Thermodynamics

 Thermodynamics was obtained from two Greek words namely ‘therme’ meaning heat and ‘dynamis’
meaning power. Thermodynamics is the science relating heat and work transfers and the related
changes in the properties of the system.

 The principles of thermodynamics are summarized in the form of four laws known as zeroth, first,
second, and the third laws of thermodynamics.

 The zeroth law of thermodynamics deals with thermal equilibrium and provides a means of
measuring temperature.

 The first law of thermodynamics deals with the conservation of energy and introduces the concept of
internal energy.

 The second law of thermodynamics dictates the limits on the conversion of heat into work and
provides the yard stick to measure the performance of various processes. It also tells whether a
particular process is feasible or not and specifies the direction in which a process will proceed. As a
consequence it also introduces the concept of entropy.

 The third law defines the absolute zero of entropy.

Application areas of thermodynamics:

 Steam power plant

 Refrigeration

 Air-conditioning and Heating Devices.

 Internal combustion engine

 Chemical power plants

 Turbines and Compressors

Different Approaches of Thermodynamics

There are two approaches from which the behaviour of matter can be studied:

Microscopic approach: In this approach the behaviour of individual molecules is taken into consideration. This
approach is also known as statistical thermodynamics.

Macroscopic approach: In this approach the average behaviour of certain quantity of the matter (group of molecules)
is taken into consideration. This approach is also known as classical thermodynamics.

 Macroscopic approach is mainly used in engineering thermodynamics because in this few variables are
required to describe the state of matter which can be easily measurable.

Concept of continuum
Matter is made up of atoms that are widely spaced in the gaseous phase. The macroscopic approach is
applicable when the smallest unit of the matter is large enough compared to the intermolecular spacing
between the atoms. Under such circumstances, the matter in a system is considered as continuous without
any hole. This is called the concept of continuum.
In the situation when the scale of the analysis is too small such that even the intermolecular spacing is of
comparable size then it cannot be considered continuous and microscopic approach should be followed.
Example: To define the density at a point we consider some limiting volume ( v ' ) such that the matter
m
around the point may be treated as continuous and average density is given by:   lim v  v ' 
v

Thermodynamic System: A thermodynamic system is defined as a definite quantity of matter or a

region of space upon which the attention is focussed in the analysis of a problem.

Surrounding: Everything external to the system is known as surrounding.

Boundary: The surface that separates the system from its surrounding is called the boundary. System and
surrounding interact through boundary in the form of Heat and Work. Boundary can be real (or) imaginary.
Boundary can be fixed (or) moving.

Universe : (System + Surrounding) put together is known as Universe.

Types of system

Closed system (Control mass): A system which can exchange energy but not mass with its
surroundings is called the closed system. This system consists of a fixed amount of mass, and no mass can
cross its boundary. But the energy in the form of heat and work can cross the boundary. Closed system is
also known as non-flow system. Example: Burning of gas inside a sealed piston cylinder arrangement.
Open system (Control volume): A system which can exchange mass as well as energy with its
surroundings is called the open system The open system is one in which both mass and energy can cross the
boundary of the system. Open system is also known as flow system.
Example: Water heaters, Turbines, Compressors, Nozzles

Isolated system: A system which can neither exchange mass nor energy with its surroundings is called
the isolated system The isolated system is one in which there is no interaction between the system and the
surroundings that neither the mass nor the energy interactions. Therefore it is of fixed mass and energy.
Example: Universe, Hot coffee in a well insulated thermo flask

Control mass: The region in space of definite quantity of matter of fixed mass bounded by a closed
surface (boundary) on which the attention is focussed for study is called the control mass. In the closed
system the mass does not cross the boundary, though its volume can change against a flexible boundary so it
analyzed as a control mass.

Control volume: The region in space bounded by a closed envelope on which the attention is focussed
for study is called the control volume. The control volume bounded by a prescribed boundary is known as
control surface. In the open system the mass flow across the boundary so it analyzed as a control volume.
Phase: If a quantity of matter is uniform throughout in physical structure and chemical composition, it is
termed as a phase. Uniformity of physical structure means that the matter is either all solid or all liquid or all
gas. Uniformity of chemical composition means that the chemical composition does not vary from one part
of the system to another.
Examples: One phase: An iron piece, a liquid contained in a vessel, a gas enclosed within a container,
mixture of gases.
Two phase: Mixture of liquid and gas
Three phase: Mixture of Solid, liquid and Gas

Homogenous and Heterogenous system

On the basis of phases the system may be classified as:
(i) Homogenous system: If the system consists of single phase it is called homogenous system.
Example: Mixture of air and water vapour, mixture of ammonia in water,

(ii) Heterogenous system: If the system consists of more than single phase it is called heterogenous
system.
Example: Mixture of ice and water , mixture of water and steam,

Pure Substance
A substance that has a fixed chemical composition throughout the system is called a pure substance.
Example: Water, hydrogen, nitrogen, and carbon monoxide
 A pure substance can also be a mixture of various chemical elements or compounds as long as the
mixture is homogeneous. Example: Air
 A mixture of two or more phases of a pure substance is still a pure substance as long as the chemical
composition of all phases is the same. Example: Mixture of ice and liquid water

