Born Haber Cycle 2

INTRODUCTION
Ionic solids are stable compounds. The

enthalpies required for the formation of the ionic
molecules do not account for stability alone.
These compounds also have additional stability
because of the lattice energy present in their
solid structure. The lattice energy present cannot
be measured. This is where the Born-Haber cycle
allows us to determine and understand the
lattice energies of the ionic solids. In order to
understand the idea of lattice energy and
calculate it, a Born-Haber cycle is used.
Born - Haber Cycle:

The Born Haber process, more commonly
referred to as the Born Haber cycle, is a method
that allows us to observe and analyse energies in
a reaction. It mainly helps in describing the
formation of ionic compounds from different
elements. The methodology further enables us
to understand the overall reaction process
through a series of steps.
The Born Haber cycle was introduced in the year

1919 by German scientists Fritz Haber and Max
Born. The Born Haber cycle is mainly used to
calculate the lattice energy. It also involves
several steps or processes, such as electron
affinity, ionization energy, sublimation energy,
the heat of formation and dissociation energy.
Ionization Enthalpy:
The energy required to take off an
electron from the neutral ion/atom. In
order to do this, there should be an
input of energy, which is why it is
always positive. Ionization energy is
noted to be increasing across the
periodic table from left to right and
decreasing from top to bottom.
However, there are some exceptions
due to the unpredictable stability of
completely filled/half-filled orbitals.
Electron Affinity:
The energy released when an
electron is added to a neutral
ion/atom. The energy released is
known to have a negative value, but
due to the definition of affinity, it is
denoted as a positive value. When
used to calculate the lattice energy,
one has to subtract the electron
affinity and not add it because of the
positive value. The electron affinity is
known for increasing from left to right
and decreasing from top to bottom in
a periodic table.
Dissociation Energy:
The energy needed to break a compound
apart. Dissociation is an endothermic
process that requires an input of energy.
Therefore, its value is always positive. The
magnitude of it is dependent on the
electronegativity of the atoms involved in
the compound.
Sublimation Energy:
It is the change in energy when a particular
compound is formed from elements. It can
be either positive or negative based on the
atoms involved and their interaction.
Hess Law:
Hess’ law, also known as Hess’s law of
constant heat summation, states, “at
constant temperature, heat energy changes
(enthalpy – ΔHrec) accompanying a chemical
reaction will remain constant, irrespective of
the way the reactants react to form
product”.
Hess’ law is based on the state function

character of enthalpy and the first law of
thermodynamics. Energy (enthalpy) of a
system (molecule) is a state function. So,
enthalpy of reactant and product molecules
is a constant and does not change with origin
and path of formation.
Example of Born - Haber cycle

Born Haber cycle of sodium chloride NaCl
(or any AB-type Mono-valent ionic solid).
The heat of the formation of sodium

chloride (ΔHf0) from the sodium metal
and chlorine gas can be experimentally
measured.
Na (s) + (1/2)Cl2 (g) → NaCl(s) ΔHf0 = -

411kJ/mol
The formation of ionic solid sodium
chloride from solid sodium metal and
gaseous chlorine is not a single-step
process but goes through several
processes. Heat changes of all the
processes except the lattice energy can
be experimentally measured.
The processes or steps in the formation

of sodium chloride are as follows:
1. Solid sodium atom sublimes to gaseous

atom by absorbing heat energy (∆Hsub).
Na (s) → Na (g),
Sublimation energy ΔHsub = + 107kJ/mol
2. Gaseous sodium atom absorbs the
ionization energy to release one electron
and forms a gaseous sodium ion.
Na(g) → Na+(g) + 1e– ,
Ionization energy ∆HIE = +502kJ/mol
3. Diatomic gaseous chlorine breaks into
two individual atoms by absorbing bond
energy, such that each chlorine atom
absorbs half of the bond energy of the
chlorine molecule.
Cl2(g) → 2Cl(g) (1/2)
Bond dissociation energy of chlorine =

