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THERMODYNAMICS NOTES

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 Thermodynamics

DR MOHD PARVEZ
Department of Mechanical Engineering
Al-Falah University, Faridabad (India)
Guest Faculty in G.B Pant Institute of Technology New Delhi (India)
 Course Objectives
The subject matter taught in this course will enable the students to:
 Understand the concept of thermodynamic systems, control volume, intensive and
extensive properties, work and heat interactions
 Understand the laws of thermodynamics and their important consequences/corollaries
 Know about ideal and real gases, pure substance and phase change
 Analyse the air standard cycles on the basis of efficiency and mean effective pressure
 Relate thermodynamic properties via partial derivatives, Maxwell relations and T – ds
equation

Unit – 2
Energy and Its Different Forms
2.1 Energy: Energy is the capacity to exert a force through a distance, and manifests itself in
various forms. Engineering processes involve the conversion of energy from one form to
another. The capacity of doing work is called energy. It is the potential to exert force from a
distance. The term energy was coined in 1807 by Thomas young and its use in thermodynamics
was proposed in 1852 by Lord Kelvin. It may be classified as:
 Stored energy
 Energy in transit
The store energy comes in the form of mechanical energy, internal energy, chemical energy and
electrical energy. A part of the store mechanical energy may take the form of either potential
energy (PE) which is gravitational energy due to height above the datum line or kinetic energy
(KE) due to velocity. The balance part of store energy is referred as internal energy. Heat and
work are two forms of energy in transition. That is, these are the only forms that cross the
boundaries of a system. Neither heat nor work can be held as stored energy. Unit of energy J
(Joule) The energy per unit mass is the specific energy in J/kg.
Energy is denoted by symbol E, therefore the total energy is mathematically given by the
equation:
E = U+ K.E + P.E
E = Total energy (kJ)
U = Total internal energy (kJ)

1
H = Total enthalpy (kJ)
K.E = Total kinetic energy (kJ)
P.E= Total kinetic energy (kJ)
2.2 Forms of Energy: There are many forms that energy can take. Some of these forms are
thermal, mechanical, kinetic, potential, electric, magnetic, chemical, and nuclear. When you sum
all of the forms of energy acting within a system you will obtain the systems total energy.
Kinetic Energy Potential Energy

Energy of movement Store energy

Thermal Energy Chemical Energy

Energy of moving particles (heat) Energy stored in food, fuel

Mechanical Energy Nuclear Energy

Energy of objects in motion Energy stored in centre of particles

Electrical Energy Gravitational Energy

Energy of particles through a wire Energy stored in an object when it is above the earth moving
2.2.1 Power: The rate of energy transfer or storage is called power.
1 W= I J/s= 1 Nm/s
1 kW=1000 W
2.3 Work: Work is defined as the force moving through a distance, the displacement being in the
direction of force. Work is force applied over distance. Examples of work include lifting an
object against the Earth's gravitation, driving a car up a hill, and pulling down a captive helium
balloon. Work is a mechanical manifestation of energy.
2.3.1 Concept of work in Mechanics: Work is the product of a force and the distance moved by
a body in the direction of force.
The differential quantity of work done ‘dW’ = F.dL
Where dL = displacement
F = Force acting in the direction of displacement. The unit of work is N.m or joule [1N.m=1
Joule]

2
The rate at which work is done by or upon, the system is known as power. The unit of power is
J/s or Watt.
2.3.2 Concept of work in thermodynamics: In thermodynamics, work is the quantity of energy
transferred from one system to another without an accompanying transfer of entropy. It is a
generalization of the concept of mechanical work in mechanics. In the SI system of
measurement, work is measured in joules (symbol: J).
The thermodynamic definition of work relates to the concept of system and surroundings.
Work refers to the energy transferred (without transfer of mass and with the help of a
mechanism) because of a property difference, other than temperature, that exits between the
system and its temperature (see Figure 2.1).
 Work is one of the basic modes of energy transfer. In mechanics the action of force on a
moving body is identified as work. In thermodynamics, work transfer is considered as
occurring between the system and surroundings
 Work is a transient which only appear at the boundary while a change of state is taking
place within a system
 If the work is done by the system on the surroundings (work output of the system) = +W
For example, when fluid expands pushing a piston outwards is to be positive
 If the work is done on the system by the surroundings (work input to the system) = – W
For example, when a force is applied to a rotating handle or to a piston to compress a
fluid, the work is said to be negative

Figure 2.1 Work

3
2.4 Heat: Heat is a form of energy associated with the kinetic energy of atoms or molecules and
capable of being transmitted through solid and fluid media by condition, through fluid media by
convection and through empty space by radiation. Heat is the energy transferred due to
temperature difference only.
 Heat transfer can alter system state
 Body, s don’t “contained” heat, heat is identified as it comes across system boundaries.
 The amount of heat needed to go from one state to another is path dependent.
 Heat like work, is a transient quantity which only appears at boundary while change is
taking place within the system.
Heat is defined as the form of energy that is transferred across the boundary by virtue of a
temperature difference which is denoted by symbol Q.
The direction of heat transfer is taken from the high temperature system to the low temperature
system. Heat flow into the system is taken to be positive and heat flow out of a system is taken as
negative as shown in Figure 2.2.
2.4.1 Sensible heat: It is the amount of heat transfer through change in temperature but without
change in phase.
2.4.2 Latent heat: It is the amount of heat transfer required to evaporate the water or to change
its state from saturated liquid to saturated vapour. It is denoted by the symbol hfg.

Q+ve

System

Q –ve
Figure 2.2 Heat convention
2.5 Joule’s experiment: It was well known that heat and work both change the energy of a
system. Joule conducted a series of experiments which showed the relationship between heat and
work in a thermodynamic cycle for a system. He used a paddle to stir an insulated vessel filled
with fluid.
Let us consider a closed system which consists of a mass of water contained in an adiabatic
vessel having thermometer and a paddle wheel as shown in Figure. Let a certain amount of work

4
W1-2 be done upon the system by paddle wheel. The quantity of work can be measured by the fall
of weight which derives the paddle wheel through a pulley. The system was initially at
temperature T1, the same as that of atmosphere and after work transfer let the temperature rise
to T2. The pressure is always 1 atmospheric. The process 1-2 undergo by the system as shown in
above Figure 2.3.

Figure 2.3 Joule’s experiment

Let the insulation now removed, the system and surrounding interact by heat transfer till the
systems returns to the original temperature T1, attaining the condition of thermal equilibrium
with the atmosphere. The amount of heat transfer Q2-1 from the system during this process can be
estimated. The system has executes the cycle, which consist of a definite amount of work input
W1-2 to the system followed by the transfer amount of heat Q2-1 from the system.
It has been found that this W1-2 is always proportional to the heat Q2-1 and the constant of
proportionality is called Joule’s equivalent or mechanical equivalent of heat.
Mathematically
(Σ𝑊)𝑐𝑦𝑐𝑙𝑒 = 𝐽(ΣQ)𝑐𝑦𝑐𝑙𝑒
ΦdW = JΦdQ
Where Φ denotes the cyclic integral for closed path
Note: Adiabatic means thermally insulated from its surrounding, however exchange work with
surrounding.

5
2.6 First law of thermodynamics: In the preceding lectures, we applied the first law of
thermodynamics, or the conservation of energy principle, to processes involving closed systems.
Energy is a conserved property, and no process is known to have taken place in violation of the
first law of thermodynamics. Therefore, it is reasonable to conclude that a process must satisfy
the first law to occur. However, as explained below, satisfying the first law alone does not ensure
that the process will actually take place.
First law of thermodynamics deals with the fact of energy conservation, which means if system
looses energy in one form it must gain energy in another form at the same point, so that total
quantity of energy remains constant. The law of conservation which state that, although energy
can change form, it can be neither created nor destroyed. However, it provides no information
about the direction in which processes can occurs, i.e. the reversibility aspects of thermodynamic
processes. The first law of thermodynamics provides no information about the inability of a
thermodynamic process to convert heat fully into mechanical work. Deals with quantity and
governs with law of conservation.
 Analysis simply provides the overall performance of the system
 Makes no distinguish between the quality and quantity
 Provides no information about the direction in which process can occurs
 Provides no information about thermodynamic process to convert heat fully into
mechanical work
 First law owes to J.P Jules, during the period 1840-1849, carried out a series of
experiments to investigate the equivalence of work and heat
 Provides the sound bases for studying the relationships amongst the various forms of
energy and energy interaction
 Based on experimental observation
It is common experience that a cup of hot coffee left in a cooler room eventually cools off as
shown in Figure 2.4.

6
 Figure 2.4
This process satisfies the first law of thermodynamics since the amount of energy lost by the
coffee is equal to the amount gained by the surrounding air. Now let us consider the reverse
process-the hot coffee getting even hotter in a cooler room as a result of heat transfer from the
room air. We all know that this process never takes place. Yet, doing so would not violate the first
law as long as the amount of energy lost by the air is equal to the amount gained by the coffee. It
is clear from the above that processes proceed in a certain direction and not in reverse direction.
The first law places no restriction on the direction of a process, but satisfying the first law does
not ensure that that process will occurs in which direction.
Another example: A rock at some elevation processes some potential energy and part of this
potential energy is converted into kinetic energy as the rock falls. Experimental data shows that,
the decrease in potential energy exactly equal to increase in kinetic energy when air resistance is
negligible.
2.6.1 First law for a cycle: Since the initial and final states are identical in a thermodynamic
cycle, the system experiences no net change in state. Therefore, the system also experiences no
net change in energy for the cycle.
∆𝐸𝑐𝑦𝑐𝑙𝑒 = 𝐸𝑓𝑖𝑛𝑎𝑙 − 𝐸𝑖𝑛𝑖𝑡𝑖𝑎𝑙 = 0
0
∆𝐸𝑐𝑦𝑐𝑙𝑒 = 𝑄𝑐𝑦𝑐𝑙𝑒 − 𝑊𝑐𝑦𝑐𝑙𝑒
𝑄𝑐𝑦𝑐𝑙𝑒 = 𝑊𝑐𝑦𝑐𝑙𝑒
In words, the first law of thermodynamics or the conservation of energy principle applied to
a cycle:
[Net energy transferred by heat for the cycle] = [Net energy transferred by work for the cycle]

7
2.6.2 First law for change in state – internal energy: The first law of thermodynamics is the
application of the conservation of energy principle to heat and thermodynamic processes: The
first law makes use of the key concepts of internal energy, heat, and system work. It is just that
W is defined as the work done on the system instead of work done by the system.

2.6.3 First law of thermodynamics for an open system: A thermodynamic system becomes an
open system, if there is an exchange of mass between the system and its surroundings in addition
to the work and heat transfer interaction. To study such systems, a concept of control volume is
required which is simply a finite region in space through which mass, momentum and energy can
transfer. The boundary of control volume is known as control surface. A control volume shown
below can be analyzed as an open system as shown in Figure 2.4.
The general first law equation for thermodynamic process is
𝑸 = ∆𝑬 + 𝑾
For application of the open system, the energy term ‘E’ will include internal energy,
gravitational, potential energy and kinetic energy.

Qc
v

Fluid flow out

Fluid flow Control volume

in Wcv

Control
Figure 2.4 Open System surface

8
2.6.4 First law for closed system for cyclic process: For any closed system taken through a
cyclic process, the network delivered to surroundings is equal to the net heat taken from
surroundings:
That is δQ = δW
2.6.4.1First law of thermodynamics for closed system: It states that the change in the internal
energy ΔU of a closed system is equal to the amount of heat Q supplied to the system, minus the
amount of work W done by the system on its surroundings.
∆𝑼 = Q – W (For closed system)
Mathematically
∆𝐸 = Q – W (For general system)
∆𝐻 = Q – W (For open system)
∆𝑈 = Q – W (For closed system)
E2 – E1 = Q1-2 – W1-2 (Ist law for a process)
𝑚𝑣22 𝑚𝑣12
Q1-2 – W1-2 = (𝑈𝑚2 + + 𝑚𝑔𝑧2 ) − (𝑈𝑚1 + + 𝑚𝑔𝑧1 )
2 2

For unit mass of the system can be written as

𝑣22 𝑣12
q1-2– w1-2 = (𝑢2 + + 𝑔𝑧2 ) − (𝑢1 + + 𝑔𝑧1 )
2 2
𝑣22 −𝑣12
q1-2– w1-2 = (𝑢2 − 𝑢1 ) + + 𝑔(𝑧2 − 𝑧1 ) (For closed system)
2

2.6.5 Perpetual Motion Machine of the first kind: An imaginary device which delivers work
continuously without absorbing energy from the surroundings is called a Perpetual Motion
machine of the first kind. Since the device has to deliver work continuously, it has to operate on
a cycle. If such a device does not absorb energy from its surroundings ∫dQ =0. From the first law,
it can be observed that ∫dW =0, if ∫ dQ = 0. Therefore such a device is impossible from first law
of thermodynamics.

2.7 pdV work and its evaluation for different thermodynamic processes: Work is an
interaction between the system and its surroundings and it is done by a system if the sole effect,
external to the boundaries of the system could be the raising of a weight or mass.
In a piston cylinder assembly the expansion of the gas gets reduces to rising of a mass against
gravitational force by manipulating the surroundings external to the system as shown in Figure
2.5.

9
𝑊 = ∫ 𝐹. 𝑑𝐿 = ∫ 𝑃𝐴. 𝑑𝐿

𝑊 = ∫ 𝑃. 𝑑𝑉 (𝑑𝑣 = 𝑑𝑖𝑓𝑓𝑒𝑟𝑒𝑛𝑡𝑖𝑎𝑙 𝑣𝑜𝑙𝑢𝑚𝑒)

where is A. dL = dV (W = Total work done) Pdv = displacement

The work done by the system = Force × distance moved
Force of the system = Pressure of gas × area of the piston
When the piston moves out from position 1 to position 2 with the volume changing from V1 to
V2, the amount of work ‘W’ done by the system will be
𝑉2
𝑊1−2 = ∫ 𝑃. 𝑑𝑉
𝑉1

Note: Work refers to the energy transferred (without transfer of mass and with the help of
mechanism) because of a property difference, other than temperature, that exists between the
system and its surroundings.

Bracket

Pulley
Piston
Gas

V2 V1 System

Mass
Figure 2.5

2.8 Study flow energy equation (SFEE): Fluid enters the control volume at section1with
velocity V1, pressure p1, specific volume v1, internal energy u1 and mass m1. Corresponding
values at the exit section2 are V2, p2, v2, u2, m2. Further during the fluid flow between the two
sections, heat q and mechanical work w may also cross the boundary of the control surface.
Study flow equation is shown in Figure 2.6.

10
 𝑚𝑉12 𝑚𝑉22
𝑄1−2 + (𝑢1 + 𝑃1 𝑣1 + + 𝑚𝑔𝑧1 ) = 𝑊1−2 + (𝑢2 + 𝑃2 𝑣2 + + 𝑚𝑔𝑧2 )
2 2

𝑉12 𝑉22
𝑄1−2 + 𝑚 (𝑢1 + 𝑃1 𝑣1 + + 𝑔𝑧1 ) = 𝑊1−2 + 𝑚(𝑢2 + 𝑃2 𝑣2 + + 𝑔𝑧2 )
2 2

We know that ℎ = 𝑢 + 𝑝𝑣
𝑉12 𝑉22
𝑄1−2 + 𝑚 (ℎ1 + + 𝑔𝑧1 ) = 𝑊1−2 + 𝑚(ℎ2 + + 𝑔𝑧2 )
2 2
𝑉22 𝑉12
𝑄1−2 −𝑊1−2 = 𝑚 (ℎ2 + + 𝑔𝑧2 ) − 𝑚 (ℎ1 + + 𝑔𝑧1 ) 𝑻𝒉𝒊𝒔 𝒆𝒒𝒖𝒂𝒕𝒊𝒐𝒏 𝒊𝒔 𝒌𝒘𝒐𝒏 𝒂𝒔 𝑺𝑭𝑬𝑬
2 2
The study flow energy equation can be written on the basis of unit mass
𝑉22 𝑉12
𝑞1−2 −𝑤1−2 = (ℎ2 + + 𝑔𝑧2 ) − (ℎ1 + + 𝑔𝑧1 )
2 2
𝑉22 − 𝑉12
𝑞1−2 −𝑤1−2 = (ℎ2 − ℎ1 ) ( ) + 𝑔(𝑧2 + 𝑧1 ) (𝑺𝑭𝑬𝑬)
2

Control surface
1

Steady Flow Plant W

Z1
Arbitrary Q 2
datum line
Z2

Figure 2.6 Study flow energy equation

2.8.1 Engineering applications study flow energy equation: The application of steady flow
energy equation can be used to study the performance of many engineering devices that undergo
thermodynamic processes, as these devices closely satisfy the conditions for steady flow
processes. For example: The engineering devices like boiler, turbine, condenser/heat exchanger,
feed water pump, cooling tower and stack of steam power plants run nonstop for many months
before these are shut for maintenance. Therefore these engineering devices must run under

11
steady state conditions and can be analyzed as steady flow devices by applying steady flow
energy equation.

