Thermodynamic potentials

Mohd Faudzi Umar

Jabatan Fizik, Universiti Pendidikan Sultan Idris
Table of Contents

Internal energy, U

Enthalpy, H

Helmholtz function, F

Gibbs function, G

Maxwell's relations
Internal energy, U
I The rst law of thermodynamics written in the form of
U(S, V ):

dU = TdS − pdV . (1)

where it can be expressed in dierential of U :
   
∂U ∂U
T = , p=− (2)
∂S V ∂V S

I We now consider if S and V are held constant thus

dU = 0, while isochoric process implies that dU = TdS .
1

I Derive Heat capacity with volume constant and hence

Z T2
∆U = CV dT (3)
T1

1V constant
Enthalpy, H
I We dene the enthalpy H by

H = U + pV (4)
where
   
∂H ∂H
T = , p=− (5)
∂S p ∂p S

I Recalling (1) thus the dierential form is

dH = (TdS − pdV ) + pdV + Vdp = TdS + VdS .
I Isobaric process implies that dH = TdS .
2

I Derive Heat capacity with pressure constant and hence

Z T2
∆H = Cp dT (6)
T1

2p constant
Helmholtz function, F
I We dene the Helmhotz function F by

F = U − TS (7)
where
   
∂F ∂F
S =− , p=− (8)
∂T V ∂V T

I Hence we nd dF = −SdT − pdV .

I Isothermal process implies that dF = −pdV thus
3

Z V2
∆F = − pdV (9)
V1

3p constant
Gibbs function, G

I We dene the Gibbs function G by

G = H − TS (10)
where
   
∂G ∂G
S =− , p= (11)
∂T p ∂p T

I Hence we nd dG = −SdT + Vdp .

I Exercise 1 : Show that
1. U = −T 2 (∂/∂T )V F /T
2. H = −T 2 (∂/∂T )p G /T
Maxwell's relations

I We now want to derive Maxwell's relations. First we

consider
   
∂f ∂f
df = − dx + dy (12)
∂x y ∂y x

and
2 2
∂ f ∂ f
= (13)
∂x∂y ∂y ∂x
I We now want to apply this on U , H , F and G . See the
whiteboard!
I Exercise 2 : Find expressions for (∂Cp /∂p)T and
(∂CV /∂V )T in terms of p , V , and T .