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7: The Gibbs-Helmholtz Equation - Chemistry LibreTexts

22.7: The Gibbs-Helmholtz Equation

22.7.0.1: Ideal gas
For a mole of ideal gas we can use the gas law to integrate volume over pressure and we get

P2
ΔG molar = RT ln( )
P1

It is customary to identify one of the pressures (P1} with the standard state of 1 bar and use the plimsoll to indicate the fact
that we are referring to a standard state by writing:

P
o o
G molar (P ) = G + RT ln( ) = G + RT ln[P ]
molar molar
1

The fact that we are making the function intensive (per mole) is usually indicated by putting a bar over the G symbol,
although this is often omitted for Gomolar

22.7.0.1: Solids
For solids the volume does not change very much with pressure (the isothermal compressibility κ is small), so can assume it
more or less constant:

G(Pf inal ) = G(Pinitial ) + ∫ V dP (from init to final) ≈ G(Pinitial ) + V ∫ dP (from init to final) = G(Pinitial ) + V ΔP

22.7.1: The Gibbs-Helmholtz Expression

G H
= −S
T T

Take the derivative under constant pressure of each side to get

∂ G/T H 1 ∂H ∂S
( ) = − + ( ) −( )
2
∂T T T ∂T ∂T
P P P

We make use of the relationship between C and H and C and S

p p

∂ G/T H CP CP
( ) = − + − (22.7.1)
2
∂T T T T
P

H
= − (22.7.2)
2
T

We said before that S is a first order derivative of G . As you can see from this derivation the enthalpy H is also a first
order derivative, albeit not of G itself, but of G/T .

∂ ΔG/T △H
( ) = −
2
∂T T
P

The last step in the derivation simply takes the step before twice -say for the G and H at the begin and end of a process-
and subtracts the two identical equations leading to a Δ symbol. In this differential form the Gibbs-Helmholtz equation
can be applied to any process.

22.7.2: Gibbs Energy as a Function of Temperature

If heat capacities are know from 0 K we could determine both enthalpy and entropy by integration:
T
Cp
S (T ) = S (0) + ∫ dT
0
T

H (T ) = H (0) + ∫ Cp dT
0

As we have seen we must be careful at phase transitions such as melting or vaporization. At these points the curves are
discontinuous and the derivative C is undefined.
p

T f us T boil

H (T ) = H (0) + ∫ Cp (T )solid dT + ΔH f us + ∫ Cp (T )liquid dT + ΔH vap + etc. (22.7.3)

0 T f us

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8/10/22, 11:39 AM 22.7: The Gibbs-Helmholtz Equation - Chemistry LibreTexts
f

T f us T boil
Cp (T )solid Cp (T )liquid
S (T ) = S (0) + ∫ dT + ΔS f us + ∫ dT + ΔS vap + etc. (22.7.4)
0
T T f us
T

T f us T boil
Cp (T )solid ΔH f us Cp (T )liquid ΔH vap
= S (0) + ∫ dT + +∫ dT + + etc. (22.7.5)
0
T Tf us T f us
T Tboil

with H (T = 0) = undefined and S (T = 0) = 0 from the third law of thermodynamics.

We also discussed the fact that the third law allows us to define S (0) as zero in most cases. For the enthalpy we cannot
do that so that our curve is with respect to an undefined zero point. We really should plot H (T ) − H (0) and leave
H (0) undefined.

Because the Gibbs free energy G = H − T S we can also construct a curve for G as a function of temperature, simply by
combining the H and the S curves (Equations 22.7.3 and 22.7.5):

G(T ) = H (T ) − T S (T )

Interestingly, if we do so, the discontinuties at the phase transition points will drop out for G because at these points
Δ H = T
trs
Δ
trs
S . Therefore, G is always continuous.
trs

The H (0) problem does not disappear so that once again our curve is subject to an arbitrary offset in the y-direction. The
best thing we can do is plot the quantity G(T ) − H (0) and leave the offset H (0) undefined.
We have seen above that the derivative of G with temperature is −S . As entropy is always positive, this means that the G-
curve is always descending with temperature. It also means that although the curve is continuous even at the phase
transitions, the slope of the G curve is not, because the derivative −S makes a jump there. Fig. 22.7 in the book shows an
example of such a curve for benzene. Note the kinks in the curve at the mp and the boiling point.

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