Born Haber Cycle, Example:CaCl2

The Born Haber cycle for the formation of calcium chloride form its constituent elements
involves following steps.

 Atomization enthalpy of calcium: This step involves the conversion of solid calcium to
gaseous state. Note that solid calcium absorbs heat energy to form gaseous calcium,
thus the products have higher energy than the reactants, this is an exothermic reaction.

Ca(s) → Ca(g) ΔH°at(Ca) = +178 kJ/mol

 Ionisation enthalpy of calcium: Calcium forms di-positive ion (Ca2+), therefore the
energy involve in the removal of first electron is called as first ionization energy and
valued 590 kJ/mol. The removal of second electron requires more energy as it is
difficult to remove electron from a cation. Hence the second ionization energy for
calcium ion is 1145 kJ/mol.
 Note that calcium atom (2.8.8.2) loses electron to achieve a stable electron arrangement
and stable state has less energy when compared to other state, thus energy is released
as calcium atom loses electrons to form gaseous -2 ion.

Ca (g) → Ca+(g) + e- Δ H°i1= +590 kJ/mol

+ 2+
Ca (g) → Ca (g) + e- ΔH°i2= +1145 kJ/mol

 Atomization enthalpy of Chlorine: This step involves dissociation of Cl2 (g) into Cl(g)
atoms. The reaction enthalpy is half of the bond dissociation enthalpy of chlorine.

½ Cl2 (g) → Cl (g) ΔHat =+121 kJ/mol

 For the formation of calcium chloride, two Cl (g) is required, therefore total atomisation
enthalpy will be double that is 242 kJ/mol.

 Electron affinity of chlorine: This is the amount of energy released during the addition
of electron in an isolated neutral gaseous chlorine atom.
 Note that chlorine atom (2.8.7) gains electron to its valance shell to achieve a stable
electron arrangement. Stable state has less energy compared to other state, thus
energy is released.

Cl(g) + e- → Cl-(g) ΔH°ea= -364 kj/mol

 Lattice enthalpy: The combination of one Ca2+ ion and two chloride ions (Cl-) to form one
mole of calcium chloride release lattice energy (ΔHlatt ).

Ca2+ (g) + 2Cl-(g) →→ CaCl2(s)

The lattice energy of calcium chloride can be calculated by using the Born Haber cycle in which
the sum of enthalpy in a cycle is zero. By applying the Hess’s Law,

Heat of formation (Δ H°f)

= Heat of atomisation (Δ H°at)+ Dissociation energy(Δ Hd°)+ (sum of Ionization energies)+

(sum of Electron affinities)+ Lattice energy

Or can be rearranging as;

Lattice energy= Heat of formation- Heat of atomization- Dissociation energy- (sum of

Ionization energies)- (sum of Electron Affinities)

*Dissociation energy refers to the energy used to convert Cl 2 to Cl, and the dissociation
energy is doubled as two Cl is required to form calcium chloride.

ΔHlatt = -796 -178-242-(590+1145) –(2 x -364)

ΔHlatt = - 796 - 1427 = - 2223 kJ/mol
Born Haber Cycle NaCl

The energy change during the formation of sodium chloride crystal from metallic sodium and
chlorine gas can be used to calculate lattice enthalpy of NaCl(s). The net enthalpy change for
the formation of NaCl ( ΔfH° ) is 411.2 kj/mol.

Νa(s) + ½ Cl2(g) → NaCl(s) ΔfH° = -411.2 kj/mol

The overall process can be explained in following steps.

 Formation of sodium chloride: The formation of one mole of sodium chloride from its
elements under standard conditions releases 411 kj/mol of heat. This is known as
standard enthalpy of formation and represented by ∆fH°.

Na(s) + ½ Cl2 (g) → NaCl(s) ∆Hf°(NaCl) = - 411 kJ/mol

 Standard enthalpy of atomization of chlorine (∆Ha°): The energy required to atomize

one mole of gaseous chlorine molecules into one mole of gaseous chlorine atoms is
known as standard enthalpy of atomization of chlorine. It’s an endothermic step as the
bonds between Cl-Cl atoms are being broken.

½ Cl2 (g) → Cl (g) ∆Ha° (Cl2) = +121 kJ/mol

 Standard enthalpy of electron affinity of chlorine (∆H ea°): The energy

released when one mole of gaseous chlorine atoms gains one mole of electrons to form
chloride ion. The electron affinity of chlorine atom is 349 kj/mol.

Cl (g) + e- → Cl-(g) ∆Hea° (Cl) = -349 kJ/mol

 Sublimation energy of sodium (∆Hs°): This is the energy required to change one mole
of solid sodium atoms into one mole of gaseous atoms. Sublimation of sodium is an
endothermic process and requires energy to change the state from a solid to a gas.

