BORN-HABER CYCLES

Specification Points Covered

3.1.8.1 Born–Haber Cycles
• Lattice enthalpy can be defined as either enthalpy of lattice dissociation or enthalpy of lattice formation
• Born–Haber cycles are used to calculate lattice enthalpies using the following data: enthalpy of formation,
ionisation energy, enthalpy of atomisation, bond enthalpy and electron affinity
• Students should be able to define each of the above terms and lattice enthalpy

Ionic Substances

• Solid Ionic substances form regular structures called giant

ionic lattices
• The positively and negatively charged ions are held together
by electrostatic interactions

When gaseous ions combine to make a solid lattice, the energy given out is defined as
the lattice enthalpy of formation.

Standard Lattice Enthalpy of Formation,

The enthalpy change when one mole of an ionic
lattice is formed from its gaseous ions under
standard conditions.

On the other hand, the standard lattice enthalpy of dissociation is defined as the enthalpy
change when one mole of an ionic lattice completely dissociates into its gaseous ions
under standard conditions. The enthalpy of formation and the enthalpy of dissociation
are opposites.

For example, when sodium chloride is formed, the lattice enthalpy of formation is:

Na+ (g) + Cl– (g) → NaCl (s)

The equation for the lattice enthalpy of dissociation of sodium chloride is:
NaCl (s) → Na+ (g) + Cl– (g)

Lattice enthalpy gives an indication of the strength of the ionic bonds. The more positive
the lattice enthalpy of dissociation, the stronger the ionic bonding, because it is harder
to break up the lattice.

There are some important definitions to know before the lattice enthalpy can be found,
as it cannot be measured directly.

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 Standard Enthalpy of Formation,
The enthalpy change when one mole of a
compound is formed from its constituent
elements in their standard states, under standard
conditions.

Na (s) + Cl (g) → NaCl (s)

This process is usually exothermic because bonds are being formed.

Standard Enthalpy of Atomisation,

The enthalpy change when one mole of gaseous
atoms are formed from an element in its
standard state.

Na (s) → Na (g)
Cl2 (s) → Cl (g)

EXAM TIP
It can be easy to confuse the state symbols when defining these processes. It is
important to get the state symbols correct when dealing with the enthalpy of
atomisation.

This process is always endothermic because bonds are being broken.

First Ionisation Energy,

The energy required to remove one mole of
electrons from one mole of gaseous atoms to
form one mole of gaseous 1+ ions.

Na (g) → Na+ (g) + e–

This process is always endothermic as energy needs to be put in to pull an electron

away from a positively charged nucleus.

Second Ionisation Energy,

The enthalpy change when one mole of
gaseous 2+ ions are formed from one mole of
gaseous 1+ ions.

Mg+ (g) → Mg2+ (g) + e–

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This process is also always endothermic as energy is needed to overcome the attraction
between the nucleus and the electron. It is much more endothermic than the first
ionisation energy because the atom is already positively charged, so the electron is
more strongly attracted to the nucleus.

Below is a schematic diagram showing the differing amounts of energy for the first and
second ionisation energies for an element in Group 1, such as sodium. It is clear that the
second ionisation energy is greater than the first. The second ionisation energy is so
high that it is very difficult to remove two electrons from a sodium atom.

First Ionisation Energy Second Ionisation Energy

First Electron Affinity,

The enthalpy change when one mole of
gaseous 1– ions are formed from one mole of
gaseous atoms.

Cl (g) + e– → Cl– (g)

This process is always exothermic because the electron is attracted to the positively
charged nucleus of an atom.

Second Electron Affinity,

The enthalpy change when one mole of
gaseous 2– ions are formed from one mole of
gaseous 1– ions.

O– (g) + e– → O2– (g)

This process is always endothermic because energy must be put in to overcome the
repulsion between an electron and a negatively charged ion.

First Electron Affinity Second Electron Affinity

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Specification Points Covered
3.1.8.1 Born-Haber Cycles
• Students should be able to:
○○ Construct Born-Haber cycles to calculate lattice enthalpy
○○ Construct Born-Haber cycles to calculate one of the other enthalpy changes
○○ Compare lattice enthalpies from Born-Haber cycles with those from calculations based on a perfect ionic
model to provide evidence for covalent character in ionic compounds

Constructing Born-Haber Cycles

In practice, it is not possible to form one mole of an ionic lattice from gaseous ions. For
this reason, the lattice enthalpy cannot be measured directly. Instead, we use Hess’ law:
the total enthalpy change is independent of the route taken.

Born-Haber Cycle for Sodium Chloride

You can use this Born-Haber cycle to calculate the lattice enthalpy of sodium chloride,
since we cannot measure it experimentally.

Below is a worked example on finding the lattice enthalpy from this Born-Haber
cycle.
∆θ

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Worked Example: Calculating Lattice Enthalpies from Born-Haber cycles
Calculate the lattice enthalpy of sodium chloride using the Born-Haber cycle for
NaCl.

Solution
There are two routes you can follow to get from
the elements in their standard states to the ionic
lattice.

This route is the direct route using the standard enthalpy of formation:

The following is the indirect route:

1. Add onto the direct route the enthalpies

of atomisation for both the sodium and
chlorine

2. Add the step for the first ionisation energy

of sodium. As this is a much higher energy
than the previous steps, the arrow needs to
be slightly longer

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 1. Now the first electron affinity of chlorine
can be added

2. Now the lattice enthalpy can be labelled,

and Hess’ Law can be used to calculate it

So, to calculate the lattice enthalpy:

Enthalpy change Value / kJ mol-1

∆EA1H (Cl) -346

∆J1H (Na) +496

∆aH (Cl) +121

∆aH (Na) +107

∆f H (NaCl) -411

(You must use a minus sign if you go the wrong way along an arrow)
Note that this value is exothermic because it is the formation enthalpy rather than the
dissociation enthalpy.

