1

LAURENTIAN UNIVERSITY
UNIVERSIT LAURENTIENNE

Date: April 13, 2003

Course and No: Chemical and Metallurgical Thermodynamics (ENGR 2227 EL)

Total no. of pages: 10 (including the cover sheet)

Questions: 11 (See below for explanation)

Professor: Dr. Ramesh Subramanian

Time Allowed: 3 hours (2:00 p.m. 5:00 p.m.)

Location: F-227



NAME:

STUDENT NO.:


(1) Please return the question sheet along with your answer booklet.

(2) You are allowed up to a maximum of 4 sheets for reference.

(3) PART I Answer any 4 out of 6 questions (4 x 10% = 40%)

PART II Answer any 2 out of 3 questions (2 x 17.5% = 35%)

PART III Answer any 1 out of 2 questions (1 x 25% = 25%)

(4) You may choose to answer 1 out 3 questions in PART II only if you answer all 6
questions in PART I.

(5) State your assumptions clearly.
2
PART I

1. Calculate the entropy change (S) when 1 mole of liquid water at
293
o
K is mixed with another mole of liquid water at 353
o
K, and
the system is allowed to reach equilibrium in an adiabatic
enclosure. Assume C
p
= 77 J/mole
o
K for water from 273
o
K to
373
o
K.


2. The activity coefficient of Zinc in Al-Zn alloys exhibits the following
relation at 477
o
C:

R T ln
Zn
= 1750 (1 X
Zn
)
2

where R is in cal/mol K and T is in K. Calculate the activity of
Aluminum in the alloy at 477
o
C for X
Zn
= 0.4.


3. Assuming ideal gas phase, calculate the excess Gibbs free energy
of a Propanol-Water regular binary solution for X
propanol
=
0.6369 using the following data:

T = 30
o
C P
o
propanol
= 60.7 mmHg

P
o
water
= 32.1 mmHg P
total
= 66.9 mmHg

Y
propanol
= 0.6462 mole fraction of Propanol in the gas phase
3
4. Lithium Bromide vapor dissociates according to the following
equilibrium reaction:

LiBr (g) == Li (g) + Br
2
(g)

The standard Gibbs free energy change (G
o
) for the above gas-
phase reaction is given by:

G
o
= 333,900 42.09 T Joules

Calculate the temperature at which the partial pressure of Lithium
(p
Li
) reaches the value of 10
-5
atm when the gas mixture is heated at
a constant total pressure of 1 atm.


5. Below its triple point (T = - 56.2 C) the saturated vapor pressure
of solid CO
2
(dry ice) is given by the equation

ln P = (-3116/T) + 16.01

where P is in atm and T is in K.

The molar latent heat of melting of solid CO
2
is 8330 joules.
Calculate molar latent heat of vaporization of CO
2
and the
saturated vapor pressure exerted by liquid CO
2
at 25 C.

4
6. A gas mixture composed of 30% CO, 10% CO
2
, 10% H
2
and 50%
N
2
on a molar basis is fed to a heat-treatment furnace at 927
o
C
where the following gas-phase equilibrium reaction takes place:
CO
2
(g) + H
2
(g) == CO (g) + H
2
0 (g)

The standard Gibbs free energy change (G
o
) for the reaction is
given by:
G
o
= - 35,987 + 32.05 T Joules

Assuming all gases behave ideally, calculate the equilibrium
composition of the product gas mixture (containing CO, CO
2
, H
2
,
H
2
O and N
2
) at 927
o
C for a total pressure of 1 atm.
5
PART II

1. The equilibrium constants for the reactions

FeO (s) + CO (g) == Fe (s) + CO
2
(g) Equilibrium Constant = K
P1


FeO (s) + H
2
(g) == Fe (s) + H
2
O (g) Equilibrium Constant = K
P2


at various temperatures are given below:

T,
o
K 873 973 1073 1173 1273

K
P1
0.900 0.673 0.535 0.453 0.396

K
P2
0.332 0.422 0.499 0.594 0.668



Using the data, calculate the equilibrium constants at all the
above temperatures for the following reaction:

CO (g) + H
2
O (g) == CO
2
(g) + H
2
(g)

Also calculate the standard heat of reaction (H
o
) for the above
reaction, assuming it to be independent of temperature.

