ChE

211, Adv. Chem. Eng. Thermodynamics

Homework 4

09/21/2015

Due Date: Monday, 09/28/2015

1. Derivation of Raoults Law:
a. Determine the relationship between the vapor pressure of a solvent
on the concentration of a (not very volatile) dissolved substance.
Consider the vapor and the solution to be ideal.
Start from the equilibrium condition:
i. ! , = !" , , !"
(Hint: This is Exercise 3.3 in your textbook. Go through the derivations as
we did in class for other derivations.)
b. Why is Raoults law not a good approximation?
c. Determine the resulting change in temperature (increase in the
boiling point).

2. An experimentalist determines that the heat capacity of a substance obey the
empirical relation Cv (T, V) = T2v2, where is a constant. The
experimentalist also discovers that the entropy and energy are zero at
absolute zero, for all volumes. Compute the per-particle thermodynamic
potentials: U(S, V), H(S, p), A(T, V), and G(T, p).
Hint: Start with the definition of heat capacity.

3. Instead of using Legendre transformation on U = U (S, V, N) to A (T, V, N),
start with S (U, V, N) and use analogous derivation to derive:
a. The Legendre transform of S with respect to U, S[U] (T, V, n).
b. Its differential dS[U]
Note: Legendre transforms of the entropy are important in statistical
mechanics and are called Massieu functions / potentials.

BCME, San Jose State University

Lilian Chang, Fall 2015