Mendoza Rmo Introduction To Chemical Thermodynamics

INTRODUCTION TO CHEMICAL
THERMODYNAMICS
INTRODUCTION TO CHEMICAL
THERMODYNAMICS
Rose Marie O. Mendoza
ARCLER
P r e s s
www.arclerpress.com
Introduction to Chemical Thermodynamics
Rose Marie O. Mendoza
Arcler Press
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ABOUT THE AUTHOR
Dr. Rose obtained her PhD in Chemical Engineering from the University
of the Philippines-Diliman in 2013. She is also a Professor in the Graduate
School Department under the Master of Engineering Program at Adamson
University since 2006, and is a Visiting Research Fellow at the Department of
Environmental Engineering and Science, and the Department of Environmental
Resource Management in Chia Nan University of Pharmacy and Science,
Tainan Taiwan since 2010. She is now taking up her Post Doctorate Degree
in Green Power: Hydrogen Generation and Fuel Cell Development at the
University of Philippines-Diliman under the Department of Mining, Metallurgy
and Materials Engineering and the University of California, Merced, USA
under the Department of Mechanical Engineering.
TABLE OF CONTENTS
List of Figures ........................................................................................................xi

List of Abbreviations ...........................................................................................xiii
Preface........................................................................ ........................................xv
Chapter 1 Introduction to Thermodynamics .............................................................. 1

1.1. Introduction ........................................................................................ 2
1.2. History of Thermodynamics ................................................................ 5
1.3. The Four Laws of Thermodynamics.................................................... 10
1.4. Applications of Thermodynamics ...................................................... 15
1.5. Thermal Efficiency ............................................................................ 16
Review Questions ................................................................................... 17
References ............................................................................................... 18
Chapter 2 Chemical Thermodynamics And Its Origin.............................................. 21

2.1. Introduction ...................................................................................... 22
2.2. History of Chemical Thermodynamics............................................... 25
2.3. Human Chemical Thermodynamics .................................................. 29
2.4. Objectives of Chemical Thermodynamics ......................................... 31
2.5. Limitations of Classic Thermodynamics ............................................ 32
Review Questions .................................................................................... 38
References ............................................................................................... 39
Chapter 3 Principles of Chemical Thermodynamics ................................................ 41

3.1. Introduction ...................................................................................... 42
3.2. Thermodynamics Equilibrium ........................................................... 45
3.3. Principles of Thermodynamics .......................................................... 48
3.4. Kinetic Theory of Gases .................................................................... 58
Chapter 4 Chemical Thermodynamics Laws ............................................................ 63
4.1. Introduction ...................................................................................... 64
4.2. Systems And Surroundings ................................................................ 65
4.3. Internal Energy.................................................................................. 68
4.4. Difference Between First And Second Law Of Thermodynamics........ 69
4.5. The Zeroth Law Of Thermodynamics................................................. 72
4.6. The First Law Of Thermodynamics .................................................... 73
4.7. The Second Law Of Thermodynamics ............................................... 75
4.8. The Third Law Of Thermodynamics ................................................... 78
4.9. Conclusion ....................................................................................... 78
References ............................................................................................... 80
Chapter 5 Chemical Energy And Chemical Thermodynamics .................................. 81

5.1. Introduction ...................................................................................... 82
5.2. Chemical Energy............................................................................... 85
5.3. Chemical Thermodynamics ............................................................... 91
References ............................................................................................... 99
Chapter 6 Thermodynamic Equilibrium In System ................................................. 101

6.1. Introduction .................................................................................... 102
6.2. Types Of Thermodynamic Equilibrium ............................................ 104
6.3. Thermodynamic Stability ................................................................ 108
6.4. Thermodynamic Vs. Kinetic Stability ............................................... 110
6.5. Thermodynamic Equilibrium Constant ............................................ 111
6.6. Theoretical Analysis On Thermodynamic Stability Of Chignolin ...... 112
6.7. Approach To Thermodynamic Equilibrium....................................... 115
Review Questions .................................................................................. 117
References ............................................................................................. 118
Chapter 7 Thermodynamics Of Chemical Mixtures ............................................... 123

7.1. Introduction .................................................................................... 124
7.2. Mixtures ......................................................................................... 125
7.3. Saturated States............................................................................... 127
7.4. Introduction To Calculations In Mixing ........................................... 128
viii
7.5. Case Of Ideal Mixtures .................................................................. 131
7.6. The Entropy In The Process Of Mixing ............................................. 134
References ............................................................................................. 141
Chapter 8 Chemical Thermodynamics And Biological

Systems ................................................................................................. 143
8.1. Introduction .................................................................................... 144
8.2. Role Of Chemical Thermodynamics In Living Organisms ................ 148
8.3. Biotechnology And Chemical Thermodynamics .............................. 152
8.4. Scientific Applications of Chemical Thermodynamics
in Biological Systems ................................................................... 153
8.5. Some Real-Life Applications of Chemical Thermodynamics ............ 155
References ............................................................................................. 161
Chapter 9 Applications of Chemical Thermodynamics .......................................... 165

9.1. Introduction .................................................................................... 166
9.2. Application of Thermodynamics In Electrical Appliances ................ 167
9.3. Application of Thermodynamics In Thermal Machines
And Heat Engines......................................................................... 173
9.4. Application of Thermodynamics In Biotechnology .......................... 176
9.5. Application of Thermodynamics In Food Processing........................ 178
9.6. Conclusion ..................................................................................... 182
References ............................................................................................. 184
Chapter 10 Future of Chemical Engineering As A Product of

Chemical Thermodynamics ................................................................... 185
10.1. Introduction .................................................................................. 186
10.2. Grand Challenges In Chemical Engineering .................................. 187
10.3. Importance of Chemical Engineering ............................................ 195
10.4. Application of Chemical Engineering ............................................ 197
10.5. Significance of Chemical Engineering Thermodynamics ................ 198
References ............................................................................................. 203
Index ..................................................................................................... 205
ix
LIST OF FIGURES
Figure 1.1: Basic principles of the thermodynamics

Figure 1.2: History of the thermodynamics
Figure 1.3: The zeroth law of the thermodynamics
Figure 1.4: The first of the thermodynamics
Figure 1.5: The second law of thermodynamics
Figure 2.1: The graph shows that during a chemical reaction, free energy
decreases until the reactions reach equilibrium. In simple words, the curve
moves based on the conditions of the reaction
Figure 2.2: Josiah Willard Gibbs: His work on the thermodynamics applications
was helpful in changing physical chemistry into a deductive science
Figure 2.3: Barometer, one of the human thermodynamic instrument
Figure 3.1: Graph shows the Carnot cycle
Figure 3.2: Mechanical equilibrium
Figure 3.3: Thermal equilibrium
Figure 3.4: Types of systems
Figure 3.5: Water enthalpy formation
Figure 3.6: Gibbs free energy for spontaneous and non-spontaneous reactions
Figure 3.7: Movement of gas particles
Figure 4.1: Systems and surroundings in the chemical reaction process
Figure 4.2: Transformation of electrical energy into light energy and heat
energy
Figure 4.3: Basic functioning of the first law of thermodynamics
Figure 4.4: Process of entropy in the second law of thermodynamics
Figure 5.1: Basic thermodynamics systems
Figure 5.2: Basic thermodynamics Engine
Figure 5.3: Enthalpy graph
Figure 5.4: Entropy system
xi
Figure 6.1: Zeroth law of thermodynamics: an example in equilibrium
Figure 6.2: An example of mechanical equilibrium
Figure 6.3: An example of thermal equilibrium
Figure 6.4: An example of chemical equilibrium: Pentacene 6-methyl
equilibrium
Figure 7.1: Solutions form an integral part of the chemical mixtures
Figure 7.2: The mixtures may be found in natural form as in that of sugar and
tea
Figure 7.3: In gypsum, some substance may be found in saturated forms
Figure 7.4: A separation of gases depicted in a system
Figure 8.1: The involvement of the chemical thermodynamics in the biological
systems have explained many phenomenon like that of metabolism
Figure 8.2: The functions that take place inside a leaf are capable of denoting
and explaining the Laws of Chemical Thermodynamics that are used in the
biological systems
Figure 8.3: Application of chemical thermodynamics in biological systems on
scientific level has helped in the detection of many serious diseases
Figure 8.4: The understand of the chemical thermodynamics at biological level
helps in explaining the changes that takes place in the genetic codes
Figure 8.5: Melting of ice explains the application of chemical thermodynamics
in relation with the Biological systems in daily life
Figure 9.1: Nicolas Léonard Sadi Carnot, the Father of thermodynamics
Figure 9.2: Application of thermodynamics in refrigeration
Figure 9.3: Representation of Carnot Heat Engine
Figure 9.4: Application of thermodynamics in studying cell behavior
xii
LIST OF ABBREVIATIONS
CO carbon monoxide
DNAs deoxyribonucleic acids
DSC differential scanning calorimetry
ITC isothermal titration calorimetry
IUPAC International Union of Pure and Applied Chemistry
MD molecular dynamics
RNAs ribonucleic acids
WRAP Waste and Resources Action Programme
PREFACE
Thermodynamics is a very significant branch of science, which deals with the

dynamics of a process that involves heat in itself. The branch of thermodynamics
has a wide range of applications across many disciplines that deal with the
understanding of matter and its transformations. The energy can be created by
the processes that are undertaken in thermodynamic conditions to be utilized in
different domains and applications.
Chemical thermodynamics deals with the dynamics of heat and energy dissipation
in the chemical processes. There are a lot of instances at which the products are
made out of chemical reactions between the compounds and substances. These
reactions may dissipate heat in the process and the calculation of these energies
and heat can provide a path for their utilization in appropriate places.
This book brings the focus of the readers to the subject of chemical
thermodynamics and explains its importance in the industrial setup and the
processes that take place and will explain the different energy requirement and
energy conversions in each unit processes involving chemical reactions.
Salient Features of the Book:
• The book begins by introducing the subject of thermodynamics to the
readers. It defines thermodynamics and lists its various laws. The book
also focuses on the history of thermodynamics, and briefly explains its
applications. It also explains the readers the meaning of thermal efficiency
and states its significance in the processes.
• The book moves further to describe chemical thermodynamics and how
it came into existence. It explains the historical perspectives related to
the field and its relation with the modern outlook of the subject. The book
also focuses on the topic of human chemical thermodynamics and lists its
various objectives and limitations.
• Moving further, the book brings the focus of readers to the principles of
chemical thermodynamics. It explains the various variables involved in
the thermodynamic processes. It explains the meaning of thermodynamic
equilibrium and the principles governing energy utilization,
transformation, and dissipation of related chemical processes. The book
also explains the readers about the kinetic theory of gases.
• The book states the various laws relating to chemical thermodynamics.
It lays down the application of all the laws related to chemical
thermodynamics and discusses the ways in which these laws can help in
certain processes.
• The book explains the release of chemical energy in the thermodynamic
processes that concern the chemical reactions. It also states the various
uses of the energy that is released in the chemical thermodynamic
processes.
• The provides information on the zeroth law that concerns equilibrium
in a system and explains the importance of attaining the equilibrium in
a process or a system. The book explains different kinds of equilibrium
that exist in nature. It also discusses thermodynamic stability and
compares it with kinetic stability. The book discusses about the constant
of thermodynamic equilibrium and approach that may be taken to achieve
the state of equilibrium.
• The book also covers discussions on mixtures and their importance in
chemical thermodynamics. It explains the meaning of solutions and
mixtures and illustrates techniques on the derivation of energy dissipated
by the process of mixing various substances which are ideal and non-
ideal in nature.
• The readers are further informed about the relation between chemical
thermodynamics and biological systems. The book explains the role of
chemical thermodynamics in the living organisms and the application of
the First Law of Thermodynamics to their existence and activities. The
book also uncovers the prospects of collaboration between biotechnology
and chemical thermodynamics and goes on with the list of various
scientific applications in the thermodynamic fields.
• The book also discusses various applications of chemical thermodynamics
in the vertical spanning from the generation of electricity to its uses in
the field of biotechnology. It also brings to the reader’s focus on the
application of chemical thermodynamics in the field of food technology
and preparation.
xvi
CHAPTER
1 INTRODUCTION TO
THERMODYNAMICS
KEYWORDS LEARNING OBJECTIVES:

• Thermodynamics In this chapter, you will learn about:
• The Zeroth Law • To understand the concept of the
Thermodynamics and its association with
• Thermal Efficiency
the different aspects of day to day functions
• Solar Panels
• To access the knowledge about
• Entropy the development of the concept of
• Pattern of Changes thermodynamics from the earlier times
• Natural Gas • To acquire the knowledge of the various
• Kinetic Theory of laws of thermodynamics and how they
Gases were formed
• Microscopic Physics • To gain knowledge about the applications
• Thermodynamic of the thermodynamics
Equilibrium • To know about the certain possible
methodologies for the different tests to
verify the four laws of Thermodynamics
• To know the about the Thermal efficiency
in the role that the laws of thermodynamics
plays in the calculation of the thermal
efficiency of any system
2 Introduction to Chemical Thermodynamics
1.1. INTRODUCTION
Thermodynamics is the science of transformation of energy from one
location or state to one more location or state. It explains the relationship
between heat and temperature and how these two are being utilized to
complete a process designed to yield specific products.
More precisely, these are the major topics of mass and energy
conservation principles; first law is concerned on the analysis of control
mass and control volume systems; properties and behavior of pure
substances; and applications to thermodynamic systems operating at
steady state conditions.
Figure 1.1: Basic principles of the thermodynamics.

Source: https://upload.wikimedia.org/wikipedia/commons/thumb/b/
b6/System_boundary.svg/2000px-System_boundary.svg.png
The word “thermodynamics” is a combination of the terms; ‘Thermo’

that denotes “Energy” and ‘Dynamics’ meaning “Pattern of changes.”
In scientific terms, the study of the deviations in the energy that is
linked with the physical and chemical aspects of the reaction is known
as thermodynamics. In usual terms, Thermodynamics is the study or
the process of gaining thee knowledge about the effect of work, heat
and energy on any natural or man-made system. When the alterations
in the energy are observed from the point of view of chemistry, it is
known as the chemical thermodynamics.
Introduction to Thermodynamics 3
Thermodynamics is the study of energy,

predominantly in terms of heat energy, that Chemical ther-
go together with the biochemical or physical modynamics is
changes. The chemical processes emit heat the study of the
interrelation of heat
energy; they are known as exothermic reactions,
and work with chem-
and these kinds of reactions have a negative ical reactions or with
enthalpy. Other reactions absorbs heat energy physical changes
and are known as endothermic reactions. of state within the
The enthalpy of endothermic reactions is confines of the laws
usually positive. Enthalpy is defined as the of thermodynamics.
thermodynamic equivalent of the total heat of
the system. It is equivalent to the internal energy
of the system plus the product of pressure and
volume.
However, specifically, Thermodynamics
deals further than heat and temperature. The
changes in the organization or disorganization
of reactants and products as deviations that
occur is described by the entropy variation of the
process. For instance, the transformation of one
gram of the water in liquid state to water vapor
or water in the gaseous state is because of the
disorder in molecules of the liquid water. The
liquid water molecules become disorganized as
it is transformed into a vapor. The increases in
disorder is characterized by a rise in entropy,
and the change in entropy is positive.
Whether a chemical reaction or physical
variation takes place, it relies on both the
enthalpy and entropy of the process. Both terms
are mutual in the free energy. Free energy is
the third in line and one of the most significant
thermodynamic term and can be simply
described as the amount of energy of a process
that can be converted to work. A spontaneous
reaction is reaction of which the changes in the
free energy is negative. When the changes in
free energy of a process is positive, this means

that. A positive internal energy indicates that
the reverse or the backward reaction is the one
that will take place because the reaction is non-
spontaneous.
Thermodynamics is one of the influential
instruments used for the understanding as to
“will the reaction take place or not.” It gives an
idea if the process is energy intensive or energy
extensive and what type of reaction is most
likely to take place naturally; the forward or the
backward reaction.
The observations and the study of alterations
in energy and chemical reaction are grounded on
the fundamental principles of thermodynamics
known as the ‘laws of thermodynamics.’ These
are the zeroth law, first law, second law and third
law of thermodynamics.
It is often said that contemporary gasoline
engines cannot be produced to be meaningfully
more effective. The same observation is listed
Electrical energy is by many scientists about the process of heat
a form of en-
ergy resulting from
transfer to the electrical energy in large-scale
the flow of elec- energy stations, whether they are powered by
tric charge. the different sources like the non-renewable
sources of energy such as coal, oil, natural gas,
or nuclear.
There are many queries that boils down to as to
“Why is that the situation?”; “Is the wastefulness
produced by the design complications can be
resolved with improved production and the usage
of superior materials?”; Is it the combination of
the few money-producing schemes by some of
the companies who control the energy market?.”
Thus, the fact that these questions are more
stimulating because it can be addresses in the
thermodynamic point of view and discloses

much more about the nature of heat transfer.
Elementary physical rules and laws control
the process through the heat transfer mechanisms
particularly in completing certain work and
functions as it takes place and which limits its
own effectiveness.
1.2. HISTORY OF THERMODY-

NAMICS
For a long period, many physicists and scientists
discussed if the heat was a watery substance, like
the enigmatic fluid, or is it from the direction
of the atoms. Many early experts, like Newton,
proposed that heat could be produced by minor
drive of the atoms, and larger amount of heat
referred as the superior velocities or kinetic
energies. Lavoisier, on the other hand, believed
that heat was a massless liquid that was referred
or called as the “caloric.”
Thermodynamics as an extensive division
of physical science had an extended ancient
expansion from the early times to the recent
times in the 20th century. The creation of the
thermometer was the primary and significant
step that has made conceivable to plan the
primary exact assumptions on the heat.
There were no precise philosophies for the
exact nature of heat for a very long period of
time and even the widely held assumptions of the
technical world in the entire eighteenth century
and the initial nineteenth century observed
heat as a matter and the quantity to denote the
actions of the Kinetic Theory were forbidden
and remained in the framework.
Figure 1.2: History of the thermodynamics.

Source: https://upload.wikimedia.org/wikipe-
dia/commons/d/dc/Thermodynamics.gif
The Caloric theory magnificently clarified

ample of the natural spectacles like gas laws
and heat transmission and it was not possible
to disprove these theories up until the eras of
1850s when the Principle of Conservation of
Energy was presented by the group of scientists
which comprised of scientists like Mayer,
Joule, Helmholz. After the Caloric theory, the
second law of thermodynamics was revealed
soon after that clarification of the inclination of
thermodynamic procedures and the dissipation
of the heat in the form of energy form the amount
of useful heat.
The concept of the kinetic theory of gases
inspired the experts of the thermodynamics to
present the perception of entropy that was a
based to verbalize the laws of thermodynamics
in a faultless mathematical procedure and
originated an innovative division of the
physics called statistical thermodynamics. The

Third Law of Thermodynamics was revealed
in the initial years of the twentieth century
after the familiarization with the idea of the Absolute tempera-
thermodynamic potentials and the development ture is the tempera-
of the absolute temperature scale. At the ture of an object on
similar period of time the technical question of a scale where 0
is taken as abso-
the thermal energy was also resolved. lute zero.
According to the detailed history reports of
the Thermodynamics, there were many trials
that were conducted by James Joule and many
others in the era of the 1840s put many earlier
concepts in uncertainty, and eventually during
the 1850s, it was acknowledged that heat is, as a
matter of fact, a form of energy.
The connection amongst the heat and energy
was significant for the expansion of the segment
of the steam engines, and in the year 1824,
scientists Sadi Carnot had apprehended near
about few of the ideas of thermodynamics in
his conversation of the effectiveness of an ideal
engine.
Around the year of 1850, Rudolf Clausius
and William Thomson Kelvin quantified both
the First Law – that entire energy is well-looked-
after – and the Second Law of Thermodynamics.
The Second Law of the Thermodynamics was
in the beginning expressed in standings of the
detail that heat does not impulsively movement
from a cooler form to a hotter.
Other inventions trailed rapidly, and Kelvin
in specific made clear about some of the laws
of the general insinuations. The concept that
vapors contain of particles in gesture had be
situated deliberated in some aspect by Daniel
Bernoulli in the year 1738, but had fall over out
of kindness, and was invigorated by Clausius in

1857.
Subsequent to this, James Clerk Maxwell in
the year 1860 consequent from the procedure
of separate molecular collisions the predictable
circulation of molecular swiftness in a gas.
Over the subsequent numerous ages, the kinetic
theory of gases industrialized speedily, and
numerous macroscopic possessions of vapors in
symmetry were calculated. In the year of 1872
Ludwig Boltzmann completed a calculation that
they supposed might label the comprehensive
period of growth of a gas, whether in symmetry
or not.
In the era of 1860s, Clausius had presented
entropy as a proportion of heat to temperature,
and had quantified the Second Law of
Thermodynamics in terms of the rise of this
amount. Boltzmann then presented that his
calculation explained the so-called H Theorem,
which circumstances that an amount an equal to
entropy in equilibrium might continuously rise
with span of time.
At first, it gives the impression that Boltzmann
had positively demonstrated the Second Law
of Thermodynamics. But then it was observed
that since molecular crashes were expected
alterable, his root could be driven in opposite,
and would then suggest the contradictory nature
of the Second Law of Thermodynamics.
Much well along it was understood that
innovative calculation of the Boltzmann
indirectly presumed that particles are
uncorrelated beforehand every collision, but not
after that, by this means making known to an
important asymmetry in the particular period of
time. In the period of early part of the 1870s,

Maxwell and Kelvin thought to have already
gained the knowledge about the Second Law.
They learned that the Second law of
Thermodynamics might not officially be found
as the resultant of the microscopic physics. But
Maxwell and Kelvin had already observed that
the Second Law of Thermodynamics should,
one way or another, be a result of the human
incapability to keep a track of the huge quantity
of the molecules. In answering to demurrals
regarding the reversibility, the scientist
Boltzmann understood near about the year 1876
that in a vapor or a gas there are number of states
that are considered as the arbitrary than seem to
be organized in a simple manner.
Though, by the dawn of the period of the
year 1930s, the Second Law of Thermodynamics
had, one mean or another, come to be usually
considered as a principle of physics whose
fundamentals should be interrogated only as an
inquisitiveness.
In spite of the negligence in the field of
Ergodic theory is
physics, though, ergodic theory became an a branch of math-
active field of pure mathematics, and from ematics that studies
the year 1920s to the year 1960s possessions dynamical systems
that are linked to ergodicity were well-known with an invariant
measure and related
for several types of simple systems. When
problems.
automatic computers became accessible in the
era of 1950s, Enrico Fermi and other scientists
began to inspect the ergodic features of nonlinear
structures of springs.
But these experts were ended up focusing
on reappearance phenomena which is associated
to solitons, and not observing the basic queries
that are linked to the Second Law. Much the
similarity occurred in the era of 1960s, when the

initial simulations of solid sphere gases were
directed to focus on the definite procedures of
long-time tails.
And by the era of 1970s, computer researches
were frequently concerned in the direction of the
ordinary difference calculations and eccentric
attractors, relatively than in the direction of
the systems with great numbers of elements, to
which the Second Law of thermodynamics is
applied. Beginning in the era of 1950s, it was
predictable that entropy is just the negative of
the data quantity that was announced in the year
1940s by Claude Shannon.
1.3. THE FOUR LAWS OF THER-

MODYNAMICS
Thermodynamic Equilibrium: If an item with a
higher temperature comes into direct connection
with an item which is at a lower temperature, it
will transmit the high temperature to the lower
temperature item. The bodies will approach
the same temperature, and avoiding further
temperature loss to, or gain from, different
bodies or systems, they will uphold a solitary
continual temperature.
1.3.1. The Zeroth Law

This law describes that if two thermodynamic
systems are respectively in thermal equilibrium
with a third system, then they are considered to
be in thermal equilibrium with each other.
In a simpler context, if both the systems one
as well as two are in equilibrium with system
three, they, thus, each have the similar amount

of energy as compared to that of the system
three. If this is the situation, then the values that
is presented in system three must be analogous
those that is present in both systems one as well
as two systems. Thus, the values of one and two
systems must also be analogous in nature, it
means that the one and two system have to be in
balance with each of the systems present.
Figure 1.3: The zeroth law of the thermodynamics.

Source: https://upload.wikimedia.org/wiki-
p e d i a / c om m ons/thum b/4/4a/T h r e e - sys -
tems-for-zeroth-law-of-thermodynamics.
svg/1170px-Three-systems-for-zeroth-law-of-
thermodynamics.svg.png
1.3.2. The First Law of Thermodynamics

The First Law of Thermodynamics deals with
the entire quantity of energy in the world.
The law describes that this entire quantity of
energy is continuous. In other terms, there has
always been, and always will be, accurately
the similar quantity of energy in the world.

Between all of the Laws of which comes
under the Thermodynamics, the first law of
the thermodynamics is relatively much easier.
The first law of the thermodynamics enlightens
that when the heat is additional combined to a
system, some of that energy stays in the system
and some leaves the system. Energy can neither
be produced nor destroyed. Energy can only
change forms. The energy that emits the system
cooperates with the area around it. Energy that
stays in the system generates an increment in the
internal energy of the system.
Figure 1.4: The first of the thermodynamics.

dia/commons/thumb/8/86/First_law_open_sys-
tem.svg/1280px-First_law_open_system.svg.
png
For instance, if you have a pot of water

at room temperature and add some heat to it,
first and foremost, the temperature and energy
of the water rises. Secondly, the system emits
some types of energy and it cooperates with the
environment around it. Perhaps heating the air

from place to place the water and making the
air rise.
For a thermodynamic cycle, the net heat
Thermodynamic
which is provided to the system age group to the cycle is a series
network done with the help of the system. of thermodynam-
ic processes which
returns a system to its
1.3.3. The Second Law of Thermodynam- initial state.
ics
The Second Law of Thermodynamics enlightens
that it is incredible to have a cyclic process that
changes the heat entirely into the form of work.
This means that no reaction is fully effective
or 100% efficient. Some amount of energy in a
reaction is always lost in the form of heat. In the
same way, a system which cannot change all of
its energy in to the form of working energy.
It is also nearly not possible to have a process
that transmits the heat from cool objects to the
warmer objects without any help of work. A
cold body cannot heat up a body which is much
warmer as compared to the cold one.
Heat naturally needs to flow from the warmer
areas to areas which are cooler. Heat needs to
flow and spread out to areas with less heat. If
heat is going to transfer from cooler areas to the
warmer areas, the system must put in some work
for it to occur.
In the Second Law of Thermodynamics, the
heat does not move instinctively from a colder
region to a hotter region, or, homogeneously, heat
at a given temperature cannot be transformed
completely into the work. Subsequently, the
entropy of a closed system, or heat energy per
unit temperature, rises over time in the direction

of some maximum value.
Figure 1.5: The Second Law of Thermodynamics.

dia/commons/0/02/Heat_flow_hot_to_cold.png
Therefore, all closed systems are shifting in

the direction to an equilibrium state in which
entropy is at a maximum level and no energy is
accessible to do useful work. This irregularity
sandwiched between forward and backward
procedures which give increment to what is
known as the “arrow of time.”
1.3.4. The Third Law

Entropy is the amount of the random action in a
system. By random, it means energy that cannot
be utilized to perform any type of work. The
Third Law of thermodynamics states that the
entropy of an object methods to a continuous as
its temperature tends to the absolute zero. The

third law of thermodynamics. The entropy of a Absolute zero is the
lowest temperature
perfect crystal of an element in its most steady
possible. At a
form which is leading toward the zero as the temperature of abso-
temperature reaches the absolute zero. This lute zero there is no
permits an absolute measure for entropy to be motion and no heat.
recognized that, from a statistical point of view,
governs the amount of randomness or disorder
in a system.
1.4. APPLICATIONS OF THERMO-

DYNAMICS
• All of the kinds of vehicles that people
use, cars, motorcycles, trucks, ships,
aero planes, and several numbers of
other types work on the basis of the
Second Law of Thermodynamics and
Carnot Cycle. They may be driven
with the help of petrol engine or diesel
engine, but the law relics the same.
• All of the refrigerators, deep freezers
as well as industrial refrigeration
systems, all kinds of air-conditioning
systems, heat pumps, etc., operate
with the help of the Second Law of
Thermodynamics.
• All of the types of air and gas
compressors, blowers, fans, run on
several numbers of thermodynamic
cycles.
• One of the most crucial area of
thermodynamics is heat transfer,
which link the transfer of heat between
two media. There are three types
of heat transfer which is known as
conduction, convection and radiation.

