THE SECOND LAW OF

THERMODYNAMICS

Ass. Prof. Dr. Ahmed Farag

 Objectives
• Introduce the second law of thermodynamics.
• Identify valid processes as those that satisfy both the first and second
laws of thermodynamics.
• Discuss thermal energy reservoirs, reversible and irreversible
processes, heat engines, refrigerators, and heat pumps.
• Describe the Kelvin–Planck and Clausius statements of the second law
of thermodynamics.
• Discuss the concepts of perpetual-motion machines.
• Apply the second law of thermodynamics to cycles and cyclic devices.
• Apply the second law to develop the absolute thermodynamic
temperature scale.
• Describe the Carnot cycle.
• Examine the Carnot principles, idealized Carnot heat engines,
refrigerators, and heat pumps.
• Determine the expressions for the thermal efficiencies and coefficients
of performance for reversible heat engines, heat pumps, and
refrigerators.
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INTRODUCTION TO THE SECOND LAW
A cup of hot coffee Transferring
does not get hotter in a heat to a paddle
cooler room. wheel will not
cause it to
rotate.

These processes
Transferring heat cannot occur even
to a wire will not though they are not
generate in violation of the
electricity.
first law.

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 Processes occur in a
certain direction, and not
in the reverse direction.

A process must satisfy both the

first and second laws of
thermodynamics to proceed.

MAJOR USES OF THE SECOND LAW

1. The second law may be used to identify the direction of processes.
2. The second law also 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.
3. 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.
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 THERMAL ENERGY
RESERVOIRS
A source supplies
energy in the
form of heat, and
a sink absorbs it.

Bodies with relatively large thermal

masses can be modeled as thermal
energy reservoirs.

• A hypothetical body with a relatively large thermal energy capacity (mass x

specific heat) that can supply or absorb finite amounts of heat without
undergoing any change in temperature is called a thermal energy
reservoir, or just a reservoir.
• In practice, large bodies of water such as oceans, lakes, and rivers as well
as the atmospheric air can be modeled accurately as thermal energy
reservoirs because of their large thermal energy storage capabilities or
thermal masses. 5
 HEAT ENGINES

The devices that convert heat to

work.
1. They receive heat from a high-
temperature source (solar energy,
oil furnace, nuclear reactor, etc.).
2. They convert part of this heat to
work (usually in the form of a
rotating shaft.)
Work can always be 3. They reject the remaining waste
converted to heat heat to a low-temperature sink
directly and (the atmosphere, rivers, etc.).
completely, but the
4. They operate on a cycle.
reverse is not true.
Heat engines and other cyclic
Part of the heat devices usually involve a fluid to
received by a heat and from which heat is
engine is converted to transferred while undergoing a
work, while the rest cycle. This fluid is called the
is rejected to a sink. working fluid.

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A steam power plant

A portion of the work output of

a heat engine is consumed
internally to maintain
continuous operation.

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 Thermal efficiency

Schematic of a
heat engine.

Some heat engines perform better Even the most efficient

than others (convert more of the heat heat engines reject
they receive to work). almost one-half of the
energy they receive as
waste heat.

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 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? A heat-engine cycle cannot be completed without
rejecting some heat to a low-temperature sink.
The answer is,
unfortunately, a firm
no for the simple
Every heat engine must waste some energy
reason that without a
heat rejection process
by transferring it to a low-temperature
in a condenser, the reservoir in order to complete the cycle, even
cycle cannot be under idealized conditions.
completed.
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The Second Law of
Thermodynamics:
Kelvin–Planck Statement
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.

No heat engine can have a thermal

efficiency of 100 percent, or as for a power
plant to operate, the working fluid must A heat engine that violates the Kelvin–
exchange heat with the environment as well Planck statement of the second law.
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.
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 REFRIGERATORS AND HEAT PUMPS

• The transfer of heat from a low-

temperature medium to a high-
temperature one requires special
devices called refrigerators.
• Refrigerators, like heat engines,
are cyclic devices.
• The working fluid used in the
refrigeration cycle is called a
refrigerant.
• The most frequently used
refrigeration cycle is the vapor-
compression refrigeration cycle.

In a household refrigerator, the freezer compartment

Basic components of a where heat is absorbed by the refrigerant serves as the
refrigeration system and evaporator, and the coils usually behind the refrigerator
typical operating where heat is dissipated to the kitchen air serve as the
conditions. condenser.
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 Coefficient of Performance

The efficiency of a refrigerator is expressed in

terms of the coefficient of performance (COP).
The objective of a refrigerator is to remove heat
(QL) from the refrigerated space.

The objective of a refrigerator is to Can the value of COPR be

remove QL from the cooled space. greater than unity?

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 Heat Pumps
The objective of a heat pump is to
supply heat QH into the warmer space.

The work supplied to a

heat pump is used to
extract energy from the
cold outdoors and carry it
into the warm indoors.

Can the value of COPHP be lower

than unity?
What does COPHP=1 represent?

for fixed values of QL and QH 13

 • Most heat pumps in operation today have a
seasonally averaged COP of 2 to 3.
• Most existing heat pumps use the cold outside air
as the heat source in winter (air-source HP).
• In cold climates their efficiency drops considerably
when temperatures are below the freezing point.
• In such cases, geothermal (ground-source) HP
that use the ground as the heat source can be
used.
• Such heat pumps are more expensive to install,
but they are also more efficient.
• Air conditioners are basically refrigerators whose
refrigerated space is a room or a building instead
of the food compartment.
• The COP of a refrigerator decreases with
decreasing refrigeration temperature.
• Therefore, it is not economical to refrigerate to a
When installed backward, an lower temperature than needed.
air conditioner functions as a
heat pump.

