ENGINEERING THERMODYNAMICS

What is Thermodynamics?

 Thermodynamics is a science dealing with Energy and its transformation and its effect on the
physical properties of substances.

 It deals with equilibrium and feasibility of a process.

 Deals with the relationship between heat and work and the properties of systems in
equilibrium.

Scope of Thermodynamics:

 Steam power plant

 Separation and Liquification Plant

 Refrigeration

 Air-conditioning and Heating Devices.

 Internal combustion engine

 Chemical power plants

 Turbines

 Compressors, etc

The principles of thermodynamics are summarized in the form of four thermodynamic laws:
 The Zeroth Law deals with thermal equilibrium and provides a means for measuring
temperatures.

The First Law deals with the conservation of energy and introduces the concept of
internal energy.

The Second Law of thermodynamics provides with the guidelines on the conversion of
internal energy of matter into work. It also introduces the concept of entropy.

The Third Law of thermodynamics defines the absolute zero of entropy. The entropy of
a pure crystalline substance at absolute zero temperature is zero.

Different Approaches of Thermodynamics :

Write the difference between Macroscopic and Microscopic approach of Thermodynamics:

Macroscopic Approach Microscopic Approach

1.Macroscopic approach is known as Classical 1. Microscopic approach is known as

Thermodynamics. Statistical Thermodynamics

2. Attention is focussed on a certain quantity of 2. A knowledge of the structure of matter

matter without taking into account the events under consideration is essential.
occuring at molecular level.
3. Only a few variables are used to describe the 3. A large no. of variables are required for a
state of the matter under consideration. complete specification of the state of matter
under consideration.

4. The values of the variables used to describe 4. The variables used to describe the state of
the state of the matter are easily measurable. matter cannot be measured easily and precisely

Define Thermodynamic System?

A thermodynamic system is defined as a definite quantity of matter or a region of space within a

prescribed boundary upon which attention is focussed in the analysis of a problem.

Surrounding: Everything external to the system is Surroundings.

Boundary:

 The surface which separates the system from the surrounding.

 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.

System and Surrounding put together is known as Universe

Interaction Between System and Surrounding

Based on the type of interaction, the systems are classified as

• CLOSED SYSTEM

• OPEN SYSTEM

• ISOLATED SYSTEM

CLOSED SYSTEM (Control Mass) : It is also termed as control mass or fixed mass analysis.

There is no mass transfer across the system boundary but energy in the form of Heat or Work
can cross the system boundary.

Eg. A certain amount of gas enclosed in a cylinder piston arrangement.

Open System(Control Volume): The open system is one in which both mass and energy can
cross the boundary of the system.

Open system is also termed as control volume analysis.

Write down the concept of Control Volume:

A large engineering problems involve mass flow in and out of a system and therefore, are
modeled as control volumes.

Control volume refers to a definite volume on which attention is focussed for energy analysis.

Examples: Nozzles, Diffusers, Turbines, Compressors,

Heat Exchanger, De-superheater, Throttling valves,

I.C engine etc.

Control Surface: The closed surface that surrounds the control volume is called CONTROL
SURFACE. Mass as well as energy crosses the control surface. Control surface can be real or
imaginary.

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.
Note:

Energy
Mass Transfer Type of System
Transfer

No Yes Closed System

Yes Yes Open System

No No Isolated System

Yes No Impossible

What do you mean by Property?

Any observable characteristics required to describe the conditions or state of a system is known
as Thermodynamic property of a system.

Properties

Intensive Extensive
(Depends on mass)
(Independent of mass)

Differentiate Intensive and Extensive Property?

Extensive Property Intensive Property

1. Extensive properties are dependent on the mass 1. Intensive properties are independent of
of a system. the mass of a system.

2.Extensive properties are additive. 2. Intensive properties are not additive.

3. Its value for an overall system is the sum of its 3. Its value remains the same whether one
values for the parts into which the system is considers the whole system or only a part
divided. of it.
4.Example:mass(m),volume(V),Energy(E),Enthalp 4.Example:Pressure(P),Temperature(T),De
y(H) etc. nsity etc.

