Tutorials and Assignments for

CHEMICAL ENGINEERING
THERMODYNAMICS-II
(3140507)

B.E. Semester 4
(Chemical)

Directorate of Technical Education, Gandhinagar,

Gujarat
 LUKHDHIRJI ENGINEERING COLLEGE, MORBI
Certificate

This is to certify that Mr./Ms. ___________________________________

Enrollment No. __________________ of B.E. Semester 4 Chemical
Engineering of this Institute (GTU Code: 031) has satisfactorily completed the
Tutorial work for the subject Chemical Engineering Thermodynamics-II
(3140507) for the academic year 2024-25.

Place: __________
Date: __________

Name and Sign of Faculty member

Head of the Department

CHEMICAL ENGINEERING THERMODYNAMICS-II (3140507)

Preface

Main motto of any laboratory/practical/field work is for enhancing required skills as well as
creating ability amongst students to solve real time problem by developing relevant competencies
in psychomotor domain. By keeping in view, GTU has designed competency focused outcome-
based curriculum for engineering degree programs where sufficient weightage is given to
practical work. It shows importance of enhancement of skills amongst the students and it pays
attention to utilize every second of time allotted for practical amongst students, instructors and
faculty members to achieve relevant outcomes by performing the experiments rather than having
merely study type experiments. It is must for effective implementation of competency focused
outcome-based curriculum that every practical is keenly designed to serve as a tool to develop
and enhance relevant competency required by the various industry among every student. These
psychomotor skills are very difficult to develop through traditional chalk and board content
delivery method in the classroom. Accordingly, this lab manual is designed to focus on the
industry defined relevant outcomes, rather than old practice of conducting practical to prove
concept and theory.
By using this tutorial, students can go through the computation practice which is require to
understand the theory concept and also get exposure of relevant practical applications of the
concept. This in turn enhances pre-determined outcomes amongst students. Each tutorial in this
manual begins with competency, industry relevant skills, course outcomes as well as practical
outcomes (objectives).
This manual also provides guidelines to faculty members to facilitate student centric activities
through each tutorial by arranging and managing necessary resources in order that the students
follow the procedures to achieve the outcomes. It also gives an idea that how students will be
assessed by providing rubrics.
Chemical engineering thermodynamics II is a crucial subject for students and professionals in the
field of chemical engineering. This subject builds upon the fundamentals of thermodynamics
(typically covered in thermodynamics I) and delves into more advanced topics and applications
that are highly relevant in chemical engineering such as:
1) Phase Equilibria: Understanding phase equilibria is essential in chemical engineering.
This knowledge is used to design separation processes such as distillation, extraction, and
crystallization. Thermodynamics II provides a deep understanding of phase equilibria and
the tools to predict and control them.
2) Chemical Reaction Equilibria: Chemical reactions are at the core of many chemical
processes. Thermodynamics II covers topics like chemical equilibrium, which is essential
for designing and optimizing chemical reactor
Chemical engineering thermodynamics II is of paramount importance for those in the field as it
equips them with the knowledge and skills needed to design, operate, and optimize chemical
processes efficiently and safely, while considering environmental and sustainability aspects. It's
a subject that bridges the gap between theory and practical application, making it an integral part
of a chemical engineer's education and career.
Utmost care has been taken while preparing this tutorial manual however always there is chances
of improvement. Therefore, we welcome constructive suggestions for improvement and removal
of errors if any.
 CHEMICAL ENGINEERING THERMODYNAMICS-II (3140507)

Practical – Course Outcome matrix

Course Outcomes (COs):

1. Explain fundamentals of solution thermodynamics, phase equilibria and reaction equilibria.
2. Evaluate the thermodynamic properties (Such as Partial molar properties, Fugacity coefficients,
activity coefficients etc.) of pure fluid and fluid mixtures.
3. Analyze the equilibrium composition of mixtures under phase and chemical-reaction equilibria.
4. Determine equilibrium conversions of reaction systems and its dependence on various operating
parameters.

Sr.
Tutorials/Assignment CO1 CO2 CO3 CO4
No.

