GOVERNMENT POLYTECHNIC, PANCHKULA

BRANCH : MECHANICAL ENGINEERING

SUBJECT : THERMODYNAMICS
SEMESTER : 3rd
 CONTENTS
1. FUNDAMENTAL CONCEPTS
1.1 INTRODUCTION TO THERMODYNAMICS

1.2 THERMODYNAMIC STATE

1.3 THERMODYNAMIC SYSTEM

1.4 BOUNDARY

1.5 SURROUNDING

1.6 UNIVERSE

1.7 TYPES OF THERMODYNAMIC SYSTEM S

1.8 PROPERTIES OF THE SYSTEM

1.9 THERMODYNAMIC EQUILIBRIUM

1.10 QUASI-STATIC PROCESS

1.11 REVERSIBLE AND IRREVERSIBLE PROCESSES

1.12 ZEROTH LAW OF THERMODYNAMICS

1.13 PRESSURE

1.14 VOLUME

1.15 TEMPERATURE

1.16 ENTHALPY

1.17 INTERNAL ENERGY

2. LAWS OF PERFECT GASES

2.1 DEFINITION OF GASES
 2.2 EXPLANATION OF PERFECT GAS LAWS

2.3 AVOGADRO’S LAW

2.4 REGNAULT’S LAW

2.5 UNIVERSAL GAS CONSTANT (R)

2.6 GENERAL GAS EQUATION & CHARACTERISTIC GAS

CONSTANT

2.7 SPECIFIC HEATS

2.8 DERIVATION OF SPECIFIC HEATS WITH CHARISTICS GAS

CONSTANT

3. THERMODYNAMIC PROCESSES
3.1 INTRODUCTION

3.2 TYPES OF THERMODYNAMIC PROCESSES

3.2.1 Isochoric process (Constant volume process )

3.2.2 Isobaric process (Constant pressure process)

3.2.3 Isothermal process (Constant temperature process)

3.2.4 Adiabatic process

3.2.5 Isentropic Process

3.2.6 Polytropic process

3.2.7 Throttling process

3.2.8 Free expansion process

4. LAWS OF THERMODYNAMICS
4.1 LAW OF CONSERVATION OF ENERGY

4.2 FIRST LAW OF THERMODYNAMICS (Joule’s Experiment)

4.3 STEADY FLOW ENERGY EQUATION

4.4 APPLICATIONS OF GENERAL STEADY FLOW EQUATION

4.5 HEAT SOURCE AND HEAT SINK

4.6 STATEMENT OF SECOND LAW OF THERMODYNAMICS

(A) Kelvin – Planck statement

(B) Clausius statement

(C) Equivalency of Kelvin Planck’s and Classius statements

4.7 PERPETUAL MOTION MACHINE (PMM)

4.8 CARNOT ENGINE

4.9 THIRD LAW OF THERMODYNAMICS

4.10 CONCEPT OF IRREVERSIBILITY

4.11 CONCEPT OF ENTROPY

 CHAPTER 1
FUNDAMENTAL CONCEPTS

INTRODUCTION TO THERMODYNAMICS
Thermodynamics is branch of physics which deals with temperature, heat and
their relation to energy, radiation, work, and properties of matter. The
thermodynamic term is derived from two Greek words ‘thermes’ meaning heat,
and ‘dynamis’ meaning motion. Thermodynamics means heat in motion. The
key concept is that heat is a form of energy corresponding to a definite amount
of mechanical work. The study of thermodynamics is comprised of important
laws of thermodynamics namely first law of thermodynamics, second law of
thermodynamics, third law of thermodynamics and Zeroth law of
thermodynamics.
The application of thermodynamic laws are found in all field of energy transfer,
mainly in steam and nuclear power plants, internal combustion engine, gas
turbine, air conditioning and refrigeration, air compressor and chemical process
plants etc.

THERMODYNAMIC STATE
The condition of a system at any instant of time described by its physical
properties is known as state of system. An operation in which properties of
system change is called a change of state.

THERMODYNAMIC SYSTEM
A quantity of the matter or part of the space which is under thermodynamic
study is called as system. It is shows in fig.1.1
 Fig. 1.1: Thermodynamic system

BOUNDARY
System and surroundings are separated by a definite border called boundary. It
can be fixed or movable. System, surroundings and boundary constitute the
universe.

SURROUNDING
Everything external to a thermodynamic system is called surroundings.

UNIVERSE
The system and the surroundings together make up the universe.

TYPES OF THERMODYNAMIC SYSTEMS

Thermodynamic systems can be broadly classified into three types. They are:
1. Open System
2. Closed system
3. Isolated system
In fig. 1.2 shows the types of thermodynamic system.
 Fig. 1.2: Types of thermodynamic system

1. Open system
An open system is a thermodynamic system which allows both mass and
energy to flow in and out of it, across its boundary.
2. Closed system
A closed system allows only energy (heat and work) to pass in and out of
it. It does not allow mass transfer across its boundary.
3. Isolated system
It does not allow both mass and energy transfer across its boundary. It is
more restrictive. In reality, complete isolated systems do not exist.
However, some systems behave like an isolated system for a finite period
of time.