Na (s) → Na (g) ∆Hs° (Na) = +107 kJ/mol

 Ionization energy of sodium (∆HIE° (Na): Removal of one mole of electron from a
gaseous metal atom involve some energy change, known as ionization
energy. Endothermic, energy needs to be absorbed to remove the electron.

Na (g) → Na+(g)+ e- (∆HIE° (Na) = +496 kJ/mol)

 Lattice enthalpy of sodium chloride (U): The enthalpy change during the formation
of one mole of sodium chloride from its constituent ions is called as lattice energy of
lattice enthalpy. It is an exothermic step and release about 786 kj energy.

Na+(g) + Cl-(g) → NaCl (s) U = -786 kj/mol

Applying Hess’s law we get.

 ∆Hf° = ∆ Hs°+ ∆ HIE°+ ∆ Ha°+ ∆ Hea°+U
Or Lattice enthalpy
∆ HL° =107 + 496 + 121 - 349 - 786 = -411 kj/mol

Born Haber cycle for the formation of sodium chloride can be represents as given.
Born Haber Cycle Problems

Solved Examples
Question 1: Calculate the standard free energy for the following reaction by using given data.

CCl4 (l) + H2O (l) → COCl2(g) + 2HCl(g)

 Heat of formation of CCl4= -135.44 kj/mol

 Heat of formation of H2O= -285.83 kj/mol
 Heat of formation of COCl2= -218.8 kj/mol
 Heat of formation of HCl= -92.307 kj/mol

Solution:

By applying Hess’s law, given data can be written as follow.

CCl4 (l) → C(s) + 2Cl2(g) ΔH1 = -(-135.44kJ/mol

H2O (l) → H2 (g) + ½ O2 (g) ΔH2 = -(-285.83 kJ/mol)
C(s) + ½ O2 (g) + Cl2(g) → COCl2(g) ΔH3= (-218.8 kJ/mol)
H2 (g) + Cl2 (g) → 2HCl(g) ΔH4 = 2(-92.307 kJ/mol)

Overall reaction: CCl4(l) + H2O(l) → COCl2(g) + 2HCl(g)

ΔH5= ΔH1+ ΔH2+ ΔH3+ ΔH4

ΔH5 = 135.44+ 285.83-218.8+ (2x -92.307)
ΔH5 = 17.9 kJ/mol

Question 2: Write all energy changes involve in Born-Haber cycle for the formation of calcium oxide
Solution:

Enthalpy of atomization of Ca(s): Ca(s) → Ca(g) ; Δ Ha°

 First ionization energy of Ca(g): Ca(g) → Ca+(g) + e- ; Δ HIE°

 Second ionization energy of Ca(g): Ca+(g) → Ca2+(g) + e- ; Δ HIE°
 Enthalpy of atomization of O2(g): ½ O2(g) → 2O(g) ; Δ Ha°
 First electron affinity of O(g): O(g)+ e-→ O(g)-; Δ Hea°
 Second electron affinity of O(g): O-(g) + e- → O2-(g) ; Δ Hea°
 Enthalpy of formation of CaO(s): Ca(s) + ½ O2(g) → CaO(s) ; Δ Hf°
 Lattice enthalpy of CaO(s) : Ca2+(g) + O2-(g) → CaO(s); Δ HLE°

Question 3: Calculate the lattice enthalpy of calcium oxide from the following data.

 Δ Ha°of Ca(s): 178 kJ/mol

 1st Δ HIE°of Ca(g): 590 kJ/mol
 2nd Δ HIE°of Ca(g): 1150 kJ/mol
 Δ Ha° of O2(g): 249 kJ/mol
 1st Δ Hea°of O(g): -141 kJ/mol
 2nd Δ Hea°of O(g): 844 kJ/mol
 Δ Hf°of CaO(s): -635 kJ/mol
Solution:

Δ Hf°+ ∆HLE° = Δ Ha°(Ca) + ∑ Δ HIE° + Δ Ha°(O) + ∑ Δ Hea°

∆HLE° = Δ Ha°(Ca)+ ∑Δ HIE°+ Δ Ha°(O) + ∑Δ Hea° - Δ Hf°

= 178 + (590 + 1150) + 249 + (-141) + 844 –(-635)
= 2870 – (-635)
= 3505 kJ/ mol

Question 4: By using Born Haber cycle for the formation of silver chloride, calculate the lattice
enthalpy of silver chloride from the following data.

 Enthalpy of atomization of Ag(s): 284 kJ/mol

 1st ionization energy of Ag(g): 731 kJ/mol
 Enthalpy of atomization of Cl2(g): 122 kJ/mol
 1st electron affinity of Cl(g): -349 kJ/mol
 Enthalpy of formation of AgCl(s): -127 kJ/mol

Solution:

∆HLE° = ∆Ha°(Ag)+ ∑∆HIE°+ ∆Ha°(Cl2)+ ∆Hea° - ∆Hf°

= 284 + (731+ 122) + (-349) – (-127)
= 788– (-127)
= 915KJmol-1