1. Tutorial 1 √
2. Tutorial 2 √
3. Tutorial 3 √
4. Tutorial 4 √
5. Tutorial 5 √
6. Tutorial 6 √
7. Tutorial 7 √
8. Assignment 1 √
9. Assignment 2 √
10. Assignment 3 √
11 Assignment 4 √
CHEMICAL ENGINEERING THERMODYNAMICS-II (3140507)

Industry Relevant Skills

The following industry relevant competency are expected to be developed in the student by
undertaking the tutorial work.
1. Computational skills will be developed.
2. Skills like time management, problem solving abilities will be developed.

Guidelines for Faculty members

1. Teacher should provide the guideline to the students.
2. Teacher shall explain basic concepts/theory related to the tutorial to the students.
3. Involve all the students in tutorial work. Individual efforts of students are needed.
4. Teacher is expected to share the skills and competencies to be developed in the
students and ensure that the respective skills and competencies are developed in the
students after the completion of the tutorials.
5. Teacher may provide additional knowledge and skills to the students even though not
covered in the manual but are expected from the students by concerned industry.
6. Give practical assignment and assess the performance of students based on task
assigned to check whether it is as per the instructions or not.
7. Teacher is expected to refer complete curriculum of the course and follow the
guidelines for implementation.

Instructions for Students

1. Students are expected to carefully listen to all the theory classes delivered by the faculty
members and understand the COs, content of the course, teaching and examination scheme,
skill set to be developed etc.
2. Students shall organize the work and solve the numerical individually.
3. Student shall develop the habits of evolving more ideas, innovations, skills etc. apart from
those included in scope of manual.
4. Student shall refer technical magazines and data books.
5. Student should develop a habit of submitting the tutorial work as per the schedule.

Common Safety Instructions

1. Behave in a responsible manner at all times in the laboratory.

2. Ask your teacher before preceding any activity.
3. Keep silence.
4. Do not eat food, drink beverages, or chew gum in the laboratory.
5. Before Living the room, turns Off Light/Fan.
CHEMICAL ENGINEERING THERMODYNAMICS-II (3140507)

Undertaking of Ethics

1. I, hereby, promise to abide by the admissible rules and regulations, concerning discipline,
attendance, etc. of the Lukhdhirji Engineering College, Morbi and also to follow the Code
of Conduct prescribed for the Students of the Institute, as in force from time to time and
subsequent changes/modifications/amendment made thereto. I acknowledge that, the
Institute has the authority for taking punitive actions against me for violation and/or non-
compliance of the same.
2. I have done all the tutorials and their calculation by my own.

Signature of Student

Enrollment of Student
 Index
(Progressive Assessment Sheet)

Assess Sign. of
Sr. Page Date of Date of
Tutorials/Assignments ment Teacher Remarks
No. No. performance submission
Marks with date

1. Tutorial 1

2. Tutorial 2

3. Tutorial 3

4. Tutorial 4

5. Tutorial 5

6. Tutorial 6

7. Tutorial 7

8. Assignment 1

9. Assignment 2

10. Assignment 3

11.
Assignment 4
 Tutorial 1
Relevant CO: 2
1. At 300 K and 1 bar, the volumetric data for a liquid mixture of benzene and cyclohexane
are represented by V = 109.4 x 10–6 – 16.8 x 10–6 x – 2.64 x 10–6x2, 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.
2. The enthalpy at 300 K and 1 bar of a binary liquid mixture is
H = 400x1 + 600x2 + x1x2(40x1 + 20x2)
where H is in J/mol. For the stated temperature and pressure, determine:
(a) Expressions for partial enthalpy for component 1 and 2 in terms of x1
(b) Numerical values for the pure component enthalpies H1 and H2
(c) Numerical values for the partial molar enthalpies at infinite dilution .
3. The volume of an aqueous solution of NaCl at 298 K was measured for a series of
molalities (moles of solute per kg of solvent) and it was found that the volume varies
with molality according to the following expression.
V = 1.003 x 10–3 + 0.1662 x 10–4m + 0.177 x 10–5m1.5 + 0.12 x 10–6m2,
where m is the molality and V is in m3. Calculate the partial molar volumes of the
components at m = 0.1 mol/kg.

