CET II (3140507) Study Material

S. S.
Agrawal Institute of Engineering &

Technology, Navsari
Chemical Engineering Department
Subject Name with Code
Chemical Engineering
Thermodynamics II
[3140507]
Study Materials
B.E. – 2nd Chemical Engineering, 4th

Semester
Index
Sr.
Content Page No.
No
1. Syllabus Copy 1
2. List of tutorial 4
3. List of Assignment 13
4. Last Five-Year Question Papers 21
5. Question bank 32
7. Reference Book 35
GUJARAT TECHNOLOGICAL UNIVERSITY
Bachelor of Engineering
Subject Code: 3140507
Semester –IV
Subject Name: Chemical Engineering Thermodynamics-II
Type of course: Professional Core Course
Prerequisite: Chemical Engineering Thermodynamics-I
Rationale: This subject introduces the concepts of fugacity, activity coefficient and other important
thermodynamic properties and its evolution for pure components and solutions. 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. The course also provides fundamental insight into the underlying thermodynamic principles of
phase equilibria and reaction equilibria to solve complex problems.
Teaching and Examination Scheme:
Teaching Scheme Credits Examination Marks Total

L T P C Theory Marks Practical Marks Marks
ESE (E) PA (M) ESE (V) PA (I)
3 1 0 4 70 30 0 0 100
Content:
Sr. Content Total
No. Hrs
1 PHASE EQUILIBRIA: 15
VAPOUR/LIQUID EQUILIBRIUM (VLE):

Introduction, The Nature of Equilibrium, The Phase Rule; Duhem’s Theorem, VLE-
Qualitative Behaviour, Azeotropic Mixtures, Retrograde condensation, Simple Models
for Vapour/Liquid Equilibrium ,Raoult’s Law, Dewpoint and Bubblepoint Calucations
with Raoult’s Law , Henry’s law, VLE by Modified Raoult’s Law, VLE from K-Value
Correlations, Flash Calculations, The Gamma / Phi Formulation of VLE,
An introduction to Equilibrium and stability, liquid- liquid equilibrium (LLE), solid-

liquid equilibrium, Vapor-Liquid-liquid equilibrium (VLLE), Solid-Liquid equilibrium
(SLE), Solid-Vapor equilibrium (SVE) etc..
2 SOLUTION THERMODYNAMICS: 18
THEORY
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
model, The Partial Molar Gibbs Energy and Fugacity, Fugacity and Fugacity Coefficient:
Pure Species and for Species in Solution ,The Ideal Solution Model , The Lewis/Randall
Page 1 of 3
w.e.f. AY 2018-19
Rule , Excess Properties , The Excess Gibbs energy and activity coefficient, nature of
excess property
APPLICATIONS
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 by Integral or Area Test Method, Models for the Excess
Gibbs Energy, Margules Equations, VanLaar Equations, Local Composition Models such
as NRTL Equation, UNIQUAC Equation, UNIFAC Method
3 CHEMICAL REACTION EQUILIBRIA: 12
The reaction coordinates, Application of equilibrium criteria 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 for gas phase and liquid phase reactions, calculation of
equilibrium conversion for single reaction, The phase rule and Duhem’s theorem for
reacting systems, introduction to multi-reaction equilibria
Suggested Specification table with Marks (Theory):
Distribution of Theory Marks
R U A N E C
Level Level Level Level Level Level
7 28 28 7 0 0
Legends: R: Remembrance; U: Understanding; A: Application, N: Analyze and E: Evaluate C: Create
and above Levels (Revised Bloom’s Taxonomy)
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
Page 2 of 3
w.e.f. AY 2018-19
Course Outcomes:
Students should be able to

Sr. CO statement Marks %
No. weightage
CO-1 Explain fundamentals of Solution thermodynamics, phase equilibria and reaction 10
equilibria.
CO-2 Apply fundamental property relations to find thermodynamic properties of 15
solutions
CO-3 Calculate maximum extent of separation possible under prevailing operating 30
conditions for various multiphase multi component systems
CO-4 Determine thermodynamic properties like fugacity, activity coefficients, 20
constants of model equations etc.. for solutions
CO-5 Determine equilibrium conversions of reaction systems and its dependence on 25
various operating parameters
List of Tutorials: Numericals/problems based on topics of each theme of content.
Major Equipment: None
List of Open Source Software/learning website:

1. Students can refer to video lectures available on the websites including NPTEL.
2. Students can refer to the CDs which are available with some reference books for the solution of problems
using softwares. Students can develop their own programs for the solutions of problems.
3. XSEOS–an Open Software for Chemical Engineering Thermodynamics
Page 3 of 3
w.e.f. AY 2018-19
List of Tutorials
Tutorial
Content
No.
To Prepare bubble point and dew point diagram.

1
To solve numerical based on flash calculations and use of raoult’s

2 law.
To solve numerical based on theory of solution thermodynamics.
3
To solve numerical based on the application of thermodynamics.
4
To solve numerical based on chemical reaction equilibrium.
5
Tutorial No: 01
Date:
Sub Code 3140507 Title of Subject Chemical Engineering Thermodynamics- II
No. Tutorial 01 : To Prepare bubble point and dew point diagram.

Binary system acetonitrile (1)/nitromethane (2) conforms closely to ideal solution behavior.
Vapor pressure for the pure species is given by following antonie equations.
1.
Prepare a P-xy diagram for a temperature of 348.15 K

Prepare T-xy diagram for a presuure of 70 Kpa.
(use Excel spreadsheet for both cases).
A mixture contains 45% (mol) methanol (A), 30% (mol) ethanol (B) and the rest 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.
2.
temperature (K) 333 343 353 363