The idea of heat transfer is utilized
in wide range of devices such as heat
exchangers, evaporators, condensers,
radiators, coolers, heaters, etc.
• Thermodynamics also take in study of
several types of power plants such as
thermal power plants, nuclear power
plants, hydroelectric power plants,
power plants which are based on the
renewable energy sources such as
solar, wind, geothermal, tides, water
waves, etc.
1.5. THERMAL EFFICIENCY

In the process of alteration of energy into work,
there is always a difficulty of receiving less out
than is already put in. The issue is that, in all
Heat engine is procedures, there is some amount of heat Qc
a system that
converts heat or ther-
that transmits energy to the atmosphere—and
mal energy—and generally a very substantial quantity at that. A
chemical energy—to method to measure how competently a machine
mechanical energy, functions is by a quantity which is known as
which can then be thermal efficiency.
used to do mechani-
cal work. Thermal efficiency, Eff, is described to be
the proportion of valuable energy output to the
energy input (or, in other context, the proportion
of what is received to what is applied. The
efficiency of a heat engine is the result of
network, W, which is separated by heat-
transferred energy.
REVIEW QUESTIONS
1. Explain the term ‘Thermodynamics.’
2. What is the basic working principle in the study of Ther-
modynamics?
3. How does bodies attain the same temperature when they
come in contact with each other?
4. Explain the different types of theories that came up during
the time of evolution of Thermodynamics as the proper
study of heat flow.
5. Explain the Zeroth Law of Thermodynamics.
6. What is the meaning of the term ‘Thermal Equilibrium?
7. Explain the Second Law of Thermodynamics and explain
the term Entropy.
8. What is the major application of the Thermodynamics in
the modern world?
9. What is the importance of the First Law of Thermodynam-
ics in relation with the thermal Equilibrium?
10. Explain the term Thermal Efficiency and its significance in
context with the various Laws of Thermodynamics.
REFERENCES
1. Bozsaky, David. (2010). The Historical Development of
Thermodynamics. Acta Technica Jaurinensis. 3. 3–15.
2. Chapter 21: Entropy and Second Law of Thermodynamics. (2019).
[ebook] phys.nthu.edu. Available at: http://www.phys.nthu.edu.
tw/~thschang/notes/GP21.pdf [Accessed 2 August 2019].
3. Chemistry LibreTexts. (2019). History of Thermodynamics. [online]
Available at: https://chem.libretexts.org/Bookshelves/General_
Chemistry/Book%3A_General_Chemistry_Supplement_(Eames)/
Thermochemistry/History_of_Thermodynamics [Accessed 2
August 2019].
4. Cliffsnotes.com. (2019). Introduction to Thermodynamics. [online]
Available at: https://www.cliffsnotes.com/study-guides/chemistry/
chemistry/thermodynamics/introduction-to-thermodynamics
[Accessed 2 August 2019].
5. Coursera. (2019). Introduction to Thermodynamics: Transferring
Energy from Here to There | Coursera. [online] Available at: https://
www.coursera.org/learn/thermodynamics-intro [Accessed 2 August
2019].
6. Courses.lumenlearning.com. (2019). Introduction to
Thermodynamics | Boundless Chemistry. [online] Available at:
https://courses.lumenlearning.com/boundless-chemistry/chapter/
introduction-to-thermodynamics/ [Accessed 2 August 2019].
7. Drake, G. (2019). Thermodynamics | Laws, Definition, &
Equations. [online] Encyclopedia Britannica. Available at: https://
www.britannica.com/science/thermodynamics [Accessed 2 August
2019].
8. EDULAB. (2019). An Introduction To Thermodynamics – EDULAB.
[online] Available at: https://edulab.com/an-introduction-to-
thermodynamics/ [Accessed 2 August 2019].
9. Eoht.info. (2019). History of thermodynamics – Hmolpedia.
[online] Available at: http://www.eoht.info/page/
History+of+thermodynamics [Accessed 2 August 2019].
10. Introduction to Thermodynamics. (2019). [ebook] can teach
candu. Available at: https://canteach.candu.org/Content%20
Library/19930202.pdf [Accessed 2 August 2019].
11. Kemani, H. (2019). Applications of Thermodynamics Laws.

Carnot, Stirling, Ericsson, Diesel Cycles. [online] Bright Hub
Engineering. Available at: https://www.brighthubengineering.com/
thermodynamics/38344-thermodynamics-integral-part-of-our-life/
12. Michaud, C. (2005). A Brief Introduction to Thermodynamics.
[ebook] cs.indiana.edu. Available at: https://www.cs.indiana.
edu/~sabry/teaching/b629/f05/thermo.pdf [Accessed 2 August
2019].
13. Opentextbc.ca. (2019). Introduction to Thermodynamics –
College Physics. [online] Available at: https://opentextbc.ca/
physicstestbook2/chapter/introduction-to-thermodynamics/
14. Texasgateway.org. (2019). 12.4 Applications of Thermodynamics:
Heat Engines, Heat Pumps, and Refrigerators | Texas Gateway.
[online] Available at: https://www.texasgateway.org/resource/124-
applications-thermodynamics-heat-engines-heat-pumps-and-
refrigerators [Accessed 2 August 2019].
15. Web-formulas.com. (2019). Introduction of Thermodynamics – Web
Formulas. [online] Available at: https://www.web-formulas.com/
Formulas_of_Chemistry/Introduction_of_Thermodynamics.aspx
16. Web.mit.edu. (2019). 1. Introduction to Thermodynamics.
[online] Available at: https://web.mit.edu/16.unified/www/FALL/
thermodynamics/notes/node9.html [Accessed 2 August 2019].
17. Wolfram, S. (2019). Historical Notes from Stephen Wolfram’s A
New Kind of Science. [online] Wolframscience.com. Available at:
https://www.wolframscience.com/reference/notes/1019b [Accessed
2 August 2019].
CHAPTER
2 CHEMICAL
THERMODYNAMICS
AND ITS ORIGIN

• Chemical In this chapter, you will learn about:
Thermodynamics • The definition and concept of chemical
• Modern thermodynamics
Thermodynamics • History and evolution of chemical
• Chemical Potential thermodynamics
• Human Chemical • Modern chemical thermodynamics
Thermodynamics • The notion of human chemical
• Thermochemistry thermodynamics
• Enthalpy • Certain objectives of chemical
thermodynamics
• Gibb’s Energy
• Limitations of the classic thermodynamics
• Isolated System
• Entropy
• Equilibrium
2.1. INTRODUCTION
Chemical thermodynamics is defined as the study of how work and
heat relate to each other in a chemical reaction as well as in change of
state. It usually consists of a series of set laws, rules that explain how
work and heat work well and also explains which of the processes can
take place spontaneously, and which of them require some help.
There are a lot of basic or fundamental principles of chemical
thermodynamics to take into account, such as the systems, enthalpy
and the laws of thermodynamics. As well, chemical thermodynamics
is mainly concerned with four specific quantities that are enthalpy,
internal energy, Gibbs free energy and entropy.
The branch of physical chemistry is directly related to the
thermodynamic phenomenon in the field of chemistry along with
the reliance of the thermodynamic properties of substances on the
aggregation state and composition of the substance.
Chemical thermodynamics is closely linked with the
thermochemistry and also with the theory of chemical equilibrium as
well as solutions, the thermodynamics of surface phenomenon and the
theory of electrode potentials.
Chemical thermodynamics is generally based on the assumptions
and conclusions of the thermodynamics, specifically on the first and
second laws of thermodynamics. The First Law of Thermodynamics
serves as the base for thermochemistry.
A key role in the thermochemical calculations is allocated to the
heat of formation of substances, distinct values for each reaction
substances makes it really possible to calculate the heat effects of the
reaction, heats of combustion play an identical role in the calculations
dealing with certain organic chemicals.
In addition to calculating the effects of heat of numerous processes,
recognition of the bond energies between several atoms based on the
spectral data are also employed, as are different approximate laws.
To understand thermodynamics, it is very beneficial to first describe
something known as system.
A system is a sequence of components that are linked with each
other. People can look at what moves in and out of a specific system.
Chemical Thermodynamics and Its origin 23
For instance, if there is coffee in a thermos flask,

we can either call the thermos flask as a system Combustion is a
or only the coffee inside it as a system. chemical reaction
between substances,
There are different types of systems in chemical usually including
thermodynamics such as open system, closed oxygen and usually
system and isolated system. accompanied by the
1. Open system: an open system per- generation of heat
mits energy as well as matter to enter and light in the form
of flame.
and leave the system.
2. Closed system: this system compris-
es walls that allow energy to pass in
and out of the system, but it does not
permit the mass to pass in and out.
3. Isolated system: this system has rig-
id walls and hence do not permit the
movement of mass and energy.
A great number of thermodynamic functions
are used in chemical thermodynamics in order
to recognize the features of a specific process.
Apart from entropy ‘S,’ whose change illustrates
in simple processes in the isolated systems, ther-
modynamic principles are greatly used.
Figure 2.1: The graph shows that during a chemi-

cal reaction, free energy decreases until the reactions
reach equilibrium. In simple words, the curve moves
based on the conditions of the reaction.
Source: http://www.shodor.org/UNChem/ad-
vanced/thermo/index.html
These thermodynamic potentials allow a

determination of the features of processes under
several conditions. In the meantime, chemical
reactions usually take place at a constant
pressure ‘p,’ temperature ‘T’ and volume ‘V.’
Following fractions have the major practical
value:
G = H – TS (1)
A = U – TS (2)
where, G is the Gibbs free energy; A the
Helmholtz free Helmholtz free energy; H the enthalpy; and U
energy is a the internal energy. Based on the Eqs. (1) and
thermodynamic (2), we have,
potential that
measures the useful ΔG = ΔH – TΔS (3)
work obtainable ΔA = ΔU – TΔS (4)
from a closed where, ΔH is the isobaric heat effects of the re-
thermodynamic action; and ΔU is the isochoric heat effects of
system at a constant
temperature and the reaction.
volume (isothermal, Spontaneous processes taking place under
isochoric). the conditions p and T constant are only possible
in a direction involving a reduction in G. the
occurrence is restricted; means equilibrium
is attained when the minimum value of G is
acquired. The processes taking place at V and T
constant is traced as per the change in A.
The magnitude and sign of ΔG (ΔA) is based
on the relationship between the Eqs. (3) and
(4), the entropy factor (TΔS) and the heat effect
ΔH (ΔU) and the entropy factor the relative
value of the heat effect rises with a reduction in
temperature, whereas that of the entropy factor,
rises with a rise in temperature.
Chemical potentials play a major role in

the chemical thermodynamics, as any kind
of transition of a specific substance from one
phase to another is only possible in the direction
comprising an equalization of potentials, upon
dissolution.
Equilibrium basically requires the chemical
potentials of every component to be equal in all
the phases of systems. From such conditions,
the phase rule has been derived which is a basic
generalization describing equilibrium in any
heterogeneous system.
2.2. HISTORY OF CHEMICAL

THERMODYNAMICS
In the field of science, the history of chemical
thermodynamics traces the foundation of the
subject of application of different types of
equations leading to the operation of the heat
engine, namely the first, second and third law
of thermodynamics to the chemical reactions,
processes, transformations, phenomenon of
chemical thermodynamics.
The details of the historical development of
chemical thermodynamics is briefed well be a
Canadian physical chemistry historian named
as Keith Laidler, “The story of how chemical
thermodynamics developed is a somewhat
tangled one, since several investigators worked
along different lines and quite independently of
one another.”
William Jensen, an American chemistry
historian summarizes that thermodynamics was
mainly categorized by three different phases or
periods. Those periods are:
• The establishment of the basic laws of

thermodynamics (1842–1865)
• The application of these laws to
the theory of chemical affinity and
equilibrium (1873–1905).
• The quantification of chemical
thermodynamics via a fusion of theory
with experimental data (1905–1923).
2.2.1. Pre-History
The beginnings to the science of chemical
thermodynamics are the science of affinity
chemistry mainly, which was introduced during
Physical chem- the making of Geoffroy’s affinity table, derived
istry is the study
from the famous query 31 of Isaac Newton, a
of macroscopic,
atomic, subatomic, subject that is classified as the prehistory of
and particulate the science of physical chemistry according
phenomena in chem- to the expert of chemical thermodynamics and
ical systems in terms chemistry historian James Partington.
of the principles,
practices, and Secondly, the traditional subjects of
concepts of physics thermodynamics such as the work of William
such as motion, Cullen on evaporative refrigeration in year
energy, force, time, 1748, Joseph Black on latent heat in year
thermodynamics,
quantum chemistry,
1761, Richard Kirwan on specific fire in year
statistical mechanics, 1777, Joao Magellan on specific heat in year
analytical dynam- 1780, Antoine Lavoisier and Pierre Laplace on
ics and chemi- reaction calorimetry in year 1782, Person on
cal equilibrium. heat capacity and Pierre Dulong and Alexis Petit
on Dulong-Petit law in year 1819.
Thirdly, it was Hess’ law in year 1840 that
the heat of reaction in progressive reactions must
be supplemented, given by Germain Hess. The
final and fourth transition phase into the newly
developing subject of chemical thermodynamics
was the thermal theory of affinity as well as
principle of maximum work, given by Julius

Thomsen in year 1854 and Marcellin Berthelot
during 1860s.
This actually argued that the release of heat is
the real driving force of the chemical affinity and
thus, the real measure of the chemical reactions.
This theory was eventually substituted by the
thermodynamics theory of affinity, as it was not
able to explain the endothermic reactions.
In one-way or another, all of this was
integrated later, into the final version of chemical
thermodynamics. At that time, it was a term that
would not become ordinary until the beginning
of 1920s completing the work of Edward
Guggenheim and Gilbert Lewis, otherwise
called modern chemical thermodynamics.
2.2.2. Modern Chemical Thermodynam-

ics (1933–Till Present)
Gilbert Lewis and Merle Randall are two
American physical chemists who are
known as the founders of modern chemical
thermodynamics. They worked for their
textbook “thermodynamics and the free energy
of chemical substances.” This was regarded
as simplified as well as applied version of
the healthy work of Gibbs as well as Edward
Guggenheim, for his book titles as “Modern
Thermodynamics by the Method of Willard
Gibbs.”
Figure 2.2: Josiah Willard Gibbs: His work on the

thermodynamics applications was helpful in chang-
ing physical chemistry into a deductive science.
Source: https://www.goodreads.com/author/
show/3986960.Josiah_Willard_Gibbs
In year 1986, John Prausnitz an American

chemical engineer in his article “The Two
Sources of Chemical Thermodynamics,” stated
that, “While the essential ideas of classical
thermodynamics were established in the 1850’s
and 60’s, application of these ideas to chemical
phenomena came later, primarily by Gibbs in
the 1870s.
However, Gibbs’ work was not appreciated
by chemists until the turn of the century and even
then, extensive application of thermodynamics
in chemistry did not occur until publication of
a path-breaking textbook by Lewis and Randall
in 1923.”
Later in year 2000, American chemical
engineers Juliana Boerio-Goates and Bevan
Ott summarize things as Randall, Lewis and

Guggenheim must be regarded as the founders
of modern chemical thermodynamics due to the
key contributions of their books in combining the
applications of thermodynamics in chemistry.
In year 2012, Salvatore Califano, an Italian
physical chemist provides the following clear
synopsis in his book “pathways to modern
chemical physics” related to the development of
modern chemical thermodynamics.
Merle Randall and Gilbert Lewis in the
Formalism is the
United States used the mathematical formalism view that holds that
created by Gibbs in various papers as well statements of math-
as Edward Guggenheim in England for the ematics and logic
assessment of free energy and a lot of other can be considered to
chemical compounds. be statements about
the consequences of
The book Thermodynamics and the Free the manipulation of
Energy of Chemical Substances by Lewis and strings using estab-
Randall and Modern Thermodynamics by the lished manipulation
rules.
Methods of Willard Gibbs are the basic classics
of the modern chemical-physics.
Prior to the publication of these books, the
most famous text of thermodynamics mainly in
Germany was the Lehrbuch der Thermodhemie
und Thermodynamik written by Otto Sackur.
This book was once translated into English
language in year 1917 by George Gibson, an
American naturalized Scotsman. It became the
official textbook of thermodynamics when it
was substituted with that of Lewis and Randall.
2.3. HUMAN CHEMICAL THERMO-

DYNAMICS
Based on the modern chemical thermodynamics,
in year 2007 Libb Thims, an American
electrochemical engineer introduced the term

“Human Chemical Thermodynamics” as the
field of the chemical thermodynamic study of
systems including reactive human molecules.
Chemical species are In case of “human thermodynamics” or “chemi-
atoms, molecules, cal thermodynamics of systems of humans
molecular fragments, viewed as molecule-like reacting things” or “hu-
ions, etc., being
subjected to a chemi-
man chemical thermodynamics,” is the study of
cal process or to a existence of humans, experience, function as
measurement. per the logic of pure as well as applied chemical
thermodynamics- specially utilizing the human
molecules, in which as human is defined as a
reactive chemical species or animate molecule.
2.3.1. Human Thermodynamic Instru-

ments
In case of human thermodynamics, a human
thermodynamic instrument such as a barometer,
thermometer, reaction calorimeter or indicator,
etc., is used to measure and evaluate the large-
scale boundaries of human molecular quantities
as the case with human system of two or
more than two people or volumes, pressure,
temperatures, heat or energy.
Figure 2.3: Barometer, one of the human thermody-

namic instruments.
Source: https://www.flickr.com/photos/ginger-
maddy/4266609887
2.3.2. Human Thermodynamics Applica-

tions
Human thermodynamics applications are
defined as the use of human thermodynamics
principles and theory in the practical
application. The study of the practical use of
human statistical thermodynamics or human
chemical thermodynamics for use in the
field of bioengineering of human systems
would be known as “human engineering
thermodynamics.”
This is similar to how chemical engineering
thermodynamics is applied in the field of
chemical engineering by a great number of
chemical engineers in the practical application
as well as development of oil refineries, etc.
2.4. OBJECTIVES OF CHEMICAL

THERMODYNAMICS
Practically, the primary aim or objective of
chemical thermodynamics is to create a standard
for determining the spontaneity or feasibility of
a given chemical or physical transformation.
Based on the first as well as the Second Law of
Thermodynamics (expressed in terms of Gibb’s
functions), a lot of additional theoretical notions
along with mathematical functions have been
established that provide a potential approach to
the solution of such issues.
Once the natural direction of a spontaneous
process is signified, it is required to know how far
the process will go before attaining equilibrium.

Solubility is a For instance, people might desire to find out the
chemical property maximum production of an industrial process,
referring to the ability the equilibrium concentration of a mixture of
for a given substance, metabolites in a cell or the equilibrium solubility
the solute, to dissolve
in a solvent.
of the atmospheric CO2 in natural waters.
The methods or approaches of
thermodynamics provide the mathematical
relations needed to estimate certain quantities.
However, the key aim of the chemical
thermodynamics is to analyze the equilibrium
and spontaneity. Well, such methods are
applicable to some other issues also.
For instance, the study of ideal and non-ideal
systems, along with the phase equilibrium is
fundamental to the effective use of the methods
of extraction, crystallization, distillation; to the
development and production of new materials,
to some metallurgical operations and to the
understanding of mineral species obtained from
geological systems.
In a same way, the changes in energy,
which supplement a chemical or physical
transformation in the form of, wither work or
heat is of major interest. The transformation can
be the fission of a uranium nucleus, combustion
of a fuel, transfer of a metabolite contrary to the
concentration gradient. The concept and method
of thermodynamics give a potential approach to
the analysis of such issues and problems.
2.5. LIMITATIONS OF CLASSIC

THERMODYNAMICS
Even though, there are several descriptions of
the chemical change that are invaded with the
language and terms of the molecular theory.

The notion of classic thermodynamics is
not dependent on the molecular theory and
hence, these notions do not need any kind of
advancement as the knowledge of molecular
structure advances.
In a formal sense, this feature is considered
as an advantage. Nevertheless, it is also a
discrete limitation as people get the information
from classic thermodynamics at a molecular
level. As compared to the molecular theory,
classic thermodynamics generally deals with
the assessable assets of the matter in huge. For
example, temperature, pressure, cell potential
volume, heat capacity, and susceptibility.
It is defined as a phenomenological and
empirical science and hence, it appears similar
to the classic mechanics. Classic mechanics is
mainly related with the conduct of macroscopic
systems, along with the velocity and the
position of a body as a function of time without
considering the molecular nature of the body.
Statistical thermodynamics or statistical
mechanics is the science that is concerned with
the properties of individual molecules as well as
their interactions to the empirical outcomes of
the classical thermodynamics.
The laws of quantum and classic mechanics
are applied to the molecules and then by
appropriate methods of statistical averaging,
the rules of macroscopic conduct that would
be anticipated from an assembly of several
molecules are formulated.
As the results of classical thermodynamics
are compared with the statistical averages over a
great number of molecules, it is not a surprise that
fluctuation phenomenon such as the shot effect,

Brownian motion or turbidity phenomenon
Brownian motion
is the random mo-
cannot be treated by classical thermodynamics.
tion of particles It has been identified that, all such kind of
suspended in a phenomena are the expressions of microscopic
fluid (a liquid or a
variations in the behavior or conduct of
gas) resulting from
their collision with comparatively few molecules that randomly
the fast-moving deviate from the average conduct of the whole
molecules in the assembly. In such submicroscopic region, this
fluid. random variation makes it quite impossible
to allocate a certain value to properties like
pressure or temperature.
Although, classical thermodynamics is
based on the assumption that a reproducible and
definite value can be easily measured always, for
such kind of properties. Together with such kind
of formal limitations, there are more limitations
that are functional also.
Though the notions of thermodynamics
provide the basis for the solution of various
chemical problems, generally the solutions
obtained are not absolute. In the language
of mathematician, it can be said that the field
of classical thermodynamics can formulate
required conditions but not sufficient or adequate
conditions.
As a result, a thermodynamic analysis
may eliminate the current reaction for the
synthesis and production of specific substance
by signifying that such kind of transformation
cannot spontaneously proceed further under any
sort of conditions available.
However, if the analysis shows that a
reaction may spontaneously proceed, almost
no statement can be made from the classical
thermodynamics showing that it will do so in
any fixed time. For instance, methods of classic

thermodynamics assume that the maximum
equilibrium production of ammonia from
hydrogen and nitrogen is acquired at low
temperatures.
So far, under such optimum thermodynamic
conditions, the reaction rate is very low that the
process is not applicable in the industrial use. As
a result, a small equilibrium yield at very high
temperature must be recognized to get a suitable
rate of reaction.
Although, the calculations in
thermodynamics provide no guarantee that
an equilibrium yield will be acquired in a
definite time, it was an outcome of such kind
of calculations for the ammonia synthesis that
a thorough search was conducted for a catalyst
that would permit equilibrium to be reached.
In a similar manner, catalysts known as
enzymes are critical factors in identifying which
reactions takes place at a substantial rate in the
biological systems. For instance, adenosine Hydrolysis is a
diphosphate is a thermodynamically unstable chemical reaction in
compound in an aqueous solution in regards which water is used
to the process of hydrolysis to adenosine to break down the
bonds of a particular
diphosphate and inorganic phosphate. substance.
However, such reaction takes place at a
slow rate in the absence of enzyme adenosine
triphosphate. This combination of enzyme
control of rate and thermodynamic control of
direction makes the finely balanced system
possible, which is a living cell.
In graphite to diamond transformation,
the outcomes of thermodynamics assume
that graphite is a stable allotrope at a certain
temperature and at all pressures below, the
transition pressure whereas diamond is a stable

allotrope at all pressures above the transition
pressure.
However, at low pressures, diamonds are
converted into graphite for kinetic reasons. In a
similar manner, at conditions in which diamond
is at thermodynamically stable phase, diamond
can be acquired from graphite only in a narrow
range of temperature just below the transition
temperature and then at a pressure adequately
high that the transition temperature is around
2000 K.
Similar to thermodynamic methods
give a limiting value for the production of a
chemical reaction, they do provide limiting
value for the work obtained from a physical
or chemical transformation. The functions of
thermodynamics predicts the work that may be
obtained if the reaction takes place with infinite
slowness, in a reversible manner.
Although, it is not possible to specify the
actual work acquired in a natural or real process
in which the time interval is finite. It is stated
that, the real work will be less than the work
acquired in reversible condition.
For instance, thermodynamic calculations
will give a value for the maximum voltage for
a battery storage that is the voltage, which is
obtained when there is no current. When there is
current, it can be presumed that the voltage will
be less than the maximum value.
In the same way, the maximum amount
of heat can be calculated, that can be further
transferred to a building from a cold environment
by the expenditure of a definite amount of work
in a heat pump, but the real performance will
be less adequate. Given a non-equilibrium

distribution of ions through a cell membrane, the
minimum amount of work needed to maintain
the distribution could be calculated. Although,
the real process that takes place in the cell needs
more work as compared to the calculated value
because the process takes place irreversibly.
Classical thermodynamics can treat limiting
cases only. Such kind of restriction is not as
severe as it may appear at first sight. In a lot of
cases, it is quite likely to approach equilibrium
closely and the thermodynamic quantities
correspond with the actual values contained by
experimental errors.
In some other situation, thermodynamic
analysis may eliminate few reactions under
certain conditions, and a major deal of time
as well as effort can be saved. In their most
controlled applications like limiting solutions
within definite boundary values, thermodynamic
approaches can decrease the amount of
experimental work required to produce a
definitive answer to a specific issue or problem.
REVIEW QUESTIONS
1. Define chemical thermodynamics.
2. Discuss the history of chemical thermodynamics.
3. State four key quantities that are mainly related to chemical
thermodynamics.
4. Explain:
a. Open system
b. Closed system
c. Isolated system
5. What do you mean by chemical potential?
6. Name the founders of modern chemical thermodynamics.
7. Illustrate the modern chemical thermodynamics.
8. Explain human thermodynamics, its principles and application.
9. What are the key objectives of chemical thermodynamics?
10. Enlist the major limitations of chemical thermodynamics.
REFERENCES
1. Eoht.info. (n.d.). History of chemical thermodynamics – Hmolpedia.
[online] Available at: http://www.eoht.info/page/History+of+chemi
cal+thermodynamics [Accessed 3 August 2019].
2. Eoht.info. (n.d.). Human chemical thermodynamics –
Hmolpedia. [online] Available at: http://www.eoht.info/page/
Human+chemical+thermodynamics [Accessed 3 August 2019].
3. Human Thermodynamics Fundamentals. (n.d.). [ebook] p.16.
Available at: http://www.humanthermodynamics.com/Human_
thermodynamics_Fundamentals__handout_.pdf [Accessed 3
August 2019].
4. Rosenberg, R. & Klotz, I. (2008). Chemical Thermodynamics.
Wiley.
5. Study.com. (n.d.). Chemical Thermodynamics: Definition &
Principles | Study.com. [online] Available at: https://study.com/
academy/lesson/chemical-thermodynamics-definition-principles.
html [Accessed 3 August 2019].
CHAPTER
3 PRINCIPLES OF
CHEMICAL
THERMODYNAMICS

• Black Hole In this chapter, you will learn about:
• Extensive Variables • Heat, work, and Carnot cycle
• Intensive Variables • Thermodynamics equilibrium
• Neutron Star • Principles of equilibrium
• Isolated System • Kinetic theory of gases
• Specific Heat Capacity
• Mechanical
Equilibrium
• Chemical Equilibrium
• Open System
• The Carnot Cycle
• Gibbs Free Energy
3.1. INTRODUCTION
Thermodynamics can be defined as the study done on the energy in
systems and the distribution of energy among the components. Talking
in terms of chemical systems, thermodynamics can be defined as the
study of reaction potential, reaction direction, reaction extent and
chemical potential.
The science that studies relationship between heat, work,
temperature and energy is referred to ad thermodynamics.
Thermodynamics is the study that basically deals with the relationship
between heat, work, energy and temperature.
By defining a system that is distinct from its surroundings is where
the application of thermodynamics principles begins. For example,
the system which has gas inside a cylinder having a movable piston, a
marathon runner, an entire steam engine, a neutron star, a black hole,
the planet earth, or even the entire universe.
3.1.1. Intensive and Extensive Variables

Intensive variable is a type of variable of state. They are often referred
to as point functions p, T, and V. as they are related to the points of a
system. Intensive variables are relatable to a finite region. They are
relatable only if their distributions are uniform.
Extensive variables are set function as they are related to a finite
region of a system. Extensive variables are volume V, internal energy
u, entropy s and mass m. Extensive variables are additive in nature.
Some quantities vary from point to point with respect to point functions
so they are considered as intensive variables. These specific quantities
are specific volume, density, and specific enthalpy.
3.1.2. Heat
The amount of energy that flows from one body to another automatically
because of their temperature difference is known as heat. Heat is not a
property of a system rather it a form of energy. Heat is transit in nature.
Because of the temperature difference, the transfer of energy occurs
Principles of Chemical Thermodynamics 43
which is termed as heat at molecular level.

