Thanks to visit codestin.com
Credit goes to www.scribd.com

Scribd
Upload
173 views9 pages

Thermodynamic Potentials

1) The document discusses several thermodynamic potentials - internal energy (U), enthalpy (H), Helmholtz free energy (F), and Gibbs free energy (G). It defines each potential and derives their differential and integral forms. 2) Maxwell's relations are derived by applying partial differentiation to the thermodynamic potentials. Relations between the partial derivatives of the potentials are obtained. 3) Two exercises are included - the first shows relationships between the potentials, and the second derives expressions for heat capacity derivatives in terms of pressure, volume, and temperature using Maxwell's relations.

Uploaded by

hariz syazwan
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
173 views9 pages

Thermodynamic Potentials

1) The document discusses several thermodynamic potentials - internal energy (U), enthalpy (H), Helmholtz free energy (F), and Gibbs free energy (G). It defines each potential and derives their differential and integral forms. 2) Maxwell's relations are derived by applying partial differentiation to the thermodynamic potentials. Relations between the partial derivatives of the potentials are obtained. 3) Two exercises are included - the first shows relationships between the potentials, and the second derives expressions for heat capacity derivatives in terms of pressure, volume, and temperature using Maxwell's relations.

Uploaded by

hariz syazwan
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
You are on page 1/ 9

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 .

You might also like