, Kpa 81.97 133.29 186.61 266.58
, Kpa 49.32 73.31 106.63 166.61
39.32 62.65 93.30 133.29
Prepare P-X-Y diagram at temperature of 1000C for a binary system Benzene(1) and Ethyl
benzene(2). Assume that Raoult’s low is valid and use the following Antonie equation.
ln = A – B/( T + C) Where in Kpa and T is in °C
3.
Component A B C
Benzene 13.8594 2773.78 220.07
Ethyl benzene 14.0045 3279.47 213.20
Mixtures of n-Pentane (1) and n-Heptane (2) conform to ideal solution behaviour. The vapour
4.
pressures of pure components are adequately described by Antoine equations. Prepare P-x-y
S. S. A GRAWAL I NSTITUTE OF E NGINEERING & T ECHNOLOG Y , N AVS ARI
CHEMICALDEPARTMENT
diagram at 70°C.
Compound A B C
n-Pentane 6.8763 1075.78 233.2
n-Heptane 6.8939 1264.37 216.64
Use Antoine equation: = Ai – Bi/(t + Ci) where pressure pisat is in torr and
temperature t is in °C,
1
CHEMICALDEPARTMENT
Tutorial No: 02
Date:
No. Tutorial 02: To solve numerical based on flash calculations and use of raoult’s law
System acetone(1)/acetonitrile(2)/nitromethane(3) at 353.15 K has the overall composition
z1 = 0.45, z2 = 0.35 and z3 = 0.20. Assuming that the Raoult’s law is appropriate to this
system, determine equilibrium pressure and vapor-liquid composition to carry out 40%
1. vaporization. Date Given: The vapor pressures of the pure species at the 353.15 K are:
= 195.75 kPa, = 97.84 kPa and = 50.32 kPa
At 303 K the vapour pressures of benzene (1) and toluene (2) are 15.75 kPa and 4.89 kPa
respectively. Determine the partial pressure and composition of the benzene vapour in
2.
equilibrium with a liquid mixture consisting of equal weight of the two components.
A mixture of A and B confirms closely to Raoult’s law. At 373 K, the vapour pressure of A
and B are 106 and 74 kPa respectively. Determine the composition of the vapour and liquid
3.
in equilibrium at 173 K and 101.3 kPa.
An equimolar solution of benzene and toluene is totally evaporated at a constant temperature

of 363 K. At this temperature, the vapour pressures of benzene & toluene are 135.4 and 54
4. kPa respectively. What are pressures at the beginning & at the end of the vaporization
process?
2
CHEMICALDEPARTMENT
Tutorial No: 03
Date:
No. Tutorial 03: To solve numerical based on theory of solution thermodynamics

The experimental pressure-volume data for benzene at 675 K from a very low pressures up
to 75 bar may be approximated by the equation V= 0.0554(1/P-0.0046).Where V is in
1.
m3/mol and pressure P is in bar. What is the fugacity of benzene at 1 bar and 675 K.
In a laboratory 30 mol % of methanol – water solution is to be prepared. How 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: ̅ = 38.632 cm3 /
2.
mol, Water: ̅ = 17.765 cm3 / mol.For the pure species at 25 0C, methanol: V1 = 40.227
cm3 / mol and water: = 18.068 cm3 / mol.
The enthalpy of a binary liquid system of species 1 and 2 at fixed T and P is represented by
the equation: H = 400 x1 + 600 x2 + x1 x2 (40x1 +20x2) where H is in J mol-1 Determine
expressions for ̅ and ̅ as functions of x1, numerical values for the pure-species
3.
enthalpies H1 and H2, and numerical values for the partial enthalpies at infinite dilution and
̅ and ̅ .
At 300 K and 1 bar ,the volumetric data for a liquid mixture of benzene and cyclohexane are
represented by V =109.4 × - 16.8 × X - 2.64 × ,where X is the mole
4. fraction of benzene and V has the units of m3/mol. Find expressions for the partial molar
volumes of benzene and cyclohexane.
A Gibbs free energy of a binary liquid mixture of Benzene (1) and Toluene (2) at fixed
temperature and pressure is represented by the equation: 𝐺 = 40 1 + 30 2 + 1 2 Where G is
5.
in J/mol. Determine chemical potential of benzene and toluene for an equimolar mixture.
Derive an expression for the fugacity coefficient of a gas obeying the equation of state P(V-
6. b)=R T and estimate the fugacity of ammonia at 10 bar and 298 K, given that b = 3.707 x
10-5 m3/mol.
3
CHEMICALDEPARTMENT
Tutorial No: 04
Date:
No. Tutorial 04: To solve numerical based on the application of thermodynamics

The azeotrope of the ethanol-benzene system has a composition of 44.8% (mol) ethanol with
boiling point of 341.4 K at 101.3 Kpa. At this temperature the vapor pressure of benzene is
1. 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).
The following data gives the composition vs total pressure for the system chloroform (1)/ethyl
alochol (2) at 328 K :
0.0311 0.9652
2. P, Kpa 40.84 84.88
Vapor pressures of chloroform and ethyl alocohol at 328 K are 82.35 and 37.30 Kpa
respectively. Estimates the Constant in Margules Equation.
Estimate activity coefficient of methanol for chloroform (1) / methanol (2) system at 35°C. The
vapour pressures of chloroform and methanol at 35°C are 39.54 kPa and 27.95 kPa
3. respectively. The mole fraction of methanol in the liquid mixture is 0.25. Margules’ parameters
are A12 = 0.738, A21 = 1.868.
Methanol (1) / acetone (2) system is described by the Van Laar activity coefficient model. At
60oC, the model parameters are 𝐴12 = 0.47 and 𝐴21 = 0.78. Estimate the activity coefficient of
4.
methanol for a solution containing 15 mol% of methanol
Water (1) – hydrazine (2) system forms an azeotrope containing 58.5% (mol) 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
5.
assume to remain constant in the temperature range involved. Vapor pressure of hydrazine at
393 K is 124.76 kPa.
Determine P-x-y data for chloroform (1) methanol (2) system at 35 ᵒC, vapor pressure of
6. chloroform and methanol is 39.54 KPa and 27.95 KPa respectively. Margules parameters are:
𝐴12=0.738 and 𝐴21=1.868.
Construct P-x-y diagram for the cyclohexane(1)-benzene(2) system at 313 K given that at 313
7. K the vapor pressures are P1s= 24.62 kPa and P2S= 24.41 kPa. The liquid phase activity
coefficients are given by
4
CHEMICALDEPARTMENT
Liquids A and B form an azeotrope containing 46.1 mole percent A at 101.3 kPa and 345 K. At
8. 345 K, the vapor pressure of A is 84.8 kPa and that of B is 78.2 kPa. Calculate the van Laar
constants.
A certain experiment was carried out in the laboratory. The results of the data are as shown
below. Verify whether the following data are thermodynamically consistent or not?
9.
5
CHEMICALDEPARTMENT
Tutorial No: 05
Date:
No. Tutorial 05: To solve numerical based on chemical reaction equilibrium.