Properties of a thermodynamic system

The measurable characteristics by which the physical condition of any thermodynamic system is described
are called the properties of the system. Example: Pressure, Volume, Temperature, mass etc.
Some features of thermodynamic properties:
(i) It is a measurable characteristic describing a system.
(ii) It has definite unique value when the system is in a particular state.
(iii) It is the function of the state of a system, so it is referred as a point function.
(iv) It does not depend on the path to attain that particular state.
2
(v) The differential of the property is exact.  dp  p
1
2  p1

(vi) The change in the value of any property of the system for a cyclic process is zero.  dp  0
 Types of properties

(i) Intensive properties: Those properties which are independent of the mass of a system are called as
intensive properties. Example: Temperature, Pressure, density etc.

(ii) Extensive properties: Those properties which are dependent of the mass of a system are called as
intensive properties. Example: Volume, Energy etc.

Extensive properties per unit mass are called the specific properties and therefore become intensive
properties. Example: Specific volume, Specific energy etc.

State: It is the condition of the system which is defined by the definite values of the properties. So the
properties are the coordinates to describe the state of any system.

Change of state: When one or more of the properties change by some operation then it is called as
change of state.

Path: The succession of states passed through a change of state is called the path of the change of state.

Process: When the path connecting the change of state is completely specified then this path is called the
process.

Cyclic process: It is defined as a series of state changes such that the final state is identical with the
initial state.
 Thermodynamic equilibrium
Thermodynamics deals with equilibrium states. A system is said to exist in a state of Thermodynamic
Equilibrium when no changes in macroscopic property is observed if the system is isolated from its
surrounding.
At the state of equilibrium, the properties of the system are uniform and only one value can be assigned to it.
A system will be in a state of thermodynamic equilibrium, if the conditions for the following three types of
equilibrium are satisfied:
1. Mechanical equilibrium: A system is in mechanical equilibrium if there is no unbalanced force
or no change in pressure at any point of the system with time.
2. Thermal equilibrium: A system is in thermal equilibrium if the temperature is the same
throughout the entire system.
3. Chemical equilibrium: A system is in chemical equilibrium if its chemical composition does
not change with time.
Quasi-static process
Quasi-static process is one that takes place so slowly that the system may be considered as passing through
the succession of equilibrium states. It can be represented as a continuous line on the property diagram.
Infinite slowness is the characteristic feature of this process.
Example: Let us consider a system of gas contained in a cylinder as shown in the fig. represented by the
properties p1, v1, t1. The weight of the piston just balances the upward force exerted by the gas. If the weight
is removed, the piston will move up due to unbalanced force till it hits the stops. The system again comes to
an equilibrium state and described by the properties p2, v2, t2. But the intermediate states passed through by
the system are non-equilibrium states which cannot be described.
Now if the single piece of weight on the piston is made up of many very small pieces of weights are
removed one by one very slowly, the departure of the state will be infinitesimally small and ever state
passed through by the system will be an equilibrium sate. Such a process is the locus of intermediate
equilibrium states is known as the Quasi-static process.

Reversible Process
A process is called reversible if the initial state together with all energies transferred or transformed during
the process can be completely restored in both system and surrounding.
Thus if a process is really reversible there is no after effects or changes in the system or in surrounding when
the process occurs in forward and then in backward direction.
In reversible process, system passes through a continuous series of equilibrium states so quasi-static process
is also a reversible process.
It is noted that reversible processes actually do not occur in nature. There are two reasons to idealize the
actual process as a reversible process: (i) They are easy to analyze (ii) they serve as idealized models to
which actual processes can be compared.
Some examples of nearest reversible process: (a) Frictionless isothermal expansion or compression of a fluid
(b) Frictionless adiabatic expansion or compression of a fluid.

Irreversible Process
A process is called irreversible if the initial state together with all energies transferred or transformed during
the process cannot be completely restored in both system and surrounding.
In an irreversible the surrounding would always be affected by loss of work and gain of low temperature heat,
which can be considered as waste heat for the surrounding.

Causes of Irreversibility:
The irreversibility of a process may be due to either one or both of the following.

(i) Lack of Equilibrium: The lack of equilibrium between the system and the surroundings or between the
two systems causes a spontaneous change which makes the process irreversible.
Examples:
1. Heat transfer through a finite temperature difference.
2. Compression or Expansion through a finite pressure difference between the system and the surroundings.
3. Mixing of substances.

(ii) Involvement of Dissipative effects: Dissipation results in the transformation of work into molecular
energy of the system.
Examples:
1. Friction.
2. Flow of electricity through a resistor.
3. Paddle wheel work transfer.

Internally and Externally Reversible Processes

A process is called internally reversible if no irreversibility occurs within the boundaries of the system
during the process. The main cause of internal irreversibility is dissipative effects (friction).

