UNIVERSITY OF MAURITIUS

FACULTY OF ENGINEERING

PAPER NO

EXAMINATION

DATE

First Semester 2006/2007

BEChEE/06F/7

BEng (Hons) Chemical and

Environmental Engineering
Level 3

Thursday
30 November 2006

SERIES

PAPER

TIME

Nov/Dec 2006

Chemical Thermodynamics
(CHE 3104)

13:30 15:30 Hours

This paper contains FOUR (4) Questions. Candidates are required to answer
Question 1 (COMPULSORY) and ANY OTHER TWO (2) Questions.

Question 1 (COMPULSORY)
If required, R = 8.314 J K-1 mol-1 or R = 8.314 kPa dm3 K-1 mol-1
(a)

Given that dg = 2 x 2 y 3 dx + 3 x 3 y 2 dy
(i)

Show that this is an inexact differential, hence obtain a suitable integrating

factor and verify the suitability of the integrating factor.

(ii)

Obtain the relation g = g(x,y).

[1 + 2 + 1 + 3 marks]

(b)

The thermodynamic equation of state may be written as U = T p p .

V T

T V

n a
For a van der Waals gas, p + 2 (V nb ) = nRT .
V

Explain the effect of changing volume on the internal energy at constant

temperature for:
(i)

An ideal gas

(ii)

A van der Waals gas

[2 + 4 marks]

(c)

An inert gas is added to the reaction system 2A(g) + B(g) ' A 2 B(g)
Discuss the effect of adding an inert gas, keeping pressure of the system constant,
on the equilibrium of the reaction. Derive any equations used.
[6 marks]

(d)

(i)

Explain the origin of osmotic pressure.

(ii)

1 g of serum albumin is dissolved in 1000 cm3 of water gives a solution

height of 4.0 mm at 30C. Calculate the relative molecular mass of serum
albumin. Density of solution may be taken to be 1.1 g/cm3.
[2 + 4 marks]

Page 1 of 4

Question 2
(a)

For the chemical reaction 1 A1 + 2 A2 ' 3 A3 + 4 A4 , show that at equilibrium

1 1 + 2 2 = 3 3 + 4 4 .
[5 marks]

(b)

The association of potassium atoms in the vapour phase to form dimers may be
represented by:

2K(g) ' K 2 (g)

Assuming that the initial amount of potassium is 2 mol and there is no dimer.
(i)

Derive an expression for K op in terms of the extent of the reaction.

(ii)

Hence discuss the effect of changing pressure on the extent of dimerisation.

(iii)

Use Le Chateliers Principle to explain the results of b(ii).

[6 + 3 + 2 marks]

(c)

The equilibrium constant for the reaction is K op = 10 at 970 K

2SO 2 (g) + O 2 ( g ) ' 2SO 3 (g)

(i)

Derive an expression for the free energy change, reaction quotient and
equilibrium constant K op .

(ii)

Hence indicate which direction the reaction below will proceed

spontaneously.
2SO 2 (g)[0.001 atm] + O 2 ( g )[0.200 atm] ' 2SO 3 (g) [0.003 atm]

[5 + 4 marks]

Page 2 of 4

Question 3
(a)

(i)

Derive

the

relation

H
U
p V

=
+ T
.
T p T V
T V T p

Given

that

thermodynamic equation of state may be written as U = T p p .

V T

(ii)

Hence show that for an ideal as, C p ,m CV ,m = R .

(iii)

What

is

the

expression

for

C p CV

for

gas

T V

obeying

the

equation p(V b ) = nRT ?. Given that b is a constant independent of

temperature.
[5 + 2 + 3 marks]

(b)

1 dm3 of oxygen gas and 4 dm3 of nitrogen gas, each at a pressure of 1 atm at 300 K
are mixed to form an ideal gas mixture of 3 dm3 at the same temperature. Derive
an equation for the entropy change for the process and hence calculate the entropy
change.
[5 + 3 marks]

(c)

Given that a substance is such that Vm,L < Vm,S . Discuss how does the shift in
boiling point due to a decrease in pressure compare with that of the shift in
melting point. Illustrate your answer by deriving equations and using diagrams.
[7 marks]

Page 3 of 4

Question 4
(a)

Derive an expression for the thermodynamics condition of equilibrium for water

at its triple point.
[5 marks]

(b)

(i)

Distinguish clearly between colligative and non colligative properties using

suitable examples.

(ii)

Derive an expression relating the depression of the freezing point of the

solvent with characteristics of the solvent and the solute.

(iii)

Use the expression in b(ii) to calculate the freezing point of a solvent with
normal freezing point 10 C, if 2 g of non-volatile solute (molar mass 80 g) is
added to 50 cm3 of the solvent (density = 1.1 g cm-3). Given freezing point
depression constant is 1.86 K kg mol-1
[3 + 5 + 4 marks]

(b)

Chemical potential may be defined in terms of free energy as

i =
ni T , p ,n

.
j j i

(i)

Is the chemical potential an extensive or intensive property? Explain your

answer.

(ii)

Derive an expression to show how chemical potential may be defined in

terms of enthalpy. Is this a partial molar quantity? Explain your answer.
[3 + 5 marks]

/nr

END OF QUESTION PAPER

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