5. Uppercase letters are used for extensive 5. Lowercase letters are used for intensive
properties except mass. properties except pressure(P) and temp.(T)

Specific property= Extensive property/mass.

Example: Specific volume (v) = Volume(V)/mass(m)

Specific enthalpy (h) = Enthalpy(H)/mass(m)

Specific entropy (s) = Entropy(S)/mass(m)

State:

 It is the condition of a system as defined by the values of all it’s properties.

 It gives a complete description of the system.

 Any operation in which one or more properties of a system change is called change of
state .

Path and Process:

 The series of state through a system passes during a change of state is Path of the system.

 If the path followed by the system during change of state is specified or defined
completely, then it is called a process.

We can allow one of the properties to remain a constant during a process.

Isothermal Constant Temperature (T)

Isobaric Constant Pressure (P)

Isochoric Constant Volume (V)

Isentropic Constant Entropy (s)

Isenthalpic Constant Enthalpy (h)

Cycle: When a system in a given initial state undergoes a series of processes and returns to
initial state at the end of process, then the system is said to have undergone a thermodynamic
cycle.

DIFFERENTIATE BETWEEN POINT FUNCTION VS PATH FUNCTION

Point Function Path Function

1. Any quantity whose change is independent of 1. Any quantity, the value of which depends
the path is known as point function. on the path followed during a change of state
is known as path function.

2. The magnitude of such quantity in a process 2. The magnitude of such quantity in a process
depends on the state. is equal to the area under the curve on a
property diagram.
3. These are exact differential. 3.These are inexact differential. Inexact
differential is denoted by δ

4. Properties are the examples of point function 4. Ex: Heat and work
like pressure(P), volume(V),Temp.(T),Energy
etc.
Thermodynamic Equilibrium

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 condition for following three
types of equilibrium are satisfied.

Thermal Equilibrium (Equality of Temperature):

A state of thermal equilibrium can be described as one in which the temperature of the system is
uniform.

Mechanical Equilibrium(Equality of Pressure):

In the absence of any unbalanced force within the system itself and also between the system and
the surroundings, the system is said to be in a state of mechanical equilibrium.

 Mechanical equilibrium is related to pressure.

 A system is in mechanical equilibrium if there is no change in pressure at any point of

the system .
Chemical Equilibrium(Equality of chemical potential):

 A system is in chemical equilibrium when its chemical composition does not change with
time, that is no chemical reaction occurs .

 It is related to chemical potential.

QUASI-STATIC PROCESS

A quasi-static process is one in which the deviation from thermodynamic equilibrium is

infinitesimal.

Characteristics:

 Infinite slowness is the characteristic feature of this process.

 A quasi-static process is thus a succession of equilibrium states.

 It can be represented as a continuous line on the property diagram.

 It is also known as a reversible process.

REVERSIBLE PROCESS

Reversible process is one which is performed in such a way that at the end of the process both
the system and surrounding may be restored to their initial state without producing any changes
in rest of the Universe.

Reasons for studying Reversible Process:

1.They are easy to analyze.

2. They served as an idealized process to which actual process can be compared.

3.They are taken for consideration because work producing devices such as steam turbine,
automobile engines etc delivers the max. work and work consuming devices like compressors,
pumps etc consumes the least work.

Characteristics of Reversible Process

 A Reversible process is carried out infinitely slowly with an infinitesimal gradient so that
every state pass through by the system is in equilibrium.

 It is possible to execute the process in either of the direction.

 No dissipative effect such as friction, loss in a resistor, etc are present.

 Heat and work interactions of the system and the surroundings in the reverse process are equal
and opposite in direction to the same in the forward process.

Examples:

1. Frictionless isothermal expansion or compression of a fluid.

2. Frictionless adiabatic expansion or compression of a fluid.

3. Elastic stretching of a solid.

4. Electric current with zero resistance.

IRREVERSIBLE PROCESS

An irreversible process is one that is carried out in such a way that the system and surrounding
can not be exactly restored to their respective initial state at the end of the reverse process, that a
net change occurs in the Universe.

