MEE 302 –

Thermodynamics II
Unit 1: Second Law of Thermodynamics

Eng. A. Kabemba
Module 1: Introduction
 Introduction

From the study of the First Law of Thermodynamics, some limitations in

the law were noted, like;

1. The non-occurrence of certain processes, and

2. The direction of process.

Need was felt to have some more laws of thermodynamics were necessary
to handle such complex situations.
 Introduction

The Second Law of Thermodynamics came up as embodiment of real

happenings while retaining the basic nature of First Law of
Thermodynamics.

Some of the potential answers provided by the Second Law;

1. Feasibility of process,
2. Direction of process, and
3. Grades of energy such as low and high
 Introduction

The Second law of thermodynamics can indicate;

1. The maximum possible efficiencies of heat engines,

2. The coefficient of performance of heat pumps and refrigerators,
3. Defining a temperature scale independent of physical properties.
Module 2: Heat
Reservoirs
Heat Reservoirs

What is a Heat Reservoir?

It is a system that has a very large heat capacity i.e. it is a body that is
capable of absorbing or rejecting finite amount of energy without any
appreciable change in its’ temperature.
Heat Reservoirs

• In general, it may be considered as a system in which any amount of

energy may be dumped or extracted out, without resulting in any change
in its temperature.
Examples:
1. The atmosphere could be an example, where a large amount of heat can
be rejected without causing any measurable change in its temperature.
2. Large rivers or the sea, can also be considered as reservoir, as dumping
of heat to it shall not cause any appreciable change in temperature.
Types of Heat Reservoirs

Heat reservoirs can be of two types, depending upon nature of heat

interaction i.e. heat rejection or heat absorption from it.

1. A Heat reservoir which rejects heat from it is called a Heat Source.

2. A heat reservoir which absorbs heat is called a Heat Sink.

Sometimes these heat reservoirs may also be called Thermal Energy

Reservoirs (TER).
Module 3: Heat
Engines
 Concept of Heat Engines

What is a Heat Engine?

It is a device which is used to convert Heat (Thermal) Energy into
Mechanical Work.

It is noted from nature, the conversion from work to heat may take place
easily but the opposite may not be as easily realised.

E.g. Frictional Works easily converts to Heat.

 Concept of Heat Engines

Heat and work have been categorised as two forms of energy;

1. Low Grade, and
2. High Grade.

• Conversion of high grade of energy to low grade of energy may be

complete(100%) and can occur directly.
• Complete(100%) conversion of low grade of energy into high grade of
energy is not possible.
 Concept of Heat Engines

• Conversion of low grade of energy (heat) into high grade of energy (work),
requires some device called the Heat Engine.

Therefore, the heat engine may be precisely defined as “a device

operating in cycle between a high temperature source and low
temperature sink to produce work”.
Concept of Heat Engines

A heat engine receives heat from

a source, transforms some
portion of heat into work and
rejects balance heat to a heat
sink. All the processes occurring
in heat engine constitute cycle.
Concept of Heat Engines
A practical arrangement
of a heat engine used in
a gas turbine plant is
also shown below for
understanding of the
physical significance of
heat engines.
Concept of Heat Engines
The Gas turbine installation shows that heat is
added to working fluid from 1–2 in a ‘heat
exchanger 1’ and may be treated as a heat
source.
The working fluid is expanded in turbine from
2–3 and produces positive work.
After expansion, the fluid goes to the ‘heat
exchanger 2’ where it rejects heat from it like
heat rejection in a heat sink.
Fluid at state 4 is sent to compressor to be
compressed back to state 1.
The work required for compression is quite
small as compared to positive work available in
turbine and is supplied by turbine itself.
Concept of Heat Engines
• Therefore, heat engine model for it shall
be as follows;
Concept of Heat Engines
The Efficiency of heat engine can be
given by the ratio of net work done to the
heat supplied.

For the gas turbine plant shown;

Since its operating in a cycle;

Concept of Heat Engines
Therefore, efficiency of heat engine can
be written as;
Module 4: Heat Pump
and Refrigerator
Concept of Heat
Pump
What is a Heat Pump?
This is a device that extracts heat from
low temperature surroundings and
sends it to a high temperature body,
while operating in a cycle.