Energy efficiency rating (EER): The amount of heat removed from the cooled
space in Btu’s for 1 Wh (watthour) of electricity consumed. 14
 The Second Law of Thermodynamics: Clasius
Statement

It is impossible to construct a device that

operates in a cycle and produces no effect other
than the transfer of heat from a lower-
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 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 A refrigerator that
contradicts the second law, and this should be taken as violates the Clausius
sufficient proof of its validity. statement of the second
law.
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 Equivalence of the Two Statements

Proof that the violation

of the Kelvin–Planck
statement leads to the
violation of the
Clausius statement.

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.

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 PERPETUAL-MOTION MACHINES

A perpetual-motion machine that A perpetual-motion machine that

violates the first law (PMM1). violates the second law of
thermodynamics (PMM2).

Perpetual-motion machine: Any device that violates the first or the second law.
A device that violates the first law (by creating energy) is called a PMM1.
A device that violates the second law is called a PMM2.
Despite numerous attempts, no perpetual-motion machine is known to have worked.
If something sounds too good to be true, it probably is.

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 REVERSIBLE AND IRREVERSIBLE PROCESSES
Reversible process: A process that can be reversed without leaving any trace on the
surroundings.
Irreversible process: A process that is not reversible.
• All the processes occurring in nature are irreversible.
• Why are we interested in reversible 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?

Two familiar reversible Reversible processes deliver the most and consume the
processes. least work. 18
 • The factors that cause a process to be irreversible are
called irreversibilities.
• They include friction, unrestrained expansion, mixing of
Friction two fluids, heat transfer across a finite temperature
renders a difference, electric resistance, inelastic deformation of
process solids, and chemical reactions.
irreversible. • The presence of any of these effects renders a process
irreversible.

Irreversibilities
(a) Heat transfer through a
temperature difference is
irreversible, and
(b) the reverse process is
impossible.

Irreversible compression
and expansion processes.
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 Internally and Externally Reversible Processes
• Internally reversible process: If no irreversibilities occur within the boundaries of
the system during the process.
• 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.

A reversible process
involves no internal and Totally and internally reversible heat
external irreversibilities. transfer processes.
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 THE CARNOT
CYCLE

Execution of
the Carnot
cycle in a
closed
system.

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)
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P-V diagram of the Carnot cycle. P-V diagram of the reversed
Carnot cycle.

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.
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 THE CARNOT
PRINCIPLES

Proof of the first Carnot principle.

The Carnot principles.

1. The efficiency of an irreversible heat engine is always less than the

efficiency of a reversible one operating between the same two
reservoirs.
2. The efficiencies of all reversible heat engines operating between the
same two reservoirs are the same. 23
THE THERMODYNAMIC TEMPERATURE SCALE
A temperature scale that is
independent of the
properties of the substances
that are used to measure
temperature is called a
thermodynamic
temperature scale.
Such a temperature scale
offers great conveniences in
thermodynamic calculations.

The arrangement of heat

engines used to develop
All reversible heat engines the thermodynamic
operating between the temperature scale.
same two reservoirs have
the same efficiency.

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 This temperature scale is
called the Kelvin scale, and
the temperatures on this
scale are called absolute
temperatures.

For reversible cycles, the heat A conceptual experimental setup to

transfer ratio QH /QL can be determine thermodynamic
replaced by the absolute temperatures on the Kelvin scale by
temperature ratio TH /TL. measuring heat transfers QH and QL.

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 THE CARNOT HEAT ENGINE

The Carnot
heat engine
is the most
efficient of all
heat engines
operating
between the
same high-
and low-
temperature No heat engine can have a higher efficiency
reservoirs. than a reversible heat engine operating
between the same high- and low-
temperature reservoirs.
Any heat Carnot heat
engine engine

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 The Quality of Energy

Can we use C
unit for
temperature
The higher the temperature
here?
of the thermal energy, the
higher its quality.

The fraction of heat that can How do you increase the thermal
be converted to work as a efficiency of a Carnot heat
function of source engine? How about for actual
temperature. heat engines?
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THE CARNOT REFRIGERATOR
AND HEAT PUMP
Any refrigerator or heat pump

Carnot refrigerator or heat pump

How do you increase the COP

No refrigerator can have a higher COP of a Carnot refrigerator or heat
than a reversible refrigerator operating pump? How about for actual
between the same temperature limits. ones?

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Summary
• Introduction to the second law
• Thermal energy reservoirs
• Heat engines
• Thermal efficiency
• The 2nd law: Kelvin-Planck statement
• Refrigerators and heat pumps
• Coefficient of performance (COP)
• The 2nd law: Clasius statement
• Perpetual motion machines
• Reversible and irreversible processes
• Irreversibilities, Internally and externally reversible processes
• The Carnot cycle
• The reversed Carnot cycle
• The Carnot principles
• The thermodynamic temperature scale
• The Carnot heat engine
• The quality of energy
• The Carnot refrigerator and heat pump

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