Chapter 6

THE SECOND LAW OF THERMODYNAMICS

McGraw-Hill | 1
 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

These processes cannot

occur even though they
are not in violation of the
first law.
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 MAJOR USES OF THE SECOND LAW
1. The second law may be used to identify the
direction of processes.
2. 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.
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 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.
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A reservoir that supplies
energy in the form of heat
is called a source, and one
that absorbs energy in the
form of heat is called a
sink.
Thermal energy reservoirs
are often referred to as
heat reservoirs since they
supply or absorb energy in
the form of heat.

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HEAT ENGINES

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.)
3. They reject the remaining
waste heat to a low-
temperature sink (the
atmosphere, rivers, etc.).
4. They operate on a cycle.

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Heat engines and other cyclic
devices usually involve a fluid
to and from which heat is
transferred while undergoing a
cycle.
This fluid is called the working
fluid.

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A steam power plant

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Thermal efficiency

The fraction of the heat input that

is converted to net work output is a
measure of the performance of a
heat engine and is called the
thermal efficiency.
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QH = magnitude of heat transfer between
the cyclic device and the high-temperature
medium at temperature TH
QL = magnitude of heat transfer between
the cyclic device and the low-temperature
medium at temperature TL

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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?

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.

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Is it possible to transfer the 85 kJ of excess
heat at 90°C back to the reservoir at 100°C
for later use?

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Net Power Production
of a Heat Engine

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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
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.
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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 where heat is absorbed by
the refrigerant serves as the evaporator,
and the coils usually behind the
refrigerator where heat is dissipated to the
kitchen air serve as the 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.

Can the value of COPR

be greater than unity?
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Heat Pumps

for fixed values of QL and QH

Can the value of COPHP

be lower than unity?
What does COPHP=1
represent?

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Performance of Refrigerators, Air Conditioners,
and Heat Pumps
Most heat pumps in operation 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.
It is not economical to refrigerate to a lower temperature than needed.

Energy efficiency rating (EER): The amount

of heat removed from the cooled space in Btu’s
for 1 Wh (watthour) of electricity consumed.
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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
contradicts the second law, and this should be
taken as sufficient proof of its validity.
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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

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.
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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?

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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

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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.

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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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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

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.

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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.

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

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THE CARNOT HEAT ENGINE

Any heat
engine

Carnot heat
engine

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Analysis of a Carnot Heat Engine

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The Quality of Energy

Can we use C unit

for temperature
here?

How do you increase the thermal

efficiency of a Carnot heat engine?
How about for actual 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 of a

Carnot refrigerator or heat pump?
How about for actual ones?

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The COP of a reversible refrigerator or heat pump is the
maximum theoretical value for the specified temperature limits.
Actual refrigerators or heat pumps may approach these values
as their designs are improved, but they can never reach them.
The COPs of both the refrigerators and the heat pumps
decrease as TL decreases.
That is, it requires more work to absorb heat from lower-
temperature media.

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Heating a House by a
Carnot Heat Pump

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 Summary
Introduction to the second law
Thermal energy reservoirs
Heat engines
Refrigerators and heat pumps
Perpetual motion machines
Reversible and irreversible processes
The Carnot cycle
The Carnot principles
The thermodynamic temperature scale
The Carnot heat engine
The Carnot refrigerator and heat pump

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