Tutorial 4

EP 209 - Thermal Physics

Question 1
Formulate a proof that the energy minimum principle implies the entropy maximum principle.
That is, show that if the entropy were not maximum at constant energy then the energy
could not be minimum at constant entropy.
Hint: First show that the permissible increase in entropy in the system can be exploited to extract heat from a reversible heat
source (initially at the same temperature as the system) and to deposit it in a reversible work source. The reversible heat source
is thereby cooled. Continue the argument.)

*Question 2
The four, most useful Maxwell relations used in thermodynamics is expressed by the mnemonic
diagram. The first Maxwell relation, obtained by taking the second derivative of U with
respect to its extensive variables V and S,
P
S

T
V

=
V

!
S

. Derive the remaining three by using only the relations:

x
y

x
y

y
z

!
f

y
z

z
x

z
x

= 1
y

=1
f

*Question 3
Show that if the Helmholtz function F is known as a function of V and T,
H =F T

F
T

G=F V

F
V

V
V

F
V

!
T

!
T

*Question 4
The latent heat of fusion for ice is 3.34105 J/kg at 0o C and at atmospheric pressure. If
the change in specific volume on melting is -9.05105 m3 /kg, then calculate the change of
melting temperature due to change of pressure.
*Question 5
Prove that during a first-order phase transition, the entropy of the entire system is a linear
function of the total volume.
*Question 6
For a pure substance, prove that in the P V plane the slope of the sublimation curve at
the triple point is greater than that of the vaporization curve at the same point.
Question 7
The specific Gibbs function of a gas is given by
P
g = RT ln
p0

AP

where A is a function of T only. Derive expressions for the equation of state of the gas and
its specific entropy. Also, deduce expressions for CP and CV .
Question 8
Find the fundamental equation of a mono-atomic ideal gas in the Helmholtz representation,
in the enthalpy representation, and in the Gibbs representation.
Question 9
A system obeys the fundamental relation
(s s0 )4 = Avu2
Calculate the Gibbs potential G(T,P,N).
Question 10
For a particular system it is found that
3
u = Pv
2
and
P = AvT 4
Find a fundamental equation, the molar Gibbs potential, and the Helmholtz potential for
this system.

Question 11
Show that for an ideal van der Waals fluid
h=

2a
v
+ RT c +
v
vb


where h is the molar enthalpy.

Assuming such a fluid to be passed through a porous plug and thereby expanded from vi
to vf , find the final temperature Tf in terms of the initial temperature Ti and the given data.
Question 12
One mole of a mono-atomic ideal gas is in a cylinder with a movable piston on the other side
of which is a pressure reservoir with Pr = 1 atm. How much heat must be added to the gas
to increase its volume from 20 to 50 liters?
Question 13
Assume that the gas of previous problem is an ideal van der Waals fluid with the van der
Waals constants of argon, and again calculate the heat required.
Hint : Question 13

Question 14
Show that the relation
=
where =

1
v

v
T


P

1
T

implies that CP is independent of the pressure such that

Cp
P T

=0

Question 15
Reduce the derivative

s
v h

(refer to section 7-3 of Callans book)

Question 16
Evaluate the change in temperature in an infinitesimal free expansion of a simple ideal gas.
Does this result also hold if the change in volume is comparable to the initial volume? Can
you give a more general argument for a simple ideal gas, not based on simply math (NO
equations!)?
Question 17
Assuming that a gas undergoes a free expansion and that the temperature is found to change
by dT, calculate the difference dP between the initial and final pressure.

Question 18
It is observed that an adiabatic decrease in molar volume of 1% produces a particular
change in the chemical potential . What percentage change in molar volume, carried out
isothermally, produces the same change in ?
Question 19
In the following fundamental equations of physical systems which one of these equations
violate the stability criteria?


1

(a) F = A NV 3T 2 (b) U = D SNV5

A and D are positive constants.
Question 20

1
2

It was found that a certain liquid boils at a temperature of 95 C at the top of a hill, whereas
it boils at a temperature of 105 C at the bottom. The latent heat is 1000cal/mole. What is
the pressure difference between the bottom and the top of the hill?