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Energy Considerations in Ionic Structures - Handout - Samuel

chemistry lecture notes

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Mohamed Weyimi
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70 views2 pages

Energy Considerations in Ionic Structures - Handout - Samuel

chemistry lecture notes

Uploaded by

Mohamed Weyimi
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Energy Considerations in Ionic Structures

Ions with the same type of charge repel each other, while ions of opposite charge attract each other.
The simplest possible ionic structure which might be stable is a gas-phase ion pair, which consists
of one cation and one anion held together by electrostatic attraction. It is relatively simple to
calculate how much energy would be gained by this association using the Coulomb law of
electrostatic attraction. The energy of the attraction is given by
E = (2.31 x 10-16 J-pm) Z+Z-/d
Since F = k x (product of the two charges)/d2, and E = Force x distance
where Z is the charge on the cation and anion and d is the distance between the ions, in pm. (NB; I
picometer = 1 x 10-12 m)

For example, the ionic radius for sodium ion is 97 pm while for chloride ion it is 181 pm, and hence
the distance of separation of the centers of the two ions is 278 pm. The molar energy for one ion
pair, is obtained by multiplying the coulombic energy of electrostatic attraction by the Avogadro
number NA.

However, association of ions of opposite charge is not normally into such simple ion pairs. It is
more common to find ions in the form of the solid ionic crystals, which are large ordered three-
dimensional arrays of ions. Some energy is responsible for the formation and stability of crystal
structures. This is referred to as the lattice energy which is defined as the enthalpy change in the
formation of an ionic lattice from the gaseous isolated ions. It is usually a large negative value
indicative of the high stability of ionic compounds.

It is not directly measurable, but can be estimated using the Born Haber Cycle, a form of a Hess’s
law of enthalpy summations. The diagram below is the Born-Haber cycle for the formation of an
ionic compound from the reaction of an alkali metal (Li, Na, K, Rb, Cs) with a gaseous halogen (F2,
Cl2).
For sodium chloride, the Born - Haber cycle is:

Born-Lande Equation
It is an expression used to calculate the lattice energy of a crystalline ionic compound. It takes into
account both the coulombic (electrostatic) interactions and the potential energy due to repulsions.
Due to its simplicity, the Born-Lande equation is a common tool for chemists in the calculation of
lattice energies.
The lattice energy, U, is given by;

EXERCISE
1. Define the term lattice energy, and discuss any two factors that affect the lattice energy of
crystals
2. Draw a well labelled Born Haber cycle for the formation of AgF
3. Given that the heat of sublimation of Ag = +285Kj/mol, the bond dissociation enthalpies of
F2 = +158kJ/mol, IE of Ag = +737kJ/mol, EA for F=-339kJ/mol, and the heat of formation
of AgF = -205kJ/mol, determine the lattice energy for AgF
4. Calculate the lattice energy for NH4F, given the following; A (NH4F) = 1.641, n = 8, and the
interionic distance between NH4+ and F- = 2.63 pm.

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