A process is called externally reversible if no irreversibility occurs outside the system boundaries during the
process. The main cause of external irreversibility is lack of equilibrium.

A process is called totally reversible, or simply reversible, if it involves no irreversibility within the system
or its surroundings.

Pressure is defined as a normal force exerted per unit area. Since pressure is defined as force per unit area,
it has the unit of N/m2, which is called a Pascal (Pa). That is, 1 Pa = 1 N/m2
Other units of pressure commonly used in practice are:
1 kilo-pascal (kPa) = 103Pa
1 mega-pacal (MPa) = 106Pa
1bar = 105Pa
1atm = 1.01325bar = 1.01325 x 105Pa

The following terms are generally associated with measurement of pressure:

Atmospheric pressure (Patm): It is the pressure exerted by the envelope of air surrounding the earth’s
surface. It is measured by Barometer.
 Fig. Barometer
A barometer is a tube sitting upside down in a container filled with mercury (Hg). When the atmospheric
pressure falls in the container, the mercury in the tube rises. The space above the mercury in the tube is a
vacuum so the atmospheric pressure will push the mercury up until the pressure of the column of the
mercury (h) balances the atmospheric pressure. Hence the height of the column measures the atmospheric
pressure.
Atmospheric pressure (Patm) = ρ g h
Where;
ρ = density of the working liquid (kg/m3)
g = acceleration of gravity (9.8 m/s2)
h = height of the working liquid in the tube (m)
P 1.01325  10 5
 For Hg, ρ = 13.6 x 103 kg/m3, so h = atm   0.760m  760mm
g 13.6  10 3  9.8
Hence; 1atm = 760mm of Hg = 76cm of Hg
P 1.01325  10 5
 For Water, ρ = 103 kg/m3, so h = atm   10.33m
g 10 3  9.8
Hence; 1atm = 10.33m of Water

Absolute Pressure (Pabs): Any pressure measured above the absolute zero pressure is termed as “Absolute
pressure”. The absolute zero pressure can exists only in complete vacuum.

Gauge Pressure (Pgauge): Any pressure measured above the atmospheric pressure is termed as “Gauge
pressure”.This is also known as positive gauge pressure.

Vacuum Pressure (Pvac): Any pressure measured below the atmospheric pressure is termed as “Vacuum
pressure”. This is also known as negative gauge pressure.

Pabs  Patm  Pgauge and Pabs  Patm  Pvac

 Manometer
A simple manometer consists of a glass U-tube containing fluid such as mercury. One of its ends connected
to the point, where pressure is to be measured and other end is open to the atmosphere.

 In fig.1 both ends are open to atmosphere, so the liquid is at the same height in both the limbs.

 In fig.2 the gauge pressure is applied at left limb and right limb is open to atmosphere, so the level of
liquid in right limb is higher than the left limb with an amount of ‘h’.
P  Patm  gh
Where;  = density of liquid (Hg), g = gravitational acceleration=9.8m/s2, h = difference of height of liquid

 In fig.3 the vacuum pressure is applied at left limb and right limb is open to atmosphere, so the level
of liquid in right limb is lower than the left limb with an amount of ‘h’.

P  gh  Patm or P  Patm  gh

Where;  = density of liquid (Hg), g = gravitational acceleration=9.8m/s2, h = difference of height of liquid

Temperature is defined as a measure of ‘hotness’ or ‘coldness’ of any body. It is the thermal state of
any body which defines its ability to transfer heat to other bodies.
When a hot body is brought into contact with a cold body, the hot body becomes cooler and the cold body
becomes hotter. After sufficient time, the temperature of both the bodies will be equal. At that point, the two
bodies are said to have reached thermal equilibrium. The equality of temperature is the only requirement for
thermal equilibrium.

Zeroth law of thermodynamics: It states that if two bodies are in thermal equilibrium with a third
body than they are also in thermal equilibrium.

Consider three bodies A, B and C. If the bodies A and B are in thermal equilibrium with C when brought
into contact, they are also in thermal equilibrium with each other. This concept is known as zeroth law of
thermodynamics.
 Zeroth law of thermodynamics serves as a basis of temperature measurement. By replacing the third body
with a thermometer, the zeroth law can be restated as two bodies are in thermal equilibrium if both have the
same temperature reading even if they are not in contact.

Temperature scales: Freezing point of water known as ice point and boiling point of water known as
steam point are taken as the reference states for all types of temperature scales.
The various types of temperature scales in use are: a) Celsius scale
b) Fahrenheit scale
c) Kelvin scale
d) Rankine scale

fig. Comparison of different temperature scale

Ideal gas equation
 The ideal-gas equation can be expressed in many different forms.