In other words, Heat Pump maintains a

body or system at temperature higher
than temperature of surroundings,
while operating in cycle.
 Concept of Heat Pump

 The heat pump transfers heat from low temperature to high temperature,
which is non spontaneous process,
 External work is required to realise such heat transfer
 The heat pump shown picks up heat Q2 at temperature T2 and rejects heat
Q1 for maintaining high temperature body at temperature T1
 To cause this heat transfer, the heat pump is supplied with work W as
shown.
 Concept of Heat Pump

 As the heat pump is not a work producing machine and its objective is to
maintain a body at higher temperature, its performance cannot be defined
using efficiency as in case of the heat engine.
 Performance of heat pump is quantified through a parameter called the
coefficient of performance (C.O.P).
 The Coefficient of performance is defined as the ratio of the desired
effect to the net work done to get the desired effect.
 Concept of Heat Pump

For a heat pump:

• Net work = W
• Desired effect = heat transferred Q1 to high temperature body at
temperature, T1.
 Concept of Heat Pump

and

so
 Concept of Refrigerator

• A Refrigerator is a device similar to heat pump but with the reverse objective.
• It maintains a body at temperature lower than that of surroundings while
operating in a cycle. A Block diagram representation of refrigerator is shown in
below.
 Concept of Refrigerator

• The Refrigerator also performs a non-spontaneous process by extracting heat

from a low temperature body to maintain it at a cool temperature. Therefore,
external work W must be done to realise this.
• The block diagram shows how a refrigerator extracts heat Q2 for maintaining
body at low temperature T2 at the expense of work W and rejects heat to the
high temperature surroundings.
 Concept of Refrigerator

The performance of the refrigerator is also quantified by the coefficient of

performance, which could be defined as:

Similarly,

so
 Concept of Refrigerator

COP values for Heat Pump and Refrigerators are interrelated as;
 Module 5:
Statements for the
Second Law of
Thermodynamics
Statements for the Second Law of Thermodynamics

• Rudolph Julius Emmanuel Clausius, a German physicist presented a first

general statement of second law of thermodynamics in 1850 after
studying the work of Sadi Carnot. It was termed as Clausius statement of
Second Law.
• Lord Kelvin and Max Planck also came up with another statement of
second law which was termed as Kelvin-Planck statement for Second
Law of Thermodynamics.
• Thus, there are two statements of second law of thermodynamics,
(although they are equivalent as explained ahead).
Clausius Statement of the Second Law of
Thermodynamics
“It is impossible to have a device that while operating in a cycle produces
no effect other than transfer of heat from a body at low temperature to a
body at higher temperature.”

• The above statement clearly indicates that if a non-spontaneous process such as the
transfer of heat from a low temperature body to a high temperature body is to be
achieved, then some other effects such as the requirement for external work is bound to
be there.

• As already seen in case of refrigerator, the external work is required to extract heat from
a low temperature body and to reject it to high temperature body
Kelvin-Planck Statement of the 2nd Law of
Thermodynamics
“It is impossible for a device operating in a cycle to produce net work
while exchanging heat with bodies at a single fixed temperature”.

It says that in order to get net work from a device operating in cycle (i.e.
heat engine), it must have heat interaction at two different temperatures or
with body/reservoirs at different temperatures (i.e. source and sink).
Statements of the 2nd Law of Thermodynamics

• Clausius’ Statement of the 2nd Law refers to the feasible operation of a

heat pump/refrigerator

• Kelvin – Planck’s Statement of the 2nd Law refers to the feasible

operation of a heat engine.
Perpetual Motion Machines of the Second Kind
(PMM-II)
Devices based on violation of the Second Law of Thermodynamics are
called Perpetual Motion Machines of the Second Kind (PMM-II).
 Perpetual The PMM-II shown in (a)
Motion • Refers to heat engine
Machines of which produces work
while interacting with
the Second only one reservoir.
Kind (PMM-
II) The PMM-II shown in (b)
• Refers to a heat pump
which transfers heat from
a low temperature to high
temperature body without
spending work.
Equivalence of the Kelvin-Planck and Clausius Statements of the 2nd
Law of Thermodynamics

Kelvin-Planck and Clausius statements of the second law of thermodynamics are

two different interpretations of the same basic fact.