However, there are some other terms by which the system or characteristics
of a sytem are described. Thear are as below:
4. Adiabatic
The process during which work is done and no heat is transferred across
the system boundary is known as adiabatic process.
 5. Homogeneous
The system that has single or uniform phase such as like solid or liquid or
gaseous is called as homogeneous system.
6. Heterogeneous
The system that has more than one phase i.e. the combination of solid,
liquid and gaseous state is called as heterogeneous system.
7. Macroscopic
In this approach a certain quantity of matter is considered without taking
into account the events occurring at molecular level. In other words this
approach to thermodynamics is concerned with gross or all behavior. This
is known as classical thermodynamics.
The values of the properties of system are their average values. For
example consider a sample of a gas in a closed container. The pressure of
the gas is the average value of the pressure exerted by millions of
individual molecules.
8. Microscopic
In microscopic study, the behavior of individual atoms and molecules of a
substance considered. This approach considers that the systems are made
up of a very large numbers of discrete particles known as molecules.
These molecules have different velocities and energies. The values of
these energies are constantly changing with time.

PROPERTIES OF THE SYSTEM

The characteristics by which the physical condition of the system is described
are called as properties of system. Some examples of these characteristics are:
temperature, pressure, volume etc. are called as properties of system.
The system properties are of two types: extensive and intensive properties.
1. Extensive properties of system
The properties of the system that depend on the mass or quantity of the
system are called extensive properties. Some examples of extensive
properties are: mass, volume, enthalpy, internal energy, entropy etc.
2. Intensive properties of the system
These properties do not depend on the quantity of matter of the system. Some
of the examples of intensive properties are: freezing point temperature,
boiling point, temperature of the system, density, specific volume etc.

THERMODYNAMIC EQUILIBRIUM
A state of thermodynamic equilibrium is said to be exist in a system if no
change in any macroscopic properties is registered and the system is assumed to
be isolated from its surroundings. A system will be in state of thermodynamic
equilibrium, if following three equilibrium conditions are satisfied:
1. Mechanical equilibrium
2. Chemical equilibrium
3. Thermal equilibrium

1. Mechanical equilibrium
A state of mechanical equilibrium is that state in which it experiences no
pressure or elastic stress within it and there is no unbalanced force between the
system and surrounding.
2. Thermal equilibrium
In the state of thermal equilibrium of the system, there is no exchange of heat
energy between the system and surrounding. Such a state is characterized by
same value of the temperature of the system and surrounding.
3. Chemical equilibrium
In the state of chemical equilibrium system does not undergo a spontaneous
change in its internal composition i.e. no chemical reaction takes place in it and
no transfer of matter takes place from one part of it to another part.

QUASI-STATIC PROCESS
The state of a system can change as a result of its interaction with the
environment. The change in a system can be fast or slow and large or small. The
manner in which a state of a system can change from an initial state to a final
state is called a thermodynamic process. For analytical purposes in
thermodynamics, it is helpful to divide up processes as either quasi-static or
non-quasi-static. A quasi-static process refers to an idealized or imagined
process where the change in state is made infinitesimally slowly so that at each
instant, the system can be assumed to be at a thermodynamic equilibrium with
itself and with the environment. For instance, imagine heating 1 kg of water
from a temperature 20ºC to 21ºC at a constant pressure of 1 atmosphere. To heat
the water very slowly, we may imagine placing the container with water in a
large bath that can be slowly heated such that the temperature of the bath can
rise infinitesimally slowly from 20ºC to 21ºC. If we put 1 kg of water at 20ºC
directly into a bath at 21ºC the temperature of the water will rise rapidly to 21ºC
in a non-quasi-static way.
 Fig. 1.3: Quasi-static process

Quasi-static processes are done slowly enough that the system remains at
thermodynamic equilibrium at each instant, despite the fact that the system
changes over time. The thermodynamic equilibrium of the system is necessary
for the system to have well-defined values of macroscopic properties such as the
temperature and the pressure of the system at each instant of the process.
Therefore, quasi-static processes can be shown as well-defined paths in state
space of the system. Since quasi-static processes cannot be completely realized
for any finite change of the system, all processes in nature are non-quasi-static.

REVERSIBLE AND IRREVERSIBLE PROCESSES

A process which can be reversed in direction and the system retraces the same
path and the same equilibrium state is known as reversible process. Fig. 1.4
shows a reversible process.
 Fig. 1.4: Reversible and irreversible processes

A process said to be irreversible if a system passes through a sequence of non-

equilibrium states. An irreversible process cannot come back to the original
state, if made to proceed in reverse direction. Fig. 4 shows an irreversible
process with dotted lines.

ZEROTH LAW OF THERMODYNAMICS

The Zeroth law of thermodynamics states that if two bodies are each in thermal
equilibrium with some third body, then they are also in equilibrium with each
other. Thermal equilibrium means that when two bodies are brought into contact
with each other and separated by a barrier that is permeable to heat, there will
be no transfer of heat from one to the other.
 Fig. 1.5: Zeroth law of thermodynamics

PRESSURE
Pressure is a measure of the force exerted per unit area on the boundaries of a
substance. The standard unit for pressure in the SI system is the Newton per
square meter or pascal (Pa). Mathematically:
P = F/A
Where F is the normal force and A is the area on which force is exerted.
Atmospheric Pressure
The pressure exerted by atmospheric air on the earth surface is called
atmospheric pressure. The atmospheric pressure varies with temperature and
altitude above sea level.
Absolute pressure
When pressure is measured with reference to absolute vacuum pressure then it
is called absolute pressure. At this pressure, the molecular momentum is zero.
 Fig. 1.6: Absolute pressure, gauge and vacuum pressure

Gauge pressure
This is the pressure measured by of pressure measuring instruments, in which
atmospheric pressure is taken as datum. The atmospheric pressure is taken as
zero this system. The instrument used to measure this pressure is known as
pressure gauge. The pressure always used to indicate the pressure above
atmospheric pressure.
Vacuum pressure
Measurement of pressure below the atmospheric pressure, in which atmospheric
pressure taken as reference. This is also known as negative pressure or suction
pressure. The instrument used to measure vacuum pressure is known as vacuum
gauge.

