P302: Statistical Mechanics

Assignment I
Last date for submission:23/8/2016
1. The following equations are purpoted to be fundamental equations of various thermodynamic systems. However, some of them are inconsistent with one or more
postulates of entropy maximum principle and consequently are not physically acceptable. Find out the inconsistent equations and indicate the postulates violated
by each. The quantities v0 , and R are positive constants.
(a)
S=

 R 1/3  N U 2/3
2

(b)
S=

 R3 1/5 
1/5
2
2
N
V
U
v0 2

(c)
S = N Rln

UV 
N 2 Rv0

(d)
S=

 S 
v0 S 2
exp
R V
NR

2. Find the three equations of state for a system with the fundamental equation
u=

2
R

s 2 v2
R
v0

and show that, for this system, = -u. Also express as a function of T and P .
3. Find the three equations of state in the entropy representation for a system with
fundamental equation
u=


R

s2 ev

2 /v 2
0

4. (a) Starting from dU = T dS P dV , show that the equation of state P V = N kB T

in fact implies that E can only depend on T .
(b) What is the most general equation of state consistent with an internal energy
that depends only on temperature?
(c) Show that for a van der Waals gas Cv is a function of temperature alone.
5. (a) Starting with the first law of thermodynamics and the definitions of CP and
CV , show that
h
 U  i V 
CP CV = P +
V T T P
where CP and CV are the specific heat capacities at constant pressure and
volume, respectively, and U and V are energy and volume of the gas.

(b) Use the above results plus the expression

P+

 U 

=T

 P 

V T
T V
to find CP CV for van der Walls gas. Use that result to show that as V
at constant P , you obtain the ideal gas result for CP CV
6. A body of constant heat capacity C, and a temperature Ti is put into contact with
a reservoir at temperature Tf . Equilibrium between the body and the reservoir is
established at constant pressure. Determine the total entropy change and prove that
it is positive for either sign of (Tf Ti )/Tf . You may regard |(Tf Ti /Tf )| < 1.
7. For an elastic filament, it is found that, at a finite range in temperature, a displacement x requires a force J = ax bT + cT x, where a, b, and c are constants.
Furthermore, its heat capacity at constant displacement is proportional to temperature, i.e., Cx = A(x)T .
(a) Use appropriate Maxwell relation to calculate S/x|T .
(b) Show that A has to be in fact independent of x, that is dA/dx = 0.
(c) Give the expression for S(T, x) assuming S(0, 0) = S0 .
(d) Calculate the heat capacity at constant tension, that is, CJ = T S/T |J as a
function of T and J.
8. Prove that

h
Cp 
p  i
2
 = T V p +

p T
T P

9. Adiabatic demagnetisation : This is an effect where there is a decrease in temperature

produced by adiabatic decrease of applied magnetic field. This is a very convenient
method of cooling below about 1K. The process is as follows: Some paramgnetic
substance is dipped in liquid helium about 1K, which acts as a bath. Now the
magnetic filed is increased from 0 to Hi so that magnetic work is done isothermally.
Now magnetic sample is thermally isolated by removing liquid helium. Then the
external magnetic field Hi is reduced to Hf , which is almost zero. This process is
adibatic and is also demagnetising. In this process we get a reduction in temperature
from Ti to Tf . Many times Tf is about one-hundredth of Ti .
(a) For the adiabatic process, show that
T 
S/H|T
 =
H S
S/T |H
(b) Using appropriate Maxwell relation show that
T 
V T H 
 =

H S
CH T H
(c) For a paramagnetic salt used in adiabatic demagnetisation, CH (H, T ) = V (b +
aH 2 )/T 2 and = a/T . Find the final temperature Hf if the magnetic field is
reduced from Hi to Hf adiabatically.