4. Will it be possible to prepare 0.1 m3 of alcohol-water solution by mixing 0.03 m3

alcohol with 0.07 m3 pure water? If not possible, what volume 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 789 and 997 kg/m3 respectively. The partial molar volumes of
ethanol and water at the desired compositions are: Ethanol = 53.6 x 10–6 m3/mol; water
= 18 x 10–6 m3/mol
5. A 30 per cent by mole methanol-water solution is to be prepared. How many cubic
metres of pure methanol (molar volume, 40.727 x 10–6 m3/mol) and pure water (molar
volume, 18.068 x 10–6 m3/mol) are to be mixed to prepare 2 m3 of the desired solution?
The partial molar volumes of methanol and water in a 30 per cent solution are 38.632
x 10–6 m3/mol and 17.765 x 10–6 m3/mol, respectively.
Rubric wise marks obtained:

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Marks
 Tutorial 2
Relevant CO: 2
1. Determine the fugacity and fugacity coefficient of steam at 623 K and 1000 kPa using enthalpy

and entropy values from steam tables. Assume that steam behaves ideally at 101.3 kPa and 623

K, H = 3176 kJ/kg; S = 8.38 kJ/kg K

Data from steam tables: At 1000 kPa and 623 K, H = 3159 kJ/kg; S = 7.3 kJ/kg K.

2. Calculate the fugacity of pure ethylene at 100 bar and 373 K. The van der Waals constants are

a = 0.453 J m3/mol2, b = 0.571 x 10–4 m3/mol, molar volume at 100 bar and 373 K = 2.072 x

10–4 m3/mol.

3. Show that the fugacity of a gas obeying the van der Waals equation of state is given by where

a and b are van der Waals constants.

4. Derive an expression for the fugacity coefficient of a gas obeying the equation of state: P (V –

b) = RT and estimate the fugacity of ammonia at 10 bar and 298 K, given that b = 3.707 x 10–5

m3/mol.

5. Estimate the fugacity coefficient at 1 bar, 5 bar, and 10 bar for a gas that follows the equation

of state PV = RT (1 – 0.00513 P), where P is pressure in bar.

6. The experimental pressure volume data for benzene at 675 K from a very low 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 P is in bar. What is fugacity of benzene at 1 bar and 675 K ?

Rubric wise marks obtained:

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Marks
 Tutorial 3
Relevant CO: 2
1. The partial pressures of acetone (A) and chloroform (B) were measured at 298 K and are reported

below

xA 0 0.2 0.4 0.6 0.8 1

PA, bar 0 0.049 0.134 0.243 0.355 0.457

PB, bar 0.386 0.288 0.187 0.108 0.046 0

Calculate the activity and activity coefficient of chloroform in acetone at 298 K,

(a) Based on the standard state as per Lewis–Randall rule

(b) Based on Henry’s law.

2. The fugacity of component 1 in binary liquid mixture of components 1 and 2 at 298 K and 20 bar

is given by where 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 f1

(c) The Henry’s law constant K1

(d) The activity coefficient γ1.

3. Estimate activity coefficient of methanol for chloroform (1) / methanol (2) system at
35oC. The vapour pressures of chloroform and methanol at 35oC 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.

Rubric wise marks obtained:

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Marks
 Tutorial 4
Relevant CO: 3
1. The Henry’s law constant for oxygen in water at 298 K is 4.4 x 104 bar. Estimate the
solubility of oxygen in water at 298 K for a partial pressure of oxygen at 0.25 bar.
2. The partial pressure of acetone (A) and chloroform (B) were measured at 298 K and
are reported below:

xB 0 0.2 0.4 0.6 0.8 1

PA, bar 0.457 0.355 0.243 0.134 0.049 0

PB, bar 0 0.046 0.108 0.187 0.288 0.386

a) Confirm that the mixtures conform to Raoult’s law for component present in excess
and henry’s law for minor component.

b) Determine Henrys law constant.

3. The vapour pressure of acetone (1) and acetonitrile (2) at 327 K are 85.12 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

4. Calculate bubble point pressure for binary mixture of Benzene (1)/Toluene (2) at T=
400, 700 and 1000 K & x1= 0.4. Draw P-x1y1 diagram at different T. Also generate T-
xy diagram at pressure P = 1, 10 and 100 atm.