VOLUME
The amount of space occupied by any substance is called volume. Its unit is m³.
TEMPERATURE
It is an intensive property which determines the degree of hotness or the level of
heat intensity of a body. The temperature of a body is measured with the help of
an instrument known as thermometer.

For the measurement of temperature of body, following types of scales are used:
1. Centigrade temperature scale (ºC)
Centigrade temperature scale also called Celsius temperature scale, is the scale
based on 0 for the freezing point of water and 100 for the boiling point of water.
Invented in 1742 by the Swedish astronomer Anders Celsius, it is sometimes
called the centigrade scale because of the 100-degree interval between the
defined points. The Celsius scale is in general use wherever metric units have
become accepted, and it is used in scientific work everywhere.

2. Fahrenheit scale (ºF)

Fahrenheit temperature scale is a scale based on 32 for the freezing point of
water and 212 for the boiling point of water, the interval between the two being
divided into 180 parts. The relationship between centigrade and fahrenheit scale
is given by

3. Absolute temperature
It is temperature below which the temperature of any substance cannot fall. For
calculations, the absolute zero temperature is taken as -273ºC in case of Celsius
scale and -460ºF in case of fahrenheit scale. The absolute temperature in Celsius
scale is called degree Kelvin (K) and in fahrenheit scale is called degree of
Rankine (ºR).
T (K) = T (ºK) + 273
T (ºR) = T (ºF) + 460
ENTHALPY
It is the sum of the internal energy added to the product of the pressure and
volume of the system. It reflects the capacity to do non-mechanical work and
the capacity to release heat. Enthalpy is denoted as H; specific enthalpy denoted
as h.
H = U +PV

INTERNAL ENERGY
It is the energy stored in a body or a system due to its molecular arrangement
and motion of molecules. It is generally denoted by U. it is function of
temperature. Internal energy is given by
ΔU = mCv (T2 - T1)
 CHAPTER 2
LAWS OF PERFECT GASES

DEFINITION OF GASES
A gas may be defined as a state of a substance, whose evaporation from its
liquid state is complete. A perfect gas or an ideal gas may be defined as a gas
which obeys all the gas laws under all conditions of temperature and pressure.
In actual practice, no gas is perfect gas, but some real gases like oxygen,
nitrogen and air etc. may be regarded as perfect gases within certain temperature
and pressure limits.

EXPLANATION OF PERFECT GAS LAWS

There are mainly three variables which control the physical properties of gas:
(i)Temperature of the gas (T), (ii) Pressure exerted by gas (P), (iii) Volume
occupied by gas (V).
Any change in above mentioned variables is given by various laws which are
based upon the experimental results.
(i) Boyle’s law, (ii) Charle’s law, (iii) Gay-Lussac law
I. Boyle’s law
This law states, at constant temperature, the volume of an ideal gas is inversely
proportional to its absolute pressure. Mathematically,
1
𝑃𝛼
𝑉
Or PV = Constant
The more useful form of the above equation is
P1V1 = P2V2 = P3V3 =................................ = constant.
The product of pressure and volume is constant for a fixed mass of ideal gas at
fixed temperature.
 II. Charle’s law
At constant pressure, the volume of an ideal gas is directly proportional to
its absolute temperature. The simplest statement of the law is:

All perfect gases change in volume by 1/273th of its original volume at 0 ºC for
every 1 ºC change in temperature, when the pressure remains constant.
Let Vo = Volume of a given mass of gas at 0 ºC
Vt = Volume of a given mass of gas at t ºC
Then according to above statement,
V =V+ 1 V ×t
t o 273 o
273+𝑡
=V ×( )=V 𝑇
o o ×
273 𝑇
Vt 𝑉
=
𝑇 𝑇
The above statement shows that the volume of a gas goes on decreasing by
1/273th of its original volume for every 1 °C decrease in temperature. Now at a
temperature of -273°C, the volume of the gas would become zero and this
temperature is called absolute zero temperature.

III. Gay-Lussac law

At constant volume, the pressure of an ideal gas is directly proportional to its
absolute temperature. Mathematically,
P 𝖺 T or 𝑃 = 𝐶𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝑇
𝑃2 𝑃3
Or 𝑃1 = = = ................................ = Constant.
𝑇1 𝑇2 𝑇3

AVOGADRO’S LAW
It implies that under similar conditions of pressure, volume and temperatures all
gases will have an equal number of molecules, independent of the weight and
density of the gas.
Equal volumes of all gases at conditions of same temperature and pressure have
the same number of molecules’, written as:
V 𝖺 n or V/n =K
Where V=volume of gas;
n= Number of moles

REGNAULT’S LAW
It is states that the specific heat capacity of a gas at constant pressure (C p) and
the specific heat capacity of a gas at constant volume (C v) do not change with
change in pressure and temperature. According to this law, Cp and Cv values of
a gas remain constant.

