Topic 5: Energetics

Born Haber Cycles & Lattice Enthalpy

Thursday, May 16, 2013

 Born-Haber Cycle
• Why are NF3 and PCl3 stable while NCl3 is
dangerously explosive?
• Born-Haber cycle provides a useful way
to account for the relative stabilities of
chemical compounds
• Relative stability of the compound is
determined by the lattice enthalpy of a
compound

Thursday, May 16, 2013

 Born-Haber Cycle

• How can we determine the lattice enthalpy of

an ionic compound?
• We can break up the formation of an ionic
compound into a series of steps
• Then take all those steps and add them up so
it is really a Hess’ Law problem!
• Recall that the enthalpy of formation for an
uncombined element is therefore = 0

Thursday, May 16, 2013

 Some Definitions
• The enthalpy of atomization is the enthalpy change that
occurs when one mole of gaseous atoms is formed
from the element in the standard state under standard
conditions
Example: ½ Cl2 (g)  Cl (g) ΔHoat = 121 kJ mol-1
• The electron affinity is the enthalpy change that occurs
when an electron is added to an isolated atom in the
gaseous state:
O (g) + e-  O- (g) ΔHo = -142 kJ mol-1
O- (g) + e-  O2- (g) ΔHo = +844 kJ mol-1
• The lattice enthalpy is the enthalpy change that occurs
from the conversion of an ionic compound in the
gaseous state into its gaseous ions
LiCl (g)  Li+ (g) + Cl- (g) ΔHo = +846 kJ mol-1

Thursday, May 16, 2013

 Born Haber Cycle for NaCl
The formation of NaCl can be considered as a five
step process
Na (s) + 1/2 Cl2 (g) NaCl (s)
1. The vaporization of sodium metal to form the gaseous
element. Na(s)  Na(g)
2. The dissociation of chlorine gas to gaseous chlorine
atoms is equal to one half of the bond energy for a Cl-Cl
covalent bond 1/2 Cl2(g)  Cl(g)
3. The ionization of gaseous sodium atoms to
Na(g)  Na+(g) + e-
4. The ionization of chlorine atoms. (This quantity is the
negative electron affinity for the element chlorine.)
Cl(g) + e-  Cl-(g)
5. The lattice energy on the formation of sodium chloride
from the gaseous ions Na+(g) + Cl-(g)  NaCl(s)
Thursday, May 16, 2013
 Born Haber Cycle Diagram

The stepwise energy changes for the formation of NaCl

Thursday, May 16, 2013
 Born-Haber Cycle for NaCl
The stepwise energy changes for the formation of NaCl:
The vaporization of sodium metal to form the gaseous
element.
Na (s)  Na (g) ∆H°sublimation = + 109 kJ mol-1

The dissociation of chlorine gas to gaseous chlorine

atoms is equal to one half of the bond energy for a Cl-Cl
covalent bond
1/2 Cl2 (g)  Cl (g) ∆H°diss = + 122 kJ mol-1

The ionization of gaseous sodium atoms to:

Na (g)  Na+ (g) + e- ∆H°ionization = + 496 kJ mol-1

The ionization of chlorine atoms. (This quantity is the

negative electron affinity for the element chlorine.)
Cl (g) + e-  Cl- (g) ∆H°elect.affinity = - 368 kJ mol-1

Thursday, May 16, 2013

Thursday, May 16, 2013
 Try it for MgCl2

Thursday, May 16, 2013

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Thursday, May 16, 2013

 Try it!
• 1. Calculate the energy released (in kJ mol-1 ) in the reaction
K (s) + 1/2 Br2 (l) --------> KBr (s)
The energy of vaporization of potassium is +89 kJ mol-1. The first ionization enthalpy of
potassium is +419 kJ mol-1.
The sum of the dissociation energy and vaporization energy for Br2 (l) is 223 kJ mol-1,
the negative electron affinity of bromine is -324 kJ mol-1, and the lattice energy of
KBr is -688 kJ mol-1.

2. Calculate the energy released (in kJ mol-1 ) in the reaction

Na (s) + 1/2 I2 (l) --------> NaI (s)
The energy of vaporization of sodium is +109 kJ mol-1. The first ionization energy of
sodium is +496 kJ mol-1.
The sum of the dissociation energy and vaporization energy for I2 (s) is 214 kJ mol-1,
the negative electron affinity of iodine is -295 kJ mol-1, and the lattice energy of NaI
is - 704 kJ mol-1.

Thursday, May 16, 2013

 Size & Charge
• How does size and charge effect the lattice
enthalpy?

12

Thursday, May 16, 2013

 Which has larger lattice
enthalpy?
KCl 701 kJ mol-1, NaCl 777 kJ mol -1
K is larger

The cation remains the same, the anion gets bigge

The larger the anion, the smaller the enthalpy

MgF2 2957 kJ mol-1

NaF 902 kJ mol-1

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Thursday, May 16, 2013

 Why the difference?

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Thursday, May 16, 2013

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Thursday, May 16, 2013