The ammonia synthesis reaction written as:
0.5 N2 (g) + 1.5 H2 (g) NH3 (g)
A mixture consisting of 0.5 mol nitrogen and 1.5 mol of hydrogen as the initial amounts of
1. reactants and with the assumption that the equilibrium mixture is an ideal gas, show that the
extent of reaction is given by
Ɛe = –
Develop expressions for the mole fractions (yi) of reacting species as functions of the reaction
coordinates for a system initially contains 2- mol CH4 and 3-mol H2O undergoing the reaction:
2.
A gas mixture Containing 3 mol of , 5 mol of and 1 mol of water vapor is undergoing the
following reaction. Develop expressions for the mol fraction of the species in terms of extent of
3. reaction.
CO2 + 3H2 3OH + H2O and CO2 + H2 2O
n–butane is isomerized to i–butane by the action of catalyst at moderate 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
4.
standard free energy of the reaction at 317 K and 391 K and average value of heat of
reaction over this temperature range.
5.
Calculate standard Gibbs free energy change and equilibrium constant at 700 K for the
reaction: N2(g) + 3H2(g) 3(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
6. ammonia are as given below.
CP, N2 –3T
CP, H2 –3T
CP, NH3 –3T
Develop expressions for the mole fractions of reacting species as functions of the reaction
7. coordinate for:
1. A system initially containing 2 mol NH3 and 5 mol O2 and undergoes the reaction:
6
CHEMICALDEPARTMENT
2. A system initially containing 3 mol H2S and 5 mol O2 and undergoing the reaction:
A gas mixture of SO2(g) O2(g) and inert A(g) in mole ratio 1: 0.5: 2 enters in a reactor at
30bar and 900K to produce SO3(g) as:
SO2(g) + 0.5 O2(g) → SO3(g).
7.
Determine the degree of conversion at equilibrium and composition of mixture leaving the
reactor. Assume the reaction mixture behaves like an ideal gas. K = 5.973 and Kφ = 1.
A gas mixture containing 30 mol% of CO, 50 mol% of H2 and 20 mol% of inert gas is to be used
for synthesis of methanol as:
CO(g) + 2H2 (g) →CH3OH (g)
8. Gases issued from the catalytic chambers are in chemical equilibrium with respect to the reaction
at 30 bar and 625K. Assume that the equilibrium mixture forms an ideal solution, K = 5x10-5 and
Kφ =1. What is the percentage conversion of CO?
9.
7
S. S. AGRAWAL INSTITUTE OF ENGINEERING &
TECHNOLOGY, NAVSARI
CHEMICAL ENGINEERING DEPARTMENT
Assignments
Name of Faculty: Prof. Heena N Katariya

Department: Chemical Engineering
Subject Name & Code: Chemical Engineering
Thermodynamics- II (3140507)
CHEMICALDEPARTMENT
Assignment No: 01
Date:
No. Questions (Unit 1 Phase equillibria)

For binary azeotropic mixture deviating positively from ideality, draw vapor-liquid
1.
equilibrium (VLE) diagrams.
Define azeotrope and explain the minimum boiling and maximum boiling
2.
azeotropes with suitable examples.
Write down Raoult's Law and Henry's Law explaining each term associated with
3.
them with their applicability.
4. Describe phase rule and Duhem’s theorem for non-reacting system.
Derive the expression of vapor composition at equilibrium using flash
5.
vaporization.
With neat diagram describe the effect of increasing pressure on binary T-x1,y1
6.
vapor-liquid equilibrium diagram.
7. Write a brief note on retrograde condensation and its application.
Distinguish between dew point and bubble point temperature.

8.
Explain in brief: ideal solutions and non-ideal solutions.
9.
Write a short note on i ) bubble point equilibria ii) dew-point equilibria iii) flash
10. vaporization
Assuming validity of Raoult’s law, draw P-x1,y1 diagram for binary mixture at 75
°C. Clearly show vapor region, liquid region, bubble point and dew point curves.
11. Data given:
At 75 °C, and
Derive the expression used to estimate fraction of initial mixture that is vaporized
12. at equilibrium using flash vaporization calculation.
1
CHEMICALDEPARTMENT
Assignment No: 02
Date:
No. Questions (Unit 2 Solution thermodynamics: theory)

Define chemical potential. What is its physical significance? Define fugacity and
1.
fugacity coefficient. Discuss any two method to evaluate fugacity coefficient.
Show that for a binary system, Henry’s law is valid for component ‘1’ then Lewis
2.
Randall rule is valid for component ‘2’.
3. How is the activity coefficient related to the excess free energy?
“All property change of mixing are zero for ideal solution” Do you agree? Explain
OR
4. For ideal gases, prove that the partial molar volume is identical with the pure-species
volume at the mixture T and P.
̅̅̅̅̅
Discuss the property change of mixing and also derive expression for volume
5. change of mixing in term of activity of species in a binary solution.
Derive the Gibbs – Duhem equation for a binary solution in terms of activity and
6. activity coefficient.
Discuss the excess Gibbs free energy and its relation with activity coefficient and
7. excess chemical potential
Derive the equation for criteria for phase equilibrium in terms of chemical
8. potential for a mixture of N components and π phases
Describe graphical interpretation of following two equations relating partial molar

properties with solution properties.
9.
̅̅̅̅ and ̅̅̅̅
2
CHEMICALDEPARTMENT
OR
Define partial molar properties and explain any one method in detail for
evaluation of partial molar properties.
Prove “Henry’s law applies to a species as it approaches infinite dilution in a binary
10.
solution, and the Gibbs/Duhem equation ensures the validity of the Lewis/Randall
rule for the other species as it approaches purity
Discuss about the ideal solution model and the Lewis/Randall rule. Give its
11. significance.
Define chemical potential. Discuss the effect of temperature and pressure on

12. chemical potential.
13.
Explain any two methods for estimating fugacity of a pure gas.
For binary mixture derive following equations to calculate fugacity coefficient from
virial equation of state.
14.
3
CHEMICALDEPARTMENT
Assignment No: 03
Date:
No. Questions (Unit 2 Solution thermodynamics: applications)

Discuss Non Random Two Liquid equation used to determine activity coefficient for
1.
vapor – liquid equilibria at low pressure
2. Describe Wilson and NRTL equations with their applications and limitations
3. Describe Poynting correction
Discuss van Laar equations used to determination of activity co-efficient for vapor –
4.
liquid equilibria at low pressure with suitable examples.
Enlist the methods to test consistency for any VLE data and describe any two in detail.
5.
(Must write area test)
Derive the Margules equations from the following expression:
6.
Explain the method of Lagrange’s undetermined multipliers for gas phase reaction to
7.
minimize total Gibbs free energy.
Discuss Wohl’s three suffix equations used to determination of activity co-efficient for
8. vapor – liquid equilibria at low pressure.
Discuss the Redlich – Kister zero area method applied to test the consistency of
9. experimental VLE data.
Discuss Margules three suffix equations used to determination of activity co-efficient for
10. vapor – liquid equilibria at low pressure.
Discuss any two group contribution methods to determine Activity coefficients.

