9/1/2014

1
EFFECT OF TEMPERATURE ON EQUILIBRIUM CONSTANT
AH
rxn
= EAH
f
(products) - EAH
f
(reactants)
vant Hoff Equation
It is possible to estimate the new value for the equilibrium constant
when there is a change in temperature by using the van't Hoff
equation,

ln
K
2
K
1
|
\

|
.
|
=
AH
R
1
T
2

1
T
1
|
\

|
.
|
where
K
1
and K
2
are the equilibrium constants
at temperatures T
1
and T
2
, respectively,
H is the enthalpy change for the reaction,
R is the ideal gas constant in thermodynamic units
(8.3145 10
-3
kJ/K mol).
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The only factor that affects the value of K for a given
equilibrium system is temperature.
For a reaction with AH
rxn
> 0, an increase in temperature
will cause K to increase.
For a reaction with AH
rxn
< 0, an increase in temperature
will cause K to decrease.
ln
K
2

K
1

= -
AH
o
rxn

R
1
T
2

1
T
1

- R = 8.314 J/molK
K
1
is the equilibrium constant at T
1

The vant Hoff equation shows this relationship:
Temperature and K

2
Problem
Predicting the Effect of a Change in Temperature
on the Equilibrium Position
PROBLEM: How does an increase in temperature affect the
equilibrium concentration of the underlined substance and
K for each of the following reactions?
PLAN: We write each equation to show heat as a reactant or product.
The temperature increases when we add heat, so the system
shifts to absorb the heat; that is, the endothermic reaction is
favored. Thus, K will increase if the forward reaction is
endothermic and decrease if it is exothermic.
(a) CaO(s) + H
2
O(l) Ca(OH)
2
(aq) AH = -82 kJ
(b) CaCO
3
(s) CaO(s) + CO
2
(g) AH = 178 kJ
(c) SO
2
(g) S(s) + O
2
(g) AH = 297 kJ
3
Sample Problem 17.14
SOLUTION:
An increase in temperature will shift the reaction to the left, so
[Ca(OH)
2
] and K will decrease.
(a) CaO(s) + H
2
O(l) Ca(OH)
2
(aq) + heat
(b) CaCO
3
(s) + heat CaO(s) + CO
2
(g)
(c) SO
2
(g) + heat S(s) + O
2
(g)
An increase in temperature will shift the reaction to the right, so [CO
2
]
and K will increase.
An increase in temperature will shift the reaction to the right, so [SO
2
]
will decrease.
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9/1/2014
2
EFFECT OF TEMPERATURE ON EQUILIBRIUM CONSTANT
Example 1:
Sulfur dioxide reacts with oxygen to form sulfur trioxide. The
equilibrium constant, K
p
, for this reaction is 0.365 at 1150 K.

2 SO
2
(g) + O
2
(g) 2 SO
3
(g)

The standard enthalpy change for this reaction (H) is 198 kJ/mol.

(a) Predict the effect on the O
2
concentration when the temperature
of the equilibrium system is increased.

(b) Use the van't Hoff equation to estimate the equilibrium constant
for this reaction at 1260 K.

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(a) This is an exothermic reaction (H = -198 kJ/mol). Increasing
the temperature of the system will cause the equilibrium to shift
to the left, consuming SO
3
and forming additional SO
2
and O
2
.
The O
2
concentration will increase.

(b) In this problem, T
1
= 1150 K, T
2
= 1260 K, and K
1
= 0.365.
Substitute these values into the van't Hoff equation and
calculate the equilibrium constant at the new temperature.
K
2
= 0.0599
Is your answer reasonable? Notice that the equilibrium constant
decreases as predicted for an exothermic reaction at a higher
temperature.
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CO(g) + 2H
2
(g) CH
3
OH(l)
AH
f
(CO(g)) = -110.5 kJ/mol
AH
f
(H
2
(g)) = 0
AH
f
(CH
3
OH(l)) = -239 kJ/mol
AH
rxn

= EAH
f
(products) - EAH
f
(reactants)
= AH
f
(CH
3
OH(l)) - AH
f
(CO(g))
= -239 kJ - (-110.5 kJ)
= -128.5 kJ
Example 2:

ln
K
2
K
1
|
\

|
.
| =
AH
R
1
T
2

1
T
1
|
\

|
.
|

ln
K
340
1.2x10
5
|
\

|
.
| =
(128500 J)
(8.314 J /K)
1
340K

1
298K
|
\

|
.
|

ln
K
340
1.2x10
5
|
\

|
.
| = 6.4
K
340
= 2.0 x 10
2

Why is K reduced?
Reaction is Exothermic.
Increase T, Shift Eq. To React.
K
eq
will then decrease
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