Advanced Thermodynamics: Homework #3 Roger Madorell Taulats

Problem 1. An approximate partition function for a dense gas is of the form:

1 2 3/2
2
(, , ) = [ ] ( ) exp( )
! 2

a) Derive expressions for the Helmholtz free energy and entropy for this
partition function:

The Helmholtz free energy is:

= ln()

We substitute the expression Q in the Helmholtz free energy equation:

1 2 3/2 2
= ln [ [ 2 ] ( ) exp( )]
!

Applying the following logarithmic property:

ln(1 2 3 4 ) = ln(1 ) + ln(2 ) + ln(3 ) + ln(4 )

We obtain:

1 2 3/2 2
= [ ( ) + ([ 2 ] ) + (( ) ) + ( )]
!

We multiply each term for -kT:

3
1 2 2 2
= ( ) ([ 2 ] ) (( ) )
!

And finally, we obtain the Helmholtz free energy expression:

1 3 2 2
= ( ) ( 2 ) ( )
! 2

To obtain the entropy expression, we know that:

=

 So, we derive the Helmholtz free energy expression term by term:

1 3 2
= ( ) [ ( 2 ) + 1] ( ) 0
! 2

And the entropy will be:

1 3 2
= ( )+ [ ( 2 ) + 1] + ( )
! 2

b) Derive the equation of state from this partition function, which one is it?

The equation of state is:

So, we derive again the Helmholtz free energy expression term by term, but now
in function of the volume:

2
= 0+0 + 2

2
= 2 =

2
+ 2 =

2
( + ) ( ) =
2

Where the last equation is the Van der Waals equation.

c) Derive an expression for the thermodynamic energy, U, and the heat

capacity at constant volume:

= +

We multiply the entropy equation obtained by T:

1 3 2 3
= ( ) + [ ( 2 )] + + ( )
! 2 2
And we make the difference between A and TS:

1 3 2 2
= ( ) ( 2 ) ( )
! 2

1 3 2 3
+ ( ) + [ ( 2 )] + + ( )
! 2 2

So, the thermodynamic energy U is:

3 2
=
2

We know that the heat capacity at constant volume is:

3
= =
2