Seat No.: ________ Enrolment No.
___________
GUJARAT TECHNOLOGICAL UNIVERSITY
BE - SEMESTER–V (NEW) - EXAMINATION – SUMMER 2018
Subject Code:2150503 Date:30/04/2018
Subject Name:Chemical Engineering Thermodynamics - II
Tim[Link] PM to 05:00 PM Total Marks: 70
Instructions:
1. Attempt all questions.
2. Make suitable assumptions wherever necessary.
3. Figures to the right indicate full marks.
Marks
Q.1 (a) A gas mixture containing 3 mol of CO2, 5 mol H2 and 1 mol water vapor is 03
undergoing the following reaction. Develop expressions for the mole fraction of
the species in terms of the extent of reaction.
CO2 + 3H2 CH3OH + H2O and CO2 + H2 CO + H2O
(b) n–butane is isomerized to i–butane by the action of catalyst at moderate 04
temperature. It is found that the equilibrium is attained at 317 K with 31 mol %
n–butane and at 391 K with 43 mol % n–butane. Assume that activities are equal
to the mole fractions, calculate the standard free energy of the reaction at 317 K
and 391 K and average value of heat of reaction over this temperature range.
(c) The enthalpy at 300 K and 1 bar of a binary liquid mixture is represented by the 07
equation: H = 400 X1 + 600 X2 + X1 X2 (40X1 + 20X2), where H is in J/mol.
Determine expressions for H 1 and H 2 as functions of X1, numerical values for
the pure species enthalpies H1 and H2, and numerical values of partial enthalpies
at infinite dilution H1 and H 2 .
Q.2 (a) A 30% by mole methanol-water solution is to be prepared. How many cubic 03
meters of pure methanol (molar volume 40.727 x 10 – 6 m3/mol) and pure water
(molar volume 18.068 x 10 – 6 m3/mol) are to be mixed to prepare 2 m3 of the
desired solution? The partial molar volumes of methanol and water in 30%
solution are 38.632 x 10 – 6 m3/mol and 17.765 x 10 – 6 m3/mol respectively.
(b) Discuss the effect of temperature and pressure on chemical potential of species 04
in the solution.
(c) Discuss the property change of mixing and also derive expression for volume 07
change of mixing in term of activity of species in a binary solution.
OR
(c) Derive the Gibbs – Duhem equation for a binary solution in terms of activity and 07
activity coefficient.
Q.3 (a) Discuss the different conditions under which the Lewis – Randall rule becomes 03
applicable.
(b) Discuss the excess Gibbs free energy and its relation with activity coefficient 04
and excess chemical potential.
(c) Derive relation between equilibrium constant and composition for homogeneous 07
gas and liquid phase reaction.
OR
Q.3 (a) Write a brief note on T – x – y diagram for partially miscible system. 03
(b) Discuss the Gamma / Phi formulation for vapor – liquid equilibrium. 04
(c) Using fundamental properties relation establish expression of standard Gibbs 07
free energy change of chemical reaction as a function of thermodynamic
equilibrium constant.
Q.4 (a) Discuss Non Random Two Liquid equation used to determine activity co- 03
efficient for vapor – liquid equilibria at low pressure.
(b) Derive the expression used to estimate fraction of initial mixture that is 04
vaporized at equilibrium using flash vaporization calculation.
(c) A mixture contains 45% (mol) methanol (A), 30% (mol) ethanol (B) and the rest 07
n-proponal (C). Liquid solution may be assumed to be ideal and perfect gas law
is valid for the vapor phase. Calculate (i) the bubble point and the vapor
composition (ii) the dew point and the liquid composition at a total pressure of
101.3 kPa. The vapor pressures of the pure liquid are given below.
Temperature, K 333 343 353 363
PA, kPa 81.97 133.29 186.61 266.58
PB, kPa 49.32 73.31 106.63 166.61
PC, kPa 39.32 62.65 93.30 133.29
OR
Q.4 (a) Discuss van Laar equations used to determination of activity co-efficient for 03
vapor – liquid equilibria at low pressure with suitable examples.
(b) Discuss the thermodynamic consistency of experimental VLE data using the 04
slopes of ln curves for a binary solution.
(c) Water (1) – hydrazine (2) system forms an azeotrope containing 58.5% (mol) 07
hydrazine at 393 K and 101.3 kPa. Calculate the equilibrium vapor composition
for a solution containing 20% (mol) hydrazine. The relative volatility of water
with reference to hydrazine is 1.6 and may be assume to remain constant in the
temperature range involved. Vapor pressure of hydrazine at 393 K is 124.76 kPa.
Q.5 (a) Discuss criteria of chemical reaction equilibrium with neat sketch. 03
(b) Discuss various methods used for evaluation of equilibrium constant. 04
(c) Calculate standard Gibbs free energy change and equilibrium constant at 700 K 07
for the reaction: N2(g) + 3H2(g) 2NH3(g) given that the standard heat of
formation and standard free energy of formation of NH3 at 298 K to be – 46100
J/mol and – 16500 J/mol respectively. The specific heat (J/mol K) as a function
of temperature for nitrogen, hydrogen and ammonia are as given below.
CP, N2 = 27.27 + 4.93 10 – 3 T
CP, H2 = 27.01 + 3.51 10 – 3 T
CP, NH3 = 29.75 + 25.11 10 – 3 T
OR
Q.5 (a) List out the factors affecting equilibrium constant and explain any two in detail. 03
(b) Consider a vessel which initially contains only no moles of water vapor. If 04
decomposition occurs according to the reaction: H2O H2 + 0.5O2
Find expressions which relate the number of moles and mole fraction of each
chemical species to the reaction co-ordinate and fractional decomposition of
water vapor.
(c) Estimate the maximum conversion of ethylene to ethanol by vapor phase 07
hydration at 250 0C and 35 bars for an initial steam to ethylene ratio of 5. The
thermodynamic equilibrium constant is 9.841 x 10 – 3 at temperature of 250 0C.
The critical properties and acentric factor of the components are given below.
Components Tc (K) Pc (bar) i
C2H4 282.4 50.4 0.085
H2O 647.3 220.5 0.344
C2H5OH 516.2 63.8 0.635
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