Note: 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 an Irreversibility:

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

(i) Lack of Equilibrium.

(ii) Involvement of Dissipative effects.

Lack of Equilibrium(Mechanical,Thermal,Chemical)

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. Free expansion or Unrestrained expansion.

4. Mixing of substances.

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. etc

Characteristics of an Irreversible Process:

1. It can be carried out in one direction only.

2. It occurs at a finite rate.

3. During an irreversible process, the system is not in equilibrium.

An irreversible process cannot be reversed without causing permanent changes in the

surroundings.
 Heat & Work Transfer

Thermodynamic Work: Work is said to be done by a system if the sole effect on things
external to the system can be reduced to the raising of a weight.

Displacement (or) pdV Work:

Expression for pdV Work:

W dW
( p * piston area * displacement )

p * A * dL
pdV
2
W12 = pdV
1
Sign Convention for work transfer:

Work done by the system is positive and Work done on the system is negative.

Work done during various Quasi-static Processes:

Constant Pressure Proces:

V2

W1 2 pdV p (V2 V1 )
V1

Constant Volume Process:

 V2

W1 2 pdV 0
V1

Constant Temperature Process:

V2

W1 2 pdV
V1

pV p1V1 C
p1V1
p
V
V2
dV V2
W1 2 p1V1 p1V1 ln
V1
V V1

Polytropic Process pV n C , where n is a constant

pV n p1V1n p2V2 n C
n
(pV )
1 1
p n
V
V2

W1 2 pdV
V1
V2
p1V1n
dV
V1
Vn
p1V1 p2V2
=
n 1

Heat Transfer: Energy transfer by virtue of temperature difference is called Heat Transfer. Heat
Transfer is also a boundary phenomenon.

Specific Heat: It is the amount of heat required to raise the temperature of unit mass of a
substance by unit degree.

For Solids and Liquids

cp = cv = c

For Gases

cp – specific heat capacity at constant pressure

cv – specific heat capacity at constant volume

Latent Heat: It is the amount of heat transferred to cause a phase change.

 FIRST LAW OF THERMODYNAMICS

 This is based on Law of Conservation of Energy.

 This is also called as First Principle.

For a closed system, undergoing a cycle

Sum of all Work transfers = Sum of all Heat Transfers

(W1+W2+W3+…..) = Σ(Q1 +Q2+Q3+……….)

Σ(W) = Σ(Q)
dW dQ

For a closed system,undergoing a Process

Whenever heat is absorbed by a system it increases its internal energy and does some work.

Q = ΔE + W

Where Q – heat absorbed by the system

W – Work output from the system

ΔE – Change in Stored Energy of the system

Show that Energy is a property of the system

For path A,

QA WA EA (1)
For path B,

QB WB EB (2)

For path B,

QC WC EC (3)

For Cycle 1-A-2-B-1,

WA WB QA QB (4)

QA WA (QB WB )

EA EB (A)

For Cycle 1-A-2-C-1,

WA WC QA QC

QA WA (QC WC )

EA EC (C)

Comparing A and C

EB EC

Enthalpy:

 It is the energy content of the flowing fluid.

 It is defined by the summation of internal energy and flow work.

H = U + PV

Note: For an ideal gas h = u + Pv.

= u + RT

So, h = f(T)

Define Cv with the help internal energy and Temperature:

The amount of heat required to raise the temperature of unit mass of a substance by 1o C in a
reversible constant volume process.
 u
Cv
T v

Cv is also defined as the change of internal energy of the substance per unit change in
temperature at constant volume.

Define Cp with the help enthalpy and Temperature:

The amount of heat required to raise the temperature of unit mass of a substance by 1o C in a
reversible constant pressure process.

h
Cp
T p

C p is also defined as the change of internal energy of the substance per unit change in
temperature at constant pressure.