6
2. The molar excess Gibbs free energy of formation of solid
solutions/alloys in the Au-Ni system can be represented by the
equation

G
XS
= X
Ni
X
Au
(24140 X
Au
+ 38280 X
Ni
14230 X
Au
X
Ni
) [1

(T/2660)] in J/mol

where T temperature in K

X
Ni
mole fraction of Ni in the solid solution/alloy

X
Au
mole fraction of Au in the solid solution/alloy

Calculate the activities of Au and Ni in the alloy at T = 1100 K for
X
Au
= 0.5.


7
3. For the gas-phase reaction

A (g) + B (g) == C

(g)

the following equilibrium mole fraction data was obtained at a total
pressure of 1 atm:

100
o
C 200
o
C

X
C
0.172 0.642

X
A
0.414 0.179

X
B
0.414 0.179

Assuming the standard heat of reaction (H
o
) for the above
reaction to be independent of temperature, calculate the
equilibrium vapor composition if equimolar quantities of A and
B are reacted at T = 150
o
C and P = 10 atm.



8
PART III

1. For the reaction

7 Cr
3
C
2
(s) + 2.5 O
2
(g) 3 Cr
7
C
3
(s) + 5 CO (g)

(a) Derive the generalized equation for the dependency of the
standard Gibbs free energy (G
o
) on temperature (T) for
the reaction.

(a) Calculate G
o
for the reaction at T = 1500 K and 298 K using
the derived generalized equation in part (a).

(b) Calculate G
o
for the reaction at T = 1500 K and 298 K using
the equation G
o
= H
o
298
- T S
o
298
.

(c) Compute the % difference of G
o
for the reaction at T = 1500
K and 298 K from the results obtained in part (b) and part (c).

Specific Heat Data C
p
in cal/mol K

For Cr
7
C
3
C
p
= 56.96 + 14.54 x 10
-3
T 10.12 x 10
5
T
-2


For CO C
p
= 6.79 + 0.98 x 10
-3
T 0.11 x 10
5
T
-2


For Cr
3
C
2
C
p
= 30.03 + 5.58 x 10
-3
T 7.46 x 10
5
T
-2


For O
2
C
p
= 7.16 + 1.00 x 10
-3
T 0.40 x 10
5
T
-2

9
Standard Molar Heat and Entropy of Formation Data

H
o
298
in cal/mol S
o
298
in cal/mol K

For Cr
7
C
3
H
o
298
= - 54,500 S
o
298
= 48.00

For CO H
o
298
= - 26,420 S
o
298
= 47.22

For Cr
3
C
2
H
o
298
= - 26,200 S
o
298
= 20.40

For O
2
H
o
298
= 0 S
o
298
= 49.00


10
2. The following values of the activity coefficients of Cadmium in
Zinc-Cadmium solutions have been obtained from E.M.F.
measurements at 527
o
C:

X
Cd
: 0.2 0.3 0.4 0.5

Cd
: 2.153 1.817 1.544 1.352

(a) Determine whether the Zn-Cd solution exhibits regular
behavior at T = 527
o
C.

(b) Assuming regular solution behavior, calculate the values of
the partial molar heat of mixing of Zinc and Cadmium,
integral molar heat of mixing, integral molar entropy of
mixing, partial molar free energy of mixing of Cadmium
and integral molar free energy of mixing for an equimolar
(X
Cd
= X
Zn
= 0.5) solution of Zn-Cd at T = 527
o
C.

(c) Assuming regular solution behavior, calculate the values of
the excess partial molar free energy of Zinc and Cadmium,
excess integral molar free energy of solution, and excess
integral molar entropy of solution for an equimolar (X
Cd
=
X
Zn
= 0.5) solution of Zn-Cd at T = 527
o
C.