Heat capacity: Heat capacity is said to be the Neutron star is the
extensive property of matter. Heat capacity is collapsed core of
a giant star which
proportional to the size of system. Unit used by before collapse
heat capacity C is energy per degree or energy had a total mass of
per kelvin. The quantity becomes independent between 10 and 29
of size and will be divide by the amount of solar masses.
substance, volume or mass, when the heat
capacity is expressed as an intensive property.
Specific heat capacity: Specific heat capacity
can be defined as the heat capacity of a substance
per unit mass. It is represented by Cp where the
subscript p indicates that at constant pressure,
the heat capacity and specific heat capacity is
applied after the heat is either added or removed.
Cp = Q/(m ΔT)
The amount of energy involved in the
change of phase from liquid to gas is known
as enthalpy of vaporization or latent heat of
vaporization. The symbol used to denote latent Heat capac-
heat of vaporization is ∆Hvap and the unit used ity is a physical
is Joule. The amount of heat either added or property of matter,
removed from a substance in the case of phase defined as the
amount of heat to
change is referred to as latent heat. be supplied to a
The latent heat is the heat that breaks down given mass of a
the intermolecular attractive forces and in material to produce
order to let the gas expand it provides energy a unit change in its
temperature.
required. A function of the pressure at which
the transformation takes place is the enthalpy of
vaporization.
3.1.3. Work
The energy transferred by the system to its
surroundings is termed as work done by a
system. Properties of system includes the forms
of energy such as, kinetic energy, potential

energy and internal energy. Work can never be
contained in a system; it is always done by a
system or on a system. For mechanical system,
work can be defined as the action of force on
any object through a distant. By formula, work
is the product of force and displacement:
W=FXd
where, W is Work (in Joules); F is force (in
Newton); and D is displacement (in meters).
3.1.3.1. pΔV Work

While plotting the pressure-volume
characteristics, the process curve is referred to
as Pressure-volume work or pΔV work. pΔV
work is the pressure – volume work and occurs
when the volume of the system changes. pΔV
work can also be referred to as boundary work.
In order to act on the boundary surface
and to make it move from its place, the system
boundary causes force which is equal to the
pressure times the surface area and this is
where the boundary work occurs. When the gas
contained in the piston-cylinder device expands
against the piston, it forces the piston to move.
By this we can calculate the piston displacement
work in a closed system.
3.1.4. The Carnot Cycle

The Carnot cycle is a model which is proposed
by Nicolas Léonard Sadi in 1824. This model
explains the relationship among pressure,
volume and temperature of gases. It also
describes the change and formation of input
of energy and also work done by it outside the
system.
Figure 3.1: Graph shows the Carnot cycle.

Source: https://commons.wikimedia.org/wiki/
File:Reversible_Carnot_Cycle.jpg
The basic principle used in heat pumps used

for heating, air conditioning and refrigeration
says that whenever a gas is compressed, the
temperature increases and hence when compared
to its environment, it becomes hotter than that.
In order to remove the heat from the hot gas, heat
exchanger is used. And when the gas is allowed
to cool it expands and which further makes the
temperature cool.
3.2. THERMODYNAMICS EQUI-

LIBRIUM
For understanding equilibrium, let’s take an
example. If there are two bodies at different
temperature in which one is hot and another
one is cold. When both the bodies are made
to contact physically with each other, both the
bodies will change their temperature. The hot
body begins to become colder and the cold one
will begins to become hotter. Ultimately, same

temperature will be achieved by both the bodies
Thermodynamic
equilibrium is an
and hence both the bodies are said to be in
axiomatic concept thermodynamic equilibrium with each other.
of thermodynamics. It When any system achieves the
is an internal state of a thermodynamic equilibrium, it remains in
single thermodynam-
ic system, or a relation the state of equilibrium infinitely and will not
between several ther- change voluntarily. In other words, when any
modynamic systems system is in equilibrium, it will not change its
connected by more macroscopic properties spontaneously.
or less permeable or
impermeable walls. When the conditions mentioned for the
following three equilibrium is satisfied only then
the system will be said to be in thermodynamic
equilibrium:
1. Mechanical equilibrium: When the
forces either within the system or be-
tween the system and the surround-
ing is balanced, then the system is
said to be in mechanical equilibrium.
Also, when the pressure throughout
the system or between the system
and the surrounding is same, it is
said to be in mechanical equilibrium.
Figure 3.2: Mechanical equilibrium.

File:Equilibrium.JPG
If there are any unbalanced forces within

the system, so in order to attain equilibrium,
they will get neutralized. When pressure of two
system are same, then both systems are said to
be in mechanical equilibrium.
2. Chemical equilibrium: When no
chemical reactions are going on
within a system, then the system is
said to be in chemical equilibrium.
Also, when there is no transfer of Diffusion is the
matter due to diffusion from one part movement of a
of system to another, then the system substance from
an area of high
is said to be in chemical equilibrium. concentration to
Two systems have achieved chemi- an area of low
cal equilibrium when their chemical concentration.
potentials are same.
3. Thermal equilibrium: Any sys-
tem is said to have achieved thermal
equilibrium, when the system is al-
ready in both mechanical as well as
chemical equilibrium and there is
no variation occurred in its proper-
ties. Thermal equilibrium is related
to temperature. The system is said to
be in thermal equilibrium, when the
temperature is uniform throughout
the system and hence not changing.
In other words, when the tempera-
tures of the two systems are same
then both the systems are said to be
in thermal equilibrium.
Figure 3.3: Thermal equilibrium.

File:CNX_Chem_05_01_HeatTrans1.jpg
3.3. PRINCIPLES OF THERMODY-

NAMICS
3.3.1. Systems in Thermodynamics

A quantity of matter or the region in space
which is defined for study or on which the
study is going in process then it is referred to as
thermodynamic system. Everything external to
system is referred to as surroundings. Boundary
can be defined as the real or imaginary surface
which tend to separate the system from
surroundings. The boundary of a system can be
both either movable or fixed.
Types of Systems in Thermodynamics:
Figure 3.4: Types of systems.

File:Diagram_Systems.png
• Open system: open system is also
named as control volume. It is the
system in which the transfer of both
Heat energy is
the mass and energy takes place. For the result of the
example, boiling of water in an open movement of tiny
vessel. In this open system example, particles called
the water and heat energy are atoms, molecules or
ions in solids, liquids
entering and leaving the boundary of
and gases.
the vessel.
• Closed system: Closed system is the
system in which the mass remains the
same but the energy is transferring
across the boundary. Boiling of water
in a closed vessel is an example for
closed system. In this system, the heat
is entering and leaving the boundary
of the vessel but the mass of the
system is same. Since it is a closed
vessel so the mass of the water is
unable to spills out of the vessel.
• Isolated system: Isolated system
is a system in which there is neither
transfer of energy nor the mass.
Thermo flask contained with tea is
an example of isolated system, since
there is transfer of neither heat or
energy across the boundary.
3.3.2. Processes in Thermodynamics

A system is said to be undergoing the
thermodynamic process, when due to change
in the properties such as temperature, pressure,
volume etc, it tends to change it state from
one thermodynamic state to final state. When

classified the thermodynamic process has eight
types.
Adiabatic Process
When in a process, there is no transfer of heat
or mass between the system or the surroundings
then the process is referred to as adiabatic
process.
Isenthalpic Process
The process occurring when the system is
surrounded by perfect insulator and so there is
no heat transfer is called as isenthalpic process.
The assumption of isenthalpic system is applied
when there is any need to find the maximum
temperature change in a system with respect to
the change in pressure.
Isentropic Process
The process in which the energy remains
constant since there is no energy dissipated in
the form of heat I termed as isentropic process.
Isentropic process can be both adiabatic as well
as reversible.
Turbines and nozzles are the examples of
systems in which pressure decreases.
Pumps and compressors are the examples of
the systems in which pressure increases.
Isobaric Process
The process in which the pressure remains
constant is called as isobaric pressure. The work
done by the system is directly proportional to the
change in volume or temperature of the system,
assuming that the quantity of gas in the process

is constant.
The ratio of the specific heats for gases k
is the ratio of heat capacity of a gas in isobaric
system Cp and the ratio of the heat capacity of
a gas in isochoric system Cv. then the equation
will be given as
k = Cp/Cv
Isochoric Process
The process in which the volume is constant is
called as isochoric process. It can also be called
as isometric or isovolumetric process.
Isothermal Process
The process in which there is no temperature
change or can say the process in which the
temperature is constant is called as isothermal
process. The energy flow in and out of the system
is also done considering the amount required to
keep the temperature of the system constant.
Reversible Process
Reversible process refers to a thermodynamic
process which can be “reversed” without
the production of energy and this process
happens when the system is in thermodynamic
equilibrium with the surroundings. As the
entropy is increases whenever there is a process
taking place in a particular time, so this system
is said to be hypothetical.
3.3.3. Entropy
The word entropy is derived from a Greek
word ‘tropee’ which means transformation.
Rudolf Clausius was the first person to use

this word entropy. Entropy is said to be the
extensive property of the system. The unit
used for measuring entropy is Joule per degree
Kelvin (J/K). The heat or energy changed per
degree kelvin is referred to an entropy. In all
mathematical calculations, specific entropy is
denoted by ‘s’ and the entropy is denoted by ‘S.’
When the system undergoes any change
from previous to final state, then this is used
in order to measure entropy of the system. The
change in entropy is denoted by ∆S and not only
S.
Factors affecting changes in entropy:
Thermal en- • Changes in Temperature: Whenever
ergy comes from there is any change in the temperature
a substance whose that will lead to change in entropy.
molecules and atoms The higher the temperature is, the
are vibrating faster
due to a rise in
higher the entropy will be.
temperature. Because when the temperature is high, the
system will have more thermal energy and
further there will be more ways to distribute that
thermal energy. Hence the entropy will increase.
• Change in Volume: When the
volume of a system is more, there
will be more ways to distribute the
molecules within the volume. And
hence the higher the entropy will be.
It can be said that the change in volume
tends to change the entropy of any system. Since
the system involving gas undergo large volume
changes, so this change is more important for
those system.
• Change in Phase: When the phase
of any system has higher microstates
then the system will have high entropy.

Gases have the most microstates so
they have the highest entropy.
Liquids have microstates less than gases
but more than solids, so they have entropy less
than gases but more than solids. And solids thus
have the lowest entropy because they have least
number of microstates.
• Mixing Substances: Whenever there
is mixing of substances, the entropy
always increases. Mixed systems
have more microstates than unmixed
systems and so tend to have more
entropy.
3.3.4. Enthalpy
In a thermodynamic system, the measure of
energy is called as enthalpy. Enthalpy is a
thermodynamic quantity and is equivalent to
the total heat content of a system. Enthalpy can
also be defined as the sum of internal energy and
the product of pressure and volume. Enthalpy is
denoted by ‘H.’
At constant pressure, the expression used
for changes in the system energy in many
physical, chemical and biological measurement
can be termed as enthalpy. The change in
enthalpy is equal to the energy transferred from
the environment through heating at constant
pressure.
Figure 3.5: Water enthalpy formation.
File:Water_enthalpy_formation.JPG
Enthalpy is an extensive unit. Enthalpy

depends upon the amount of substance it
contains and the size of system. SI unit used by
enthalpy is Joule (J).
H = U + pV (Enthalpy in extensive units)
Enthalpy is the energy contained within
a system excluding the kinetic energy and the
potential energy of the system as a whole. It is
the thermodynamic quantity which is equal to
the total heat contained by a system.
Enthalpy change is
the name given to Enthalpy change:
the amount of heat
evolved or absorbed At constant pressure, the amount of heat which
in a reaction carried is evolved and absorbed in a reaction can be
out at constant termed as enthalpy change. It is denoted by the
pressure.
symbol ΔH, read as “delta H.”
Standard enthalpy changes:

When under standard conditions and everything
is in their standard states, a reaction carries
out then it is referred to as standard enthalpy
changes. Standard states can also be termed as
‘reference states’
Standard conditions mentioned above are:
• Standard temperature: 298 K (25°C)
• Standard pressure: 1 bar or in pascals:
100 kPa
When solutions are involved, standard
concentration of 1 mol dm–3
Some important types of enthalpy change:
• Standard enthalpy changes of
formation, ΔH °F: When the
elements are in standard condition
and with everything in its standard
states, and one mole is compound is
formed from that element (which is in
standard conditions) then the enthalpy
changes taking place in this compound
formation will be termed as standard
enthalpy changes of formation.
• Standard enthalpy changes of
combustion, ΔH °C: When one mole
of compound is burned completely
in oxygen being under standard
conditions and everything being in
its standard states, then the enthalpy
change occurred will be termed as
the standard enthalpy changes of
combustion.
3.3.5. Internal Energy

In the process of random, disordered motion
of molecules, some energy is involved. So, the
energy associated is termed as internal energy.
It is separated in scale from the macroscopic
ordered energy associated with moving objects;
it refers to the invisible microscopic energy on

the atomic and molecular scale.
For example, the glass of water kept on the
table at room temperature will have no apparent
energy (neither kinetic nor potential). But
when seen at a microscopic scale, there will be
movement of molecules at high speed travelling
at around hundreds of meters per second. But
when the water in the glass is tossed then there
will be macroscopic motion as well.
3.3.6. Gibbs Free Energy

At constant pressure or temperature, when
reversible or maximum work is done by a system
then the measure of the potential involved in
doing that maximum amount of work is referred
to as Gibbs free energy.
In 1876, Josiah Willard Gibbs defined this
thermodynamic property. He defined Gibbs free
energy in order to predict if at constant pressure
and temperature, any process will occur
spontaneously or not.
Gibbs free energy is denoted by G and is
defined as
G = H – TS
where, H = enthalpy; T = temperature; S =
entropy.
Gibbs free energy uses SI unit kJ that is
kilojoule.
Figure 3.6: Gibbs free energy for spontaneous and

non-spontaneous reactions.
File:Gibbs_free_energy.JPG
Changes in Gibbs free energy:

At constant temperature and pressure, whenever
there is change in the free energy for a process, Closed system is a
then there is a change in the Gibbs free energy physical system that
doesn›t exchange
as well. Under constant temperature and any matter with its
pressure in a closed system, the maximum non- surroundings, and
expansion work which is obtained is referred to isn›t subject to any
as the change in Gibbs free energy change. For net force whose
spontaneous processes, ΔG is negative and for source is external to
the system.
non-spontaneous processes, ΔG is positive. And
at equilibrium condition, ΔG is zero.
Sign of Gibbs energy:

In order to determine if a chemical reaction is
spontaneous or not, the sign of Gibbs free energy
is used. If the sign of Gibbs free energy change
ΔG is positive, then for the reaction additional
energy is required and if the sign of Gibbs free
energy ΔG is negative, then the reaction have
enough energy to occur spontaneously and
hence is favorable. Although, reaction occurring
spontaneously does not mean that the reaction
will occur quickly too. For example, the reaction

in which rust that is iron oxide is formed from
iron is spontaneous, but it is too slow to witness.
Another example can be, formation of graphite
from diamond. The reaction involved is
C(s)diamond → C(s)graphite
At room temperature that is 25oC, this reaction
has the Gibbs energy change ΔG with a negative
sign. The formation of graphite from diamond
is a spontaneous reaction but it is also too slow
to witness.
3.4. KINETIC THEORY OF GASES

The motion of molecules and also the
microscopic and macroscopic consequences of
such motion in gases is all related to the kinetic
theory of gases. In order to determine some
of the equilibrium properties of gases, kinetic
theory is used. But the methods of statistical
thermodynamics are more useful than kinetic
Scattering is a theory for deducing equilibrium properties.
general physical
process where some The kinetic theory is important because it
forms of radiation, has the ability to explain both the equilibrium
such as light, sound, phenomena as well as the non-equilibrium
or moving particles,
phenomena. Examples of non-equilibrium
are forced to deviate
from a straight phenomena can be scattering of molecules of
trajectory by one gas by other molecules or transfer of heat in a
or more paths due less non-uniform gas.
to localized non-
uniformities in the
medium through
which they pass.
Figure 3.7: Movement of gas particles.

File:Kinetic_theory_of_gases.svg
Statements on which the whole kinetic
theory of gases is based on are as follows:
• Tiny particles of matter are found in
gases and they are in constant motion.
• Gas particles that is the tiny particles
contained in gas constantly collide
with each other and also collide with
the walls of container. Because of
constant collisions of particles, there
is no net loss of energy and so the
collisions are referred to as elastic.
• As the size of gas particles are very
small as compared to the distance that
separates them, they are separated at
large distances and so each particle
gets much area to move freely.
• Interactive forces such as attraction or
repulsion are not there in between the
particles of gas.
• The average speed of the particles
depends upon the temperature of
gas. Increasing and decreasing
temperature further increases or
decreases the speed of the particles,
respectively.
Kinetic theory also states that the collision
between the particles contained in the gas and the
wall causes the pressure in the gas. The average
speed of the gas molecules is dependent on the
temperature of gas. If constant temperature
is maintained in the gas, then the speed of the
particles in the gas moves at constant speed. But
when the temperature starts increasing then the
speed of gas particles starts increasing. Similarly,
when the temperature of gas is decreased then
the speed of gas molecules starts decreasing.
Volume of the container affects the pressure
of the gas. Like when the volume of the container
is decreased then the molecules will get less
distance to travel and so they more often hit the
walls of the container which will result in high
pressure. And if the volume is increased then the
distance will increase and molecules will hit the
wall less often hence reducing the pressure.
3.4.1. Assumptions of Kinetic Theory

• All the gases contain molecules and
the molecules of a gas are alike and
different from each other. It can say
that a gas will have same group of
atoms.
• Comparing the distance between the
molecules of a gas, the size of the
molecules of the gas is very small.

• The molecules contained in gas act as
perfect elastic spheres.
• While obeying the Newton’s law of
motion, the molecules are always in
a random motion and molecules will
have velocities ranging from zero to
infinity in all direction.
• The molecules in the gas collide
with each other and with the walls of
container during their random motion.
And the collisions are elastic either
it is collision within the molecules
or the collision with the walls. And
so, conserve momentum and kinetic
energy.
• A molecule moves in a straight line
and the distance it covers between the
two successive collisions is referred
to as free path. Comparing with the
time taken by the molecule to cover
the free path, the time during which a
collision takes place is negligible.
• Other than the forces that act during
the collision, no force acts on the
molecules. And so, the molecules
move with uniform velocity between
the collisions.
REVIEW QUESTIONS
1. Define chemical thermodynamics.
2. What is heat and heat capacity? Give the SI unit of heat
capacity.
3. What is pΔV work?
4. What is the basic principle of the Carnot Cycle?
5. Briefly explain the types of thermodynamic equilibrium.
6. What is system, surroundings and boundaries? Name the
types of system.
7. Give the name of the processes of thermodynamics.
8. What is Gibbs free energy? Give the equation for the same.
9. Briefly explain the kinetic theory of gases.
10. Write down the assumptions of kinetic theory of gases.
CHAPTER
4 CHEMICAL
THERMODYNAMICS
LAWS

• Work In this chapter, you will learn about:
• Heat • Explain the meaning of thermodynamics;
• Statement • Describe the role of systems and
surrounding in transformation of energy
• Expression
from one state to another;
• Systems and
• Describe the meaning of chemical
Surroundings
thermodynamics;
• Transformation of
• Explain the two types of internal energy;
Electrical Energy
• Explain the key difference between the first
• Chemical Energy
and second law of thermodynamics;
• Routine Activities
• Explain the zeroth law of thermodynamics;
• Cold Reservoir
• Describe the importance of First Law of
• Name Entropy Thermodynamics;
• Explain the role of second law of
thermodynamics;
• Examine the third law of thermodynamics.
4.1. INTRODUCTION
It is worth noticing that everything is thermodynamics. The
thermodynamics concept is not only limited to physics or chemistry
and it has not only predefined set of laws that are applied to electronic
instruments, planes, cars, refrigerators. It is a scientific concept that
a person experience in their day to day life or experience during their
different activities or works.
One of the major problems with thermodynamics is that it is just
the way energy works, thus there are higher chances to miss the energy.
Mostly everyone notices one thing in his life that whenever they clean
their table, bed or any other thing, after certain times, it again gets
messier, that’s the Second Law of Thermodynamics at work, where
everything gets disorganized after certain period of time.
The way food gets cooked through gas stoves by passing heat, it is
considered as the First Law of Thermodynamics at work, which means
transferring energy in the form of heat to your food. Thermodynamics
is not only concerned with the study of work and heat; it’s the study or
research of how energy and everything whether it is living or nonliving
works. Thus, it can be said that Thermodynamics is the study of life.
4.1.1. Thermodynamics
Thermodynamics can be defined as a branch that is concerned with
the transfer or movement of energy from one state to another and
the relationship exist between the temperature and heat with energy
and work done. In other way, it can also be defined as the science
stream that is primarily concerned with the study and research of the
combined effects of work and heat on the variation in the state of
matter confined by the laws of thermodynamics.
Laws of thermodynamics play an important role in maximize
the use of energy released from chemical reaction. For example, in
chemical reactions heat energy is produced, which with the help of
laws of thermodynamics can be converted into different usable forms.
It is important to note that the energy can be easily transformed
from one form to the other forms and this can be used by various
Chemical Thermodynamics Laws 65
manufacturing industries for multiple purposes

on the basis of energy transformation.
It is well known that whenever chemical
reactions occur, lot of energy released during
the process. The laws of thermodynamics are
mainly concerned with the change in energy
during the chemical reaction process and are not
deal with the speed or rate at which the reaction
is proceeding.
4.1.2. Chemical Thermodynamics

Chemical thermodynamics can be defined as
the study or learning of the link between heat,
work, or chemical reaction or is associated with
the change in the state of physical thing that is
considered as the laws of thermodynamics.
There are some general terms that are used
in this context such as energy, heat and work. In
this chapter we discuss about the role of system
and surroundings in thermodynamic laws and
various types of thermodynamic laws.
4.2. SYSTEMS AND SURROUND-

INGS
It is important to note that we all live in an
environment in which energy and matter
constantly change. It is a continuous process and
never ends. For example, lets analyze the eating
process, after consuming food, a person intake
chemical energy of food, it is then converted
by body in order to utilize it. Now, as the body
consumes the energy released from the food, it
can allow person to do work or other activities
in their day to day life.
Matter is any
substance that has Figure 4.1: Systems and surroundings in the chemi-
mass and takes up cal reaction process.
space by having
volume.
dia/commons/thumb/b/b6/System_boundary.
svg/2000px-System_boundary.svg.png
The entire process of this exchange of

energy, where energy transforms from one
form to another form all happens within a set
of systems and surroundings. When a person
boil water in a container, then the water which is
put into the container, then the water is enclosed
within a metal container, it is called system. The
rest of the thing within which all this process
occur that is kitchen or even house is called
surroundings.
In a vessel, when water start boiling, then
some proportion of water is transformed into
steam, which gradually releases from the spout
at the top. This transformed energy then released
itself from the container, which is called system,
to the surroundings outside of it. This is the
transference of energy, thermodynamics at work,
and matter between systems and surroundings.
The real meaning of the system may differ
from person to person. For example, for one
person, the container might be the system and
to another the kitchen or the entire house be the

system, and the neighborhood the surroundings,
thus a personal perspective plays a role in
this. The main point in thermodynamic is that
every system is contained within a defined
boundary, and on the other side of the boundary
are the surroundings. In thermodynamics there
are primarily three types of systems that are
discussed below:
Energy is the
• An open system is defined a type of
quantitative
system in which energy and matter property that must
can be exchanged between a system be transferred to an
and its surroundings. object in order to
• A closed system is a type of system perform work on, or
to heat, the object.
in which there is a possibility only
with energy, not matter, to be ex-
changed between a system and its
surroundings.
• An isolated system can be defied a
system in which there is possibility
neither with energy now with matter
to be exchanged between a system
and its surroundings. However, it is
very difficult to find a system that is
completely isolated.
If it is assumed that the entire universe can
be considered as a system, then the question
arise that what are the boundaries of universe,
and what are its surroundings? There are so
many complex question or problems that are
yet to be solved. For an electronic instrument
manufacturer, thermodynamics provides
various useful ways and technique to design
the product. It is worth noticing that most of the
principles that a physicist work with to calculate
and analyze circuits like Kirchhoff’s Law are
based on the foundations of thermodynamics.
4.3. INTERNAL ENERGY

Internal energy can be defined as the total energy
content that is present in the system. The energy
means all energy that is present or the energy of
system. There are various types of energy that is
existed in the system such as kinetic energy and
potential energy.
It is well known that during the chemical
reaction process, there is transformation or
change in the form of energy from one state
to another and thermodynamics laws help in
assessing various associated with the particles
of the system.
• Factors affecting the internal en-
ergy
The energy in a system may change because of
the following reasons:
– Transfer or passing of heat passes into
or out of the system;
– When the work is carrying on or by the
system or when the matter takes entry
into or leaves the system.
4.3.1. Work
The total work that the system done means
the entire amount of energy that is switched
between the surroundings and systems. There
are large number of external factors that are
primarily responsible for governing the work
such as change in temperature, volume, pressure
or external force.
4.3.2. Heat
Figure 4.2: Transformation of electrical energy into

light energy and heat energy.
Source: https://cdn.pixabay.com/pho-
to/2019/03/15/10/32/pear-4056741_960_720.
jpg
In thermodynamics, heat can be defined as the

kinetic energy released by the molecules of the
substance. Both thermodynamics and heat play
an important role in guiding the engineers and
designers in carrying out their processes or
procedures and how to efficiently and effectively
utilized the energy that is released during the
chemical reactions economically. Heat energy
moves from high level of temperature to low
level of temperature.
4.4. DIFFERENCE BETWEEN FIRST

AND SECOND LAW OF THERMO-
DYNAMICS
The first law of the thermodynamics is basically
concerned with the conservation of energy,
while on the other hand, the Second Law of

Thermodynamics maintains that few of the
thermodynamics processes are not at all possible
and does not completely follow the First Law of
Thermodynamics.
Some of the key points that are able to
differentiate between that First and the Second
Law of Thermodynamics are discussed below.
4.4.1. Statement
The First Law of Thermodynamics explained
that it is not possible to create or destroy energy
but can be easily shift from one state to another.
While on the other hand the theory of second
law, which do not oppose first law, explains that
Entropy is a measure the transformed energy which change from one
of the number of form to another is not always fully utilized.
ways in which a
system may be Thus, it can be assumed that the degree of
arranged, often taken disorders which is called entropy of an isolated
to be a measure of system never reduces or fall, in fact it always
«disorder».
increases.
4.4.2. Expression
The equation or formula which is used to define
First Law of Thermodynamics can be defined
as ΔE = Q + W, which is used to determine the
value, in case of two out of three values are
known, while the equation or formula used
to determine the value of the Second Law
of Thermodynamics can be denoted as ΔS =
ΔS(system) + ΔS(surrounding) > 0.
4.4.3. Expression implies that

In the First Law of Thermodynamics, expres-
sions can define as the total change or trans-
formation in the internal energy of a system is
equal to the total flow of heat into the system
and the total work done on the system by the
surrounding.
While, on the other hand, in the Second
Law, the whole transformation in the entropy is
the total value of change occurred in the entropy
of the system and surrounding that is enhanced
for any actual purpose and cannot be less than 0.
4.4.4. Examples
Examples of the First Law of Thermodynamics
includes electric bulb, in which the fuse converts
the electric energy into heat energy, also known
as thermal energy, and light energy, also known
as radiant energy. In addition, the process known
as photosynthesis in which plant convert the
sunlight (radiant or light energy) into chemical
energy is also the example of the First Law of
Thermodynamics.
On the other hand, the example of the
Second Law of Thermodynamics include the
process by which the machine converts the fuel
into useful energy but the real value of energy
released by fuel is not fully utilized by machine.
Also, the room in which the heater installs use
electrical energy to produce heat, but the room,
in exchange, can not provide the same energy
to heater.
4.5. THE ZEROTH LAW OF THER-