UNIVERSAL GAS CONSTANT (R)

When the molecular mass of any gas is multiplied by its specific gas constant/
characteristic gas constant (R). R is explained in the next topic. It is observed
that the product R is always the same for all gases. This product is called
universal gas constant and it is denoted as R. In SI system the value of the
universal gas constant is 8.314 kJ/mole.K.
Ru = MR
Where M = molecular mass of gas in kg mole,
R = Gas constant.
Ru = 8314.3J/kg mole/K

GENERAL GAS EQUATION & CHARACTERISTIC GAS

CONSTANT
The Combined gas law or General Gas Equation is obtained by combining
Boyle's law, Charles's law, and Gay-Lussac's law. If temperature and pressure
are kept constant, then the volume of the gas is directly proportional to the
number of molecules of gas.
Let us consider the pressure exerted by the gas to be ‘P’
The volume of the gas be – V
Temperature be – T
Universal gas constant – R
According to Boyle’s Law,
1 1
P𝖺 or V𝖺
𝑉 𝑃

According to Charles’ Law,

V𝖺𝑇
From above two laws, we have
1
V 𝖺 and T both
𝑃
𝑇
V𝖺
𝑃

PV 𝖺 𝑇
PV = CT
Where C is a constant and value of C depends upon the mass and other
properties of the gas. The general gas equation may be written as:
Pv = RT
If m is the mass of gas in kg, then the equation can be written as:
PV = mRT
Where,
R is the gas constant, called characteristic gas constant which has a
value of 287 J/kgK.
SPECIFIC HEATS
The amount of heat required to raise the temperature of its unit mass through
one degree. Solid and liquid have only one specific heat. Gas has mainly two
types of specific heat:
a) Specific heat at constant pressure (Cp)
The amount of heat required to raise the temperature of its unit mass through
one degree, when its pressure is kept constant.
Q = mCpdT
b) Specific heat at constant volume (Cv)
The amount of heat required to raise the temperature of its unit mass through
one degree, when its volume is kept constant.
Q = mCvdT

c) Specific Index
It is the ratio of specific heat at constant pressure to specific heat at constant
volume is known as specific heat index. It is denoted by γ.
γ = Cp/Cv

DERIVATION OF SPECIFIC HEATS WITH CHARISTICS

GAS CONSTANT/
RELATIONSHIP BETWEEN CP, CV AND R
Let us consider m kg of a gas enclosed in a container and is being heated at
constant pressure.
Let T1 = Initial temperature of the gas,
T2 = Final temperature of the gas,
V1= Initial volume of gas,
V2 = Final volume of gas,
 Cp = Specific heat at constant pressure,
Cv = Specific heat at constant volume,
P = Absolute constant pressure.
We know that heat supplied to the gas at constant pressure,
Q = mCp (T2-T1) ............................... (i)
We also know that a part of this heat is utilisec in doing external work, while
the remaining part of heat is used in increasing the internal energy of gas.
i.e. Q = W + dU ................................................... (ii)
now heat utilised for external work,
W = P(V2 – V1) ............................... (iii)
And increase in internal energy
dU = mCv (T2 – T1) ........................... (iv)
Putting the values of W and dU in equation (ii)
Q = P(V2 - V1) + mCv(T2 – T1) .................................... (v)
Using characteristic gas equation, we have
PV1 = mRT1 (For initial condition)
PV2 = mRT2 (For final condition)
P (V2 – V1) = mR (T2 – T1)
Putting the value of P (V2 – V1) from equation (vi) in equation (v), we get
Q = mR(T2 – T1) + mCv(T2 – T1)
Now putting the value of Q from equation (i) in above equation, we get
mCp (T2 – T1) = mR(T2 – T1) + mCv(T2 – T1)
or Cp = R + Cv
or Cp - Cv = R
The equation may be written as
𝐶𝑝
CV [ − 1] = R
𝐶𝑣
Cv(γ – 1) = R
𝑅
Cv =
𝛾−1
The value of r in S.I. unit is taken as 287 J/kg K
The equation may also be written as
Cp = Cv+R
Dividing both sides by Cv , we get
𝐶𝑝 𝑅
=1+
𝐶𝑣 𝐶𝑣
𝑅
𝛾 =1+
𝐶𝑣
 CHAPTER 3
THERMODYNAMIC PROCESSES

INTRODUCTION
When the system changes from one thermodynamic state to the final
thermodynamic state due to change in pressure, temperature, volume etc, the
system is said to have undergone thermodynamic process. The various types of
thermodynamic processes are: isothermal process, adiabatic process, isochoric
process, isobaric process and reversible process.

