Course No.

: CHE F213
Course Title : Chemical Engineering
Thermodynamics
Instructor-in-Charge : Banasri Roy
Instructors (Tutorial) : Somak Chatterjee
Banasri Roy

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Outline
• Scope & Objective
• Recommended Books.
• Course plan.
• Evaluation Scheme.
• Important information

• History of thermodynamics
• Introduction to Chemical Engineering
Thermodynamics.

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Scope & Objective
• Develop ability to analyze heat, energy, and work requirement/transfer for
simple physical and chemical processes
• Determination of equilibrium constants, free energy, and other essential
conditions for simple physical and chemical changes.
• Analyze essential conditions (temperature, pressure, composition, etc.) for
simple physical and chemical changes.
• Apply thermodynamic principles in estimation/calculation of power
input/output, efficiency, etc., of simple industrial processes used for
converting heat in to other form of power (electrical, mechanical, etc.).
• Application of thermodynamic principals for understanding the criterion (G,
equilibria constant, etc. ) of simple chemical reaction at equilibria, degree of
conversion, composition and effect of P, inert gas addition, excess reactants,
products on conversion, etc.
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Recommended Books
Prescribed Text Book (TB)
• T1: Smith, J M, H C Van Ness and M M Abbott (Adapted by: B
I Bhatt), Introduction to Chemical Engineering Thermodynamics (7th
ed.), Tata McGraw Hill, Special Indian Edition 2010.
Use any other book/edition at your own risk

Reference Books (RB)

• RB1: Rao, Y V C, Chemical Engineering Thermodynamics, Universities Press, 1997.
• RB2: Narayanan K V, A Textbook of Chemical Engineering Thermodynamics,
Prentice Hall of India, 2nd ed., 2013.
• RB3 Sandler, Stanley I., Chemical, Biochemical and Engineering Thermodynamics, 4th
Edition, Wiley (India Pvt. Ltd. : Wiley Student Edition), 2006.
• RB4 Cengel, Y A and M A Boles, Thermodynamics : An Engineering Approach (SI
Units), 7th Edition, Tata McGraw Hill Education (India) Pvt. Ltd., (Special Indian
Edition, 2011: Sixth Reprint, 2013!)
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Course Plan (The following course plan is tentative. Changes according to
the class need may occur )

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CH4 + H2O ⇌ CO + 3 H2
CO + H2O ⇌ CO2 + H2
Could a solarized gas turbine
system (SGTS) be used
commercially for power
generation? How could it make
better?

• What is SGTS?
• Working design ?
• Thermodynamic analysis
(T, P, Eff….etc.,?)
• Cost analysis
• Etc. (solar methane steam reformer)

Fig. 1. Schematics of a simple

solar hybrid gas turbine system
(SHGT) (a) and a solar
reforming gas turbine system
(b).
Source: Ni et al, Thermodynamic analysis of a gas turbine cycle combined with fuel reforming for solar
thermal03-08-2019
power generation, Energy, 137, 20-30(2017) 15
Could a Solid Oxide Fuel Cell (SOFC) power plant, directly fed by biogas, be
used commercially for power generation? How could it make better?

• What is SOFC?
• Working design ? Source : Prodromidis & Coutelieris,
• Thermodynamic analysis (T, P, Eff….etc.,?) Thermodynamic analysis of
• Cost analysis biogas fed solid oxide fuel cell
• Etc.
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power plants , RE, 108, 1-
16
10(2017)
Important informations
• Chamber consultation hour : M 4-5 PM
• The notices, if any, concerning the course, will be
displayed on the NALANDA only.
• Make-up will be granted for genuine cases only.
Certificate from authenticated doctor, say from the
Medical Center, must accompany make-up
application (only prescription or vouchers for
medicines will not be sufficient). Prior permission of
IC is compulsory.
• No make-up will be granted for the tutorial, and
class participation tests.
• Students will not be allowed to enter class after
10 min.
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Important informations
• Solutions of all evaluation components (TT, CP,
Exams) will be discussed in class only.

• The answer sheets of all evaluation

components (TT, CP, Exams) will be distributed
in class.

• After 1st distribution, It will be responsibility of

the student to track the paper(s).

• Instructor(s) will not be responsible for any

misplace.
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 History of thermodynamics
https://en.wikipedia.org/wiki/History_of_thermodynamics

https://en.wikipedia.org/wiki/Timeline_of_thermodynamics

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Horror vacui
Nature abhors a vacuum

• Aristoteles (around 350 BC): Horror vacui became the prevailing

axiom for 1800 years.
• Evangelista Torricelli (1644): Invented the barometer and thereby
recognized vacuum.
• Otto von Guericke (1654): Convincing demonstrations of Magdeburg
hemispheres.

