Homework 4

1. The Clausius-Claperyron equation can only be applied to first-order transitions. Derive

the second Ehrenfest equation which applies to continuous second-order phase transitions
in which the volume remains constant through the transition. Hint: For second-order
transitions, volume does not change through the transition.
Ehrenfest equation

d
d

i
1
-i
2
o
1
-o
2
(thermal expansion coefficient o

1
(

, isothermal compressibility i -

1
(

)
2. Express the van der Waals equation of state in terms of reduced coordinates
t ,
c
, j ,
c
, ,
c
. ((,)

c
0 (
2
,
2
)

c
0)
(van der Waals equation)
3.
(a) Solve problem 1 in Chapter 11 of your textbook.
(b) Liquid helium boils at temperature
0
=4.2K when its vapor pressure is equal to j
0
=1
atm. We pump on the vapor and reduce the pressure toa much smaller value j. Assuming
that the latent heat is approximately independent of temperature and that the helium
vapor density is much smaller than that of the liquid, calculate the approximate
temperature
:
of the liquid in equilibrium with its vapor at pressure j. Express your
answer in terms of ,
0
,j,j
0
, and any other required constants.
4, 5, 6.
Solve problem 3, 4 and 6 in Chapter 11 of your textbook.
7.
Consider a mixture of A and B molecules that is ideal in every way but one: The
potential energy due to the interaction of neighboring molecules depends upon whether
the molecules are like or unlike. Let n be the average number of nearest neighbors of
any given molecule. Let n
0
be the average potential energy associated with the
interaction between neighboring molecules that re the same (A-A or B-B), and let n

be the potential energy associated with the interaction of a neighboring unlike pair (A-B).
There are no interactions beyond the range of the nearest neighbors; the values of n
0
and n

are independent of the amounts of A and B; and the entropy of mixing is the
same as for and ideal mixture.
(a) Derive the total potential energy when the system is unmixed.
(b) Find a formula for the total potential energy when the system is mixed, in terms of
x, the fraction of B.(Assume that the mixing is totally random.)
(c) Subtract the results of parts (a) and (b) to obtain the change in energy upon mixing.
Simplify the result as much as possible; you should obtain an expression proportional to
x(1-x). Sketch this function vs. s, for both possible signs of n

-n
0
.
(d) For the case n

-n
0
0, plot a graph of the Gibbs free energy of this system vs. s
at several temperatures. Discuss the implications.
(e) Find an expression for the maximum temperature at which this system has a
solubility gap.