Chapter 5

second law of thermodynamics

Debre Markos Univesity
Mechanical Engineering
Department
Engineering Thermodynamics I

Prepared and Presented By: - Tariku Negash

The second law of thermodynamics:
 The level of entropy in the universe is steadily increasing. Systems tend to move from
ordered behaviour to more random behaviour.
 states that processes occur in a certain direction, not in just any direction. Physical
processes in nature can proceed toward equilibrium spontaneously:
 Gases expand from a high pressure to a low pressure.
 Water flows down a waterfall.
 Heat flows from a high temperature to a low temperature.

Once it has taken place, a spontaneous process can be reversed, but it will not reverse
itself spontaneously. Some external inputs, energy, must be expended to reverse the
process.

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E.g. As it falls down the waterfall, water can be
collected in a water wheel, cause a shaft to rotate, coil
a rope onto the shaft, and lift a weight. So the energy
of the falling water is captured as potential energy
increase in the weight, and the first law of
thermodynamics is satisfied. However, there are
losses associated with this process (friction). Allowing
the weight to fall, causing the shaft to rotate in the
opposite direction, will not pump all of the water back
up the waterfall.

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.

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 Spontaneous processes can proceed only in a particular direction. The first law of
thermodynamics gives no information about direction (quantity); it states only that
when one form of energy is converted into another.
 We know by experience that heat flows spontaneously from a high temperature to a
low temperature.
 But heat flowing from a low temperature to a higher temperature with no expenditure
of energy to cause the process to take place would not violate the first law.
Joule's experiments: - ‘energy in the form of heat could not be completely converted into
work; however, work energy can be completely converted into heat energy.’
Therefore: - Heat and Work are not completely interchangeable forms of energy.
The second law of thermodynamics that controls the direction processes may take and
how much heat is converted into work.
A process will not occur unless it satisfies both the first and the second laws of
thermodynamics.

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Some Definitions
To express the second law in a workable form, we need the following definitions.
1. Heat (thermal) reservoir
 A heat reservoir is a sufficiently large system in stable equilibrium to which and from
which finite amounts of heat can be transferred without any change in its temperature.
 E.g large bodies of water such as oceans, lakes, and rivers (mass x specific heat)
Since mega joules of waste energy dumped in large rivers
by power plant don’t cause any significant change in water temperature
 A high temperature heat reservoir from which heat is
transferred is sometimes called a heat source(supplies energy).
 A low temperature heat reservoir to which heat is transferred
is sometimes called a heat sink (absorbs energy).
2. Work reservoir
 A work reservoir is a sufficiently large system in stable equilibrium to which and from
which finite amounts of work can be transferred adiabatically without any change in its
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pressure.
Thermodynamic cycle
A system has completed a thermodynamic cycle when the system undergoes a series of
processes and then returns to its original state, so that the properties of the system at
the end of the cycle are the same as at its beginning. Thus, for whole numbers of cycles.
E.g.
Pf  Pi , Tf  Ti , u f  ui , v f  vi , etc.
Heat Engine
A heat engine is a thermodynamic system operating in a thermodynamic cycle to which
net heat is transferred and from which net work is delivered.
The system, or working fluid, undergoes a series of processes
that constitute the heat engine cycle.
E.g.

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Thermal Efficiency,  th
The thermal efficiency is the index of performance of a work-producing device or a heat
engine and is defined by the ratio of the net work output (the desired result) to the heat
input (the costs to obtain the desired result).

N.B. The thermal efficiency is always less than 1 or less than 100 percent.

Cyclic devices such as heat engines,

refrigerators, and heat pumps often
operate between a high-temperature
reservoir at temperature TH and a low-
temperature reservoir at temperature
TL. th

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Thermal Efficiency,  th
The thermal efficiency is the index of performance of a work-producing device or a heat
engine and is defined by the ratio of the net work output (the desired result) to the heat
input (the costs to obtain the desired result).

N.B. The thermal efficiency is always less than 1 or less than 100 percent.

Cyclic devices such as heat engines,

refrigerators, and heat pumps often
operate between a high-temperature
reservoir at temperature TH and a low-
temperature reservoir at temperature
TL. th

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Example 5-1
A steam power plant produces 50 MW of net work while burning fuel to produce 150 MW
of heat energy at the high temperature. Draw the system and determine the cycle
thermal efficiency and the heat rejected by the cycle to the surroundings.
Wnet , out Wnet , out  QH  QL
 th 
QH QL  QH  Wnet , out
50 MW
  0.333 or 33.3%  150 MW  50 MW
150 MW
 100 MW
Kelvin-Planck statement of the second law
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.
He states that no heat engine can produce a net amount
of work while exchanging heat with a single reservoir
only. In other words, the maximum possible efficiency is
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less than 100 percent.
 REFRIGERATORS AND HEAT PUMPS
a. REFRIGERATORS
 The transfer of heat from a low-temperature Basic components of a refrigeration
medium to a high-temperature one requires system and typical operating conditions.
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.
The objective of a refrigerator is to remove QL from the
cooled space.