2.9 Free expansion: Free expansion is an irreversible process in which a gas expands into an
insulated evacuated chamber. It is also called Joule expansion. Real gases experience a
temperature change during free expansion. For an ideal gas, the temperature doesn't change, and
the conditions before and after adiabatic free expansion satisfy as shown in Figure 2.7.
Consider two vessels 1 and 2 interconnected by a short pipe with a valve A and perfectly
thermally insulated. Initially let the vessel 1 filled with a fluid at certain pressure and let 2 be
completely evacuated (vacuum). When the value A is opened the fluid in 1 will expand rapidly
to fill both vessels 1 and 2. The pressure finally will be lower than the initial pressure in vessel 1.
This is known as free expansion. This process is highly irreversible.
Now applying First law of thermodynamics

𝑄 = (𝑢2 − 𝑢1 ) + 𝑊

In this process no work is done W=0

The system is isolated, so no heat is transferred

Q=0

The process is therefore, Adiabatic but irreversible

𝑢2 − 𝑢1 = 0

[𝑢2 = 𝑢1 ] {In a free expansion the internal energy initially equals the initial energy finally}

𝐶𝑉 𝑇1 = 𝐶𝑉 𝑇2

𝑇1 = 𝑇2

Vessel 1 Vessel 2

Figure 2.7 Free expansion

12
For a perfect gas undergoing a free expansion, the initial temperature is equal to the final
temperature.
2.9 Throttling processes: Throttling is the expansion of fluid from high pressure to low
pressure. This process occurs when fluid passes through an obstruction (partially opened valve or
small orifice) placed in the fluid flow passage. Throttling process is used for finding the dryness
fraction of wet steam.
From SFEE

𝑉12 𝑑𝑄 𝑉22 𝑑𝑤
ℎ1 + + 𝑍1 𝑔 + = ℎ2 + + 𝑍2 𝑔 + 𝑥
2 𝑑𝑚 2 𝑑𝑚
𝑑𝑄
=0
𝑑𝑚
𝑑𝑤𝑥
=0
𝑑𝑚

Changes of P.E are very small and ignored. Thus the SFEE reduces to
𝑉12 𝑉22
ℎ1 + = ℎ2 +
2 2
Pipe velocity in throttling is very low. So the K.E is also negligible
ℎ1 = ℎ2
Enthalpy of the fluid before throttling is equal to the entropy of fluid after throttling.
 Throttling is the expansion of fluid from high pressure to low pressure.
 This process occurs when fluid passes through an abstraction ( partially opened value or a
small orifice)
 The enthalpy of the fluid before throttling is equal to the enthalpy of the fluid after
throttling ℎ1 = ℎ2
 The pressure drop is realized without a work or heat interaction. W=0 Q=0
 No change in P.E.
 The purpose of throttling process involves change in the phase of the fluid.
Used:
 Used for finding the dryness fraction of wet steam
 The flow through the expansion valve of a vapour compression refrigeration system.

13
 Unit – 3
Second Law of Thermodynamic and Its Necessity
3.1 Limitation of first law of thermodynamics: It has been observed that energy can flow from
a system in the form of heat or work. The first law of thermodynamics sets no limit to the
amount of the total energy of the system which can be caused to flow as work. A limit is
imposed however, as a result of the principle enunciated in the second law of thermodynamics
which states that heat will flow naturally from one energy reservoir at a high temperature to
another at a lower temperature, but not in the opposite direction, without assistance.
The first law of thermodynamics establishes equivalence between the quantity of heat used and
the mechanical work but does not specify the conditions under which conversion of heat into
work is possible, neither the direction in which heat transfer can take place. This gap has been
bridged by second law of thermodynamics.
 No distinction between heat and work.
 No provision for quantifying the quality of heat.
 No accountability for the work lost in the process.
 No information about the optimal conversion of energy.
3.2 Heat engine: It is a device that converts part of heat into mechanical work and remaining
heat reject to a sink. Or work can be converted to heat directly and completely, but converting
heat to work requires the use of some special devices. These devices are called heat engines.
A heat engine is a thermodynamic device used for continuous production of work from heat.
Both heat and work interactions take place across the boundary of this device. A heat engine is
characterized by the following futures:
 Reception of heat Q1 from a high temperature source at temperature T1.
 Partial conversion of heat received to mechanical work W.
 Rejection of remaining heat Q2 to a low temperature sink at temperature T2.
 They receive heat from a high temperature source (solar energy, oil furnace, nuclear
reactor).
 They convert part of this heat to work (usually in the form of a rotating shaft).
 They reject the remaining waste heat to a low temperature sink (the atmosphere, rivers
etc.).

14
  They operate on a cycle.
Heat engines and other cyclic devices usually involve a fluid to and from which heat is
transferred while undergoing a cycle. This fluid is called the working fluid. The term heat engine
is often used in work producing devices that do not operate into thermodynamic cycle.
𝑄𝑖𝑛 = 𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 ℎ𝑒𝑎𝑡 𝑠𝑢𝑝𝑝𝑙𝑖𝑒𝑑 𝑡𝑜 𝑠𝑡𝑒𝑎𝑚 𝑖𝑛 𝑏𝑜𝑖𝑙𝑒𝑟 𝑓𝑟𝑜𝑚 ℎ𝑖𝑔ℎ 𝑡𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒 𝑠𝑜𝑢𝑟𝑐𝑒 (𝑓𝑢𝑟𝑛𝑎𝑐𝑒)
𝑄𝑜𝑢𝑡
= 𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 ℎ𝑒𝑎𝑡 𝑟𝑒𝑗𝑒𝑐𝑡𝑒𝑑 𝑓𝑟𝑜𝑚 𝑠𝑡𝑒𝑎𝑚 𝑖𝑛 𝑐𝑜𝑛𝑑𝑒𝑛𝑠𝑒𝑟 𝑡𝑜 𝑙𝑜𝑤 𝑡𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒 𝑠𝑖𝑛𝑘 (𝑡ℎ𝑒 𝑎𝑡𝑚𝑜𝑠𝑝ℎ𝑒𝑟𝑒, 𝑟𝑖𝑣𝑒𝑟)
𝑊𝑖𝑛 = 𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑤𝑜𝑟𝑘 𝑟𝑒𝑞𝑢𝑖𝑟𝑒𝑑 𝑡𝑜 𝑐𝑜𝑚𝑝𝑟𝑒𝑠𝑠 𝑤𝑎𝑡𝑒𝑟 𝑡𝑜 𝑏𝑜𝑖𝑙𝑒𝑟 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒

𝑊𝑜𝑢𝑡 = 𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑤𝑜𝑟𝑘 𝑑𝑒𝑙𝑖𝑣𝑒𝑟𝑒𝑑 𝑏𝑦 𝑠𝑡𝑒𝑎𝑚 𝑎𝑠 𝑖𝑡 𝑒𝑥𝑝𝑎𝑛𝑑𝑠 𝑖𝑛 𝑡𝑢𝑟𝑏𝑛𝑒

𝑊𝑛𝑒𝑡,𝑜𝑢𝑡 = 𝑊𝑜𝑢𝑡 − 𝑊𝑖𝑛 (kJ)
The performance of H.E is given by net work output to the heat supplied to the working medium
and this ratio is called thermal efficiency.
𝑁𝑒𝑡 𝑤𝑜𝑟𝑘 𝑜𝑢𝑡𝑝𝑢𝑡 𝑊
𝜂𝑡ℎ = =
𝑇𝑜𝑡𝑎𝑙 ℎ𝑒𝑎𝑡 𝑠𝑢𝑝𝑝𝑙𝑖𝑒𝑑 𝑄1
Applying to First law 𝑊 = 𝑄1 − 𝑄2
𝑄1 − 𝑄2 𝑄2
𝜂𝑡ℎ = =1−
𝑄1 𝑄1
Source, T1

Q1

H.E W

Q2

Sink, T2

Figure 3.1 Heat engine

15
3.2.1 Thermal reservoirs: It is defined a large body (system) of infinite heat capacity, which is
capable of absorbing or rejecting an unlimited quantity of heat without suffering appreciable
changes in its thermodynamic coordinates as shown in Figure 3.1.
3.2.1.1 Source: The thermal energy reservoir high temperature (Source) from which heat Q1 is
transferred to the system operating in a heat engine cycle is called source.
3.2.1.1 Sink: The thermal energy reservoir lower temperature (Sink) to which heat Q2 is rejected
from the system during a cycle is called sink.
Example: A typical source is a constant temperature furnace where fuel is continuously burnt
and a typical sink is a river or sea or the atmosphere itself.
3.3 Second law of thermodynamics: The first law of thermodynamics gives no information
about direction; it merely states that when one form of energy is converted to another, the
quantities of energy involved are conserved regardless of feasibility of the process.
The second law of thermodynamics establishes the difference in the quality of different forms of
energy and explains why some processes can occur while other cannot. The second law of
thermodynamics has been confirmed experimentally. The second law of thermodynamics defines
the fundamental quality entropy as a randomized energy state unavailable for direct conversion
to work. It also states that all spontaneous processes, both physical and chemical proceed to
maximize entropy i.e. to become more randomized and convert energy to a less available form.
 Distinguish between quantity and quality
 Provides information of direction in which process occurs
 Heat flows from upper to lower
 It clearly identified and quantified the sources of losses in the system and answer why
actual operational performance of the system differ from design one
 It deals with quality and do not conserved
 Conformed experimentally
 Also state that the process both physical and chemical proceed to maximized entropy to
became more randomized and convert it to energy
There are two classical statements of the second law, known as the Kelvin-Planck statement and
Clausius statement.

16
3.3.1 Kelvin-Planck statement
 In ideal conditions, a heat engine must reject some heat to a low temperature reservoir in
order to complete the cycle
 That is, no heat engine can convert all the heat it receives to useful work
 This limitation on the thermal efficiency of heat engines forms the basis for Kelvin –
Planck statement of second law of thermodynamics, which is expressed as follows:
“It is impossible to construct a device that will operates in a cycle and produces no effect
other than rising of a weight and exchange of heat with a single reservoir”
That is, heat engine must exchange heat with a low temperature sink as well as a high
temperature source to keep operating.
𝑊𝑛𝑒𝑡 𝑄𝐿
η= = 1−
𝑄𝐻 𝑄𝐻

In effect, it states that it is impossible to construct a heat engine that operates in a cyclic process,
receives a given amount of heat from a high temperature body, and does an equal amount of
work. The only alternatives are that some heat must be transferred from the working fluid at a
lower temperature to a low temperature body. This implies that it is impossible to build a heat
engine that has a thermal efficiency of 100% as show in Figure 3.2. From the above statement
we concludes that:
 Kelvin – Planck statement can also be expressed as no heat engine can have a thermal
efficiency of 100% or as for a power plant to operate, the working fluid must exchange
heat with environment as well as the furnace
 Impossibility of having a 100% efficient heat engine is not due to friction
 It is a limitation that applies to both the idealized and actual heat engine
 It may however be noted that first law of thermodynamics does not put any restriction as
to the fraction of heat drawn from a heat source for its conversion into work, so such an
engine will, of course not violate first law of thermodynamics.

17
 Figure 3.2 Kelvin-Planck statement
3.3.2 The Clausius statement
Clausius statement is related to refrigerators or heat pumps. The clausius statement is expressed
as follows:
“It is impossible to construct a device that operates in a cycle and produces no effect other
than the transfer of heat from a cooler body to a hotter body or (transfer of heat from a
lower temperature body to a higher temperature body)”
OR
Heat cannot flow of itself from a body at lower temperature to a body at higher temperature
without expenditure of external mechanical work as shown in Figure 3.3.
In this effect, it states that it is impossible to construct a refrigerator that operates without an
input of work. This is also implies that the COP is always less than infinity.
 It is common knowledge that heat does not, of its own violation, transfer from a cold
medium to wormer one.
 The Clausius statement does not imply (to make suggestion) that a cyclic device that
transfer heat from a cold medium to a wormer one is impossible to construct
 It simply states that a refrigerator cannot operate unless its compressor is driven by an
external power source, such as electric motor
 This way, the net effect on the surroundings involves the consumption of some energy in
the form of work, in addition to the transfer of heat from a colder body to warmer one.
 Therefore, a house hold refrigerator is in complete compliance with the Clausius
statement of second law of thermodynamics.

18
 Figure 3.3 Clausius statement
Note: Both Kelvin – Planck and Clausius statements of second law of thermodynamics are
negative statement and a negative statement cannot be proved.
3.3.3 Equivalence of Kelvin-Planck and Clausius statements
Though the two statements appear to be different, but they are equivalent, they mean the same
thing. This is verified as follows:
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 device 1, which absorbs energy Q1 as heat from a thermal
reservoir at TH. Equivalent amount of work W (W=Q1) is performed.
Consider another device 2 operating as a cycle, which absorbs energy Q L 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 TL to a high temperature reservoir at TH
without receiving any aid from an external agent, which is the violation of the Clausius
statement.

19
Likewise let us assume that the Clausius statement is incorrect. So we have a device 1, cyclically
working transferring heat Q from a low temperature reservoir at TL to a high temperature
thermal reservoir at TH . Consider another device 2, 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 TL as shown in Figure 3.4.
If the two devices are combined (shown in figure 3.4 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.

Figure 3.4 Equivalence of Kelvin-Planck and Clausius statements

20
3.3.4 Combined first & second law of thermodynamics equation
According to First Law of a system:
𝛿𝑄 − 𝛿𝑊 = 𝑑𝐸
If kinetic energy & potential energy will be zero. Then
𝛿𝑄 − 𝛿𝑊 = 𝑑𝑢 (1)
According to Second law of thermodynamics for a system
𝛿𝑄
𝑑𝑠 = 𝑇

𝛿𝑄 = 𝑇𝑑𝑠 (2)
Substitute the value of𝛿𝑄 in equation (1) we get
𝑇𝑑𝑠 − 𝛿𝑊 = 𝑑𝑢
For unit mass of a system can be written as
𝑇𝑑𝑠 = 𝛿𝑊 + 𝑑𝑢 (3)
We know that
𝛿𝑊 = 𝑑𝑢 + 𝑝𝑑𝑣 (Put in equation 3)
𝑇𝑑𝑠 = 𝑑𝑢 + 𝑝𝑑𝑣 (4)
Equation (4) for reversible process
We also know that enthalpy is equal to
ℎ = 𝑢 + 𝑝𝑣 (5)
Differentiate the above equation we get
𝑑ℎ = 𝑑𝑢 + 𝑝𝑑𝑣 + 𝑣𝑑𝑝
𝑑ℎ = 𝑇𝑑𝑠 + 𝑣𝑑𝑝
or
𝑇𝑑𝑠 = 𝑑ℎ − 𝑣𝑑𝑝 (6)
The equation (4) & (6) is a combined first and Second law of thermodynamics
3.4 Refrigerator: It is a device which can maintain the space temperature lower than the
surroundings by rejecting heat from lower temperature space to higher temperature surrounding
at the cost of mechanical work.
When the main purpose of the machine is to remove heat from the cooled space, it is called a
refrigerator. A refrigerator operates between the temperature of the surrounding and temperature
below that of surrounding.