(i) PV  mRT (P=Pressure, V=Volume, m=mass, R=gas constant, T=Temperature)

m m
(ii) P  RT  RT (    density )
V V
V
(iii) P  RT
m
V
Pv  RT (  v  specific volume)
m
 
R m   R m
(iv) PV  m T  RT  n RT ( R  ) and ( (n  )
M M M M

R =Universal gas constant=8.314kJ/kmolK
M = Molecular weight
n = no. of moles
PV PV
(v) Ideal gas equation for change of state : 1 1  2 2 =constant
T1 T2
 P-V-T Relation for different thermodynamic processes
1. Isochoric process: Volume (V) =constant

P1 P2
V1  V2  Constant; and 
T1 T2
1. Isobaric process : Pressure (P) =constant

V1 V2
P1  P2  Constant; and 
T1 T2
2. Isothermal process : Temperature (T) =constant

T1  T2  Constant; and P1V1  P2V2


3. Adiabatic process : PV  Constant & ∆Q = 0

1  1

  V2  P1   T2  P2  
Q  0 and P1V1  P2V2 or   or  
V1  P2  T1  P1 
 4. Polytropic process : PV n  Constant
1 n 1
V2  P1  n T2  P2  n
P1V1  P2V2    
n n
or or
V1  P2  T1  P1 

(P-V diagram of different Thermodynamic processes)

Energy and its forms

Energy: Energy is defined as the capacity to do work. The S.I unit of energy is Joule (J).
Energy may be broadly classified as: (i) Stored energy (ii) Energy in transition

(i) Stored energy: It is contained with in the system boundaries.

Example: (a) Kinetic energy (b) Potential energy and (c)Internal energy

(a) Kinetic energy (K.E): This energy is due to the velocity of the mass of the body. It is given
by:
1
K .E  mv 2 , where; m = mass of the body, and v = velocity of body
2

(b) Potential energy (P.E): This energy is due to the elevation of the mass of the body in
gravitational field. It is given by:
P.E  mgh , where; m = mass of the body, g = gravitational acceleration and h = elevation

(c) Internal energy (U): This energy is due to the kinetic and potential energies of the molecules.
Hence it is also called as microscopic form of energy. The internal energy is the sum of the
following energies:
(i) Translational, rotational and vibration energy of molecules
(ii) Spin energy of electrons
(iii) Potential energy of molecules
(iv) Molecular binding energy
(v) Magnetic or electric dipole energy

Internal energy stored within the system due to the movement and arrangement of the molecules,
which is the function of temperature. Internal energy is given by:
U  mCv T , where; m = mass of the body, Cv = Specific heat at constant volume and
T =Change in temperature

 Total stored energy (E) of the system is given by: E = U + K.E + P.E

(ii) Energy in transition: Energy which can cross the boundary of the system is called as energy in
transition. Example: Work & Heat
 Work
Thermodynamic work: “Work is said to be done by a system on the surrounding if the sole effect external to
the system could be reduced to the raising of a weight through a distance”.

Sign Convention for work done: Work done by the system is positive and Work done on the system is
negative.
Types of work: The work interaction between system and surrounding may be classified as follows:
(i) Displacement work
(ii) Paddle wheel work or Stirring work
(iii) Flow work
(i) Displacement work
Displacement work is defined as a work that occurs at the boundary of a thermodynamic system when the
volume of a working fluid changes. It is associated with the change in volume of a working fluid in an
expansion or compression process. It is positive in expansion process and negative in compression process.

Expression of displacement work: Consider a gas in a container with a movable piston on top. If the gas
expands, the piston moves out and work is done by the system on the surroundings as shown in fig.

Displacement work (W) =  dW   Fds   ( PA)ds   P( Ads )   PdV

The integral (  PdV =  dA ) represents the area under the curve on a pressure versus volume diagram.
Therefore the work depends on the path followed hence it is a path function and not a property of the
system.

Displacement work (  PdV ) for different non-flow processes

(i) Isobaric process (P=Constant)
(ii) Isochoric process (V=Constant)

(iii) Isothermal process (T=Constant)

(iv) Polytropic process (PVn = Constant)

 (v) Adiabatic process (PVγ = Constant) γ (adiabatic index = Cp/Cv) > 1
 1
 
P1V1  P2V2 P1V1   P2   
W12   1  
 1   1   P1  
 
(vi) Paddle wheel work or Stirring work

(vii) Flow work

The amount of the work which is required to push the fluid into and out of the system in a flow process
(open system) is called as flow work. The flow work is due to the pressure of the flowing fluid.

If a working fluid with pressure (P), through an area (A), moves a distance (L) , the flow work required to
move the fluid is given by: W  FxL  PxAxL  PxV (Joule)

Flow work per unit mass: w  Pxv (Joule/kg)

 Heat
Heat is defined as the form of energy that is transferred between system and its surroundings by virtue of a
temperature difference. There cannot be any heat transfer between two bodies that are at the same
temperature.