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 Vacuum (force)
Condensing water can be used to create a partial vacuum upon which
the atmosphere can do mechanical work.
• Denis Papin (1690): Demonstrated the principle of atmospheric work
(boiler, cylinder and condenser the same thing).

• Thomas Newcomen (1712): The first practical atmospheric steam

engine (with separate cylinder and boiler).

• James Watt (1769):

The improved
atmospheric steam
engine (with separate
cylinder, boiler and
condenser).
Pressure (force)
Boiling water can be used to create a pressure which is
suitable for mechanical work.

• Heron of Alexandria (ca. 50): Invented the aeolipile.

Ignored for 1800 years.
• Richard Trevithick (1808): “Catch me who can”.
• Charles A. Parsons (1884): Reaction turbine.
• Gustaf de Laval (1888): Impulse turbine.
Caloric (French)
An invisible fluid which transfer heat from one body to another without
being created or destroyed.

• Antoine Lavoisier (1783): Introduced the caloric to remedy the flaws

of phlogiston theory.
• Sadi Carnot (1824): Reflections on the motive power of fire (steam
engine analysis).
 The 1st law of thermodynamics
The energy of the universe is constant (Clausius)

• Benjamin Thompson alias Count Rumford, (1798): “An

experimental inquiry concerning the cource of the heat
which is excited by friction”.
• Julius Robert von Mayer (1842): “On the forces of the
inanimate nature”-"energy can be neither created nor
destroyed"
• James Prescott Joule (1843): Measurements on the
mechanical equivalent of heat.
• Hermann Helmholtz (1847): ”On the Conservation of
Energy”.
• Rudolf J. E. Clausius (1865): “The energy of the universe
is constant”.
The 2nd law of thermodynamics
The entropy of the universe tends to a maximum (Clausius)

• Sadi Carnot (1824): “Reflections on the motive power of fire”.

• Clapeyron (1833): The first version of the second law based
on a study of steam engines.
• Rudolf J. E. Clausius (1854): Proposes the function dQ/T as a
way to compare heat flows.
• Rudolf J. E. Clausius (1865): “The entropy of the universe
tends to a maximum”.
The 0th law of thermodynamics
If two systems A and B are in (thermal) equilibrium,
and B and C are also in equilibrium, then A and C are
in equilibrium (Maxwell).

• Santorre Santorio (1575): Used an early

thermoscope (differential thermometer).
• Gabriel Daniel Fahrenheit (1714): The first
mercury thermometer.
• Anders Celsius (1742): Observations on two
persistent degrees on a thermometer.
• Lord Kelvin (1848): A scale of absolute
temperature based on the theory of Carnot.
• James Clerk Maxwell (1872): “Two systems A and
B in thermal equilibrium with a third system C, are
in thermal equilibrium with one another”.
The 3rd law of thermodynamics
The entropy tends to zero in the limit of zero temperature. It
requires that Cp approaches zero faster than T itself.

• Walther Nernst (1906): In the limit of absolute zero

temperature, both the entropy change and the heat
capacity go to zero.
• Albert Einstein (1907): Quantum mechanic model for the
specific heat of solids deriving the law of Dulong and Petit.
The rise and fall
In no other discipline have the same equations been published so
many times by different authors in different notations and therefore
claimed as his own by each (Truesdell).
• Rudolf J. E. Clausius (1865): i) “The entropy of the universe
tends to a maximum”. ii) “The energy of the universe is
constant”.
• Josiah Willard Gibbs (1876): On the equilibrium of
heterogenous substances.
• Constantine Caratheodory (1908): Investigations about the
foundation of thermodynamics.
• The next 60 years nothing important happens!
• Clifford A. Truesdell (1983): “The tragicomical history of
thermodynamics”.
INTRODUCTION

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What is thermodynamics?
• It is a science dealing with energy and its transformation and equilibrium.

• Energy is available in several forms and it transforms from one form to

the other when the material under consideration interacts with the
surroundings.

• During this interaction, the state of the matter and its properties change
and the matter exchanges energy either as heat or work or both with
surroundings.

• Thermodynamics relates the change in the state of the matter to the

energy exchanged as heat and work with the surroundings.

• Exchange of energy can not take place beyond a certain extent and the
matter reaches a dead state or equilibrium.