21
Typically the thermodynamic system in a refrigerator analysis will be a working fluid, a
refrigerant that circulates around a loop, as shown in Figure 3.5. The internal energy (and
temperature) of the refrigerant is alternately raised and lowered by the devices in the loop. The
working fluid is colder than the refrigerator air at one point and hotter than the surroundings at
another point. Thus heat will flow in the appropriate direction, as shown by the two arrows in the
heat exchangers.
Starting in the upper right hand corner of the diagram, we describe the process in more detail.
First the refrigerant passes through a small turbine or through an expansion valve. In these
devices, work is done by the refrigerant so its internal energy is lowered to a point where the
temperature of the refrigerant is lower than that of the air in the refrigerator. A heat exchanger is
used to transfer energy from the inside of the refrigerator to the cold refrigerant. This lowers the
internal energy of the inside and raises the internal energy of the refrigerant. Then a pump or
compressor is used to do work on the refrigerant, adding additional energy to it and thus further
raising its internal energy. Electrical energy is used to drive the pump or compressor. The
internal energy of the refrigerant is raised to a point where its temperature is hotter than the
temperature of the surroundings. The refrigerant is then passed through a heat exchanger (often
coils at the back of the refrigerator) so that energy is transferred from the refrigerant to the
surroundings. As a result, the internal energy of the refrigerant is reduced and the internal energy
of the surroundings is increased. It is at this point where the internal energy of the contents of the
refrigerator and the energy used to drive the compressor or pump are transferred to the
surroundings. The refrigerant then continues on to the turbine or expansion valve, repeating the
cycle.
The performance of a refrigerator is expressed in terms of COP which represents the ratio of
desired effect to work input
𝑑𝑒𝑠𝑖𝑟𝑒 𝑒𝑓𝑓𝑒𝑐𝑡
𝐶𝑂𝑃 =
𝑤𝑜𝑟𝑘 𝑖𝑛𝑝𝑢𝑡
In refrigerator, desire effect is the amount of heat interacted Q2 from the space being cooled i.e.
space at low temperature
𝑄2 𝑄2
𝐶𝑂𝑃𝑟𝑒𝑓. = =
𝑊 𝑄1 −𝑄2

Generally 𝐶𝑂𝑃𝑟𝑒𝑓. = (3 to 4)

22
 Figure 3.5 refrigerator
3.5 Refrigerating Machine: A refrigerating machine is a device which will be either cool or
maintain a body at a temperature below that of the surroundings. Hence heat must be made to
flow from a body of low temperature to the surrounding at high temperature.
The following refrigerating systems are used in refrigerating engineering: vapour compression,
absorption, steam jet, and air cycle.
3.5.1Vapour compression Cycle

QK

Condenser

Throttle
Valve

Compressor

Evaporator

QE

Figure 3.6 Vapour compression cycle

23
1. Heat Qe absorbed in the evaporator by the evaporation of liquid refrigerant at a low pressure
(R22) and corresponding law saturated temperature T0.
2. To evaporated refrigerant vapour is compressed to high pressure Pk in the compressor,
consuming work W. The pressure after compression is such that the corresponding saturation
temperature Tk is higher than the temperature of the surrounding.
3. Heat Qk is then rejected in the condenser to the surrounding at high temperature Tk.
Consider that a room is maintained at constant temperature of 25 0C. In the Air – conditioner, the
air from the room is drawn by a fan and is made to pass over a cooling coil, the surface of which
is maintained say, at temperature of 10 0C. After passing over the coil, the air is cooled (for
example 15 0C) before being supplied to room. After pick up to the room heat, the air is again
return to the cooling coil at 25 0C. Now in the cooling coil, a liquid working substance called
refrigerant, enters at a temperature say 5 0C and evaporates, thus absorbing its latent heat of
vaporization from the room. This equipment in which the refrigerant evaporates is called
evaporator as shown in Figure3.6.
After evaporation, the refrigerant becomes vapour. To enable it to condense back and to release
the heat which absorbed from the room while passing through the evaporator its pressure is
raised by a compressor. Following this, the high pressure vapour enters the condenser. In
condenser, the outside atmospheric air, say 45 0C in summer is circulated by a fan. After picking
up the latent heat of condensation from the condensing refrigerant, the air is let out into the
environment at 55 0C.
Unit of refrigerating capacity
Standard unit of refrigeration is Ton refrigeration (1TR)
1 TR = 50 Kcal/min
1 TR = 3.5167 Kw
3.5.2 Absorption refrigeration system
Another form of refrigeration that becomes economically attractive when there is a source of in
expensive thermal energy at a temperature of 100 to 200 0C is absorption refrigeration. Some
examples of inexpensive thermal energy sources includes geothermal energy, solar energy and
waste heat from cogeneration or process steam plants and even natural gas when it is available at
a relatively low price.

24
As the name implies absorption refrigeration system (ARS) involves the absorption of refrigerant
by transport medium. The most widely used ARS is the ammonia – water system. Where,
ammonia (NH3) serves as a refrigerant and water (H2O) as a transport medium. Other ARS
include water – lithium bromide and water – lithium chloride system, where water serves as
refrigerant. The latter two systems are limited to applications such as air – conditioning where
the minimum temperature is above the freezing point of water. To understand the basic
principles involved in AR, we examine the NH3 – H2O system. The ammonia – water
refrigeration machine was patented by Frenchman Ferdinand Carre in 1859. This system looks
like the vapour compression system, except that the compressor has been replaced by a complex
absorption mechanism consisting of an absorber, a pump, a generator, a regenerator, a valve and
a rectifier. Once the pressure of NH3 is raised by the components in the box, it is cooled and
condensed in the condenser by rejecting heat to the surroundings is throttled to the evaporator
pressure and absorbs heat from the refrigerated space as it flows through the evaporator.
Ammonia vapour leaves the evaporator and enters the absorber, where it dissolves and reacts
with water to form NH3 – H2O. This is an exothermic reaction, thus heat is released during this
process. The amount of NH3 that can be dissolved in H2O is inversely proportional to the
temperature. Therefore, it is necessary to cool the absorber to maintain its temperature as low as
possible, have to maximize the amount of NH3 dissolved in water. The liquid NH3 + H2O
solution, which is rich in NH3, is then pumped to the generator. Heat is transferred to the solution
from source to vaporize some of the solution. The vapour, which is rich in NH3, passes through a
rectifier which separates the water and returns it to the generator. The high pressure pure Nh3
vapour then continues its journey through rest of the cycle. The hot NH3 + H2O solution, which
is weak in Nh3, then passes through a regenerator, where it transfer some heat to the rich
solution living the pumped is throttled to the absorber pressure. Compared with VCS, ARS have
one major advantage:
 A liquid is compressed instead of a vapour
The steady flow work is proportional to the specific volume and thus the work input for ARS is
very small (on the order of one percent of the heat supplied to generator) and often neglected in
the cycle analysis. The operation of these systems is based on heat transfer from external source.
Therefore, ARS are often classification as heat driven system as shown in Figure 3.7.

25
 Figure 3.7 Absorption refrigeration system

3.6 Heat pump: It is a device which can maintain the temperature above then the surrounding by
supplying heat from low temperature surroundings to high temperature space at the cost of
mechanical work.
If the objective is to reject energy as heat to a high temperature body (space heating in winter) it
is called as heat pump and the atmosphere acts as high temperature reservoir.
A simple heat pump has four basic components: (1) condenser, (2) expansion valve, (3)
evaporator, and (4) compressor as shown in Figure 3.8. In the heating mode, heat transfer occurs
to the working fluid in the evaporator (3) from the colder outdoor air, turning it into a gas. The
electrically driven compressor (4) increases the temperature and pressure of the gas and forces it
into the condenser coils (1) inside the heated space. Because the temperature of the gas is higher
than the temperature in the room, heat transfer from the gas to the room occurs as the gas
condenses to a liquid. The working fluid is then cooled as it flows back through an expansion
valve (2) to the outdoor evaporator coils.
 Another device that transfers heat from a low temperature medium to a high temperature
one is the heat pump.
 The objective of a heat pump is to maintain a heated space at a high temperature.

26
  This is accomplished by absorbing heat from a lower temperature source such as well
water or cold outside air in winter and supplies this heat to the high temperature medium
such as house.
𝐷𝑒𝑠𝑖𝑟𝑒𝑑 𝑜𝑢𝑡𝑝𝑢𝑡
 𝐶𝑂𝑃𝐻𝑃 =
𝑅𝑒𝑞𝑢𝑖𝑟𝑒𝑑 𝑖𝑛𝑝𝑢𝑡

𝑄𝐻 𝑄𝐻 1
 𝐶𝑂𝑃𝐻𝑃 = = = 𝑄
𝑊𝑛𝑒𝑡,𝑖𝑛 𝑄𝐻 −𝑄𝐿 1− 𝐿
𝑄𝐻

Worm Indoor
20 0C

Wnet, in

Cold outdoor at 4 0C

Figure 3.8 Heat pump

3.6.1 Application of heat pump

 Describe the use of heat engines in heat pumps and refrigerators

 Demonstrate how a heat pump works to warm an interior space
 Explain the differences between heat pumps and refrigerators
 Calculate a heat pump’s coefficient of performance
3.7 Carnot Cycle: The Carnot Cycle has the highest possible efficiency, which works on
reversible cycle. This cycle was suggested by the French engineer Sadi Carnot in 1824. Any

27
fluid may be used to operate the Carnot cycle, which performed in a cylinder as shown in Figure
3.9.

Heat source at
T1 Piston

Cylinder

Heat sink at T2

Figure 3.9 Carnot Cycle

Heat is caused to flow into the cylinder by the application of heat from a higher energy source to
the cylinder during expansion and to flow from the cylinder by the application of a low
temperature energy source to the head during compression.
The cycle consists of the following four successive processes.
I. Isothermal expansion
II. Adiabatic expansion
III. Isothermal compression
IV. Adiabatic compression
Stage1: (Process1-2) Hot energy source is applied. Heat Q1 is taken in and the fluid expands
isothermally and reversibly at constant temperature T1.
Stage2: (Process2-3) The cylinder became a perfect insulator so that no heat flow take place.
The fluid expands adiabatically and reversibly whilst temperature falls from T1 to T2. Therefore,
the process is an isentropic.
Stage3: (Process3-4) Cold energy source (Sink) is applied. Heat Q2 flow from the fluid and it is
compressed isothermally and reversibly at a constant lower temperature T2.
Stage3: (Process 4-1) The cylinder head became a perfect insulator so that no heat flow occurs.
The compression is continued adiabatically and reversibly during which temperature is raised
from T1 to T2.
The work delivered by the system during the cycle is represented by the enclosed area of the
cycle. Again for a closed cycle, according to the first law of thermodynamics the work obtained

28
is equal to the difference between heat Q1 supplied by the source and the heat Q2 rejected to the
sink.
According to law of conservation of energy
Heat supplied = Work done + Heat rejected
Work done = Heat supplied – Heat rejected
𝑊 = 𝑄1 − 𝑄2
𝑊𝑜𝑟𝑘 𝑜𝑢𝑡𝑝𝑢𝑡 𝑄1 −𝑄2 𝑇1
Thermal efficiency 𝜂𝑡ℎ = = =1−
𝐻𝑒𝑎𝑡 𝑠𝑢𝑝𝑝𝑙𝑖𝑒𝑑 𝑏𝑦 𝑡ℎ𝑒 𝑠𝑜𝑢𝑟𝑐𝑒 𝑄1 𝑇2

Note: The four processes are physically very different from each other and thus they each
require particular equipment as shown in Figure below:

1
Heat in
2

P
4
3
Heat out

V
 1-2: Heat supply (Isothermal expansion process) Boiler
 2-3: Work output obtained (Adiabatic expansion process) Turbine
 3-4: Vapour is condensed (Isothermal compression process) Condenser
 4-1: Pressure of wet vapour raised (Adiabatic compression process)Pump or compressor
2.8 Carnot theorem:
Carnot theorem states that no heat engine working in a cycle between two constant temperature
reservoirs can be more efficient than a reversible engine working between the same reservoirs. In
other words it means that all the engines operating between a given constant temperature source
and a given constant temperature sink, none, has a higher efficiency than a reversible engine as
shown in Figure 3.10.

29
Carnot's theorem, developed in 1824 by Nicolas Léonard Sadi Carnot, also called Carnot's rule,
is a principle that specifies limits on the maximum efficiency any heat engine can obtain. The
efficiency of a Carnot engine depends solely on the difference between the hot and
cold temperature reservoirs.
 Carnot theorem states that no heat engine working in a cycle between two constant
temperature reservoirs can be more efficient than a reversible engine working between
the same reservoirs.
 In other words it means that all the engines operating between a given constant
temperature source and a given constant temperature sink, none, has a higher efficiency
than a reversible engine.

Figure 3.10 Carnot theorem

2.9 Thermodynamic temperature scale:

To define a temperature scale that does not depend on the thermometric property of a substance,
Carnot principle can be used since the Carnot engine efficiency does not depend on the working
fluid. It depends on the temperatures of the reservoirs between which it operates as shown in
Figure 3.11.

30
 Figure 3.11 Thermodynamic temperature scale
Consider the operation of three reversible engines 1, 2 and 3. The engine 1 absorbs energy Q 1 as
heat from the reservoir at T1, does work W1 and rejects energy Q2 as heat to the reservoir at T2.
Let the engine 2 absorb energy Q2 as heat from the reservoir at T2 and does work W2 and rejects
energy Q3 as heat to the reservoir at T3.
The third reversible engine 3, absorbs energy Q1as heat from the reservoir at T1, does work
W3 and rejects energy Q3 as heat to the reservoir at T3.
h1 = W1 / Q1 = 1- Q2/Q1 = f(T1,T2)
or, Q1/Q2 = F(T1,T2)
h2 = 1- Q3/Q2 = f(T2,T3)
or, T2/T3 = F(T2,T3)
h3 = 1- Q3/Q1 = f(T1,T3)
T1/T3 = F(T1,T3)
Then , Q1/Q2 = (Q1/Q3)/(Q2/Q3)
Or, F(T1,T2) = F(T1,T3) /F(T2,T3)

31
Since T3 does not appear on the left side, on the RHS also T3 should cancel out. This is possible
if the function F can be written as
F (T1, T2) = f (T1) y (T2)
f (T1) y (T2) = {f(T1) y (T3)} / {f(T2) y (T3)}
Therefore, y (T2) = 1 / f(T2)
Hence, Q1 / Q2 = F (T1,T2) = f(T1)/ f(T2)
Now, there are several functional relations that will satisfy this equation. For the thermodynamic
scale of temperature, Kelvin selected the relation
Q1/Q2 = T1/T2
That is, the ratio of energy absorbed to the energy rejected as heat by a reversible engine is equal
to the ratio of the temperatures of the source and the sink.
The equation can be used to determine the temperature of any reservoir by operating a reversible
engine between that reservoir and another easily reproducible reservoir and by measuring
efficiency (heat interactions). The temperature of easily reproducible thermal reservoir can be
arbitrarily assigned a numerical value (the reproducible reservoir can be at triple point of water
and the temperature value assigned 273.16 K).
The efficiency of a Carnot engine operating between two thermal reservoirs the temperatures of
which are measured on the thermodynamic temperature scale, is given by
h1 = 1- Q2/Q1 = 1 T2/T1
The efficiency of a Carnot engine, using an ideal gas as the working medium and the temperature
measured on the ideal gas temperature scale is also given by a similar expression.
SOLVED EXAMPLES
Example 3.1 An engine inventor claims to have developed an engine that takes in 140 MJ at a
temperature of 405 K and rejects 45 MJ at a temperature of 205 K while producing 20 KWh of
mechanical work. Find if the claim of inventor is true or false.
Solution: Q1 = J 40 MJ, Q2 = 45 MJ, W = 20 KWh
W = 20 KWh= 20x 3600 KJ = 72 MJ.
W + Q2 = (72 + 45) MJ = 117 MJ
Q1 = 140MJ
Thus Q1 = W + Q2 àViolating 1st law of thermodynamics (energy not conserved)
(Th) max = 1 – T2 / T1 = 1 – 205 / 405 = 0.49

32
( Th) claimed = W / Q1 = 72 / 140 = 0.51
Thus (Th)claimed > (Th)max à It violates the 2nd law also.
Thus the claim is false.
Example 3.2 If a refrigerator is sued for heating purposes in winter so that the atmosphere
becomes the cold body and the room to be heated becomes the hot body, how much heat would
be available for heating for every 1.5 KW input to the driving motor? The COP of the
refrigerator is 6, and the electromechanical efficiency of the motor is 80%.
Solution:
Here motor efficiency= 0.8
Motor output / input = 0.8
Motor output / 1.5 = 0.8

Motor output= 0.8 x 1.5 KW = W to Refrigerator

COP net = Q2 / W
6 = Q2 / 0.8 x 1.5 or Q2 = 7.2 KW
Q1 = W + Q2 = 0.8 x 1.5 + 7.2 = 8.4 kw
Heat available = 8.4 kw.
Example 3.3 An electric storage battery which can exchange heat only with a constant
temperature atmosphere goes through a complete cycle of two processes. In process 1-2, 2.8
KWh of electrical work flow into the battery while 732 KJ of heat flow out to the atmosphere.
During process 2 – 1, 2.4 KWh of work flow out of the batten;. (a) Find the heat transfer in
process 2 – 1 (b) What is the maximum possible work of 2 – 1 process if 1 – 2 process has

33
occurred as above? (c) What will be the heat transfer in the condition of maximum possible work
output in process 2 – 1?
Solution: For process 1 – 2
Q1-2= U2-U1 + Wl-2
– 732 = u 2 – U1 – 2.8 x 36oo
U2 – U; = 9348 KJ
For process 2 – 1
Q2-1 = ul – U2 + w2-1 = – 9348 + 2.4 X 3600 = – 708 KJ Ans. (a)
(Negative sign shows that heat flow out of the system)
Q2-1 = U1 – U2 + w2-l
For maximum work Q2-1 = 0
W2-1) max = U2-U1 = 9348KJ. Ans. (b)
Q2-1 = 0 for maximum work. Ans. (c)

34
 Unit – 4
Entropy and principle of entropy growth

4.1 Entropy

In this chapter we introduce, a new thermodynamic property “entropy” that is simply a measure
of the amount of molecular disorder within a system. In this regard, a system possessing a high
degree of molecular disorder (such as high temperature gas) has a very high entropy value.
Entropy is the most used and often abused concept in science, but also in philosophy and society.
Further confusions are produced by some attempts to generalize entropy with similar, but not the
same concepts in other disciplines.
Definition: Entropy is defined as the degree of randomness of the system. The concept of
entropy in thermodynamics comes in 1850 after Rudolf Clausius a German physicist. Entropy is
defined as the measure of randomness or disorderness in thermodynamic system.
In statistical mechanics, entropy is an extensive property of a thermodynamic system. It is
closely related to the number Ω of microscopic configurations that are consistent with the
macroscopic quantities that characterize the system.
4.1.1 Physical concept of entropy
The physical meaning of phenomenological, thermodynamic entropy is reasoned and elaborated
by generalizing Clausius definition with inclusion of generated heat, since it is irrelevant if
entropy is changed due to reversible heat transfer or irreversible heat generation. Irreversible,
caloric heat transfer is introduced as complementing reversible heat transfer. It is also reasoned
and thus proven why entropy cannot be destroyed but is always generated (and thus overall
increased) locally and globally, at every space and time scales, without any exception. It is
concluded that entropy is a thermal displacement (dynamic thermal-volume) of thermal energy
due to absolute temperature as a thermal potential (dQ = TdS), and thus associated with thermal
heat and absolute temperature, i.e., distribution of thermal energy within thermal micro-particles
in space.
Entropy is probably the most misunderstood of thermodynamic properties. While temperature
and pressure are easily measured and the volume of a system is obvious, entropy cannot be
observed directly and there are no entropy meters. What's the solution?

