GUJARAT TECHNOLOGICAL UNIVERSITY

CHEMICAL ENGINEERING (05)

CHEMICAL ENGINEERING THERMODYNAMICS – II
SUBJECT CODE: 2150503
B.E. 5th SEMESTER

Type of course: Chemical Engineering

Prerequisite: Chemical Engineering Thermodynamics- I

Rationale: This course introduces the basic thermodynamics concepts of multiphase equilibrium in pure and
multi-component systems. Starting with ideal gas mixtures and ideal solutions, the concepts of bubble and
dew points are introduced to enable flash calculations and design of process components. Subsequently,
various levels of non-ideality and complexity are introduced: 1) activity coefficient models for non-ideal
liquid mixtures, 2) fugacity calculations of gas and liquid phases from equations-of-state, 3) systems with
chemical reactions. The course provides fundamental insight into the underlying thermodynamic principles,
as well as practice with advanced computational techniques to solve complex problems.

Teaching and Examination Scheme:

Teaching Scheme Credits Examination Marks Total

L T P C Theory Marks Practical Marks Marks
ESE PA (M) ESE (V) PA
(E) PA ALA ESE OEP (I)
3 2 0 5 70 20 10 30 0 20 150

Content:

Sr. No. Content Total % Weightage

Hrs

1 Vapour/Liquid Equilibrium (VLE): Introduction 12 22

The Nature of Equilibrium, the Phase Rule, Duhem’s Theorem, VLE-
Qualitative Behaviour, Azeotropic Mixtures, Maximum Boiling
Azeotrope, Minimum Boiling Azeotrope, Simple Models for
Vapour/Liquid Equilibrium ,Raoult’s Law, Dewpoint and Bubblepoint
Calucations with Raoult’s Law ,VLE by Modified Raoult’s Law,VLE
from K,Value Correlations, Flash Calculations
2 Solution Thermodynamics: Theory 12 22
Fundamental Property Relation, The Chemical Potential as a Criterion for
Phase Equilibria, Partial Properties, Equations Relating Molar and Partial
Molar Properties , The Partial Molar Gibbs Energy and the Generalized
Gibbs-Duhem Equation, Partial Properties in Binary Solutions, Relations
among Partial Properties, The Ideal Gas Mixture , The Partial Molar Gibbs
Energy and Fugacity, Fugacity and Fugacity Coefficient: Pure Species,
Fugacity and Fugacity Coefficient: Species in Solution ,The Ideal Solution
Model , The Lewis/Randall Rule , Excess Properties , The Excess Gibbs
Energy and the Activity Coefficient, Nature of Excess Property
3 Solution Thermodynamics: Applications 12 22
Liquid-Phase Properties from VLE Data ,Composition Dependence of
Liquid- Phase Fugacities for Species in a Binary Solution, Excess Gibbs
 Energy, Data Reduction, Thermodynamic Consistency, Integral or Area
Test Method , Models for the Excess Gibbs Energy, Margules Equations,
VanLaar Equations, Calculations with Margules and VanLaar Equations,
Local Composition Models, NRTL Equation, UNIQUAC Equation,
UNIFAC Method, Enthalpy/ Concentration Diagrams
4 Chemical Reaction Equilibria: 12 22
The reaction coordinates, Application of the criteria for equilibrium to
chemical reactions, the standard Gibbs free energy change and the
equilibrium constant, effect temperature on equilibrium constant,
evaluation of the equilibrium constant, Relation of equilibrium constant to
composition, calculation of equilibrium conversion for single reaction,
The phase rule and Duhem’s theorem for reacting systems, multireaction
Equilibria
5 Phase Equilibria: 6 12
The Gamma / Phi Formulation of VLE, Equilibrium and stability, liquid-
liquid equilibrium, solid- liquid equilibrium, osmotic equilibrium and
osmotic pressure

Suggested Specification table with Marks (Theory):

Distribution of Theory Marks

R Level U Level A Level N Level E Level C Level

7 28 21 7 7 -

Legends: R: Remembrance; U: Understanding; A: Application, N: Analyze and E: Evaluate C: Create and above
Levels (Revised Bloom’s Taxonomy)

Note: This specification table shall be treated as a general guideline for students and teachers. The actual
distribution of marks in the question paper may vary slightly from above table.

Reference Books:

1. Smith J.M, Van Ness H.C., Abbott M. M, "Introduction to Chemical Engineering Thermodynamics",
the McGraw Hill Companies, Inc., USA, 7th Ed., 2005.
2. Elliot J. R. and Lira C.T., "Introductory Chemical Engineering Thermodynamics", Prentice Hall,
1999.
3. Hougen O.A., Watson K.M., and Ragatz R.A., “Chemical Process Principles Part,II”
Thermodynamics, John Wiley 1970.
4. Perry’s chemical engineers handbook, 7th edition, McGraw,Hill, USA, 2000.
5. K.V.Narayanan “A Text book of chemical Engineering thermodynamics”, Prentice Hall of India
6. Stanley I. Sandler, “Chemical, Biochemical and Engineering Thermodynamics”, Wiley
India Pvt. Ltd., 4th ed., 2007.
7. B.G. Kyle,"Chemical Process Thermodynamics", 2nd Edn., Prentice Hall of India Pvt.Ltd., New
Delhi, 2000.
8. J.M.Prausnitz, R.N. Litchtenthaler, Molecular thermodynamics of fluid phase Equilibria, 3rd
Edition,Prentice Hall.
9. Stanley M. Walas, Phase-Equilibria in Chemical Engineering,Wiley India Private Limited
Course Outcome:

After learning the course the students should be able to:

1. Solution thermodynamics fundamentals. Application of Raoult’s law and its variation to obtain VLE
for binary systems.
2. Understand partial molar properties of components in a particular phase, and apply to calculations
of heat of mixing, volume, and entropy changes on processing of ideal and real mixtures.
3. Azeotrope and its importance.
4. Estimating thermodynamic properties like fugacity, activity from the network of equations.
5. Solution Thermodynamics calculating the thermodynamic properties from experimental data.
Different Activity coefficient models.
6. Data reduction to get constants of different activity coefficient models.
7. Predict the equilibrium products and their concentration in equilibrium when dealing with systems
involving chemical reactions. The topic will include Homogeneous and Heterogeneous reaction. You
will also get an introductory knowledge of multi reaction equilibrium.

List of Open Source Software/learning website:

1. Students can refer to video lectures available on the websites including NPTEL lecture series.
2. Students can refer to the CDs available with some reference books for the solution of problems using
software/spreadsheets. Students can develop their own programs/spreadsheets for the solution of
problems.

ACTIVE LEARNING ASSIGNMENTS: Preparation of power-point slides, which include videos,

animations, pictures, graphics for better understanding theory and practical work – The faculty will allocate
chapters/ parts of chapters to groups of students so that the entire syllabus to be covered. The power-point
slides should be put up on the web-site of the College/ Institute, along with the names of the students of the
group, the name of the faculty, Department and College on the first slide. The best three works should submit
to GTU.
Seat No.: ________ Enrolment No.___________

GUJARAT TECHNOLOGICAL UNIVERSITY

BE - SEMESTER–V (NEW) - EXAMINATION – SUMMER 2017
Subject Code: 2150503 Date: 01/05/2017
Subject Name: Chemical Engineering Thermodynamics-II
Time: 02:30 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.
 Seat No.: ________ Enrolment No.___________

GUJARAT TECHNOLOGICAL UNIVERSITY

BE - SEMESTER–V (NEW) - EXAMINATION – SUMMER 2016
Subject Code:2150503 Date:09/05/2016
Subject Name:Chemical Engineering Thermodynamics - II
Time:02:30 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.

Q.1 (a) Discuss the consistency tests for VLE data by using Gibbs-Duhem equation. 07
(b) The following table gives composition v/s total pressure data for the system 07
chloroform (1)/ethanol (2) at 328 K:
x1 0.0331 0.9652
P, kPa 40.84 84.88
Vapour pressures of chloroform and ethanol at 328 K are 82.35 kPa and 37.30
kPa respectively. Estimate the constants in the Margules equation.
Q.2 (a) Show that for a binary system, Henry’s law is valid for component ‘1’ then 07
Lewis Randall rule is valid for component ‘2’.
(b) The azeotrope of the ethanol-benzene system has a composition of 44.8 mol% 07
ethanol with boiling point of 341.4 K at 101.3 kPa. At this temperature, the
vapor pressure of benzene is 68.9 kPa and the vapor pressure of ethanol is 67.4
kPa. What are the activity coefficients in a solution containing 10% ethanol.
(Use VanLaar equations).
OR
(b) Write a brief note on retrograde condensation and its application. 07
Q.3 (a) Define fugacity and fugacity coefficient. Discuss any two methods to evaluate 07
fugacity coefficient.
(b) Define azeotropes and explain minimum boiling and maximum boiling 07
azeotropes with suitable examples and neat diagrams.
OR
Q.3 (a) Mixtures of n-Pentane (1) and n-Heptane (2) conform to ideal solution 07
behaviour. The vapour pressures of pure components are adequately described
by Antoine equations. Prepare P-x-y diagram at 700C.
Compound A B C
n-Pentane 6.8763 1075.78 233.2
n-Heptane 6.8939 1264.37 216.64
Use Antoine equation: log10pisat = Ai – Bi/(t + Ci) where pressure pisat is in torr
and temperature t is in 0C.
(b) What is gamma-phi formulation of VLE? Draw block diagrams for the BUBL P 07
and DEW P calculations. Write all necessary equations.
Q.4 (a) Define partial molar properties and explain various methods for evaluation of 07
partial molar properties.

1
 (b) The enthalpy of a binary liquid system of species 1 and 2 at fixed T and P is 07
represented by the equation:
H = 400 x1 + 600 x2 + x1 x2 (40x1 +20x2) where H is in J mol-1
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 for the partial
 
enthalpies at infinite dilution H 1 and H 2 .
OR
Q.4 (a) Derive Margules equations from the following expression: 07
GE
 A21 x1  A12 x2
x1 x2 RT
(b) Explain T-x-y diagram for partial miscible system. 07
Q.5 (a) Explain the effect of temperature and pressure on equilibrium constant. 07
(b) Derive from the first principles, ΔG0 = - RT lnK. 07
OR
Q.5 (a) Discuss the criteria of chemical equilibrium. 07
(b) Write in brief a note on feasibility of chemical reactions. 07

*************

2
 Seat No.: ________ Enrolment No.___________

GUJARAT TECHNOLOGICAL UNIVERSITY

BE – SEMESTER – V (NEW) EXAMINATION – WINTER 2015

Subject Code: 2150503 Date:08/12/ 2015

Subject Name: Chemical Engineering Thermodynamics-II
Time:10:30am to 1:00pm Total Marks: 70
Instructions:
1. Attempt all questions.
2. Make suitable assumptions wherever necessary.
3. Figures to the right indicate full marks.

