Born–Haber cycle

The Born–Haber cycle is an approach to

analyze reaction energies. It was named
after the two German scientists Max Born
and Fritz Haber, who developed it in 1916.
The cycle is concerned with the formation
of an ionic compound from the reaction of
a metal (often a Group I or Group II
element) with a halogen or other non-
metallic element such as oxygen.
Born–Haber cycles are used primarily as a
means of calculating lattice energy (or
more precisely enthalpy[note 1]), which
cannot otherwise be measured directly.
The lattice enthalpy is the enthalpy change
involved in the formation of an ionic
compound from gaseous ions (an
exothermic process), or sometimes
defined as the energy to break the ionic
compound into gaseous ions (an
endothermic process). A Born–Haber
cycle applies Hess's law to calculate the
lattice enthalpy by comparing the standard
enthalpy change of formation of the ionic
compound (from the elements) to the
enthalpy required to make gaseous ions
from the elements.

This latter calculation is complex. To make

gaseous ions from elements it is
necessary to atomise the elements (turn
each into gaseous atoms) and then to
ionise the atoms. If the element is
normally a molecule then we first have to
consider its bond dissociation enthalpy
(see also bond energy). The energy
required to remove one or more electrons
to make a cation is a sum of successive
ionization energies; for example, the
energy needed to form Mg2+ is the
ionization energy required to remove the
first electron from Mg, plus the ionization
energy required to remove the second
electron from Mg+. Electron affinity is
defined as the amount of energy released
when an electron is added to a neutral
atom or molecule in the gaseous state to
form a negative ion.

The Born–Haber cycle applies only to fully

ionic solids such as certain alkali halides.
Most compounds include covalent and
ionic contributions to chemical bonding
and to the lattice energy, which is
represented by an extended Born-Haber
thermodynamic cycle.[1] The extended
Born–Haber cycle can be used to estimate
the polarity and the atomic charges of
polar compounds.

Example: Formation of
lithium fluoride

Born–Haber cycle for the standard enthalpy change of

formation of lithium fluoride. ΔHlatt corresponds to UL
in the text.
The enthalpy of formation of lithium
fluoride (LiF) from its elements lithium and
fluorine in their stable forms is modeled in
five steps in the diagram:

1. Enthalpy change of atomization

enthalpy of lithium
2. Ionization enthalpy of lithium
3. Atomization enthalpy of fluorine
4. Electron affinity of fluorine
5. Lattice enthalpy

The same calculation applies for any

metal other than lithium or any non-metal
other than fluorine.
The sum of the energies for each step of
the process must equal the enthalpy of
formation of the metal and non-metal,
.

V is the enthalpy of sublimation for

metal atoms (lithium)
B is the bond energy (of F2). The
coefficient 1/2 is used because the
formation reaction is Li + 1/2 F2 → LiF.
is the ionization energy of the
metal atom:
 is the electron affinity of non-
metal atom X (fluorine)
is the lattice energy (defined as
exothermic here)

The net enthalpy of formation and the first

four of the five energies can be determined
experimentally, but the lattice energy
cannot be measured directly. Instead, the
lattice energy is calculated by subtracting
the other four energies in the Born–Haber
cycle from the net enthalpy of formation.[2]

The word cycle refers to the fact that one

can also equate to zero the total enthalpy
change for a cyclic process, starting and
ending with LiF(s) in the example. This
leads to

which is equivalent to the previous

equation.

See also
ionic compound
ionic liquids

Notes
1. The difference between energy and
enthalpy is very small and the two terms are
interchanged freely in this article.

References
1. H. Heinz and U. W. Suter Journal of
Physical Chemistry B 2004, 108, 18341-
18352.
2. Moore, Stanitski, and Jurs. Chemistry:
The Molecular Science. 3rd edition. 2008.
ISBN 0-495-10521-X. pages 320-321.

External links
ChemGuy on the Born-Haber Cycle

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Haber_cycle&oldid=821422139"

Last edited 3 days ago by Dirac66

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