Sign Convention for heat: Heat added to the system is positive and Heat removed from the system is
negative.
Specific heat
The specific heat is defined as the heat required, per unit mass of a system to raise its temperature by one
degree.
dQ  mcdT
dQ dq dQ
c  ( dq  = heat required for unit mass)
mdT dT m

Specific heat at constant volume (cv): The specific heat at constant volume is defined as the amount of
heat required at constant volume, per unit mass of a system to raise its temperature by one degree.
 dq 
It is given by: cv   
 dt V
So heat transfer at constant volume: dQ  mcv dT

Specific heat at constant pressure (cp): The specific heat at constant pressure is defined as the amount of
heat required at constant pressure, per unit mass of a system to raise its temperature by one degree.
 dq 
It is given by: c P   
 dt  P
So heat transfer at constant pressure: dQ  mcP dT

Comparison of Heat & Work

Similarities:
1.Both heat & work are energy in transition; they are never stored in a system.
2.Both heat & work represent energy crossing the system boundary; hence they are boundary
phenomenon.
3.Both heat & work are not properties of the system; hence their differentials are not exact.
4.Both heat & work are path functions because they are represented by a path followed during
the process.

Dissimilarities:
1.Heat transfer is the energy interaction due to temperature difference only. All other energy
interactions are termed as work transfer.
2.A stationery system cannot do work but such restriction does not exist for heat transfer.
3.Entire quantity of work can be converted into heat but entire quantity of heat cannot be
converted into work.
4.Heat is low grade energy whereas the work is high grade energy.
 Point function & Path function
Point function Path function
Any quantity whose change is independent of the Any quantity whose change depends of the path
path followed during a change of state and followed during a change of state is called path
depends only on end states is called point function.
function.
Example: Pressure, Volume, Temperature Example: Heat, Work
2 2
These are exact differential.  dP  P2  P1 These are inexact differential.  dW  W2  W1
1 1

Enthalpy (H)
Enthalpy is the sum of internal energy and the product of pressure & volume of the system.

H = U + PV (kJ)

For unit mass: h = u + Pv (kJ/kg)

At constant pressure heat transfer to a closed system is equal to change in enthalpy:

dQ  dH  mcP dT

For unit mass: dq  dh  cP dT

 Enthalpy of an ideal gas depends on temperature only.

Relation between Specific heat at constant volume (cv) and Specific heat at constant pressure (cp)

We know that; H = U + PV

or dH = dU + d(PV)

or mcP dT = mcv dT + d (mRT ) (Ideal gas equation: PV = mRT)

or mcP dT = mcv dT + mRdT

or c p  cv  R

cp
Ratio of specific heat (adiabatic index) = 
cv

For mono-atomic gases;   1.67

For di-atomic gases;   1.4
The difference of specific heat = c p  cv  R (gas constant)
For atmospheric air:   1.4 , c p  1.005 kJ/kg-K, cV  0.718 kJ/kg-K, R =0.287 kJ/kg-K
 First law of thermodynamics
 First law of thermodynamics is based on Law of Conservation of Energy. It states that energy can be
neither created nor destroyed during a process; it can only change forms.

 “Conservation of energy principle” can be expressed as follows:

The net change in the total energy of the system during a process is equal to the difference between
the total energy entering and the total energy leaving the system during that process.

(Total energy entering the system) – (Total energy leaving the system) = (Change in the total energy of the system)
Ein  Eout  Esystem
This relation is often referred to as the “energy balance” and is applicable to any kind of system
undergoing any kind of process.

 In thermodynamic processes the energy entering or leaving the system is

always in the form of heat & work. And the change in the total energy of the system is the
summation of changes in Kinetic energy, Potential energy and Internal energy. So the energy balance
equation is given by:
Q  W  Esystem  (K .E  P.E  U )
 First law of thermodynamics for closed system, undergoing a cyclic
process:
When a system undergoes a thermodynamic cycle then the net heat supplied to the system from the
surroundings is equal to net work done by the system on its surroundings because the initial state &
final state are identical and there is no change in the energy stored by the system.
QCYCLE  W CYCLE  0 Or QCYCLE  W CYCLE Or  Q   W
So the first law of thermodynamics can be stated as: “Heat and work are mutually convertible in a
closed system undergoing a cyclic process”
OR
“When a system undergoes a thermodynamic cycle then the net heat supplied to the system from the
surroundings is equal to net work done by the system on its surroundings”.

 Verification of First law of thermodynamics by Joule’s Experiment:

Joule used an apparatus as shown in fig. which consists of known mass of water in an insulated tank
having thermometer & paddle wheel. The water was stirred with the help of paddle wheel driven by
a falling weight and an amount of work is done on the system. Due this work interaction, the
temperature of water increases, which is recorded by thermometer. Further the insulation from the
tank is removed. The system & the surrounding interact by heat transfer till the system return to its
initial state. The amount of heat transfer is also recorded. In this way a cycle is executed which is
repeated for different work input followed by heat transfer. It has been found that the work input in
the cyclic process is always proportional to the heat transfer.
 Q  W or  Q  J  W or  Q   W [ J=Joule’s equivalent=1(S.I System)]
 Corollaries of First law of thermodynamics
Corollary1. First law of thermodynamics for closed system, undergoing a change of state:
When a system undergoes a change of state during which both heat transfer and work transfer are
involved, the net energy transfer will change the energy of system.
Q  W  Esystem  (K .E  P.E  U )
Closed systems are generally assumed to be stationery and there is no change in velocity and
elevation during a process. So K .E  0, P.E  0,
Hence the first law for closed system undergoing a change of state: Q  W  U
The above equation indicates: The energy is always conserved during any process. And the energy
of the system (internal energy) is a property of the system because its change depends only on the
end states.