Q.1 (a) Explain any two methods for estimating fugacity of a pure gas. 07
(b) Discuss about the ideal solution model and the Lewis/Randall rule. 07
Q.2 (a) Define partial molar properties. Discuss various methods for evaluation 07
of partial molar properties.
(b) Define chemical potential. Discuss the effect of temperature and pressure 07
on chemical potential.
OR
(b) The experimental pressure-volume data for benzene at 675 K from a very low 07
pressures up to 75 bar may be approximated by the equation V= 0.0554(1/P-
0.0046).Where V is in m3/mol and pressure P is in bar. What is the fugacity of
benzene at 1 bar and 675 K.
Q.3 (a) What are azeotropes? With proper phase diagrams, distinguish between 07
minimum and maximum boiling azeotropes.
(b) Binary system acetonitrile(1)/ nitro methane (2) confirms closely to Roult’s 07
law. Vapor pressures of pure species are given by the following Antoine
equations, where P is in kPa and T is in K . Prepare T- x1,y1 diagram at a
pressure of 70 kPa .
2945.47 2972.64
ln 𝑃1s = 14.2724 – ln 𝑃2s = 14.2043 –
𝑇+224.00 𝑇+209.00
OR
Q.3 (a) Enlist the methods to test consistency for any VLE data and describe any two 07
in detail.
(b) Discuss any two group contribution methods to determine Activity coefficients. 07
Q.4 (a) How is the activity coefficient related to the excess free energy? 07
(b) In a laboratory 30 mol % of methanol – water solution is to be prepared. How 07
many cm3 of pure methanol and pure water are to be mixed to prepare 2000cm3
of desired solution? Partial molar properties of methanol and water are given
below.
Methanol: V 1̅ = 38.632 cm3 / mol, Water: V 2̅ = 17.765 cm3 / mol.
For the pure species at 25 0C, methanol: V1 = 40.227 cm3 / mol and water: V2
= 18.068 cm3 / mol.

OR
Q.4 (a) Prove “Henry’s law applies to a species as it approaches infinite dilution in a 07
binary solution, and the Gibbs/Duhem equation insures validity of the the
Lewis/Randall rule for the other species as it approaches purity”.
(b) The azeotrope of the ethanol-benzene system has a composition of 44.8% 07
(mol) ethanol with boiling point of 341.4 K at 101.3 Kpa. At this temperature

1
 the vapor pressure of benzene is 68.9 Kpa and the vapor pressure of ethanol is
67.4 Kpa. What are the activity co-efficient in a solution containing 10%
alcohol.(Use Van Laar equation).
Q.5 (a) The water-gas shift reaction CO (g) + H2O(g) CO2(g) + H2(g) is carried 10
out under the different sets of condition described below. Calculate the
fraction of steam reacted in each case. Assume the mixture behaves as an ideal
gas.
i) The reactants consist of 1 mol of H2O vapor and1 mol of CO. The
temperature is 1100K and the pressure is 1 bar.
ii) Same as (i) except that the pressure is 10 bar.
iii) Same as (i) except that 2 mol of N2 is included in the reactants.
iv) The reactants are 2 mol of H2O and 1 mol of CO. Other conditions are the
same as in (i).
v) The reactants are 1 mol of H2O and 2 mol of CO. Other conditions are the
same as in (i).
vi) The initial mixture consists of 1 mol of H2O, 1 mol of CO and 1 mol of
CO2. Other conditions are the same as in (i).
Assume for the given reaction at 1100K, value of K = 1.
(b) Discuss phase rule and Duhem’s theorem for reacting systems. 04
OR
Q.5 (a) (i) Discuss the effect of temperature on equilibrium constant. 05
(ii)What is the criterion of chemical reaction equilibria? 05
(b) Discuss about liquid – liquid equilibrium (LLE). 04

*************

2
 Seat No.: ________ Enrolment No.___________

GUJARAT TECHNOLOGICAL UNIVERSITY

BE - SEMESTER–V (OLD) - EXAMINATION – SUMMER 2017
Subject Code: 150503 Date: 01/05/2017
Subject Name: Chemical Engineering Thermodynamics-II
Time: 02:30 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.
4. Draw neat sketches wherever required.
Q.1 (a) What is partial molar quantity? Discuss its physical significance and 07
importance.
(b) Prove that ∆G0 = -RT lnK 07

Q.2 (a) Write in brief on various methods of evaluating the equilibrium constant. 07
(b) Prepare a block diagram for BUBLT and DEWT for systems following Raoult’s 07
law.
OR
(b) Write a brief note on Ideal and non ideal solutions 07
Q.3 (a) Write in brief on the effect of temperature on equilibrium constant 07
(b) Discuss the statement “Raoult’s law is applicable to the solvent when Henry`s law to 07
the solute”.
OR
Q.3 (a) Assuming Raoult's law to be valid, prepare a P-xy diagram for a temperature of 100°C 07
for the following systems of Benzene(l)/ Ethyl benzene(2) using the Antoine equation.
ln Psat = A –[B (t +C)] where Psat is in kPa and t is in C
Component A B C
Benzene 13.86 2,774 220.1
Ethyl benzene 14.00 3,279 213.20
(b) For a binary system, if the activity coefficient for component ‘1’ is 07
lnγ1 = βx22, then derive the expression for component ‘2’.
Q.4 (a) Write a brief note on retrograde condensation. 07
(b) Derive the equation for the criteria for phase equilibria in terms of fugacity for a 07
mixture of N components and  phases.
OR
Q.4 (a) The enthalpy of a binary liquid mixture of species 1 and 2 at fixed T and P is 07
represented by the equation: H  400 x 1  600 x 2  x 1 x 2 ( 40 x 1  20 x 2 )
Where H is in J mol-1. Calculate values of H1, H2, H 1 , H 2 .
(b) Outline the method to determine P-T Flash calculations 07