Can the value of COPR be greater than unity?-

Because of the amount of heat removed from the refrigerated
space can be grater than the amount of work input

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b. HEAT PUMP
 A heat pump is a thermodynamic system operating in a thermodynamic cycle that
removes heat from a low-temperature body and delivers heat to a high-temperature
body.
 To accomplish this energy transfer, the heat pump receives external energy in the
form of work or heat from the surroundings.
 Refrigerator is a device that operates on a thermodynamic cycle and extracts heat
from a low-temperature medium.
 Heat pump is also operates on a thermodynamic cycle but rejects heat to the high-
temperature medium.

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 Heat Pump Systems
For heating mode
High pressure vapor refrigerant is sent to
the indoor heat exchanger coil. The
refrigerant gives up its energy to the inside
air and condenses to a liquid. The liquid is
throttled to a low pressure and
temperature to the outdoor coil and
receives energy from the outside air. The
refrigerant vaporizes, enters the
compressor to be compressed to the high
pressure, and the cycle is completed.

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 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.

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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EXAMPLE 5–2
The food compartment of a refrigerator is maintained at 4 by removing heat
from it at a rate of 360 kJ/min. If the required power input to the refrigerator is
2 kW, show sckematically and determine
(a) the coefficient of performance of the refrigerator and
(b) the rate of heat rejection to the room that houses the refrigerator.
EXAMPLE 5–3
A heat pump is used to meet the heating requirements of a house and maintain
it at 20 . On a day when the outdoor air temperature drops to 2 the house is
estimated to lose heat at a rate of 80,000 kJ/h. If the heat pump under these
conditions has a COP of 2.5, determine
(a) the power consumed by the heat pump and
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(b) the rate at which heat is absorbed from the cold outdoor air.
Clausius statement of the second law
He states that 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

 Both the Kelvin-Planck and the Clausius statements of the second law are negative
statements, and negative statement can’t be proved. Like any other physical law, the
second law of thermodynamics is based on the experimental observations.
 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
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
themodynamics. Any device that violates the Kelvin–Planck statement also violates the
Clausius statement, and vice versa.
The output of the engine drives a heat pump that transfers an amount of heat QL from
the low-temperature thermal reservoir and an amount of heat QH + QL to the high-
temperature thermal reservoir. The combination of the heat engine and refrigerator in
the left figure acts like a heat pump that transfers heat QL from the low-temperature
reservoir without any external energy input. This is a violation of the Clausius statement
of the second law.
Proof that the violation of the Kelvin–Planck
statement leads to the violation of the
Clausius statement.

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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.
Despite numerous attempts, no perpetual-motion machine is known to have worked. If
something sounds too good to be true, it probably is.

A perpetual-motion machine that violates

A perpetual-motion machine that violates the second law of thermodynamics
the first law (PMM1). link (PMM2).
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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?

Fig.1 Two familiar

reversible processes.

Fig. 2 Reversible processes deliver the most and

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consume the least work.
 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, etc…

1. Friction renders a 2. unrestrained expansion 3. heat transfer across a

process irreversible.
finite temperature difference

Therefore, The presence of any of these effects renders

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a process irreversible
The Carnot Cycle
French military engineer Nicolas Sadi Carnot (1769-1832) was among the first to study
the principles of the second law of thermodynamics. Carnot was the first to introduce
the concept of cyclic operation and devised a reversible cycle that is composed of four
reversible processes, two isothermal and two adiabatic

Process 1-2:Reversible isothermal heat addition at high temperature, TH > TL, to the
working fluid in a piston-cylinder device that does some boundary work.
Process 2-3:Reversible adiabatic expansion during which the system does work as
the working fluid temperature decreases from TH to TL.

