BITS, PILANI, GOA CAMPUS, FIRST SEMESTER 2018 – 2019

COMPREHENSIVE EXAM: CHEMICAL ENGINEERING THERMODYNAMICS

(CLOSED BOOK)
COURSE CODE: CHE F 213

DATE: 12/12/18 TIME: 180 minutes MAX. MARKS: 80

(ALL QUESTIONS ARE COMPULSORY. MAKE SUITABLE ASSUMPTIONS WHEREVER

NECESSARY)

1. Please answer the following

(a) Please derive the four fundamental property relations (using 1st and 2nd Laws of Thermo
as well as definitions of thermodynamic potentials) and hence derive the four Maxwell’s
relations. [2+ 2 = 4 Marks]

(b) Prove the following: [2 + 2 = 4 Marks]

dT  V 
(i) dS  C P   dP {S and H = f(T,P)}
T  T  P
dT  P 
(ii) dS  CV   dV {S and H = f(T,V)}
T  T V

(c) 1 mol ideal gas at 27oC expands isothermally and reversibly from an initial volume of 2
dm3 to a final volume of 20 dm3 against a pressure that is gradually reduced. Calculate :
(i) Q, heat transferred (ii) W, work done (iii) ∆U, change in internal energy (iv) ∆A,
change in Helmholtz energy (v) ∆G, change in Gibbs free energy (vi) ∆S, change in
entropy. [1+1+1+1+1+1+1 = 6 Marks]

(d) For a two-phase system, prove (Clausius-Clapeyron equation): [2 + 4 = 6 Marks]

dP sat H

dT T V

Hence, solve:
The heat of vaporization of water is 40820 Jmol-1, the molar volume of liquid water is
0.019 dm3mol-1 and the molar volume of steam is 30.199 dm3mol-1 all at 100oC and 1
atm. What would be the change in the boiling point of water at 100 oC if the atmosphere
pressure is changed by 1 mm?

2. Please answer the following:

 RT 
P
1
(a) Starting from ln  
RT  V 
P 0
dP , prove that:
P 
[ 5 Marks]

v
1
RT v 
ln   Z  1  PdV

where,  is fugacity coefficient

1
(b) Hence, continuing from (a), for fugacity coefficient for a van der Waals gas, derive the
following expression: [ 5 Marks]

PV  b  a
ln   Z  1  ln 
RT RTV

(c) Using the expression derived in (b), please find the fugacity coefficient and fugacity for
n-octane vapor at 427.85K and 0.215MPa. The van der Waals constants for n-octane are
a = 3.789 Pa (m3/mol)2 and b = 2.37 × 10-4 m3/mol (Given, V = 15.675×10-3 m3/mol)
[4 + 1 = 5 Marks]

(d) (i) State Raoult’s Law with equation

(ii)At 60oC the vapor pressures of pure benzene and toluene are 0.513 and 0.185 bar,
respectively. For a solution (assume ideal) with 0.6 mole fraction toluene. What are
the partial pressures of components and what are the mole fractions of each in the
vapor? (Saturation pressures of benzene and toluene are 0.513 and 0.185 bars,
respectively) [1+2+2 = 5 Marks]

3. (a) Please derive the Summability relation and Gibbs Duhem equation [2 + 3 = 5 Marks]

(b) Using the Summability relation, for two arbitrary components (1 & 2) please prove:
[2.5 + 2.5 = 5 Marks]

dM dM
M 1  M  x2 and M 2  M  x1
dx1 dx1
(c) Hence using the results in (b), if H E  x1 x2 (40 x1  20 x2 ) at constant T and P, then
prove: [ 5 Marks]

H 1E  20  60 x12  40 x13 and H 2E  40x13

(d) Beginning with the ideal solution model iig  Giid  Gi  RT ln xi , prove that:
[2.5 + 2.5 = 5 Marks]
G   xi Gi  RT  xi ln xi
id
and S id
  xi S i  R xi ln xi

4. (a) (i) Define Excess property and using result obtained in 3(d), prove: [ 2 Marks]

S mix   R  xi ln xi for an ideal mixing process

(iii) For the system chloroform and benzene at 308K, the enthalpy of mixing is
expressed by

H E  x(1  x)[h0  h1 (1  2 x)  h2 (1  2x) 2 ] Jmol -1

2
 For an equimolar mixture, H E  423 Jmol -1 ,
h0  h1  h2  1275 Jmol -1
h0  h1  h2  1935 Jmol -1

Calculate: 1. The constants h0, h1 and h2 [2 Marks]

E
2. Prepare a table for H vs x{0,0.1,0.2,..1.0} [2 Marks]
3. Find S mix for an equimolar mixture [2 Marks]
4. Considering TS mix  TS E , find G E [2 Marks]

(b) Wilson’s equation for estimating the activity coefficient is given by:
[2.5+2.5=5 Marks]
  12  21 
ln  1   ln( x1  x 2  12 )  x 2   
 1
x  x 
2 12 x 
1 21  x 2 

  12  21 
ln  2   ln( x 2  x1  21 )  x1   
 x1  x 2  12 x1  21  x 2 
V2   A12  V   A21 
where,  12  exp  and  21  1 exp 
V1  RT  V2  RT 
Also, given: (i) A12 = 1718 cal/mol and A21 = 166.6 cal/mol
(iv) P1
sat
 3.23 mm Hg; P2
sat
 187.1 mmHg
(v) 1  0.8144 g/ml (1 mole/88g);  2  0.6603 g/ml (1 mole/86g)

Find the composition of the vapor in equilibrium with a liquid containing 20 mole%
n-pentanol at 30oC. Also calculate the equilibrium pressure.

(c) Show that the molar free energy of mixing is minimum when: [2.5 + 2.5 = 5 Marks]

(i) Binary system two gases are present in equimolar ratio

(ii) Ternary system when three gases are present in ratio of 1/3

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