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Assignment 7

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.

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.

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?

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