Corollary2. First law of thermodynamics for isolated system:

An isolated system is one in which both heat and work interaction are absent. Q  0, W  0
Therefore; E system  0 or E system  constant
The above identity indicates: The energy of a system remains unchanged if the system is isolated
from its surroundings.

Corollary3. Perpetual Motion Machine of First Kind (PMM-1): A device that violates the first
law of thermodynamics by producing work without absorbing any energy from its surrounding is
called Perpetual Motion Machine of First Kind (PMM-1).
A PMM-1 is not possible. Because energy is neither created nor destroyed, but only gets
transformed from one form to another.

Fig.PMM-1
 Energy of the system (Internal energy): Property of the system

Consider a system which changes its state from 1 to 2 by following path A, and returns from state 2
to 1 by following the path B. So the system undergoes a cycle.
First law for path A: QA  WA  E A ..............................................(i)
First law for path B: QB  WB  EB ...............................................(ii)

The processes A & B together execute a cycle, for which:

QCYCLE(1 A21)  W CYCLE(1 A21)  0 ..................................................(iii)
From equation (i), (ii) & (iii): E A  E B  0, or E A  E B .............................(a)
Similarly, the system returned from state 2 to 1 by following the path C instead of path B.
So, E A  EC .............................(b)
From equation (a) & (b): E B  EC
Therefore it is seen that the change in the energy of the system between two states does not depend
on the path, hence it is a property of the system.
 For a thermodynamic system: E  K .E  P.E  U
& for a closed system: K .E  0, P.E  0, so E  U
Hence we can say that the internal energy is the property of the system.

Internal Energy (U)

For a constant volume process: Q  W  U or Q   PdV  dU or Q  0  dU
Q  mcv dT  dU or dU  mcv dT
 So heat transferred at constant volume increases the internal energy of the
system and it is given by: dU  mcv dT
Enthalpy (H)

For a constant pressure process: Q  W  U or Q  PdV  dU or Q   d ( PV )  dU

or Q  d ( PV )  dU or Q  dU  d (PV ) or Q  d (U  PV ) or Q  mc p dT  dH
or dH  mcP dT
 So heat transferred at constant pressure increases the enthalpy of the
system and it is given
by: dH  mc p dT
 Applications of First law to closed system (non-flow processes)

1. Isochoric process: Volume (V) =constant

 Work done: W   PdV  0

 Change in Internal energy: dU  mcv dT  mcv (T2  T1 )

 Heat transfer: Q  dU (because W  0 )

 Change in Enthalpy: dH  mcP dT  mcP (T2  T1 )

2. Isobaric process : Pressure (P) =constant

 Work done: W   PdV  P(V2  V1 )

 Change in Internal energy: dU  mcv dT  mcv (T2  T1 )

 Heat transfer:
Q  dU  W  mcv (T2  T1 )  P(V2  V1 )  mcv (T2  T1 )  mR(T2  T1 )  m(T2  T1 )(cv  R)  mc p (T2  T1 )

 Change in Enthalpy: dH  mcP dT  mcP (T2  T1 )

3. Isothermal process : Temperature (T) =constant

V2 P
 Work done: W   PdV  P1V1 ln  P1V1 ln 2
V1 P1

 Change in Internal energy: dU  0 (because dT  0 )

 Heat transfer: Q  W (because dU  0 )

 Change in Enthalpy: dH  0 (because dT  0 )

4. Adiabatic process : PV   Constant & ∆Q = 0

P1V1  P2V2 mR(T1  T2 )

 Work done: W   PdV  
 1  1

 Change in Internal energy: dU  mcv dT  mcv (T2  T1 )

 Heat transfer: Q  0

 Change in Enthalpy: dH  mcP dT  mcP (T2  T1 )

 5. Polytropic process : PV n  Constant
P V  P2V2 mR(T1  T2 )
 Work done: W   PdV  1 1 
n 1 n 1

 Change in Internal energy: dU  mcv dT  mcv (T2  T1 )

P1V1  P2V2 mR(T1  T2 )

 Heat transfer: Q  dU  W  mcv (T2  T1 )   mcv (T2  T1 ) 
n 1 n 1

mR(T2  T1 ) mR(T1  T2 )  1 1   n
or Q    mR(T1  T2 )    mR(T1  T2 )
 1 n 1  n  1   1   1

 n  n
Q  mR(T1  T2 )  x Polytropic work done
 1  1

 Change in Enthalpy: dH  mcP dT  mcP (T2  T1 )

Internal Combustion Engines

Introduction: The engines which develop power by combustion of fuel within the engine itself are called
internal combustion engines. The examples of internal combustion engines are petrol and diesel engines
used in cars, trucks etc. The engines in which power is developed by combustion of fuel outside the engine
are called external combustion engines like steam engine. In an internal combustion engine power is
developed from the combustion of fuel which is a chemical reaction. Due to combustion of fuel hot gases
are produced at sufficiently high pressure. This pressure is used to move the piston linearly. This linear
motion of piston is then converted into rotary motion.