Antoine equation: where, P in KPa, T in K

A1=14.1603, B1=2948.78, C1 = -44.5633

A2=14.2515, B2=3242.38, C2 = -47.1806

5. For binary system Methanol (1)/Benzene (2) draw the P-xy diagram using NRTL model at
T=353K.
Data Given:

Antoine equation: where, P in KPa, T in K

A B C
Methanol 7.2059 1582.3 -33.45
Benzene 6.0306 1211 -52.35
 For NRTL equation:
G12-G22 G21-G11 A12
3291.942 4691.332 0.479

6. To find azeotropic composition and Temperature for Given system Benzene (1), Isopropanol
(2) at P =101.325 pressure using WILSON model.
Data Given:

Antoine equation: where, P in KPa, T in K

Antoine Equation Parameter:

A B C
1 6.0306 1211 -52.35
2 6.8651 1359.5 -75.65

For Wilson equation:

Molar volume:
V 1= 89.41 cm3/mol
V 2= 76.92 cm3/mol

WILSON Equation Parameter:

a12= 392.702 cal/mol
a21= 813.9198 cal/mol

Rubric wise marks obtained:

Rubrics 1 2 3 4 5 Total

Marks
 Tutorial 5
Relevant CO: 3
1. For a system in which the following reaction occurs,

Assume there are present initially 2 mol of CH4, 1 mol of H2O, 1 mol of CO, and 4 mol
of H2. Determine an expression for the mole fraction yi as function of .
2. Consider a vessel which initially contains only no mol of water vapour. If
decomposition occurs according to the reaction,

Find expression which relates the number of moles and the mol fraction of each
chemical species to the reaction co-ordinate .
3. Consider a system in which the following reactions occur:

where the number (1) and (2) indicate the value of j, the reaction index. If there are 2 mol CH4
and 3 mol H2O initially present, determine expressions for the yi as a function of and .

4. The water-gas-shift reaction is carried out under the different sets of conditions

described below. Calculate the fraction of steam reacted in each case. Assume the

mixture behaves as an ideal gas.

(a) The reactants consists of 1 mol of water vapour and 1 mol of carbon monoxide. The

temperature is 1100 K and the pressure is 1 bar.

(b) Same as (a) except that the pressure is 10 bar.

(c) Same as (a) except that 2 mol of N2 is included in the reactants.

(d) The reactants are 2 mol of H2O and 1 mol of CO,other conditions are the same as in (a).

(e) The reactants are 1 mol of H2O and 2 mol of CO. Other conditions are the same as in (a).

(f) The intial mixture consists of 1 mol of H2O, 1 mol of CO, and 1 mol of CO2 . other

conditions are the same as in (a).

(g) Same as (a) except that the temperature is 1650 K.

5. Estimate the maximum conversion of ethylene to ethanol by vapor-phase hydration at 250 oC

and 35 bars for an initial steam to ethylene ratio of 5.

Rubric wise marks obtained:

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Marks
 Tutorial 6
Relevant CO: 4

4. Develop expressions for the mole fractions of reacting species as functions of the
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)

5. A gas mixture which contained 1 mol CO, 1 mol water vapor and 1 mol 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.

6. In a laboratory investigation, acetylene is catalytically hydrogenated to ethylene at 120

o
C and 1 bar. If the feed is an equi-molar mixture of acetylene and hydrogen, what is
the composition of the product stream at equilibrium?

Rubric wise marks obtained:

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Marks
 Tutorial 7: MS- Excel based Numerical
Relevant CO: 3
1) Calculate bubble point temperature for binary mixture of Benzene (1)/Toluene (2) at P = 1atm

& x1=0.4 using Goal Seek.

2) Then generate T-xy diagram at pressure P = 1, 10 and 100 atm.(Note: Use Macro)

Antoine equation: where, P in KPa, T in K

A1=14.1603, B1=2948.78, C1 = -44.5633

A2=14.2515, B2=3242.38, C2 = -47.1806

Rubric wise marks obtained:

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Marks
 Assignment 1
Relevant CO: 1
1) Define what phase equilibrium is and provide an example from everyday life or a
chemical engineering process.
2) List and explain the conditions that must be satisfied for a system to be in phase
equilibrium.
3) Draw a simple phase equilibrium diagram for a pure substance (e.g., water) and label
the regions corresponding to solid, liquid, and vapor phases.
4) Explain the concept of phase equilibrium in binary systems and provide an example of
a binary system where phase equilibrium is important.

Rubric wise marks obtained:

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Marks
 Assignment 2
Relevant CO:

1) Define fugacity, fugacity co efficient, activity and activity co efficient

2) Discuss the phase rule and Duhem’s theorem.

