Chemistry 360

Fall 2014
Dr. Jean M. Standard
October 10, 2014

The Gibbs-Helmholtz Equation

Derivation of the Gibbs-Helmholtz Equation
The Gibbs-Helmholtz equation provides information about the temperature dependence of the Gibbs free energy.
The derivation of the Gibbs-Helmholtz equation begins with the fundamental equation for the Gibbs free energy G,

dG = SdT + VdP .

(1)

Using the relationships for an exact differential, we have that

# G &
% ( = S .
$ T 'P

(2)

Substituting this result for S into the equation defining the Gibbs free energy, G = H TS , yields

# G &
G = H + T% ( .
$ T 'P

(3)

Dividing both sides of Eq. (3) by T leads to the result

# G &
G
H
=
+ % ( .
$ T ' P
T
T

(4)

The Gibbs-Helmholtz equation involves the partial derivative with respect to temperature (at constant pressure) of
G /T . Taking the partial derivative gives
the quantity on the left side of Eq. (4),

# (G /T ) &
G
1 # G &
%
( = 2 +
% ( .
T $ T 'P
T
$ T ' P

(5)

Note that in Eq. (5), since G is a function of temperature, G = G (T ) , the product rule was employed in order to
1/T out from the right side of Eq. (5) yields
evaluate the derivative of G /T . Factoring

# (G /T ) &
# G & 1* G
+ % ( /.
%
( =
,
$ T 'P .
T+ T
$ T ' P

(6)

Substituting the relation for G /T from Eq. (4) gives the result

# (G /T ) &
# G & 1* G
+ % ( /
%
( =
,
$ T 'P .
T+ T
$ T ' P

1
T

02 * H
# G & # G & 42
+ % ( / + % ( 5
1 ,
$ T ' P .
$ T 'P 62
32 + T

# (G /T ) &
H
%
( = 2 .

T
T
$
'P
Equation (7) provides one form of the Gibbs-Helmholtz equation.

(7)

2
Another useful form of the Gibbs-Helmholtz equation may be obtained by considering the derivative

# (G /T ) &
# (G /T ) &
%%
(( = T 2 %
( .
$ T ' P
$ (1/T ) 'P

(8)

2
The result in Eq. (8) may be derived by making the substitution u = 1/T such that du = dT /T . Substituting the
result for the partial derivativeon the right from Eq. (7) leads to the primary form for the Gibbs-Helmholtz equation,

# (G/T ) &
%%
(( = H .
$ (1/T ) 'P

(9)

Written in terms of the change in free energy, the Gibbs-Helmholtz equation is

$ ( G /T ) '
&&
)) = H .
% (1/T ) (P

(10)

Exploring the Temperature Dependence

of the Gibbs Free Energy Change
For an endothermic reaction, the slope of the Gibbs-Helmholtz equation given in Eq. (10) is positive, as illustrated in
Figure 1.

Endothermic case

G/T
slope = Ho > 0

Thigh

Tlow

1/T
Figure 1. Typical Gibbs-Helmholtz plot for an endothermic reaction.

From Figure 1, we see that as the temperature increases (from right to left along the x-axis), the Gibbs free energy
change decreases (as long as the final and initial temperatures are not too different from one another); that is,

For T final > T initial ,

G final < G initial .

(11)

Note that if the Gibbs free energy change at the initial temperature was negative (indicating a spontaneous process),
then increasing the temperature further decreases the Gibbs free energy change (in other words, the value becomes

more negative).

3
For an exothermic reaction, the slope for the Gibbs-Helmholtz equation given in Eq. (10) is negative, as illustrated
in Figure 2.

Exothermic case

slope = Ho < 0

G/T

Thigh

Tlow

1/T
Figure 2. Typical Gibbs-Helmholtz plot for an exothermic reaction.

From Figure 2, we see that as the temperature increases (from right to left along the x-axis), the Gibbs free energy
change also increases (as long as the final and initial temperatures are not too different from one another); that is,

For T final > T initial ,

G final > G initial .

