Statistical Molecular

Thermodynamics
Christopher J. Cramer

Video 8.7

P and T Dependence of G
 Pressure Dependence of G
⎛ ∂G ⎞
We know already (see Video 8.4): ⎜ ⎟ = V
⎝ ∂P ⎠T
P2
integrating ΔG = ∫ P1
VdP (constant T)
P2 1 P2
For 1 mole of ideal gas: ΔG (T ) = RT ∫ dP = RT ln
P1 P P1
€ P = P :
ΔG (T ) = G (T,P ) − G (T,1 bar) = RT ln P
If P1 = 1 bar, 2
1 bar
€
Rearranged:
G (T,P ) = G°(T ) + RT ln P
€
The standard molar Gibbs free energy. One mole adjustment to P
of ideal gas at one bar. Depends on T alone. from one bar.

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 Temperature Dependence of G
divide by T
G H
G = H − TS = −S
T T
Differentiate wrt T at constant P:

⎡ ∂(G /T ) ⎤ H 1 ⎛ ∂H ⎞ ⎛ ∂S ⎞
⎢ ⎥ = − 2 + ⎜ ⎟ − ⎜ ⎟
⎣ ∂T ⎦ P T T ⎝ ∂T ⎠ P ⎝ ∂T ⎠ P
H CP CP
=− 2 + −
T T T video 7.1

⎡ ∂(G / T ) ⎤ H ⎡ ∂( ΔG /T ) ⎤
⎢ ⎥ = − The Gibbs-Helmholtz ΔH
2 ⎢ ⎥ = − 2
⎢⎣ ∂T€ ⎥⎦ T equation ⎣ ∂T ⎦ P T
P
e.g., for a reaction

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 Temperature Dependence of G
As we know how to determine H(T) and S(T) individually, we
can also use,
G (T ) = H (T )− TS (T )
Using H(0) as the reference for enthalpy/free energy,

G (T )− H (0 ) = H (T )− H (0 )− TS (T )

Tfus
s
Tfus C Ps (T ) Δ H
H (T )− H (0 ) = ∫ C (T )dT + Δ fus H
P
S (T ) = ∫ dT + fus
0 0 T Tfus
Tvap
+∫ C Pl (T )dT + Δ vap H Tvap C Pl (T ) Δ vap H
Tfus +∫ dT +
Tfus T Tvap
T
+ ∫ C Pg (T )dT TC Pg (T ʹ′)
Tvap +∫ dT ʹ′
Tvap T ʹ′
(see video 5.8) (see video 7.3)
 Benzene Example: G at 1 Bar
dG = − SdT + VdP G decreases with increasing T

Continuous at phase
Benzene
transitions since
equilibrium implies
same G

Δ trsG = 0
Discontinuous slope at
phase transitions

⎛ ∂G ⎞
⎜ ⎟ = − S
⎝ ∂T ⎠ P
S (g) > S (l) > S (s)
G (T )− H (0 ) = H (T )− H (0 )− TS (T )