MODYNAMICS
The Zeroth Law of Thermodynamics is of the
view that when two of the systems are in thermal
equilibrium with a third system, then it can be
said that both first and second systems are also
in thermal equilibrium with each other. It can be
explained with the help of an example.
Suppose, if system X is in equilibrium with
system Z and; System Y is also equilibrium with
system Z; Then it can be said that both system X
and system Y are also in equilibrium with each
other.
This law plays a very important role as it
allows to determine heat flow direction between
systems. For example, suppose if an engineer
already knows the temperature of a set of
connected systems, then it will be easy for him
to determine the exact direction of heat and how
it will travel on the basis of thermal equilibrium.
Note that in this chapter, we have discussed
Zeroth Law first, but this law was introduced
in the last. First three laws of thermodynamics
were introduced in the 18th century. Later, zeroth
law needed when the scientists realized the need
to define the movement of temperature. This
law required to come in first position but it then
it would result in renumber of all the existing
laws, resulting in confusion to existing literature.
4.6. THE FIRST LAW OF THERMO-

DYNAMICS
Figure 4.3: Basic functioning of First Law of Ther-

modynamics.
dia/commons/thumb/8/86/First_law_open_sys-
tem.svg/1280px-First_law_open_system.svg.
png
The First Law of Thermodynamics is one of

the most important laws. It is basically concerned
with the total amount of energy that is present in
the world, in particular, is of the view that this
energy remains consistent, neither increase nor
decrease. In other term, thermodynamics can
be explained as the total amount of energy that
cannot be created or destroyed. It can only be
transformed or change from one form to other
or from one object to another.
This law may seem kind of abstract, but with
the help of certain examples, it can be understood
that the applicability of this law exists in real
life situation and every person can experience
the transformation or change of energy in his
day-to-day life. For example:
• When a person switch on the light,

electrical energy transformed into
light energy. This process is based
Light energy is a
kind of kinetic en-
on the First Law of Thermodynamics.
ergy with the ability • When a batsman hit the ball with bat,
to make types the kinetic energy of the bat shift to
of light visible to ball, resulting in moving the ball.
human eyes.
• Plants during the process of
photosynthesis, change the sunlight
energy into chemical energy to make
their food.
• When a person consuming food, then
the energy of the food changed by the
body into kinetic energy that allows
a person to move, do their routine
activities.
It is important to note that all this
transformation of energy is not fully utilized. In
fact, in certain scenario, some proportion of the
initial released energy is thermal energy. When
the energy is shifted from one item to another,
then the released thermal energy is called by the
more recognized name, which is heat. It is a fact
that when a bulb illuminates, it produced not
only light energy butt also heat energy.
This same case is also applied to the
moving ball because of the friction and to the
transformation of sunlight energy by plant.
In a way to know the importance of this heat
generation, study of the Second Law of
Thermodynamics will be helpful.
4.7. THE SECOND LAW OF THER-

MODYNAMICS
Figure 4.4: Process of entropy in the Second Law of

Thermodynamics.
dia/commons/e/e0/Figure_06_02_02.jpg
There are various ways to explain the

meaning of second law, the simple meaning of
second law is that heat will automatically move
from a hotter to a colder body. In the second
law, the property of thermodynamics systems
recognized by the name entropy.
It can be understood with the help of various
examples: in the arrangement of the molecules,
it is generally seen that the water molecules exist
in the ice cube are well organized as compare to
the water molecules present in the boiling water.
Whereas in the ice cubes, the water molecules
are in a well-defined manner, in boiling water,
they float unpredictably. Therefore, it can be
assumed that the entropy of the ice cube is lower
as compared to that of gas. In the similar manner,

when a plate is in pieces on the floor, its entropy
is greater than it is in one piece in the sink.
A meaning of the entropy can be explained with

the help of equation discuss above. The dS,
which means the change in entropy of a system
can be measured by dividing (δQ) with common
temperature (T), temperature that present at the
time of transformation.
The equation explained above is a method
to explain the second law of thermodynamics
in context of entropy. The formula is based on
the assumption that the entropy of an isolated
natural system will always remain consistent or
may increase as the energy is slowly towards
disorder. The second law is primarily based on
this assumption that the heat cannot instantly
shift from the cold item (less entropy) to the hot
item (greater entropy) and if it is possible, then
the equation is not valid at all.
However, refrigerators are exception to this
equation as they can instantly freeze items to
lower temperature as compared to the normal
air. But it does not mean that it questions the
validity of the second law as these are not
isolated systems, requiring an extra effort to
shift energy from one object to another. The
fridge normally produces heat energy all over
its body and if switched off, will naturally return
to thermal equilibrium with the room.
It is important to note that the validity of
this equation will not be as same as other laws
of physics, which never change whether time
was going forwards or backwards. For example,
suppose a boiling point if remain as it is, would

Boiling point is
never become a block of ice cubes. It is also the temperature at
true in case of smashed plate as it independently which the vapor
does not reassemble itself, as this would result pressure of a liquid
in decreasing the entropy of the system in equals the external
defiance of the second law of thermodynamics. pressure surrounding
the liquid.
According to an engineer, there are certain
processes that are impossible to reverse.
A scientist, in order to gain an insight into
this matter, examined the functioning of steam
engines, which basically works by burning the
fuel to supply heat to a cylinder containing steam,
which then increases and passes on a piston to
then do something useful. The particular part of
energy that is extracted from fuel in a way to do
some important thing is called work, while the
remaining proportion that does not come into
any use and got wasted is called heat.
It can be concluded that it’s possible to
know in advance the maximum efficiency of a
steam engine in order to assess the difference Actual energy is a
between the actual energy produced and the measure, transmis-
sible, and trans-
actual energy that is utilized by the engine. formable condition,
The basic fact behind the functioning of heat whose presence
engine is the process of naturally flow of heat causes a substance
to tend to change its
from hot to cold item. Suppose a scenario, when
state in one or more
there is no cold reservoir, then there will be no respects
flow of heat and the engine will not be able to
work. As it is a fact that cold reservoir is always
above the level of absolute zero, no heat engine
can be able to perform with 100% efficiency.
Therefore, the engines that are manufactured
in a well design manner always heat up steam
(or other gas) to the highest possible level of
temperature and then gradually release the
exhaust at a minimum level of temperature.
Even the most advance engine can give

efficiency of approximately 60% and the diesel
engines mostly used in cars work with only 50%
efficiency.
4.8. THE THIRD LAW OF THERMO-

DYNAMICS
The third law of thermodynamics states that
the entropy of a system reached to a consistent
value, when the temperature falls to the absolute
zero value. When the entropy of a system is at
an absolute zero value, then it is actually a zero
value, and in mostly all scenario, it is measured
by the total number of available ground states.
Specifically, the entropy of a pure crystalline
substance (perfect order) at absolute zero
temperature is zero. This statement is valid only
in a case when the perfect crystal has only one
state with minimum level of energy.
4.9. CONCLUSION
In the end, it is concluded that thermodynamics
is concerned with that part of science that
analysis and determine the interaction between
different systems. Previously, the laws of
thermodynamics are concerned with classical
or equilibrium states and now it is extended to
nonequilibrium states.
The laws of thermodynamics basically
work in system and surroundings. The laws of
thermodynamics applied during the chemical
reaction process, when the energy releases and
transform from one state to another.
REVIEW QUESTIONS
1. What do you mean by the term thermodynamics?
2. Explain in detail the meaning of chemical thermodynam-
ics?
3. What is the role of systems and surrounding in transforma-
tion of energy from one state to another?
4. Explain the two types of internal energy?
5. Explain in detail the key difference between the first and
the Second Law of Thermodynamics with examples?
6. Explain in detail the zeroth law of thermodynamics?
7. Describe the importance of the First Law of Thermody-
namics?
8. What is the role of the Second Law of Thermodynamics?
9. What do you mean by the Third Law of Thermodynamics?
10. What are the different types of systems?
REFERENCES
1. BYJUS. (2019). Thermodynamics – Laws of Thermodynamics,
Applications | Chemistry. [online] Available at: https://byjus.com/
chemistry/thermodynamics/ [Accessed 3 August 2019].
2. C, R. (2019). Difference Between First and Second Law of
Thermodynamics (with Comparison Chart) – Bio Differences.
[online] Bio Differences. Available at: https://biodifferences.com/
difference-between-first-and-second-law-of-thermodynamics.html
3. Chemistry LibreTexts. (2019). The Four Laws of Thermodynamics.
[online] Available at: https://chem.libretexts.org/Bookshelves/
Physical_and_Theoretical_Chemistry_Textbook_Maps/
Supplemental_Modules_(Physical_and_Theoretical_Chemistry)/
Thermodynamics/The_Four_Laws_of_Thermodynamics
4. Courses.lumenlearning.com. (2019). The Three Laws of
Thermodynamics | Introduction to Chemistry. [online] Available
at: https://courses.lumenlearning.com/introchem/chapter/the-three-
laws-of-thermodynamics/ [Accessed 3 August 2019].
5. Eagle Blog. (2019). The Three Laws of Thermodynamics | EAGLE
| Blog. [online] Available at: https://www.autodesk.com/products/
eagle/blog/three-laws-thermodynamics/ [Accessed 3 August 2019].
6. Jha, A. (2019). What is the second law of thermodynamics?
[online] the Guardian. Available at: https://www.theguardian.com/
science/2013/dec/01/what-is-the-second-law-of-thermodynamics
7. Khan Academy. (2019). The laws of thermodynamics. [online]
Available at: https://www.khanacademy.org/science/biology/
energy-and-enzymes/the-laws-of-thermodynamics/a/the-laws-of-
thermodynamics [Accessed 3 August 2019].
8. Physicsforidiots.com. (2019). Thermodynamics | Physics for
Idiots. [online] Available at: http://physicsforidiots.com/physics/
thermodynamics/ [Accessed 3 August 2019].
9. Thermopedia.com. (2019). THERMODYNAMICS. [online]
Available at: http://thermopedia.com/content/1195/ [Accessed 3
August 2019].
CHAPTER
5 CHEMICAL ENERGY
AND CHEMICAL
THERMODYNAMICS

• Chemical Energy In this chapter, you will learn about:
• Heat and Work • Deep insights of chemical energy
• Enthalpy Graph • Application of chemical energy
• Biological Possessions • Deep information of chemical
thermodynamics
• High-Moisture
Biomass • Explanation of chemical
thermodynamically systems
• The Law of
Conservation of • Explanation of heat and work
Energy • Explanation of energy
• Stoichiometry • Explanation of enthalpy
• Symmetry Calculations • Explanation of entropy
• Explosives • Explanation of Gibbs free energy
• Air Bag
5.1. INTRODUCTION
Energy is the aptitude to do work, where work is drive of an item
by some force. Humans use energy every day, and energy comes in
dissimilar forms one such type of energy is chemical energy. Chemical
energy is energy that is kept in chemicals, which have their examples
as sugar and gasoline. As chemical energy is kept energy, it is a kind
of potential energy, which is energy deposited in objects due to their
location.
An efficient example of potential energy would be that of a bike
on peak of a hill where the bike’s spot is raised and has the capability
to roll down the hill. In the circumstance of chemicals, the location
refers to the numerous atoms that being located together within the
chemical.
Chemical Energy is unconfined when bonds comprise in a
chemical reaction, usually producing heat as a by-product which is
known as exothermic reaction.
The chemical energy being kept in biological possessions can be
changed into important yet efficient energy services which consists of
heat, power, and transportation fuels. This chapter presents definitions
such as energy crop, by-product and waste, and categorized biological
resources in accordance to their arrangement in four groups:
lignocellulosic biomass, sugar and starches, oil biomass, and high-
moisture biomass.
Usually primary and secondary alteration technologies for those
sections are also momentarily being looked up. Biomass is observed
as the renewable energy foundation with greatest potential, but
ecological and socio-economic effects of bioenergy systems should
be precisely being analyzed in order to assure them of sustainable
systems.
Chemical energy being produce in the connections of atoms and
molecules. Usually, there is a reorganization of electrons and protons,
which been named as a chemical reaction, which creates electric
charges. The law of Conservation of Energy specifies that energy can
be move or converted but never destroyed. So, a chemical reaction
that plummets the energy in a system will donate the energy being lost
Chemical Energy and Chemical Thermodynamics 83
to the environment, typically as heat or light.

On the other hand, a chemical reaction Lignocellulosic
that hike the energy in an arrangement will biomass refers to
have taken this supplementary energy from the plant biomass that
environment. is composed
of cellulose,
Basically put, chemical energy is the hemicellulose, and
possible of a chemical system to experience an lignin.
alteration from one system to another and to
communicate an alteration on another system
this may be chemical, but can also include other
energy-necessitating processes like electron
current or pressure-volume work respectively.
Chemical energy is a notion that is connected
to every single procedure of life on earth and
controls the cars that we drive.
Chemical energy participates in a crucial
role into each and every one of our regular lives.
With the help of simple reactions and redox
chemistry, the contravention and creation of
bonds, energy can be mined and joined into a
practical fashion.
Chemical energy is the potential energy being
kept in the preparation of atoms that to within
molecules. Contravention chemical bonds needs
energy, while starting new chemical bonds gives
off energy. The greater energy that’s being gives
off when a bond being originated, the more
stable that bond is. These bonds are stable since
the same amount of energy been required to be
put into these bonds to destroy them again this
is a classic example of conservation of energy.
When bonds between atoms are being
destroyed or created, this is called a chemical
reaction.
The technical chastisement that deals
with the sections of chemistry and physic is
usually known as physical chemistry, and it

is in that region that a thorough research of
thermodynamics happens in place. Physics deals
itself greatly with the procedure of proceedings
Chemical nature” is
a very wide concept in nature. Surely, changes in energy though
of every characteris- measured, whether it be heat, light, work, etc.
tic that a material has Are clearly corporeal events that also have a
other from its physi- chemical nature to them.
cal hardness and its
atomic structure. Thermodynamics is the basic research of
energy whose changes supplementary physical
and chemical vicissitudes. The term itself
obviously suggests what is happening which
is indicated by the term “thermo” here from
temperature, meaning energy, and “dynamics,”
which clearly means the variation over time.
Thermodynamics can be unevenly condensed
with these topics:
• Heat and Work;
• Energy;
• Enthalpy;
• Entropy; and
• Gibbs Free Energy.
There are numerous basic ideologies of
chemical thermodynamics to deliberate: systems,
the laws of thermodynamics, and enthalpy.
Chemical thermodynamics is also concerned
with four particular quantities: internal energy,
enthalpy, entropy and the Gibbs free energy.
Chemical reactions obey two fundamental laws.
The first of these, the law of conservation of
mass, states that matter can be neither created
nor destroyed. The law of conservation of mass
is the sole base for all the stoichiometry and
symmetry calculations one has learned thus far
in field of chemistry.
5.2. CHEMICAL ENERGY

Chemical Energy is unconfined when bonds
form in a chemical reaction, often creating heat
as a by-product which is termed as exothermic
reaction.
There are two most vital terms to observe in
the study of chemical energy.
• Exoergic: An exothermic or
sometimes being called as exoergic
nuclear reaction is a reaction that
gives off energy when chemical bonds
being created.
• Endoergic: an endothermic or
sometimes being termed, as
endoergic reaction is one that needs
a contribution of energy to take
home. One can observe that energy
is often required to break up bonds
before creating new bonds. For
instance: throughout photosynthesis,
energy from the sun is required/used
to destroy the CO2 and H2O bonds.
Glucose is being originated and O2
bond is created as a result.
Batteries, biomass, petroleum, natural gas,
and coal are basic example of kept chemical
energy. Typically, once chemical energy is
unconfined from a material, that material is
distorted into a completely new substance.
Figure 5.1: Basic thermodynamics engine.

dia/commons/3/35/Thermodynamics_1.png
For instance, when an explosive goes off,

chemical energy kept in it is moved to the
environs as thermal energy, sound energy and
kinetic energy.
Organic resources for energy, also called
biomass, are a massive variety of materials
being created from living or recently existing
organisms. Fossil resources have also starting
birth in organisms but as an end result of
processes that happened over the period of
millions of years ago. Biological resources were
the primary source of vigor and supplies used by
Man and stayed the main one until the growth of
fossil fuels in the mid nineteenth century.
In the ten years of 1970, as an importance of
the oil shock that elevated the petroleum value,
there was a rehabilitated attention in biomass as

another energy source, and numerous research
and demonstration agendas arose worldwide as
stated by famous researcher Klass in the year
1998. Currently, biomass is again in attention as
a high-possible renewable resource.
Organic resources that are being kept as
chemical energy in the bonds amid their atoms. Solar energy is
This energy is basically first hand being fixed by radiant light and heat
plants that create organic matter with the help from the Sun that
is harnessed using
of solar energy and impressive carbon dioxide a range of ever-
with the help of Bioenergy is the valuable energy evolving technologies
being figured out from biological properties. It such as solar heating,
is the most used renewable energy in the world, photovoltaics, so-
in some extend due to the use of biomass in lar thermal energy, so-
lar architecture,
developing countries, which is done through molten salt pow-
low-efficiency conversion systems, such as er plants and artificial
open-air fires. photosynthesis.
Though, modern bioenergy schemes are
needed to be extremely efficient in order to gain
favorable energy and financial equilibria and
environmental assistances.
Numerous ways are being attained for
changing biological properties into energy
amenities which are heat, power, and
transportation fuels. The main reason of the
change way found to be dependent, on one
hand, on the nature of the biological resource,
and, on the other hand, on the required energy
service. Eventually, in every route, the vigor in
the biomass is unconfined by burning, which
contraries photosynthesis freeing carbon and
energy in the form of heat.
The change of biomass can include primary
and secondary change procedures. Biomass can
be straight rehabilitated into heat and power,
or can chiefly converted into a more suitable

energy transporter and then into the required
energy facility through secondary conversion.
Main conversion comprises thermochemical
procedures such as combustion, gasification,
pyrolysis, and biochemical procedures such
as fermentation, anaerobic digestion, and
transesterification. Subordinate alteration
consists of boilers, gas turbines or gas engines,
and internal combustion engines.
Boilers make use of the heat being emitted
during combustion to heat water or generate
steam for heat source or for driving a steam
turbine, gas turbines or gas engines use vaporous
energy transporters for creation of electricity
and mechanical power, and internal combustion
engines are used in vehicles as stated by famous
researcher Sims in the year 2002.
Numerous energy-rich molecules are
readily available on Earth; these are particles
that can experience chemical reactions that
make vigor readily available for usage. The
most predominant energy-rich particle that is
available on Earth is oxygen, just two oxygen
Radiant heat is the particles being joined together and forming O2.
transfer of electro-
These molecules relate with other molecules to
magnetic radiation
which describes give off energy.
the heat exchange of Nearly any molecule that’s a collection of
energy by photons. carbon atoms especially with hydrogen and
oxygen will react with oxygen to create carbon
dioxide. Wood and other resources can be burned
when there is oxygen available in what is called
a combustion reaction. Burning wood alters
this chemical potential energy and releases it as
radiant heat. Many other fuels can be scorched
in similar reactions.
5.2.1. Application of Chemical Energy

Chemical energy is basically released if it is
exothermic reaction or absorbed if it is termed as
endothermic reaction during a chemical reaction.
In an exothermic reaction, heat is getting taken
out, making warmth. In an endothermic reaction,
the heat is engrossed, letting off cooling.
1. Air bags are triggered by a chemical
reaction in the bag. A sensor lights
up an electrical circuit, and then so-
dium aside is being torched. The re-
action that happens makes nitrogen
gas, which engrosses the bag at a tre-
mendously fast rate.
2. Ammonia and bleach when being
put together develop a chemical re-
action. Toxic vapours grow into a
chemical being called as chloramine
gas. This has the possible to form
hydrazine, which can be the reason
to cause enema, headaches, nausea,
and seizures.
3. Baking soda and vinegar creates
carbon dioxide gas when varied. As
this gas produces in capacity, it puts
weight on whatever vessel it is in,
and will explode out of an inaugural
in the container, creating a volcano
effect. This chemical reaction is safe,
making it a great science activity for
the scholars.
4. Batteries have two terminals: the
anode and the cathode. They’re de-
tached by an electrolyte, a chemical
that makes the anode and cathode to
transfer a charge. When something’s
being linked to a battery, chemical

reactions take place along the elec-
trodes to create electricity. Of course,
one can’t see the energy in the bat-
tery when the battery is just lying
around; it is when the electricity is
created by the energy is observed.
5. Explosives: when an explosive goes
off, chemical energy that was stored
in it is changed and transferred into
sound energy, kinetic energy, and
thermal energy. Just because chemi-
cal energy is being free, it doesn’t
understand that an explosion will
happen. But, when a solid substance
quickly transformers into a hot, in-
creasing gas, one may be observed
at an explosion. Take TNT, for in-
stance. Two units of solid TNT can
promptly alteration into fifteen units
of hot gas, creating a dark and sooty
explosion.
6. Food: chemical energy in food is
free when the food is processed and
the particles of food are wrecked
down into lesser pieces. Our bodies
digest food by mixing it with acids
and enzymes in the stomach. This
procedure turns carbohydrates into
glucose. The stomach with the help
of small intestine then release that
glucose into the bloodstream, plate-
ful as energy for our bodies.
7. Heating packs which are being used
to warm up cold hands or calm sore
muscles have chemicals inside them.
A lot of them work by “cracking”
or bending them. This is because

they’re being completely filled with
iron. Once you crack the heating
pack, the iron is bare to the air. As
the iron being reacted to the oxygen,
it converts into iron oxide, a chemi-
cal that can generates heat.
8. Petroleum is a mixture of oil and
natural gas being constitute of hun-
dreds of particles containing carbon
and hydrogen. When petroleum is a
vapor, it’s careful natural gas. When
petroleum is a liquid, it’s careful
crude oil. One can then extract that
energy by scorching it and by means
of it to fuel cars, heat homes, and
more.
9. Wood, when dry, provisions chemi-
cal energy. This chemical energy is
unconfined as the wood burns, and it
is transformed into heat, or thermal
energy. This also creates light ener-
gy. As a consequence of burning, the
wood turns into a completely new
substance, which is ashes.
5.3. CHEMICAL THERMODYNAM-

ICS
It has been severely noticed that upstairs of the
houses are hotter than the downstairs That’s also
thermodynamics. And the way a thermos flask
can keep coffee warm yes, it is thermodynamics.
Chemical thermodynamics is the research of
how heat and work being connect to each other
both in vicissitudes of state and in chemical
reactions. It includes a series of rules and laws
that clarify how heat and work well, work,

and clarifies which procedures can happen
impulsively and which essential some help.
There are numerous basic values of chemical
Enthalpy (H) is
the sum of the thermodynamics to reflect: schemes, the laws
internal energy (U) of thermodynamics, and enthalpy. Chemical
and the product of thermodynamics is also concerned with four
pressure and volume particular quantities: internal energy, enthalpy,
(PV) given by the entropy and the Gibbs free energy.
equation: H=U+PV.
5.3.1. Systems in Chemical Thermody-

namics
To comprehend thermodynamics, it’s obliging
to first describe something called a system. A
system is a sequence of mechanisms that are
linked together. In a nutshell, it’s the section of
the world one is focusing on. one can observe at
what gets in and out of a particular system. For
instance, if one has coffee in a thermos flask,
one can either call the coffee itself the system,
or the whole thermos flask which consists of the
walls of the container.
There are numerous types of systems in
chemical thermodynamics: isolated systems,
closed systems, and open systems.
An isolated system is one that has rigid
walls and doesn’t allow the transfer of energy
or mass. The walls are perfectly insulating. A
closed system has walls that let energy pass in
and out of the system, but that don’t allow mass
to enter or escape. And an open system allows
both energy and matter to enter and leave.
5.3.2. Heat and Work

Heat and work are both forms of energy. They are
also connected kinds, in that one can be distorted
into the other. Heat energy such as steam engines
can be used to do work such as pushing a train
down the track. Work can be changed into heat,
such as might be knowledgeable by rubbing
one’s hands together to warm them up.
Work and heat can both be explained using
the same section of measure. Occasionally the
calorie is the unit of measure, and mentions to
the quantity of heat needed to raise one gram
of water 1°C. Heat energy is being sledded in
kilocalories, or thousand calories.
Characteristically, we use the SI units of
Joules (J) and kilojoules (kJ). One calorie of
heat is equal to 4.187 J. one will also observe
the term specific heat, the heat needed to raise
one gram of a substance to 1°C. Specific heat,
given by the symbol “C,” is usually defined by
the equational relation:
C = q/MΔT
where: C = specific heat in cal/g-°C; q = heat
added in calories; m = mass in grams; and ΔT
= rise in temperature of the material in °C. The
value of C for water evidently is 1.00 cal/g-°C.
The standards for specific heat that are being
projected in the researches and books are usually
registered at a specific pressure and/or volume,
and one need to be focused on to these settings
when being used the values from the researches
in problems or computer models.
5.3.3. Energy
One might recall the First Law of
Thermodynamics, which is basically that energy
cannot be shaped or destroyed. Energy can only
transform. Chemically, that typically defined
as energy is transforming to work, energy in
the form of heat transform from one section to
another, or energy is kept up in the constituent
chemicals. One has observed how to calculate
work which is elementary.
Heat is definite as that energy that is moved as
a consequence of a temperature change between
a system and its environs. Mathematically,
one can observe at the variation in energy of
a scheme as being a purpose of both heat and
work:
ΔE = q + w
where: ΔE is the change in internal energy of
a system; q is the heat flowing into the system;
w is the work being done by the system.
If q is positive, one projects that the reaction
is endothermic, that is, heat movement into the
reaction from the outdoor surroundings. If q is
negative, then the response is exothermic, that is,
heat is assumed off to the outside surroundings.
Heat production is
5.3.4. Enthalpy
a side product of
Enthalpy is a stimulating idea: it is distinct by
metabolic processes,
the continuous its alteration somewhat than a single object. A
occurrence of which state property, the term enthalpy originates from
provides the energy the Greek “heat inside.” If one has a chemical
basis of life. system that experiences some kind of alteration
but has a secure volume, the heat production
is equal to the alteration in internal energy
mathematically it has been stated as q = ΔE.
Figure 5.2: Enthalpy graph.

dia/commons/7/7f/Stage_enthalpy_for_degree_
of_reaction_%3D0_in_a_turbine..jpg
We will explain the enthalpy alteration, ΔH,

of a system as being equivalent to its heat output
at constant pressure:
dH = q at constant pressure
where: ΔH = change in enthalpy. We define
enthalpy mathematically itself as:
H = E + PV
where: H = enthalpy; E = energy of the
system; PV = pressure in atm times volume in
liters.
5.3.5. Entropy
Entropy is an amount of the ailment of a system.
Take any room as an instance. Left to itself, the

room will get hike in entropy in simpler language
it gets messier if no work cleaning up is being
happened to cover the complaint. Work must
be complete to keep the entropy of the system
down low. Entropy must come from the second
law of thermodynamics, which explains that all
systems tend to reach a state of equilibrium.
Figure 5.3: Entropy system.

dia/en/0/01/Schematic_diagram_of_a_heat_en-
gine02.jpg
The meaning of entropy is that when an

impulsive alteration happens in a system, it will
continuously be originating that if the complete
entropy vicissitudes for all complicated is
intended, a positive value will be got. Just, all
spontaneous vicissitudes in an isolated chemical
system occur with an increase in entropy.
Entropy, like temperature, pressure, and
enthalpy, is also a state property and is being
projected in the different researches by the

symbol “S.” Like enthalpy, one can calculate the
change of S (ΔS).
Δ S = S Final – S initial or Δ S = S (products)
– S (reactants)
where: ΔS is alteration in entropy; S final
and S initial are the final and early entropies,
correspondingly.
5.3.6. Gibbs Free Energy