Application of First law to different Thermodynamic process:

Process Index=n Q W= PdV P-V-T Relation

Rev. Const.Vol. Q U W=0 P1 P2

T1 T2
= mCv (T2 T1 )

Rev.Const.pressure n=0 Q H W P(V2 V1 ) V1 V2

T1 T2
= mC p (T2 T1 ) = mR(T2 T1 )

Rev. Isothermal n=1 V2 V2 PV

1 1 PV
2 2
Q W PV
1 1 ln W PV
1 1 ln
V1 V1

Rev.Adiabatic n=γ Q=0 PV

1 1 PV
2 2 PV PV
W 1 1 2 2
1

Rev.Polytropic n Q U W PV
1 1 PV
2 2 PV n
PV n
W 1 1 2 2
n 1
 MODULE-2

SECOND LAW OF THERMODYNAMICS

State the limitations of first law of thermodynamics?

1. First Law places no restriction on the direction of a process.

2. It does not ensure whether the process is feasible or not.

3. This law does not differentiate heat and work. It is concerned with the quantity of energy and
the transformation of energy from one form to another with no regard to its quality.

Aspects of the second law

1. To identify the direction of process.

2. Establishing conditions for equilibrium.

3. It also asserts that energy has quality as well as quantity.

3. It is also used in determining the theoretical limits for the performance of heat engines and
refrigerators.

4. Defining a temperature scale independent of the properties of any thermometric substance.

Thermal Energy Reservoir (TER): It is a hypothetical body with a relatively large thermal
energy capacity that can supply or absorb finite amount of heat without undergoing any change
in temperature. Examples: Oceans, rivers, atmospheric air etc.

 TER that supplies energy in the form of heat is called a source

 TER that absorbs energy in the form of heat is called a sink

Heat Engines: Heat engine is a cyclic device, used to convert heat to work. Heat engine can be
characterized by the following points.

1. They receive heat from a high temperature source (solar energy, oil-furnace etc.)

2. They convert part of this heat to work (usually in the form of a rotating shaft)

3. They reject the remaining waste heat to a low temperature sink (the atmosphere, rivers, etc)

4.They opertate on a cycle.

Q1 = amount of heat supplied to steam in boiler from a high-temperature source.

Q2 = amount of heat rejected from steam in condenser to a low temperature sink.

W = net work output of this heat engine.

Thermal efficiency: The fraction of the heat input that is converted to net work output is a
measure of the performance of the heat engine.

Net work output

Thermal efficiency( )
Total heat input

W
th
Q1

Q2
th 1
Q1

Refrigerator: Refrigerators are cyclic devices, used to transfer heat from a low temperature
medium to a high temperature medium.

The working fluid used in the refrigeration cycle is called a refrigerant. The most frequently used
refrigeration cycle is the vapor-compression refrigeration cycle.

Coefficient of Performance (COP)

Desired output Q2
COPR
Re quired input W

Q2
COPR
Q1 Q 2
 (Refrigerator)

Heat Pumps: Heat pumps are another cyclic devices, used to transfer heat from a low
temperature medium to a high temperature medium.

The objective of a heat pump is to maintain a heated space at a high temperature. This is
accomplished by absorbing heat from a low temperature source, such as cold outside air in
winter and supplying this heat to the high temperature medium such as a house.

Desired output Q1
COPHP
Re quired input W

Q1
COPHP
Q1 Q 2

Relation between COPHP and COPR

COPHP = COPR +1
Statements of Second Law

Kelvin-Planck Statement of the Second law

It is impossible for any device that operates on a cycle to receive heat from a single reservoir and
produce a net amount of work.

(A heat engine that violates the Kelvin-Planck statement)

Clausius Statement:

It is impossible to construct a device that operates in a cycle and produce no effect other than the
transfer of heat from a low temperature body to a high temperature body.
A refrigerator that violates the Clausius
statementof the second law

Equivalence of Kelvin Planck and Clausius Statements:

The equivalence of the statement is demonstrated by showing that the violation of each
statement implies the violation of other.