(1/2) ∆Hdiss= (1/2) 242 = +121kJ/mol
4. Chlorine atom accepts an electron to
form a chloride ion and releases energy
equivalent to electron affinity.
Cl(g) + 1e– → Cl– (g)
Electron affinity = ∆HEA = -355kJ/mol
5. Gaseous sodium ion and gaseous

chloride ion combine to form a solid
sodium chloride molecule and releases
energy equivalent to lattice energy.
Na+(g) + Cl– (g) → Na+ Cl– (s)
Lattice energy = ∆HLE = U = ?
The summation of enthalpy of all the
processes (from step 1 to step 5) give the
net enthalpy of the formation of solid
crystalline sodium chloride from sodium
and chlorine in their standard conditions
of solid and gas, respectively. This should
be equal to the experimentally measured
enthalpy of the formation of solid sodium
chloride.
So, ΔHf0 = ΔHsub + ∆HIE + (1/2) ∆Hdis +
∆HEA + U or ΔHf0 – (ΔHsub + ∆HIE + (1/2)
∆Hdis + ∆HEA + U)=0
411 + 107 + 502 +121 -355 +U = 0
Here, except lattice energy, all other

enthalpies can be experimentally measured.
The lattice energy of the sodium chloride
solid = U = ΔHf0 – (ΔHsub + ∆HIE + ½ ∆Hdis +
∆HEA).
= -411 -107 -502 -121 +355
= – 786kJ/mol
Example 2: Lattice energy of magnesium
oxide (or any AB-type Divalent ionic solid).
The heat of the formation of magnesium
oxide (ΔHf0) from the magnesium metal and
oxygen gas can be experimentally measured.
Mg (s) + (1/2) O2 (g) → MgO(s)
ΔHf0 = -602kJ/mol
The processes or steps in the formation of
magnesium oxide are as follows:
1. Solid magnesium atom sublimes to a
gaseous atom by absorbing heat energy
(∆Hsub).
Mg (s) → Mg (g), Sublimation energy ΔHsub
= + 136kJ/mol
2. Gaseous magnesium atom releases two

electrons in two steps with corresponding
ionization energies.
Mg(g) → Mg+(g) + 1e–, ionization energy
∆H1IE= +738kJ/mol
Mg+(g) → Mg2+(g) + 1e–, ionization energy
∆H2IE= +1450kJ/mol
So energy of ionization = ∆HIE = 738 + 1450 =
2188kJ/mol.
3. Diatomic oxygen breaks into two
individual atoms by absorbing bond energy,
such that each chlorine atom absorbs half of
the bond energy of the chlorine molecule.
O2(g) → 2O(g) (1/2) bond dissociation
energy of oxygen = (1/2) ∆Hdiss= (1/2) 498 =
+249kJ/mol
4. Oxygen atom accepts two electrons to

form an oxide ion and releases energy
equivalent to two-electron affinities.
O(g) + 1e– → O– (g) Electron affinity = ∆H1EA
= -142kJ/mol
O–(g) + 1e– → O2- (g) Electron affinity =
∆H2EA = +798kJ/mol
The total energy released as electron affinity
by the oxygen atom is = ∆HEA = +656kJ/mol
5. Gaseous magnesium ion and gaseous
oxide ion combine to form a solid
magnesium oxide molecule and releases
energy equivalent to lattice energy.
Mg2+(g) + O2- (g) → Mg2+O2- (s)
Latticeenergy = ∆HLE = U = ?
The summation of enthalpy of all the

processes from the starting step to the final
step gives the net enthalpy of the formation
of solid crystalline magnesium oxide from
magnesium and oxygen in their standard
conditions of solid and gas, respectively. This
should be equal to the experimentally
measured enthalpy of the formation of solid
magnesium oxide
So, ΔHf0 = ΔHsub + ∆HIE + (1/2) ∆Hdis +
∆HEA + U or ΔHf0 – (ΔHsub + ∆HIE + (1/2)
∆Hdis + ∆HEA + U) = 0
602 + 136 + 2188 + 249 +656 + U = 0
Here, except lattice energy, all other
enthalpies can be experimentally measured.
The lattice energy of the magnesium oxide
solid = U = ΔHf0 – (ΔHsub + ∆HIE + (1/2)
∆Hdis + ∆HEA).
= -602 – 136 – 2188 – 249 -656 = -3831kJ/mol

Born Haber Cycle 2

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INTRODUCTION

Ionic solids are stable compounds. The

Born - Haber Cycle:

The Born Haber cycle was introduced in the year

Hess’ law is based on the state function

Example of Born - Haber cycle

The heat of the formation of sodium

Na (s) + (1/2)Cl2 (g) → NaCl(s) ΔHf0 = -

The processes or steps in the formation

1. Solid sodium atom sublimes to gaseous

Bond dissociation energy of chlorine =

5. Gaseous sodium ion and gaseous

411 + 107 + 502 +121 -355 +U = 0

Here, except lattice energy, all other

2. Gaseous magnesium atom releases two

4. Oxygen atom accepts two electrons to

The summation of enthalpy of all the

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