TYPES OF THERMODYNAMIC PROCESSES

The important thermodynamic processes are:
A. Reversible non-flow processes
1. Isochoric process (Constant volume process )
2. Isobaric process (Constant pressure process)
3. Isothermal process (Constant temperature process)
4. Adiabatic process
5. Hyperbolic process
6. Polytropic process
7. Throttling process

Isochoric process (Constant volume process )

In this process the volume of system remains constant. The main characteristic
of this process is that the displacement work is eliminated. An example of this
process is the heating or cooling of a gas stored in a rigid cylinder. Since the
volume of the gas does not change, no external work is done, and work
transferred W is zero.
Therefore from 1st law of thermodynamics for a constant volume process:
Q1-2 – W21-2 = U2 - U1
But, W = ∫ 𝑃𝑑𝑉 = 𝑈 - 𝑈 …………. (dV = 0 )
1-2 1 2 1
Q1-2 = U2 - U1
Q1-2 = mCv (T2 -T1)
Thus, during a constant volume process, the heat transfer equals the change in
internal energy of the system.

Isobaric process (Constant pressure process)

The process, during which the pressure of the system remains constant, is called
as isobaric process. If the temperature of a gas is increased by the addition of
heat while the gas is allowed to expand so that its pressure is kept constant, the
volume of the gas will be increase in accordance with Charles law. Since the
volume of the gas increases during the process, work is done by the gas at the
same time that its internal energy also changes. Therefore for constant pressure
process, assuming constant specific heats and ideal gas behaviour,
If the work is carried out quasi-statically,

Then, from first law of thermodynamics,

Or
Also

Or

Thus, the heat supplied at constant pressure is equal to change in enthalpy of the
system.

Isothermal process (Constant temperature process)

According to Boyle’s law, when a gas is compressed or expanded at constant
temperature, the pressure will vary inversely with the volume. Since the gas
does work as it expands, if the temperature is to remain constant, energy to do
the work must be supplied from an external source. When a gas is compressed,
work is done on the gas and if the gas is not cooled during the process the
internal energy of the gas will increase by an amount equal to the work of
compression. Therefore if the temperature of the gas is to remain constant
during the process gas must reject heat to the surroundings. Since there is no
temperature increase in the system change in internal energy becomes zero. And
the amount of work done will be the amount of heat supplied.
From first law of thermodynamics,

But

Now as

Or
For quasi-static process,

Or

Or

Or

Or

Hence, the heat supplied during isothermal process is equivalent to non-flow

work during the process.

Adiabatic process
The process during which work is done and no heat is transferred across the
system boundary is known as adiabatic process.
Heat transferred, Q1-2 = 0
From first law of thermodynamics,
Q1-2 – W1-2 = U1 – U2
Or Q1-2 – W1-2 = ΔU ……………….. Q1-2 = 0
Or – W1-2 = ΔU ……………….. (i)
Work done = Change in internal energy
For perfect gases, we know that
ΔU = m × Cv × (T2 – T1) ............................................................ (ii)
2
Also W1-2 = ∫1 𝑃𝑑𝑉 ………………... (iii)
Putting the values of ΔU and W1-2 from equations (ii) and (iii) in equation (i),
we get

Or ………. (iv)
But

Or
……….. (v)
Putting the value of P from equation (v) in equation (iv), we get

Or

……. (vi)
Now
 ………. (vii)
Putting the value of R/Cv from (vii) in equation (vi), we get

Integrating between the limits, we get

It should be noted that during reversible adiabatic process, entropy remains
constant, so the process is also known as isentropic process.
Condition for isentropic process:
1. The process should be frictionless.
2. No heat should be transferred.
3. Work should be done by the gas or on the gas.
4. In real practice, isentropic process is not possible.

Isentropic Process
If an adiabatic process is reversible then it is called Isentropic process i.e.,
reversible adiabatic process is known as isentropic process. For an adiabatic
process to qualify as isentropic process, then it should be frictionless. All the
other properties of this process are same as that of adiabatic process.

Polytropic process
It is found that in actual practice many processes approximate to a reversible
process of the PVn = Constant, where n is called polytropic index. Both vapours
and perfect gases follow this type of process closely. Work done during the
process from state 1 to state 2 by system,
 Throttling process
The throttling process is an irreversible steady flow expansion process in which
a perfect gas is expanded through an orifice of minute dimensions such as a
narrow throat or as lightly opened valve.
Due to fall in pressure during expansion, the gas should come out with a large
velocity, but due to high frictional resistance between the gas and the walls of
the aperture, there is no considerable change in velocity. The kinetic energy of
the gas is converted into heat which is utilized in warming the gas to its initial
temperature. Since no heat is supplied or rejected during the throttling process
and also no work is done. There is no change in enthalpy from one state to
another, h1 = h2; no work is done, W = 0; and the process is adiabatic, Q = 0.

Free expansion process

The expansion of gas in perfect vacuum is called free expansion. Consider a
properly insulated cylinder with a partition and stopper. Now place some gas on
one side and evacuate other side. When stopper is removed the gas expands
freely to the other side of cylinder. This process is called free expansion or
irreversible isothermal process.

Since it is properly insulated no heats enters or leave the cylinder (adiabatic)

and temperature of gas remains constant i.e., isothermal. The matter inside
cylinder does not cross the system boundaries (walls of cylinder) hence work
done is 0. Since temperature is constant, there is no change in internal energy of
system.

Since, dU = 0, Thus, internal energy of system remains constant.

