Second Law of

Thermodynamics

Dr. Rakesh Kumar Maurya

Associate Professor
Department of Mechanical Engineering
Indian Institute of Technology Ropar
IIT Ropar
Rupnagar, India (140001)
 Introduction to the Second Law
Figure 6–4
Figure 6–1 Figure 6–2
Processes occur in a certain direction,
A cup of hot coffee does not Transferring heat to a wire and not in the reverse direction.
get hotter in a cooler room. will not generate electricity.

Figure 6–5
Copyright © McGraw-Hill Education. Permission required for reproduction or display. A process must satisfy both the first and
second laws of thermodynamics to proceed.
Figure 6–3
Copyright © McGraw-Hill Education. Permission required for reproduction or
display. Transferring heat to a paddle
wheel will not cause it to rotate.

These processes cannot

occur even though they Violation of the second law of thermodynamics
are not in violation of the is easily detected with the help of a property,
first law. called entropy.
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Major Uses of the Second Law
The second law may be used to identify the direction of processes.
The second law asserts that energy has quality as well as quantity.
The first law is concerned with the quantity of energy and the transformations of energy
from one form to another with no regard to its quality. The second law provides the
necessary means to determine the quality as well as the degree of degradation of energy
during a process.
The second law of thermodynamics is also used in determining the theoretical
limits for the performance of commonly used engineering systems, such as
heat engines and refrigerators, as well as predicting the degree of completion
of chemical reactions.
In fact, the second law defines perfection for thermodynamic processes. It
can be used to quantify the level of perfection of a process and to point in the
direction to eliminate imperfections effectively.

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Application of Second Law and Inferences
To predict the direction of a process.
To establish the conditions for equilibrium.
To evaluate the best theoretical performance of the cycles and other devices.
To assess quantitatively the factors that prevent the accomplishment of best
theoretical performance.
To define the temperature scale that is independent of the properties of a
thermometric substance

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Thermal Energy Reservoirs A hypothetical body with a
relatively large thermal energy
Figure 6–7 capacity (Mass x Specific heat)
A reservoir that supplies A source supplies energy in the
that can supply or absorb finite
amounts of heat without
energy in the form of heat is form of heat, and a sink absorbs it. undergoing any change in
called a source, and one that temperature is called a thermal
absorbs energy in the form energy reservoir, or just a
of heat is called a sink. reservoir.
Thermal energy reservoirs In practice, large bodies of water
are often referred to as heat such as oceans, lakes, and rivers
as well as the atmospheric air
reservoirs since they supply can be modeled accurately as
or absorb energy in the form thermal energy reservoirs
of heat. because of their large thermal
energy storage capabilities or
thermal masses.

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Heat Engines
Figure 6–8
Work can always be converted to heat directly
and completely, but the reverse is not true.

• Heat engines and other cyclic

devices usually involve a
Copyright © McGraw-Hill Education. Permission required for reproduction or display. fluid to and from which heat
is transferred while
undergoing a cycle.
• This fluid is called the
working fluid.

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Heat Engine Example W net,out = Q H − QL
A steam power plant Figure 6–10 Wnet,out QL
Schematic of a steam power plant. th = or th = 1 −
QH QH
Q in = amount of heat supplied to
steam in boiler from a high-
temperature source (furnace) Figure 6–13
Q out = amount of heat rejected Schematic of a heat engine.
from steam in condenser to a low-
temperature sink (the atmosphere,
a river, etc.)
W out = amount of work delivered
by steam as it expands in turbine
W in = amount of work required to Copyright © McGraw-Hill Education. Permission required for reproduction or display.
compress water to boiler pressure
W net,out = W out − W in ( kJ )
W net,out = Q in − Q out ( kJ )
ME579-Advanced Thermodynamics Rakesh K Maurya @ IIT Ropar
Heat Engines
Can we save Qout?
In a steam power plant, the condenser is the device where large quantities of
waste heat is rejected to rivers, lakes, or the atmosphere.
Can we not just take the condenser out of the plant and save all that waste
energy?
The answer is, unfortunately, a firm no for the simple reason that without a
heat rejection process in a condenser, the cycle cannot be completed.

Every heat engine must waste some energy by transferring it to a low-

temperature reservoir in order to complete the cycle, even under idealized
conditions.

