Thermodynamics: An Engineering Approach, 6th Edition

Yunus A. Cengel, Michael A. Boles

McGraw-Hill, 2008

Chapter 6
THE SECOND LAW OF
THERMODYNAMICS

Mehmet Kanoglu

Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
 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.
2
INTRODUCTION TO THE SECOND LAW
A cup of hot coffee
does not get hotter in
a cooler room.
Transferring
heat to a
paddle wheel
will not cause
it to rotate.

These processes
Transferring cannot occur
heat to a wire even though
will not they are not in
generate
violation of the
electricity.
first law.
3
 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. 4
 THERMAL ENERGY RESERVOIRS

Bodies with relatively large thermal

masses can be modeled as thermal A source supplies energy in the form
energy reservoirs. of heat, and a sink absorbs it.

• 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
1. The devices that convert heat to
work.
2. They receive heat from a high-
temperature source (solar energy,
oil furnace, nuclear reactor, etc.).
3. They convert part of this heat to
work (usually in the form of a
Work can always rotating shaft.)
be converted to
4. They reject the remaining waste
heat directly and heat to a low-temperature sink
completely, but the (the atmosphere, rivers, etc.).
reverse is not true.
5. They operate on a cycle.
6. 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 transferred while undergoing a
converted to work, cycle. This fluid is called the
while the rest is working fluid.
rejected to a sink.
6
A steam power plant

A portion of the work output

of a heat engine is consumed
internally to maintain
continuous operation.

7
Thermal efficiency

Schematic of
a heat engine.

Some heat engines perform better

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

8
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,
A heat-engine cycle cannot be completed without unfortunately, a firm
rejecting some heat to a low-temperature sink. no for the simple
reason that without a
Every heat engine must waste heat rejection process
some energy by transferring it to a in a condenser, the
low-temperature reservoir in order cycle cannot be
completed.
to complete the cycle, even under
idealized conditions.
9
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 A heat engine that violates the
must exchange heat with the Kelvin–Planck statement of the
environment as well as the furnace. second law.
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.
10
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
refrigeration system and the evaporator, and the coils usually behind the
typical operating conditions. refrigerator where heat is dissipated to the kitchen
air serve as the condenser.
11
 Coefficient of Performance
- Refrigerator
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? Yes!
12
 Heat The work
supplied to a
Pumps heat pump is
used to extract
The objective energy from the
of a heat cold outdoors
pump is to and carry it into
supply heat the warm
QH into the indoors.
warmer
space.

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.
When installed backward, • The COP of a refrigerator decreases with
an air conditioner decreasing refrigeration temperature.
functions as a heat pump. • Therefore, 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.
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. A refrigerator that
To date, no experiment has been conducted that violates the Clausius
contradicts the second law, and this should be statement of the second
taken as sufficient proof of its validity. law.

15
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.
16
PERPETUAL-MOTION MACHINES

A perpetual-motion machine that violates

A perpetual-motion machine that the second law of thermodynamics
violates the first law (PMM1). (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.
17
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 processes deliver the most and consume

reversible processes. the least work.
18
 IRREVERSIBILITIES
Friction
renders a • The factors that cause a process to be
process irreversible are called irreversibilities.
irreversible. • 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.
(a) Heat
transfer
through a
temperature
difference is
irreversible, Irreversible
and (b) the compression
reverse and
process is expansion
impossible. processes. 19
 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.
20
 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)
21
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.
22
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.

All reversible heat The arrangement of heat

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

24
 This temperature scale is
called the Kelvin scale,
and the temperatures on
this scale are called
absolute temperatures.

For reversible cycles, the A conceptual experimental setup

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

25
THE CARNOT HEAT ENGINE
The Carnot
heat engine
is the most
efficient of
all heat
engines
operating
between the
same high-
and low-
temperature
reservoirs.
No heat engine can have a higher
efficiency than a reversible heat engine
operating between the same high- and
low-temperature reservoirs.
Any heat Carnot heat
engine engine

26
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 How do you increase the

can be converted to work thermal efficiency of a Carnot
as a function of source heat engine? How about for
temperature. actual heat engines?
27
THE CARNOT REFRIGERATOR
AND HEAT PUMP Any refrigerator or heat pump

Carnot refrigerator or heat pump

How do you increase the

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

28
Summary
• Introduction to the second law
• Thermal energy reservoirs
• Heat engines
ü Thermal efficiency
ü The 2nd law: Kelvin-Planck statement
• Refrigerators and heat pumps
ü Coefficient of performance (COP)
ü The 2nd law: Clasius statement
• Perpetual motion machines
• Reversible and irreversible processes
ü Irreversibilities, Internally and externally reversible processes
• The Carnot cycle
ü The reversed Carnot cycle
• The Carnot principles
• The thermodynamic temperature scale
• The Carnot heat engine
ü The quality of energy
• The Carnot refrigerator and heat pump 29