Q.5 (a) Carry out thermodynamic analysis of any one important industrial reaction 07
(b) Write a brief note on Van’t Hoff Equilibrium box 07
OR
Q.5 (a) How is equilibrium conversion evaluation for heterogeneous system? 07
(b) Write short note on the Langrange method of undetermined multiple used for multiple 07
reaction equilibrium.
*******

1
 Seat No.: ________ Enrolment No.___________

GUJARAT TECHNOLOGICAL UNIVERSITY

BE - SEMESTER– V • EXAMINATION – WINTER 2016

Subject Code: 150503 Date: 19/11/2016

Subject Name: Chemical Engineering Thermodynamics-II
Time: 10:30AM – 01:00PM Total Marks: 70
Instructions:
1. Attempt all questions.
2. Make suitable assumptions wherever necessary.
3. Figures to the right indicate full marks.

Q.1 (a) Discuss various methods for checking the consistency of experimental VLE 07
data.
(b) Define partial molar properties and explain various methods for the evaluation 07
of partial molar properties.
Q.2 (a) Derive the relation between standard free energy change and equilibrium 07
constant from the first principle.
(b) In a laboratory 30 mol % of methanol – water solution is to be prepared. How 07
many m3 of pure methanol and pure water are to be mixed to prepare 2 m3 of
desired solution? Partial molar properties of methanol and water are given
below.
Methanol: V1 = 38.632 cm3 / mol, Water: V2 = 17.765 cm3 / mol.
For the pure species at 25 0C,
methanol: V1 = 40.227 cm3 / mol and water: V2 = 18.068 cm3 / mol.
OR
(b) Derive the equation for the criteria for phase equilibrium in terms of fugacity 07
for a mixture of N components and π phases.
Q.3 (a) Discuss minimum and maximum boiling azeotropes giving examples for each 07
with neat diagrams.
(b) Construct P-x-y diagram for the cyclohexane(1)/benzene(2) system at 40oC. Use 07
the following expressions for the liquid-phase activity coefficients: ln γ1 = 0.458
x22, ln γ2 = 0.458 x12. At 40oC, p1sat = 0.243 atm and p2sat = 0.241 atm.
OR
Q.3 (a) Define fugacity coefficient. Discuss any two methods to evaluate fugacity 07
coefficient.
(b) The experimental pressure-volume data for benzene at 675K from a very low 07
pressure to about 75 bar may be approximated by the equation V = 0.0561 (1/P
– 0.0046), where V is in m3/mol and pressure P is in bar. What is fugacity of
benzene at 1 bar and 675 K?
Q.4 (a) Write short notes on any two: 07
(i) Bubble-point equilibria, (ii) Dew-point equilibria, (iii) Flash vaporization
(b) Write a brief note on retrograde condensation and its application. 07
OR
Q.4 (a) Discuss any two group contribution methods to determine activity coefficient. 07
(b) For a binary system, if the activity coefficient for component ‘1’ is lnγ1 = βx22, 07
then derive the expression for component ‘2’.
Q.5 (a) Explain briefly evaluation of equilibrium conversion for heterogeneous 07
reactions.
(b) Write in brief a note on feasibility of chemical reaction. 07
1
 OR
Q.5 (a) In the synthesis of ammonia, stoichiometric amounts of nitrogen and hydrogen 07
are sent to a reactor where the following reaction occurs.
N2 + 3H2 →2NH3
The equilibrium constant for the reaction at 675 K is 2 x 10─4. Determine the
percent conversion of nitrogen to ammonia at 675 K & 20 bar.
(b) Write the effect of temperature and pressure on equilibrium constant. 07

*************

2
 Seat No.: ________ Enrolment No.___________

GUJARAT TECHNOLOGICAL UNIVERSITY

BE - SEMESTER–V- EXAMINATION – SUMMER 2016
Subject Code: 150503 Date: 09/05/2016
Subject Name: Chemical Engineering Thermodynamics-II
Time: 02:30 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.

Q.1 (a) Explain the procedure for Bubble T calculation. 07

(b) Discuss the lagrangian undetermined multiplier method for multi reaction equilibria. 07

Q.2 (a) A binary liquid mixture consists of 60 mol % ethylene and 40 mol % propylene. At 07
423 K, the vapor pressure of ethylene and propylene are 15.2 atm and 9.8 atm
respectively. Calculate the total pressure and equilibrium composition of the vapor
phase by assuming ideal solution.
(b) Derive Gibbs-Duhem equation. 07
OR
(b) Derive the equation for fugacity of liquid. 07