The free energy of a system, represented by the
letter “G,” is defined as the energy of a system
that is free to do work at constant temperature
and pressure. Mathematically, it is defined as:
G = H – TS
where: G is the energy (sometimes called
the free energy); H is the enthalpy; T is the
temperature; and S is the entropy of the system.
One can also calculate the change in G
the same way as you calculate the change in
enthalpy or entropy:
ΔG = G(products) – G(reactants)
where: ΔG is change in free energy. A pop-up
calculator is available to calculate the enthalpy
and Gibbs free energy changes in reactions.
REVIEW QUESTIONS
1. What is chemical energy?
2. Describe chemical thermodynamics
3. Explain types of system
4. Explain thermodynamic processes
5. Describe enthalpy
6. Explain entropy
7. Describe properties of enthalpy changes
8. Describe Gibbs free energy in terms of chemical thermo-
dynamics
9. Explain the correlation between heat and work
10. Explain the application of chemical energy
REFERENCES
1. 2012books.lardbucket.org. (2019). Chemical Thermodynamics.
[online] Available at: https://2012books.lardbucket.org/
books/principles-of-general-chemistry-v1.0/s22-chemical-
thermodynamics.html [Accessed 3 August 2019].
2. Campbell, A., Hanania, J., Jenden, J., Lloyd, E., & Donev, J. (2018).
Chemical Energy – Energy Education. [online] Energyeducation.ca.
Available at: https://energyeducation.ca/encyclopedia/Chemical_
energy [Accessed 3 August 2019].
3. Chem.libretexts.org. (2016). 19: Chemical Thermodynamics.
General_Chemistry/Map%3A_Chemistry_-_The_Central_
Science_(Brown_et_al.)/19%3A_Chemical_Thermodynamics
4. Eschooltoday.com. (2019). What is Chemical Energy?. [online]
Available at: https://www.eschooltoday.com/energy/kinds-of-
energy/what-is-chemical-energy.html [Accessed 3 August 2019].
5. Koo, S., & Nolte, B. (2019). Chemical Energy. [online] Chemistry
LibreTexts. Available at: https://chem.libretexts.org/Bookshelves/
Thermodynamics/Energies_and_Potentials/Chemical_Energy
6. Nicholson, J. (2017). Chemical Energy. [online] Chemistry Libre
Texts. Available at: https://chem.libretexts.org/Bookshelves/
Thermodynamics/Energies_and_Potentials/Chemical_Energy
7. Paz, A. (2013). Biological Resources for Energy. [online] science
direct. Available at: https://www.sciencedirect.com/science/article/
pii/B9780124095489058814 [Accessed 3 August 2019].
8. Shapley, P. (2012). Chemical Thermodynamics. [online] Butane.
chem.uiuc.edu. Available at: http://butane.chem.uiuc.edu/pshapley/
GenChem2/B1/1.html [Accessed 3 August 2019].
9. Simmons, J. (2019). What is Chemical Energy? – Definition &
Examples – Video & Lesson Transcript | Study.com. [online]

Study.com. Available at: https://study.com/academy/lesson/what-
is-chemical-energy-definition-examples.html [Accessed 3 August
2019].
10. Solarschools.net. (2019). Chemical Energy – Knowledge Bank –
Solar Schools. [online] Available at: https://www.solarschools.net/
knowledge-bank/energy/types/chemical [Accessed 3 August 2019].
11. Thermodynamics, C. (2008). Chemical Thermodynamics. [online]
Shodor.org. Available at: http://www.shodor.org/UNChem/
advanced/thermo/index.html [Accessed 3 August 2019].
12. Wood, D. (2019). Chemical Thermodynamics: Definition &
Principles. [online] Study.com. Available at: https://study.com/
academy/lesson/chemical-thermodynamics-definition-principles.
html [Accessed 3 August 2019].
13. Your Dictionary. (2019). Examples of Chemical Energy. [online]
Available at: https://examples.yourdictionary.com/examples-of-
chemical-energy.html [Accessed 3 August 2019].
CHAPTER
6 THERMODYNAMIC
EQUILIBRIUM IN
SYSTEM

• Thermodynamics In this chapter, you will learn about:
Stability • Thermodynamics equilibrium in system
• Kinetic Stability • Types of thermodynamic equilibrium
• Thermodynamics • Stability with respect to the thermodynamic
Equilibrium Constant • Thermodynamic versus kinetic stability
• Hydraulic • Thermodynamic equilibrium constant
Equilibrium
• Theoretical analysis on thermodynamic
• Mechanical stability
Equilibrium
• Approach to the thermodynamic
• Equilibrium State equilibrium
• Lechatelier’s • Mechanical equilibrium
Principle
• Thermal equilibrium
• Metastable
Equilibrium
• Thermodynamic
Potential
• Hydrophobic
Connections
• Intramolecular
Hydrogen
6.1. INTRODUCTION
The state of a system in which the properties have certain, unaffected
standards as long as exterior circumstances are remain unaffected
is known as an equilibrium state. A thermodynamic system which
is said to be in a thermodynamic equilibrium if it is in a chemical
equilibrium, mechanical equilibrium, radiative equilibrium, and
as well as in thermal equilibrium. Therefore, when the appropriate
aspects or factors stop to fluctuate or change with change in time.
A kind of equilibrium, which is sometime not stated or cited, is
known as a hydraulic equilibrium. A hydraulic equilibrium, which is
very important with respect to the living systems. For instance, two
in line or neighboring cells taking in to the consideration under their
closeness sometimes are enormously near to the thermal equilibrium
as well as hydraulic equilibrium.
Hydraulic equilibrium is generally only attained with a quick
method because of the membrane permeability of cells and
osmosis. In equilibrium there exists a state of balance. This balance
in thermodynamics means there are no changes in the phase, or
unbalanced capacities or possibilities within the system.
Figure 6.1: Zeroth law of thermodynamics: an example in equilibrium.

Thermodynamic equilibrium is a state which is obtained with
the help of system when a system fulfills the all three types of the
equilibriums. These three types of the equilibriums are thermal
equilibrium, chemical equilibrium and the third equilibrium is known
Thermodynamic Equilibrium in System 103
as mechanical equilibrium. Conditions of the

Thermodynamic equilibrium of a system is
Chemical equi-
described and well defined with the help of librium is the
the Zeroth law of thermodynamics. According state in which
to this Zeroth law of thermodynamics, in the both reactants
thermodynamics, stated that, if the first object and products
is in equilibrium with the second object and the are present in
concentrations
second object is in equilibrium with the third which have no
object, then first and third objects will also be further tendency to
in equilibrium. change with time,
so that there is no
Therefore, the objects which are in the
observable change
thermodynamic equilibrium, all of them in the properties of
objects will have the exact same temperature as the system.
compared to one another.
In simple words, the thermodynamic
equilibrium in the system is defined as the state
of a system in which qualities have certain,
unaffected standards as long as exterior settings
are remain unchanged or untouched is known as
an equilibrium state.
Equilibrium in the context of the
thermodynamic takes place when the same
temperature exists all over the system. The
states of dynamic equilibrium are allocated
with the help of the classical thermodynamics.
At thermodynamic equilibrium, the state of the
system is evaluated with the help of the thorough
parameters or aspect values. These parameters
or aspects are pressure, temperature, etc.
Thermalization is a type of process
which takes in to the direction towards the
thermodynamic equilibrium. The word
equilibrium means a state of balance. In an
equilibrium state, there are no potentials which
are not balanced (or driving forces) with the
system. A system that is in equilibrium deals
with no modifications or changes when it is

Thermalization isolated from its surroundings.
is the process of
physical bodies
reaching thermal 6.2. TYPES OF THERMODYNAMIC
equilibrium through EQUILIBRIUM
mutual interaction
The thermodynamic equilibrium in term
equilibrium means, equivalence of all potential
difference, equivalence of all force which are
acting on that body or object, etc., for which the
system can be alter or change from its original
state.
Let’s assume there are two systems, and these
two systems are in the similar state and they are
in equilibrium with respect to each other. Now,
these two systems are altered or vice-versa at
that moment the settings or circumstances of
the systems are changed or altered which means
there is a potential difference between the two
systems which is different or exterior force are
acting on the system, etc.,
Therefore, the system which is in
thermodynamic equilibrium if it cannot be
changed or altered from its original state. A
system which is in thermodynamic equilibrium
satisfies the following conditions.
• mechanical equilibrium (no
unbalanced forces);
• thermal equilibrium (no temperature
differences); and
• chemical equilibrium.
6.2.1. Mechanical Equilibrium (No Un-

balanced Forces)
Two systems are supposed to be in the thermal
equilibrium if their temperatures are same with

respect to the each other.
Figure 6.2: An example of mechanical equilibrium.

pedia/commons/thumb/f/fc/WeightNormal.
svg/1280px-WeightNormal.svg.png
Thermal equilibrium means there is no

change of any things which are owned by
the system. Here the things which are owned
with the help of the system are in touch with
its diathermal wall of the surrounding. In the
diathermal wall, the heat cannot flow.
Therefore, when any of the system makes
any contact with its surroundings with the help
of a diathermal wall and if there is no on spot
alterations or changes of its nature or behavior
then it could be saying that the system which is
existing, is in thermal equilibrium.
6.2.2. Thermal Equilibrium (No Temper-

ature Differences)
Two systems are said to be in mechanical
equilibrium when the pressures of the both of
the systems are exact with respect to the each
other.
Figure 6.3: An example of thermal equilibrium.

dia/commons/0/02/Heat_flow_hot_to_cold.png
When any force which is not balanced

is inattentive in the system then this state of
the equilibrium is said to be the Mechanical
Equilibrium. Mechanical Equilibrium means
force that are not balanced or unbalanced is
Gravitational absent force is entirely absent in the system or
force is a force that between two systems and the surroundings of
attracts any two
objects with mass.
the system.
If the system and the surroundings of the
system is present in the mechanical equilibrium
then the pressure of the system for both of the
bodies are equal with respect to each other. But
the pressure cannot be the exact all over the
course of the system of gravitational force of
the system.
6.2.3. Chemical Equilibrium

Chemical equilibrium is the state with respect
to the thermodynamic equilibrium in which the

chemical events or content of the reactants as
well as the concentration of the products have
no overall modification or change over the
period of time. Two systems are said to be in
diffusive equilibrium if the chemical potentials
of the both of the objects or bodies are similar
with respect to each other.
Figure 6.4: An example of chemical equilibrium:

Pentacene 6-methyl equilibrium.
dia/commons/thumb/3/3c/Pentacene_6-meth-
yl_equilibrium.svg/3470px-Pentacene_6-meth-
yl_equilibrium.svg.png
A system that will not undergo in to the

chemical reaction is known as the chemically
equilibrium system. Chemically equilibrium
means there is no chemical reaction or transfer
of the chemical is taking place from one part to
the other part.
Any of the above three conditions of the
equilibrium are not fulfilled in any system is
known as the non-equilibrium state. In the state
of the non-equilibrium, unbalanced or those
forces which are not balanced took participation
between the systems and the surroundings of
the system or pressure which is not balanced
will be non-identical or some chemical reaction
can take place between the system and system
cannot hold the original state of the system.
6.3. THERMODYNAMIC STABIL-

ITY
In the general case of a state or a condition of
the equilibrium is considered with the help of
the minimum value of the capabilities of the
thermodynamics that work as a proportional
to the variables which are not dependent under
the situations of the experiment. For instance,
when the volume of the entropy and the number
of the moles of the elements are independent
variables, then the internal energy of the system,
which is denoted with the help of the U, must
be the minimal, if the system is to be in the
thermodynamic equilibrium.
Thermodynamic stability follows from this
Thermodynamic need that the first variation which is denoted
stability occurs when
with the help of the δU, must be equal to the
a system is in its
lowest energy state, or value of zero under the small fluctuation or
chemical equilibrium variation of the variables and at a constant total
with its environment. entropy, as well as the number of the particles.
Lack of change or alteration in the
temperature as well as the pressure for all of
the phases and the equivalence of the values of
the chemical capabilities for all of the elements
which are in coexisting phases follow from this
matter of the fact, as a condition or setting of the
equilibrium.
Even when these types of the setting or
state are getting satisfied, there is no assurance
declaration or guarantee of the stability with
respect to the thermodynamics. Yet another
condition, a positive value of the second
variation, which is denoted with the help of the
δ2U, follows from the condition of the minimum
internal energy which is again denoted with the
help of the U. this take in to the direction towards

a number of thermodynamic inequalities,
which are the conditions of the thermodynamic
stability.
For instance, one of these types of the
conditions is a positive value of the capacity
of the heat of the system at a volume which is
constant, another is reduction in the pressure
with the increment in volume at the temperature
which is again constant.
In the general case, thermodynamic stability
can be expressed as the subsequent ideologies
or philosophies which is, an external impact that
eradicates any type of the system from a state
of the equilibrium encourages in that system
process that are working in the direction to
respond according to the effects of the impact.
Lechatelier’s Principle is a principle of an
entire theory in relation with the context of the
thermodynamic stability for both homogeneous
as well as heterogeneous system which was
established in the time period of the late
nineteenth century with the researcher named as
J. W. Gibbs.
Metastable equilibrium can also have the Metastable equi-
qualities of the thermodynamic equilibrium up librium is defined
as the state in which
to some point. Even though the Metastable
a system remains
equilibrium which work according to the for a long period of
minimum internal energy which is denoted by time, and any slight
the symbol U or the minimum of some other type disturbance causing
of the thermodynamic potential, this reduces the the system to deviate
from the meta-
above principle, which define the most stable
stable state does not
state. result in the system
passing into another
state.
6.4. THERMODYNAMIC VS. KI-

NETIC STABILITY
Substance search for to be in its lowermost
energy state. This is a law which is recognize
by the universe. Therefore, when a substance or
material is at lower energy, then the substance
is at a more stable state. The relative energies of
the reactants as well as the products will choose
the stability with respect to the Thermodynamic.
This thermodynamic stability is independent of
the pathway taken with the help of the reactants
as well as products.
• Thermodynamic stability can be
credited to the chemical potential
energy. When the two chemicals
react with each other to form new
products, the energy which is emitted
is the potential energy of the reactant.
Thermodynamic stability is general
which is measured comparative to a
standard.
• The chemicals that are stable are non-
reactive in nature and those types of
chemicals will have low potential
energy. Chemicals that are much
more reactive in behavior under the
appropriate circumstances are those
having high potential energy.
• Kinetic stability is connected to the
speed of the reaction and henceforth
has to do with the pathway between
the reactants as well as the products.
• Kinetic stability is largely depend
on the activation energy which is
essential to begin the process of the
reaction.
• The reaction potential energy of the
intermediate evaluates the activation
energy.
• The reaction will be slow at low
temperatures if the activation energy
is high. Then the reaction can be made
with much speed with the help of the
increment in the temperature.
• The reaction will be quick even at low
temperatures if the activation energy
is low. Increment in the speed of the
reaction is seen with the help of the
increment in the temperature for these
types of reactions.
• Kinetic stability evaluate the rate
constant (k). Thermodynamic stability
explains the equilibrium constant
which is denoted with the help of (K).
• Both are independent of one another
as well as the relative stability of
reactants and products is the same not
with standing of the mechanism of the
reaction or reaction pathway.
• The energy of activation (EaEa) hinge
on the reaction pathway as well as the
specific intermediate(s) which took
participation.
6.5. THERMODYNAMIC EQUILIB-

RIUM CONSTANT
When two systems are in mechanical
equilibrium, chemical equilibrium and thermal
equilibrium with each other they are said to be
in thermodynamic equilibrium. Let us take the
instance of cold oil and hot water. When hot

boiling water is poured in to the vessel which is
already filled with the help of cold oil, at first,
they both keep their temperatures.
After some interval of time, water will start
to lose its temperature and oil will start to gain
some temperature as well. This reaction or
process will continue until the both of them that
is water and oil obtained similar temperatures.
This condition is known as a state in which both of
them are in thermodynamic equilibrium. Severe
properties for example volume, temperature,
pressure, etc., Governs the thermodynamic
equilibrium which is accomplished with the
help of the system.
A system as an isolated system is said to
be in thermodynamic equilibrium when there
is no alteration, modification or change is seen
or noted in the macroscopic properties of the
system such as entropy, and internal energy etc.
A system which is substantially stable and
does not undergo on spot alterations or changes
is said to be in thermodynamic equilibrium.
The macroscopic qualities will not alter or get
changed when a system is in thermodynamic
Molecular biology equilibrium.
is a branch of biol-
ogy that concerns
the molecular basis 6.6. THEORETICAL ANALYSIS ON
of biological activity
between biomolecules THERMODYNAMIC STABILITY
in the various systems OF CHIGNOLIN
of a cell, including the
interactions between Sympathetic the leading issue behind
DNA, RNA, proteins thermodynamic constancy of proteins stays a
and their biosynthesis,
challenging subject in biochemistry, biophysics,
as well as the
and molecular biology. Numerous theories
defining protein constancy have been stated.
In the year 1936, Pauling and Mirsky stated

that a protein attained an exclusively defined
conformation which is being held in place by
N-H···O hydrogen bonds amid the nitrogen
and oxygen atoms in the peptide chain, the
interaction energy of each bond being about
5 kcal/mol.
Three years later, Bernal optional that the
hydrophilic remains of a protein were bare to
the aqueous solution, while the hydrophobic
shares were in interaction with each other in the
inner of the protein. In the year 1951, Pauling’s
group exposed the greatest significant structural
rudiments in spherical proteins: alpha helices
and beta sheets.
They, also, stated out that the bone marrow
N-H and O starting intramolecular hydrogen
bonds were about 2 kcal/mol more variant than
those starting intermolecular hydrogen bonds
with nearby water molecules. In 1959, one of
the famous researchers Kauzmann obvious in
his powerful review that hydrophobic lure was a
leading factor in the thermodynamic constancy
of the folded conformation for many globular
proteins.
This has been reinforced by the following
experimental explanations:
• the alteration in Gibbs energy for
moving a small nonpolar molecule
from an aqueous solution to a
biological solvent is large and
negative.
• the complete effect of electrostatic
connections on protein constancy is
unimportantly small.
• many nonpolar remains are certainly
situated in the inner of globular

proteins.
In the late year of 1980s, it developed
likely to inspect the leading factor behindhand
protein constancy by smearing site-directed
mutagenesis.
It was projected that:
• both hydrophobic connections and
intramolecular hydrogen attachment
donated considerably to protein
stability.
• the improvement of van der Waals
interactions just because of the
too tight stuffing in the protein
interior created by the spare of small
hydrophobic remains with greater
ones caused in augmented protein
stability.
• the result of hydrogen bonding of
peptide groups on protein stability
was similar to that of hydrogen
attachment of side chains.
These observations suggest the rank of
intramolecular interactions in protein stability.
Yet, the thermodynamic constancy of proteins
has been basically modeled as according to
famous researcher hydrophobic communication
hypothesis done by the Kauzmann.
Molecular dynamics (MD) imitations are a
strong tool that makes everyone to examine large
conformational changes in proteins generalized
ensemble MD imitations have been practical to
calculate temperature and pressure dependence
of free energy profile of proteins and peptides.
Long equilibrium MD simulations have been
performed to characterize folding pathways and
free energy changes.
6.7. APPROACH TO THERMODY-

NAMIC EQUILIBRIUM
The possessions of a macroscopic traditional
system containing of some 1020 particles are
strong-minded by a probability density function
W of the complete Γ space of moments and
organizes of all the molecules. This likelihood
density function is that of the collaborative
on behalf of the entirety of all experimental
systems ready rendering to the macroscopic
specifications.
The entropy is always to be explained as the
negative of k times the integral over the different
phase space of W lnWhΓ.
Though, the total probability density
Liouville
function W, even for a thermodynamically equation is a
isolated system, does not obey the famous fundamental equa-
Liouville equation, ∂W/∂t=LW, since small tion of statistical
variations due to its interaction with the rest mechanics. It
of the universe unavoidably ‘smoothes’ W, by provides a complete
description of the
flattening the direct many‐body relations in its system both at
logarithm. equilibrium and
This flattening is the reason of the entropy also away from
equilibrium.
upsurge, and in schemes near room temperature
and above, in which there is heat transmission
or chemical species dispersal, the flattening
keeps the true entropy mathematically equal
to that incidental from the local temperatures,
pressures, and compositions.
This, though, is by no means unavoidably
general. The standard of thermodynamic
separation is not that the whole probability
thickness function W is genuine by the
surroundings, but that abridged probability

density purposes w in the Γ space of n = 2,3,...
particles change in time as if the scheme were
genuine by the surroundings.
This standard is adequate to give an exactly
definable technique of “smoothing” the whole
probability density function. The smoothing
contains of replacing the direct many‐body
associations in ln W by their average n‐body
values, n = 2,3,..., such that the lesser reduced
probability density functions w are genuine.
REVIEW QUESTIONS
1. Explain the concept of the thermodynamic equilibrium in
system.
2. What are the various types of the thermodynamic equilib-
rium?
3. Describe the basic concept of the stability in the context of
thermodynamics.
4. Differentiate between the term thermodynamic and kinetic
stability.
5. What do you understand by the thermodynamic equilib-
rium constant?
6. What is the mechanical equilibrium?
7. Explain the theoretical analysis on the thermodynamic sta-
bility.
8. Define the term thermal equilibrium.
9. What are the various approaches to the thermodynamic
equilibrium?
10. What is the basic principle of chemical equilibrium?
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thefreedictionary.com/Thermodynamic+Stability [Accessed 3
August 2019].
CHAPTER
7 THERMODYNAMICS OF
CHEMICAL MIXTURES

• Chemical Mixtures In this chapter, you will learn about:
• Body Fluids • Mixtures and the saturates states of
mixtures
• Colliding Jets
• Various cases that are known to be famous
• Pulsating Injectors
for ideal mixtures
• Gasoline
• The entropy that is involved in the process
• Chemical Potential of mixing
• Gibbs Equation • Various calculations that take place during
• Raoult’s Law the mixing process
• Superfluid Helium
(II)
7.1. INTRODUCTION
A solution may be defined as a substance that is formed in the event
of homogeneous mixing of two or more than two elements, so that it
results in a single form of occurrence. The analysis of solutions holds
importance due to the fact that there are many biological and chemical
processes that are going on in the systems that comprises of quite a lot
of components.
It is important to comprehend the way the thermodynamic
chemical mixtures behave, so that any kind of system, whether it is in
ideal or non-ideal form, can be studied, for the purpose of extracting
knowledge about the properties corresponding to molecular forms of
systems, that may be significant for explanation of certain processes.
Figure 7.1: Solutions form an integral part of the chemical mixtures.

Source: https://upload.wikimedia.org/wikipedia/commons/b/b8/
Chemical_solutions.jpg
There are many real gases that tend to act in similar manner to
ideal gases when they are observed under standard temperature and
pressure. This makes provisions for the combination of the learning
about ideal systems and solutions, with those of thermodynamics that
Thermodynamics of Chemical Mixtures 125
takes place at standard state.

This combination is done to get a Plasma is a
mathematical form of the impacts that take hot ionized gas
place during the mixing on the properties consisting of
corresponding to thermodynamics of a supposed approximately
solution in gas phase that can be expressed in equal numbers of
positively charged
equation form. ions and negatively
charged electrons.
7.2. MIXTURES
A mixture may be defined as a system that can
be analyzed from the perspective of two or more
different aspects. An example of this can be
given in air as a mixture of oxygen and nitrogen.
Although, the air is generally considered as
a pure substance in most cases where the
composition does not alter.
In this case, oxygen may, on its own, be
treated as an original mixture of 99.8% of atoms
of its isotopic form, 16O and the remaining 0.2%
of the atoms corresponding to the isotope 18O.
Another example can be found in the instance
of a completely ionized plasma that may be
considered as a mixture of ions and electrons.
More instances of the mixture may be found in
the components of a container containing butane
that may be perceived as a mixture of vapor and
liquid, in which both separately are the mixture
of propane and butane.
The analysis that is generally conducted
is of the chemical substances that are found in
simple non-reacting form and make up either
one phase system or a system that has more than
one phases, and the cases where these mixtures
tend to exchange compounds across various
phases or across various environments.
Many compounds that exist naturally, are

mixtures that are composed of pure chemical
substances such as air, sea water, tap water,
natural gas, wine, coffee, body fluids, gasoline,
antifreeze, and so forth. The substances can be
found in such large numbers due to the fact that
the entropy naturally tends to increase in the
process of mixing.
Though there might be a case in which
reducing the energy can go against this idea,
an example of this being that of equilibrium of
liquid vapor that is found under gravity.
Hence, there must be some amount of
energy that must be given to a mixture in order
to separate the elements of the substance. Also,
there needs to be some introduction of energy for
the fastening of the process of mixing in some
natural processes for practical applications.
Figure 7.2: The mixtures may be found in natural

form as in that of sugar and tea.
Source: https://live.staticflickr.
com/2642/4169031076_d1624cf515_b.jpg
This is done by many methods that may

involve mechanical stirrers, electromagnetic
forces, ultrasound vibrations and nozzles,
colliding jets, pulsating injectors and swirls in
the flow systems.
The time taken in mixing may be really less
in gases, as can be felt in the detection of smell
on the opening of a fragrance bottle, more in the
liquids, like in the case of sugar getting soluble
in a cup of tea, or greatly increased in solids, as
in the case of glass painting or glass staining, Miscibility is the
that remains there for the view of the people for property of two
many centuries. substances to mix in
all proportions (that
Mixtures generally tend to make up systems is, to fully dissolve
with more than one phase. An exception of this in each other at
happens only in case when the elements are any concentration),
completely perfect for mixing, or in the case forming a
homogeneous solution.
when there is a gap in miscibility and the state
of the mixture is found to be unsaturated.
7.3. SATURATED STATES

A state of saturation in thermodynamics may
be defined as one in which all the phases are in
equilibrium. For the study of changes in phases
in the case of pure substances, the focus of study
was on saturated states of vapor, liquid and solid.
In the case of mixtures, saturation in regard
to one of its elements may be defined as the
state at which the mixture cannot dissolve any
more amount of the element in itself. The state
of unsaturated mixtures can be converted to
saturated form, by adding increased amount of
component.
Figure 7.3: In gypsum, some substance may be

found in saturated forms.
Source: https://www.nps.gov/whsa/learn/im-
ages/WHSA-Gypsum-Landing-Page.jpg?maxw
idth=1200&maxheight=1200&autorotate=false
This may also be done by altering the pressure

conditions or the temperature condition, while
keeping the composition of the mixture as it is.
Though, there are certain mixtures that exist in
unsaturated form, which cannot be converted to
the saturated forms by any means.
7.4. INTRODUCTION TO CALCU-

LATIONS IN MIXING
If there is an open system that comprises of
many chemicals that may react with each other
and can exchange work and mass with the
surrounding atmosphere that encompasses it,
the relation between the states of equilibrium is
given by the Gibbs equation that goes by:
I K
TdS =dE + PdV − ∑ µi dni + ∑ Fk dlk (1)
i =1 k =1
In this equation the symbol Fk represents the

forces that may be there on the system and getting
applied through the differential displacements.
In general, the lower case notations in the
symbols will represent the intensive quantities,
that are taken per every mole, and may be given
by h, s, e and so forth. On the other hand, the
upper case notations will represent the extensive
quantities and will be given by H, S, E and so
forth.
The symbols that denote the physical
characteristics such as temperature, heat
capacity and pressure, will be written in capital
letter. The meaning of one mole is given a name
that goes by ‘Avogadro’s number,’ which is
6.0221415 X 1023.
The extent to which the extensive energy
of the system may be altered by introducing
or taking out a differential number of moles
belonging to a type i, which is given by dni, is
known as the chemical potential energy of the
system in a unit mole and is given by µ i. Gibbs equation is
In case that the system is closed, which a thermodynamic
equation used for
means that no mass can be exchanged with the
calculating changes
surroundings, and that the system is away from in the Gibbs
the effect of external forces, the relation in terms energy of a system
of Gibbs equation will be given by: as a function of
temperature.
I
TdS =dE + PdV − ∑ µi dni (2)
i =1
In this case the variety in which the quantity

of moles of the type i changes, take place by
the means of chemical reactions that happen
inside the boundaries of the closed system. The
primary point of distinctness between the Eqs.
(1) and (2) may be understood by the fact that in

a closed system, the variations in the quantity of
moles is related to a condition that there should
be no change in the number of atoms of any of
the elements in the system.
The equation 7.2 suggests that:
 ∂S 
µi (E, V, n1 ,..., n I ) = − T  
 ∂ni  E ,V,n j≠i
(3)
In case that no reaction take place, the equation
9.2 solves down to be written as
TdS = dE + PdV (4)
If the second law of thermodynamics is to be
considered, it suggests that in a closed and iso-
lated system and for any procedure
TdS ≥ dE + PdV (5)
The slopes of the spaces may result in a rise
in the entropy, if found in any variable inside
the system. Making the velocity gradient, that
represents the release of kinetic energy, and
the temperature gradient, which talks about the
distribution of temperature, even, makes for the
most significant physical procedures.
This is because they have a major role to
play in the rising of entropy that takes place
in a system that does not react while a non-
equilibrium process is going on. In case that the
system comprises of some chemical elements
that can combine with each other, then the
variations in the entropy may also be made by
evening out the concentration variables of the
existing elements.
In another case in which the elements can
react with each other, the entropy variations
can be made by varying the energy used or
released in the chemical binding of the present
elements that might be involved in the reactions.