H = U + PV
 CHAPTER 4
LAWS OF THERMODYNAMICS

LAW OF CONSERVATION OF ENERGY

The law of conservation of energy states that energy can neither be created nor
destroyed - only converted from one form of energy to another. This means that
a system always has the same amount of energy, unless it’s added from the
outside. Some examples of conservation of energy are as follow:

1. Conversion of electrical energy into heat energy by flowing of current

through a resistance.
2. Conservation of water energy into heat energy during power generation in
a hydroelectric power plant.
FIRST LAW OF THERMODYNAMICS (JOULE’s
EXPERIMENT)
It is special case of law of conservation of energy and may be explained as
follow for the following systems:

First law for a closed system undergoing a cycle

Let us consider a closed system which consist of a known mass of water, (m)
contained in an adiabatic vessel having a thermometer and a paddle wheel as
shown in fig.

Fig. 4.1 Joule experiment apparatus

Let a certain amount of work (W1-2) be done upon the system by the paddle
wheel. The quantity of work can be measured by the fall of weight which
derives the paddle wheel through a pulley. The system initially was at
temperature (T1), the same as that of the atmosphere and after the work transfer
let the temperature rise to (T2). The process 1-2 undergone by the system is
shown in the figure 8, in generalized thermodynamic coordinates X, Y.
 Fig. 4.2 Cyclic process
The system and the surrounding interact by heat transfer till the system returns
to the original temperature (T1), attaining the condition of thermal equilibrium
with the atmosphere. The amount of heat transfer (Q 2-1) from the system during
the process (2-1) shown in the figure above, can be estimated from,
Q2-1 = mCp (T2 – T1)
The systems thus execute a cycle, which consist of a definite amount of work
input (W1-2) to the system followed by the transfer of an amount of heat (Q 2-1)
from the system.

The work (W1-2) is always proportional to the heat (Q2-1) and constant of
proportionality is called the Joule's equivalent or mechanical equivalent of heat.
If the cycle involves many more heat and work quantities, the same result will
be found,

Where,
J = Joule's equivalent.
∮ = Denotes the cyclic integral for the closed path.
This is the first law for a closed system undergoing a cycle. It is accepted as a
general law of nature, since no violation of it has ever been demonstrated. In
this, the algebraic summation of all energy transfer i.e. heat energy transfer and
work energy transfer across the system boundaries will be zero.
 First law for a closed system undergoing a change of state
Let we have one closed system which is undergoing a change of state and
energies i.e. work energy and heat energy both are crossing the system
boundaries. Net energy will be stored within the system in the form of internal
energy. The Q heat energy enters the system from surrounding and work energy
W leave the system or we can also say that system is doing work W on the
surrounding by taking Q amount of heat energy from the surrounding.

(Q-W) will be the net energy and it will be accumulated within the system and
hence there will be increment in internal energy of the system as (Q-W) amount
of energy will be stored within the system during this process. Therefore
according to the first law of thermodynamics, we have following equation for
above thermodynamic process where system is under a change of state.
Q - W = ∆U
Where, ∆U is increase in internal energy of the system during the process.
Let we have one system where multiple energies are crossing the system
boundary in a process as shown in figure, “Sign convention used for heat and
work energy transfer across the system boundary “and we will write here the
equation of energy transfer across the system boundary according to the first
law of thermodynamics for this process.
 Q1 + Q2 - Q3 - W1+W2+W3 = ∆U
This equation shows the change in internal energy or change of system energy.

Limitations of First law first law of thermodynamics (Joule’s experiment)

1. No restriction on the direction of the flow of heat: the first law establishes
definite relationship between the heat absorbed and the work performed
by a system. The first law does not indicate whether heat can flow from a
cold end to a hot end or not. For example: we cannot extract heat from the
ice by cooling it to a low temperature. Some external work has to be
done.
2. Does not specify the feasibility of the reaction: first law does not specify
that process is feasible or not for example: when a rod is heated at one
end then equilibrium has to be obtained which is possible only by some
expenditure of energy.
3. Practically it is not possible to convert the heat energy into an equivalent
amount of work.
To overcome this limitations, another law is needed which is known as second
law of thermodynamics. The second law of thermodynamics helps us to predict
whether the reaction is feasible or not and also tell the direction of the flow of
heat.
STEADY FLOW ENERGY EQUATION
Before going for the energy equation, let us first discuss the conditions which
must be satisfied for the steady flow process.
1. The mass flow through the system remains constant.
2. Fluid is uniform in composition.
3. The only interaction between the system and surroundings are work and
heat.
4. The state of fluid at any point remains constant with time.
5. In the analysis only potential, kinetic and flow energies are considered.

Fig. 4.3 Steady flow process

Let P1, P2 = Pressure of working substance at inlet and outlet of system,
Z1, Z2 = Datum height at inlet and outlet,
C1, C2 = Velocity of working substance at inlet and outlet,
Q = Heat supplied to the system,
W = Work delivered by the system,
V1, V2 = Volume of working substance entering and leaving the system,
U1, U2 = Internal energy of working substance at inlet and outlet,
m = Mass of working substance
We know that energy entering the system is

Similarly, energy leaving the system is

From assumption

Also, we know that,

And

The above equation is known as steady flow energy equation. Mass flow rate
(m) of the working substance in a steady flow is given by

APPLICATIONS OF GENERAL STEADY FLOW EQUATION

Some of the important applications of general steady flow equations are as
follows:

1. Turbine
A turbine is a rotary steady state steady flow machine whose purpose is the
production of shaft power at the expense of the pressure of the working fluid.
Two general classes of turbines are steam and gas turbines depending on the
working substance used. Usually, changes in potential energy are negligible, as
is the inlet kinetic energy. Often the exit kinetic energy is neglected (if in a
problem, the flow velocities are specified, the kinetic energy term should be
included). Normally, the process in the turbine is adiabatic and the work output
reduces to decrease in enthalpy from the inlet to exit states.