Q.3 (a) List the methods to evaluate fugacity coefficient in mixture and explain any one 07
briefly.
(b) Explain the concept of activity coefficient. 07
OR
Q.3 (a) Discuss Lewis Randall rule and Henry’s law briefly. 07
(b) Define non ideality of mixture and compare positive and negative deviation from 07
ideality.
Q.4 (a) Calculate the fugacity of i-butane at 20 atm and 90 oC using the virial equation of 07
state. Take second virial coefficient B = -4.28*10-4 m3/mol.
(b) List the various activity models and describe their limitations. 07
OR
Q.4 (a) Prove that enthalpy change of mixing for ideal gas is zero. 07
(b) Calculate the free energy change of mixing of 0.7 moles of helium with 0.3 moles of 07
argon at 25 oC and 1 atm. Assume that the gases behave ideally.
Q.5 (a) A system initially charged with 3 mol CH4 and 4 mol H2O is undergoing the 07
reaction: CH4 + H2O CO + 3H2 and CH4 + 2H2O CO2 + 4H2. Derive the
expression for the mole fractions of the components in terms of extent of the
reactions.
(b) Derive the phase equilibrium criteria in terms of chemical potential. 07
OR
Q.5 (a) Explain the solid gas reaction equilibrium by taking the example of decomposition 07
of CaCO3.
(b) Explain the phase rule for reaction equilibria. 07

*************
1
 Seat No.: ________ Enrolment No.___________

GUJARAT TECHNOLOGICAL UNIVERSITY

BE - SEMESTER–V EXAMINATION – WINTER 2015

Subject Code: 150503 Date:08/12/2015

Subject Name: Chemical Engineering Thermodynamics – II
Time: 10:30am to 1:00pm Total Marks: 70
Instructions:
1. Attempt all questions.
2. Make suitable assumptions wherever necessary.
3. Figures to the right indicate full marks.

Q.1 (a) Derive the equation for criteria for phase equilibrium in terms of chemical 07
potential for a mixture of N components and π phases.
(b) Write a brief note on ideal solutions and non-ideal solutions. 07

Q.2 (a) Discuss various methods for checking the consistency of experimental VLE data. 07

(b) Define activity coefficient. Discuss Margules and Wilson equations with their 07
merits and demerits.
OR
(b) The experimental pressure-volume data for benzene at 675K from a very low 07
pressure to about 75 bar may be approximated by the equation V = 0.0561 (1/P –
0.0046), where V is in m3/mol and pressure P is in bar. What is fugacity of
benzene at 1 bar and 675 K?
Q.3 (a) The excess Gibbs energy of a particular ternary liquid mixture is represented by 07
the empirical expression with parameters A12, A13, and A23 functions of T and P
only:
GE
 A12 x1 x2  A13 x1 x3  A23 x2 x3
RT
i) Determine the implied expressions for ln γ1, ln γ2, and ln γ3.
ii) Determines expressions (or values) for ln γ1 for the limiting case x1 = 0.
(b) Write a brief note on excess properties. 07

OR
Q.3 (a) At 300 K and 1 bar, the volumetric data for a liquid mixture of benzene and 07
cyclohexane are represented by
V = 109.4 × 10-6 − 16.8 ×10-6 x − 2.64 ×10-6 x2, where x is the mole fraction of
benzene and V has the units of m3/mol. Find the expressions for the partial molar
volumes of benzene and cyclohexane.
(b) Construct P-x-y diagram for the cyclohexane(1)/benzene(2) system at 40oC. Use 07
the following expressions for the liquid-phase activity coefficients: ln γ1 = 0.458
x22, ln γ2 = 0.458 x12. At 40oC, p1sat = 0.243 atm and p2sat = 0.241 atm.
Q.4 (a) Write a short note on phase diagram for completely immiscible systems. 07
(b) Derive the expression of vapor composition at equilibrium using flash 07
vaporization.
OR

1
Q.4 (a) An equimolar solution of benzene and toluene is totally evaporated at a constant 07
temperature of 363 K. At this temperature, the vapour pressures of benzene &
toluene are 135.4 and 54 kPa respectively. What are pressures at the beginning &
at the end of the vaporization process?
(b) Calculate the equilibrium constant at 298 K of the reaction 07
N2O4 (g) → 2NO2 (g)
Given that the standard free energies of formation at 298 K are 97,540 J/mol for
N2O4 and 51,310 J/mol for NO2.
Q.5 (a) Develop expressions for the mole fractions of reacting species as functions of the 07
reaction coordinate for:
(i) A system initially containing 2 mol of NH3 & 5 mol of O2 and undergoing the
reaction 4NH3(g) + 5O2(g) → 4NO(g) + 6H2O(g)
(ii) A system initially containing 3 mol of H2S & 5 mol of O2 and undergoing the
reaction 2H2S(g) + 3O2(g) → 2H2O(g) + 2SO2(g)
(b) Explain briefly evaluation of equilibrium conversion for heterogeneous reactions. 07

OR
Q.5 (a) Derive the relation between standard free energy change and equilibrium constant 07
from the first principle.
(b) Discuss the effect of pressure and temperature on equilibrium constant for 07
chemical reaction equilibrium.

*************

2
 Seat No.: ________ Enrolment No.___________
GUJARAT TECHNOLOGICAL UNIVERSITY
BE - SEMESTER–V • EXAMINATION – SUMMER • 2015

Subject Code: 150503 Date: 11-05-2015

Subject Name: Chemical Engineering Thermodynamics - II
Time: 02.30 pm - 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.
Q.1 (a) Discuss various methods for determination of partial molar properties. 07
(b) Derive the relation between standard free energy change and 07
equilibrium constant from the first principle.

Q.2 (a) Discuss various methods to determine equilibrium constant. 07

(b) Estimate the fugacity of iso-butane at 15 atm and 87οC using the 07
compressibility factor correlation Z= 1+ (BP/RT), given that the second
virial coefficient B = -4.28 *10-4 m3/mol.
OR
(b) Write a brief note on retrograde condensation. 07

Q.3 (a) Write in brief on the effect of pressure on equilibrium constant 07

(b) Discuss the criteria of chemical equilibrium. 07

OR
Q.3 (a) Prepare T-x,y diagram at temperature of pressure of 101.33 kPa for a 07
binary system Benzene(1) and Ethyl benzene(2). Assume that Raoult’s
law is valid and use the following Antonie equation.

lnPisat = A – B/( T + C), where Pisat in kPa and T is in 0C.

