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Chapter 9 looks at forces that keep atoms together.

Ionic molecules and the Born-Haber cycle


The formation of an ionic solid can be described by the following equation. M(s) + 1/2X2(g) MX(s)
The energetics or enthalpy associated with this process cannot be determined directly. You have been recently
presented with the processes of ionization (loss of an electron from a gaseous atom), electron affinity (gain of
an electron by a gaseous atom) and lattice energy (change in energy when two gaseous ions form an ionic
solid). These can be used, according to Hesss Law to calculate the energetics of formation of an ionic solid.
Note that the starting materials are in their elemental state.
Lets use the formation of NaF(s) as an example.
The following steps must occur:
Process
Na(s) Na(g) sublimation
Na(g) Na+(g) ionization
F2(g) 2F(g) bond breaking
F(g) F-(g) electron affinity
Na+(g) + F-(g) NaF(s) lattice energy

Na(s) + F2(g) NaF(s)


Energy change
109 kJ/mol
495 kJ/mol
154 kJ/mol
-328 kJ/mol
-923 kJ/mol

When these equations and the energetics are added, the net result is the formation of the ionic solid with an
enthalpy of formation Hf of 570 kJ
Na(s) Na(g) sublimation
Na(g) Na+(g) + e- ionization
F2(g) F(g) bond breaking
F(g) + e- F-(g) electron affinity
Na+(g) + F-(g) NaF(s) lattice energy
Na(s) + F2(g) NaF(s)

109 kJ/mol
495 kJ/mol
(154 kJ/mol)
-328 kJ/mol
-923 kJ/mol
-570 kJ/mol

A second example:
What is the lattice energy associated with Ca2+(g) and Cl-(g) coming together to form CaCl2?
Ca2+(g) + 2Cl-(g) CaCl2(s)
sublimation energy of calcium
first ionization of calcium
second ionization of calcium
bond dissociation of Cl2(g)
electron affinity of Clenthalpy of reaction

+178 kJ/mol
+590 kJ/mol
+1150 kJ/mol
+244 kJ/mol
-349 kJ/mol
-326 kJ

Ca(s) Ca(g)
Ca(g) Ca+(g) + eCa+(g) Ca2+(g) + eCl2(g) 2Cl(g)
2Cl(g) 2Cl-(g)
Ca2+(g) + 2Cl-(g) CaCl2(s)
Ca(s) + Cl2(g) CaCl2(s)

178 kJ
590 kJ
1150 kJ
244 kJ
2(-349 kJ)
x
-326 kJ

The role of the lattice energy in stabilizing ions


Consider the formation of CaO:
Ca(s) + O2(g) CaO(s)
The following step are required:
Ca(s) Ca(g)
Ca(g) Ca+(g) + eCa+(g) Ca2+(g) + e O2(g) O(g)
O(g) + e- O-(g)
O- + e- O2-(g)
O2-(g) + Ca2+(g) CaO(s)
Ca(s) + O2(g) CaO(s)

sublimation
first ionication
second ionization
bond energy
electron affinity of O
electron affinity of Olattice energy
enthalpy of reaction

+178 kJ/mol
+589 kJ/mol
+1040 kJ/mol
(+247 kJ/mol)
-141 kJ/mol
+878 kJ/mol
-3,100 kJ/mol
-309 kJ

Note that the formation of O2- is endothermic (-141 kJ/mol + 878 kJ/mol = 737 kJ/mol) and the gaseous O2- ion
is not stable. However, it can be formed, if it is stabilized by association with Ca2+. Note the large exothermic
lattice energy.

If the lattice energy increases with charge and the association of oppositely charged ions is a stabilizing force,
can NaF form, with Na+2 and F-2?
Na2+(g) + F2-(g) NaF(s)
Na(s) Na(g)
Na(g) Na+(g) + eNa+(g) Na2+ + e F2(g) F(g)
F(g) + e- F-(g)
F-(g) + e- F2-(g)
Na2+(g) + F2-(g) NaF
Na2+(g) + F2-(g) NaF(s)

sublimation
first ionization
second ionization
bond energy
electron affinity
electron affinity
lattice energy
enthalpy of reaction

109 kJ/mol
495 kJ/mol
4560 kJ/mol
77 kJ/mol
-328 kJ/mol
+1250 kJ/mol
-3692 kJ/mol
+2471 kJ

Ca2+(g) + 2Cl-(g) CaCl2(s)


sublimation energy of calcium
first ionization of calcium
second ionization of calcium
bond dissociation of Cl2(g)
electron affinity of Clenthalpy of reaction

+178 kJ/mol
+590 kJ/mol
+1150 kJ/mol
+244 kJ/mol
-349 kJ/mol
-326 kJ

Ca(s) Ca(g)
178 kJ
Ca(g) Ca+(g) + e590 kJ
Ca+(g) Ca2+(g) + e1150 kJ
Cl2(g) 2Cl(g)
244 kJ
2Cl(g) 2Cl-(g)
2(-349 kJ)
Ca2+(g) + 2Cl-(g) CaCl2(s)
x
Ca(s) + Cl2(g) CaCl2(s)
-326 kJ

Ca(s) + O2(g) CaO(s)


The following step are required:
Ca(s) Ca(g)
sublimation
+178 kJ/mol
+
Ca(g) Ca (g) + e
first ionication
+589 kJ/mol
Ca+(g) Ca2+(g) + e- second ionization
+1040 kJ/mol
O2(g) O(g)
bond energy
(+247 kJ/mol)
O(g) + e- O-(g)
electron affinity of O -141 kJ/mol
2O + e O (g)
electron affinity of O- +878 kJ/mol
O2-(g) + Ca2+(g) CaO(s) lattice energy
-3,100 kJ/mol
Ca(s) + O2(g) CaO(s) enthalpy of reaction -309 kJ

Na2+(g) + F2-(g) NaF(s)


Na(s) Na(g)
sublimation
109 kJ/mol
+
Na(g) Na (g) + e
first ionization
495 kJ/mol
Na+(g) Na2+ + esecond ionization
4560 kJ/mol
F2(g) F(g)
bond energy
77 kJ/mol
F(g) + e- F-(g)
electron affinity
-328 kJ/mol
2F (g) + e F (g)
electron affinity
+1250 kJ/mol
Na2+(g) + F2-(g) NaF lattice energy
-3692 kJ/mol
2+
2Na (g) + F (g) NaF(s)
enthalpy of reaction +2471 kJ