To establish equivalence, the following statements may be proved:

1. A system based on violation of Kelvin-Planck statement leads to violation of
the Clausius statement.

2. A system based on violation of Clausius statement leads to violation of the

Kelvin-Planck statement.
Equivalence of the Kelvin-Planck and Clausius Statements
of the 2nd Law of Thermodynamics
Statement 1: A system based on violation of Kelvin-
Planck statement leads to violation of the Clausius
statement.
• Assume a heat engine produces net work while
exchanging heat with only one reservoir at a
temperature T1 thus based on violation of Kelvin
Planck statement.
• Let us also have a perfect heat pump operating
between two reservoirs at temperatures T1 and T2.
The work requirement of heat pump may be met
from the work available from heat engine.
• The layout below explains the proposed
arrangement.
Equivalence of the Kelvin-Planck and Clausius Statements
of the 2nd Law of Thermodynamics
Statement 1: A system based on violation of Kelvin-
Planck statement leads to violation of the Clausius
statement.

If the heat pump takes input work from output of heat

engine then,

Q3 = Q2 + W and W= Q1

or

Q3 = Q1 + Q2
Equivalence of the Kelvin-Planck and Clausius Statements
of the 2nd Law of Thermodynamics
Statement 1: A system based on violation of
Kelvin-Planck statement leads to violation of
the Clausius statement.

• The combination of a heat engine and a heat pump shall

thus result in an equivalent system working as a heat
pump transferring heat from low temperature T2 to high
temperature T1 without expense of any external work.

• This heat pump is based on violation of Clausius

statement and therefore not possible. Hence, it shows
that violation of Kelvin Planck statement leads to
violation of the Clausius statement.
Equivalence of the Kelvin-Planck and Clausius Statements
of the 2nd Law of Thermodynamics
Statement 2: A system based on violation of
Clausius statement leads to violation of the
Kelvin-Planck statement.

Assume a heat pump which is operating in

cycle transfers heat from a low temperature
reservoir to a high temperature reservoir
without the expense of any work, thus based
on violation of Clausius statement
Equivalence of the Kelvin-Planck and Clausius Statements
of the 2nd Law of Thermodynamics
Statement 2: A system based on violation of
Clausius statement leads to violation of the
Kelvin-Planck statement.

• The heat pump transfers heat Q1 to a high

temperature reservoir while extracting heat Q2
from the low temperature reservoir.
• Mathematically, as no work is done on pump,
so

Q2 = Q1
Equivalence of the Kelvin-Planck and Clausius Statements
of the 2nd Law of Thermodynamics
Statement 2: A system based on violation of
Clausius statement leads to violation of the
Kelvin-Planck statement.

• Let us also have a heat engine between

same temperature limits of T1 and T2, and
produce net work W.

• The heat engine receives heat Q3 from the

source which may be taken equal to Q1.
Equivalence of the Kelvin-Planck and Clausius Statements
of the 2nd Law of Thermodynamics
Statement 2: A system based on violation of
Clausius statement leads to violation of the
Kelvin-Planck statement.
Let us now devise for heat rejected from heat pump to
be given directly to the heat engine.
• In such a situation, the combination of a heat pump
and a heat engine results in an equivalent heat engine
which produces work ‘W’ while exchanging heat with
only one reservoir at temperature T2.
• The Arrangement is shown by dotted lines.
• This type of equivalent system is producing work as a
result of only one heat interaction and thus is a
violation of the Kelvin Planck statement.
Equivalence of the Kelvin-Planck and Clausius Statements
of the 2nd Law of Thermodynamics
• We have shown that violation of Clausius statement also causes violation of Kelvin
Planck statement.
• Hence the Clausius and Kelvin-Planck statements are equivalent.

Conceptually the two statements explain the basic fact that:

1. Net work can’t be produced without having heat interactions taking place at two
different temperatures.

2. A non-spontaneous process such as heat flow from low temperature body to a high
temperature body is not possible without spending work.
 Module 6:
Reversibility &
Irreversibility of
Thermodynamic
Processes
Reversibility & Irreversibility of Thermodynamic
Processes
• Thermodynamic processes can be classified based on their reversibility,
which determines the potential for regaining the initial state of the
system and the associated work and heat transfer.
• The change of state in Thermodynamic processes can occur in two ways;
1. The system restores to its original state by reversing the factors
responsible for occurrence of the initial process, i.e. Follows the same
Path in the forward and reverse process
2. The system restores to its original state but not by reversing the factors
responsible for occurrence of the initial process, i.e. Does no follow the
same Path in the forward and reverse process.
 Reversible Processes

• Thermodynamic system capable of restoring its original state by reversing the

factors responsible for occurrence of the process is called Reversible System
and the thermodynamic process involved is called Reversible Process.