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What thermodynamics can do?
• It can predict
• State of equilibrium and related conditions
• Dictates limits beyond which a given process at specified conditions can not
proceeds.
• Suppose an engineer is designing a heat engine to continuously
convert the energy possessed by the matter into the work.
• In the above case thermodynamics will tell us
• Maximum efficiency of the engine.
• Whether a given process proceed in a given direction under certain
conditions.
• In this way thermodynamics finds wide applications in
• Chemical Engineering (heat transfer, mass transfer, fluid mechanics, …….)
• Mechanical Engineering
• Aerospace engineering

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Commonly used terms in thermodynamics
• System. A system is a portion of the universe which is selected for investigations.
The system may be water taken in a beaker, a balloon filled with air, an aqueous
solution of glucose, a seed, a plant, a flower, a bird, animal cell etc.
I. An open system. It is a system which has permeable boundary across which the
system can exchange both the mass (m) and energy (U) with the surroundings. In
terms of symbolic notation it may be stated that in an open system
∆m ≠ 0 and ∆U ≠0.
I. A closed system. It is a system with impermeable boundary across which the
system cannot exchange the mass (m) but it can exchange energy (U) with the
surroundings. In terms of symbolic notation it may be stated that in an open
system ∆m = 0 but ∆U ≠0
II. An isolated system. It is a system with rigid and adiabatic boundary across which
neither exchange of mass (m) nor energy (U) between the system and the
surroundings is not permissible.
In terms of symbolic notation it may be
stated that in an isolated system ∆m = 0
and ∆U =0. Milk kept in a thermos flask is
an example of an isolated system.
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• Surroundings. The rest of the universe, which can interact with the system,
is called surroundings. For practical purposes the environment in the
immediate vicinity of the system is called the surroundings. The boundary
may be real or even imaginary
• Boundary. The space that separates the system and the surroundings is
called the boundary. The system and surroundings interact across the
boundary
Types of transfers permitted by types of wall
type of wall type of transfer
Matter Work Heat
permeable to
x x
matter
permeable to
energy but
x
impermeable to
matter
adiabatic x x
adynamic
andimpermeable x x
to matter
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Extensive and intensive properties
Extensive property. A property which depends directly on the size of the system.
Volume, mass and amount (mole) are extensive properties.

Characteristics of an extensive property

• An extensive property of the entire system is greater than any of its smaller parts.
• The sum of the properties of subsystems is equal to the same property of the
entire system. This means that the extensive properties are additive.

Intensive property. A property which does not depend on the size of the system.
Density, temperature and molarity are intensive properties.

Characteristics of an intensive property

• An intensive property of a homogeneous system is the same as that of any of its
smaller parts.
• The intensive properties are nonadditive.

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Principles of thermodynamics
• Thermodynamic principles can be summarized in the form of
four laws
• Zeroth law of thermodynamics
• First law of thermodynamics
• Second law of thermodynamics
• Third law of thermodynamics
• Zeroth law: it is about thermal equilibrium between a set of
bodies.
• First law: It relates the changes in the energy of matter under
consideration with the energy exchanged as heat and work with
its surroundings.
• Second law: it dictates the limit to which the energy possessed
by matter can be converted into work. It is a mean of comparing
the performance of several device.
• Third law: it defines the absolute zero of entropy.

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Macroscopic and Microscopic approaches
• Macroscopic Approach
• When the state of matter under
consideration is described in terms of
macroscopically measurable quantities like
temperature, pressure, composition,
volume.
• The structure of the matter under
consideration is not taken into account.
• Macroscopic approach is adopted in
classical thermodynamics.
In this subject we are going to focus on
classical and Equilibrium
thermodynamics and its applications to
analyze problems concerning a chemical
engineer.
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• Microscopic approach
• Now, all matter consists of a large number
of microscopic particles called atoms and
molecules.
• So, the gas mixture in the reactor can be
considered as an assembly of a large
number of molecules and these molecules
move at random with independent
velocities. In this way, the state of a
molecule can be specified in terms of its
position coordinates (x, y, z) and the
velocity components (Vx, Vy, Vz) in the x, y
and z directions.
• Hence, to describe the state of a collection
of a large number of molecules we have to
specify a large number of variables.
• These large number of variables can not be
measured.
• A knowledge of structure of matter is
essential in this approach.
• Microscopic approach is adopted in
statistical thermodynamics.
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Work
• Work W is performed whenever a force acts through a
distance. dW = F dl
• Where F is the component of force acting along the line
of the displacement dl.
• When integrated this equation yields the work of a finite
process.
• By convention, work is regarded as positive when the
displacement is in the same direction as the applied force
and negative when they are in opposite directions (e.g.
friction force).