(12)

Note in this case that if the Gibbs free energy change at the initial temperature is negative (indicating a spontaneous
process), then increasing the temperature increases the Gibbs free energy change (in other words, the value becomes

less negative).

Example Gibbs-Helmholtz Calculation

Determine the standard molar Gibbs free energy change at 500 K for the reaction

2 H 2 ( g) + O 2 ( g)

2 H 2O () .

(13)

The standard molar Gibbs free energy change at 500 K may be estimated from the available values at 298 K using
the Gibbs-Helmholtz equation,

$ G ! /T
r
&
& (1/T )
%

) ')
)
(P

= H r! .

(14)

If we approximate the partials by finite changes (as when estimating the slope of a line), the Gibbs-Helmholtz
equation becomes

G r! /T

(1/T )

H r! ,

$ G ! '
$1'
r
or &
) H r! & ) .
%T (
T
%
(

(15)

4
The changes are defined as the differences in the higher temperature (500 K in this case) and 298 K,

#1&
1
1
% ( =

$T '
Tf
Ti
# G ! &
G r! T f
r
and %
( =
Tf
$ T '

( )

G r! (T i )
.
Ti

(16)

Inserting these relations into the approximate Gibbs-Helmholtz equation,

# G ! &
#1&
r
%
( H r! % (
$T '
$ T '
G r! T f

( )

Tf

G r! (T i )
Ti

#1
1&
(.
H r! %%

T i ('
$T f

(17)

Substituting the temperatures,

G r! T f

( )

Tf

G r! (T i )
Ti

!
!
G 500
G 298

500 K
298 K

%1
1(
*
H r! ''

T i *)
&T f
% 1
1 (
!
H 298

'
* .
298 K )
& 500 K

(18)

Here, it has been assumed that the standard molar enthalpy of reaction is constant and the value at 298 K (available
in tables) has been used.
Solving for the unknown standard molar Gibbs free energy change at 500 K, we have

!
G 500
500 K

!
or G 500

!
% 1
G 298
1 (
!
+ H 298

'
*,
298 K
298 K )
& 500 K

+ G !

% 1
1 (.
!
+ H 298

'
*0 .
298 K )/
& 500 K
, 298 K

( 500 K) -

298

(19)

In order to complete the determination of the Gibbs free energy change at 500K, the values of the Gibbs free energy
and the enthalpy
of reaction at 298 K are required. These values may be obtained from the tables in the appendix.
The standard molar enthalpies and Gibbs free energies of formation at 25C of the reactants and products are:
Compound
H2 (g)
O2 (g)

H !f

G !f

(kJ/mol)

(kJ/mol)

H2O (g)

0
285.83

0
237.18

The standard molar enthalpy of reaction at 25C is

!
H 298
= 2 H !f ( H 2O) 2 H !f ( H 2 ) H !f () 2 )

= 2 (285.83kJ/mol) 2 ( 0 kJ/mol) ( 0 kJ/mol)

!
H 298
= 571.66 kJ/mol.

(20)

5
The standard molar Gibbs free energy of reaction at 25C is
!
G 298
= 2 G !f ( H 2O) 2 G !f ( H 2 ) G !f (O 2 )

= 2 (237.18 kJ/mol) 2 ( 0 kJ/mol) ( 0 kJ/mol)

!
G 298

= 474.36 kJ/mol.

(21)

Now we can substitute these values into the expression above to get the standard molar Gibbs free energy of reaction
at 500 K,

+ G !
% 1
1 (.
!
!
298
G 500
( 500 K) + H 298

'
*0
298 K )/
& 500 K
, 298 K
+ 474.36 kJ/mol
% 1
1 (.
( 500 K) + (571.66 kJ/mol) '

*0
298 K
298 K )/
& 500 K
,
!
G 500
449.9 kJ/mol.

(22)

Here we observe that in this case, as a result of the exothermic enthalpy of reaction, the standard molar Gibbs free
energy change at
500 K is larger (less negative) than the value at 298 K.