ME579-Advanced Thermodynamics Rakesh K Maurya @ IIT Ropar

The Second Law of Thermodynamics: Kelvin–Planck
Statement
It is impossible for any device that Figure 6–18
operates on a cycle to receive heat
A heat engine that violates the Kelvin–
from a single reservoir and
Planck statement of the second law.
produce a net amount of work.

No heat engine can have a thermal

efficiency of 100 percent, or as for a
power plant to operate, the working fluid
must exchange heat with the environment
as well as the furnace.
The impossibility of having a 100%
efficient heat engine is not due to friction
or other dissipative effects. It is a
limitation that applies to both the
idealized and the actual heat engines.

ME579-Advanced Thermodynamics Rakesh K Maurya @ IIT Ropar

The Second Law of Thermodynamics: Clasius Statement
Figure 6–25
It is impossible to construct a device that A refrigerator that violates
operates in a cycle and produces no effect other the Clausius statement of the
than the transfer of heat from a lower- second law.
temperature body to a higher-temperature body.
It states that a refrigerator cannot operate
unless its compressor is driven by an external
power source, such as an electric motor.
This way, the net effect on the surroundings
involves the consumption-n of some energy in
the form of work, in addition to the transfer of
heat from a colder body to a warmer one.
To date, no experiment has been conducted
that contradicts the second law, and this should
be taken as sufficient proof of its validity. Copyright © McGraw-Hill Education. Permission required for
reproduction or display.

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 Equivalence of the Two Statements
Figure 6–26
Proof that the violation of the Kelvin–Planck statement leads to Both the Kelvin–Planck and the Clausius statements
the violation of the Clausius statement. of the second law are negative statements, and a
negative statement cannot be proved.

The second law of

thermodynamics is based on
experimental observations. To
date, no experiment has been
conducted that contradicts the
second law, and this should be
Copyright © McGraw-Hill Education. Permission required for reproduction or display. taken as sufficient proof of its
validity.
The Kelvin–Planck and the Clausius statements are equivalent in their consequences,
and either statement can be used as the expression of the second law of
thermodynamics.
Any device that violates the Kelvin–Planck statement also violates the Clausius
statement, and vice versa.
ME579-Advanced Thermodynamics Rakesh K Maurya @ IIT Ropar
Reversible And Irreversible Processes
Reversible process: A process that can be
Figure 6–30
reversed without leaving any trace on the
Reversible processes deliver the most and
surroundings. consume the least work.
Irreversible process: A process that is not
reversible.
All the processes occurring in nature are
Reversible processes can be viewed
irreversible.
as theoretical limits for the
Why are we interested in reversible corresponding irreversible ones.
processes?
(1) they are easy to analyze and
(2) they serve as idealized models
(theoretical limits) to which actual processes
can be compared.
Some processes are more irreversible than
others.
We try to approximate reversible processes.
Why?
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Reversible And Irreversible Processes
The factors that cause a process to be irreversible are called irreversibilities.
They include friction, unrestrained expansion, mixing of two fluids, heat
transfer across a finite temperature difference, electric resistance, inelastic
deformation of solids, and chemical reactions.
The presence of any of these effects renders a process irreversible.
Irreversibilities Figure 6–32
Figure 6–31 Irreversible compression and expansion
Friction renders a process irreversible. processes.

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Copyright © McGraw-Hill Education. Permission required for reproduction or display.

ME579-Advanced Thermodynamics Rakesh K Maurya @ IIT Ropar

Internally and Externally Reversible Processes

Internally reversible process: If no Figure 6–34

irreversibilities occur within the boundaries
A reversible process involves no
of the system during the process.
internal and external irreversibilities.
Externally reversible: If no
irreversibilities occur outside the system
boundaries.
Totally reversible process: It involves no
irreversibilities within the system or its
surroundings.
A totally reversible process involves no
heat transfer through a finite temperature
difference, no nonquasi-equilibrium
changes, and no friction or other dissipative
effects.

ME579-Advanced Thermodynamics Rakesh K Maurya @ IIT Ropar

Conditions for Reversibility /Irreversibility
Natural processes involves one or both the following features
The conditions for the mechanical, thermal or chemical equilibrium namely thermodynamic
equilibrium are not satisfied.
Dissipative effects such as friction, viscosity, inelasticity, electric resistance, and magnetic
hysteresis are present.
Reversible process must not posses these features. Process will be reversible:
It is performed quasi-statically
It is not accompanied by dissipative effects.