35
In Short
 Does it really make sense to describe entropy in terms of the disorder of a system?
 Entropy is dynamic - something which static scenes don't reflect
 The entropy of a system can be increased or decreased by energy transports across the
system boundary
 A system can only generate, not destroy, entropy
 It is low entropy sources that are being used up and low entropy energy is useful energy
Thermodynamics deals with the relation between that small part of the universe in which we are
interested the system and the rest of the universe the surroundings. Thermodynamic properties
depend on the current state of the system but not on its previous history and are either extensive
their values depend on the amount of substance comprising the system, eg volume - or intensive
their values are independent of the amount of substance making up the system, eg temperature
and pressure. Entropy is a thermodynamic property, like temperature, pressure and volume but,
unlike them, it cannot easily be visualized.
Heat is a form of energy. Entropy is a measure of the "disorganization" or "randomness" of the
universe. The way I like to explain entropy has to do with thinking about how molecules move.
If you have molecules in a solid, like ice for example, those molecules really aren't moving
around that much and they're very ordered in their structure. If you add energy to the ice (like, by
leaving it out on a hot day), the molecules in the ice begin to move more quickly and are less
ordered as the ice melts to water. If you boil water (which again adds energy to the molecules in
the water), then you end up with gas, and molecules in a gas are incredibly unorganized and
move very quickly. So, heat increases entropy because it adds energy to a system, which makes
the system more "disorganized" or "random".
The concept of entropy emerged from the mid19th century discussion of the efficiency of heat
engines. Generations of students struggled with Carnot's cycle and various types of expansion of
ideal and real gases, and never really understood why they were doing so.
 Entropy is not a measurement of order or disorder in a system, but a measurement of a
system's probability to change. A container of gasoline is very likely to change its state,
yet once someone has lit a match and burned the gasoline, you are left with products that
are less likely to change entropy has increased.

36
  Entropy the measure of a systems thermal energy per unit temperature, that is
unavailable for doing useful work. Because work is obtained from ordered molecular
motion, the amount of entropy is also a measure of the molecular disorder or randomness
of a system. For example: An object is kept at room temperature say 298 K and its
temperature is increased to 398 K by addition of heat. There is another object at 1000 K
and its temperature increased to 1100 k. in both the cases, heat addition will almost be
same, and so will be the enthalpy changes. But in first case there is a change of 25% and
in second one just 10%. So we required another term, which is entropy. In
thermodynamics, this ratio is called entropy.
 A system with maximum entropy wills never change. The second law of thermodynamics
states that entropy never decreases. That's just how our universe works. No known
chemical reaction, physical phenomena or biological event has ever made the universe’s
entropy do decrease.
 A thermodynamic quantity representing the amount of energy in a system that is no
longer available for doing mechanical work.
 All spontaneous processes are irreversible hence it has been said that entropy of the
universe is increasing that is more and more energy became unavailable for conversion
into work.
 The measure of a system thermal energy per unit temperature that is unavailable for
doing useful work. Because work is obtained from ordered molecular motion, the amount
of entropy is also measure of the molecular disorder or randomness of system.
 It is a property and depends on state and its concept comes from Second Law of
thermodynamics.
𝑑𝑄
𝑑𝑠 =
𝑇
Where ds = change in entropy
T= Temperature
Q= Heat Unit kJ/kg-K
Valid for reversible process

37
When a system undergoes a process then total quantity of energy of the system remains constant.
But the system might loose its quality of energy during the processes. This loss of quality of
energy is called is called entropy.
4.1.2 Temperature – entropy plot
When a system is taken, reversible from initial state 1 to final state 2, then
2
𝑄𝑟𝑒𝑣 = ∫ 𝑇𝑑𝑠
1

This implies that the area under a curve for a reversible process plotted on T – S coordinate
represents the quantity of heat interaction during the process as shown in Figure 4.1.

T T
1

𝛿𝑄 =Tds
2
Adiabatic
process
2
1

S S
S1 S2 S1 = S2

ds

Figure 4.1 Figure 4.2

 During a reversible adiabatic process, 𝜹𝑸 = 𝟎 and so S = constant. The reversible
adiabatic process is represented by a vertical (constant entropy) line on T – S diagram as
shown in Figure 4.2.
 During a reversible isothermal process, T = constant and therefore,
2
𝑄𝑟𝑒𝑣 = 𝑇 ∫1 𝑑𝑆 = (𝑆2 − 𝑆1 )
The reversible isothermal process is represented by a horizontal (constant temperature) line on T
– S diagram as shown in Figure 4.3.

38
 T T
Isothermal
process Q1
a b
1 2
S2
Q2

d c
S S
S1 S2 ds

Figure 4.3 Figure 4.4

 Carnot cycle consists of two reversible consists of two reversible isothermals and two
reversible adiabatics. Accordingly a Carnot cycle would plot as rectangle on T – S
diagram as shown in Figure 4.4.
Process a – b: Isothermal expansion at constant temperature T1 during which heat Q1 is supplied
to the system
Q1 = area under the process line a – b = T1dS
Process b – c: Adiabatic expansion during which work is done by the system
Process c – d: Isothermal compression at constant temperature T2 during which heat Q2 is
rejected by the system
Q2 = area under the process line c – d = T2dS
Process d – a: Adiabatic compression during which work is done on the system
Efficiency of Carnot cycle,
𝑤𝑜𝑟𝑘 𝑑𝑜𝑛𝑒 𝑝𝑒𝑟 𝑐𝑦𝑐𝑙𝑒 𝑄1 − 𝑄2 𝑇1 𝑑𝑆 − 𝑇2 𝑑𝑆 𝑇1 − 𝑇2
ƞ= = = =
ℎ𝑒𝑎𝑡 𝑠𝑢𝑝𝑝𝑙𝑖𝑒𝑑 𝑝𝑒𝑟 𝑐𝑦𝑐𝑙𝑒 𝑄1 𝑇1 𝑑𝑆 𝑇1
The area of the rectangle abcd represents the work output per cycle and it equals,
Q1 – Q2 = (T1 – T2) dS
4.1.3 Entropy generation: Entropy generation is a path function which comes to whenever a
system undergoes a thermodynamic process and entropy is generated due to irreversibility nature
of process.
𝑄1−2
𝑆1 + + 𝑆𝑔𝑒𝑛1−2 + 𝑆2
𝑇
𝑄1−2
𝑆𝑔𝑒𝑛1−2 = (𝑆2 − 𝑆1 ) −
𝑇

39
4.2 Concept of high and low grade energy: Based on the thermodynamic concepts, an energy
source can be called as high grade or low grade, depending on the ease with which it can be
converted into other forms. Thus electrical energy is called high grade energy, as it is very easy
to convert almost all of it into other energy forms such as thermal energy (say by using an
electrical heater). Whereas, it is not possible to convert thermal energy completely into electrical
energy (typical efficiencies of thermal power plants are around 30 percent), hence thermal
energy is called low grade energy. Naturally, high grade energy sources are more expensive
compared to low grade energy sources.
4.2.1 High grade energy: High grade energy is the energy that can be completely transformed
into mechanical work (shaft work) without any loss. Examples are:
 Mechanical work
 Tidal energy
 Electrical work
 Kinetic energy of jets
 Tidal energy
 Animal and manual energy
 Wind energy
Electrical and chemical energy are high grade energy, because the energy is concentrated in a
small space. Even a small amount of electrical and chemical energy can do a great amount of
work. The molecules or particles that store these forms of energy are highly ordered and compact
and thus considered as high grade energy. High-grade energy like electricity is better used for
4.2.2 Low grade energy: Low grade energy is the energy that cannot be completely converted
into mechanical work. For example:
 Thermal energy
 Nuclear energy
 Heat available from combustion of fuel, such as coal and wood
Heat is low grade energy. Heat can still be used to do work (example of a heater boiling water),
but it rapidly dissipates. The molecules in which this kind of energy is stored (air and water
molecules) are more randomly distributed than the molecules of carbon in a coal. This disordered
state of the molecules and the dissipated energy are classified as low grade energy.

40
4.3 Available and unavailable energy: Complete conversion of low grade energy into a high
energy is not possible. That parts of the low grade energy which is available for conversion into
work is called available energy or energy, and the rest is unattainable energy, called unavailable
energy or energy as shown in Figure 4.5. In otherworld’s we say that, the source of energy can
be divided into two groups i.e. high grade energy (mechanical work, electrical energy, water
power, wind power) and low grade energy (heat or thermal energy, heat derived from nuclear
fusion or combustion of fossil fuels). That part of the low grade energy which is available for
conversion is referred to as available energy, while the part which is not available is known as
unavailable energy.
It was Maxwell (1871) who first coined the term available energy however he credited Kelvin
with the original ideas.

Figure 4.5 Available and unavailable energy

4.4 Law of degradation of energy: The first law of thermodynamics says that the total quantity
of energy in the universe remains constant. This is the principle of the conservation of energy.
The second law of thermodynamics states that the quality of this energy is degraded irreversibly.
This is the principle of the degradation of energy.
In otherworld’s, the available energy of a system decreases as its temperature or pressure
decreases and approaches equilibrium to the surroundings. When the heat is transferred from a
system, its temperature decreases and hence the quality of its energy deteriorates. The
degradation is more for energy loss may be the same, but quality wise the losses are different.
While the first law states that energy is always conserved quantity wise, the second law
emphasizes that energy always degrades quality wise. When a gas is throttled adiabatically from
a high pressure region to low pressure region, the enthalpy (or energy per unit mass) remains
constant, but there is a degradation of energy or available work. The same holds good for

41
pressure drop due to friction of a fluid flowing through an insulated pipe. If the first law of
thermodynamics is the law of conservation of energy, the second law of thermodynamics is also
known as the law of degradation of energy.
 The available energy of a system depends on the pressure and temperature of the system.
When heat is transferred from a system to the surroundings, its temperature decrease and
hence the quality of the energy degradation. This degradation of energy is more when
heat is transferred at a high temperature then at a low temperature
 Quantum of energy loss may be the same, but quality wise the loss of available energy is
different
4.5 Useful work: The energy available for work transfer less the work absorbed in moving the
environmental is called the useful work or net work. In thermodynamics, work performed by a
system is the energy transferred by the system to its surroundings, which are fully accounted for
solely by macroscopic forces exerted on the system by factors external to it, that is to say, factors
in its surroundings. The rate at which work is performed is power.
For example: To calculate efficiency you simply need to divide the useful output work by the
input work. Then multiply the work output and work input by 100% to express efficiency in a
percentage. For example, a machine can do 765 J of work if 1000 J of work is put into it.
Whenever 'work' is done energy is transferred from one place to another. The amount of work
done is expressed in the equation: work done = force x distance. Power is a measure of how
quickly work is being done. Power is expressed in the equation: power = work done / time take

4.5.1 Dead state: In 1865, Rudolf Clausius formulated that: the energy of the universe remains
constant and its entropy tends to a maximum. Thus, because an increase in the entropy and

42
disorder is associated with a decreased ability to perform work, the universe will ultimately reach
a dead state.
Definition
When the system is in equilibrium with the surroundings, it must be in pressure and temperature
equilibrium with the surrounding. It must also be in chemical equilibrium with the surrounding
i.e. there should not be any chemical reaction or mass transfer. The system must have zero
velocity and minimum potential energy. This state of the system is known as the dead state.
In otherworld’s dead state means when a system comes under the complete thermodynamic
equilibrium with its reference environment. At that state exergy is zero. (Energy involved).
4.6 Availability
Useful work is available from a finite system as long as there exit positive pressure and
temperature differentials between the system and surrounding. And in that process the system
undergoes a change of state. The availability of a given system is defined as the maximum useful
work that can be obtained in a process in which the system comes to equilibrium with the
surroundings or attains the dead state.
The availability (A) of a given system is defined as the maximum useful work that is obtainable
in a process in which the system comes to equilibrium with its surrounding.
When a system is subjected to a process from its original state to the dead state the maximum
amount of useful work that can be achieved under ideal conditions is known as available or
availability of the system as shown in Figure 4.6.
 Yields the maximum work producing potential or the minimum work requirement of a
process
 Allows evaluation and quantitative comparison of options in a sustainability context

4.6.1 Flow process: It is one in which fluid enters the system and leaves it after work interaction,
which means that such processes occur in the systems having open boundary permitting mass
interaction across the system boundary.
4.6.2 Non flow process: It is the one in which there is no mass interaction across the system
boundaries during the occurrence of process. Different type of non flow process of perfect gas
are given: (1) constant volume process (2) constant pressure process (3) Isothermal process (4)
adiabatic process (5) polytropic process

43
4.6.3 Steady flow process: It is a process during which a fluid flows through a control volume
steadily. That is, the fluid properties can change from point to point within the control volume,
but at any fixed point they remain the same during the entire process.

Figure 4.6 shows the availability of the system

4.6.4 Exergy: Exergy is the useful work potential of the energy possessed by a body. Once the
exergy is wasted, it cannot be recovered. Exergy destroyed whereas energy is conserved.
4.7 Second law efficiency
A common measure on energy use efficiency is the first law efficiency ƞI.
The first law efficiency is defined as the ratio of the output energy of a device to the input energy
of the device
𝑂𝑢𝑡𝑝𝑢𝑡 𝑊𝐺𝑇 + 𝑊𝑆𝑇 − 𝑊𝐶 − 𝑊𝑃
ƞ𝐼 = =
𝐼𝑛𝑝𝑢𝑡 𝑚. 𝑓. 𝐿. 𝐻. 𝑉
LIMITATION: First law concerned only with the quantities of energy & disregards the forms in
which the energy exits.
On the other hand, second law of thermodynamics which provides a means of assigning a
quantity index to energy.
The second law efficiency ƞII of a process is defined as the ratio of the minimum available energy
(or exergy) which must be consumed to do a task divided by the actual amount of available
energy (or exergy) consumed in performing the task.

44
 𝑚𝑖𝑛𝑖𝑚𝑢𝑚 𝑒𝑥𝑒𝑟𝑔𝑦 𝑖𝑛𝑡𝑎𝑘𝑒 𝑡𝑜 𝑝𝑒𝑟𝑓𝑜𝑟𝑚 𝑡ℎ𝑒 𝑔𝑖𝑣𝑒𝑛 𝑡𝑎𝑠𝑘 𝐸𝑥𝑒𝑟𝑔𝑦 𝑜𝑢𝑡𝑝𝑢𝑡
ƞ𝐼𝐼 = =
𝑎𝑐𝑡𝑢𝑎𝑙 𝑒𝑥𝑒𝑟𝑔𝑦 𝑖𝑛𝑡𝑎𝑘𝑒 𝑡𝑜 𝑝𝑒𝑟𝑓𝑜𝑟𝑚 𝑡ℎ𝑒 𝑠𝑎𝑚𝑒 𝑡𝑎𝑠𝑘 𝐸𝑥𝑒𝑟𝑔𝑦 𝑖𝑛𝑝𝑢𝑡

4.8 Third law of thermodynamics (Nernst Law)

The third law of thermodynamics states that the entropy of a system approaches a constant value
as the temperature approaches absolute zero. The entropy of a system at absolute zero is typically
zero, and in all cases is determined only by the number of different ground states it has.
Specifically, the entropy of a pure crystalline substance (perfect order) at absolute zero
temperature is zero. This statement holds true if the perfect crystal has only one state with
minimum energy.