11.
The activity Coefficients in a binary system are given by and .
Show that if the system forms an azeotrope, then azeotropic composition is given by
12.
[ ]
4
CHEMICALDEPARTMENT
Assignment No: 04
Date:
No. Questions (Unit 1 Phase equillibria)

What is gamma-phi formulation of VLE? Draw block diagrams for the BUBL P and
1. DEW P calculations. Write all necessary equations.
2.
Write a brief note on solid - vapor equilibrium.
3.
If for a liquid phase, show by stability analysis that LLE is predicted
for A ≥ 2.
4.
Briefly describe constant pressure liquid/liquid solubility diagrams.
5.
Discuss about liquid – liquid equilibrium (LLE).
6.
Write a brief note on T – x – y diagram for partially miscible system.
Discuss the Gamma / Phi formulation for vapor – liquid equilibrium. Draw block
7. diagrams for the BUBL P and DEW P calculations. Write all necessary equations.
5
CHEMICALDEPARTMENT
Assignment No: 05
Date:
No. Questions (Unit 3 Chemical reaction equillibria)

Derive relation between equilibrium constant and composition for homogeneous
1.
gas and liquid phase reaction.
2. Discuss criteria of chemical reaction equilibrium with neat sketch.
3. Discuss various methods used for evaluation of equilibrium constant.
4. List out the factors affecting equilibrium constant and explain any two in detail.
5. Explain the effect of temperature and pressure on equilibrium constant.
6. Write in brief a note on feasibility of chemical reactions.

Explain the method of Lagrange’s undetermined multipliers for gas phase reaction to
7.
minimize total Gibbs free energy.
For an ideal gas, the exact mathematical expressions can be developed for the effect of T
and P on the reaction co-ordinate at equilibrium. For conciseness we let ∏ .Then
we can write the mathematical relations:
8.
Using fundamental properties relation establishes expression of standard Gibbs free

9.
energy change of chemical reaction as a function of thermodynamic equilibrium constant.
Name of Faculty Prof. Heena N katariya
Date of Submission
Sign of Faculty
6
CHEMICALDEPARTMENT
7
Seat No.: ________ Enrolment No.___________

BE - SEMESTER–IV(NEW) EXAMINATION – WINTER 2022
Subject Code:3140507 Date:20-12-2022
Subject Name:Chemical Engineering Thermodynamics II
Time:10:30 AM TO 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.
4. Simple and non-programmable scientific calculators are allowed.
MARKS
Q.1 (a) Explain the significance of phase equilibria. 03
(b) Discuss Lewis-Randall rule along with its limitations. 04
(c) Define azeotrope and explain the minimum boiling and maximum 07
boiling azeotropes with suitable examples.
Q.2 (a) Discuss: ideal solutions and non-ideal solutions. 03

(b) For a closed system consisting two phases in equilibrium, explain 04
Chemical Potential and Phase Equliibria.
(c) Explain in brief about fundamental property relation. Derive 07
Gibbs/Duhem equations relating molar and partial molar properties.
OR
(c) At 300 K and 1 bar ,the volumetric data for a liquid mixture of benzene 07
and 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.
Q.3 (a) Discuss about liquid – liquid equilibrium (LLE). 03

(b) An equimolar solution of benzene and toluene is totally evaporated at a 04
constant 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?
(c) Write a short note on flash vaporization. 07
OR
Q.3 (a) Explain gamma-phi formulation of VLE. 03
(b) A mixture of A and B confirms closely to Raoult’s law. At 373 K, the 04
vapour pressure of A and B are 106 and 74 kPa respectively. Determine
the composition of the vapour and liquid in equilibrium at 173 K and
101.3 kPa.
(c) Write a brief note on retrograde condensation and its application. 07
Q.4 (a) Define activity and activity co efficient 03

(b) Liquid A and B form an azeotrope containing 46.1 mole percent A at 04
101.3 kPa and 345 K, the vapour pressure of A is 84.8.kPa and that of B
is 78.2 kPa. Calculate the Van Laar Constants.
(c) List out various methods for evaluation of fugacity coefficient of pure 07
component. Discuss any two in detail.
OR
Q.4 (a) Define fugacity and fugacity co efficient 03
(b) For a binary system, if the activity coefficient for component ‘1’ is lnγ1 04
= βx22, then derive the expression for component ‘2’.
1
(c) Discuss various methods for checking the consistency of experimental 07
VLE data.
Q.5 (a) Explain the different factors affecting equilibrium conversions. 03

(b) Discuss various methods to determine equilibrium constant. 04
(c) Using the fundamental properties relation for single phase reaction, 07
show that
∆G0 = – RT lnK
OR
Q.5 (a) Write a brief note on multi reaction equilibria. 03
(b) Develop expressions for the mole fractions (yi) of reacting species as 04
functions of the reaction coordinates for a system initially contains 2-
mol CH4 and 3-mol H2O undergoing the reaction:
CH4 + H2O → CO + 3H2………(1)
CH4 + 2H2O → CO2 + 4H2………(2)
(c) Explain effect of temperature, pressure and total stoichiometric number 07
on equilibrium constant.
*************
2

BE - SEMESTER–IV (NEW) EXAMINATION – SUMMER 2022
Subject Code:3140507 Date:08-07-2022
Time:10:30 AM TO 01:00 PM Total Marks: 70
Instructions:
MARKS
Q.1 (a) State and explain Duhemn Theorem. 03
(b) Evaluate the fugacity coefficient at 5 bar for a gas that follows the equation of 04
state PV = RT (1 – 0.005 P), where P is pressure in bar.
(c) In the laboratory of mass transfer, will it be possible to prepare 0.12m3 of 07
alcohol-water solution by mixing 0.04m3 alcohol with 0.08m3 pure water? If
not possible, Assess the volume which should have been mixed in order to
prepare a mixture of the same strength and of the required volume? Density of
ethanol and water are 789kg/m3 and 997kg/m3 respectively.
Data: The partial molar volumes of ethanol and water at the desired
compositions are: Ethanol = 53.6*10–6m3/mol; Water = 18*10–6m3/mol.
Q.2 (a) Derive the equation for determination of fugacity of pure gases using any two 03
methods.
(b) Prove that for a multi component system, chemical potential of each component 04
is the same in all phases.
(c) Molar volume of binary solution is expresses as: 07
H = 400x1 + 600 x2 + (40x1 + 20 x2 )x1 x2
(i) Acquire the expression for partial molar enthalpies.
(ii) Compute pure component enthalpy
(iii) Compute enthalpy at infinite dilution.
OR
(c) Prove that if Henry’s law is obeyed by component 1 in a binary solution over 07
certain concentration range, Lewis–Randall rule (Raoult’s law) will be obeyed
by component 2 over the same concentration range.
Q.3 (a) For a binary solution consider M1 and M2 are properties of component 1 and 03
component 2 in a solution. Derive equations to calculate partial properties of
component 1 and component 2 in a solution.
(b) The activity coefficients for component 2 in a binary solution can be represented 04
by lnγ2 = Ax1 + Bx12 , where A and B are concentration independent
parameters. Derive an expression for lnγ1 .
(c) The ethanol-benzene system forms azeotrope with azeotropic composition of 07
44.8mol% ethanol with boiling point of 341.4K at 101.3kPa. At this
temperature the vapor pressure of benzene is 68.9kPa and the vapor pressure of
ethanol is 67.4kPa. Compute the activity co-efficient in a solution of Ethanol-
Benzene containing 20mol% ethanol using Van Laar equation.
OR
Q.3 (a) State applications and limitations of Wilson and NRTL equation. 03
1
(b) Write steps to determine Bubble point temperature using Raoult’s Law. 04
(c) A certain experiment was carried out in the laboratory. The results of the data are as 07
shown below. Verify whether the following data are thermodynamically consistent
or not?
x1 0 0.2 0.4 0.6 0.8 1.0