• After reversal of a process there is no trace of the process having occurred, i.e.
state changes during the forward process are the same as the states passed
through during the reverse process.

• Reversibility can only be realised if the system maintains its Thermodynamic

Equilibrium throughout the occurrence of process.
 Reversible Processes

• A Reversible process is an Idealized process that occurs infinitely slowly,

allowing the system to remain in thermodynamic equilibrium at every
stage.
• No internal or external friction, heat transfer occurs through infinitesimal
temperature differences, and expansion/compression is perfectly
controlled
Example:
A piston slowly expanding against a perfectly balanced external pressure,
maintaining thermal equilibrium with the surroundings
 Irreversible Processes

• Real-world processes that involve a degree of irreversibility due to friction,

heat transfer through finite temperature differences, and non-equilibrium
conditions

• Irreversibility is the characteristic of the system which prevents the system

from retracing the same path upon reversal of the factors causing the state
change.

• Irreversible Systems are those which do not maintain equilibrium during the
occurrence of a process.
 Irreversible Processes

Factors Responsible for Irreversibility

Factors responsible for the nonattainment of equilibrium are generally the
reasons responsible for irreversibility, including;
• Presence of friction,
• Energy dissipation into heat occurs, reducing the potential for work
extraction or complete cycle reversal
Examples:
Friction in engine pistons, combustion with heat loss to the surroundings,
rapid expansion or compression leading to shock waves
 Reversible and Irreversible
Processes PV Diagram
The Reversible and Irreversible
processes are shown on the p-v
diagram below;

Reversible Process: 1 – 2 and 2 – 1

Irreversible Process: 3 – 4 and 4 – 3
 Quasi-static Processes

• Properties describe the state of a system only when the system is in equilibrium.
• How then can we describe the states of a system during a process if the actual
process occurs only when equilibrium does not exist?
• The Quasi-static’ considerations, approximates real processes as reversible by
occurring very slowly, allowing the system to nearly reach equilibrium at each
stage
• The Quasi – static consideration is useful for theoretical analysis and cycle
modelling, representing the limiting case of reversible processes.
• Quasi-static literally refers to “almost static” and the infinite slowness of the
occurrence of a process is considered as the basic premise for attaining near
equilibrium in the system.
 Module 7:
Carnot Cycle and
Carnot Engine
Carnot Cycle and Carnot Engine
Nicholas Leonard Sadi Carnot, an engineer in the French army
originated use of the cycle (Carnot) in thermodynamic analysis
in 1824, and these concepts provided basics upon which the
Second Law of Thermodynamics was stated by Clausius and
others.

What is the Carnot Cycle?

A Carnot cycle is a reversible thermodynamic cycle
comprising of four reversible processes.
Carnot Cycle and Carnot Engine
Thermodynamic processes
constituting Carnot cycle are;
1. Reversible isothermal heat addition
process, (1–2, Qadd)
2. Reversible adiabatic expansion
process (2–3, Wexpn +ve)
3. Reversible isothermal heat release
process (3–4, Qrejected)
4. Reversible adiabatic compression
process (4–1, Wcompr –ve)
Carnot Cycle and Carnot Engine
The Carnot cycle is shown on a P–V diagram between
states 1, 2, 3, 4, and 1. A reciprocating piston cylinder
assembly is also shown below P–V diagram.
• Process 1 –2 is the isothermal heat addition process of
the reversible type in which heat is transferred to system
isothermally.
• In the piston cylinder arrangement, heat Qadd can be
transferred to the gas from a constant temperature
source T1 through a cylinder head of conductor type.
• First law of thermodynamics applied on 1–2 yields;
Qadd = U2 – U1 + W1–2.
• For the perfect gas as working fluid in isothermal
process no change in internal energy occurs, therefore,
• U2 = U1 and
• Qadd = W1–2
2.2.2 Carnot Cycle and Carnot
Engine
Process 2–3 is reversible adiabatic expansion process
which may be had inside cylinder, with the cylinder
head being replaced by insulating type cylinder head
so that complete arrangement is insulated, and
adiabatic expansion carried out.