Fig. 4.4 Turbine

H1 = H2 + W
W = H1 – H2
This shows that the work done by the system is due to the decrease in enthalpy
of working substance.

2. Pump
A pump is a device which lifts the water from lower level and delivers it to
higher level as shown in fig. the pump is run by an external device, therefore
work is –ve in this case. Also the change in internal energy of water is zero i.e.
Q = 0 and U1-U2 = 0.
 Fig. 4.5 Pump

3. Boiler

Fig. 4.6 Boiler

A boiler is a device shown in fig which is used to generate the steam after
heating the water. In this system, there is no change in kinetic energy and
potential energy. Also there is no work done by system.
Therefore, from general energy equation,
H1 + Q = H2
Q = H2 – H1
This show that the heat supplied to the system in a boiler is used to increase the
enthalpy of the system.

4. Compressor
Compressor is used to increase the pressure of air. There are mainly two types
of compressors:
a) Rotary compressor
In this case, the compressor is insulated, so that no transfer of heat takes place
(Q = 0) and also, the work is done on the system. From energy equation

Also the change in K.E. and P.E. are negligible.

H1 = H2 – W
W = H2 – H1
It shows that work is done to increase enthalpy.
b) Reciprocating compressor
The rate of flow is low as compared to rotary compressor, so there is large area
in contact with surroundings. Amount of heat transfer in appreciable and cannot
be ignored.
Therefore,
H1 – Q = H2 – W
The –ve sign of Q and W indicate that in reciprocating compressor, heat is
rejected and work is done on the system.

5. Nozzle
It is a device which is used to increase the velocity of working substance at the
cost of pressure drop. The nozzle is considered to be insulated so that there is no
transfer of heat from or to the system (Q = 0). Also there is no change in
potential energy and no external work is done by the system. From general
energy equation,

Fig. 4.7 Nozzle

Now, C1 is very small as compared to C2, so C1 may be ignored. From general

energy equation,

Above relation shows that the increase in K.E. will results in decrease in
enthalpy.
6. Evaporator
It is device which is used in refrigeration system. In evaporator, liquid
refrigerant receives heat and leaves as vapors refrigerant. In thus system, kinetic
energy and potential energy can be neglected. Also there is no work done by the
system.

Fig. 4.8 Evaporator

H1 + Q = H2
Q = H2 – H1

HEAT SOURCE AND HEAT SINK

Fig. 4.9 Heat Source and heat Sink

Ideally sink and source are thermal reservoirs of infinite thermal capacities. This
means you can extract (source) or reject (sink) heat from them without changing
their temperature. Practically such device does not exist; these are just concepts
to make study of thermodynamic systems like heat engine and refrigerator easy.

STATEMENT OF SECOND LAW OFTHERMODYNAMICS

The Second Law of Thermodynamics states that the state of entropy of the
entire universe, as an isolated system, will always increase over time. The
second law also states that the changes in the entropy in the universe can never
be negative. However, in some cases where the system is in thermodynamic
equilibrium or going through a reversible process, the total entropy of a system
and its surroundings remains constant. The second law is also known as the law
of degradation of energy.
There are two statements on the second law of thermodynamics which are;
1. Kelvin- Plank statement
2. Clausius statement
3.
(A) Kelvin – Planck statement
It is impossible for any device that operates on a cycle, to receive heat from a
single reservoir and produce a net amount of work. In other words, no heat
engine converts or can convert whole of the heat energy into mechanical work
and there will always be a heat rejection.
Let us assume that heat energy (Q1) at temperature T1 is supplied to heat engine
from source and heat energy (Q2) at temperature T2 is rejected to the sink. Then
remaining or net energy (Q1 – Q2) will be converted into mechanical work
(Wnet). The ratio of maximum mechanical work obtained to the total heat
supplied to the engine is known as thermal efficiency of heat engine.
 Fig. 4.10 Heat engine

If Q2 = 0 (i.e., Wnet = Q1, or efficiency = 1), the heat engine produces work in a
complete cycle by exchanging heat with only one reservoir, thus violating the
Kelvin-Planck statement of second law is known as perpetual motion machine
of second kind (PMM-II).

(B) Clausius statement

It is impossible to construct a device operating in a cycle that can transfer heat
from a colder body to warmer without consuming any work. Therefore, heat
cannot flow is itself from a body at a higher temperature. The applications of
this law are found in a heat pump and refrigerator.

(C) Equivalency of Kelvin Planck’s and Classius statements

To prove that violation of the Kelvin-Planck Statement leads to a violation of
the Clausius Statement, let us assume that Kelvin-Planck statement is incorrect.
Consider a cyclically working heat engine (E), which absorbs energy Q 1 as heat
from a thermal reservoir at TH. Equivalent amount of work W (W = Q1) is
performed.
Consider refrigerator (R) operating as a cycle, which absorbs energy QL as heat
from a low temperature thermal reservoir at TL and rejects energy QH (QH = QL
+ W). Such a device does not violate Clausius statement.