Value of constant
Component A B C
Benzene 13.8594 2773.78 220.07
Ethyl benzene 14.0045 3279.47 213.20

(b) For a binary system, if the activity coefficient for component ‘1’ is 07
lnγ1 = βx22, then derive the expression for component ‘2’.
Q.4 (a) Write a brief note on Area tests 07
(b) Write in brief on Equilibrium conversion charts 07
OR
Q.4 An equimolar mixture of CO(g) and H2O(g) enters a reactor which is 14
maintained at 10 bar and1000 K. the reaction involved is
CO(g) + H2O(g)→ CO2(g) + H2(g)
Given that the equilibrium constant for this reaction is 1.5 at 1000 K,
Calculate the degree of conversion and the composition of the gas
mixtures that leaves the reactor. The reaction mixture can be considered
1
 to behave as ideal gas mixture.

Q.5 The azeotrope of the benzene- cyclohexane system has a composition of 14

53.2 mole percent benzene with a boiling point of 350.6 K at 101.3 kPa.
At 350.6 K, the vapor pressure of pure benzene is 100.59 kPa and that
of cyclohexane is 99.27 kPa Calculate the Vanlaar constants for the
system and determine the activity coefficients for a solution containing
10 mole percent benzene.

OR
Q.5 (a) Write a brief note on Excess properties. 07

(b) In case of flash vaporization, explain the methodology adopted to 07

calculate the flash?

****************

2
 Seat No.: ________ Enrolment No.___________

GUJARAT TECHNOLOGICAL UNIVERSITY

BE - SEMESTER–V • EXAMINATION – WINTER • 2014
Subject Code: 150503 Date: 03-12-2014
Subject Name: Chemical Engineering Thermodynamics - II
Time: 10.30 am - 01.00 pm Total Marks: 70
Instructions:
1. Attempt all questions.
2. Make suitable assumptions wherever necessary.
3. Figures to the right indicate full marks.

Q.1 (a) Define partial molar properties. Explain analytical and graphical methods to 07
determine partial molar properties of components in mixtures.
(b) Define chemical potential. Discuss the effect of temperature and pressure on 07
chemical potential.
Q.2 (a) Define ideal solution. Discuss Henry’s law for dilute solutions. 07
(b) Derive the relation between standard free energy change and equilibrium constant 07
from first principle.
OR
(b) In the synthesis of ammonia, stoichiometric amounts of nitrogen and hydrogen are 07
sent to a reactor where the following reaction occurs.
N2 + 3H2 →2NH3
The equilibrium constant for the reaction at 675 K is 2 x 10─4. Determine the percent
conversion of nitrogen to ammonia at 675 K & 20 bar.
Q.3 (a) Write a note on T-x, y diagram for partially miscible system. 07
(b) Discuss the effect of temperature and pressure on equilibrium constant. 07
OR
Q.3 (a) Discuss the criteria of chemical equilibrium. 07
(b) Write a brief note on feasibility of chemical reaction. 07
Q.4 (a) Briefly discuss about thermodynamic consistency test of VLE data. 07
(b) The azeotrope of the ethanol – benzene system has a composition of 44.8 % 07
(mol) ethanol with a boiling point of 341.4 K at 101.3 kPa. At this temperature, the
vapour pressure of benzene is 68.9 kPa and the vapour pressure of ethanol is 67.4
kPa. What are the activity coefficients in a solution containing 10% alcohol (use van
Laar equation)
OR
Q.4 (a) Stating the significance, discuss the various forms of Gibbs - Duhem equation in 07
detail.
(b) Develop expressions for the mole fractions of reacting species as functions of the 07
reaction coordinate for:
(i) A system initially containing 2 mol of NH3 & 5 mol of O2 and undergoing the
reaction
4NH3(g) + 5O2(g) → 4NO(g) + 6H2O(g)
(ii) A system initially containing 3 mol of H2S & 5 mol of O2 and undergoing the
reaction
2H2S(g) + 3O2(g) → 2H2O(g) + 2SO2(g)

1
Q.5 (a) Show that the van Laar equation & Margules equation are consistent with Gibbs - 07
Duhem equations.
(b) Acetic acid is esterified in the liquid phase with ethanol at 100°C (373.15 K) and 07
atmospheric pressure to produce ethyl acetate and water according to the reaction:
CH3COOH(l) + C2H5OH(l) → CH3COOC2H5(l) + H2O(l)
If initially there is one mole of each acetic acid and ethanol, estimate the mole
fraction of ethyl acetate in the reacting mixture at equilibrium. The value of ∆Hº 298
and ∆Gº298 for the above reaction are – 3640 J and – 4650 J respectively. Assume
that the heat of reaction is independent of temperature and the liquid mixture
behaves as ideal solution.
OR
Q.5 (a) An equimolar solution of benzene and toluene is totally evaporated at a constant 07
temperature of 363 K. At this temperature, the vapour pressures of benzene &
toluene are 135.4 and 54 kPa respectively. What are pressures at the beginning & at
the end of the vaporization process?
(b) Write short notes on any two: 07
(i) Bubble-point equilibria; (ii) Dew-point equilibria; (iii) Flash vaporization

*************

2
 Seat No.: ________ Enrolment No.___________

GUJARAT TECHNOLOGICAL UNIVERSITY

BE - SEMESTER–V • EXAMINATION – SUMMER • 2014
Subject Code: 150503 Date: 19-06-2014
Subject Name: Chemical Engineering Thermodynamics -II
Time: 10.30 am - 01.00 pm Total Marks: 70
Instructions:
1. Attempt all questions.
2. Make suitable assumptions wherever necessary.
3. Figures to the right indicate full marks.