γ1 0.576 0.655 0.748 0.856 0.950 1.0
γ2 1.0 0.985 0.930 0.814 0.626 0.379
Q.4 (a) Explain Liquid-Liquid Equilibrium with suitable example. 03

(b) Define azeotrope and explain maximum and minimum boiling azeotrope with 04
a neat diagram.
(c) Assuming Raoult’s law to be valid for the system benzene (1)–ethyl benzene 07
(2) and the vapour pressures are given by the Antoine equation:
𝐵
ln Pi sat = ⌈𝐴 − (𝑇+𝐶)⌉, where P is in kPa and T is in K.
Species, i A B C
1 13.8858 2788.51 -52.41
2 14.0045 3279.47 -60.00
Construct the P-x-y diagram at 100°C.
OR
Q.4 (a) What is retrograde condensation and write its application in chemical 03
industry.
(b) Two suffix Margules equation is the simplest expression for excess Gibbs free 04
energy. GE=βx1x2 where β is an empirical constant. Derive the expression for
the activity coefficient of component 1 that results from this equation.
(c) Assuming the validity of Raoult’s law, Evaluate for the system of Acetone (1), 07
Acetonitrile (2) and Nitromethane (3), given the mole fraction of component
x1 = 0.30 and x2=0.40and temperature T = 75°C, Compute y1 and P.
𝐵
ln Pi sat = ⌈𝐴 − ( )⌉ , where P is in kPa and T is in K.
𝑇+𝐶
Component A B C
Acetone(1) 14.3916 2795.82 230.0
Acetonitrile (2) 14.2724 2945.47 224.0
Nitromethane (3) 14.2043 2972.64 209.0
Q.5 (a) Describe phase rule for reacting systems 03

(b) The water–gas shift reaction takes place at 373K, CO + H2O→ CO2 +H2 04
The equilibrium constant KP for this reaction at 537K = 9.8 x 10–4. The heats
of formation at 298K are: CO = –110,525J/mol, CO2 = –393,509 J/mol,
H2O= –241,818 J/mol. Calculate the equilibrium constant at 1000 K.
(c) A gas mixture containing 1.25 moles hydrogen, 0.75 moles oxygen and 0.25 07
mole water initially, is undergoing the following reaction:
𝐻2 + 1/2𝑂2 → 𝐻2 𝑂
(i) Derive expressions for the mole fractions of various components in the
reaction mixture in terms of the extent of reaction.
(ii) Explain how the conversion of limiting reactant is related to the extent of
reaction.
OR
Q.5 (a) How would you predict the feasibility of a chemical reaction from the value 03
of standard free energy change?
(b) What is the effect of temperature on equilibrium constant? Using Van’t Hoff 04
equation predict the effect of increasing temperature on endothermic and
exothermic reactions.
2
(c) Consider a system in which the following reactions occur: 07
CH4+ H2O→ CO+3H2……….. (1)
CH4 + 2H2O→ CO2 +4H2 …….(2)
If 3mol CH4 and 4mol H2O are initially present, Compute the mole fraction
of the product gases for ε1= 0.25 and ε2=0.5
3

BE - SEMESTER–IV (NEW) EXAMINATION – WINTER 2021
Subject Code:3140507 Date:05/01/2022
Time:10:30 AM TO 01:00 PM Total Marks: 70
Instructions:
Q.1 (a) Discuss the criteria of chemical reaction equilibrium. 03

(b) Explain in brief T-x-y diagram for binary solutions. 04
(c) Discuss and derive the various forms of Gibbs-Duhem Equation. 07
Q.2 (a) Define: 1. Partial Molar Properties 2. Raoults law 3. Activity 03
coefficient
(b) Derive van’t Hoff equation which predicts the effect of temperature on the 04
equilibrium constant.
(c) Discuss in brief Minimum and maximum boiling azeotropes with 07
diagrams.
OR
(c) Water (1) – hydrazine (2) system forms an azeotrope containing 58.5% 07
(mol) hydrazine at 393 K and 101.3 kPa. Calculate the activity
coefficients and 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 assumed to remain constant in the
temperature range involved. The vapor pressure of hydrazine at 393 K is
124.76 kPa.
Q.3 (a) Write a short note on Activity in solution. 03
(b) Prove that if Henry’s Law is obeyed by component 1 in a binary solution 04
over certain concentration range, Lewis-Randall rule (Raoult’s law) will
be obeyed by component 2 over the same concentration range.
(c) Derive the relationship equation for equilibrium constant and standard free 07
energy change.
OR
Q.3 (a) Discuss the Lewis-Randall rule and its significance. 03
(b) Derive the equation for effect of temperature on the chemical potential. 04
(c) In the synthesis of ammonia, stoichiometric amounts of nitrogen and 07
hydrogen are sent to a reactor where the following reaction occurs:
N2 + 3H2  2NH3
The equilibrium constant for the reaction at 675 K may be taken equal to
2*10-4. Determine the % conversion of nitrogen to ammonia at 675 K and
20 bar.
Q.4 (a) Discuss various methods for evaluation of equilibrium constant. 03
(b) Discuss the thermodynamic consistency of experimental VLE data using 04
the slopes of lnγ curves for a binary solution.
(c) Define excess property. Derive the relationship between excess Gibbs free 07
energy and activity coefficient.
OR
Q.4 (a) Discuss in brief phase rule for reacting systems. 03
(b) State and explain Wilson equation for activity coefficient in a binary 04
mixture.
1
(c) The Enthalpy at 300 K and 1 bar of a binary liquid mixture is 07
Where H is in J/mol. For the stated temperature and pressure, determine:

1. Expressions for and in terms of
2. Numerical values for pure components enthalpies H1 and H2
3. Numerical values for the partial molar enthalpies at infinite dilution.
Q.5 (a) A gas mixture which contained 1 mol CO, 1 mol water vapor and 1 mol 03
CO2 is undergoing the following reaction at a temperature of 1100 K and a
pressure of 1 bar.
CO(g) + H2O(g)  CO2(g) + H2(g)
The equilibrium constant for the reaction is K=1. Assume that the gas
mixture behaves as ideal gas. Calculate the fractional dissociation of
steam.
(b) Discuss the determination of Fugacity of pure gases by using 04
compressibility factor method.
(c) Discuss the criteria of phase equilibrium for a homogeneous closed 07
system. Also develop criteria of equilibrium under various sets of
constraints.
OR
Q.5 (a) Define equilibrium constant K of a chemical reaction. How it is related to 03
Kf and KP ?
(b) The density of gaseous ammonia at 473 K and 50 bar is 24.3 kg/m3. 04
Estimate its fugacity.
(c) Construct P-x-y diagram for the cyclohexane(1)-benzene(2) system at 313 07
K given that at 313 K the vapor pressures are P1S = 24.62 kPa and P2S =
24.41 kPa. The liquid phase activity coefficients are given by
2

BE - SEMESTER–IV (NEW) EXAMINATION – SUMMER 2021
Time:02:30 PM TO 05:00 PM Total Marks:70
Instructions:
MARKS
Q.1 (a) Explain the significance of studying phase equilibria. 03

(b) Liquid A and B forms an azeotrope containing 46.1 mole percent A at 101.3 04
kPa and 345 K. The vapour pressure of A is 84.8 kPa and B is 78.2 kPa at
345 K. Calculate activity coefficient for A and B at an azeotropic condition.
(c) Write a short note on flash vaporization. 07
Q.2 (a) Write a brief note on ideal solutions and non-ideal solutions. 03
(b) Explain the residual volume method for calculating fugacity of pure gaseous 04
component.
(c) A mixture of A and B confirms closely to Raoult’s law. At 373 K, the vapour 07
pressure of A and B are 106 and 74 kPa respectively. Determine the
composition of the vapour and liquid in equilibrium at 173 K and 101.3 kPa.
OR
(c) The vapour pressure of acetone (1) and acetonitrile (2) at 327 K are 85.12 07
kPa and 39.31 kPa respectively. Assuming that the solutions formed by these
are ideal, calculate the total pressure 𝑎𝑛𝑑 𝑦1 𝑎𝑡 327 𝐾 𝑎𝑛𝑑 𝑥1 = 0.5.
Q.3 (a) Discuss about partial molar properties. 03

(b) What is vaporisation equilibrium constant? How do you estimate the bubble- 04
point temperature of a multicomponent system?
(c) A Gibbs free energy of a binary liquid mixture of Benzene (1) and Toluene 07
(2) at fixed temperature and pressure is represented by the equation:
𝐺 = 40𝑋1 + 30𝑋2 + 𝑋1 𝑋2
Where G is in J/mol. Determine chemical potential of benzene and toluene
for an equimolar mixture.
OR
Q.3 (a) Write Lewis-Randall rule and its significance. 03
(b) What is Poynting correction? 04
(c) The fugacity of component 1 in binary liquid mixture of components 1 and 2 07
at 298 K and 20 bar is given by
𝑓1̅ = 50𝑥1 − 80𝑥12 + 40𝑥13
where 𝑓̅1 is in bar and x1 is the mole fraction of component 1. Determine:
a) The fugacity (f1 ) of pure component 1
b) The fugacity coefficient (∅1 )
c) The activity coefficient (𝛾1 )for an equimolar mixture
Q.4 (a) Define fugacity and fugacity co efficient. 03

(b) Discuss Wilson equation with merits and demerits. 04
1
(c) From vapour–liquid equilibrium measurements for ethanol–benzene system 07
at 318 K and 40.25 kPa it is found that the vapour in equilibrium with a liquid
containing 38.4% (mol) benzene contained 56.6% (mol) benzene. The system
forms an azeotrope at 318 K. At this temperature, the vapour pressures of
ethanol and benzene are 22.9 and 29.6 kPa respectively. Determine the
composition and total pressure of the azeotrope. Assume that van Laar
equation is applicable for the system.
OR
Q.4 (a) Define activity and activity co efficient. 03
(b) Discuss any one group contribution method to determine Activity 04
coefficients.
(c) Discuss various methods for checking the consistency of experimental VLE 07
data.
Q.5 (a) Explain gamma-phi formulation of VLE. 03
(b) Define the reaction coordinate. 04
(c) Derive from the first principles, ΔG0 = - RT lnK. 07
OR
Q.5 (a) Discuss about liquid – liquid equilibrium (LLE). 03
(b) Write in brief a note on feasibility of chemical reaction. 04
(c) Calculate the equilibrium constant at 298 K of the reaction 07
𝑁2 𝐻4(𝑔) → 2𝑁𝑂2(𝑔)
Given that the standard free energy of formation at 298 K are 97540 J/mol
for N2O4 and 51310 J/mol for NO2.
*************
2

BE- SEMESTER–IV (NEW) EXAMINATION – WINTER 2020
Time:02:30 PM TO 04:30 PM Total Marks:56
Instructions:
1. Attempt any FOUR questions out of EIGHT questions.
Q.1 (a) Write down Raoult’s law and Henry’s law explaining each term associated with them 03
with their applicability.
(b) Write a brief note on retrograde condensation and its application. 04
(c) Define azeotrope and explain the minimum boiling and maximum boiling azeotropes 07
with suitable examples.
Q.2 (a) Discuss the phase rule and Duhem’s theorem. 03

