LATTICE ENERGY: THE BORN-HABER CYCLE

Ionic solids tend to be very stable compounds. The enthalpies of formation of the ionic
molecules cannot alone account for this stability. These compounds have an additional
stability due to the lattice energy of the solid structure. However, lattice energy cannot
be directly measured. The Born-Haber cycle allows us to understand and determine the
lattice energies of ionic solids.

INTRODUCTION
This module will introduce the idea of lattice energy, as well as one process that allows
us to calculate it: the Born-Haber Cycle. In order to use the Born-Haber Cycle, there are
several concepts that we must understand first.

LATTICE ENERGY
Lattice Energy is a type of potential energy that may be defined in two ways. In one
definition, the lattice energy is the energy required to break apart an ionic solid and
convert its component atoms into gaseous ions. This definition causes the value for the
lattice energy to always be positive, since this will always be an endothermic reaction.
The other definition says that lattice energy is the reverse process, meaning it is the
energy released when gaseous ions bind to form an ionic solid. As implied in the
definition, this process will always be exothermic, and thus the value for lattice energy
will be negative. Its values are usually expressed with the units kJ/mol.
Lattice Energy is used to explain the stability of ionic solids. Some might expect such an
ordered structure to be less stable because the entropy of the system would be low.
However, the crystalline structure allows each ion to interact with multiple oppositely
charge ions, which causes a highly favorable change in the enthalpy of the system. A lot
of energy is released as the oppositely charged ions interact. It is this that causes ionic
solids to have such high melting and boiling points. Some require such high
temperatures that they decompose before they can reach a melting and/or boiling
point.

BORN-HABER CYCLE
There are several important concept to understand before the Born-Haber Cycle can be
applied to determine the lattice energy of an ionic solid; ionization energy, electron
affinity, dissociation energy, sublimation energy, heat of formation, and Hess's Law.
Ionization Energy is the energy required to remove an electron from a neutral atom
or an ion. This process always requires an input of energy, and thus will always have
a positive value. In general, ionization energy increases across the periodic table
from left to right, and decreases from top to bottom. There are some excepts, usually
due to the stability of half-filled and completely filled orbitals.
Electron Affinity is the energy released when an electron is added to a neutral atom
or an ion. Usually, energy released would have a negative value, but due to the
definition of electron affinity, it is written as a positive value in most tables.
Therefore, when used in calculating the lattice energy, we must remember to
subtract the electron affinity, not add it. In general, electron affinity increases from
left to right across the periodic table and decreases from top to bottom.
Dissociation energy is the energy required to break apart a compound. The
dissociation of a compound is always an endothermic process, meaning it will
always require an input of energy. Therefore, the change in energy is always
positive. The magnitude of the dissociation energy depends on the electronegativity
of the atoms involved.
Sublimation energy is the energy required to cause a change of phase from solid to
gas, bypassing the liquid phase. This is an input of energy, and thus has a positive
value. It may also be referred to as the energy of atomization.
 The heat of formation is the change in energy when forming a compound from its
elements. This may be positive or negative, depending on the atoms involved and
how they interact.
Hess's Law states that the overall change in energy of a process can be determined
by breaking the process down into steps, then adding the changes in energy of each
step. The Born-Haber Cycle is essentially Hess's Law applied to an ionic solid.

USING THE BORN-HABER CYCLE

STEP 1
Determine the energy of the metal and nonmetal in their elemental forms. (Elements in
their natural state have an energy level of zero.) Subtract from this the heat of
formation of the ionic solid that would be formed from combining these elements in the
appropriate ration. This is the energy of the ionic solid, and will be used at the end of
the process to determine the lattice energy.

STEP 2
The Born-Haber Cycle requires that the elements involved in the reaction are in their
gaseous forms. Add the changes in enthalpy to turn one of the elements into its gaseous
state, and then do the same for the other element.

STEP 3
Metals exist in nature as single atoms and thus no dissociation energy needs to be
added for this element. However, many nonmetals will exist as polyatomic species. For
example, Cl exists as Cl2 in its elemental state. The energy required to change Cl2 into
2Cl atoms must be added to the value obtained in Step 2.

