PHYS 203, Thermal Physics I.

Assignment 7

Due March 8, 2012

1. (a) Express the chemical potential of an ideal gas in terms of the tem-
perature T and the volume V:

µ = cP T − cv T ln T − R T ln V − s0 T + const.

(Hint: find the entropy S = S(T, V ); use G = U − T S + P V and

write µ = G/n.)
(b) Similarly, find µ in terms of T and P. Show that the chemical
potential at the fixed temperature T varies with pressure as
P
 
µ = µ0 + R T ln ,
P0
where µ0 is the value of µ at the reference point (P0 , T ). This
expression is of great use in chemistry.

2. A container of volume V is divided by partitions into three parts con-

taining one kilomole of helium gas, two kilomoles of neon gas and three
kilomoles of argon gas, respectively. The temperature of each gas is
initially 300 K and the pressure is 2 atm. The partitions are removed
and the gasses defuse into one another.

(a) Calculate the kilomole fraction and the partial pressure of each gas
in the mixture.
(b) Calculate the change in the entropy and the Gibbs energy of the
system in the mixing process.

1
3. A container is initially separated by a diathermal wall into 2 compart-
ments of equal volume. The left compartment is filled with 1 kilomole
if neon gas at a pressure of 4 atmospheres and the right with the argon
gas at 1 atmosphere. The gases may be considered ideal. The whole
system is initially at temperature T = 300K, and is thermally insulated
from the outside world. Suppose the diathermal wall is removed.

(a) What is the new temperature of the system? The new pressure?
(b) What is the change in the entropy of the system?
(c) What is the change in the Gibbs function of the system?

4. (a) The infinitesimal change of the Gibbs free energy for and open
system is given by

dG = −S dT + V dP + µ dn.

Using this, calculate G for a van der Waals gas, assuming a fixed
amount of the gas at a given, fixed temperature. Show that

n2 b R T 2 n2 a
G = −n R T ln(V − n b) + − + C(T ),
V − nb V
where the integration constant C(T ) is, in general, different for
different temperatures.
(b) (Bonus) Fix the parmeters a, b and the integration constant C(T ) at
some particular values and using your favorite graphic application
plot G as a function of the pressure along a subcritical isotherm, say
T = 0.9Tc . What parts of the resulting curve correspond to a stable
thermodynamical equilibrium? Where does the phase transition
gas → liquid take place?