(b) At 303 K, vapour pressures of benzene (1) and toluene (2) are 15.75 kPa and 4.89 kPa 04
respectively. Determine the partial pressure and composition of the benzene vapour in
equilibrium with a liquid mixture consisting of equal weight of the two components.
(c) Define partial molar properties. Discuss various methods for evaluation of partial 07
molar properties.
Q.3 (a) Estimate activity coefficient of methanol for chloroform (1) / methanol (2) system at 03
35oC. The vapour pressures of chloroform and methanol at 35o are 39.54 kPa and
27.95 kPa respectively. The mole fraction of methanol in the liquid mixture is 0.25.
Margules’ parameters are A12 = 0.738, A21 = 1.868.
(b) Discuss the area test for checking the thermodynamic consistency of experimental 04
VLE data.
(c) The enthalpy at 300 K and 1 bar of a binary liquid mixture is represented by the 07
following equation:
H = 400 X1 + 600 X2 + X1 X2 (40X1 + 20X2), where H is in J/mol. Determine
expressions for H1 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.4 (a) Methanol (1) / acetone (2) system is described by the Van Laar activity coefficient 03
model. At 60oC, the model parameters are 𝐴12 = 0.47 and 𝐴21 = 0.78. Estimate the
activity coefficient of methanol for a solution containing 15 mol% of methanol.
(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) Using fundamental property relations, establish the expression of standard Gibbs free 07
energy change of a chemical reaction as a function of the thermodynamic equilibrium
constant.
Q.5 (a) Define K-value and explain its importance in vapour-liquid equilibrium calculations. 03
1
(b) Derive the expression of vapour composition at equilibrium using flash vapourization. 04
(c) Derive the Gibbs – Duhem equation for a binary solution in terms of activity and 07
activity coefficient.
Q.6 (a) Write a brief note on ideal solutions. 03

2 𝐺𝐸 04
(b) Derive the Margules equations from the expression = 𝐴21 𝑥1 + 𝐴12 𝑥2 .
𝑥 1 𝑥2 𝑅𝑇
(c) The experimental pressure volume data for benzene at 675 K from a very low pressure 07
to about 75 bar may be approximated by the equation, V = 0.0561(1/P – 0.0046),
where V is in m3/mol and P is in bar. What is fugacity of benzene at 1 bar and 675 K
?
Q.7 (a) Discuss the Gamma/Phi formulation for vapor-liquid equilibrium. 03

(b) Discuss criteria of chemical reaction equilibrium with neat sketch. 04
(c) The vapour pressures of acetone (1) and acetonitrile (2) can be evaluated by the 07
following Antoine equations:
2940.46 2945.47
ln p1sat = 14.5463 - and ln psat
2 = 14.2724 -
T - 35.93 T - 49.15
where T in K and pisat in kPa. Assuming that the solution formed is ideal, calculate:
i) x1 and y1 at 327 K and 65 kPa
ii) T and y1 at 65 kPa and x1 = 0.4
Q.8 (a) Discuss about liquid-liquid equilibrium (LLE). 03

(b) Develop expressions for the mole fractions of reacting species as functions of the 04
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)
(c) Explain effect of temperature, pressure and total stoichiometric number on 07
equilibrium constant.
*********
2
S. S. A GRAWAL I NSTITUTE OF E NGINEERING T ECHNOLOGY NAVSARI
Subject Name : Chemical Engineering Thermodynamics II (3140507)
Question Bank for GTU Exam
Unit 1 Phase Equilibrium
1. Define azeotrope and Discuss in brief Minimum and maximum boiling azeotropes with diagrams.
2. Explain the significance of studying phase equilibria.
3. Write short note on VLE for completely immiscible systems with neat diagram.
4. Write a brief note on retrograde condensation and its application.
5. Write a short note on flash vaporization Derive the expression of vapour composition at equilibrium using flash
vapourization.
6. For binary azeotrope mixture deviating positively form ideality, draw vaporliquid equilibrium (VLE) diagrams.
7. What is vaporisation equilibrium constant? How do you estimate the bubblepoint temperature of a multicomponent
system?
8. With neat diagram, describe the effect of increasing pressure on binary T-x1-y1 vapour-liquid equilibrium (VLE)
diagram.
9. Write a short note on bubble point equilibria and dew-point equilibria.
10. Write Raoult‟s law and Henry‟s law explaining each term associated with them with their applicability.
11. Write a brief note on ideal solutions and non-ideal solutions
12. Discuss the phase rule and Duhem‟s theorem OR Discuss phase rule for non reacting systems in brief.
13. Explain gamma-phi formulation of VLE.
14. Discuss about liquid – liquid equilibrium (LLE).
15. With proper nomenclature draw three types of constant- pressure liquid liquid solubility diagram.
16. Explain in brief T-x-y diagram for binary solutions. Write a short note on Bubble point equilibria.
17. Define K-value and explain its importance in vapour-liquid equilibrium calculations.
Unit 2 Solution Thermodynamics Theory
1. Discuss and derive the various forms of Gibbs-Duhem Equation. OR Derive summability relation for partial molar
properties.
2. Discuss the excess Gibbs free energy relation with activity coefficient and chemical potential. OR Derive the
relationship between excess Gibbs free energy and activity coefficient.
3. “All property change of mixing are zero for ideal solution” Do you agree? Explain OR For ideal gases, prove that
the partial molar volume is identical with the pure-species volume at the mixture T and P.
̅̅̅̅̅
4. Describe graphical interpretation of following two equations relating partial molar properties with
solution properties. (Tangent intercept method)
̅̅̅̅ and ̅̅̅̅
Or With neat diagram explain tangent-intercept method to estimate partial molar volume of a binary solution.
5. Define activity and activity co efficient. Write a short note on Activity in solution.
6. Prove that if Henry‟s Law is obeyed by component 1 in a binary solution over certain concentration range, Lewis-
Randall rule (Raoult‟s law) will be obeyed by component 2 over the same concentration range. OR Show that for a
binary system, Henry‟s law is valid for component „1‟ then Lewis Randall rule is valid for component „2‟.
7. Discuss the Lewis-Randall rule and its significance
8. Define chemical potential and state its significance. Derive the equation for effect of temperature on the chemical
potential.
9. Discuss the criteria of phase equilibrium for a homogeneous closed system. Also develop criteria of equilibrium
under various sets of constraints. OR Derive the equation for criteria for phase equilibrium in terms of chemical
potential for a mixture of N components and π phases. OR For a closed system consisting two phases in
equilibrium, explain Chemical Potential and Phase Equliibria.
10. Define fugacity and fugacity coefficient. Discuss any two methods to evaluate fugacity coefficient.
11. Define Excess properties What is Poynting correction?
12. Write a short note on „fugacity of a pure liquid
13. Explain any two methods for estimation of fugacity of pure gas. (Explain the residual volume method for
calculating fugacity of pure gaseous component. Discuss the determination of Fugacity of pure gases by using
compressibility factor method.)
14. Derive the equation for the criteria for phase equilibrium in terms of fugacity for mixture of N components and Л
phases
15. Discuss excess Gibbs free energy in brief
16. Define “Partial Molar property”. Describe different methods to determine partial molar properties in detail. OR
For a binary solution consider M1 and M2 are properties of component 1 and component 2 in a solution. Derive
equations to calculate partial properties of component 1 and component 2 in a solution.
17. For binary mixture derive following equations to calculate fugacity coefficient from virial equation of state.
Unit 2 Solution thermodynamics : Application
1. Discuss various methods for checking the consistency of experimental VLE data. OR Discuss the thermodynamic
consistency of experimental VLE data using the slopes of lnγ curves for a binary solution and area test. OR
Discuss any two methods to check consistency of experimental VLE data in detail. OR Discuss the Redlich –
Kister zero area method applied to test the consistency of experimental VLE data.
2. Derive the Gibbs – Duhem equation for a binary solution in terms of activity and activity coefficient.
3. State and explain Wilson equation for activity coefficient in a binary mixture. Discuss Wilson equation with merits
and demerits
4. The activity Coefficients in a binary system are given by and . Show that if the system
forms an azeotrope, then azeotropic composition is given by
[ ]
5. The activity coefficients for component 2 in a binary solution can be represented by lnγ2 = Ax1 + Bx12 , where A
and B are concentration independent parameters. Derive an expression for lnγ1 .
6. For a binary system, if the activity coefficient for component „1‟ is lnγ 1 = βx22, then derive the expression for
component „2‟.
7. Derive the Margules equations from the following expression:
8. Discuss van Laar equations applicable in determination of activity coefficient for VLE at low pressure with
suitable examples.
9. Discuss van Laar and Margulies Equations in detail
10. Two suffix Margules equation is the simplest expression for excess Gibbs free energy. G E=βx1x2 where β is an
empirical constant. Derive the expression for the activity coefficient of component 1 that results from this equation.
11. State applications and limitations of Wilson and NRTL equation.
12. Write short note on group contribution method. Discuss any one group contribution method to determine Activity
coefficients.
Unit 3 Chemical Reaction Equilibria
1. Derive van‟t Hoff equation which predicts the effect of temperature on the equilibrium constant.
2. Derive the relationship equation for equilibrium constant and standard free energy change. Or Using fundamental
property relations, establish the expression of standard Gibbs free energy change of a chemical reaction as a
function of the thermodynamic equilibrium constant. OR Derive from the first principles, ΔG0 = - RT lnK.
3. Discuss criteria of chemical reaction equilibrium with neat sketch. OR Write in brief a note on feasibility of
chemical reaction.
4. Explain effect of temperature, pressure and total stoichiometric number on equilibrium constant.
5. Discuss various methods for evaluation of equilibrium constant.
6. Discuss in brief phase rule for reacting systems
7. Define equilibrium constant K of a chemical reaction. How it is related to Kf and KP ?
8. For an ideal gas, the exact mathematical expressions can be developed for the effect of T and P on the reaction co-
ordinate at equilibrium. For conciseness we let ∏ .Then we can write the mathematical relations:
(Bold highlighted questions indicates frequently asked questions)

