CHM 421/621 Assignment 3

October 6, 2019

Due on 16th Oct., 2019.

1. A particular system obeys the relations

U = PV
P = BT 2

where B is a constant. Find the fundamental equation of this system

2. A system obeys the equations
NU
P =
N V − 2AV U
1 1
U 2V 2
T = 2C exp(AU/N )
N − 2AU
Find the fundamental equation.
3. If a monatomic ideal gas is permitted to expand into an evacuated
region, thereby increasing its volume from V to λV , and if the walls are
rigid and adiabatic, what is the ratio of the initial and final pressures?
What is the ratio of the initial and final temperatures? What is the
difference of the initial and final entropies?
4. The mechanical equation of state for a van der Waals gas is given by
RT a
P = − 2
v−b v
where a, b are constants and v is the molar volume.

1
 ∂ 1 ∂ 1



(a) Show that ∂(1/v) T u
= ∂(u/a) T v
.
1 cR
(b) Check whether the thermal equation of state T
= u+a/v
satisfies
the above condition.
(c) Using the above thermal and mechanical relations derive the en-
tropic fundamental relation for the van der Waals gas.

5. For a van der Waals gas, find the relationship between the volume and
the temperature in a quasi-static adiabatic expasion. Use the funda-
mental equation obtained in the previous problem.

6. In the temperature range of interest a system obeys the equations

T = Av 2 /s P = −2Avln(s/s0 )

where A is a positive constant. The system undergoes a free expansion

from v0 to vf (with vf ¿ v0 ). Find the final temperature Tf in terms
of the initial temperature T0 , v0 and vf . Find the increase in molar
entropy.