Chemical Engineering Thermodynamics CHEN 2001

Thermodynamics CHEN5025

Maximum Marks 50 Max Time 2 Hr

Please attempt all questions. Please be neat, precise and to the point. Sheets of formulae are
attached for your ready reference. Please note that some of the formulae may not be needed to
solve this question paper. All questions carry equal marks.

Q1. Van der Waal’s equation of state for a gas is derived from the generic cubic equation of state

for which a(T) = a and ε= σ =0. The constants a and b are given by the following equations:

The units of a and b are cm6 bar and cm3 respectively. For propane at 320 K and 9.6283 bar,
find the vapour or vapour-like root for 1 mol of propane at these conditions using van der
Waal’s equation of state. Tc = 369.8 K and Pc = 42.48 bar for propane. Take R = 83.14 cm3
bar/mol.K. Give your answer to the nearest cm3.

(10 Marks)

Q2. One mol of an ideal gas is expanded isothermally but irreversibly at 140 °C from 6 bar to 2
bar. The work produced is 70% of the work of reversible isothermal expansion. Heat is
transferred from a hot reservoir at 300 °C to the gas. R = 8.314 J/mol.K and Cp = (7/2)R.

(a) Calculate the entropy changes of the gas, the hot reservoir and ∆S total .
(b) Find the maximum work that can be extracted from an ideal gas at 140 °C and 6 bar, if
the surroundings are at 25 °C and 1 bar.

(10 Marks)

Page 2 of 7
Q3. Show that an isotherm in the vapour region of a Mollier diagram (co-ordinates H-S) has a
slope given by
𝜕𝜕𝜕𝜕 1
� � = (𝛽𝛽𝛽𝛽 − 1)
𝜕𝜕𝜕𝜕 𝑇𝑇 𝛽𝛽

At 300 °C, if superheated steam undergoes an enthalpy change of -30.6 kJ/kg, calculate the
corresponding specific entropy change, if β = 0.00393 K-1. Give your answer to 3 decimal
places.

(10 Marks)

Q4. The reaction of styrene (C 6 H 5 CH-CH 2 ) with hydrogen reaches equilibrium at 650 °C and 5
bar. If the system initially contains 2 mols of H 2 for each mol of styrene, calculate the
equilibrium composition. Assume ideal gas behaviour, with the equilibrium constant K =
1.3667 at 650 °C.

𝐶𝐶6 𝐻𝐻5 𝐶𝐶𝐶𝐶 − 𝐶𝐶𝐻𝐻2 (𝑔𝑔) + 𝐻𝐻2 (𝑔𝑔) → 𝐶𝐶6 𝐻𝐻5 𝐶𝐶2 𝐻𝐻5 (𝑔𝑔)

(10 Marks)

Q5. A liquid mixture of methanol (1)/methylacetate (2) is at equilibrium with its vapour at 45 °C.
The system forms an azeotrope at 45 °C for which 𝑥𝑥1𝑎𝑎𝑎𝑎 = 𝑦𝑦1𝑎𝑎𝑎𝑎 = 0.325 . The following
equations provide a correlation for the activity coefficients:
lnγ 1 = Ax 2 2 and lnγ 2 = Ax 1 2
In addition, the following Antoine equations provide vapour pressures:
3643.31
ln P 1 sat = 16.59158 − 𝑇𝑇−33.424
2665.54
ln P 2 sat = 14.25326 − 𝑇𝑇−53.424
where T in in kelvins and the vapour pressures are in kPa.

Determine the equilibrium pressure P and vapour compositions {y i } at 45 °C when x 1 = 0.7.

Give your answers to 2 decimal places.

(10 Marks)

Formulae from Page 4 to 7

End of Examination Paper
Page 3 of 7
 Semester 2 and Trimester 3B 2015
CHEN2001 Chemical Engineering Thermodynamics

Formula Sheet
Note: These formulae have been provided for your ready reference. But it does
not guarantee that all the formulae needed to solve this question papers have
been included.

T2

∫ CV dT
∆U idealgas =
T1

T2

∫ CP dT
∆H idealgas =
T1

Q = RT Ln (V 2 /V 1 ) = RT Ln (P 1 /P 2 )

W = -R (T 2 – T 1 )

TVγ-1 = constant

TP(1-γ)/ γ = constant

PVγ = constant

 ∂S 
CP = T  
 ∂T P
 ∂S 
CV = T  
 ∂T V

F = 2 −π + N

Page 4 of 7
 Semester 2 and Trimester 3B 2015
CHEN2001 Chemical Engineering Thermodynamics

Basic Thermodynamic Relations:

Maxwell Relations:

___________________________________________________________________________

where and

___________________________________________________________________________

Page 5 of 7
 Semester 2 and Trimester 3B 2015
CHEN2001 Chemical Engineering Thermodynamics

+ ≥0

__________________________________________________________________________
yi P = xiγ i Pi sat

y i P = xi H i
 ∂M   ∂M 
d (nG ) = (nV )dP − (nS )dT + ∑ µ i dni   dP +   dT − ∑ xi dM i = 0
i  ∂P  T , x  ∂T  P , x i

H ig = ∑ yi H iig
i

S ig = ∑ yi S iig − R ∑ yi ln yi
i i

G ig = ∑ yi Giig + RT ∑ yi ln yi
i i

µ iig = Γi (T ) + RT ln( yi P )

GiR = RT ln φi

fi
φi ≡
P
Gi R = RT ln φˆi

fˆi
φˆi ≡
yi P

µ iid = Gi (T , P ) + RT ln xi

V id = ∑ xiVi H id = ∑ xi H i
i i

S id = ∑ xi S i − R ∑ xi ln xi
i i

G id = ∑ xi Gi + RT ∑ xi ln xi
i i

d ln fˆ1 d ln fˆ2
x1 + x2 =0
dx1 dx1

GE
= ∑ xi ln γ i
RT i

Page 6 of 7
 Semester 2 and Trimester 3B 2015
CHEN2001 Chemical Engineering Thermodynamics

  nG E 
 ∂  
ln γ i =   
RT
 ∂ni 
 
  P ,T ,n j

∑ν µ
i
i i =0

___________________________________________________________________________
− RT ln K = ∆G o

d ln K ∆H 0
=
dT RT 2
v
P
∏ (y )
νi
K =   i
 P0  i

∆G 0 = ∆H 0 − T ∆S 0

END OF FORMULA SHEET

Page 7 of 7