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The Carnot Cycle
Figure 6–36
Execution of the Carnot cycle in a closed system.

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Reversible Isothermal Expansion (process 1-2, TH = constant)

Reversible Adiabatic Expansion (process 2-3, temperature drops from TH to TL)
Reversible Isothermal Compression (process 3-4, TL = constant)
Reversible Adiabatic Compression (process 4-1, temperature rises from TL to TH)

ME579-Advanced Thermodynamics Rakesh K Maurya @ IIT Ropar

The Carnot Cycle
Figure 6–37
Figure 6–38
P-V diagram of the Carnot cycle.
P-V diagram of the reversed Carnot cycle.

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The Reversed Carnot Cycle

The Carnot heat-engine cycle is a totally reversible cycle.
Therefore, all the processes that comprise it can be reversed, in which case it
becomes the Carnot refrigeration cycle.
ME579-Advanced Thermodynamics Rakesh K Maurya @ IIT Ropar
The Carnot Principles
1. The efficiency of an irreversible heat Figure 6–39
engine is always less than the efficiency
of a reversible one operating between The Carnot principles.
the same two reservoirs.
2. The efficiencies of all reversible heat
engines operating between the same two
reservoirs are the same.

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ME579-Advanced Thermodynamics Rakesh K Maurya @ IIT Ropar

Proof of the first Carnot principle

• (a) A reversible and an irreversible heat engine

operating between the same two reservoirs
(the reversible heat engine is then reversed to • (b) The equivalent combined
run as a refrigerator) system

ME579-Advanced Thermodynamics Rakesh K Maurya @ IIT Ropar

Second Law for closed System
The second-law idea began with Sadi Carnot’s vision of the functioning of heat
enginesn a class of systems that even in his time were not “simple.”
So instead of retracing Said Carnot’s steps, we look back at a class of simpler
examples, the experiments of Count Rumford and Joule.
The essence of the second law is that in the Rumford and Joule experiments
the apparatuses received work and rejected heat. It was never the other way
around;
in fact, all the attempts to construct a heat engine that would operate cyclically
as a closed system while in possible contact with a single temperature reservoir
have failed.

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Second Law for closed System
Planck summarized these observations this way: “It is impossible to construct
an engine which will work in a complete cycle, and produce no effect except
the raising of a weight and the cooling of a heat-reservoir” .
A similar statement had been made in 1851 by William Thomson (Lord Kelvin):
“It is impossible, by means of inanimate material agency, to derive mechanical
effect from any portion of matter by cooling it below the temperature of the
coldest of the surrounding objects,”
which is followed by the following footnote: “If this axiom be denied for all
temperatures, it would have to be admitted that a self-acting machine might be
set to work and produce mechanical effect by cooling the sea or earth, with no
limit but the total loss of heat from the earth and sea, or, in reality, from the
whole material world” [2].

ME579-Advanced Thermodynamics Rakesh K Maurya @ IIT Ropar

Second Law for closed System
For Cycle in Contact with One Temperature Reservoir

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Cycle in Contact with Two Temperature Reservoirs

Please refer to the text book and class notes for detailed derivation

ME579-Advanced Thermodynamics Rakesh K Maurya @ IIT Ropar

Cycle in Contact with Any Number of Temperature
Reservoirs

Please refer to the text book and class notes for detailed derivation

ME579-Advanced Thermodynamics Rakesh K Maurya @ IIT Ropar

Process in Contact with Any Number of Temperature
Reservoirs

Please refer to the text book and class notes for detailed derivation

ME579-Advanced Thermodynamics Rakesh K Maurya @ IIT Ropar

ME579-Advanced Thermodynamics Rakesh K Maurya @ IIT Ropar
ME579-Advanced Thermodynamics Rakesh K Maurya @ IIT Ropar
ME579-Advanced Thermodynamics Rakesh K Maurya @ IIT Ropar
ME579-Advanced Thermodynamics Rakesh K Maurya @ IIT Ropar
ME579-Advanced Thermodynamics Rakesh K Maurya @ IIT Ropar