The inequality that is mentioned as 7.5, may
be utilized to decide the direction in which
the thermodynamic system will proceed as it
approaches towards achieving the equilibrium
state.
7.5. CASE OF IDEAL MIXTURES

Suppose that there is a mixture of various
chemicals and elements with varying mole
numbers given by n1, n2, n3 and so on till nI.
There is V volume in the system and possesses
an extensive internal energy E. The function that
describes the extensive entropy of the system is
given by S (E, V, n1, n2, n3, …, nI).
In an ideal mixture, each and every molecule
is characterized by the similar intermolecular
forces. The forces corresponding to the surface,
such as surface tension and surface energy, may
be considered as negligible. In such mixtures
there is no change in enthalpy in the event of the
combination of various mixtures.
In the case of ideal mixtures, Raoult’s Law
is applicable. Raoult’s Law establishes that
the vapor pressure corresponding to a specific
element of the ideal mixture is same as the vapor
pressure corresponding to the number of times
of the pure component and the mole fraction of
that element in the mixture.
In an ideal mixture the volume taken by the
mixture is same as the sum of individual volumes
of the pure forms of the elements present in the
mixture. In the same manner, the internal energy
of the system of mixture is same as the sum of
internal energies exhibited individually by the
pure form of elements in the mixture. Almost all

the real mixtures exhibit ideal behavior to some
Ideal mixture is extent, as per their occurrence and properties.
a solution with The most appropriate instance of ideal mixture
thermodynamic
may be given by a combination of ideal gases
properties analogous
to those of a mixture in a mixture. Another example of ideal mixtures
of ideal gases. may be given by liquid mixtures, for instance
the mixture of benzene and toluene, in which
the molecules of the elements are similar to each
other in chemical occurrence, and hence they
show ideal behavior.
The mixtures such as those of water and
alcohol may differ drastically from exhibiting
ideal behavior as they are made up of quite
different molecules.
Suppose that all the mole numbers of the mix-
ture are multiplied by a same factor α.
= n1 α= n1 , n2 α=
n2 , n3 α n3=
,..., nI α nI (6)
If the ideal assumptions are taken into account,
the extensive properties of the system will be
multiplied by exactly same component.
= E α= E , V αV (7)
In the same manner the scaling of the extensive
entropies will take place and will be given by:
S (E, V, n1 ,..., n I ) = α S ( E , V , n1 ,..., nI ) (8)
The postulates that imbibe this scaling and mul-
tiplication are defined as homogeneous func-
tions of order one. On differentiating the Eq.
(8) with respect to α, the resulting one takes the
form:
∂S  ∂S I
∂S   
E +V + ∑ ni = S ( E , V , n1 ,..., nI )
∂E ∂V i =1 ∂ni (9)
On further operation that involving multiplying
the Eq. (9) by α and then putting the value of Eq.
(8), the resulting equation is:
∂S ∂S I
∂S
E +V + ∑ ni =
S ( E , V , n1 ,..., nI )
∂E ∂V i =1 ∂ni (10)
The Gibs equation in this case is given by:
dE P I
µ
dS = + dV − ∑ i dni
T T i =1 T (11)
Going by the Eq. (11), entropy’s partial deriva-
tives may be given by:
∂S 1
=
∂E T
∂S P
=
∂V T
∂S µ
= − i
∂ni T (12)
On substituting the Eq. (12) in (10), a great re-
sulting equation is achieved for an ideal mix-
ture, which is given by:
I
∑ ni µi
E + PV − TS =
i =1
Gibbs free energy
(13) is a measure of the
This equation is known by the name of Duhem- potential for revers-
Gibbs relation. The collection of the state vari- ible or maximum
work that may be
ables that is shown in the Eq. (13), is known as done by a system at
the Gibbs free energy. constant temperature
G = E + PV – TS = H – TS (14) and pressure.
The Eq. (13) shows the expression for extensive
Gibbs free energy that is found in ideal mixture.
This is expressed in the form of chemical poten-
tials and mole numbers.
I
G = ∑ ni µi
i =1 (15)
This is a significant result that elaborates that
the chemical potential in the element i does not
actually represent a new state variable. In fact,
it is given in the form of pre-existing state vari-
ables like enthalpy, entropy and temperature.
The chemical potential of the element i is known

as its molar Gibbs free energy.
µ i = gi = hi – Tsi (16)
The enthalpy that is indicated in the Eq. (16)
incorporates the chemical enthalpy that is
related and generated from the production of the
compound from the elements that are present in
it.
7.6. THE ENTROPY IN THE PRO-

CESS OF MIXING
Taking reference to the adiabatic system that is
depicted in the Figure 7.4, and which comprises
of a set of moles that go by n1, n2, n3 to nI,
that belong to gas compounds that have been
separated into several volumes that vary in
amounts, in a manner that they are found at the
same pressure and temperature.
Figure 7.4: A separation of gases depicted in a sys-

tem.
The number of moles present in the system in
total is given by:
I
N = ∑ ni
i =1 (17)
The calculation of entropy that is present in each
mole of the ideal gas is done by applying the
Gibbs Equation as:
dT dP
=ds C p − Ru
T P (18)
In this equation, the unit in which Cp is
expressed is Joules/mole-Kelvin. The depiction
of properties that are exhibited by gas are
described by referring to a set pressure and
temperature. The temperature for reference is
globally accepted as Tref = 298.15 K and the
pressure for reference is given by:
P° = 105 N/m2 = 105 Pascals = 102kPa (19)
This is also given by 1 bar.
The pressures around the world are
represented by P° and the notation in the form
of superscript ‘°’ is used to make reference to
the property of compound that is taken into
consideration at a standard pressure. Though, in
the year 1999, the International Union of Pure and
Applied Chemistry (IUPAC) made a suggestion
that in the assessment of the properties of all the
compounds, the value of standard pressure must
be taken as 100kPa.
Before this suggestion came into action, the
value of standard pressure at which the properties
were assessed was taken as 101.325kPa, which is
1 atmosphere at the sea level. All the evaluation
before 1999 have been done according to this
value.
The change that took place in the depiction
while making the shift was a slight variation
in the standard entropy of the compound at the
same temperature. The variations are also found
to be there in the heat capacity and enthalpy of
the substance.
However, the IUPAC remains as the standard
organization that has been recommending
various standards for the calculations that are
carried out in chemistry and for the purpose of

nomenclature of chemical substances.
This change of pressure does not change
Heat capacity is any part of heat capacity in the ideal mixture
a physical property of gases. In addition, quite a lot of condensed
of matter, defined substances have very little effect on the heat
as the amount of capacity with variation in pressure.
heat to be supplied
to a given mass of a This is the reason due to which the properties
material to produce of various substances can be deduced at standard
a unit change in its pressure and they can further be utilized to
temperature.
explain many of the chemical conditions and
happenings that incorporate a wide range of
mixtures that are in condensed in gas phase.
The discrepancies in the deduction happen
only in cases when the tabulation of the
thermodynamic properties comes through phase
changes or some crucial situations in which
there is quite a remarkable shift from the laws
for ideal gases or ones in which the condensed
phases undergo quite a lot of compressibility.
The entropy corresponding to one mole of
the i-th gas compound, after integration of Eq.
(18) from the temperature of reference and the
standard pressure, may be given by:
T dT  P 
si (T, P) − sio (T
=ref ) ∫
Tref
− Ru In  o 
C pio (T)
T P 
(20)
In the Eq. (20), the calculation of molar heat
capacity, which is given by C°pi, is carried out at
standard pressure as function of temperature. At
the reference temperature, the standard entropy
of the compound of gas is given by:
Tref dT o
sio (Tref ) = ∫ C pio (T) + si (0)
0 T (21)
The integration in the Eq. (21) is done at Pres-
sure same as P°. For the proper calculation of

the standard entropy, the value of heat capacity
is required to be brought down to absolute zero.
Across all the substances that exist, except
for superfluid helium (II), the value of heat
capacity comes down quite quickly with the
temperature tending closer to zero. This happens
in order to make sure that the integral equation
(21) comes to one result, notwithstanding the
probable singularity at temperature equal to
zero.
When the third law is taken into account, the
value of entropy at absolute zero, which is given
by s°i (0), is supposed to be typically zero in
case of a pure substance that may be found in its
simplest crystalline form. In case of substance
that exist in pure form and in alloy form, for
example carbon monoxide (CO), in which there
is a possibility of several crystalline forms, the
value of entropy obtained at absolute zero may
not be zero.
This results in the revision of the calculated
data for entropy as the time goes on according to
the findings of the new researches, as they keep
on being available. In most cases, the constant
of entropy is quite small.
The expression for entropy for a single mole
of the i-th compound of gas is given by:
 P 
=
sio (T, P) sio (T) − R u In  o 
P  (22)
The whole impact of pressure that may be seen
on the system is expressed in a logarithmic
form of entropy. The expression for extensive
entropy of the entire system prior to the process
of mixing is given by:
I I I
 P 
Sbefore = ∑=
ni si (T, P) ∑ n s (T) − ∑ n R
i
o
i i u In  o 
i =1 i =1 i =1  P  (23)
In case the partition between the gases, that are
shown in the Figure 7.4, is removed from the
system, after the substances have completely
mixed, every gas on its own occupies the whole
volume. Then the entropy of the i-th compound
is given by:
 P 
si (T,=
Pi ) sio (T) − R u In  io 
P  (24)
In this equation, Pi refers to the partial pressure
that is exerted by the i-th compound. There is
no change in the enthalpy in the process of mix-
ing due to the fact that the mixture is in its ideal
state. The enthalpy of the mixture would not be
zero in case that the pressure goes to such high
levels, that the potential energy corresponding
to the forces between the molecules becomes
noticeable and effective.
The expression for the entropy of the system,
once the mixing id done, is given by:
I I I
 P 
S after = ∑=
ni si (T, P) ∑ n s (T) − ∑ n R
i
o
i i u In  io 
i =1 i =1 i =1  P  (25)
The change that has happened in entropy cater-
Dalton’s law ing to the process of mixing can be given by:
states that in a
 I I
 Pi    I I
 P 
mixture of non- S after − S=  ∑ ni si (T) − ∑ ni R u In  o   −  ∑ ni si (T) − ∑ ni R u In  o  
o o
before
 i =1 i =1  P    i =1
(26) i =1  P 
reacting gases,
the total pressure After the common terms on both sides in the Eq.
exerted is equal (26) are eliminated, the equation becomes:
to the sum of the I
 P 
partial pressures − Sbefore R u ∑ ni In  o  > 0
S after=
of the individual i =1 P  (27)
gases. This indicates, without doubt, that there is a rise
in the entropy of the system.
This procedure is governed by a law that goes
by the name, Dalton’s Law of partial pressures,
which is given by the equation

PiV = niRµ T (28)
The deductions that can be made from this is that
in addition to the rise in entropy on the mixing of
gases, an equilibrium state can be attained at the
point where the entropy is recorded maximum.
REVIEW QUESTIONS
1. What do you understand by the term ‘Solution.’ Explain.
2. Why is the analysis of solutions important?
3. Describe the Dalton’s Law of partial pressures.
4. Describe the methods used for fastening the process of natural
mixing.
5. In what scenario is there a possibility that the enthalpy of the
mixture would not be zero?
6. What is the value of entropy at absolute zero of a pure sub-
stance?
7. What is the standard value of pressure and temperature?
8. Which law is applicable in the case of ideal mixtures and why?
9. Illustrate the relationship between the states of equilibrium.
Also, describe which law is used to explain the same.
10. What do you understand by the chemical potential energy of
the system in a unit mole and what is its standard unit?
REFERENCES
1. Chemistry LibreTexts. (2019). Thermodynamics of Mixing.
Thermodynamics/Ideal_Systems/Thermodynamics_of_Mixing
2. Martinez, I. (2019). Mixtures. [ebook] Available at: http://webserver.
dmt.upm.es/~isidoro/bk3/c07/Mixtures.pdf [Accessed 3 August
2019].
3. Nieto, R., González, M., & Herrero, F. (1999). Thermodynamics
of mixtures: Functions of mixing and excess functions. American
Journal of Physics, [online] 67(12), pp.1096-1099. Available
at: https://www.researchgate.net/publication/243492076_
Thermodynamics_of_mixtures_Functions_of_mixing_and_
excess_functions [Accessed 3 August 2019].
4. Nptel.ac.in. (n.d.). NPTEL: Chemical Engineering – Chemical
Engineering Thermodynamics. [online] Available at: https://nptel.
ac.in/courses/103101004/42 [Accessed 3 August 2019].
5. Thermodynamics of reacting mixtures. (n.d.). [ebook] Available
at: https://web.stanford.edu/~cantwell/AA283_Course_Material/
AA283_Course_Notes/AA283_Aircraft_and_Rocket_Propulsion_
Ch_09_BJ_Cantwell.pdf [Accessed 3 August 2019].
CHAPTER
8 CHEMICAL
THERMODYNAMICS
AND BIOLOGICAL
SYSTEMS

• The Maximum In this chapter, you will learn about:
Entropy • To understand the role of chemical
• The Consequential thermodynamics in biological systems
Investigational • To understand the significance of the
Information chemical thermodynamics and the
• Investigational importance of the laws of thermodynamics
Measurement in context with the living organisms
• ATP Molecules • To gain knowledge about the connection
between the biotechnology and chemical
• The Avogadro’s
thermodynamics
Number
• To understand the basic concept of the
• Flagella
application of chemical thermodynamics in
• Deoxyribonucleic daily life of living organisms
Acids (DNAs)
• To gain knowledge about the conceptual
• The Ribonucleic relation between the involvement of the
Acids (RNAs) chemical thermodynamics
• Energy Landscape • To understand about the basic application
Theory of the chemical thermodynamics in the
• The Normo-Thermic bodily functions of living organisms
Level of Temperature
• Cataracts and Sickle-
Cell Anemia
8.1. INTRODUCTION
The laws of the chemical thermodynamics usually explain the
physical measures such as energy, entropy, temperature, volume of
any thermodynamic system and the connection amongst the attributes
of heat and work. It is already explained that the laws of chemical
thermodynamics are widespread, general and signify the embodiment
of the physical sciences.
But it is near about perplexing to observe that the biologists
do not have always had a relaxed association with the field of
chemical thermodynamics. This uneasiness initiates in the apparently
incompatible variances amongst the corporeal or physical or simple
procedures that are explained by the chemical thermodynamics and the
complicated biological procedures which are complicated in nature.
As it is well known, the chemical thermodynamic arrangements
or systems tries to approach the state of equilibrium. For any isolated
system in the universe of chemical thermodynamics, it explains that
an isolated system or arrangement should reach the condition of the
highest randomness or the maximum entropy.
Figure 8.1: The involvement of the chemical thermodynamics in the bio-

logical systems have explained many phenomena like that of metabolism.
Chemical Thermodynamics and Biological Systems 145
pedia/commons/thumb/2/22/ATP-3D-vdW.
png/800px-ATP-3D-vdW.png
Though, near about every biological

arrangement that have ever existed does not ever
attain the state of equilibrium and is observed
to “transform” to the conditions or states of the
advanced stage, rather than achieving the state
of disorder. It is very clearly evident that this
kind of inconsistency can be clarified by merely
noticing that the biological or living bodies
or systems are not totally secluded and are
not in the ideal state of equilibrium with their
respective environment.
But this single phenomenon itself enlightens
why does the biological bodies or systems
can be arranged in a particular order but it
never explains by what means these biological
systems came to be in this state. Of all the
countless procedures that promote the rise of
the level of entropy in the entire universe why
does the natural or biological elements prefer to
make arrangement in a some of its subsystems?
Basically, the question here arises that why does
it happens that the life produces the order out of
the state of complete disorder or chaos?
Even though, the biological or natural
systems are majorly the systems in the state of
non-equilibrium, the study of the equilibrium
thermodynamics has been widely used by the
biochemists. In the decremental approach of
the scientists that has been widely accepted,
the biologists have certainly secluded some of
the particular procedures and have observed
those isolated processes in vitro under the
approachable equilibrium situations.
This kind of approach or methodology has

majorly two benefits:
• Firstly, the processes that are adapted
for investigational measurements
are very much simple under the
equilibrium situations.
• Secondly, the consequential
investigational information can be
observed and studied by the means
of well-recognized equilibrium
thermodynamic laws.
One such instance of a procedure that
Biological system is
has been under observation to the elucidated
a complex network description of the biophysical aspect of the
of biologically biological system is the process of protein
relevant entities. folding. This process describes what are major
On the micro to the reasons that cause the linear amino acid series
nanoscopic scale,
examples of bio-
to get transformed into a complicated structure
logical systems are of a three-dimensional arrangement. These
cells, organelles, structures or arrangements are important for
macromolecular the proper functioning of the protein inside any
complexes and living system or living body.
regulatory pathways.
Scientist named as Anfinsen supposed in the
era of the year 1950s that the amino acid series
itself decided the three-dimensional arrangement
of the protein. More particularly, this was the
observation made in the case of ribonuclease
A folds. The Ribonuclease impulsively to its
initial state in vitro.
Thus, the theory of protein folding has one of
its dominant creeds, the main series of a protein.
Anfinsen theory linking the three-dimensional
structure to the arrangement, or amino acid
sequence, has been discovered to put on to a
better or greater grade in a diversity of minor
proteins. Greater proteins, nevertheless, need the
help of additional “chaperone” proteins to carry

out the completion of the folding procedures of
the protein.
From a chemical thermodynamic view-
point, the stability of the protein totally relies
on the free energy alteration amongst the folded
and unfolded conditions of the protein. These
folded and unfolded states are denoted by the
following expression: “RT ln K = ΔG = ΔH
TΔS.” In this expression, the term ‘R’ denotes
the Avogadro’s number.
The value of Avogadro’s Number is equal
to 6.0221415 x 1023. The term ‘T’ refers to the
absolute temperature of the reaction. The term
‘K’ is the equilibrium constant that is used in the
reaction. The term ‘ΔG’ refer to the Gibb’s free
energy change that takes place in between the
folded and the unfolded state of the protein. The
term ‘ΔH’ denotes the enthalpy variation and the
term ‘ΔS’ explains the entropy variations that
take place while the change of state of protein
from folded to unfolded.
The enthalpy change, ΔH, links to the Binding energy is
binding energy, such as the dispersion forces, the minimum en-
electrostatic interactions, van der Waals ergy required to
disassemble a system
potentials and the hydrogen bonding forces. On of particles into
the other hand, the hydrophobic reactions are separate parts.
usually explained by the usage of the entropy
term, ‘ΔS.’ Quantified by the free energy change,
the maximum free energy change takes place
when the ‘ΔS’ attains the value of 0. This value
is measured by the equilibrium constant when
the enthalpy change ‘ΔH’ attains the value of 0.
These highest possible constancies
can happen at varied and different level of
temperatures and both of the constants are used
in varied conditions. Irrespective of which one

of the constants is to be used, nevertheless,
the constancy of the folded state of the protein
diminishes as the level of temperature is either
upgraded to a higher level or downgraded to
a lower level from the normo-thermic level of
temperature.
While the experts all over the world have
observed that the separate states and excited
conditions in basic arrangements and particles
such as atoms and nuclear components, the
explanation of the complicated arrangements
like that of the proteins needs higher involvement
than these kinds of basic prototypes, the ground
condition of the folded state of the protein is
highly degenerate and as such, the experts and
scientists all over the world use the method
of Energy Landscape to explain it in a more
adequate manner.
In explaining the folding process of the
protein by the Energy Landscape method, it
is explained that the energy of a protein is a
function of the topological positioning of the
atoms in the protein sequence. It is observed
that the chemical thermodynamics of protein
consistency is demonstrated in a very efficient
manner by the means of the Energy landscape
theory.
8.2. ROLE OF CHEMICAL THER-

MODYNAMICS IN LIVING OR-
GANISMS
The major obstacle for every living organism in
this biosphere is to access the energy from the
environment for their own usage. The energy
has to be obtained by the living organisms in

such a form that they can convert or change the
derived energy into the operational energy that
can be utilized by them to perform their daily
functions. The cells that are present inside the
living organisms have transformed themselves
in order to adapt this kind of transformation
processes in an accomplished manner and meet
the needs of the body of the living organisms in
a proper manner.
Chemical energy that are deposited inside
the biological groups of atoms like that of sugars
and fats can change themselves with the help of
a chain of the chemical reactions, that take place
at cellular level, into the form of energy inside
ATP molecules. Energy that is present inside the
ATP molecules is very easy to access and can be
used at any time to perform the bodily functions.
There are many instances of the kinds of the
functions that the cells inside the body of the
living organisms require to perform.
These functions include the creation of
complicated molecules or groups of atoms,
carrying of the materials from one part of body
to another, providing power to the pounding
motion of the cilia or flagella, constricting
muscle fibers to initiate movement, and the
process of reproduction.
8.2.1. The First Law of Thermodynamics

The cells that are present inside the body of the
living organisms are the exact examples of the
transducers of energy. These living cells are
proficient in changing or inter-transforming
into the form of chemical, electromagnetic,
mechanical, and osmotic energy with the

presence of the extraordinary effectiveness.
An instance of usage of the First Law
of Thermodynamics from the aspect of the
chemical thermodynamics inside any living
organism is the energy transformation inside a
leaf.
Figure 8.2: The functions that take place inside a

leaf are capable of denoting and explaining the Laws
of Chemical Thermodynamics that are used in the
biological systems.
Bond energy (E)
is the measure dia/commons/f/f4/Leaf_1_web.jpg
of bond strength in a
chemical bond. The leaves obtain the radiant energy
exclusively from the sun. Apart from using the
sun as the source of energy, the leaves also draw
their energy from the environment in which
they grow. Some part of this energy is released
back to the environment as the radiant energy
and also in the form of heat. On the other hand,
the rest of the part of energy is deposited inside
the photosynthetic yields as the chemical bond
energy.
Even though, the radiant energy captivated

by leaf has been altered, but the entire quantity
of the energy inside the leaf will always remain
constant.
Total energy captivated by the living cell
system of the leaf is always equal to the sum of
the Energy that is released back from the leaf
and the energy that is deposited inside the leaf
as the product of the photosynthetic products.
8.2.2. The Second Law of Thermodynam-

ics
The main function of the living cell is to attain,
change, and use the energy to perform the
function that may be viewed as very easy. Still,
the Second Law of Thermodynamics from the
chemical thermodynamics viewpoint elucidates
the reason why these kinds of the functions are
tougher to perform than they are viewed.
No part of the functions of the energy
transmissions that are observed, in the company
of all the other energy transmissions and
conversions in the entire universe, is entirely
effective. In every part of the function of energy
transmission, some amount of the energy is
dissipated in the method that is not fit to use.
In many of the instances, the form of
the dissipation of the energy is usually the
heat energy. In the aspect of the Chemical
Thermodynamics, the scientists and chemists
describe the heat energy as the kind of energy
that transmits from one kind of system to another
kind of system that is not performing any kind
of function.
8.3. BIOTECHNOLOGY AND

CHEMICAL THERMODYNAMICS
As the field of biotechnology takes over the
world, it is suitable to recollect that the inordinate
feature of the chemical thermodynamics is its
comprehensive variety of applicability. As a
consequence, there is a growth in the researches
that are used for explaining by what means the
chemical thermodynamics can be utilized to
notify procedures for ancient and innovative
biological goods for the industry and medicine.
A specific area of application of the chemical
thermodynamics is concerned with the filtration
of the liquid state proteins by the method of the
careful precipitation.
Figure 8.3: Application of chemical thermody-

namics in biological systems on scientific level has
helped in the detection of many serious diseases.
Source: https://media.defense.gov/2016/
Sep/09/2001628494/780/780/0/160802-F-
FX606–001.JPG
Some instances have been observed that

have explained that how does the liquid protein–
protein forces can be considered or quantified

to produce a probability of average force and
by what means does that probability is then
utilized simultaneously with the chemical
thermodynamic prototype to create a liquid–
liquid and liquid–crystal state of equilibria.
Such kind of equilibria are beneficial not
only for the filtration procedures but these
Sickle cell ane-
kinds of equilibria are also very useful for the mia is an inherited
studying and understanding of the diseases like form of anemia —
Alzheimer’s, cataracts and sickle-cell anemia a condition in
that might have been caused by the process of which there aren›t
protein agglomeration. enough healthy red
blood cells to carry
adequate oxygen
throughout your body.
8.4. SCIENTIFIC APPLICATIONS
OF CHEMICAL THERMODYNAM-
ICS IN BIOLOGICAL SYSTEMS
The main procedure in the process of reversal of
the biology of the worldwide arrow-of-time exist
inside the process of the production of the huge
groups of the atoms or the macromolecules of
biological systems, the nucleic acid and protein
chain molecules of the biological systems.
These kinds of the macromolecules or polymers
display exact number of series of the subdivi-
sions. There are some units, which are repeated.
These units are derived from the four distinct
and different nucleotides in every single of the
deoxyribonucleic acids (DNAs) and the ribonu-
cleic acids (RNAs) and from the twenty distinct
and different amino acid deposits of the proteins.
Figure 8.4: The image illustrates that the chemical

thermodynamics at biological level helps in explain-
ing the changes that takes place in the genetic codes.
Source: https://cdn.pixabay.com/pho-
to/2017/09/26/17/57/dna-2789567_960_720.
png
Consequently, a consideration, of how

the biological systems attains direction in the
Genetic code is difficult situations of disorder and opposites the
the set of rules entire worldwide direction of arrow-of-time, has
used by living
cells to translate
as its foundation a knowledge of the chemical
information thermodynamics. This knowledge helps in
encoded within gaining the knowledge for the whereabouts
genetic material of the location of the detailed protein
(DNA or mRNA orders, the Genetic Code, and the chemical
sequences) into
proteins.
thermodynamics of protein function.
It proceeds from the present-day dealings
in taking considerations of the macroscopic
characteristics of the topics rather than
concentrating entirely on the numerical

atmosphere of the data and information. Along
with the dealings of data and information, this
also creates an actual struggle to connect certain
the slightly less discussed characteristics of the
chemical thermodynamics that have to do with
the modeling of the biological systems and
processes.
This means the scientific application of
the chemical thermodynamics helps to link the
aspect of chemical thermodynamics as a form
of worldviews, approaches and clarifications. In
these conditions, the chemical thermodynamics
is a perfect instance where there is a presence
of the systems thinking, and a framework of
the methodology, which is operationally and
theoretically diverse from the mechanics.
8.5. SOME REAL-LIFE APPLICA-

TIONS OF CHEMICAL THERMO-
DYNAMICS
Living systems are comprised of complicated
molecular configurations whose complete
bonding energy is less negative as compared to
that of their chemical precursors (for instance,
Morowitz’s estimation of E = 0.27 ev/atom) and
whose thermal and configurational entropies are
also least in number as compared to than that of
their chemical precursors.
Therefore, the Gibbs free energy of living
systems is pretty high as compared to the
simple composites from which they are actually
made. The creation and preservation of living
systems at the stages of the energy that are well
detached from equilibrium needs constant work
to be performed on the living system, even as

conservation of hot water in a water boiler needs
that constant work to be performed on the living
system.
In living plants, the movement of the energy
by the system is provided mainly by solar
radioactivity. In fact, the leaves of the green
plants offer comparatively big surface areas for
each unit volume for most of the plants, enabling
them to “capture” the essential solar energy to
preserve themselves far from equilibrium.
This solar energy is transformed into the
essential valuable work in order to preserve
the plant in its complicated, high-energy
conformation by a complex procedure which
is known as photosynthesis. Mass, for instance,
water and carbon dioxide, also moves by the
green plants, offering essential raw materials,
but it does not provide energy. In the process
of gathering and storing valuable energy, plants
provides assistance to the complete organic
world.
In case of animals, the movement of energy
Energy flow refers flow by the living system is offered by consuming
to the flow of
high-energy biomass, either it can be plant or
energy through a
food chain, and is animal. The contravention down of this energy-
the focus of study in rich biomass, and the following oxidation of
ecological energet- part of it (for instance, carbohydrates), offers
ics. a constant source of energy as well as it also
provides with the raw materials.
The conservation of the compound, high-
energy situation that is linked with natural life
is not possible away from a constant source
of energy. A source of energy by itself is not
adequate, though, to clarify the beginning
or conservation of living systems. The other
critical feature is a way of changing this energy

into the essential valuable work in order to
create and sustain compound living systems
from the simple bio monomers that establish
their molecular structure blocks.
8.5.1. Sweating in a Crowded Room