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 EXAM TIP
A lot of the errors in Born-Haber cycle calculations come from either not knowing
the definitions properly or forgetting to include a minus sign. It is very important
to take care with signs in this section.

Note that calculations involving Group 2 elements (such as MgCl2) are a bit more
complicated. They require an extra step compared to the sodium chloride example.
• There are two moles of chlorine ions in each mole of MgCl2, so the atomisation
enthalpy of chlorine needs to be doubled
• Group 2 elements form 2+ ions, so the second ionisation energy of the element
must also be included
• The first electron affinity of chlorine also needs to be doubled as two moles of Cl-
ions are being formed

Finding Other Quantities from Born-Haber Cycles

Any of the enthalpy values used in a Born-Haber cycle can be calculated in exactly the
same way as previously seen.

Worked Example: Calculating other quantities from Born-Haber cycles

Calculate the second electron affinity of oxygen using the Born-Haber cycle for
MgO.

Solution

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 You can work your way around the arrows in exactly the same way as the previous
example.

Enthalpy change Value / kJ mol-1

∆LEH (MgO) -3888

∆EA1H (O) -142

∆I2H (Mg) +1450

∆I1H (Mg) +736

∆aH (O) +496

∆aH (Mg) +150

∆f H (MgO) -602

So, to calculate the second electron affinity of oxygen:

Theoretical Lattice Enthalpies

• A purely ionic model of a lattice
assumes that all of the ions are
spherical, and have evenly distributed
charge around them
• However, the experimental lattice
enthalpy value can differ from the
calculated value
• This is evidence that some ionic
compounds have partially covalent
character
• Positive ions normally polarise
neighbouring negative ions
• More polarisation = more covalent
character
• Small, positively charged ions (like H+) are more polarising than large positive
ions, and large negatively charged ions (like I–) are more polarisable than small
negative ions (like F–)

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Specification Points Covered
3.1.8.1 Born–Haber Cycles
• Cycles are used to calculate enthalpies of solution for ionic compounds from lattice enthalpies and enthalpies
of hydration
• Students should be able to:
○○ Define the term enthalpy of hydration
○○ Perform calculations of an enthalpy change using these cycles

Dissolving a Solid
In order to dissolve an ionic compound, the ionic lattice must be broken up. This occurs
in two steps.

Dissolving an Ionic Solid

1. The bonds between the ions in the lattice break — this is an endothermic process

2. Bonds between the ions and the water are made — this is exothermic, and is
known as hydration

These two steps together have an overall enthalpy change which is called the standard
enthalpy of solution, .

Standard Enthalpy of Solution,

The enthalpy change when one mole of solute
dissolves completely in sufficient solvent
under standard conditions to form a solution
in which the molecules or ions are far enough
apart not to interact with each other.

For example, when NaCl dissolves completely in water:

NaCl (s) → Na+ (aq) + Cl– (aq)

The associated enthalpy change is the enthalpy of solution.

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Hydration of Ions
This is where free ions are incorporated into the solution.
• The interactions between the solvent and the solute need to be of a similar
strength to the interactions between the positively and negatively charged ions in
the lattice for the ions to dissolve
• Ions dissolve well in polar solvents, like water, because of the favourable
electrostatic interactions between the oppositely charged ions in the solvent and
the ions
This process is accompanied by a new enthalpy change, .

Standard Enthalpy of Hydration,

The enthalpy change when one mole of
aqueous ions is formed from gaseous ions
under standard conditions.

For example:
Cl– (g) → Cl– (aq)

This is an exothermic process. It is governed by the same factors as the lattice enthalpy
(charge on the ions and the geometry of the structure).

Born–Haber Cycles for Dissolving

We can use the enthalpy of solution and the enthalpy of hydration to provide another
path to calculate the lattice enthalpy of dissociation / formation.
NaCl (s) → Na+ (g) + Cl– (g) Lattice enthalpy of dissociation (endothermic)
Na+ (g) + Cl– (g) → NaCl (s) Lattice enthalpy of formation (exothermic)

It is important to remember that the lattice enthalpy of formation is the opposite,

and therefore the negative, of the lattice enthalpy of dissociation. Remember that
dissociation is endothermic, whilst formation is exothermic. A cycle for finding the
enthalpy of solution can be presented in two ways.

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 Worked Example: Enthalpy of Solution for Sodium Chloride
Using the data below, and either of the cycles above, find the enthalpy of solution
for sodium chloride.

Lattice enthalpy of NaCl = –787 kJ mol–1

Standard enthalpy of hydration for Na+ = –406 kJ mol–1
Standard enthalpy of hydration for Cl– = –363 kJ mol–1

Solution
1. Using the above Born–Haber cycle or the Hess–style cycle, we can find another
pathway for the enthalpy change of a solution:

2. We can now substitute in the numbers from the data given in the question:

EXAM TIP
Both of these diagrams use the same calculation, so this worked example applies
to both cycles. Just remember that in the Hess cycle style, the enthalpy of
hydration for Na is combined with the enthalpy of hydration for Cl, so these values
need to be added together first to use as an overall enthalpy of hydration.

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