CASE-1: Violation of Kelvin-planck statement leads to violation of Clausius statement

Violation of Kelvin-Planck
statement
Thus violation Kelvin Planck Statement has lead to the violation of
Clausius Statement

CASE-2: Violation of Clausius statement leads to violation of Kelvin-planck statement

Thus Violation of Clausius Statement has lead to violation of Kelvin Planck Statements
Carnot Cycle: Carnot cycle is a reversible cycle that is composed of four reversible processes,
two isothermal and two adiabatic.

 Process 1 - 2 (Reversible Isothermal Heat Addition)

 Process 2 – 3 (Reversible Adiabatic Expansion)

 Process 3 – 4 (Reversible Isothermal Heat Rejection)

 Process 4 – 1 ( Revesible Adiabatic Compression)

Σ(Q net)cycle = Σ( Wnet)cycle

Qadd – Qrej = We – Wc

Wnet Qadd - Qrej

Qadd Qadd
Qrej
=1-
Qadd
From T-S diagram
T2 ( S)
=1
T1 ( S)

T2
=1
T1
Carnot’s Theorem:

1. The efficiency of an irreversible heat engine is always less than efficiency of a reversible one
operating between the same two reservoirs.

2. The efficiencies of all reversible heat engines operating between the same reservoirs are the
same.

Clausius Inequality

Q
The cyclc integral of is always less than or equal to zero.
T

Q
Mathematically it can be expressed as 0 . The equality in the Clausius inequality holds
T
for totally or just reversible cycle and the inequality for the irreversible ones.

Reversible Engine

Q1 T1
Q2 T2
(or )
Q1 Q2
T1 T2
Q1 Q2
0
T1 T2
dQ
0
T
For an Irreversible Engine

Q1 Q2I Q1 Q2R

and therefore

Q2I Q2R

Consequently, for an irreversible heat engine

Q Q1 Q2I 0

Q Q1 Q2I
0
T T1 T2

So we conclude that for all irreversible heat engine

Q
0
T

Entropy:

Q
Entropy is defined as dS
T rev

The T ds Relations:

Qrev dU Wrev

But Qrev TdS

and Wrev PdV

Thus, The first TdS equation is obtained as

TdS dU PdV
The second TdS equation is obtained by using the definition of enthalpy h u pv.
dH dU d ( PV ) dU PdV VdP

TdS dH VdP (Since TdS dU PdV )

The TdS equations can be written on a unit mass basis as

Tds du Pdv

Tds dh vdP
Entropy change of an ideal gas

The entropy change between two states of an ideal gas canbe obtained from the ideal gas
equation and the combined equation of the first first and second laws.

Tds = du + Pdv
T
But, s 2 s1 cv ln 2
T1
du = cv dT and P = (RT)/v
Therefore,
RT
Tds = cv dT dv
v
or
2 2 2
dT dv
ds cv R
1 1
T 1
v
T2 v2
s2 s1 cv ln R ln
T1 v1

Again, Tds = dh vdP

Now,
dh = c p dT and v = (RT)/P
dT RT
ds = c p dP
T PT
2 2 2
dT dP
ds cP R
1 1
T 1
P
T2 P2
s2 s1 c p ln R ln
T1 P1

Entropy change for different process:

Process Entropy change s2 s1

Reversible constant volume process T2

s2 s1 cv ln
T1
Reversible constant pressure process T
s 2 s1 c p ln 2
T1
Reversible isothermal process P2 v2
s2 s1 R ln or s2 s1 R ln
P1 v1
Reversible adiabatic process s2 s1

Polytropic process 2 2 2
dT dv
ds cv R
1 1
T 1
v
2 2 2
dT dP
or ds cp R
1 1
T 1
P

Internal Combustion engine

Spark ignition engine Compression ignition engine

These engines are petrol engine and These engines are diesel engine and
they work on Otto cycle they work on Diesel cycle

Basic components of IC engine