Figure 3.5 Third law of thermodynamics

At absolute zero temperature, the entropy of all homogeneous crystalline (condenser) substances
in a state of equilibrium became zero as shown n Figure 3.5. When expressed mathematically:
𝑑𝑡 𝑠 = 0 T 0
This implies that at absolute zero temperature.
The third law provides an absolute base from which the entropy of each substance can be
measured. The entropy relative to this base is referred to as the absolute entropy. Further this law
is helpful in:

45
  The third law of thermodynamics states that the entropy of a system approaches a
constant value as the temperature approaches absolute zero.
 Absolute zero: The lowest temperature that is theoretically possible.
 Measure of chemical affinity i.e. the action of chemical forces of the reacting substances.
 Explaining the behaviour of solids at very low temperature.
 Analyzing the chemical and phase equilibrium.
4.9 Enthalpy: Enthalpy is defined as, the sum of the internal energy and flow energy (pressure
volume product) is called enthalpy. Thus, the quantities of u, p and v are the properties of
enthalpy. Enthalpy is very useful thermodynamic property for the analysis of thermodynamic
substance. It is an extensive property of a system.
Enthalpy is also properties of:
Q1-2 = H2 – H1
Thus the amount of heat supplied to a system during an isobaric process (constant pressure)
equal to difference in enthalpies at the end and at the beginning of the process
H2– H1 = Q1-2 = mCp (T2 – T1)
Cp = heat capacity at constant pressure (kJ/K)
Cp = Rate of change of specific enthalpy w.r.t change of temperature when process is control out
at constant pressure.
Internal energy change is equal to the heat transferred in a constant volume process involving no
work other than pdv work, where
H = U + PV where H= Enthalpy U = Internal energy V = volume P = pressure
Unit kJ/kg
For ideal gas the enthalpy h = u + RT
Internal energy of an ideal gas depends only on temperature.
4.10 Internal energy: The energy associated with various kinds of motion of molecules
(translation, rotational, vibrational) which define a certain system is called internal energy.
The microscopic forms of energy are those related to the molecular structure of a system and the
degree of molecular activity and can be viewed as the sum of the kinetic energy and potential
energy of molecules and they are independent of outside reference frame. The sum of all
microscopic forms of energy is called the internal energy of a system and denoted by symbol U.

46
As mentioned in earlier sections internal energy represents the microscopic energy within a
system. The internal energy is basically the sum of different types of microscopic energies, such
as the, sensible energy, latent energy, chemical energy, and nuclear energy.
Sensible energy is the kinetic energy of the particles within the system. This includes both
rotational kinetic energy, and transverse kinetic energy. Latent energy on the other hand is the
associated energy that determines that phase of the system. In other words a certain amount of
internal energy is required for the system to have solid phase, a liquid phase, or a gas phase. The
chemical energy is the measurement of the energy between the atomic bonds of the molecule.
Finally, nuclear energy is the amount of energy of associated to the nuclear bonds of an atoms
nucleus.
The term internal energy firstly appeared in the works of Rudolph Clausius and William Rankine
in the second half of nineteenth century. For example:
 The molecules of a gas move through space with some velocity, and thus process some
kinetic energy. This is known as the translational energy.
 The atom of polyatomic molecules rotates about an axis, and the energy associated with
this rotational energy.
 The atoms of a polyatomic molecule may also vibrate about their common Centre of
mass, and the energy associated with this back and forth motion is the vibrational kinetic
energy.
In this Part, we introduce the second law of thermodynamics, which asserts that
 Processes occur in a certain direction and that
 Energy has quality as well as quantity.
 A process cannot take place unless it satisfies both the first and second laws of
thermodynamics.
In this part, the thermal energy reservoirs, reversible and irreversible processes, heat engines,
refrigerators, and heat pumps are introduced first. Various statements of the second law are
followed by a discussion of perpetual-motion machines and the absolute thermodynamic
temperature scale. The Carnot cycle is introduced next, and the Carnot principles are examined.
Finally, idealized Carnot heat engines, refrigerators, and heat pumps are discussed.

47
 Unit – 5
Concept of ideal and perfect gas
5.1 Introduction

An ideal gas is defined as, one in which all collisions between atoms or molecules are perfectly
elastic and in which there is no intermolecular attractive forces. One can visualize it as a
collection of perfectly hard spheres which collide but which otherwise do not interact with each
other and does not change its phase during the thermodynamic process and obeys a set of
common rules governing change of its properties. In such a gas, all the internal energy is in the
form of kinetic energy and any change in internal energy is accompanied by a change in
temperature. Ideal gases are defined as having molecules with negligible size with an average
molar kinetic energy dependent only on temperature. At low temperature, most gases behave
enough like ideal gases that the ideal gas law can be applied to them.
What is an ideal gas?
Gases are complicated. They are full of billions and billions of energetic gas molecules that can
collide and possibly interact with each other. Since it’s hard to exactly describe a real gas, people
created the concept of an ideal gas as an approximation that helps us model and predict the
behavior of real gases. The term ideal gas refers to a hypothetical gas composed of molecules
which follow a few rules:
(1) Ideal gas molecules do not attract with each other. The only interaction between ideal gas
molecules would be an elastic collision upon impact with each other or an elastic
collision with the walls of the container.
(2) Ideal gas molecules themselves take up no volume. The gas takes up volume since the
molecules expand into a large region of space, but the Ideal gas molecules are
approximated as point particles that have no volume in and of themselves.
If this sounds too ideal to be true, you're right. There are no gases that are exactly ideal, but there
are plenty of gases that are close enough that the concept of an ideal gas is an extremely useful
approximation for many situations. In fact, for temperatures near room temperature and pressures
near atmospheric pressure, many of the gases we care about are very nearly ideal.

48
If the pressure of the gas is too large (e.g. hundreds of times larger than atmospheric pressure), or
the temperature is too low (e.g. −200 0C, 200 0C) there can be significant deviations from the
ideal gas law.

An ideal gas can be characterized by three state variables: absolute pressure (P), volume (V), and
absolute temperature (T). The relationship between them may be deduced from kinetic
theory and is called the ideal gas law and can be expressed as:
PV = nRT = NkT
where
n = number of moles

R = universal gas constant = 8.3145 J/mol K

N = number of molecules

k = Boltzmann constant = 1.38066 x 10-23 J/K = 8.617385 x 10-5 eV/K

k = R/NA

NA = Avogadro's number = 6.0221 x 1023 /mol

There are three types of gas laws such as:

1. Boyle’s Law

2. Charles’ Law
3. Gay-Lussac’s Law
4. Avogadro’s Law
Boyle’s Law

It is stated that, if the state of a gas changes at constant temperature, then the volume of a given
mass of perfect gas is inversely proportional to the absolute pressure, means the volume of the
gas increases as the pressure decreases. The volume of the gas decreases and the pressure
increases. (If you squeeze a gas sample, you make its volume smaller).
1
𝑉∝( )
𝑝
Or pV = constant

49
Thus the products of absolute pressure and volume of a given quantity of gas is constant when
temperature remains constant. This law is valid only at low pressure or at high temperature.

P Isothermal
r
e
s
s
u
r
e T3
T2
T1
where
𝑇1 < 𝑇2 < 𝑇3
Volume
For any two points on the p-V diagram we get
𝑝1 𝑉1 = 𝑝2 𝑉2
Note: the process occurring at constant temperature is known as isothermal process.
Charles’ Law
If the state of a perfect gas, changes at constant pressure, then the volume of a given mass of
perfect gas varies and directly proportional to its absolute temperature. Also, at a constant
pressure, the volume of a gas increases as the temperature of the gas increases and the volume
decreases when the temperature decreases.
𝑉∝𝑇
when p = remains constant
or
𝑉
= 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝑇
It was found that by Gay – Lussac and Regnault that at constant pressure, the change in volume
1
of any perfect gas corresponding to a unit degree temperature change is given by 273 of its

volume at 0 0C.
• increase Average Kinetic Energy
• increase the speed of the particles
For example; the walls of a flexible container expand – think of hot air balloons

50
Let V0 = Volume of the gas at 0 0C
Vt = Volume of the gas at t 0C v
o
l
u Vt
m
e V0

Tabs

Temperature T

Avogadro’s Law
If a gas, under identical conditions of temperature and pressure, equal volumes of all gases have
same number of molecules then it is known as Avogadro’s law.
In other words, Avogadro’s law said that, equal volumes of gases at the same temperature and
pressure contain equal numbers of molecules.
For example: Choice any two ideal gases which having the same volume, same pressure and
same temperature and may be denoted by M1 and M2 respectively.
Now according to Avogadro’s law, each gas will contain the same number of molecules, say n
Therefore, the masses of the gases would be:
𝑚1 ∝ 𝑛 𝑀1 = 𝑘 𝑛 𝑀1
𝑚2 ∝ 𝑛 𝑀2 = 𝑘 𝑛 𝑀2
Where k is proportionality constant
Now calculate the densities of gases say, 𝜌1 and 𝜌2 then
𝑚1 = 𝜌1 𝑉 and 𝑚2 = 𝜌2 𝑉
Where V1 = V2= V is the volume of each gas
After putting the values of masses we get
𝜌1 𝑉 𝑘 𝑛 𝑀1
=
𝜌2 𝑉 𝑘 𝑛 𝑀2
Or
𝜌1 𝑀1
=
𝜌2 𝑀2
Behaviour of ideal gases:

51
  An ideal gas does not condense to a liquid at low temperatures
 An ideal gas does not have forces of attraction or repulsion between particles
 An ideal gas is composed of particles that have no volume
 The volume of the individual particles can be assumed to be negligible
 It expresses behavior that real gases approach at low pressure and high temperature
Perfect gas
Perfect gas also called ideal gas, a gas that conforms, in physical behavior, to a particular,
idealized relation between pressure, volume and temperature called the general gas law. This law
is a generalization containing both Boyle’s law and Charles’s law as special cases and states that
for a specified quantity of gas, the product of the volume v and pressure p is proportional to the
absolute temperature T i.e., in equation form, pv = kT, in which k is a constant. Such a relation
for a substance is called its equation of state and is sufficient to describe its gross behavior.
The general gas law can be derived from the kinetic theory of gases and relies on the
assumptions that
1. The gas consists of a large number of molecules, which are in random motion and obey
Newton’s laws of motion
2. The volume of the molecules is negligibly small compared to the volume occupied by the gas
3. No forces act on the molecules except during elastic collisions of negligible duration.
Although no gas has these properties, the behavior of real gases is described quite closely by the
general gas law at sufficiently high temperatures and low pressures, when relatively large
distances between molecules and their high speeds overcome any interaction. A gas does not
obey the equation when conditions are such that the gas, or any of the component gases in a
mixture, is near its condensation point, the temperature at which it liquefies.
The general gas law may be written in a form applicable to any gas, according to Avogadro’s
law, if the constant specifying the quantity of gas is expressed in terms of the number of
molecules of gas. This is done by using as the mass unit the gram-mole; i.e., the molecular
weight expressed in grams. The equation of state of n gram-moles of a perfect gas can then be
written as pv/t = nR, in which R is called the universal gas constant. This constant has been
measured for various gases under nearly ideal conditions of high temperatures and low pressures,
and it is found to have the same value for all gases: R = 8.314472 joules per mole-kelvin.

52
Real gases

Real gas, in contrast, has real volume and the collision of the particles is not elastic, because
there are attractive forces between particles. As a result, the volume of real gas is much larger
than of the ideal gas, and the pressure of real gas is lower than of ideal gas. All real gases tend to
perform ideal gas behavior at low pressure and relatively high temperature. In real gases,
particles attract each other reducing the pressure. Real gases behave more like ideal gases as
pressure approaches zero.
Deviation from perfect gas model – Vander walls equation of state
The behavior of real gases usually agrees with the predictions of the ideal gas equation to within
5% at normal temperatures and pressures. At low temperatures or high pressures, real gases
deviate significantly from ideal gas behavior. In 1873, while searching for a way to link the
behavior of liquids and gases, the Dutch physicist Johannes van der Waals developed an
explanation for these deviations and an equation that was able to fit the behavior of real gases
over a much wider range of pressures.
Van der Waals realized that two of the assumptions of the kinetic molecular theory were
questionable. The kinetic theory assumes that gas particles occupy a negligible fraction of the
total volume of the gas. It also assumes that the force of attraction between gas molecules is zero.
The first assumption works at pressures close to 1 atm. But something happens to the validity of
this assumption as the gas is compressed. Imagine for the moment that the atoms or molecules in
a gas were all clustered in one corner of a cylinder, as shown in the Figure below.

At normal pressures, the volume occupied by these particles is a negligibly small fraction of the
total volume of the gas. But at high pressures, this is no longer true. As a result, real gases are not

53
as compressible at high pressures as an ideal gas. The volume of a real gas is therefore larger
than expected from the ideal gas equation at high pressures.
Van der Waals proposed that we correct for the fact that the volume of a real gas is too large at
high pressures by subtracting a term from the volume of the real gas before we substitute it into
the ideal gas equation. He therefore introduced a constant (b) into the ideal gas equation that was
equal to the volume actually occupied by a mole of gas particles. Because the volume of the gas
particles depends on the number of moles of gas in the container, the term that is subtracted from
the real volume of the gas is equal to the number of moles of gas time’s b.
P (V - nb) = nRT
When the pressure is relatively small, and the volume is reasonably large, the nb term is too
small to make any difference in the calculation. But at high pressures, when the volume of the
gas is small, the nb term corrects for the fact that the volume of a real gas is larger than expected
from the ideal gas equation.
Therefore, in 1073, Vander Waals, proposed an equation of state which can be regarded as a
modification of the ideal gas law. It represents one of the earliest attempts to develop an equation
of state which is more accurate than ideal gas law. It takes into account the effect of the volume
occupied by the gas molecules as well as the effect of attractive forces between the molecules. In
the modified ideal gas equation V, is written as (V – b) where b is the constant of volume
occupied by the gas molecules.
Van der Waals equation (for a real gas) may be written as:
𝑎
(𝑃 + 𝑣2 ) (𝑉 − 𝑏) = 𝑅𝑇

where P = pressure
T = Temperature
The constant a and b are specific constants and depend upon the type of the fluid considered, v
represents the volume per unit mass and R is gas constant.
𝑅𝑇 𝑎
𝑃= − 2
𝑉−𝑏 𝑣
𝑉𝑐 = 3𝑏
8𝑎
𝑇𝑐 =
27𝑅𝑏
𝑎
𝑃𝑐 =
27𝑏 2

54
 3𝑎
𝑅𝑐 = (𝑉 − 𝑏)
𝑣𝑐4 𝑐
Points to be remember:
The concept of perfect gas that obeys the equation of state PV = RT, stems from the kinetic
theory of gases that makes the following assumption about the gas molecules:
 The collision of molecules with one another and with the walls of the container is
perfectly elastic
 There is no molecular attraction between the particles of gas, and that they are in a state
of continues motion
 The volume occupied by the gas molecules is negligible as compared to the volume of
the gas
Limitation of Vander Waals equation
 The value of constants a & b are varying with change in temperature. Therefore, the
equation does not gives correct results
 The Vander Waals equation can be compared with ideal gas equation considering the
𝑃𝑉
value of at critical point of the gas
𝑅𝑇
Compressibility chart
The generalized compressibility is a useful tool of predicting the properties of gases or gas
mixture with acceptable accuracy for most engineering purposes. However, the chart is awkward
to use when volume is one of the known properties and either pressure or temperature is
unknown, because the answer must be found by trial and error method.
In other words we also explain that, many equations of state were gives for real gases by
different investigators which are accurate in different ranges of pressure and temperatures. These
equations do not give accurate results for all pressure and temperatures because of the difference
in their compressibility behavior.
To plots isothermals on chart Z Vs Pr to gives the value of Z. this chart is known as
compressibility chart. Naturally, there would be different charts for different gases. The
generalized compressibility charts in terms of reduce properties as shown. It is very useful in
predicting the properties of substances for which more precise data are not available.

55
 Generalized compressibility chart
Compressibility factor Z
To quantify deviation of real behavior from the ideal gas behavior, we introduce a new term
namely, the compressibility factor. The compressibility factor Z is defined as the ratio of the
actual volume to the volume predicted by the ideal gas law at a given temperature and pressure.
𝑃𝑣
The ratio = 𝑍 is called compressibility factor.
𝑅𝑇
For an ideal gas z = 1. The magnitude of Z for a certain gas at a particular pressure and
temperature gives an indication of the extent of deviation of the gas from ideal gas behavior.
Law of corresponding states
According to Vander walls, the theorem of corresponding states (or principle/law of
corresponding states) indicates that all fluids, when compared at the same reduced temperature
and reduced pressure, have approximately the same compressibility factor and all deviate from
ideal gas behavior to about the same degree.
The critical constants are characteristic properties of gases. The reduced variables of a gas which
is obtained by dividing the actual variable by corresponding constant.

56
 𝑃
𝑃𝑟 = (Reduced pressure)
𝑃𝑐
𝑉𝑚
𝑉𝑟 = (Reduced volume)
𝑉𝑚,𝑐
𝑇
𝑇𝑟 = (Reduced volume)
𝑇𝑐

The observation that real gases at the same reduced volume and reduced temperature exert the
same reduced pressure is called the law of corresponding state as shown in Figure.

