BITS, PILANI, GOA CAMPUS, FIRST SEMESTER 2019 – 2020

COMPREHENSIVE EXAM: CHEMICAL ENGINEERING THERMODYNAMICS

DATE: 02/12/19 TIME: 180 minutes MAX. MARKS: 80

(ALL QUESTIONS ARE COMPULSORY. MAKE SUITABLE ASSUMPTIONS WHEREVER

1. Please answer the following

(a) 1 kmol of water is heated at constant pressure of 14 bar from a temperature of 294K
(21oC) to the boiling point and then completely vaporized at this pressure. Determine
the portion of the heat transferred that is unavailable for transformation to work in a
heat engine assuming the heat sink to be at 283K [8 Marks]
Data: Boiling point of water at 14 bar = 468K
Latent heat of vaporization = 1960 kJ/kg
CP of water = 4.187 kJ/(kg.K)

(b) An ideal gas at 300K and 1000 kPa enters a rigid and insulated apparatus. This gas
leaves the apparatus in two streams in equal quantities, one is at 360K and 100 kPa and
the other is at 240K and 100 kPa. Calculate the total entropy change. Is the process
thermodynamically possible? Data: CP = 30kJ/(kmol.K) [4 Marks]

2. Please answer the following

(a) Starting from the combined 1st and 2nd Laws, derive the four Fundamental Property
relations and Maxwell’s relations (in detail). [4 Marks]

   V / T P 
 
(b) Prove: dU    P  T   dv  CV dT [4 Marks]
 
  V / P  
T 

 H   T CV
(c) If S  S (T , V ), Prove :    
 V  P  V
(symbols have usual meanings) [6 Marks]

(d) Prove the following: [6 Marks]

  CP  CV   
dH  CP dT  V   dP
  

1
3. (a) Please derive Gibbs – Duhem equation expression for constant pressure and constant
temperature (in detail starting from basic assumption of Gibbs energy as function of
mole numbers) [6 Marks]

dM dM
(b) Derive (for a binary sytem) : M1  M  x2 and M 2  M  x1 , where (M is any
dx1 dx1
thermodynamic property of solution and M1 and M 2 are respective partial properties
of components. [6 Marks]

(c) Using expressions derived in (b) solve: [8 Marks]

The molar volume of a binary mixture at T and P is given by:

4. (a) Benzene (1) and ethyl benzene (2) form an ideal solution [6 Marks]
Vapor pressure of benzene and ethyl benzene are given by Antoine equation :
2788.51
ln P1sat  13.8858 
T  52.41
3279.47
ln P2sat  14.0045 
T  60
sat
where P is in kPa and T is in K
Prepare a P-x-y table at 373 K

(b) Tabulate P-x1-y1 data for the system Cyclohexane (1) – Benzene (2) at 313K.
Data: At 313 K, the vapor pressure of Cyclohexane is 24.62 kPa and Benzene is 24.41
kPa. The liquid phase activity coefficients are given by: [6 Marks]

ln  1  0.458 x22 , ln  2  0.458 x12

(c) Ethanol and hexane form an azeotrope containing 33.2 mole% ethanol boiling at 331.9
K at 101.3 kPa. The vapor pressures of ethanol and hexane at 331.9 K are 411.25 kPa
and 72.24 kPa, respectively. [8 Marks]
(i) Calculate the van Laar constants
(ii) Calculate the vapor composition for a solution containing 50 mole% hexane
boiling at a temperature of 331.9K

2
 Given (van Laar constants) :
2 2
 x ln  2   x1 ln  1 
A  ln  1 1  2  , B  ln  2 1  
 x1 ln  1   x2 ln  2 
and
Ax22 Bx12
ln  1  , ln  2 
 A / B  x1  x2   x1   B / A  x2 
2 2

(d) Derive the expression in detail [8 Marks]

Z 1
P
f
ln  dP
P 0 P
Hence, determine the fugacity of oxygen at 20oC (293K) and 100 bar
Data: a=1.0, b= - 0.753×10-3 and c = 0.15×10-5
Z = a + bP + cP2

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when you fail, and both are equally important.” - Ellen DeGeneres