Process 3-4:The system is brought in contact with a heat reservoir at TL < TH and a
reversible isothermal heat exchange takes place while work of compression is done on
the system.
Process 4-1:A reversible adiabatic compression process increases the working fluid
temperature from TL to TH
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The Carnot Cycle
Carnot was the first to introduce the concept of cyclic operation and devised a reversible
cycle that is composed of four reversible processes, two isothermal and two adiabatic
The four reversible processes that make up the Carnot cycle are as follows:
Reversible Isothermal Expansion (process 1-2, TH = constant) (1)
Reversible Adiabatic Expansion (process 2-3, temperature drops from TH to TL) : (2)
Reversible Isothermal Compression (process 3-4, TL = constant) : (3)
Reversible Adiabatic Compression (process 4-1, temperature rises from TL to TH) : (4)

1
3

2
4

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Draw the P-v diagram Carnot heat engine
THE CARNOT PRINCIPLES
The second law of thermodynamics puts limits on the operation of cyclic devices as
expressed by the Kelvin-Planck and Clausius statements. A heat engine cannot operate
by exchanging heat with a single heat reservoir, and a refrigerator cannot operate
without net work input from an external source.
1. The efficiency of an irreversible heat engine is always less than the efficiency of a
reversible one operating between the same two reservoirs.  th   th , Carnot
2. The efficiencies of all reversible heat engines operating between the same two
reservoirs are the same.

The Carnot principles. Proof of the first Carnot principle. 25

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 o
heat engines used to
develop the
For reversible cycles, the heat A conceptual experimental setup to thermodynamic
transfer ratio QH /QL can be determine thermodynamic temperature scale.
replaced by the absolute temperatures on the Kelvin scale by
temperature ratio TH /TL. measuring heat transfers QH and QL. 26
This temperature scale is called the Kelvin scale, and the temperatures on this
scale are called absolute temperatures.

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
reservoirs. efficiency than a reversible heat engine
operating between the same high- and
Any heat Carnot heat low-temperature reservoirs.
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 How do you increase the thermal

can be converted to work efficiency of a Carnot heat engine?
as a function of source How about for actual heat engines?
temperature.
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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

No refrigerator can have a higher COP COP of a Carnot refrigerator
than a reversible refrigerator operating or heat pump? How about
between the same temperature limits. for actual ones? 29
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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Reversed Carnot Device Coefficient of Performance

If the Carnot device is caused to operate in the reversed cycle, the reversible heat
pump is created. The COP of reversible refrigerators and heat pumps are given in a
similar manner to that of the Carnot heat engine as

QH
QL 1 QH QL
COPR   COPHP  
QH  QL QH  1 QH  QL QH  1
QL QL
TL 1 TH
 
TH  TL TH  1 TH TL
 
TL TH  TL TH  1
TL

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 Example 6-2
A Carnot heat engine receives 500 kJ of heat per cycle from a high-temperature heat
reservoir at 652oC and rejects heat to a low-temperature heat reservoir at 30oC.
Determine
(a) The thermal efficiency of this Carnot engine.
(b) The amount of heat rejected to the low-temperature heat reservoir.
a. b.
TH = TL QL T
 th , rev  1   L
652oC TH QH TH
QH (30  273) K ( 30  273) K
 1   0.328
WOU ( 652  273) K (652  273) K
HE
T  0.672 or 67.2% QL  500 kJ ( 0.328)
Q
 164 kJ
L
TL = 30 Co

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 Example 6-3

An inventor claims to have invented a heat engine that develops a thermal efficiency
of 80 percent when operating between two heat reservoirs at 1000 K and 300 K.
Evaluate his claim.
TH = 1000 K

TL
QH
 th , rev  1
TH
WOUT
HE 300 K
 1
QL 1000 K
TL = 300 K  0.70 or 70%

The claim is false since no heat engine may be more efficient than a Carnot engine
operating between the heat reservoirs.

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 Example 6-4

An inventor claims to have developed a refrigerator that maintains the refrigerated

space at 2oC while operating in a room where the temperature is 25oC and has a
COP of 13.5. Is there any truth to his claim?
TH = 25oC
QL TL
COPR  
QH
QH  QL TH  TL
(2  273) K
R
Win 
(25  2) K
QL
 1196
.
TL = 2oC

The claim is false since no refrigerator may have a COP larger than the COP for the
reversed Carnot device.
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Example 6-5

A heat pump is to be used to heat a building during the winter. The building is to be
maintained at 21oC at all times. The building is estimated to be losing heat at a rate
of 135,000 kJ/h when the outside temperature drops to -5oC. Determine the minimum
power required to drive the heat pump unit for this outside temperature.

Q Lost

W in
21 oC

Q H
HP
Q L
-5 oC

The heat lost by the building has to be supplied by the heat pump.

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 Using the basic definition of the COP

  kJ Q H
QH  QLost  135000 COPHP 
h W net , in
Q H TH Q H
COPHP   W net , in 
 
QH  QL TH  TL COPHP
(21  273) K 135,000 kJ / h 1 h 1 kW
 
(21  ( 5)) K 1131
. 3600s kJ / s
 3.316 kW
 11.31

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THERMAL POWER PLANT

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First law

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 Expansion Valve

Condenser

Evaporator

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

1
3

2 4

What is the reversed of

this diagram ?

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