# BIRLA INSTITUTE OF TECHNOLOGY & SCIENCE PILANI

First Semester 2006-2007
CHE C311 CHEMICAL ENGINEERING THERMODYNAMICS 14 Dec. 2006
Time: 3 hrs COMPREHENSIVE EXAMINATION Max. Marks: 120
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_
Note: The question paper consists of two parts, PART-A (CLOSED BOOK) of 40
marks and PART-B (OPEN BOOK) of 80 marks. PART-B question paper and the
answer book will be supplied after the PART-A answer book is submitted.
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_
PART- A
CLOSED BOOK Max. Marks: 40
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_
Q.1 (8 x 5 = 40 Marks)
(a) Starting with Redlich/Kwong equation, derive the corresponding forms of the
equation suitable for iterative calculation of vapor volume as well as the liquid
volume. In each case specify the value of V for the first iteration.
(b) Derive the following expression for entropy change of an ideal gas.

1
2
1
2
ln ln
P
P
R
T
T
c S
P
− 〉 〈 · ∆
(c) Starting with the relation
dP
T
V
T V dT c dH
P
P 1
]
1

¸

,
_

¸
¸

− + ·
, derive an expression
for
T
P
P
c

,
_

¸
¸

. What is the result of application of this relation to an ideal gas?
(d) Discuss briefly the working principle and applications of an ejector.
(e) Sketch
y x t , −
diagrams for low to moderate pressure for nonideal binary
systems with positive/negative deviations from ideality and with or without an
azeotrope.
(f) Derive an expression relating the fugacity of a subcooled liquid to fugacity
coefficient of saturated vapor and the Poynting factor.
(g) Write Margules equation for
RT
G
E
as a function of mole fractions
1
x
and
2
x
.
Derive corresponding expressions for
1
ln γ
and
2
ln γ
. Also express the two
constants of the Margules equation in terms of the infinite dilution activity
coefficients.
(h) Determine the number of degrees of freedom for a chemically reactive mixture
consisting of ZnO(s), ZnSO
4
(s), SO
2
(g) and O
2
(g).
******** ******** ******** ********(End of PART-A)
1
PART-B
OPEN BOOK Max. Marks: 80
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_
Note: For problems requiring solution by iteration, full credit will be given for
carrying out the first complete iteration.
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_Q.2 (25 Marks)
A rigid vessel of 0.5-m
3
volume contains steam at 7000 kPa and 290°C. Heat is
transferred to the vessel till the temperature reaches 400°C. Determine the final
pressure and the heat transferred using
(a) Data from steam tables.
(b) Appropriate generalized correlations.
Q.3 (20 Marks)
Calculate the molar volume, fugacity and fugacity coefficient at 400 K and 30 bar for
a mixture of methane (1)/propane (2) containing 35-mole% methane, using the
following methods.
(a) Assume the mixture to be an ideal solution and use Redlich/Kwong equation to
determine the properties of pure species.
(b) Use Pitzer’s generalized virial coefficient correlation for mixtures without making
the ideal solution assumption.
Q.4 (20 Marks)
The pure component vapor pressures for methanol (1)/water (2) system are given by
the following equations.

240 ) / (
3644
6 . 16 ) / ln(
1
+ °
− ·
C t
kPa P
sat

226 ) / (
3800
3 . 16 ) / ln(
2
+ °
− ·
C t
kPa P
sat
(a) Using Raoult’s law, do the following.
(i) Calculate the liquid and vapor compositions of the equilibrium mixture
at 80°C and 101.33 kPa.
(ii) Determine V (fraction vaporized), L (fraction remaining in the liquid
phase),
1
x

and
1
y , if a liquid stream of overall composition,
1
z =
0.47 is flashed at 80°C and
) ( 5 . 0
d b
P P P + ·
, where b
P
and d
P

are
the bubble point and dew point pressures respectively.
(b) Use modified Raoult’s law and Wilson equation to perform a DEW T calculation,
given that
1
y = 0.58 and P = 101.33 kPa. The values of Wilson equation
parameters for the system are as follows.

1 3
1
7 . 40

· mol cm V
1 3
2
1 . 18

· mol cm V

1
12
107

· calmol a
1
21
470

· calmol a
2
Q.5 (15 Marks)
Consider the methanol synthesis reaction, CO (g) + 2 H
2
(g) → CH
3
OH (g). Starting
with 2 moles of hydrogen per mole of carbon monoxide (no methanol), the reaction is
allowed to proceed to equilibrium at 150°C. If the mole fraction of methanol in the
equilibrium mixture is to be 0.5, calculate the pressure at which the reaction is to be
carried out and the mole fractions of other species in the equilibrium mixture. Assume
ideal gas behavior.
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3

z1 = 0. fugacity and fugacity coefficient at 400 K and 30 bar for a mixture of methane (1)/propane (2) containing 35-mole% methane.7cm 3 mol −1 V2 = 18 .6 − 1 ln( P2sat 3644 (t / °C ) + 240 3800 / kPa ) = 16 . (b) Use Pitzer’s generalized virial coefficient correlation for mixtures without making the ideal solution assumption. (ii) Determine V (fraction vaporized). Heat is transferred to the vessel till the temperature reaches 400°C. (i) Calculate the liquid and vapor compositions of the equilibrium mixture at 80°C and 101.58 and P = 101.33 kPa. The values of Wilson equation parameters for the system are as follows. full credit will be given for carrying out the first complete iteration. using the following methods. Marks: 80 _______________________________________________________________________ _ Note: For problems requiring solution by iteration. where Pb and Pd are the bubble point and dew point pressures respectively. do the following.5-m3 volume contains steam at 7000 kPa and 290°C.3 − (t / °C ) + 226 (a) Using Raoult’s law. (b) Appropriate generalized correlations. Determine the final pressure and the heat transferred using (a) Data from steam tables. Q. L (fraction remaining in the liquid phase). ln( P sat / kPa ) = 16 . (a) Assume the mixture to be an ideal solution and use Redlich/Kwong equation to determine the properties of pure species.3 (20 Marks) Calculate the molar volume. _______________________________________________________________________ _Q. V1 = 40 . given that y1 = 0. if a liquid stream of overall composition.PART-B OPEN BOOK Max. Q.5( Pb + Pd ) .2 (25 Marks) A rigid vessel of 0.4 (20 Marks) The pure component vapor pressures for methanol (1)/water (2) system are given by the following equations.47 is flashed at 80°C and P = 0. x1 and y1 .33 kPa. (b) Use modified Raoult’s law and Wilson equation to perform a DEW T calculation.1cm 3 mol −1 a12 = 107 calmol −1 a 21 = 470 calmol −1 2 .

5. the reaction is allowed to proceed to equilibrium at 150°C. ******** ******** ******** ******** ******** 3 . CO (g) + 2 H2 (g) → CH3OH (g). Starting with 2 moles of hydrogen per mole of carbon monoxide (no methanol). If the mole fraction of methanol in the equilibrium mixture is to be 0. calculate the pressure at which the reaction is to be carried out and the mole fractions of other species in the equilibrium mixture.Q.5 (15 Marks) Consider the methanol synthesis reaction. Assume ideal gas behavior.