Q.1 (a) What is Chemical Potential? Derive necessary equation for criteria for phase 07
equilibrium in multi component system.
(b) Define partial molar properties. Discuss various methods for evaluation of partial 07
molar properties.

Q.2 (a) Discuss the various forms of Gibbs-Duhem equation in detail. 07

(b) Discuss in detail: ideal solutions and non-ideal solutions. 07
OR
(b) List out various methods for evaluation of fugacity coefficient of pure component. 07
Discuss any two in detail.

Q.3 (a) Prove that ΔG0 = − R T InK 07

(b) At 300 K and 1 bar ,the volumetric data for a liquid mixture of benzene and 07
cyclohexane are represented by
V=109.4 × 10-6 − 16.8 ×10-6 x − 2.64 ×10-6 x2, where x is the mole fraction of
benzene and V has the units of m3/mol. Find expressions for the partial molar
volumes of benzene and cyclohexane.
OR
Q.3 (a) Discuss the effect of pressure and temperature on equilibrium constant for chemical 07
reaction equilibrium.
(b) Mixtures of n-Pentane (1) and n-Heptane (2) confirm to ideal solution behavior. 07
Prepare P-x-y diagram at 700C.
Use Antoine equation: log10P = A – ( B / ( T + C ) ) where pressure P is in Torr and
temperature T is in 0C.
A B C
n-Pentane 6.87632 1075.780 233.205
n-Heptane 6.89386 1264.370 216.640
Q.4 (a) Discuss various methods for checking the consistency of experimental VLE data. 07

(b) Calculate the equilibrium constant at 298 K of the reaction 07

N2O4 (g) → 2NO2 (g)
Given that the standard free energies of formation at 298 K are 97,540
J/mol for N2O4 and 51,310 J/mol for NO2.
OR
Q.4 (a) Write a brief note on multi reaction equilibria. 07
(b) The azeotrope of the ethanol-benzene system has a composition of 44.8 mole 07
percent ethanol with a boiling point of 68.24oC at 760 mmHg. At 68.24oC, the
vapor pressure of pure benzene is 517 mmHg and that of ethanol is 506 mmHg.
Calculate the van Laar constants for the system and determine the activity
coefficients for a solution containing 10 mole percent ethanol.
1/2
Q.5 (a) Discuss any two group contribution methods to determine Activity coefficients. 07
(b) Discuss retrograde condensation and its application. 07
OR
Q.5 (a) Write short note on “Phase diagrams for completely immiscible systems.” 07
(b) Discuss factors affecting equilibrium conversion. 07

*************

2/2
Seat No.: ________ Enrolment No.___________
GUJARAT TECHNOLOGICAL UNIVERSITY
BE - SEMESTER–V • EXAMINATION – WINTER 2013
Subject Code: 150503 Date: 04-12-2013
Subject Name: Chemical Engineering Thermodynamics-II
Time: 10.30 am - 01.00 pm Total Marks: 70
Instructions:
1. Attempt all questions.
2. Make suitable assumptions wherever necessary.
3. Figures to the right indicate full marks.

Q.1 (a) Define Chemical potential and prove that for a multi component system, 07
the chemical potential of each component is the same in all phases.
(b) Define ideal solution. Discuss Henry’s law for dilute solutions. 07

Q.2 (a) What is partial molar property ? Derive general form of Gibbs- Duhem 07
equation.
(b) Define fugacity coefficient . Discuss any two methods to evaluate fugacity 07
coefficient.
OR
(b) A container is divided into two compartments. One contains 3 moles of 07
hydrogen at 298 K and 1 bar and the other contains 1 mol of nitrogen at
298 K and 3 bar. Calculate the free energy of mixing when the partition is
removed. Assume gases behave ideally.

Q.3 (a) Discuss vapor-liquid equilibria for non ideal solutions with neat sketch. 07
(b) The vapour pressures of acetone(1) and acetonitrile (2) can be evaluated 07
by the following Antoine equations, where P is in kPa and T is in K.

Assuming ideal solutions, calculate

1) and at 327 K and 65 kPa 2) P and at 327 K and = 0.4

OR
Q.3 (a) Discuss minimum and maximum boiling azeotropes giving examples for 07
each with neat diagrams.
(b) Calculate the bubble temperature of a binary liquid mixture of benzene (1) 07
and toluene (2) at 760 Torr. The mole fraction of benzene in the liquid is
0.4047. Antoine equations are given below where P is inTorr and T is in
.

Q.4 (a) Define activity coefficient. Discuss Margules equation and Wilson 07
equation with their merits and demerits.
(b) The van Laar constants A and B for the system nitro methane (1) and CCl4 07
(2) at 45 are 2.230 and 1.959 respectively. Calculate the activity
coefficients of the components in a solution with 30 mol % CCl4.
OR
Q.4 (a) Enlist the methods to test consistency for any VLE data and describe any 07
two in detail.
 (b) Binary system acetonitrile(1)/ nitro methane (2) confirms closely to 07
Roult’s law. Vapor pressures of pure species are given by the following
Antoine equations, where P is in kPa and T is in . Prepare P-
diagram at 75 .