57
 UNIT – 6
Mixture of perfect gases
6.1 Introduction

The working fluids employed in most of the heat engines was focused on a single component,
simple system or pure substances, such as water. In practice however, we also deals with mixture
of gases such as, air combustion products. Another important example is: the air we breathe in is
a mixture of oxygen and nitrogen and the fuel oil used in automobiles is a mixture of several
hydrocarbons. The gas inside the automobile cylinder is a mixture of CO2, CO, H2O, O2, N2,
SO2, oxides of nitrogen and unburned hydrocarbon. The constituent of the above gases are
assumed to be ideal, do not interact with one another chemically and the gas mixture obeys the
laws of ideal homogenous gases. Each gas in the mixture behaves independently, occupies the
entire volume of the mixture and exerts its own pressure on the walls of the container.
A solution is created when two or more components mix homogeneously to form a single phase.
Studying solutions is important because most chemical and biological life processes occur in
systems with multiple components. Understanding the thermodynamic behavior of mixtures is
integral to the study of any system involving either ideal or non-ideal solutions because it
provides valuable information on the molecular properties of the system.
The mixtures of various gases, so called gas mixtures, are considered as special cases of mixtures
(solutions). It is of great interest to examine a gas mixture each component of which considered
as an ideal gas. Thus, the total volume of a mixture of gases is equal to the sum of the partial
volumes of its components.
In thermodynamics the concepts of a pure substance and a mixture is used. By a pure substance
we mean a substance all molecules of which are similar, or a substance which does not change
chemically. A mixture, consisting of several pure substances, is referred to as a solution.
Examples of pure substances are water, ethyl alcohol, nitrogen, ammonia, sodium chloride, and
iron. Examples of mixtures are air, consisting of nitrogen, oxygen and a number of other gases,
aqueous ammonia solutions, aqueous solutions of ethyl alcohol, various metal alloys. The pure
substances making up a mixture are called components or constituents.

58
Mass

The composition of a mixture is usually specified in terms of mass (mi) each component. The
total mass (m) of a mixture is the sum of the masses of all the constituent species that is:

𝑚 = ∑ 𝑚𝑖
𝑖

Or say, the mass per mole of a substance is called its molar mass. Since the standard unit for
1
expressing the mass of molecules or atoms is defined as 12 of the mass of a 12C atom, it follows

that the molar mass of a substance measured in grams per mole, is exactly equal to its mean
molecular or atom mass.
Mole
The mole is the standard method in chemistry for communicating how much of a substance is
present. The mole is the amount of substance of a system which contains as many elementary
entities as there are atoms in 0.012 kilogram of carbon-12. When mole is used, the elementary
entities must be specified and may be atoms, molecules, ions, electrons, other particles. In other
words, if the analysis of a mixture is based on the number of moles of the constituent species
then, it is called molar analysis. The total number of moles (N) of a mixture is given by the sum
of the number of moles of constituent species that is:

𝑁 = ∑ 𝑁𝑖
𝑖

Mass fraction

The mass fraction of each component of a mixture is defined as the ratio of mass of a given
component to the mass of the entire mixture. The mass fraction (∅𝑖 ) of the component i is given
by
𝑚𝑖
∅𝑖 =
𝑚
Mole fraction

Mole fraction is another way of expressing the concentration of a solution or mixture. It is equal
to the moles of one component divided by the total moles in the solution or mixture. 𝑦𝑖 = the
component that is being identified for mole fraction.

59
Mole fraction is defined as the ratio of moles of one component to the total number of moles of
all the components present in solution.
Or the mole fraction of each component of a mixture is defined as the ratio of the moles of each
constituent gas to the total number of moles contained in the gas mixture, therefore, the mole
fraction (𝑦𝑖 ) of components i is given by

𝑁𝑖
𝑦𝑖 = where N = total no of moles
𝑁
𝑛𝐴
𝑦𝐴 =
𝑛𝐴 + 𝑛𝐵 + 𝑛𝐶

𝑛𝐵
𝑦𝐵 =
𝑛𝐴 + 𝑛𝐵 + 𝑛𝐶

𝑛𝐶
𝑦𝐶 =
𝑛𝐴 + 𝑛𝐵 + 𝑛𝐶

where (𝑁𝑖 ) is the number of moles of component i. all the mass fraction (∅𝑖 ) and mole fraction
(𝑦𝑖 ) are not independent and there exit relationship between them

∑ ∅𝑖 = 1

and

∑ 𝑦𝑖 = 1

The mass (𝑚𝑖 ) of a component i is related to the number of moles (𝑁𝑖 ) and the molar mass (𝑀𝑖 )
of the component i.
𝑚𝑖 = 𝑁𝑖 𝑀𝑖
Similarly, the molar mass of mixture is
𝑚 ∑ 𝑚𝑖 ∑ 𝑁𝑖 𝑀𝑖
𝑀= = = = ∑ 𝑦𝑖 𝑀𝑖
𝑁 ∑ 𝑁𝑖 ∑ 𝑛𝑖
𝑖

Volume fraction
The volume of the gas sample is measured at atmospheric pressure and temperature is held at
constant by means of water jacket round the gas simple.
Let us consider a volume V of a gaseous mixture at a temperature T, consisting of three
constituent A, B and C. Let us further assume that each of the constituent is compressed to a

60
pressure p equal to the total pressure of the mixture and let the temperature remains constant.
The partial volume then occupied by the constituents will be 𝑉𝐴, 𝑉𝐵 𝑎𝑛𝑑 𝑉𝐶
Now using the equation
𝑃𝑉 = 𝑚𝑅𝑇
𝑃𝐴 𝑉 𝑃𝑉𝐴
𝑚𝐴 = =
𝑅𝐴 𝑇 𝑅𝐴 𝑇
Now equating the two values for 𝑚𝐴 we have
𝑃𝐴 𝑉 𝑃𝑉𝐴
=
𝑅𝐴 𝑇 𝑅𝐴 𝑇
i.e. 𝑃𝐴 𝑉 = 𝑃 𝑉𝐴
𝑃𝐴 𝑉
𝑉𝐴 =
𝑃
In general therefore
𝑃𝑖
𝑉𝑖 = 𝑉
𝑃
𝑃𝑖 𝑉
∑ 𝑉𝑖 = 𝑉 = ∑ 𝑃𝑖
𝑃 𝑃
Therefore

∑ 𝑉𝑖 = 𝑉

Or 𝑉 = 𝑉𝐴 + 𝑉𝐵 + 𝑉𝐶

Delton’s law of partial pressure

If a gas mixture contains 𝑁𝐴 molecules of an ideal gas A, 𝑁𝐵 moles of another ideal gas B, 𝑁𝐶
moles of a third ideal gas C----- etc, then the equation of state of the mixture in a state of
equilibrium is
𝑃𝑉 = (𝑁𝐴 + 𝑁𝐵 + 𝑁𝐶 + −−)𝑅𝑀 𝑇

where N = no of moles

P = total pressure (kN m2)

V = total volume (m3)

𝑅𝑀 = universal mole gas constant = 8.3144 KJ/ Kmole K

61
 𝑁𝐴 𝑅𝑀 𝑇 𝑁𝐵 𝑅𝑀 𝑇 𝑁𝐶 𝑅𝑀 𝑇
𝑃= + + ±−−−−
𝑉 𝑉 𝑉

where 𝑃𝐴 , 𝑃𝐵 , 𝑃𝐶 , ----------etc. stands for partial pressure of components A,B,C etc.

𝑁𝐴 𝑅𝑀 𝑇 𝑁𝐵 𝑅𝑀 𝑇 𝑁𝐶 𝑅𝑀 𝑇
𝑃𝐴 = , 𝑃𝐵 = , 𝑃𝐶 =
𝑉 𝑉 𝑉

Hence, Delton’s law of partial pressure states that: the sum of partial pressures of individual
components of a gas mixture is total pressure of the system as shown in Fig.
Partial pressure is defined as the pressure which each individual components of a gas mixture
would exert if it alone occupied the volume of the mixture at the same temperature.

Amagat Leduc law for partial volume

The partial (reduced) volume of a gas components the volume, of ideal gas occupy if its
temperature and pressure were equal to these parameters of the mixture. Let us consider a
volume V of a gases mixture at a temperature T, consisting of three constituent A, B, C. Let us
further assumed that each of the constituent is compressed to a pressure P equal to the total
pressure of the mixture and let the temperature remains constant. The partial volume then
occupied by the constituent, will be

62
𝑉𝐴 , 𝑉𝐵 , 𝑉𝐶 − − − − −

Now using the gas equation

𝑃𝑣 = 𝑚𝑅̅ T

For each component gases

𝑃𝑉𝑎 = 𝑁𝐴 𝑅̅ 𝑇

𝑃𝑉𝑏 = 𝑁𝐵 𝑅̅ 𝑇

𝑃𝑉𝑐 = 𝑁𝐶 𝑅̅ 𝑇

Adding

𝑃(𝑉𝐴 + 𝑉𝐵 + 𝑉𝐶 ) = (𝑁𝐴 + 𝑁𝐵 + 𝑁𝐶 )𝑅̅ 𝑇 = 𝑁𝑅̅ 𝑇 where N = Total no of moles

and

𝑉 = (𝑉𝐴 + 𝑉𝐵 + 𝑉𝐶 )

The above equation states that the total volume of a mixture of ideal gases is equal to the sum of
the partial (reduced) volume of the constituent gases. This is known as Amagat – Leduc law for
partial volume.
Equivalent gas constant

The gas constant is also known as the molar, universal or ideal gas constant denoted by the
symbol R and is equivalent to the Boltzmann constant, but expressed in unit of energy per
temperature increment per mole i.e., pressure – volume product, rather than energy per
temperature increment per particles.
The gas constant R is 8.314 J/mole K. convert the numerical value of R so that its unit are
Cal/mole k where 1cal = 4.184 J
Thermodynamic properties of gas mixture

When different gaseous components, having the same temperature and pressure are allowed to
mix adiabatically, their molecules take part in inter diffusion and uniform, homogenous gases
mixture is produce.

63
The internal energy, enthalpy and entropy of a gaseous mixture are equal to the sum of the
internal energies, the enthalpies and entropies which each component of the gas mixture would
have, if each alone occupied the volume of the mixture.
Specific heats of a mixture
Specific heat at constant volume (Cv)
Specific heat at constant pressure (Cp)
𝑚𝐶𝑣𝑚 = 𝑚𝐴 𝐶𝑉𝐴 + 𝑚𝐵 𝐶𝑉𝐵 + 𝑚𝑐 𝐶𝑉𝐶 + − − − − − −

𝑚𝐴 𝐶𝑉𝐴 +𝑚𝐵 𝐶𝑉𝐵 +𝑚𝑐 𝐶𝑉𝐶

𝐶𝑣𝑚 = +−−−−−− and
𝑚

𝑚𝐶𝑝𝑚 = 𝑚𝐴 𝐶𝑝𝐴 + 𝑚𝐵 𝐶𝑝𝐵 + 𝑚𝐶 𝐶𝑝𝑐 + − − − − − −

𝑚𝐴 𝐶𝑝𝐴 + 𝑚𝐵 𝐶𝑝𝐵 + 𝑚𝐶 𝐶𝑝𝑐
∴ 𝐶𝑝𝑚 = +−−−−−−
𝑚
Entropy of mixture (S)
The total entropy of a mixture of gases is the sum of partial entropies of the individual
components:
𝑚𝑆𝑚 = 𝑚𝐴 𝑆𝑚𝐴 + 𝑚𝐵 𝑆𝑚𝐵 + 𝑚𝐶 𝑚𝑚𝐶 + − − − − −
𝑚𝐴 𝑆𝑚𝐴 + 𝑚𝐵 𝑆𝑚𝐵 + 𝑚𝐶 𝑚𝑚𝐶
𝑆𝑚 = + −−−−−
𝑚
𝑆 = ∅𝑖 𝑆𝑖
𝑚𝐴
∅𝐴 =
𝑚

64
 UNIT – 7

Pure substances

Introduction
A pure substance is a substance of constant chemical composition throughout it mass. It refers to
the substance with chemical homogeneity and constant chemical composition is a pure substance
as it meets both the above requirements. Any substance if it undergoes a chemical reaction
cannot be pure substance.
 A substance that has a fixed chemical composition throughout (water, nitrogen, helium
and carbon dioxide are all pure substances).
 A mixture of various chemical elements or compounds also qualifies as a pure substance
as long as the mixture is homogeneous (Air is a mixture of several gases, but it is often
considered as a pure substance because it has a uniform chemical composition (Fig. 7.1).
 A mixture of two or more phases of pure substance is still a pure substance as long as the
chemical composition of all phases is the same (A mixture of liquid and gaseous water is
a pure substance, while a mixture of liquid and gaseous air is not - Fig. 7.2).

Figure 7.1

Figure 7.2

65
Properties of pure substances
The behavior of properties of pure substance have to be studied and mathematical formulations
be made for their estimation.
Pure substance is used for operating various systems such as steam is used for power generation
in steam power plants. Hence thermodynamic properties that can be vary independently over
wide range in a particular phase. Various dependent properties looked into a head shell be
enthalpy, internal energy, specific volume, entropy etc.
P – V diagram for pure substance
On P – V diagram region marked S shows the solid region mark SL shows solid – liquid mixture
region, mark L+V shows liquid – vapour mixture region, mark C+L shows compressor liquid
region. Triple point line is also shows and it indicates coexistence of solid, liquid and gas in
equilibrium. Region marked S +V and lying below triple point line is sublimation region where
solid gets transferred directly into vapours. The term saturation temperature designates the
temperature at which vaporization takes place at a given pressure and this pressure is called the
saturation pressure for the given temperature.
 P – V diagram for water whose volume decreases on melting

T – S diagram for pure substance

The T-s diagram for a substance is shown in Fig. The curve from A to F is a typical isobar
representing a series of reversible isobaric processes in which solid is transformed finally into
vapour. Thus,

66
AB - isobaric heating of solid to its melting point
BC - isobaric isothermal melting
CD - isobaric heating of liquid to its boiling point
DE - isobaric isothermal vaporization
EF - isobaric heating of vapour (superheating)
The area under the line BC represents the heat of fusion at the particular temperature, and the
area under the line DE represents the heat of vaporization. Similarly, the heat of sublimation is
represented by the area under any sublimation line. It is obvious from the diagram that heat of
vaporization decreases as the temperature rises and becomes zero at the critical point and also
that the heat of sublimation is equal to the sum of heat of fusion and the heat of vaporization at
the triple point.

P – T diagram for pure substance

If the pure substance is heated at low pressure until its triple point (pressure and temperature at
which three phases of a pure substance coexist) is reached and while heating the vapor pressure
of a solid is measured at various temperatures and then plotted on a p-T diagram, shown in Fig.
These plotted points represent the coexistence of solid and vapour and the line through these
points is called sublimation curve.
If the pure substance at triple point is further heated until the critical point is reached and while
heating the vapor pressure of a liquid is measured at various temperatures and then plotted on a

67
p-T diagram, the results will appear as shown in Fig. The results of these plotted points represent
the coexistence of liquid and vapor and the line through these points is called vaporization curve.

Phase transformation
Phase transformation is done when a substance changes from a solid, liquid, or gas state to a
different state. Every element and substance can transition from one phase to another at a
specific combination of temperature and pressure.
There are six ways a substance can change between these three phases; melting, freezing,
evaporating, condensing, sublimination, and deposition. These processes are reversible and each
transfers between phases differently:
Melting: The transition from the solid to the liquid phase
Freezing: The transition from the liquid phase to the solid phase
Evaporating: The transition from the liquid phase to the gas phase
Condensing: The transition from the gas phase to the liquid phase
Sublimination: The transition from the solid phase to the gas phase
Deposition: The transition from the gas phase to the solid phase

68
The above graph shows the phase diagram of water. At the beginning we have ice at -20 ºC. Ice
gain heat in the interval of points A and B, and its temperature becomes 0 0C that is the melting
point of it. We have only ice in the 1st region. As you can see between the points B and C,
temperature of the mass does not change, because its state is changing in this interval. Gained
heat is spent on t breaking the bonds of molecules. 2nd region includes both water and ice. After
melting process completed, in the 3rd region there is only water and temperature of water starts to
increase. When the temperature of the water becomes 100 0C, it starts to boil and evaporation of
it speeds up. In region 4 our mass exists in two state, water and steam. After completion of
evaporation, all water converted to the steam and in region 5 we have only vapour of water.
Formation of steam at constant pressure
There are stages during the formation of steam:
1. Heat of water up to boiling point
2. Evaporation and conversion of water into dry saturated steam
3. Further heating to get superheated steam
The process of steam generation is shown in T – Q, T – V, p – V diagrams below:
The temperature-heat content diagram (T-Q diagram) is widely applied to the thermodynamic
analysis and synthesis of process systems as shown in Figure.