Classification of I.C Engines: Internal Combustion (IC) Engines may be classified as:

1. According to number of strokes per cycle:

(a) Two stroke

(b) Four stroke.

2. According to the fuel being used:

(a) Petrol Engine

(b) Diesel Engine

(c) Gas engine

 (d) Dual fuel engines

(e) Liquefied Petroleum Gas Engines.

3. According to working cycles:

(a) Otto Cycle (Constant volume)

(b) Diesel Cycle (Constant pressure)

(c) Dual Cycle

4. According to number of cylinder:

(a) Single Cylinder engine

(b) Multi cylinder

5. According to the type of Cooling:

(a) Air cooled engine

(b) Water cooled engine

6. According to the engine RPM:

(a) Slow speed (< 1000 rpm)

(b) Medium Speed (1000 – 3000 rpm)

(c) High Speed (> 3000 rpm)

7. According to the arrangement of cylinder:

(a) Radial Engine

(b) Inline engine

(c) V engine

8. According to the type of ignition system:

(a) Spark ignition (b) Compression ignition

Main Parts of I.C Engines:

1. Cylinder: It provides a cylindrical closed space to allow movement of piston and to admit the charge. It is
made of grey cast iron or iron alloyed with other elements as nickel, chromium etc. The fuel is burnt inside
the cylinder. The internal diameter of cylinder is called bore.

2. Piston: The piston reciprocates within the cylinder and transmits the force exerted by expanding gases to
crank via connecting rod. The piston is accurately machined to running fit in the cylinder bore and is
provided with several grooves in which piston rings are fitted.

3. Piston Rings: Piston is equipped with piston rings to provide a good sealing between the cylinder valves
and piston. The rings are installed in the grooves in the piston. The rings are of two types:

a) Compression rings b) Oil control ring.

4. Connected Rod: It is attached to the piston at its small end by means of a gudgeon pin. The big end
bearing is connected to crank pin. It is made of forged steel.

5. Crank Pin: Crank pin is the region on crank shaft on which the big end of connecting rod is attached.
These pins are eccentrically located with respect to the axis of the crank shaft.

6. Crank Shaft: It is a rotating member which receives the power transmitted by piston connecting rod
assembly via crank. It is made of forged alloy steel or carbon steel.

7. Crank Web or counter weights: It is provided in the crank shaft to counter act the tendency of bending
of the crank shaft due to centrifugal action.

Terminologies used in I.C Engines:

1. Top dead and Bottom dead Centre: These are two extreme positions between which the piston
reciprocates inside the cylinder. TDC & BDC have relevance to opening and closing of valves and the crank
shaft rotation.

2. Bore: The inner diameter of cylinder is bore. In automobile engines it varies from 40 to 120 mm.

3. Stroke: Displacement of piston with in a cylinder between TDC and BDC is called stroke.

4. Swept Volume (Vs): Volume of charge sucked into cylinder when piston travels from TDC to BDC
during suction stroke.

5. Clearance Volume (Vc): It is the volume occupied by charge in the space provided between TDC and
end of the cylinder.

6. Engine Capacity (VE): Capacity of the engine is defined as the sum of swept volume of all cylinders.
7. Compression Ratio: Ratio of initial volume to the final compressed volume is called compression ratio.
CR for petrol engine varies from 6.5 – 12 where as for diesel engine it varies from 16 – 23.

Working Principle of Two strokes Petrol Engine:

In two stroke cycle petrol engine, there are two strokes of the piston and one revolution of the crankshaft to
complete one cycle. In two stroke engines ports are used instead of valve i.e. suction port, transfer port and
exhaust port. These ports are covered and uncovered by the up and down movement of the piston. The top of
the piston is deflected to avoid mixing of fresh charge with exhaust gases. The exhaust gases are expelled
out from the engine cylinder by the fresh charge of fuel entering the cylinder. The mixture of air and petrol
is ignited by a spark produced at the spark plug. The two stroke of the engine are-

First Stroke- Assuming the piston to be at the BDC position. The inlet port is converted by the piston
whereas the transfer port and exhaust port are uncovered.

The piston moves from BDC to TDC. The air petrol mixture enters the cylinder. On the upward movement
of the piston, first of all the transfer port is converted and then immediately, the exhaust port is covered.
Simultaneously the suction port also gets uncovered, the upward movement of the piston helps to compress
the air fuel mixture at the top and creates partial vacuum at the bottom in the crankcase which gets filled
with air fuel mixture by the atmospheric pressure. At the end of the stroke, the piston reaches the TDC
position completing the compression stroke as shown in Fig. (a) and (b).

