CHEN 354 Chemical Engineering Thermodynamics II Spring 2016

Due Wednesday, February 10th, 2016

Partial Molar Properties

Problem 1. The molar volume (cm3mol-1) of a binary liquid mixture at T and P is given by:
= 1201 + 702 + 1 2 (151 + 82 )
a) Find expressions for the partial molar volume of species 1 and 2 at T and P.

b) Plot values of V, 1 and 2 vs x1. Identify the following points in the graph: V1, V2, 1 , and

2 with their respective values.



c) Demonstrate that 1 = 2 =0
1 1 =1 1 1 =0

Problem 2. The molar enthalpy (J.mol-1) of a binary liquid mixture of species 1 and 2 at T and P is
given by:
= 3751 + 2732 + 1 2 (451 + 362 )

a) Find expressions for the partial molar enthalpy of species 1 and 2 at T and P.
b) Use the expressions found in numeral a) to demonstrate the summability relation, which states
that = 1
1 + 2 2
c) Plot values of H, 1 , and
1 and 2 vs x1. Identify the following points in the graph: H1, H2,


2 with their respective values.

Problem 3. The partial molar volume of species a in a binary mixture (a + b) at constant T and P is
given by:
= 0 0.22
0
Where is the molar volume of pure species a, and xb the mol fraction of species b. If the molar
volume of pure species b is 0 , derive an expression for . Draw a sketch showing , and xb.

Problem 4. The Gibbs-Duhem equation can be deduced by combining the total derivative of property
M (P, T, xi) in terms of P, T and x:

= + +
, ,
:
and the total derivative of M in terms of partial molar

=

a) Use these two equations to derive the Gibbs-Duhem equation:

+ = 0
, ,
b) Deduce an expression for Gibbs-Duhem equation for M = G (Gibbs free energy) of a binary
mixture at constant T and P. Give your answer in terms of chemical potential.
c) Briefly comment on the importance and applications of the Gibbs-Duhem equation.
d) Demonstrate that the expressions for the molar volume and molar enthalpy given in problems 1
and 2 respectively, satisfy the Gibbs-Duhem equation.