3) For a closed system consisting two phases in equilibrium, explain Chemical Potential and Phase
Equliibria

4) Explain in brief about fundamental property relation. Derive Gibbs/Duhem equations relating
molar and partial molar properties.

5) List out various methods for evaluation of fugacity coefficient of pure component. Discuss any
two in detail.

6) Discuss the determination of Fugacity of pure gases by using compressibility factor method.

7) Discuss any one group contribution method to determine Activity coefficients

Rubric wise marks obtained:

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Marks
 Assignment 3:
Relevant CO: 3
1) Given the temperature and pressure for a binary system, explain how to determine the
phase(s) present and their compositions using phase equilibrium data.
2) Discuss the criteria of phase equilibrium for a homogeneous closed system. Also develop
criteria of equilibrium under various sets of constraints.
3) Using the fundamental properties relation for single phase reaction, show that ∆G0 = – RT lnK

Rubric wise marks obtained:

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 Assignment 4:
Relevant CO: 4

1. Explain effect of temperature, pressure and total stoichiometric number on equilibrium

constant.

2. Discuss in detail various methods to determine equilibrium constant.

3. Discuss various methods for checking the consistency of experimental VLE data.

4. Discuss in details feasibility of chemical reaction.

Rubric wise marks obtained:

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 Rubrics for evaluation of tutorial and assignment work

Needs
Satisfactory Inadequate
Criteria Excellent (4) Good (3) Improvemen
(2) (0)
t (1)

Student Student Student Student Student fails

demonstrates shows a clear grasps the struggles to to
a deep understandin problem but understand comprehend
understandin g of the overlooks the problem, the
g of the problem and some minor missing problem's
Problem
problem, identifies details or significant requirement
Understanding
correctly most relevant relevant data. data or s and
identifying data and variables. relevant
all relevant variables. data.
data and
variables.

Student Student Student Student Student

selects an chooses an applies a attempts a applies an
appropriate appropriate suitable methodology incorrect or
methodology methodology methodology but with inappropriat
and applies it and mostly but with major errors, e
Methodology/Applicat
accurately, applies it significant making the methodolog
ion
showing a accurately errors or solution hard y.
clear and with minor omissions. to follow.
logical step- errors.
by-step
solution.

Student's Student's Student's Student's Student's

calculations calculations calculations calculations calculations
are flawless, are mostly contain are mostly are entirely
with accurate accurate, significant incorrect, incorrect or
Mathematical numerical with only errors or leading to an absent.
Accuracy values and minor inconsistenci inaccurate
proper units numerical es that affect final result.
throughout. errors or unit the final
inconsistenci result.
es.

Student's Student's Student's Student's Student's

Writing Clarity
written written written written written
 explanations explanations explanations explanations explanations
are are clear, are generally lack clarity, are unclear,
exceptionally well- clear but may coherence, disorganized
clear, well- structured, lack some and effective , and fail to
structured, and mostly structure or organization, communicat
and effective in coherence, making it e the
effectively conveying affecting the difficult to solution
convey the the solution communicati understand process and
solution process and on of the the solution reasoning.
process and reasoning, solution process and
reasoning. with minor process and reasoning.
areas of reasoning.
confusion.

Solution is Solution is Solution is Solution is Solution is

exemplary, solid, passable but below unsatisfactor
showcasing indicating a demonstrates average, with y, failing to
exceptional good grasp of significant numerous meet basic
understandin the material room for deficiencies expectations
g, and improvement in in most or
Overall Quality
application, acceptable in several understanding all criteria.
and performance key areas. , application,
communicati in all aspects. and
on of the communicatio
process n.
calculation.
CHEMICAL ENGINEERING THERMODYNAMICS-II (3140507)

Tutorials
/Assignments are
prepared by

Prof Bhavi M Pandya

Associate Professor of Chemical Engineering Department
Government Engineering College, Valsad

Prof. Akshaysinh R. Magodara

Associate Professor of Chemical Engineering Department
Government Engineering College, Valsad

Branch
Coordinator Dr.
R. K. Mewada
Professor and Head of Chemical Engineering Department

L. E. College, Morbi

Committee

Chairman Dr N M Bhatt
Professor of Mechanical Engineering Department

L. E. College, Morbi