Reference Books
Smith J.M, Van Ness H.C., Abbott M. M, "Introduction to Chemical Engineering

Thermodynamics", the McGraw Hill Companies, Inc., USA, 7th Ed., 2005.
K.V.Narayanan “A Text book of chemical Engineering thermodynamics”, Prentice Hall of India.
J.M.Prausnitz, R.N. Litchtenthaler, Molecular thermodynamics of fluid phase Equilibria, 3rd

Edition,Prentice Hall.

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S. S.

Agrawal Institute of Engineering &

Chemical Engineering Department

Subject Name with Code

B.E. – 2nd Chemical Engineering, 4th

4. Last Five-Year Question Papers 21

Type of course: Professional Core Course

Prerequisite: Chemical Engineering Thermodynamics-I

Teaching and Examination Scheme:

Teaching Scheme Credits Examination Marks Total

VAPOUR/LIQUID EQUILIBRIUM (VLE):

An introduction to Equilibrium and stability, liquid- liquid equilibrium (LLE), solid-

Suggested Specification table with Marks (Theory):

Distribution of Theory Marks

1. Smith J.M, Van Ness H.C., Abbott M. M, "Introduction to Chemical Engineering

Students should be able to

List of Tutorials: Numericals/problems based on topics of each theme of content.

Major Equipment: None

List of Open Source Software/learning website:

To Prepare bubble point and dew point diagram.

To solve numerical based on flash calculations and use of raoult’s

No. Tutorial 01 : To Prepare bubble point and dew point diagram.

Prepare a P-xy diagram for a temperature of 348.15 K

temperature (K) 333 343 353 363

= 195.75 kPa, = 97.84 kPa and = 50.32 kPa

An equimolar solution of benzene and toluene is totally evaporated at a constant temperature

No. Tutorial 03: To solve numerical based on theory of solution thermodynamics

In a laboratory 30 mol % of methanol – water solution is to be prepared. How many cm3 of

No. Tutorial 04: To solve numerical based on the application of thermodynamics

2. P, Kpa 40.84 84.88

No. Tutorial 05: To solve numerical based on chemical reaction equilibrium.

n–butane is isomerized to i–butane by the action of catalyst at moderate temperature. It is

CHEMICAL ENGINEERING DEPARTMENT

Name of Faculty: Prof. Heena N Katariya

No. Questions (Unit 1 Phase equillibria)

Distinguish between dew point and bubble point temperature.

No. Questions (Unit 2 Solution thermodynamics: theory)

Describe graphical interpretation of following two equations relating partial molar

Define chemical potential. Discuss the effect of temperature and pressure on

No. Questions (Unit 2 Solution thermodynamics: applications)

3. Describe Poynting correction

Discuss any two group contribution methods to determine Activity coefficients.

No. Questions (Unit 1 Phase equillibria)

No. Questions (Unit 3 Chemical reaction equillibria)

3. Discuss various methods used for evaluation of equilibrium constant.

5. Explain the effect of temperature and pressure on equilibrium constant.

6. Write in brief a note on feasibility of chemical reactions.

Using fundamental properties relation establishes expression of standard Gibbs free

Name of Faculty Prof. Heena N katariya

GUJARAT TECHNOLOGICAL UNIVERSITY

Q.2 (a) Discuss: ideal solutions and non-ideal solutions. 03

Q.3 (a) Discuss about liquid – liquid equilibrium (LLE). 03

Q.4 (a) Define activity and activity co efficient 03

Q.5 (a) Explain the different factors affecting equilibrium conversions. 03

GUJARAT TECHNOLOGICAL UNIVERSITY

x1 0 0.2 0.4 0.6 0.8 1.0

Q.4 (a) Explain Liquid-Liquid Equilibrium with suitable example. 03

Q.5 (a) Describe phase rule for reacting systems 03

GUJARAT TECHNOLOGICAL UNIVERSITY

Q.1 (a) Discuss the criteria of chemical reaction equilibrium. 03