In a crowded area, every single person begins
to sweat. The body begins to cool down by
transporting the high temperature of the body
to the sweat. Sweat disperses adding high
temperature to the crowded area. Once more, this
begin because of the First and the Second Law
of Thermodynamics in action. One thing, which
is important for every single person to keep in
mind, is that the high temperature or heat is not
gone but it is moved achieving equilibrium with
maximum entropy.
Figure 8.5: Melting of ice explains the application

of chemical thermodynamics in relation with the
Biological systems in daily life
Source: https://cdn.pixabay.com/
photo/2016/02/26/22/08/ice-
cubes-1224804_960_720.jpg
8.5.2. Melting of Ice Cube

The ice cubes that are inserted in drinks to cool
the drinks and trap the heat from the drink. It
is observed that if the drink is not consumed
within a period of time, it again reaches back
to the normal temperature or room temperature.
This happens because the drink takes in
the heat that is present in the atmosphere. This
phenomenon can be explained by the first law
of chemical thermodynamics and second law of
chemical thermodynamics in accordance with
the biological thermodynamics.
8.5.3. Emotions of the Living Organisms

As a matter of fact, the principles of the chemical
thermodynamics can explain the emotions
like the experiences of accomplishment and
pleasure. Many of the people across the world
do not believe this phenomenon.
For instance, consider a family of
human beings as a complicated and adaptive
arrangement or system which is containing a
definite quantity of energy at any moment of
time. There is a need to flourish and live for
every human being. The source of the energy
which helps this family in living and prospering
comes from food.
Every human being requires a level of
psychological and sensitive inspiration from
the surroundings. In this case, the factor of
entropy acts as the most important factor of the
system. Entropy is an amount of possessions
that are being taken away from the life or
business/work, according to the second law of
chemical thermodynamics, higher is the rate of

the entropy. This leads to the faster frequency of
worsening of lifetime and profession.
REVIEW QUESTIONS
1. Explain the term ‘chemical thermodynamics’ in context
with biological systems.
2. What is the basic principle for the study of chemical ther-
modynamics in relation with the Biological Systems?
3. Explain the role of the first law and second law of chemical
thermodynamics in the lifetime of living organisms.
4. With the help of the example of a leaf, explain how does
the laws of chemical thermodynamics helps in the conser-
vation of the energy.
5. How are biotechnology and chemical thermodynamics
linked with each other?
6. Explain the formation of DNA and RNA in relation with
Chemical Thermodynamics.
7. How does the connection of chemical thermodynamics
with biotechnology help in the treatment of the serious
diseases like Alzheimer’s and cataract?
8. Explain the difference between the functionality of the
plants and the animals in context with chemical thermo-
dynamics.
9. How does the relation of chemical thermodynamics and
biological system explain phenomenon of melting of ice
cubes?
10. How does the chemical thermodynamics explain the emo-
tion and mental equilibrium of the living organisms?
REFERENCES
1. Bailey, R. (2018). These Are the Laws of Thermodynamics in
Biological Systems. [online] ThoughtCo. Available at: https://www.
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casegroup.rutgers.edu/lnotes/Thermodynamics_lecture.pdf
3. Demirel, Y. (2016). Thermodynamics and Biological Systems.
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researchgate.net/publication/290999678_Thermodynamics_and_
Biological_Systems [Accessed 3 August 2019].
4. Devireddy, R. (2012). Thermodynamic Analysis of Biological
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analysis-of-biological-systems-2157-7544.1000e101.
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6. Khandelwal, S. (2019). Laws of Thermodynamics and Biological
System. [online] Biology Discussion. Available at: http://
www.biologydiscussion.com/plants/plant-physiology/laws-of-
thermodynamics-and-biological-system/23784 [Accessed 3 August
2019].
7. Khemani, H. (n.d.). Applications of Thermodynamics Laws.
Carnot, Stirling, Ericsson, Diesel cycles. [online] Bright Hub
Engineering. Available at: https://www.brighthubengineering.com/
thermodynamics/38344-thermodynamics-integral-part-of-our-life/
8. Kontogeorgis, G. (n.d.). Thermodynamics for Biotechnology.
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doi/10.1002/9780470747537.ch19 [Accessed 3 August 2019].
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in Biological Sciences? Is It Possible to Connect with Some Natural

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Systems. [ebook] Leeds: School of Process, Environmental and
Materials Engineering. Available at: https://pdfs.semanticscholar.or
g/41d9/195d8aa1525156f05941932e60e818bda391.pdf [Accessed
3 August 2019].
12. Mizutani, T. (2019). Application of Thermodynamics to Biological
and Materials Science. [ebook] Rijeka: InTech. Available at:
http://www.issp.ac.ru/ebooks/books/open/Application_of_
Thermodynamics_to_Biological_and_Materials_Science.pdf
13. Mollerup, J. (2006). Applied thermodynamics: A new frontier for
biotechnology. Fluid Phase Equilibria, [online] 241(1–2), 205–
215. Available at: https://www.sciencedirect.com/science/article/
pii/S0378381205005261.
14. Opentextbc.ca. (2019). Applications of Thermodynamics: Heat
Pumps and Refrigerators – College Physics. [online] Available
at: https://opentextbc.ca/physicstestbook2/chapter/applications-
of-thermodynamics-heat-pumps-and-refrigerators/ [Accessed 3
August 2019].
15. Opentextbc.ca. (n.d.). The Laws of Thermodynamics – Biology
2e. [online] Available at: https://opentextbc.ca/biology2eopenstax/
chapter/the-laws-of-thermodynamics/ [Accessed 3 August 2019].
16. Prausnitz, J. (2003). The Journal of Chemical Thermodynamics.
Elsevier, [online] 35(1), 21–39. Available at: https://www.
sciencedirect.com/science/article/pii/S0021961402003051
17. Salamon, P., Konopka, A., & Salamon, A. (n.d.). Thermodynamics
for Systems Biology. [ebook] San Diego: Department of Mathematics
and Statistics, San Diego State University. Available at: http://www.

sci.sdsu.edu/~salamon/Thermo_for_SystemsBio.pdf [Accessed 3
August 2019].
18. Sites.google.com. (2019). 1st and 2nd Laws of Thermodynamics
(as Applied to Living Systems) – VS IB Environmental Science
& Systems. [online] Available at: https://sites.google.com/site/
vsenvironmentalsciencesystems/1-systems-models/1st-and-2nd-
laws-of-thermodynamics-as-applied-to-living-systems [Accessed 3
August 2019].
19. Socratic.org. (2017). How Do the First and Second Laws of
Thermodynamics Apply to Living Systems? | Socratic. [online]
Available at: https://socratic.org/questions/how-do-the-first-
and-second-laws-of-thermodynamics-apply-to-living-systems
20. Tadashi, M. (2011). Application of Thermodynamics to
Biological and Materials Science. [online] www.intechopen.com.
Available at: https://www.intechopen.com/books/application-of-
thermodynamics-to-biological-and-materials-science [Accessed 3
August 2019].
21. Thermodynamics of Biological Systems. (2019). [ebook] Available
at: http://core.ecu.edu/biol/evansc/PutnamEvans/5800PDF/
Thermodynamics.pdf [Accessed 3 August 2019].
22. Toppr-guides. (n.d.). Applications of Thermodynamics: Laws,
History, Applications, Examples. [online] Available at: https://
www.toppr.com/guides/chemistry/thermodynamics/applications-
of-thermodynamics/ [Accessed 3 August 2019].
CHAPTER
9 APPLICATIONS OF
CHEMICAL
THERMODYNAMICS

• Bioenergetics In this chapter, you will learn about:
• Cell Behavior • The chapter helps to gain an understanding
of chemical thermodynamics in the various
• Chiller Pipes
electrical appliances
• Gas Power Cycles
• It helps in understanding the application of
• Heat Engines thermodynamics in thermal engines
• Heat Pumps • It also aims to make the reader aware of its
• Heating Unit applications in biotechnology
• HVACs (Heating • The learner should also be able to
and Ventilation Air understand the role of thermodynamics in
Conditioning Units) food processing
• Radiator
• Refrigerator
• The Compressor
• The Expansion
Valves
• The Outdoor Fan
9.1. INTRODUCTION
Thermodynamics is a significant influence on the daily life. Its
application surrounds living beings. Whether a person is travelling
in a vehicle, or sleeping in the comfort of an air-conditioned room,
or watching sports on television, the application of chemical
thermodynamics is related to all aspects of life.
Nicolas Léonard Sadi Carnot is considered the father of
thermodynamics. The cycles and theorems he proposed went on to play
a significant role in the creation of automobiles that is an integral part
of human life. It led to the invention of all types of engines on which
the modern transport system operates. There were other noteworthy
contributions as well in the field of thermodynamics.
Thermodynamics involve study of various laws namely:
• the First Law of Thermodynamics;
• the Second Law of thermodynamics;
• the Third Law of Thermodynamics; and
• the Zeroth Law of Thermodynamics.
These laws have helped find out the cause of many mysteries that
surrounds us. This helps in not only gaining spiritual wisdom and
attaining materialistic achievement, but also explains the existence of
life on Earth.
The study of thermodynamics includes a study of systems and the
environment. The different thermodynamic processes aid in using the
knowledge of thermodynamic law for various applications.
Applications of Chemical Thermodynamics 167
Figure 9.1: Nicolas Léonard Sadi Carnot, the Father

of thermodynamics.
pedia/commons/thumb/f/f8/Sadi_Carnot_01.
jpg/402px-Sadi_Carnot_01.jpg
9.2. APPLICATION OF THERMO-

DYNAMICS IN ELECTRICAL AP-
PLIANCES
Chemical thermodynamics has its application in
various appliances that are useful in the daily
life.
9.2.1. Refrigerator
Refrigerator is used by household to keep food
cool and preserve them during hot periods. There
are many complex mechanisms working inside
refrigerators. The basic principle that works in
case of refrigerators is that compression of gases
makes it hotter and expansion makes them cool.
In layman terms, refrigerator has a pipe
partly inside and partly outside and the form
a continuous loop. The pipe is filled with
gas. Inside the refrigerator, the pipe becomes
gradually wider. This expands the gas and cools
it while it flows through the pipe. Outside the
refrigerator, there is a pump which compresses
the gas and cools it down.
The gas circulates round the loop. It
expands when it passes inside the appliance and
compresses when outside. As a result, it absorbs
heat from inside and carries it outside the way
conveyor belts do.
The refrigerator uses a liquid coolant which
enters an expansive valve. There is a sudden
Coolant is decrease in pressure which cools the liquid,
a substance, expands it and converts it into gas. The coolant
typically liquid or then passes around the chiller cabinet, inside
gas, that is used to
reduce or regulate
which it absorbs the heat from the products
the temperature of stored and removes the heat. The compressor
a system. causes the temperature and pressure of the
coolant to increase.
It then passes through thin radiator pipe at
the back of the fridge. It then releases its heat and
is converted to its liquid state in the process. The
coolant then again passes through the insulated
cabin first, then through the expansion valve.
This cycle goes on. This way, the heat absorbed
from the food inside the refrigerator is cooled

when the coolant passes through the radiator.
Figure 9.2: Application of thermodynamics in re-

frigeration.
dia/commons/thumb/4/42/Refrigeration_PV_
diagram.svg/720px-Refrigeration_PV_dia-
gram.svg.png
9.2.2. Air Conditioner

Air conditioner is an appliance which draws
heat from inside and releases it outside. Air
conditioner consists of two units, the internal
and the external. The internal one draws the heat
and the external one released the heat outside.
This is how the simplest air conditioning units
operate. They have fans both inside and outside
which circulates the air fast. Some units also
have a heating element to warm the room during
cold months.
These units are called HVACs (heating
and ventilation air conditioning units). More
complex units have long ducts that can cool an
entire building, the principle however remains

the same.
The warm air from the area that has to be
cooled is sucked through a grille located at the
base of the unit. The air then passes through
chiller pipes which circulates the coolants. The
mechanism is similar to refrigerator. The chiller
pipes cool the air flowing in.
Humidity is the The unit also contains a dehumidifier which
concentration of removes excess humidity. After that the air
water vapour present
passes through a heating unit. This part can be
in air. Water vapour,
the gaseous state of turned up to make to use the unit as a heater.
water, is generally There is a fan at the top which forces air through
invisible to the hu- another grille inside the room. If the heating
man eye. unit is switched off the air that re-enters is cold
which reduces the temperature of the room.
During this time a coolant passes through the
chiller pipes absorbing heat from the air that is
blowing past the pipes. This process evaporates
the coolant which turns into hotter gas. This way
the unit absorbs heat from inside the room and
releases it outside drawing out the heat in the
process.
The mechanism is similar to a refrigerator,
where the coolant passes through a compressor
which converts it back to its liquid state and
continues recycling through the loop. The
outdoor unit of the air conditioner contains metal
plates that scatter the warm air outside. The
outdoor fan expedites this process. Gradually
the indoor heat is propelled outside this way.
9.2.3. Air Evaporator/Cooler

An evaporative cooler also called desert cooler is
an appliance that evaporates water and maintain
the indoor. It works on water’s enthalpy of

vaporization. The temperature of dry air can
be reduced significantly through evaporation
of water. This process uses much less energy
that air conditioning. In case the air is too dry,
evaporative cooling can add more moisture to
the air and increase the comfort level of the
users. The cooling capacity of the unit depends
on wet bulb depression.
• Dry Bulb Temperature: This is the
temperature of the air as recorded
by a regular thermometer which is
exposed to the air.
• Wet Bulb Temperature: This is the
temperature of the air as recorded
by a thermometer which is covered
by a water-soaked cloth. This is the
temperature that air can reach by
evaporation alone.
The two temperatures are used to measure
the humidity. Evaporation occurs when
humidity in the air has not reached 100%. This
is when the air begins to absorb the water. A
given volume of hair has the capacity to hold a
certain volume of water, and the ability to hold
more moisture would depend on its saturation
level. Humidity refers to the moisture that the
air is already holding. Energy is consumed when
water is evaporated. This energy is drawn from
air by transfer of heat. Air that passes through
evaporative air cooler releases heat and converts
to vapor.
Evaporative air cooling has a pump which
passes water to a cooling pad from a reserve. The
cooling pad becomes wet. A fan propels outside
air through the cooling pad, in the process the
air is cooled by evaporation. It is important that

the cooling pads are fully wet while the machine
is running. Moreover, the motor and system fan
must be of the optimum size as per the area that
has to be cooled. These factors are important to
ensure effective cooling.
9.2.4. Heat Pumps

A basic heat pump comprises of four units:
• Condenser
• Expansion valve
• Evaporator
• Compressor
A working fluid is used which is generally
a non-CFC refrigerant. The evaporator is the
outdoor coil which holds the working fluid
and where heat transfer occurs. The working
fluid absorbs heat from the outdoor air and
coverts into gas. The compressor which runs
on electricity increases the temperature and
pressure of the gas. It then propels it through the
condenser coils within the heated area.
Evaporator coil
is the part of an air This gas is hotter than the room air. Therefore,
conditioner or heat heat is transferred from the gas to the room.
pump that absorbs The gas is converted into fluid state again. This
the heat from the air
fluid then passes through the expansion valve
in your house. It is
located inside the air where it is cooled. Finally, it passes through the
handler or attached evaporator coil in the outdoor unit.
to the furnace.
9.2.5. Microwave Oven

Ovens use microwave to heat food, hence
the name. Microwaves lie between infrared
radiation and radio waves on the electromagnetic
circle. Household microwave ovens use wave

frequency of about 2,450 megahertz. At this
frequency, waves react with the food. The fat,
sugar and water present in the food absorbs
them. After absorption, they undergo structural
change and converted into atomic motion. This
generates heat. This wave is not absorbed by
glass, plastic or ceramics. Hence only the food
is heated while the container does not melt or
break.

DYNAMICS IN THERMAL MA-
CHINES AND HEAT ENGINES
The principle of thermodynamics has extensive
application in heat engine. A heat engine
generates activity from heat, example steam
engine. Not all engines are heat engines, but
90% of the motive power generated can be
attributed to them.
9.3.1. Thermal Aspect of Heat Engines

The working of heat engines is based on the
principles of thermodynamic. Thermal problem
in engines include heat transfer problems.
Sometimes the engine becomes very hot and has
problem cooling down.
This is crucial for all kinds of engines. This
problem arises due to friction, interface due to
thermal expansion, problems of sealing, etc.
9.3.2. Carnot Cycle

Nicholas Leonard Carnot in 1824, came up with
a thermodynamic model of heat engine based

on steam engine to illustrate the fundamentals
of the working – the idea of a generic working
fluid, performing a generic cyclic process,
interacting with generic heat reservoirs.
Carnot at that point inferred that all in
heat engines temperature limited the energy-
conversion efficiency. In order to attain the
maximum efficiency, the working fluid had to
follow the following process:
• It should be capable of isentropic
compression, i.e., heat transfer is not
required for change in temperature.
• An isothermal heat input from the hot
source, at the hot-source temperature.
• It should be capable of an isentropic
expansion without the requirement of
heat.
• An isothermal heat rejection, i.e., the
ability to reject cold source, in most
cases the environment.
Carnot arrived at these points by rationally
evaluating the engines. According to him “any
engine with friction would have less efficiency
than one without,” “among all engines
exchanging heat at different temperatures, the
one with highest efficiency only exchanges heat
at the two extreme temperatures (the hottest
and the coldest),” and “all reversible engines
working with the same couple of temperature
extremes have the same efficiency.”
Figure 9.3: Representation of Carnot heat engine.

pedia/commons/thumb/2/22/Carnot_heat_en-
gine_2.svg/1280px-Carnot_heat_engine_2.svg.
png
9.3.3. Gas Power Cycles

Heat engines contain a working fluid like
other appliance that work on the principle of
thermodynamics. This fluid circulates absorbing
heat from a hot source and releasing it to the
environment. In this process, it also does some
mechanical work. Gases are very effective as
working substances. They have the ability to
convert thermal to mechanical energy by the
actions of expansion and compression. Liquids
on the other hand have very less compressibility. Compressibility
is a measure of the
Gas cycles are those where the working relative volume
substance remain in the gas phase throughout change of a fluid or
the operation. Vapor cycles are those where solid as a response
gas converts to liquid at one part of the cycle to a pressure
(or mean stress)
and then again to gas form. There are many gas change.
cycles that have been proposed of which several
are in use:
• The Otto Cycle: It is used in petrol
engine
• The Diesel Cycle: It is used in engines
that run on diesel
• The Mixed Cycle: It is a mix of the

Otto and Diesel cycle and exceeds
their performance
• The Brayton Cycle: It is used in gas
turbine engine
• The Stirling Cycle: It is used in
specific appliances

DYNAMICS IN BIOTECHNOLOGY
Thermodynamics is integral to biotechnology
and biological sciences. Biotechnology is making
rapid advancement and thermodynamics has a
role to play in it. There is a growing literature
describing how chemical the can be used to
inform processes for old and new biochemical
products for industry and medicine.
9.4.1. Precipitation
Thermodynamics in particular explains
how aqueous proteins separate by selective
precipitation. Phase diagrams can explain
this process and that the construction of
phase diagram would require the quantitative
intermolecular forces between proteins.
Aqueous protein–protein forces can be
calculated or measured to yield a potential of
mean force that potential is then used along with
a statistical thermodynamic model to establish
liquid–liquid and liquid–crystal equilibria. This
process is not only applicable for separation
process but is also explains various diseases like
cataract, Alzheimer’s sickle-cell anemia that are
a result of protein agglomeration.
9.4.2. Bioenergetics
Another application of thermodynamics is
in bioenergetics. Thermodynamics helps the
experts to take decisions on the basis of feasibility
of biochemical reactions and the energy
Membrane trans-
consumption in the process. It is comprehensive port system is
and includes all metabolic activities, growth and the transport
development process, membrane transport system by which
system, cellular respiration, enzymatic reactions various molecules
enter into and
and many other processes. Thermodynamics
out of cell across
helps predict whether a particular reaction will cell membrane.
occur or not and the reasons behind it.
For biotechnological aspect this would help
how to transform the biological process so that a
non-spontaneous reaction becomes spontaneous.
It provides assistance to biotechnologist so
that they can demonstrate how a selectively
permeable biomemberane shows its selectivity.
Similarly, the manner in which enzymes are able
to act as catalyst for biological processes.
9.4.3. Cell Behavior

A biotechnologist has to have knowledge of
fermentation process. It helps them measure the
transfer of heat between a cell and the environment
and estimate the optimum temperature at which
the rate of production for a specific product is
high. Cells are complex systems that operate on
the principle of thermodynamics.
They undergo a series of chemical reactions
which includes thermo-electro chemical pro-
cess, energy transformations, transport phenom-
ena, etc., Moreover, cells alter their process if
their surrounding changes. In disease state there
are various thermo-electro-biochemical behav-
ior, which are different from normal healthy

state.
All living systems generate heat, which
occurs because of their internal irreversibility
which is released into the environment. This
flow of heat represents information, analysis
of which represents an opportunity to study the
reactions of the cells and to control them. This
approach facilitates the analysis of heat inflows
and outflows and their reaction to changes
in the surroundings. The bioengineering
thermodynamics bases are summarized and
used to analyses possible controls of the calls
behavior based on the control of the ions fluxes
across the cells membranes.
Figure 9.4: Application of thermodynamics in

studying cell behavior.
dia/commons/thumb/b/b6/System_boundary.
svg/2000px-System_boundary.svg.png

DYNAMICS IN FOOD PROCESS-
ING
Food industry uses various biophysical
techniques for processing and preserving food
and value-added products. This processing

is done to increase the shelf-life of the food
and prevent microbial contamination during
storage. The food components transform during
processing.
All the nutrients like carbohydrates,
proteins, vitamins and lips alter in the process.
This change occurs at the macromolecular level
and causes changes in food, both structural and
functional. This has an impact on the physical,
nutritional and organoleptic properties of food.
Foods are complex biological systems. They
contain a combination of various components,
which may have high or low molecular weight
along with their complexes and aggregates.
Food exists in various states, solids, liquids,
liquid-solid, solid-gas, etc.,
The biophysical techniques address the
diverse range of compositions and structures.
The techniques are based on an understanding
of the processing and the method of storage
on food. The physical properties of food are Calorimetry is the
analyzed and, on that basis, effective processing science or act of
and storage methods are used. measuring changes
in state variables
of a body for the
9.5.1. Calorimetry Principles for Food purpose of deriving
the heat transfer
Analysis associated with
changes of its state
Calorimetry is a science that is concerned with
due, for example, to
the amount of heat released or absorbed when chemical reactions,
chemical reaction takes place. Calorimetry is physical changes,
very useful for investigating food material. or phase transitions
under specified
constraints.
Most of the food processing involves transfer
of heat, i.e., heat treatment. In heating process,
the food absorbs heat, whereas in freezing and
cooling, the food releases heat. Thermal charac-

terization of food systems and their components
leads to data that can be related directly to the
processing protocols.
Heat transfer and energy balance calculations
are made on the basis of thermal properties of
food materials. Hence, it is important to have
a credible database that can helps predicting
how food materials would react to heat transfer.
Calorimetry facilitates the optimization of food
process.
The structural arrangement of food
materials and their components alters during
heat transfer. Moreover, the state of the food
also changes in the process. The calorimetric
techniques enable thermal analysis. There are
many physicochemical effects can be seen
in the temperature range between -50°C and
300°C. These reactions could be endothermic
or exothermic. In endothermic reactions, heat
is absorbed and in exothermic reactions heat
is released. Calorimetry helps in evaluation
of product formulation and process condition
in terms of their thermodynamic and thermal
Perturbation is a stability in their various states. This helps in
small change in the optimizing the design for food processing.
movement, quality, or The perturbation in food caused by heat is
behaviour of some-
thing, especially an
measured using calorimetry principles. There
unusual change. are two distinct ultrasensitive methods that deal
with application of thermodynamic techniques
in food engineering. They are isothermal titration
calorimetry (ITC) and differential scanning
calorimetry (DSC). In DSC perturbation refers
to variance on the temperature. In Isothermal
Titration Calorimetry perturbation refers to
addition of materials.
Calorimeter technique is useful but its

effectiveness and correctness depends on
the use of appropriate equipment and careful
analysis of data. The calorimetry experiment
uses ultrasensitive instrumental set up. Hence
the data generated is influenced greatly by the
surrounding conditions during experiment.
Haines provided the guidelines for choosing
calorimetry parameters, which are as follows:
• Time Scale: In measurement
systems that are changing constantly,
detection of events would require the
experimental time scale to correspond
with the time scale of the observed
event.
• Magnitude of the heat flow: The
accuracy of the amount of heat
is important in measuring the
magnitude of heat. For instance, if
small quantities of energy is passed
then it becomes difficult to detect the
magnitude of heat flow. An increase
in the scanning rate accelerates the
signal. The downside is that it may
affect the equilibrium conditions,
which requires models beyond the
standard equilibrium thermodynamics
treatment of calorimetric data.
• Moisture loss during experiment:
Samples chosen generally have high
moisture and has to be sealed when
during experiment so that no loss
occurs due to evaporation, else it
can result in inaccurate estimation of
temperature and transition enthalpy
change.
• Interpretation of overlapping peaks:

Samples are composed of various
food components which change due
to heat transfer at similar temperature.
DSC measures the thermodynamic and
thermal stability of protein. The data can be used
to understand the forces that preserve the folded
structure and also how they are linked to protein
and solution conditions. This method helps in
gaining insight into the unfolding mechanism
and aggregation.
Isothermal titration calorimetry facilitates
the estimation of amount of heat transferred
when protein interacts with another molecule.
The models are used to study association
reaction which offers in-depth thermodynamic
characterization. The techniques of modern
calorimetry help predict the stability of protein
and its interactions with other molecules as a
function of temperature and solution conditions.
9.6. CONCLUSION
The principles of thermodynamics have various
applications in the daily life. It covers various
fields ranging from electrical appliances, thermal
engines, biotechnology, and food chemistry.
In the near future there will be a substantial
increase in the application of thermodynamics in
the field of chemical engineering. Experimental
thermodynamics has a more proactive role to
play in establishing the conceptual basis on
which theoretical models will be built.
REVIEW QUESTIONS
1. Who is the father of thermodynamics and what is his con-
tribution to this field?
2. How does the cooling in refrigeration work based on the
principle of chemical thermodynamics?
3. How does air conditioner and air cooler function? What is
the difference between their operations?
4. How does transfer of heat occur in heat pumps?
5. How does a microwave heat food and how does the con-
tainer containing the food not melt in the process?
6. Explain how thermodynamics is applied in heat engines?
7. Name the gas power cycles and their applications in the
modern world.
8. Explain the how thermodynamics help explain the process
of precipitation.
9. Explain two other applications of thermodynamics in bio-
technology.
10. Explain the calorimetry principle of food analysis.
REFERENCES
1. Giri, P. (2014). An Overview of Thermodynamics in Food Chemistry.
[ebook] Burdwan, India: Modern Chemistry & Applications.
Available at: https://www.researchgate.net/publication/276319980_
An_Overview_on_the_Thermodynamic_Techniques_used_in_
Food_Chemistry/download [Accessed 3 August 2019].
2. Lucia, U. (2015). Theoretical Biology and Medical Modeling.
[online] /tbiomed.biomedcentral.com. Available at: https://tbiomed.
biomedcentral.com/articles/10.1186/s12976-015-0024-z [Accessed
3 August 2019].
3. Martinez, I. (n.d.). Thermal Machines and Heat Engines. [ebook]
Available at: http://webserver.dmt.upm.es/~isidoro/bk3/c17/Power.
pdf [Accessed 3 August 2019].
4. Opentextbc.ca. (n.d.). Applications of Thermodynamics: Heat
Pumps and Refrigerators – College Physics. [online] Available
at: https://opentextbc.ca/physicstestbook2/chapter/applications-
of-thermodynamics-heat-pumps-and-refrigerators/ [Accessed 3
August 2019].
5. UKEssays.com. (2018). Thermodynamics Field Can Contribute
Our Daily Life Philosophy Essay. [online] Available at: https://
www.ukessays.com/essays/philosophy/thermodynamics-field-can-
contribute-our-daily-life-philosophy-essay.php [Accessed 3 August
2019].
6. Umair Akram, M. (2015). Applications of thermodynamics. [online]
Slideshare.net. Available at: https://www.slideshare.net/ui12008/
applications-of-thermodynamics [Accessed 3 August 2019].
CHAPTER
10 FUTURE OF
CHEMICAL
ENGINEERING AS A
PRODUCT OF
CHEMICAL
THERMODYNAMICS

