Chemistry 360

Spring 2012
Dr. Jean M. Standard
March 28, 2012
The van't Hoff Equation
The van't Hoff equation provides information about the temperature dependence of the equilibrium constant. The
van't Hoff equation may be derived from the Gibbs-Helmholtz equation, which gives the temperature dependence of
the Gibbs free energy. For the standard Gibbs free energy, the Gibbs-Helmholtz equation is


!
"
#G
!
T
$
%
&
'
(
)
"
1
T
( )
$
%
&
&
&
'
(
)
)
)
P
= #H
!
. (1)
Substituting the expression

!
"G
!
= #RT lnK
eq

and dividing both sides by R, the first form of the van't Hoff
equation is obtained,


!
" lnK
eq
"
1
T
( )
#
$
%
%
&
'
(
(
P
= )
*H
!
R
. (2)
From this form of the van't Hoff equation, we see that at constant pressure, a plot with
!
lnK
eq
on the y-axis and
!
1 T on the x-axis has a slope given by

!
"#H
!
R. This is the origin of LeChatelier's Principle for the heat absorbed
or evolved during the course of a chemical reaction.
For an endothermic reaction, the slope is negative and so as the temperature increases, the equilibrium constant
increases, as illustrated in Figure 1.
lnK
eq
1/T
Endothermic case
T
high
T
low
slope = -!H
o
/R < 0
Figure 1. Typical van't Hoff plot for an endothermic reaction.
An example endothermic reaction may be written in the following form,
A + B + heat C . (3)
For such a reaction, LeChatelier's Principle predicts that if the temperature increases, the system must shift to the
right in order to alleviate the stress of additional heat. A shift to the right leads to an increase in products and a
decrease in reactants, which increases the equilibrium constant as predicted by the van't Hoff equation.
2
For an exothermic reaction, the slope is positive and so as temperature increases, the equilibrium constant decreases,
as illustrated in Figure 2.
lnK
eq
1/T
Exothermic case
T
high
T
low
slope = -!H
o
/R > 0
Figure 2. Typical van't Hoff plot for an exothermic reaction.
An example exothermic reaction may be written in the following form,

A + B C + heat . (4)
For this type of reaction, LeChatelier's Principle predicts that if the temperature increases, the system must shift to
the left in order to alleviate the stress of additional heat. A shift to the left leads to a decrease in products and an
increase in reactants, which decreases the equilibrium constant as predicted by the van't Hoff equation.
An integrated form of the van't Hoff equation may be obtained at constant pressure by multiplying Eq. (2) by
!
d 1 T ( ) and integrating,


!
d lnK
eq
= "
#H
!
R
d 1 T ( )
d lnK
eq
1
2
$
= "
#H
!
R
d 1 T ( )
1
2
$
lnK
2
" lnK
1
= "
#H
!
R
1
T
2
"
1
T
1
%
&
'
(
)
*
.

The integral on the right side was obtained assuming that the standard molar enthalpy of reaction is constant over the
temperature range. Combining the natural logs, the integrated form of the van't Hoff equation is

!
ln
K
2
K
1
"
#
$
%
&
'
= (
)H
!
R
1
T
2
(
1
T
1
"
#
$
%
&
'
. (5)
Finally, an additional linear form of the van't Hoff equation may be obtained starting from the relation

!
"G
!
= #RT lnK
eq
. (6)
Solving for the natural log,


!
lnK
eq
= "
#G
!
RT
.
(7)
3
At any given temperature, the change in Gibbs free energy may be written from the definition of the Gibbs free
energy as

!
"G
!
= "H
!
# T"S
!
.
(8)
Substituting this relation into Eq. (5), the linear form of the van't Hoff becomes


!
lnK
eq
= "
#H
!
RT
+
#S
!
R
.
(9)
This equation indicates that a plot with
!
lnK
eq
on the y-axis and
!
1 T on the x-axis has a slope given by

!
"#H
!
R
(as we saw before from Eq. (2)) and an intercept given by

!
"S
!
R , as illustrated in Figure 3. Note that in this
figure, the slope is drawn for an endothermic reaction for example purposes.
lnK
eq
1/T
slope = -!H
o
/R
intercept = !S
o
/R
Figure 3. The slope and intercept of a van't Hoff plot.