If the two devices are now combined, the combined device (enclosed by the
dotted boundary) transfers heat QL from the low temperature reservoir at T L to a
high temperature reservoir at TH without receiving any work from an external
device, which is the violation of the Clausius statement.
Likewise let us assume that the Clausius statement is incorrect. So we have a
refrigerator (R), cyclically working transferring heat Q from a low temperature
reservoir at TL to a high temperature thermal reservoir at TH. Consider heat
engine (E), which absorbs heat Q1 from a high temperature reservoir at TH does
work W and rejects energy Q as heat tot the low temperature reservoir at T L as
shown in figure.
If the two devices are combined (shown in figure by a dotted enclosure), then
the combined device receives energy (Q1-Q) as heat from a thermal reservoir
and delivers equivalent work (W=Q1-Q) in violation of the Kelvin-Planck
statement. Therefore violation of Clausius statement leads to the violation of the
Kelvin-Planck statement. Hence, these two statements are equivalent.

(D)Heat pump: It is a device operating in cyclic process which maintains the

temperature of a hot body at a temperature higher than the temperature of
surroundings. Heat pump operates between atmospheric temperature and hot
body temperature. Performance of a heat pump is measured by a term known as
coefficient of performance which is defined as the ratio of maximum heat
transfer to the amount of work done.

Fig.4.11 Heat pump

 (D) Refrigerator: A refrigerator is a device operating in a cycle which
maintains a body at a temperature lowers than the temperature of the
surroundings. A refrigerator works between the cold body temperature
and the atmospheric temperature.

Fig. 4.12 Refrigerator

PERPETUAL MOTION MACHINE (PMM)

A device that violates the first law of thermodynamics (by creating energy) is
called a Perpetual motion machine of the first kind.

A device that violates the second law of thermodynamics is called a Perpetual

motion machine of the second kind.
CARNOT ENGINE
Carnot engine is a theoretical thermodynamic cycle proposed by Leonard
Carnot. It gives the estimate of the maximum possible efficiency that a heat
engine during the conversion process of heat into work and conversely, working
between two reservoirs, can possess. It is an idealized engine whose working is
perfectly reversible. This engine uses an ideal gas as the working substance and
performs a 4-stroke process to complete one cycle. The reversible cycles cannot
be achieved in practice because of irreversibility’s associated with real
processes. But, the reversible cycles provide upper limits on the performance of
real cycles.

Consider a gas in a cylinder‐piston (closed system). The Carnot cycle has four
processes:
1. Reversible isothermal expansion (1-2): The cylinder containing ideal gas is
working substance allowed to expands slowly at this constant temperature (TH).
2. Reversible adiabatic expansion (2-3): The cylinder‐piston is now insulated
(adiabatic) and gas continues to expand reversibly (slowly). So, the gas is doing
work on the surroundings, and as a result of expansion the gas temperature
reduces from TH to TL.

3. Reversible isothermal compression (3-4): The gas is allowed to exchange

heat with a sink at temperature TL as the gas is being slowly compressed. So,
the surroundings are doing work (reversibly) on the system and heat is
transferred from the system to the surroundings (reversibly) such that the gas
temperature remains constant at TL.

4. Reversible adiabatic compression (4-1): The gas temperature is increasing

from TL to TH as a result of compression.

THIRD LAW OF THERMODYNAMICS

This law states, ‘At absolute zero temperature, the entropy of system is zero’.
Zero entropy means the absence of all molecular, atomic, nuclear and electronic
disorders. It has two important consequences, it defines the sign of the entropy
of any substance at temperatures above absolute zero as positive, and it provides
a fixed reference point that allows us to measure the absolute entropy of any
substance at any temperature.

CONCEPT OF IRREVERSIBILITY
A process is said to be reversible if both the system and the surroundings can be
restored to their respective initial states, by reversing the direction of the
process. A reversible process is a process that can be reversed without leaving a
trace on the surroundings. Processes that are not reversible are called
Irreversible processes.
Irreversibilities
The factors that cause a process to be irreversible are called irreversibilities.
1. Friction
2. Unrestrained expansion
3. Mixing of two gases
4. Heat transfer across a finite temperature difference
5. Spontaneous chemical reactions
6. Expansion or Compression with finite pressure difference
7. Mixing of matter at different states

CONCEPT OF ENTROPY
The term entropy means transformation. It is a function of quantity of heat
which shows the possibility of conversion of that heat into work. As a matter of
fact, it is difficult to define entropy. But change of entropy of a substance can be
easily defined. In a reversible process, over a range of temperature, the increase
or decrease of entropy when multiplied by the absolute temperature gives the
heat absorbed or rejected by the working substance. Mathematically,
ðO = 𝑇𝑑𝑆
Where, T = Absolute temperature, dS = Change in entropy

Fig. 4.13 T-S diagram

The relation between heat and entropy is given by Clausius. To prove this, let us
consider the heating of a working substance by reversible process. Entropy is
represented on the abscissa and absolute temperature on the ordinate. This
diagram is known as temperature – entropy diagram.
ðO
dS =
𝑇
Importance of entropy: The change in entropy represents the maximum
amount of work done per degree drop in temperature. In other words, change in
entropy may be regarded as the rate of availability or unavailability of heat for
transformation into work.