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Work in the piston cylinder arrangement
• Consider a piston cylinder arrangement involving the change in the volume
of the fluid with work.
• The force exerted by the piston on the fluid is equal to the product of the
piston area (A) and the pressure of the fluid.
• The displacement of the piston is equal to the total volume change of the
fluid divided by the area of the piston.
𝑉𝑡
dW=-P Ad
𝐴
dW=-P d𝑉 𝑡
𝑉2𝑡
Integrating = - ‫𝑑 𝑡 𝑉׬‬ 𝑉𝑡
1

• The negative sign in these equations are made

necessary by the sign convention adopted for work.
• As volume change during compression is negative.
This negative sign make the work positive during
compression (according to sign convention).

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 Kinetic theory

• Daniel Bernoulli (1733): Gave birth to kinetic gas theory.

Forgotten until 1859.
• John Herapath (1816): Awaked kinetic theory. Ignored.
• John James Waterston (1843): Awaked kinetics theory.
Ignored.
• James Clerk Maxwell (1859): Rigorously established
kinetic theory.
• Ludwig Boltzmann (1871): Ergodic theorem.
Energy
1. Kinetic Energy: when a body of mass m, acted upon by a force F, is
displaced a distance dl during a differential interval of time dt, the work
done is given by

dW = f dl = m a dl (m = mass, a = acceleration, u = velocity of the body)

𝑑𝑢
Here, a ≡
𝑑𝑡
𝑑𝑢 𝑑𝑙 𝑑𝑙
So, dw = dl = m 𝑑𝑡 𝑑𝑢. Here u ≡ 𝑑𝑡
m 𝑑𝑡
dw = m u du
• This equation can be integrated for a finite change in velocity from u1 to u2
𝑢 𝑢22 𝑢12 𝑚 𝑢2
W=m ‫ 𝑢׬‬2 𝑢 𝑑𝑢 = m
2
−
2
=Δ
2
1

• Now, each of the quantities ½ mu2 is a kinetic energy.

• This term was introduced by Lord Kelvin in 1856.
1
𝐸𝑘 ≡ 𝑚 𝑢2
2
Symbol ≡ (triple bar)
x ≡ y means x is defined to be another name for y, under certain assumptions taken in context.
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Potential Energy
• If a body of mass m is raised from an initial elevation z1 to a
final elevation z2, an upward force at least equal to the weight
of the body must be exerted on it, and force must move
through the distance z2 – z1.
• As the weight of the body is the force of gravity on it, the
minimum force required is given by Newton’s law:
F = ma = mg
• The minimum work required to raise the body is the product
of this force and the change is elevation:
W = F (z2 – z1) = mg(z2 – z1) = Δ (mzg)
• The quantity (mzg) is the potential energy
Ep ≡ mzg

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Energy Conservation
• In any examination of physical processes, an attempt is made
to find or to define quantities which remain constant
regardless of the changes which occur. For example mass (m).
• What is the use of law of conservation of mass?
• Answer: other conservation principles could be of comparable
values.
• The discussion about energy that we have so far show that
work done on a body is equal to the change in a quantity
(energy) which describe the condition of the body in relation
to its surroundings.
• Now, if the work done on a body can be recovered then the
body by virtue of its velocity or elevation contains the ability to
do the work.
• This capacity of the body to do work is given name energy
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• Hence the work of accelerating a body produces a change in its
kinetic energy
W = Δ EK = Δ (m u2/2)
• Also, work done on a body in elevating it produces a change in
its potential energy.
W = Δ EP = Δ (m z g)
• If an elevated body, allowed to fall freely, gains in kinetic
energy and lose in potential energy so that its capacity for
doing work remains unchanged.
Δ EK + ΔEP = 0
m u22/2 – mu21 /2 + m z2 g – m z1 g = 0
• The validity of this equation has been confirmed by countless
experiments.

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Problem 1.17

The turbines in a hydroelectric plant are fed by water falling

from a 50 m height. Assuming 91% efficiency for conversion
of potential to electricity , and 8% loss of the resulting
power in transmission, what is the mass flow rate of water
required to power a 200-watt light bulb?

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Problems for self Study
Smith, J M, H C Van Ness and M M Abbott Ch1:

1.3,
1.5,
1.12,
1.22,
1.23,
1.70

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What will we do in the next class (6th August, 2019)
?
• Start Ch 2 of Smith, J M, H C Van Ness and M M Abbott

1. Identify different forms of energies,

2. Understand applications of 1st law
3. Understand concepts of Enthalpy, Heat capacity, Mass
and energy balance for open systems.

• SOLVE PROBLEMS from Chs 1 & 2

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Thank You!

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