• During adiabatic expansion say work Wexpn is

available,

Q2–3 = 0
From the first law of thermodynamics;

0 = (U3 – U2) + Wexpn

or Wexpn = (U2 – U3)

Carnot Cycle and Carnot Engine
Process 3–4 is reversible isothermal heat rejection
for which cylinder head of insulating type may be
replaced by conducting type as in 1–2 and heat
(Qrejected) be extracted out isothermally.

From first law of thermodynamics applied on

process 3–4,

–Qrejected = (U4 – U3) + (–W3–4)

for perfect gas internal energy shall remain
constant during isothermal process. Thus, U3 = U4
–Qrejected = –W3–4
or Qrejected = W3–4
Carnot Cycle and Carnot Engine
Process 4–1 is the reversible adiabatic
compression process with work requirement
for compression.
In the piston cylinder arrangement cylinder
head of conducting type as used in 3–4 is
replaced by insulating type, so that the whole
arrangement becomes insulated and adiabatic
compression may be realised, from the first
law applied on process 4–1

For adiabatic process;

Q4–1 = 0
⇒ 0 = (U1 – U4) + (–Wcompr)
Carnot Cycle and Carnot Engine
Or

Efficiency of a reversible engine is

given by;

Where;
Carnot Cycle and Carnot Engine
Heat is only supplied during process
1 – 2;
Therefore;

Therefore, efficiency becomes;

Carnot Cycle and Carnot Engine
For a Cycle;
Carnot Cycle and Carnot Engine
• Heat addition takes place at high
temperature
• Heat rejection occurs at low
temperature
Therefore;
Carnot Cycle and Carnot Engine
The Piston-cylinder arrangement shown and discussed for realizing Carnot cycle is not
practically feasible as;
1. Frequent change of cylinder head i.e. of insulating type and diathermic type for adiabatic and
isothermal processes is very difficult.
2. Isothermal heat addition and isothermal-heat rejection are practically very difficult to be
realized
3. Reversible adiabatic expansion and compression are not possible.
4. Even if near reversible isothermal heat addition and rejection is to be achieved then time
duration for heat interaction should be very large i.e. infinitesimal heat interaction occurring at
dead slow speed.
5. Near reversible adiabatic processes can be achieved by making them to occur fast. In a piston-
cylinder reciprocating engine arrangement such speed fluctuation in a single cycle is not
possible
Carnot Theorem and its Significance
Carnot Theorem and its Corollaries
The Carnot theorem states that “any engine cannot have
efficiency more than that of reversible engine operating between
same temperature limits.”
Corollaries of Carnot Theorem
1. Efficiency of all reversible engines operating between same
temperature limits is same.
2.Efficiency of a reversible engine does not depend on the
working fluid in the cycle.
Thermodynamic Efficiency
• Thermodynamic Efficiency is the Ratio of the net work output of a
cycle to the heat input from the high temperature source
• It represents the fraction of heat converted into useful work, with higher
values indicating a more efficient engine

For the Carnot cycle, efficiency depends only on the absolute

temperatures of the hot and cold reservoirs:
Carnot Efficiency and Limitations
• The Carnot cycle, a theoretical reference cycle with four reversible processes,
defines the upper limit of efficiency for any heat engine operating between
two fixed temperatures
• Carnot efficiency depends only on the absolute temperatures of the hot and
cold reservoirs : η = 1 - Tc / Th
• Real engines incur irreversibilities due to friction, finite heat transfer rates, and
incomplete combustion, leading to lower efficiencies than the Carnot limit
• Measured by the ratio of net work output to the heat input from the high-
temperature source: η = W / Qh
• Real engine cycles, like Otto and Diesel, have specific formulas for their
thermal efficiency, incorporating factors like compression ratio and specific
heat capacities of the working fluid
Carnot Efficiency and Limitations
• These efficiencies are always lower than the Carnot
efficiency for the same temperature range due to
irreversibilities