69
Let us consider 1 kg of ice below freezing point i.e., at – 10 0C (263 K) initially at point 1

Temp T (k)

6
Evaporation
Superheating of
4 steam
373
5
2 Heating of water
273
3 Melting of ice
Heating of ice
263
1

Heat input Q
Temp T (k)

4
373
5
3'
277
3
273 2

Volume, v

70
A pressure–volume diagram (P-V diagram) is used to describe corresponding changes in volume
and pressure in a system and is commonly used in thermodynamics.

Process 1 – 2: (Heating of ice)

 Heating of ice take place, temperature of ice increases to 0 0C at state point 2
Process 2 – 3: (Melting of ice)
 As further het is added, the ice starts melting at constant temperature. The phase changes
from solid to liquid which is called fusion of ice.
 The amount of heat required to transform solid into liquid at constant temperature is
called latent heat of fusion.
 Latent heat of fusion of ice is equal to 335 KJ/kg
 At state point 3 ice completely changes to water
 It can be seen from T – v diagram that there is decrease in volume during melting of ice
i.e., water at 0 0C is heavier than ice at 0 0C. for other substance there is increase in
volume during melting
Process 3 – 4: (Heating of water)
 As heat is continued to be supplied, the water temperature increases from 0 0C to 100 0C
i.e. boiling point (saturation temperature) at atmospheric pressure
 Again as seen in T – v diagram, the volume of water decreases from state point 3 to 3′ i.e.
from 0 0C to 4 0C. It means that the water has maximum density at 4 0C
 The heat supplied to a substance is called sensible heat if it changes the temperature of it

71
Process 4 – 5: (Evaporation)
 On heating water at 100 0C, it starts evaporating. This evaporation takes place at constant
temperature until all the liquid is converted to vapour at state point 5
 The heat supplied to change the liquid into vapour form at constant temperature is called
latent heat of vaporization
 Latent heat of vaporisations of water is equal to 2256.9 kJ/kg

Process 5 – 6: (Superheating)
 Superheating of dry saturated steam takes place as heat is supplied thereafter.
Temperature increases with heat supplied
 Now condenser P – v diagram (Figure 3), the horizontal distance between the saturated
liquid line and saturated vapour line decreases as the pressure is increased. The point is
reached where this distance is zero which is called the critical point (C)
 At critical point liquid is directly converted to vapour without any phase change as liquid
and vapour are indistinguishable
 The temperature and pressure at critical point are called critical temperature and critical
pressure respectively. For water critical values are:
Tc = 374.1 0C
Pc = 220.9 bar
Steam
Steam is the most common working substance employed as working medium in steam engines,
steam turbines for power generation. There occurs a change in the properties of steam during a
process and helps to attain the desired effect.
Steam also finds application in process industries, and also acts as heat carrying agent in heat
exchange equipments.
Properties of steam
When water is heated it starts boiling at certain temperature and starts converting into vapour.
Water can exist in any one of the three states: Solid, liquid and gas
 Water start boiling at 100 0C (That is saturated temperature) or the boiling point
temperature at any pressure is called saturated temperature
 The water vapour is commonly known as steam. At this state enthalpy is much higher

72
  If whole of water has evaporated the resultant steam will contain no water particles and
steam is known as dry saturated steam
Volume (V)
Volume is defined as; the space occupied by a substance and is measured in m3.
The specific volume (v) of a substance is defined as the volume per unit mass and is measured in
m3/kg.
Specific volume (v) for wet steam
𝑣 = 𝑢𝑓 + 𝑥 𝑢𝑓𝑔
Internal energy (u)
The energy content with the system is known as internal energy.
Internal energy is the microscopic energy i.e., the energy stored in the molecular motions. It is
the energy stored in the molecular structure due to heat and work interaction.
It is developed due to various kind of motion of molecules (vibration, translation, rotational)
motion within the system.
𝑢 = ℎ − 𝑃𝑣
Entropy (S)
Enthalpy is a measure of the degree of randomness of molecules comprising the system. Higher
the disorder, greater in the increase in entropy kJ/kg
For wet steam
𝑆 = 𝑆𝑓 + 𝑥 𝑆𝑓𝑔
Enthalpy (H)
Enthalpy is the sum of flow energy and internal energy. Enthalpy is defined as heat content in a
substance. Enthalpy per unit mass is known as specific enthalpy (h).
𝐻 = 𝑢 + 𝑃𝑣
It is defined as the total heat content in a substance. It is represented by ′H′. Enthalpy per unit
mass is known as specific enthalpy and is denoted by ′h′.
𝐻
ℎ=
𝑚
Enthalpy change during formation of superheated steam at 250 0C from ice at – 10 0C are
calculated BELOW:

73
Process 1 – 2:
Enthalpy change during heating of ice from – 10 0C to 0 0C
(dh)1-2 = Ci dt
Where Ci = specific heat of ice
dt = change in temperature
(dh) = 2.09 [0 – (– 10)] = 20.9 kJ/kg
Process 2 – 3: Latent heat of fusion
(dh) = 335 kJ/kg
Process 3 – 4:
dh = Cw dt = 4.186 x (100-0) = 418.6 kJ/kg
Process 4 – 5: Latent heat of vaporisation
dh = 2256.9 KJ/kg
Process 5 – 6:
dh = Cst dt = 2.1 (250 – 100) = 315 KJ/kg
where
hs = enthalpy of solid
hf = enthalpy of liquid
hg = enthalpy of gas
Enthalpy of fusion = ℎ𝑓 − ℎ𝑠 = ℎ𝑠𝑓
Enthalpy of vaporization = ℎ𝑔 − ℎ𝑓 = ℎ𝑓𝑔
Enthalpy of sublimation = ℎ𝑔 − ℎ𝑠 = ℎ𝑠𝑔
Enthalpy of wet steam of dryness fraction x

ℎ𝑤𝑒𝑡 = (1 − 𝑥)ℎ𝑓 + 𝑥ℎ𝑔 = ℎ𝑓 + 𝑥(ℎ𝑔 − ℎ𝑓 )

ℎ𝑤𝑒𝑡 = ℎ𝑓 + 𝑥ℎ𝑓𝑔

Saturated steam
Steam is formed by heating the water upto boiling point which results in the formation of water
vapour.
When the molecules escaping from the liquid becomes equal to the molecules returning to it, the
steam is called saturated steam. The saturated steam has a maximum density at a given
temperature and is in thermal equilibrium with the liquid.

74
Saturated steam may be dry or wet.
 When the saturated vapour contains particles of a liquid evenly distributed over the entire
mass of vapour, it is called as wet saturated steam
 When saturated vapour which contains no liquid particles is called dry saturated steam.
For dry saturated steam X = 1
Superheated steam
When the temperature of the steam is higher than its saturation temperature it is called
superheated steam. The temperature is denoted by 𝑡𝑠𝑢𝑝
The difference between superheated temperature and saturation temperature is called degree of
superheat.
𝐷𝑒𝑔𝑟𝑒𝑒 𝑜𝑓 𝑠𝑢𝑝𝑒𝑟ℎ𝑒𝑎𝑡 = 𝑡𝑠𝑢𝑝 − 𝑡𝑠𝑎𝑡
Evaporation
Evaporation is the process of a substance in a liquid state changing to gaseous state due to an
increase in temperature or pressure.
The process of vapour generation when the molecules at the surface of the liquid having greater
kinetic energy escapes to the surrounding atmosphere is called evaporation.
Evaporation of liquid occurs at any temperature however rates of evaporation increase with
temperature.
Vaporization: Refers to the process that involves change from the liquid phase to vapour phase.
Boiling: When heat is added to a liquid it, starts boiling and vapours gets generated both from
the free surface of liquid and inside it.
 Boiling refers to the process of vapour formation that take place in the whole mass of
liquid.
 All the liquid gets converted into vapour, when vaporization takes place in an infinite
space i.e., in open vessel.
 Boiling takes place at a definite temperature which depends upon physical properties of
liquid and pressure.
 Standard atmosphere pressure (p=1.01325bar) water boil at 100 0C.
Saturated pressure
The pressure at a specific temperature at which the boiling takes place is called saturated
pressure. Or it is the pressure for a given temperature at which a substance undergoes a phase

75
change. The saturated pressure of water at 373 k is 1.01325 bar, it is denoted by 𝑃𝑠𝑎𝑡 . It is also
called vapour pressure.
Saturated temperature
The temperature at a specific pressure at which the boiling takes place is called saturation
temperature. It remains constant until all the liquid is converted into vapour. Or it refers to the
temperature for a given pressure at which a phase change of a substance takes place. It is denoted
by 𝑡𝑠𝑎𝑡 .
Triple point
It corresponds to the temperature at which pure substance can coexist in solid, liquid and gaseous
phases in equilibrium. The corresponding temperature and pressure are referred to as the triple
point temperature (Tt) and the triple point pressure (Pt), respectively. The triple point of water is
273.01 K, i.e., 0.01 0C and Pt = 0.612 Kpa.
Critical point
It refers to a particular set of pressure and temperature condition at which the density of vapour
equal to the density of liquid of a substance. That is, it refers to the point of the highest pressure
and temperature condition at which liquid coexist with its vapour for the last time. Above this
critical point, the substance is all vapour and below it, it is all liquid. The critical point of water is
22.12 MPa/647.15 K (374.14 0C).
 Vapour above critical point is called gas
Superheated vapour
Any vapour having temperature more than the saturated temperature corresponding to any given
pressure is called superheated vapour. The difference of temperatures of superheated vapour and
saturated vapour at the same pressure is known as degree of superheat.
∆𝑇𝑠𝑢𝑝 = 𝑇𝑠𝑢𝑝 − 𝑇𝑔
Latent heat
The latent heat of vaporization is the quantity of heat required to vaporize unit mass of liquid
into vapour or condense unit mass of vapour into liquid.
 The amount of heat required for conversion of I kg of water into dry saturated steam at
constant temperature is called latent heat of evaporation denoted by ℎ𝑓𝑔
 The total heat (enthalpy) of dry saturated steam will be sum of enthalpy of liquid plus
enthalpy of saturated steam

76
 ℎ𝑔 = ℎ𝑓 + ℎ𝑓𝑔
 The process of steam formation takes place at constant pressure, hence change of entropy
is given by
𝑇2
𝐶𝑝 𝑙𝑛
𝑇1
 The enthalpy of steam is generally measured above 0C. hence entropy of 1 kg of water at
saturated temperature
𝑇𝑠
𝑆𝑓 = 𝐶𝑝 𝑙𝑛
273
𝑇𝑠 = 𝑡𝑠 + 273
 Entropy of evaporation (dry steam)
ℎ𝑓𝑔
𝑆𝑓𝑔 =
𝑇𝑠
 Total entropy of saturated steam
𝑆𝑔 = 𝑆𝑓 + 𝑆𝑓𝑔
𝑠 𝑇 ℎ𝑓𝑔
𝑆𝑔 = 𝐶𝑝 𝑙𝑛 273 + 𝑇𝑠

Steam table
 Since steam does not behave like a perfect gas, hence simple laws of perfect gases does
not apply to vapour. Various properties of steam at different conditions were studied
experimentally. The data was then used to obtain suitable equations of state which was
then utilized to obtain comprehensive data on steam properties
 The steam tables contains values of specific volume, enthalpy and entropy for saturated
liquid and dry saturated vopur for different values of pressure (P) or corresponding
saturation temperature (tsat)
 The properties of superheated steam are tabulated separately. These properties depend
upon both pressure and temperature i.e. degree of superheat
 Interpolation is used for find the values of properties for intermediate values of pressure
and temperature. A sample of steam table is shown below:

77
 Table 1: Properties of saturated steam (pressure table)

Absolute Saturated Specific volume Specific enthalpy kJ/kg Specific entropy

pressure temperature m3/kg kJ/kg -K
0
(bar) ( C)
P tsat vf vg hf hfg hg sf sfg sg
10 179.9 0.00117 0.194 763.6 2013.6 2776.2 2.1382 4.4446 6.5825
30 233.8 0.001216 0.0666 1008.4 1793.9 2802.3 2.6455 3.5382 6.1837

Table 2: Properties of saturated steam (temperature table)

Temperature Absolute Specific volume Specific enthalpy kJ/kg Specific entropy

0 3
( C) pressure m /kg kJ/kg -K
(bar)
tsat P vf vg hf hfg hg sf sfg sg
10 0.0123 0.0010004 106.4 42.0 2477.7 2519.7 0.151 8.750 8.901
50 0.1235 0.001012 12.03 209.3 2382.7 2582.7 0.704 7.372 8.076

Throttling calorimeter
 It is a device used to measure the quality of wet steam
 It is based on the principle of Joule – Thompson expansion
 Part of the wet steam flowing through the mains is the throttled to a low pressure (usually
Patm)
 Steam in the calorimeter becomes superheated and the temperature is measured
 By knowing the P & T of steam in the calorimeter its enthalpy can be determined
 Throttling is isenthalpic
ℎ𝑖 = ℎ𝑒

78
  Knowing the enthalpy and pressure of steam in the mains, its quality can be determined
using relation
ℎ𝑒 = ℎ𝑖 = 𝑥ℎ𝑔 + (1 − 𝑥)ℎ𝑓 = ℎ𝑓 + 𝑥ℎ𝑓𝑔
𝑤ℎ𝑒𝑟𝑒
𝑥 𝑖𝑠 𝑡ℎ𝑒 𝑞𝑢𝑎𝑙𝑖𝑡𝑦 𝑜𝑓 𝑠𝑡𝑒𝑎𝑚 𝑖𝑛 𝑡ℎ𝑒 𝑚𝑎𝑖𝑛
ℎ𝑔 𝑖𝑠 𝑡ℎ𝑒 𝑒𝑛𝑡ℎ𝑎𝑙𝑝𝑦 𝑜𝑓 𝑠𝑎𝑡𝑢𝑟𝑎𝑡𝑒𝑑 𝑣𝑎𝑝𝑜𝑢𝑟 𝑎𝑡 𝑝𝑖
ℎ𝑓 𝑖𝑠 𝑡ℎ𝑒 𝑒𝑛𝑡ℎ𝑎𝑙𝑝𝑦 𝑜𝑓 𝑠𝑎𝑡𝑢𝑟𝑎𝑡𝑒𝑑 𝑙𝑖𝑞𝑢𝑖𝑑 𝑎𝑡 𝑝𝑖
𝑀𝑎𝑠𝑠 𝑜𝑓 𝑣𝑎𝑝𝑜𝑢𝑟 𝑇𝑜𝑡𝑎𝑙 𝑚𝑎𝑠𝑠 − 𝑀𝑎𝑠𝑠 𝑜𝑓 𝑙𝑖𝑞𝑢𝑖𝑑
𝑥= =
𝑇𝑜𝑡𝑎𝑙 𝑚𝑎𝑠𝑠 𝑇𝑜𝑡𝑎𝑙 𝑚𝑎𝑠𝑠

he Pi

Steam mains
Thermometer

Te

Pe
Calorimeter
he

To pot

Figure Throttling calorimeter

Dryness fraction
Saturation steam may contain liquid particles and is called wet steam. The ratio of mass of dry
saturated vapour to the total mass of the mixture is called dryness fraction. It is denoted by (𝑥)

79
 𝑚𝑔 𝑚𝑔
𝑥= =
𝑚 𝑚𝑓 − 𝑚𝑔
Where
m = total mass of the mixture
𝑚𝑔 = mass of dry saturated steam
𝑚𝑓 = mass of water
When dryness fraction is expressed in percentage it is called quality of steam
There is another term wetness fraction denoted by (𝑦)
𝑚𝑓
𝑦=
𝑚𝑓 + 𝑚𝑔
Also 𝑦 = 1 − 𝑥
 When wetness fraction is expressed in percentage it is called priming.
 Saturated steam which does not contain any liquid particles is called dry saturated steam
i.e. dryness fraction is 1 and quality is 100%.
Ex: Calculate the dryness fraction of steam which has 1.25 kg of water in suspension with 40 kg
of steam.
Solution: Ms = 40 Kg
Mw =1.25Kg
𝑚𝑠 40
Dryness fraction x = 𝑚 = 40+1.25 = 0.9696
𝑠 +𝑚𝑤

80
 UNIT – 8

Air standard and power cycles

Introduction

The working fluid is air, which continuously circulates in a closed loop (cycle). Air is considered
as ideal gas. All the processes in (ideal) power cycles are internally reversible. The exhaust
process is modeled by a heat-rejection process that restores the working fluid (air) at its initial
state.
The working fluid of heat engines is subjected to a series of changes (in temperature, volume,
pressure, etc.), known as thermodynamic air standard cycles, through which the energy absorbed
as heat is converted into mechanical work. Internal combustion engines do not operate on a
thermodynamic cycle as it involves an open system. However, it is often possible to analyze the
open cycle by imagining one or more processes that would bring the working fluid at the exit
conditions back to the condition of the starting point. The actual gas power cycles are rather
complex.
To reduce the analysis to a manageable level, the following approximations, commonly known
as air standard assumptions, are made:
1. The working medium is a perfect gas.
2. There is no change in the mass of the working medium.
3. All the processes that constitute the cycle are reversible.
4. Heat is supplied from a constant high-temperature source.
5. Some heat is assumed to be rejected to a constant low-temperature sink during the
cycle.
6. There are no undesired heat losses from the system to the surroundings.
7. The working medium has constant specific heats throughout the cycle.
8. The physical properties (cp, cv, μ,γ) of the working fluid are constant.