STEP 4
Both the metal and nonmetal now need to be changed into their ionic forms, as they
would exist in the ionic solid. To do this, the ionization energy of the metal will be
added to the value from Step 3. Next, the electron affinity of the nonmetal will be
subtracted from the previous value. It is subtracted because it is a release of energy
associated with the addition of an electron.
*This is a common error due to confusion caused by the definition of electron affinity,
so be careful when doing this calculation.

STEP 5
Now the metal and nonmetal will be combined to form the ionic solid. This will cause a
release of energy, which is called the lattice energy. The value for the lattice energy is
the difference between the value from Step 1 and the value from Step 4.
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The diagram below is another representation of the Born-Haber Cycle.

EQUATION
The Born-Haber Cycle can be reduced to a single equation:
Heat of formation= Heat of atomization+ Dissociation energy+ (sum of Ionization
energies)+ (sum of Electron affinities)+ Lattice energy
*Note: In this general equation, the electron affinity is added. However, when plugging
in a value, determine whether energy is released (exothermic reaction) or absorbed
(endothermic reaction) for each electron affinity. If energy is released, put a negative
sign in front of the value; if energy is absorbed, the value should be positive.
Rearrangement to solve for lattice energy gives the equation:
Lattice energy= Heat of formation- Heat of atomization- Dissociation energy- (sum of
Ionization energies)- (sum of Electron Affinities)

REFERENCES
1. Cheetham, A.K. and P. Day. Solid State Chemistry. Oxford: Clarendon Press, 1992.
2. Jenkins, H. Donald B. "Thermodynamics of the Relationship between Lattice Energy
and Lattice Enthalpy." Journal of Chemical Education. Vol. 82, P. 950-952. Coventry,
West Midlands, UK: University of Warwick, 2005.
3. Ladd, Mark. Crystal Structures: Lattices and Solids in Stereoview. Chichester:
Horwood, 1999.
4. Ladd, Mark. Chemical Bonding in Solids and Fluids. Chichester: Horwood, 1994.
5. Suzuki, Takashi. Free energy and Self-interacting Particles. Boston: Birkhauser, 2005.

PROBLEMS
1. Define lattice energy, ionization energy, and electron affinity.
2. What is Hess' Law?
3. Find the lattice energy of KF(s).
Note: Values can be found in standard tables.
4. Find the lattice energy of MgCl2(s).
5. Which one of the following has the greatest lattice energy?
a. A) MgO
b. B) NaC
c. C) LiCl
d. D) MgCl2
6. Which one of the following has the greatest Lattice Energy?
a. NaCl
b. CaCl2
 c. AlCl3
d. KCl

SOLUTIONS
1. Lattice energy: The difference in energy between the expected experimental value
for the energy of the ionic solid and the actual value observed. More specifically, this
is the energy gap between the energy of the separate gaseous ions and the energy of
the ionic solid.
Ionization energy: The energy change associated with the removal of an electron
from a neutral atom or ion.
Electron affinity: The release of energy associated with the addition of an electron to
a neutral atom or ion.
2. Hess' Law states that the overall energy of a reaction may be determined by
breaking down the process into several steps, then adding together the changes in
energy of each step.
3. Lattice Energy= [-436.68-89-(0.5*158)-418.8-(-328)] kJ/mol= -695.48 kJ/mol
4. Lattice Energy= [-641.8-146-243-(737.7+1450.6)-(2*-349)] kJ/mol= -2521.1 kJ/mol
5. MgO. It has ions with the largest charge.
6. AlCl3. According to the periodic trends, as the radius of the ion increases, lattice
energy decreases.

REFERENCES
1. Ralph, William, F.Geoffrey, and Jeffry. General Chemistry. Ninth ed. New
Jersey:Pearson Education, Inc. 2007. p500;513-515.
2. Combs, Leon. "Lattice Energy". Dr. Leon L. Combs. 1999. http://erkki.kennesaw.edu
/genchem8/ge00002.htm
3. Picture of NaCl diagram http://intro.chem.okstate.edu/1314f0...BornHaber2.GIF
4. Housecroft, Catherine E. and Alan G. Sharpe. Inorganic Chemistry. 3rd ed. England:
Pearson Education Limited, 2008.174-175.