Second Stroke- Just before the completion of the compression stroke, the compressed charge is ignited in
the combustion chamber, by means of an electric spark produced by the spark plug. Combustion of air fuel
mixture pushes the piston in the downward direction, on the power stroke producing useful work. The
movement of the power action is over, the exhaust port is uncovered. The exhaust gases escape to the
atmosphere. Further movement of the piston covers the inlet port and the fresh charge is compressed in the
crankcase. Simultaneously the transfer port is also uncovered. The compressed mixture of air fuel enters the
combustion chamber. The deflected shape of the piston avoids inter-mixing of the fresh charge and exhaust
gases i.e. the fresh charge rises to the top of the cylinder and pushes out most of the exhaust gases. Thus the
three actions, power, exhaust and induction are completed from TDC to BDC position completing one cycle
i.e. two stroke of the piston and one revolution of the crankshaft as shown in Fig. (c) and (d).

Working Principle of Four strokes Petrol Engine:

In four stroke petrol engine or spark ignition engine all the events of the cycle i.e. suction, compression,
expansion and exhaust take place in two revolutions of the crank shaft I.e. 720° of the crank rotation. Thus
each stroke is of 180° crank shaft rotation. Therefore the cycle of operation for an ideal four stroke engine
consists of the following four strokes:

a) Suction Stroke- The piston moves from Top Dead Centre (TDC) to Bottom Dead Centre (BDC).
The inlet valve opens and a fresh charge of fuel and air mixture enters the cylinder. The exhaust
valve remains closed. When the piston reaches Bottom Dead Centre (BDC), the inlet valve also
closed.
b) Compression Stroke- The piston moves from Bottom Dead Centre (BDC) to Top Dead Centre
(TDC) position. Both the valves remain closed. The charge drawn during suction stroke is
compressed in this stroke.
c) Expansion or Power or Working Stroke- Just before the piston completes its compression stroke,
the charge is ignited by the spark plug and the rapid explosion takes place. The expansion of hot
gases pushes the piston down to BDC position. Both the valve remains closed and the useful work is
obtained from the engine.
 d) Exhaust Stroke- The piston moves from BDC to TDC, the exhaust valve opens and the inlet valve
remains closed. The piston pushes the exhaust gases out through the exhaust valve to the atmosphere
till it reaches the TDC position and the cycle is completed.

Working Principle of Two stroke Diesel Engine:

The working principle of a two stroke diesel engine is discussed below:

1st stroke: To start with let us assume the piston to be at its B.D.C. position (Fig. a). The arrangement of the
ports is such that the piston performs the two jobs simultaneously.

As the piston starts rising from its B.D.C. position, if closes the transfer port and the exhaust port. The air
which is already there in the cylinder is compressed (Fig. b).

At the same time with the upward movement of the piston, vacuum is created in the crank case. As soon as
the inlet port is uncovered, the fresh air is sucked in the crank case. The charging is continued until the crank
case and the space in the cylinder beneath the piston is filled (Fig. c) with the air. At the end of the stroke,
the piston reaches the T.D.C. Position.
2nd stroke: Slightly before the completion of the compression stroke, a very fine sprays of diesel injected
into the compressed air. The fuel ignites spontaneously.

Pressure is exerted on the crown of the piston due to the combustion of the air and the piston is pushed in the
downward direction producing some useful power (Fig. c). The downward movement of the piston will first
close the inlet port and then it will compress the air already sucked in the crank case.

Just the end of power stroke, the piston uncovers the exhaust port and the transfer port simultaneously. The
expanded gases start escaping through the exhaust port and at the same time transfer port (Fig. d) and thus
the cycle is repeated again.

The fresh air coming into the cylinder also helps in exhausting the burnt gases out of the cylinder through
the exhaust port (Fig. d). This is known as scavenging.
Working Principle of Four stroke Diesel Engine:

Four-stroke cycle Diesel engine or Compression ignition engine or constant pressure cycle engine is meant
for heavy duty applications, like heavy motor vehicles, stationary power plants, ships and big industrial
units, train locomotive , tractor and bus application. In this the air compressed in the engine cylinder and
fuel is injects through injector.

a) Suction Stroke-The inlet valve opens during this stroke and only air is sucked into the engine
cylinder. The exhaust valve remains closed. When the piston reaches Bottom Dead Centre (BDC),
the suction stroke is completed as shown in Fig. (1) and inlet valve also closes.

b) Compression Stroke- The piston moves from Bottom Dead Centre (BDC) to Top Dead Centre
(TDC) position. Both the valves remain closed. The air drawn during suction stroke is compressed.

c) Expansion or Power or Working Stroke- Just before the piston completes its compression stroke,
the diesel injected gets ignited and the rapid explosion takes place. The expansion of hot gases
pushes the piston down to BDC position. Both the valve remains closed and the useful work is
obtained from the engine.

d) Exhaust Stroke- The piston moves from BDC to TDC, the exhaust valve opens and the inlet valve
remains closed. The piston pushes the exhaust gases out through the exhaust valve to the atmosphere
till it reaches the TDC position and the cycle is completed.