Q.5 (a) Discuss effect of temperature and pressure on equilibrium constant. 07

(b) Methanol is produced according to the following reaction 07
CO(g) + 2H2(g) → CH3OH (g)
Estimate the degree of conversion of CO into methanol at 500 K and
5 bar if
1) An equimolar mixture of CO and H2 is fed to the reactor
2) CO and H2 the ratio 1: 4 enters the reactor.
Use relation Ka = Kɸ Ky PƩνi ,
given that Ka = 4.973 × 10 3 , Kɸ= 1
OR
Q.5 (a) Write short note on equilibrium with simultaneous reactions. 07
(b) For the following reaction prove that ∆ G°= RTln K 07
aA + bB → lL + mM

*************
Seat No.: ________ Enrolment No.___________
GUJARAT TECHNOLOGICAL UNIVERSITY
BE - SEMESTER–V • EXAMINATION – SUMMER 2013
Subject Code: 150503 Date: 21-05-2013
Subject Name: Chemical Engineering Thermodynamics – II
Time: 10.30 am - 01.00 pm Total Marks: 70
Instructions:
1. Attempt all questions.
2. Make suitable assumptions wherever necessary.
3. Figures to the right indicate full marks.
Q–1

(a) State Lewis - Randall rule and Henry’s law. Derive the mathematical expression for fugacity and fugacity
coefficient. [07]

(b) Explain in brief: ideal solutions and non-ideal solutions. [07]

Q–2

(a) Discuss the various form of Gibbs-Duhem equations in detail. [07]

(b) Explain effect of temperature, pressure and total stoichiometric coefficient on equilibrium constant. Also
discuss relation of equilibrium constants to composition. [07]

OR

(b) Define azeotropes and explain the minimum boiling and maximum boiling azeotropes with suitable
examples. [07]

Q–3

(a) Explain the equilibrium conversion in heterogeneous system and multireaction system with at least one
example. [07]

(b) Mention different activity coefficient model equations. Explain any one of them in detail. [07]

OR

Q–3

(a) Explain the reaction coordinate and its physical significance. Explain the different factors affecting
equilibrium conversions. [07]

(b) Derive the expression of vapor composition at equilibrium using flash vaporization [07]
Q–4

(a) Calculate standard Gibbs free energy change and equilibrium constant at 700 K for the reaction:

N2 (g) + 3 H2 (g) ® 2 NH3 (g)

For given reaction: DH0 = - 92000 J / mol and DG0 = - 33000 J / mol. The standard heat of formation and free
energy of NH3 at 298 K is - 46000 J / mol and - 16500 J / mol respectively. Specific heat for nitrogen,
hydrogen and ammonia is given below and should be in J/mol K.

CP, N2 = 27.27 + 4.93 x 10-3 T, CP, H2 = 27.01 + 3.51 x 10-3 T and CP, NH3 = 29.75 + 25.11 x 10-3 T [07]

(b) The excess Gibbs energy of a particular ternary liquid mixture is represented by the empirical expression
with parameters A12, A13, and A23 functions of T and P only:

GE
= A12 x1 x2 + A13 x1 x3 + A23 x2 x3
RT

(i) Determine the implied expressions for ln γ1, ln γ2, ln γ3.

(ii) Determines expressions (or values) for ln γ1 for the limiting cases: X1 = 0, xl = 1, x2 = 0, and x3 = 0. [07]

OR

Q – 4 For the system methanol and methyl acetate, the following equation provide reasonable correlation for
activity coefficient. ln g1 = A X22 ln g2 = A X12

A = 2.771 – 0.00523 T

3643. 31 2665. 54
ln P1 = 16 . 591- = 14 . 253 -
sat sat
ln P2
T - 33 . 424 T - 53 . 424

(i) Calculate T and {yi} for P= 101.33 kPa, X1 = 0.85

(ii) Calculate T and {Xi} for P= 101.33 kPa, y1 = 0.40 [14]

Q–5

(a) Discuss the application of equilibrium criteria to chemical reaction and develop expressions for the mole
fractions of reacting species as functions of the reaction coordinate for:

A system initially contains 2-mol NH3 and 5-mol O2 undergoing the reaction:

4NH3 (g) + 5O2 (g) ® 4NO (g) + 6H2O (g)

A system initially contains 3-mol H2S and 5-mol O2 undergoing the reaction:

2H2S (g) + 3O2 (g) ® 2H2O (g) + 2SO2 (g) [07]

(b) In a laboratory 30 mol % of methanol – water solution is to be prepared. How many m3 of pure methanol
and pure water are to be mixed to prepare 2 m3 of desired solution?

Partial molar properties of methanol and water are given below.

Methanol: V1 = 38.632 cm3 / mol, Water: V2 = 17.765 cm3 / mol.

For the pure species at 25 0C, methanol: V1 = 40.227 cm3 / mol and water: V2 = 18.068 cm3 / mol. [07]

OR

Q–5

(a) Using the fundamental properties relation for single phase reaction, show that [07]

DG0 = – RT lnK

(b) The ammonia synthesis reaction written as: 0.5 N2 (g) + 1.5 H2 (g) ® NH3 (g) with 0.5 mol nitrogen and 1.5
mol hydrogen as the initial amounts of reactants and with the assumption that the equilibrium mixture is an
ideal gas, show that: [07]

ee = 1 – (1+1.299KP) – 0.5

******************