Calculate the lattice energy of sodium oxide.

Theoretical and experimental lattice energy

For any ionic compound to be considered a perfect ionic compound, its experimental and
theoretic lattice energy values will have a very small percentage difference of about 1% or
2%. The experimental value is calculated using the data from the BHC while its theoretical
value is calculated using the Born-Lande expression which is based on an ideal ionic model
that ionic bonds are 100%. Imperfect ionic crystals e.g. AgCl, AgBr, AgI have a greater
degree of covalent character compared to ionic character. The following assumptions are
made about perfect ionic crystals such as group I halides e.g. NaCl
- Ions are separate entities with a uniform charge distribution around it’s particle
- Ions are charged spheres
- Ions are in contact (touch one another)
Some theoretical and experimental lattice energy values in kJmol-1 for of some sodium and
silver halides are shown on the table below.
Halide Experimental Theoretical Percentage difference
lattice energy lattice energy
NaCl - 780 - 770 (-780 - - 770)/-780 x 100 = 1.3%
AgCl - 921 - 769 (-921 - - 769)/-921 x 100 = 16.5%
ZnS - 3739 - 3430 (-3739 - - 3430)/-3739 x 100 = 8.3%

The percentage difference = [(Experiment L.E – theoretical L.E) /experimental L.E] x 100.
A higher percentage discrepancy in the values shown on the table above means a higher
degree of covalent characters. Experimental values are larger than theoretical values because
experimental values take into account the extra energy contributed by covalent character
while the theoretical value ignores this energy. Ionic lattices with covalent character are
stronger than lattices which are 100% ionic.
The greater the difference in electronegativity, the more the ionic character of a bond and
smaller the percentage difference in experimental and theoretical lattice energy.

Pure 100% ionic bond Ionic bond with covalent character.

THE NEN SERIES A-Level chemistry notes 2023-2024 school year prepared by Nkemzi E.N