Advanced Thermodynamics: Homework #1 Roger Madorell Taulats

Problem 1. Read Exercise 1.2 from the book by Widom for the energy distribution
function Q(E) and reproduce the plot given as a function of E/ and try to plot
values of E / E = 1/50 and 1/100.

The function is:

/1 2
1 ( )
() = /
/

For the values of / = 1/5, 1/10 1/20 we obtain the following plot:

12

10

8
Q(E)

0
0 0,5 1 1,5 2
E/

1/5 1/10 1/20

And For the values of / = 1/50 1/100 we obtain the following plot:

60

50

40
Q(E)

30

20

10

0
0 0,2 0,4 0,6 0,8 1 1,2 1,4 1,6 1,8 2
E/
1/50 1/100

The peak factors for the different values of / are:

 / () peak values
1/5 2.8
1/10 5.6
1/20 11.3
1/50 28.2
1/100 56.4

Problem 2. The probability of observing a closed, thermally equilibrated system

with a given energy E is Q(E) W (E) exp(E / kT) exp[lnW (E) E / kT]. Both
lnW (E) and E / kT are of the order of magnitude of the number of particles in the
system, N, which suggests that Q(E) is a very narrow distribution centred on the
most probable value of E. Verify this suggestion by performing a steepest descent
calculation with Q(E), that is, expand lnQ(E) in powers of E E E and truncate
the expansion after the quadratic term. The term E is the average value of E,
which usually corresponds to the most likely or thermodynamic value (U). Use this
expansion to estimate for 0.001 moles of an ideal monatomic gas the probability of
observing a spontaneous fluctuation in E of the size of E =10^-6E.

The probability in a canonical ensemble is:

() () exp ( ) = exp[() ]

If we apply logarithms to each side we obtain:

() = ()

Then we apply the Taylors series:

() 2 2 ()
() = (0 ) + +
2! 2

( ) 2 2 ( )
() = ( ) + +
2 2

As we can observe in the previous figure, the function Q(E) has a maximum at , which
means that the first derivative (the second term of the series expansion) is equal to 0. The
third term is going to be negative because the second derivative in a maximum is always
negative. So we obtain:

2 2 ( )
() = ( ) +
2 2
And:

( ) = ( )

We substitute the previous equation and we apply the second derivative to each term:

2

2 ( ) (( ) ) 2 ( ) ()
2
= =
2 2 2 2

We develop the last term:

2 ( )
= ( ) = ( 1 ) = 0
2

The term ( ) must be replaced in to another equation depending on U in order to

develop it:

= ()

() =

2 2
)) =
(( ( ) = ( )
2 2
We know that:

=

So:

1
1 ()
( )=

We apply the following property to the previous equation:

() ()
=

And we derivate:
 1
() 1
=
2

1
() 1
=
2

( ) =

1 1 1
=
2 2

1 1
() = ( ) + 2 ( 2 )
2

2
() = ( )
2

() 2
( )= 2
( )

() 2
= exp ( 2 )
( )

For a monoatomic ideal gas:

3 3
= ; = =
2 2

= 0.001 6.02 1023 1021

We substitute:

2
3 3
() (106 2 ) (106 )2
= ( ) = ( 2 ) = (3 1012 )
( ) 3
2 2 2 2 4

3
= ( 1012 (1021 )) = exp(109 ) 0
4

The result can be approximated to 0, but is not 0, that means that the probability of
observing a closed, thermally equilibrated system with the given conditions is
improbable, but not impossible.