Another assumption that is often utilized to simplify the analysis, even more, is that air has
constant specific heats whose values are determined at room temperature (250C). When the
assumption is utilized, the air standard assumptions are called cold air standard assumptions. A
cycle for which air standard assumptions are applicable is frequently referred to as an air
standard cycle.

81
 In what are known as air standard cycles, or ideal cycles, the constant volume, constant pressure
and adiabatic processes are put together to form theoretical engine cycles which we can show on
the p/V diagram. The actual p/V diagram is different from what is possible in practice, because,
for instance, we assume that the gas is air throughout the cycle when in fact it may
be combustion gas. We also assume that valves can open and close simultaneously and that
expansion and compressions are adiabatic.
Air standard cycles are reference cycles which give an approximation to the performance
of internal combustion engines.
Otto cycle – P-V and T-S diagram
The Otto cycle was given by Dr. Nikolaus August Otto. Otto cycle produces a successful four
stroke cycle engine in 1876. It is a gas power cycle that is used in spark ignition engine (i.e.
petrol engine) for its working. The entire modern petrol engine works on Otto cycle. It consist of
four processes, Two isentropic (reversible adiabatic) processes and two isochoric (constant
volume) processes. It has low compression ratio ranges from 7:1 to 10:1. Here we will try to
understand this cycle with help of its P-V and T-S diagram.
The four processes of this cycle are as follows:
1. Isentropic (reversible adiabatic) compression
2. Constant volume (Isochoric) heat addition
3. Isentropic (reversible adiabatic) Expansion
4. Constant volume heat rejection.
Before starting to understand these four processes, lets us first understand about isentropic and
isochoric process.
1. Isentropic process: It is a thermodynamic process in which the entropy of the system remains
unchanged (i.e. entropy remains constant). There is no dissipation of heat takes place during
isentropic process, so sometime isentropic process called as reversible adiabatic process.
2. Isochoric process: The process which takes place at constant volume is called isochoric process.
How Otto cycle works?

82
Now, with the help of P-V and T-S diagram, we can easily understand all the process of Otto
cycle.
Process 1-2: Isentropic compression
This process involves the motion of piston from TDC to BDC. The air that is sucked into
cylinder during suction stroke undergoes reversible adiabatic (isentropic) compression. Since the

83
air is compressed, the pressure increases from P1 to P2, the volume decreases from V1 to V2,
temperature rises from T1 to T2, and entropy remains constant
Process 2-3: Constant volume heat addition
This process is an isochoric process i.e. the heat is added to the air at constant volume. The
piston in this process rest for a moment at TDC and during this time heat is added to the air
through external source. Due to the heat addition, the pressure increases from P2 to P3, pressure,
volume remains constant (i.e. V2=V3), temperature increases from T2 to T3 and entropy
increases from S2 to S3.
The amount of heat added is given by

Process 3-4: Isentropic expansion

In this process, the isentropic (reversible adiabatic) expansion of air takes place. The piston
moves from TDC to BDC. Power is obtained in this process which is used to do some work.
Since this process involves expansion of air, so the pressure decreases from P3 to P4, volume
increases from V3 to V4, temperature falls from T3 to T4 and entropy remains unchanged (i.e.
S3=S4)
Constant volume heat rejection
In this process, the piston rest for a moment at BDC and rejection of heat takes place at constant
volume. The pressure decreases from P4 to P1, Volume remains constant (i.e. V4=V1),
temperature falls from T4 to T1.
The amount of heat rejected in this process is given by

When this cycle is used in four stroke petrol engine than two process increases. One is suction of
air fuel mixture inside the cylinder which takes place at constant atmospheric pressure and other
one is exhaust of gases out of the engine cylinder at constant atmospheric pressure. These two
processes are not shown in ideal Otto cycle that we have discussed above.

84
 Summary in tabular form
Position of
S. no Process Operation piston Change in parameter

V: Decreases from V1 To V2

T: Increases from T1 to T2

P: Increases from P1 to P2

1-2: Isentropic S: Entropy remains constant

1. Compression Compression of air. BDC to TDC (S1=S2)

V: Remains constant (V2 = V3 )

T: Increases from T2 to T3

P: Increases from P2
2-3: Constant Heat is added in the
to P3
Volume Heat form of spark and At TDC for a
2. Addition combustion occurs. moment S: Increases from S2 to S3

V: Increases from V3 to V4

T: Decreases from T3 to T4

P: Decreases from P3 to P4
Expansion of air
3-4: Isentropic takes place due to S: Entropy remains constant
3. Expansion heat addition. TDC to BDC (S3=S4)

V: Volume remains constant(V4 =

V1 )

T: Decreases from T4 to T1
4-1: Constant
P: Decreases from P4 to P1
Volume Heat Heat is rejected to a At BDC for a
4. Rejection sink. moment S: Decreases from S4 to S1

85
Thermal efficiency

The efficiency of Otto cycle is given by

Application
It is used in all two stroke and four stroke petrol engines of motorcycles, cars, and other light
duty vehicles.
Diesel cycle – P-V and T-S Diagram
The diesel cycle was invented by Rudolph Diesel in 1893. He put forward an idea by which we
can attain higher thermal efficiency, with a high compression ratio. All diesel engine works on
this cycle. Diesel is used as fuel in this cycle as it can be compressed at higher compression ratio.
It is also known as constant pressure cycle because heat is added in it at constant pressure. It has
high thermal efficiency and compression ratio (11:1 to 22:1) as compared with Otto cycle.
The engine that is put forward by Rudolph consists of an enclosed air in the cylinder. The
cylinder walls are perfectly non-conductors of heat, but the bottom is a perfect conductor of heat.
It has a hot body, cold body and an insulating cap, which are alternately brought in contact with
the cylinder.
The ideal Diesel cycle consist of 4 process, two isentropic processes, one constant pressure and
one constant volume process.
Processes
The 4 process are as follows
1. Isentropic (reversible adiabatic) Compression
2. Constant pressure heat addition
3. Isentropic Expansion
4. Constant volume heat rejection.

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Process 1-2: Isentropic compression
In this process the piston moves from BDC to TDC and compression of air takes place
isentropically. It means that during compression the entropy remains constant and there is no
flow of heat out of the cylinder walls (non-conductors) happens. Here the air is compressed so
the pressure increases from P1 to P2, volume decreases from V1 to V2, Temperature increases
from T1 to T2 and entropy remains constant ( i.e. S1 = S2).
Process 2-3: Constant Volume Heat Addition
In this process the, the hot body is kept in contact with the cylinder and heat addition to the air
takes place at constant pressure. During this process, the piston rest for a moment at TDC. The
pressure remains constant (i.e. P2 = P3), volume increases from V2 to V3, temperature increases
from T2 to T3, entropy increases from S2 to S3.
Process 3-4: Isentropic expansion
In this process, after heat addition, the expansion of air takes place isentropically and work is
obtained from the system. The piston moves downward during this process and reaches to BDC.
The pressure falls from P3 to P4, Volume increases from V3 to V4, temperature falls from T3 to
T4 and entropy remains constant (i.e. S3= S4).
Process 4-1: Constant volume heat rejection
In this process, the piston rest at BDC for a moment and the cold body is brought in contact with
the cylinder and the heat rejection takes place at constant volume. The pressure decreases from
P4 to P1, temperature decreases from T4 to T1, entropy decreases from S4 to S1 and volume
remains constant (i.e.V4 = V1).
This is the four working process of diesel cycle engine that we have discussed. Now we will
discuss how this cycle is implemented in the 4 stroke diesel engine. When this cycle is used in 4-
stroke diesel engine than we have 2 extra processes. One is suction process and other one is
exhaust
process. For heat addition diesel is used as fuel which burns and adds heat.
Let’s discuss all the process in detail
0-1: Suction process (Suction stroke)
1-2: Isentropic compression process (compression stroke)
2-3: Constant volume heat addition (ignition and combustion of fuel)
3-4: Isentropic Expansion (power stroke)

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4-1: Constant volume heat rejection (coolant comes in contact with cylinder walls)
1-0: Exhaust process (Exhaust stroke)
Process 0-1: Suction process
In this process, the inlet valve opens and suction of air takes place at atmospheric pressure. It is
called as suction stroke.
Process 1-2: Isentropic Compression
The air sucked is now compressed is entropically. Due to the compression, the temperature of the
air increases to such level at which the diesel gets ignites. It is called as compression stroke.
Process 2-3: Constant Pressure Heat Addition
At the end of the compression, the piston is at TDC and at this time, the diesel fuel is injected
into the cylinder through fuel injector in atomized form. As this atomized diesel fuel comes in
contact with the hot compressed air, it gets ignited and combustion process starts. The
combustion of fuel adds heats to the engine.
Process 3-4: Isentropic Expansion
The combustion process adds a large amount of heat and this creates a large force on the piston
head and it moves downward from TDC to BDC. It is the power stroke.
Process: 4-1: Constant Volume Heat Rejection
The piston is at BDC and the coolant comes in contact with the cylinder walls and takes away
heat from the engine and makes it cool. After that piston moves upward.
Process: 1-0: Exhaust Process
In this process, the piston moves from BDC to TDC and exhaust valve opens. All the burnt gases
left in the cylinder escapes out through exhaust valve. It is the exhaust stroke.
This is how a four stroke compression engine works.

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How diesel cycle works?
Now, with the help of P-V and T-S diagram, we can easily understand all the process of Diesel
cycle.

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Summary
Summary of diesel cycle with operation, position of piston and changes in different parameters
are given below:

Position of
S. no Process Operation piston Change in parameter

V: Decreases from V1 To V2
T: Increases from T1 to T2
1-2: Isentropic P: Increases from P1 to P2
1. Compression of air BDC to TDC
compression S: Entropy remains constant (S1=S2)
At TDC for a
moment and V: Increases from V2 To V3
2-3: Constant Heat is added from moves T: Increases from T2 to T3
Pressure heat an external source slightly P: Remains constant (P2 = P3)
2. addition (hot body) downward. S: Increases from S2 to S3

V: Increases from V3 to V4
Expansion of air
T: Decreases from T3 to T4
3-4: Isentropic takes place due
P: Decreases from P3 to P4
3. expansion to heat addition. TDC to BDC
S: Entropy remains constant (S3=S4)
V: Volume remains constant(V4 =
V1)
4-1: Constant
T: Decreases form T4 to T1
volume heat Heat is rejected to a At BDC for a
P: Decreases from P4 to P1
4. rejection sink moment
S: Decreases from S4 to S1

Application
Diesel cycle is used where more power is needed with less amount of fuel. Mainly it is used in
two stroke and 4 stroke diesel engines.
Dual cycle– P-V and T-S Diagram
Dual cycle, or limited pressure cycle, is a thermodynamic cycle that combines the Otto cycle and
the Diesel cycle. In the dual cycle, combustion occurs partly at constant volume and partly at
constant pressure.

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Dual cycle in thermodynamics is a mixed cycle from the Otto cycle and the diesel cycle. We
have already discussed these cycles with the P-V and T-S diagrams in the previous articles. In
this article, we are going to discuss the Dual cycle with the P-V diagram and the T-S diagram.
The Otto cycle is a constant volume cycle and the Diesel cycle is a constant pressure cycle. In a
practical scenario, in the constant volume cycle, the combustion might not take place at the
constant volume because of the chemical reaction during the combustion need some time to take
place.
Similarly, in the Constant pressure cycle, the combustion might not take place at the constant
pressure because of the uncontrolled rapid combustion. So this is the difference between the air
standard cycles and the practical engine
This Dual cycle is a compromise between the Otto cycle and the Diesel Cycle. So it is called the
mixed cycle or Limited pressure Cycle.

The P-V and T-S diagram for the Dual cycle is shown below.

0 → 1 and 1 → 0

When the engine is working on the full throttle, the Process 0 → 1 and 1 → 0 represents the
suction and the exhaust process of Thermodynamic cycle in the P-V diagram and the effect of
these two processes considered as nullified.
1→2
The process 1 → 2 is the isotropic compression of the air in the cylinder while piston moves
from the bottom dead centre (BDC) to the top dead centre (TDC)
2→3&3→4

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During the process, 2 → 3 First the heat is supplied at a constant volume and then the remaining
part of heat will be added at the constant pressure process 3 → 4.
4→5&5→1
These two processes 4 → 5 & 5 → 1 will represent the isotropic expansion (Piston moves from
the Top dead centre to the bottom dead centre) and the constant volume heat rejection
respectively.
Thermal Efficiency
Thermodynamically, the efficiency of the Dual cycle is given by

Work done by the system = Heat supplied (QS) - Heat rejected (QR)

W = QS – QR

From the processes 1 → 2

Where r is the Compression Ratio

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Now from the process 2 → 3 constant Volume process

(Substituted the T2 in the above equation)

Where rp is the pressure ratio in the constant volume process which is equal to the P3/P2

From the 3 → 4 Constant pressure process

(Substituted the T3 & T2 in the above equation)

Where rcrc is the Cut-Off ratio in the constant pressure process which is equal to the V4/V3
From the Isotropic process 4 → 5

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(Substituted the T4 & T3 & T2 in the above equation)
Let’s substitute all these above equations in the main efficiency equation

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From the above equation, we can observe that the value of rp >1 results in increased efficiency
for the given value of rc and γ.
Where rc = 1 then it will give the Otto cycle efficiency and with the rp = 1 it will gives the diesel
cycle efficiency.
Conclusion
We have discussed the mixed cycle called dual cycle with the P-V and T-S diagrams and also we
have derived an equation for the efficiency of the dual cycle.
In a dual cycle, the system executing the cycle undergoes a series of five processes: two
isentropic (reversible adiabatic) processes alternated with two isochoric process and one isobaric
process:

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Isentropic compression(compression stroke) – The gas is compressed adiabatically from state 1
to state 2, as the piston moves from intake valve closing point (1) to top dead center. The
surroundings do work on the gas, increasing its internal energy (temperature) and compressing it.
On the other hand the entropy remains unchanged. The changes in volumes and its ratio (V1 / V2)
are known as the compression ratio. The compression ratio is smaller than the expansion ratio.
Isochoric compression (ignition phase) – In this phase (between state 2 and state 3) there is a
constant-volume (the piston is at rest) heat transfer to the air from an external source while the
piston is at rest at top dead center. This process is similar to the isochoric process in the Otto
cycle. It is intended to represent the ignition of the fuel–air mixture injected into the chamber and
the subsequent rapid burning. The pressure rises and the ratio (P3 / P2) is known as the
“explosion ratio”.
Isobaric expansion (power stroke) – In this phase (between state 3 and state 4) there is a
constant-pressure (idealized model) heat transfer to the air from an external source (combustion
of the fuel) while the piston is moving toward the V4. During the constant pressure process,
energy enters the system as heat Qadd, and a part of work is done by moving piston.
Isentropic expansion (power stroke) – The gas expands adiabatically from state 4 to state 5, as
the piston moves from V3 to bottom dead center. The gas does work on the surroundings (piston)
and loses an amount of internal energy equal to the work that leaves the system. Again the
entropy remains unchanged.
Isochoric decompression (exhaust stroke) In this phase the cycle completes by a constant-
volume process in which heat is rejected from the air while the piston is at bottom dead center.
The working gas pressure drops instantaneously from point 5 to point 1. The exhaust valve opens
at point 5. The exhaust stroke is directly after this decompression. As the piston moves from
bottom dead center (point 1) to top dead center (point 0) with the exhaust valve opened, the
gaseous mixture is vented to the atmosphere and the process starts anew.
During the Dual cycle, work is done on the gas by the piston between states 1 and 2 (isentropic
compression). Work is done by the gas on the piston between stages 2 and 3 (isobaric heat
addition) and between stages 2 and 3 (isentropic expansion). The difference between the work
done by the gas and the work done on the gas is the net work produced by the cycle and it
corresponds to the area enclosed by the cycle curve. The work produced by the cycle times the
rate of the cycle (cycles per second) is equal to the power produced by the Diesel engine.

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 Thermal efficiency for dual cycle
In general the thermal efficiency, ηth, of any heat engine is defined as the ratio of the work it
does, W, to the heat input at the high temperature, QH.
The thermal efficiency, ηth, represents the fraction of heat, QH that is converted to work. Since
energy is conserved according to the first law of thermodynamics and energy cannot be
converted to work completely, the heat input, QH, must equal the work done, W, plus the heat
that must be dissipated as waste heat QC into the environment. Therefore we can rewrite the
formula for thermal efficiency as:

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