Code No: RR310802 Set No.

1
III B.Tech I Semester Supplimentary Examinations, November 2007
CHEMICAL ENGINEERING THERMODYNAMICS-II
(Chemical Engineering)
Time: 3 hours Max Marks: 80
Answer any FIVE Questions
All Questions carry equal marks
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1. (a) Calculate the heat required to raise the temperature of 10 kg of ethylene from
1000 C to 7000 C using the following data:

T(K) 298 500 700 1000

Cp(j/mol) 43.5 63.4 78.4 94.3
(b) List the various methods for calculating the latent heat of vapourisation.[10+6]

2. One method for the manufacture of “synthesis gas” (primarily a mixture of CO

and H2 ) is the catalytic reforming of CH4 with steam at high temperature and
atmospheric pressure;
CH4(g) + H2 O(g) → CO(g) + 3H2(g) ∆H298 = 205, 813 J
The only other reaction which occurs to an appreciable extent is the water-gas-
shift reaction,
CO(g) + H2 O(g) → CO2(g) H2(g) ∆H298 = −41, 166 J
If the reactants are supplied in the ratio, 2 mol steam to 1 mol CH4 and if heat is
supplied to the reactor so that the products reach a temperature of 1,300 K, the
CH4 is completely converted and the products stream contains 17.4 mol % CO.
Assuming the reactants to be preheated to 600 K, calculate the heat requirement
for the reactor. [16]

3. Derive the relation for the calculation of Gibbs free energy of ideal gas mixture.

[16]

4. (a) The van Laar constants A and B for the system 1-propane
i. chlorobenzene
ii. are 1.1239 and 1.2586 respectively. Calcualte γ1 , γ2 at x1 = 0.2,0.4and 0.6
mol/mol.
(b) Calculate the heat of formations of LiCl in 12 moles of H2 O at 250 C. It is
given that heat of formation of Licl (∆H298 ) − 408.6103 and the heat evolved
when mixing of one mole of Licl in 12 moles of H2 O is 336143. [8+8]

5. (a) Characterize ideal solutions.

(b) Two substances A and B are known to form ideal solution. An equimolar
vapor mixture of A and B initially at 100 C and 100 Kpa is isothermally
compressed till the mixture condenses. Determine the pressures at which

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Code No: RR310802 Set No. 1
condensation begins and terminates and also the compositions of the vapor
and liquid phases. The saturation pressures of A and B at 100 C are 120 Kpa
and 150 Kpa, respectively. [6+10]

6. For the system methanol(1)-water (2)make the following calculations using WIL-
SON equation:
The pure component vapour pressures are given by :

3644.30
ln P1sat /kP a = 16.5938 − t/0 C+239.76
3799.89
ln P2sat /kP a = 16.2620 − t/0 C+226.35

(a) BUBL P at t = 60 0 C ; x1 = 0.3

(b) Dew P at t = 60 0 C ; y1 = 0.3
(c) P-t flash at t = 60 0 C ; P = (Pbubl + Pdew ) / 2 ; z1 = 0.3 [16]
nio +vi ε
7. (a) Prove yi = no +vε
, all notations have their usual measuring.
(b) Derive an equation for reaction co-ordinate and explain how this equation can
be used for practical purposes. [8+8]

8. (a) Derive Van’tHoff equation from the fundamentals and discuss its applications.
(b) It is desired to produce industrial methanol from the synthesis gas according
to the reaction
CO(g) + 2H2 (g) → CH3 OH(g)Calculate the equilibrium conversion at 1.5 bar
and 30000 C if the stoichiometric quantities are used in the above reaction.
(K30000 C=1.9×10−2 ).
[8+8]

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Code No: RR310802 Set No. 2
III B.Tech I Semester Supplimentary Examinations, November 2007
CHEMICAL ENGINEERING THERMODYNAMICS-II
(Chemical Engineering)
Time: 3 hours Max Marks: 80
Answer any FIVE Questions
All Questions carry equal marks
⋆⋆⋆⋆⋆

1. If the heat capacity of a substance is correctly represented by an equation of the

form, CP = A + BT + CT 2
Show that the error resulting when < Cp >H is assumed equal to CP evaluated at
the arithmetic mean of the initial and final temperature is C(T2 − T1 )2 / 12. [16]

2. (a) Calculate the heat of reaction of the following reaction:

B + 6E → 2D, ∆Hr0 =?
0
Given: 2A + B → 2C, ∆Hr1 = -1000 (kJ/mol)
0
And A + D → C + 3E, ∆Hr2 = -2000 (kJ/mol)

(b) Explain: Hess’s law, standard enthalpy of reaction, mole of reaction, standard
state used in heat effects calculations. [8+8]

3. (a) What is the property that is the contribution of a component as it exists in a

solution and defines it mathematically? Give two examples.
(b) It is required to prepare 3 m3 of a 60 mole percent ethanol − water mixture.
Determine the volumes of ethanol and water to be mixed in order to prepare
the required solution. The partial molar volumes of ethanol and water in 60
mole percent ethanol-water mixture are: V1 = 57.5 x 10−6 m3 /mol (ethanol);
V2 = 16 x 10−6 m3 /mol; The molar volumes of the pure components are:
Ethanol, v1 = 57.9x10−6 m3 /mol, Water, v2 = 18 x 10−6 m3 /mol. [8+8]

4. (a) Show that the partial molar mass of a species in a solution is equal to its molar
mass (molecular weight).
(b) The excess Gibbs free energy of a binary liquid mixture at T and P is given
E
by G
RT
= ( -2.6 x1 -1.8x2 )x2 x1 . For the given T and P, find lnγ1 . and lnγ2 .
(c) Define acitivity and activity coefficient. [4+8+4]

5. (a) The excess Gibbs energy for a binary system is given by :

GE / RT = A X1 X2
Obtain the corresponding expressions for ln γ1 and ln γ2
(b) Describe the vapor/liquid equilibrium calculation procedure for BUBL P .
vapor and liquid phases can be considered as non-ideal. [8+8]

6. Explain with flowchart for Flash calculations along with relevant equations. [16]
RT Hil −His
7. Prove:ψi = exp RT 2
dT for SLE. All notations have their usual meaning. [16]
Tmi

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Code No: RR310802 Set No. 2
8. Derive an equation from the fundamentals to describe the effect of temperature on
‘K’ in terms of ∆H 0 , ∆α ∆β ∆γ etc. Discuss the practical application of above
derived equation with reference to any chemical reaction. [16]

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Code No: RR310802 Set No. 3
III B.Tech I Semester Supplimentary Examinations, November 2007
CHEMICAL ENGINEERING THERMODYNAMICS-II
(Chemical Engineering)
Time: 3 hours Max Marks: 80
Answer any FIVE Questions
All Questions carry equal marks
⋆⋆⋆⋆⋆

1. (a) Explain the role of thermodynamics is studying the heat effects accompanying
phase changes and chemical reactions.
(b) Consider water at 2270 C. Calculate its latent heat by using the clapyron equa-
tion and clasius clapeyron equation and compare the results. Use vapour data
at 290 and 510K. [8+8]

T(K) 490 500 510

P sat (Mpa) 2.181 2.637 3.163
V g (m3 /kg) 0.0915 0.0758 0.06323
V 1 (m3 /kg) 0.00118 0.00120 0.00122

2. If ∆CP = ∆B(T ) + ∆C(T 2 ) + ∆A ,

Derive ∆H o T = ∆H 1 + ∆A.T + ∆B 2
T2 + ∆B 3
2
T All notations have their usual
meaning. [16]

3. (a) Derive an expression for estimating fugacity of a liquid at a given T and P.

(b) The partial molar volume of methanol in a methanol
i. water
ii. solution at x1 (mol.fraction) = 0.3881 is 39.176 x 10−6 m3 /mol. The
density of the mixture is 905.376 kg/m3 . Calculate the partial molar
volume of water in the solution. [8+8]

4. Define property change of mixing and derive the relations for the calculation of
thermodynamics properties for ideal solutions. [16]

5. For a binary system, the excess Gibbs energy of the liquid phase is given by an
equation of the form : GE / RT = A x1 x2 , where A is a function of temperature
only. Using modified Raoult’s law, show that :
P1sat
(a) α12 (x1 = 0) = P2sat
exp(A)
(b) Henry’s law constant for species ‘1’ is given by, k1 = P1sat exp (A)
(c) At every temperature at which azeotrope exists, xaz
1 andP
az
are related as :
"  paz  #
ln
 p1az 
sat
1
xaz
= 1+ p
[6+6+4]
1 ln
psat
2