• Biomedical In this chapter, you will learn about:
• Cycle Evaluation • To understand the concept of future of
chemical engineering.
• Green Chemicals
• To know the concept of product of
• Industrial Ecology
chemical thermodynamics.
• Modeling
• To understand the grand challenges in
• Multiscale chemical engineering.
Engineering
• To learn about the importance of chemical
• Optimization engineering.
• Reaction Engineering • To learn about the application of chemical
• The Haber-Bosh engineering.
Process. • To gain knowledge about the significance
• Unit Operations of chemical engineering thermodynamics.
10.1. INTRODUCTION
The administration of flows and alterations of constituents and energy
in industrial plants is associated with chemical engineering. The
chemicals, petrochemicals, plastics, water, energy, pharmaceuticals
and food are containing of process industries whose subject is
engineering. The mechanical engineers convert products into devices
and machines while chemical engineers convert raw materials into
products
The processes of chemical engineering are regulated by physical
chemistry and physics rules that determine the feasibility and
productivity. The changes in thermodynamics due to changes in
energy are very important. The primary method to improvement and
modeling is mathematics.
10.1.1. Optimization and Modeling

The planning and placement of materials, amenities, and manufacture
at full efficiency in the most economically feasible manner as possible
is defined as optimization. Modeling is the building of theoretical
mathematical experimental models of complex process systems,
normally with the help of computers is called as modeling.
The combination of primary scientific principles forms the basis of
solving problems in a general and step-by-step manner. The methods
of conversion of energy are regulated by the laws of thermodynamics
as it is the branch of physical science. The thermodynamics is very
important as it defines what is feasible.
There is lack of knowledge of existence of thermodynamics
in economists. One factor that has led to the degradation and
contamination of our planet is that the traditional economics does
not give value to restrictions of thermodynamics and it is causing the
dilapidation and pollution of our planet.
Chemical engineering is considered as an in important subject
in the field of industrial ecology. The learning of the flows of
materials and energy in industrial and consumer tasks, and the impact
of these flows on the environment, and of the effects of economic,
Future of Chemical Engineering As a Product of Chemical.... 187
political, controlling and social factors on the

flow utilization and conversion of resources is Industrial ecol-
defined as industrial ecology. ogy is a young
science that
Even the primary methods used in industrial studies indus-
ecology, that contains life cycle evaluation and trial systems with
material flow responsibility, are amalgamation the goal of finding
of basics of chemical engineering. ways to lessen
their environmental
impact.
10.2. GRAND CHALLENGES IN
CHEMICAL ENGINEERING
The manufacturing and conversion of
chemicals, energy and matter by the application
of physical and life sciences, mathematics and
economics is described as chemical engineering
that is also known as process engineering. The
processes of separation, and unit, control and
active reproduction and kinetics and reaction
engineering, heat, mass and momentum transport
all are included in chemical engineering.
There are large number of applications of
chemical engineering and it has traditionally
established and is applied in a variety of fields,
containing climate change, environmental
systems, biomedical, new materials and
complex systems, though it has been invented
and normally implemented in petrochemical
and the heavy chemical industry.
The main element is ammonia for best
growth of plant in fertilizer. The farming is being
done in the condition of scarcity of nitrogen
with the cultivation of arable lands that are
adequate to feed only two billion people till in
1913 the discovery of the Haber-Bosh process.
The agriculture has witnessed the revolution in
growth of both production of crops and human
nutritional values by avoiding the restrictions

forced by natural nitrogen fixation method by
Haber–Bosch pro- the invention of low-cost fertilizer.
cess is an artificial
nitrogen fixation pro- The human mind is now free to discover
cess and is the and apply its full to focus on creativity
main industrial pro- and connectivity in various ways that was
cedure for the previously not possible for humans by the
production of
advent of chemical and electronic technologies
ammonia today.
that has successfully separated the part of
memory and storage the human brain from its
analytical capability. Increasingly sophisticated
application of mathematical principles to the
phenomena of physics, chemistry and biological
sciences, from the atomic level to intergalactic
scales.
The human beings are now better prepared
understand natural and anthropogenic
happenings and can control it and are prepared
for changes that is not possible to control by
implementation of latest mathematical principles
to the happenings of physics, chemistry and
biological sciences, from the atomic level to
intergalactic level.
The boundaries of chemical engineering are
challenged in tackling industrial and practical
problems. The implementation of science and
the connection between chemistry, society,
and industry is together defined as chemical
engineering. The implementation of practical
model systems and equations innovated with
well-behaved systems to complex industrial
challenges generally broke the limitations in
chemical engineering.
The various methods based on field and
applications of chemical engineering are
discussed in the following subsections.
10.2.1. Reaction Engineering

• Combination of organic, inorganic
and biochemical catalysis to decrease
energy of activation, increase
selectivity, reduce energy usage, by-
products (separation) and replace
toxic organic solvents and reagents
based on scarce elements by reactions
in aqueous or bio-based solvents
using green chemical principles.
• The use of process of photosynthesis
to change solar energy and carbon
dioxide into glucose, ligno-cellulosic
polymers and the by products using
catalyst that are enzyme or water-
based systems.
• The choice of medicine and learning
and improving transfer of matter,
and its limitations. The control of
immunologic reactions and the
implementation consist of the targeted
destruction of cancer cells, bacteria,
fungi, and viruses.
• The use of kinetics of reaction to
decrease side reactions by making to
broke away in easier manner and in
more effective way by regulating the
rate of removal of reactant and product
by Predictive reaction engineering.
10.2.2. Unit Operations and Transport

Phenomena
• More selective, specific, and the
low energy process of broking down
gas-gas and liquid-liquid systems by
being choosier and more effective in

implementation.
Osmosis is the spon-
taneous net movement
• The detachment of membrane by high
of solvent molecules fluctuation and anti-fouling reverse
through a selectively osmosis process.
permeable membrane • Improved separation of the use of
into a region of higher
solute concentration, in
fractional distillation, and other
the direction that tends methods ton better the detachment
to equalize the solute of heat sensitive chemicals that have
concentrations on the same boiling points.
two sides.
• The liquids that has especially
high solid concentration should be
transported by better procedures for
pumping.
10.2.3. Biomedical
• Develop an engineering approach
to model and regulate (control)
The behavior and working of the
human body and mental processes
can be controlled by innovating
and implementing the engineering
methods.
• In the human body the implementation
of replication and pans to control
the various categories, varying from
DNA and RNA, the cell, tissues, and
organs, and the complete human body
to provide better quality of life to
people with genetic and associated
diseases.
• The grafting of sensors in human
body to control blood pressure, blood
lipid concentrations and heart rate
and they are normally non hostile to
human body.
• In the branch of medical science of
oncology and in supplying medicine
in human bodies and for choosing in
nanotechnology.
• The replication and rebirth of
organs by better biomaterials and
biotechnology.
10.2.4. Energy
• For betterment of living standards
of the large number of people in less
developed countries the less expensive
energy is very important factor. There
is a basic struggle to manufacture net
energy with less effect on environment
as the greenhouse gases generated by
human activity are causing the slow
increase in global warming.
• The thermodynamics is the most
financially feasible method and
chemical engineers have the
accountability to verify and making
sure the balance of energy. The
manufacturing of chemicals from
renewable matter and use of green
chemistry is the further result of the
test, and it is lingering responsibility
of chemical engineers to find out
the processes and reactions with
positive thermodynamics and balance
of energy, and the improvement of
these processes by regular work with
economists, environmental scientists,
and society normally.
• The top demand of energy has

continuously remained the important
problem and is solved by permitting
the circulation of solar energy that is
derived from wind and ocean currents
and the through storage of solar
energy. The innovation of repeatable
methods for storage of energy and
consumption that have features of
instant start and switching off is now
of great importance.
• There is a great profit in seizing and
storing solar energy in a method that
replicate the natural photosynthetic
process in order to store solar energy
in chemical bonds, instead as heat,
or separation of electronic charge
despite the fact that fast and controlled
release of large amount of electrical
energy is of great benefit to fulfill the
requirements of society.
• In the manmade photosynthetic
reaction that by grasping the sunlight
consumes carbon dioxide, then the
two main tasks can be fulfilled in
one effort. The innovation of latest
refractory materials that can bear
the temperatures needs to start the
reaction, heat exchange, and proper
break down of products of reaction
are the left gap in technology.
10.2.5. Multiscale Engineering

The large number of challenges in materials
and processes can be fulfilled by connecting the
nano, micro, and meso scales to the macro scale.
• It is necessary for molecular

engineering to use improved
molecular active replications for the
progress of nanotechnology.
• The same products can be formed
by using the materials that can be
converted to get the initial matter, or
in a variety of products of less value,
the biodegradable quality product
should be final.
10.2.6. Green Chemicals

• The components should be utilized
to its fullest capacity to derive the
full benefit of renewable feedstock.
Because biomass has a low energy
density compared to fossil carbon
sources, the productivity of energy of
biomass processing needs serious re-
evaluation together with the progress
of smaller mobile chemical plants that
can be taken to the regions wherever
biomass is present in abundance
in rainy season. These types of re-
examination will not include the
social and community profits that are
feasible.
• The construction of new chemical
roads that create more bright use of
the structures of polysaccharides
and lignin and this form the basis
of better utilization of biomass. The
bimolecular mechanisms by which
there are some insects in the families
of Hemiptera, and Hymenoptera that
can modify cell diversity and tissue
development in higher plants to their

benefit by bimolecular mechanisms,
by encouraging the development of
galls and associated, generally high
ordered protective structures, build
by the host plant that surely guarantee
the detailed multidisciplinary studies.
Molecular biology • Chemical engineers have the
is a branch of biol- conventional utilization of heat,
ogy that concerns pressure, and pH to speed up the
the molecular basis
chemical reactions, but the evaluation
of biologi-
cal activity between of the molecular biology of organisms
biomolecules in the and their enzymes that has become
various systems of so developed in order to withstand
a cell, including high temperatures, pressures and
the interactions
pH ranges that found in deep ocean
between DNA,
RNA, proteins and outlets and volcanic pools seems to be
their biosynthesis, in its start.
as well as the The advancement in chemical engineering
regulation of these
has been of great importance. The mechanical
interactions.
engineering and applied chemistry have come
together to form the chemical engineering,
and there are regularly new threats in the field
of chemical engineering it has now developed
grown into a fully-fledged broad subject.
The present and new products are produced
in the most efficient and sustainable method in
concept of energy and by-products by making
sure that there should be efforts to improve the
process. The continuous construction of new
facilities and altering older ones in an order that
they have a permission to function and use the
technologies on which society is dependant to
give the basic standards of living.
10.3. IMPORTANCE OF CHEMICAL

ENGINEERING
The planet earth is slowly plunging into the
crisis as birds and animals’ species are going
into extinction at the speed as during the ice age
and no one with some knowledge can neglect
it except the people that cannot approve the
concept of climate change. Anyone who feels a
responsibility to future generations knows that
the human beings have to change the way of
living, and that great effort in this direction is
preparing the food as required and not to waste
the resources.
The branch of engineering can make an
important input in the direction of social and
economic theory is a thing that has surprised the
society.
The productivity of resources can be
increased by the use of circular economy. The
circular economy is a normal example of mindset
of chemical engineer and it has so much to
contribute. A circular economy is an alternative
to a In the conventional direct economy the
practice of manufacturing, utilization and
then dumping to keep resources in use for the
maximum period, and deriving the maximum
benefit from it till the time it is in practical
use, then recycling and then again creating the
products from it in other form.
Although some advocates, it is clear to
anyone with a chemical engineering background
that the vital parameter to achieve resource
productivity is to get best value from materials
and products in utilization and then store and
slowly decreasing the circulation in the market
but the individuals having no concept of the

circular economy yet learn as the increase in the
rate of recycling. The service life of products
that are use should be serviced to increase their
life that is residence time the concept defined by
the chemical engineers.
This simple realization still eludes those
who focus on recycling as the way to promote
the circular economy, although fortunately
it is recognized in the Waste and Resources
Action Programme (WRAP) in the UK, in the
EU Circular Economy Action Plan and in the
work of the Club of Rome. The conclusion is so
obvious that it was highlighted six years ago in a
short article in the Chemical Engineer magazine
(PDF) in 2011.
From the very start the chemical engineering
mindset has been implemented then, the proper
concept of the circular economy meaning
and necessity has come in front of world.
Deliberately extending the product life extension
intentionally shows the type of development in
system that has happened at such a large extent.
The author Walter Stahel in his book The
Performance Economy has defined some of
the consequences. The total change in business
thinking and a not following the pattern is
required that is in mind and ruling since the
industrial revolution to increase the product
life. There is an understanding towards selling
services instead of material products; and
towards renting in place of purchasing directly;
in the direction of refurbishing used products
instead of recycling or dumping them.
The energy or raw materials is the necessity
in place of labor in re-engineering. The efficiency
of labor will be decreased but in same instance

there is betterment in energy productivity of
the economy. Though, productivity of labor in
context of economy is the lowest level grade.
The combination of betterment of efficiency of
workers with the requirement to grow expert
jobs. The definition needs the diverse types
of standards defining them. For example, the
output measured in labor utilized per unit of
material or energy.
This line of thinking runs contrary to
conventional economic thinking, which is not
to say that it is misconceived. New thinking
must be developed with input from different
disciplines, not just the economists who tend to
dominate this debate.
10.4. APPLICATION OF CHEMICAL

ENGINEERING
The fundamental principles of chemical
engineering underlie the operation of processes
extending well beyond the boundaries of the
chemical industry, and chemical engineers Heat transfer is
are employed in a range of operations outside the process of trans-
traditional areas. The manufacturing contains fer of heat from
the various chemical reactions that pose the high temperature
issue in engineering of the product like plastics, reservoir to low
temperature
polymers, and artificial fibers, with various reservoir.
thoughts controlling their production like
movement of liquid and heat transfer.
The issue of transfer of matter is called as
dyeing. The production of pulp and paper contain
the contemplation about the movement of fluid
and heat transfer. These types if issues can be
discovered in modern regular manufacturing
of foodstuffs though the level and materials

are not the same. The solution is necessary for
the availability of modern medicines due to
chemical engineering issues displayed by the
pharmaceuticals industry.
The nuclear industry makes similar demands
on the chemical engineer; particularly the
solution is necessary for the production of fuel
and reprocessing due to issues shown by nuclear
industry. Chemical engineers are involved in
many sectors of the metals processing industry,
which extends from the production of steel
to parting of rare metals industries of metals
processing industry; the role of chemical
engineers cannot be ignored.
The chemical engineering application can
also be seen in the fuel industries. In the second
half of the 20th century, considerable numbers
of The large number of chemical engineers are
employed in space exploration sector in the mid
of the 20th century, and are doing design of fuel
cells to the production of rocket fuels.
There is the hope around the world in the
community of scientist that it is possible that
chemical engineering will provide the answer
to at least two of the world main issues; that is
availability of necessary fresh water in all areas
through desalination of seawater and regulation
of environment through prevention of pollution.
10.5. SIGNIFICANCE OF CHEMI-

CAL ENGINEERING THERMODY-
NAMICS
The laws of thermodynamics give the basic
factors under which all process of real world
happens, though they are based on theoretical

principles. The drawing of the design of a
chemical process plant is the great application
of the knowledge of basic principles of chemical
engineering. The principal matter of such
knowledge is found in chemical engineering.
The right mixture essential for transforming
in to products first is required to be washed
and purified as essentially, they are rocks. The
large number of different methods are in science
for this type of process of purification; For
Liquid–liquid
example, distillation, liquid-liquid extraction,
extraction is a
precipitation from solutions, crystallization, and method to separate
other similar process. compounds or metal
These types of methods to extract the complexes, based on
their relative solubil-
material involves birth of two or more stages, ities in two different
and in one of which the required raw material is immiscible liquids,
glued in the tank or flask, and then it is used or usually water (polar)
in some cases heated to get substances in a purer and an organic sol-
stage. The devices that are used to detached the vent (non-polar).
matter in the process can contain more than half
of the total capital investment in the normal
chemical plant.
In the chemical reaction the required raw
material is put and then the process is started,
and the moment the all material matches the
right mixture then the chemical reaction starts
to produce the new product. The formation of
ideal types of conditions in which the reactor
can work is necessary to produce the needed
product. Though, getting the pure form of
material is rare.
There is a reason behind this and it is that the
raw material is never completely gets changed
into the new product molecules and so the vapor
leaving the reactor is not a pure substance. It has
been observed that and it is a normal knowledge

that the planned chemical reaction is carried
together with the single side reaction.
The other side reaction causes the creation
of side products, that causes the poisoning of
the raw material. Thus, the steam coming out
of the reactor is stored then again subject to
purification process produce product with the
necessitate features.
The principles of the law of thermodynamics
have a huge involvement in the procedures of
purification and reaction. The measurement of
the basic elements that are behind the design
and working of chemical plants is possible only
by these chemicals.
• In the present units of processing
conditions there is some limit
on greatest possible amount of
purification.
• In the prevailing conditions the
maximum amount of purification that
is possible.
• The required circumstances necessary
for detaching of elements and process
in reaction.
• The targeted range of detachment
and reaction, and as a result the plant
energy load that needs the amount of
energy to reach it.
• The calculation of the above
parameters tends to constitute 50–70%
of the pressure during the calculation
faced in the phases of primary process
plant design constitutes 50–70% of
the standards.
Though, the principles of chemical

engineering thermodynamics are necessary and
is essential to gain the target of plant design and
operation.
REVIEW QUESTIONS
1. Explain future of chemical engineering as a product of
chemical thermodynamics?
2. Define the various grand challenges in chemical engineer-
ing?
3. What is importance of chemical engineering?
4. Explain the application of chemical engineering?
5. Define the significance of chemical engineering thermo-
dynamics?
6. Explain the reaction engineering in challenges of chemical
engineering?
7. What is unit operations and transport phenomenon in chal-
lenges of chemical engineering?
8. Explain the concept of energy in challenges of chemical
engineering?
9. Explain the concept of biomedical in challenges of chemi-
cal engineering?
10. Explain the concept of Multiscale Engineering.
REFERENCES
1. Clift, R. (2017). Why Chemical Engineers—Not Just Economists—
Are Key To A Circular Future. [online] GreenBiz. Available
at: https://www.greenbiz.com/article/why-chemists-not-just-
economists-are-key-circular-future [Accessed 3 August 2019].
2. Elliott, J., & Lira, C. (2012). Introductory Chemical Engineering
Thermodynamics: Basic Concepts | 1.1 Introduction | Inform IT.
[online] Informit.com. Available at: http://www.informit.com/
articles/article.aspx?p=1845240 [Accessed 3 August 2019].
3. Garnier, G. (2014). Grand Challenges in Chemical Engineering.
[online] US National Library of Medicine National Institutes of
Health. Available at: https://www.ncbi.nlm.nih.gov/pmc/articles/
PMC3988393/ [Accessed 3 August 2019].
4. Hanson, C. (n.d.). Chemical Engineering. [online] Encyclopaedia
Britannica. Available at: https://www.britannica.com/technology/
chemical-engineering#ref64680 [Accessed 3 August 2019].
5. Nptel.ac.in. (2013). NPTEL: Chemical Engineering – Chemical
Engineering Thermodynamics. [online] Available at: https://nptel.
ac.in/courses/103101004/10 [Accessed 3 August 2019].
INDEX
A Cell membrane 37
Cellular respiration 177
Absolute zero value 78 Cellulosic polymers 189
Accountability 191 Chemical reaction 3, 4
Adiabatic system 134 Chemical reaction process 65, 66,
Affinity 26, 27 68, 78
Aggregation state 22 Chemical substances 27
Amino acid 146, 153 Chemical thermodynamic prototype
Ammonia synthesis 35 153
Anaerobic digestion 88 Chemical thermodynamics 22
Aqueous protein–protein forces 176 Chemical transformation 36
Aqueous solution 35 Chiller cabinet 168
B Chloramine gas 89
Classical thermodynamics 37
Biodegradable quality 193 Closed system 23
Bioengineering 31 Conduction 16
Biological thermodynamics 158 Configurational entropies 155
Biophysical techniques 178, 179 Contravention chemical bonds 83
Biotechnology 176 Convection 16
Bonding energy 155 Crystalline substance 78
Boundary surface 44 Crystallization 32
C D
Caloric theory 6 Dehumidifier 170
Calorimetry 179, 180 Deoxyribonucleic acids (DNAs)
Carbon monoxide (CO) 137 153
Depression 171 Generic cyclic process 174

Diathermal wall 105 Generic heat reservoirs 174
Dilapidation 186 Gibbs Equation 123, 134
Dynamic equilibrium 103 Gibbs free energy 22, 24
Global warming 191
E
H
Electrical energy 69, 71, 74
Electromagnetic circle 173 Heat capacity 43, 51, 62
Electronic instruments 64 Heat energy 3, 13
Endoergic reaction 85 Heat engine 77
Endothermic reaction 89 Heat exchanger 45
Energy conservation 2 Heat generation 74
Energy landscape theory 148 Heating element 169
Energy productivity 197 Heating unit 170
Energy-rich biomass 156 Heat movement 94
Energy transformation 150 Heat transfer mechanisms 5
Enigmatic fluid 5 Heat-transferred energy 16
Enthalpy change 147 Heterogeneous system 25
Entropy variation 3 High-energy biomass 156
Enzymatic reactions 177 High-moisture biomass 82
Equational relation 93 Homogeneous solution 127
Ergodicity 9 Human engineering thermodynam-
Evaporation 171, 172, 181 ics 31
Evaporative cooling 171 Human nutritional values 188
Exhibiting ideal behavior 132 Human thermodynamic instrument
Exothermic reaction 82, 85, 89 30
Expansion valve 168, 172 HVACs (heating and ventilation air
Extensive energy 129 conditioning units) 169
Extensive entropy 131, 137 Hydraulic equilibrium 102
Extensive variables 42 Hydroelectric power 16
Hydrogen bonding forces 147
F Hydrophobic reactions 147
Fermentation process 177
I
First Law of Thermodynamics 64,
70, 71, 73, 74, 79 Ideal mixture 131, 132, 133, 136
Free energy 3, 4 Industrial revolution 196
Infrared radiation 172
G Intensive variables 42
Gas turbine engine 176 Intermolecular attractive forces 43
Index 207
Intermolecular forces 176 Modern chemical thermodynamics

Internal combustion engines 88 27, 29, 38
Internal energy 3, 4, 12 Modern transport system 166
International Union of Pure and Ap- Molecular dynamics (MD) 114
plied Chemistry (IUPAC) 135 Molecular nature 33
Intramolecular hydrogen bonds 113 Molecular swiftness 8
Investigational information 146
N
Isenthalpic system 50
Isolated chemical system 96 Nanotechnology 191, 193
Isolated natural system 76 Natural photosynthetic process 192
Isolated system 49 Non-equilibrium process 130
Isothermal heat 174 Normo-thermic level 148
Isothermal process 51 Numerical atmosphere 155
Isothermal titration calorimetry 182
Isovolumetric process 51 O
K Oncology 191
Optimization 186
Kinetic stability 110, 111, 119 Organic chemicals 22
Kinetic Theory 1, 5 Organic matter 87
Osmotic energy 150
L
Oxidation 156
Light energy 69, 71, 74
P
Lingering responsibility 191
Liquid–crystal equilibria 176 Perturbation 180
Liquid–crystal state 153 Photosynthesis 156
Liquid state 168, 170 Physical chemistry 22, 25, 26, 28
Living cell 151 Physical science 5
Living cell system 151 Physical transformation 31, 32
Potential energy 44, 54
M
Pounding motion 149
Macroscopic motion 56 Predominant energy-rich particle 88
Macroscopic ordered energy 55 Probability density 115, 116
Macroscopic traditional system 115 Probability density function 115,
Man-made system 2 116
Membrane permeability 102 Protein agglomeration 153
Metals processing industry 198 Protein constancy 112, 113, 114
Microscopic energy 56
R
Microscopic physics 9
Modern chemical physics 29 Radiant energy 150, 151
Radiation 16 Thermodynamic analysis 34, 37

Raoult’s Law 123, 131 Thermodynamic constancy 112,
Reaction engineering 187, 189, 202 113, 114
Redox chemistry 83 Thermodynamic control 35
Renewable energy 16, 82, 87 Thermodynamic Equilibrium 1, 10
Repulsion 59 Thermodynamic inequalities 109
Ribonucleic acids (RNAs) 153 Thermodynamic law 166
Thermodynamic stability 109, 110,
S 117, 119
Saturation 127 Thermodynamic system 46, 48, 53,
Second Law of Thermodynamics 102
64, 70, 71, 74, 75, 79, 80 Thermo-electro-biochemical behav-
Solar energy 156, 189, 192 ior 178
Solitary continual temperature 10 Three-dimensional structure 146
Sooty explosion 90 Topological positioning 148
Spontaneous reaction 3, 58 Total capital investment 199
Standard pressure 135, 136 Total energy 68
Statistical thermodynamics 58 Toxic organic solvents 189
Stoichiometry 84 Transformed energy 66, 70
Sunlight energy 74
V
Superfluid helium 137
Surface tension 131 Vaporization 43, 171
T W
Temperature gradient 130 Waste and Resources Action Pro-
Thermal characterization 180 gramme (WRAP) 196
Thermal efficiency 1, 16
Z
Thermal energy 7, 16
Thermal expansion 173 Zeroth Law 72
Thermochemistry 22

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INTRODUCTION TO CHEMICAL

Rose Marie O. Mendoza

e-book Edition 2020

ISBN: 978-1-77407-393-3 (e-book)

© 2020 Arcler Press

ISBN: 978-1-77407-254-7 (Softcover)

List of Figures ........................................................................................................xi

Chapter 1 Introduction to Thermodynamics .............................................................. 1

Chapter 2 Chemical Thermodynamics And Its Origin.............................................. 21

Chapter 3 Principles of Chemical Thermodynamics ................................................ 41

Chapter 5 Chemical Energy And Chemical Thermodynamics .................................. 81

Chapter 6 Thermodynamic Equilibrium In System ................................................. 101

Chapter 7 Thermodynamics Of Chemical Mixtures ............................................... 123

Chapter 8 Chemical Thermodynamics And Biological

Chapter 9 Applications of Chemical Thermodynamics .......................................... 165

Chapter 10 Future of Chemical Engineering As A Product of

Index ..................................................................................................... 205

Figure 1.1: Basic principles of the thermodynamics

Thermodynamics is a very significant branch of science, which deals with the

KEYWORDS LEARNING OBJECTIVES:

Figure 1.1: Basic principles of the thermodynamics.

The word “thermodynamics” is a combination of the terms; ‘Thermo’

Thermodynamics is the study of energy,

free energy of a process is positive, this means

thermodynamic point of view and discloses

1.2. HISTORY OF THERMODY-

Figure 1.2: History of the thermodynamics.

The Caloric theory magnificently clarified

physics called statistical thermodynamics. The

of kindness, and was invigorated by Clausius in

time. In the period of early part of the 1870s,

similarity occurred in the era of 1960s, when the

1.3. THE FOUR LAWS OF THER-

1.3.1. The Zeroth Law

three, they, thus, each have the similar amount

Figure 1.3: The zeroth law of the thermodynamics.

1.3.2. The First Law of Thermodynamics

the similar quantity of energy in the world.

Figure 1.4: The first of the thermodynamics.

For instance, if you have a pot of water

environment around it. Perhaps heating the air

unit temperature, rises over time in the direction

Figure 1.5: The Second Law of Thermodynamics.

Therefore, all closed systems are shifting in

1.3.4. The Third Law

its temperature tends to the absolute zero. The

1.4. APPLICATIONS OF THERMO-

conduction, convection and radiation.

1.5. THERMAL EFFICIENCY

11. Kemani, H. (2019). Applications of Thermodynamics Laws.

KEYWORDS LEARNING OBJECTIVES:

For instance, if there is coffee in a thermos flask,

Figure 2.1: The graph shows that during a chemi-

These thermodynamic potentials allow a

Chemical potentials play a major role in

2.2. HISTORY OF CHEMICAL

• The establishment of the basic laws of

principle of maximum work, given by Julius

2.2.2. Modern Chemical Thermodynam-

Figure 2.2: Josiah Willard Gibbs: His work on the

In year 1986, John Prausnitz an American

Ott summarize things as Randall, Lewis and

2.3. HUMAN CHEMICAL THERMO-