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Code No: RR310802 Set No. 3
6. Estimate V,H R and S R for an equimolar mixture of CO2 and propane at 450 K
and 140 bar by the Redlich/kwong equations. [16]
Data:
ij Tcij (K) pcij (bar) Vcij (cm3 /mol) Zcij Wij
11 304.2 73.83 94.0 0.274 0.224
22 369.8 42.48 200.0 0.276 0.152
12 335.4 54.62 140.4 0.275 0.188

7. (a) What are the criteria for chemical reaction equilibrium. Discuss in detail?
(b) For a system in which the following reaction occurs:
CH4 + H2 O → CO + 3H2
Assume there are present initially 2 mol CH4 , 1mol H2 O, 1 mol CO and 4 mol
H2 . Determine expressions for the mole fractions yi as function of E. [8+8]

8. (a) Derive the equation from the fundamentals, ∆G0 = - RTlnK

(b) Discuss the importance of equilibrium constant and its effect on equilibrium
conversion. [8+8]

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Code No: RR310802 Set No. 4
III B.Tech I Semester Supplimentary Examinations, November 2007
CHEMICAL ENGINEERING THERMODYNAMICS-II
(Chemical Engineering)
Time: 3 hours Max Marks: 80
Answer any FIVE Questions
All Questions carry equal marks
⋆⋆⋆⋆⋆

1. (a) Discuss the integral form of Clausius Clapeyron equation and it’s applications.
(b) The mean heat of vaporisation of water in the temperature range between
900 C and 1000 C is 542 Cal. g −1 . Calculate the vapour pressure of water at
900 C, the value at 100.00 C being 76.0 cm. [8+8]

2. (a) Explain: Standard heat of reaction, enthalpy of formation, enthalpy of com-

bustion.
(b) Calculate the standard heat of the following reaction at 298K:
C5 H12 (g) + 802 (g) → 5CO2 (g) + 6H2 O(1)
The standard heats of formation are as follows:
CO2 (g) = (-393.509)kJ
H2 O(g) = (-241.818)kJ
C5 H12 (g) = (-146.76)KJ.
The latent heat of vapourization of water at 298K = 43.967 kJ/mol. [9+7]
n
3. (a) Develop a general equation for calculation of Inφi values from compressibility
factor data.
(b) Estimate the value of fugacity of 1-butene vapor at 2000 C and 70bar. Given
data:
ω= 0.191,φ0 = 0.627, φ1 = 1.096. [10 + 6]

4. (a) What is meant by data reduction? Explain how P − x − y data is reduced?

(b) The excess Gibbs free energy of a binary liquid mixture at T and P is given
E
by G RT
= ( 1.42x1 + 0.59x2 )x2 x1 . The vapour pressures are P1Sat = 82.37
Kpa, P2Sat = 37.31 Kpa. For given T and P, Using Margules equation find
γ1 , γ2 and γ1α , γ2α . [8+8]

5. Elucidate the vapor-liquid equilibrium of binary systems with the help of p-x-y and
t-x-y diagrams. [16]

6. Calculate the fraction of liquid, liquid composition and vapor composition in a two
phase system consisting of acetone
acetonitrile - nitromethane at 800 C and 110 Kpa. The overall composition of the
mixture is Z=0.45, Z=0.35 and Z=0.2. The vapor pressures of the components (1),
(2) and are 195.8 Kpa, 97.84 Kpa and 50.32 Kpa respectively. [16]

7. (a) What are the criteria for chemical reaction equilibrium. Discuss in detail?

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Code No: RR310802 Set No. 4
(b) For a system in which the following reaction occurs:
CH4 + H2 O → CO + 3H2
Assume there are present initially 2 mol CH4 , 1mol H2 O, 1 mol CO and 4 mol
H2 . Determine expressions for the mole fractions yi as function of E. [8+8]

8. Carbon deposits in reactors are removed by passing hydrogen:

C +2H2 ⇔ CH4 In one such process at a pressure of 2 bar and 10000 K the effluent
gas contained 15 mole % CH4 and 85 mole % H2 . If the standard free energy for
this reaction at 10000 K is 21000 KJ / K mole, can greater amount of methane be
obtained under these conditions? What will be the quantity of CH4 obtained if
pressure is 1 atm? [16]

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