Th S

The
Second
dL
Law off Th
Thermodynamics
d
i

Ref. 1: Cengel & Boles, Chapter 6

Objectives

IIntroduce
t d
th
the secondd llaw off thermodynamics
th
d
i
Discuss: thermal energy reservoirs, reversible and irreversible
processes heat engines,
processes,
engines refrigerators,
refrigerators and heat pumps
Discuss: the KelvinPlanck and Clausius statements of the second
law of thermodynamics and the concepts of perpetual-motion
machines
Apply the second law of thermodynamics to cycles and cyclic
devices
Describe the Carnot cycle;
y ; examine the Carnot pprinciples,
p , idealized
Carnot heat engines, refrigerators, and heat pumps
Determine the expressions for the thermal efficiencies and
coefficients
ffi i t off performance
f
(COP) ffor reversible
ibl hheatt engines,
i
hheatt
pumps, and refrigerators
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The second law of thermodynamics

The

first law places no restriction on the direction of a

process, and satisfying the first law does not guarantee
that the process will occur

The

second law of thermodynamics asserts that:

processes occur in a certain direction and

the energy has quality as well as quantity

A process can occur when and only when it satisfies both

the first and the second laws of thermodynamics
y
3

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The second law of thermodynamics

Physical processes in nature can proceed toward equilibrium

spontaneously:
Water flows down a waterfall
Gases expand from a high pressure to a low pressure
Heat flows from a high temperature to a low temperature
Q (heat transfer)
possible

impossible

A spontaneous process may be reversed, but it will not reverse

it lf spontaneously
itself
t
l
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The second law of thermodynamics

The

second law also asserts that energy has a quality

Preserving the quality of energy is a major concern of

engineers
For example, the energy stored in a hot container (higher

temperature) has higher quality (ability to work) in

comparison with the energy contained (at lower temperature)
in the surroundings
The

second law is also used in determining the

theoretical limits for the performance of commonly used
engineering systems, such as heat engines and
refrigerator
fi
t

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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
Examples:
p
Lakes,, rivers,, atmosphere,
p
, oceans

heat source a high temperature heat reservoir

from which heat is transferred

A
6

heat sink a low temperature heat reservoir to

which heat is transferred

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A work reservoir 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 pressure

Thermodynamic cycle a series of processes that returns to

it original
its
i i l state
t t
the p
properties
p
of the system
y
at the end of the cycle
y are the

same as at its beginning

Pf = Pi , Tf = Ti , u f = ui , v f = vi , etc.
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Heat Engines
Heat engine a thermodynamic system operating in a
thermodynamic cycle in which convert heat to work
Characteristics:
They receive heat from a high-temperature source (nuclear

reactor, burner/furnace, etc.)

They convert part of this heat to work
They reject the remaining waste heat to a low-temperature

sink
They operate in a cycle
8

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Heat Engines

The following figure illustrates a steam power plant as a heat

engine operating in a thermodynamic cycle
Energy source
Qin

Source, TH
Qin

Boiler
Turbine

Win

Wnet = Wout - Win

Wout

Heat
Engine

Wnet

Pump
Qout
C d
Condenser
Qout
Energy
gy sink ((lake,, river))
9

Sink, TL
Wnett = Qini - Qoutt
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Thermal Efficiency, th

Thermal efficiency 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)
Desired Result
th =
Required Input

For a heat engine the desired result is the net work done and the input is
the heat supplied to make the cycle operate.
operate

th =
where
h
10

Wnet , out
Qin

Wnet , out = Wout Win

Qin Qnet

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Thermal Efficiency, th

th always less than 1 or less than 100 percent

Applying the first law to the cyclic heat engine

The cycle thermal efficiency may be written as

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Thermal Efficiency, th

The thermal efficiencies of work-producing devices are in

general low
Ordinary spark-ignition automobile engines, th ~ 20%-25%
Diesel engines,
engines th ~ 30%-40%
Power plants th ~ 40%-60%

Is it possible to save the rejected heat Qout in a power cycle?

The answer is NO. Without the cooling
g in condenser the cycle
y cannot

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

temperature reservoir in order to complete the cycle, even in idealized

cycle.
12

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Example 1
A steam power plant produces 50 MW of net work while burning fuel to
pproduce 150 MW of heat energy
gy at the high
g temperature.
p
Determine the
cycle thermal efficiency and the heat rejected by the cycle to the
surroundings.
th =
QH = 150 MW

Wnet = 50 MW

Wnet , out
QH

50 MW
=
= 0.333 or 33.3%
150 MW
Wnet , out = QH QL
QL = QH Wnet , out
= 150 MW 50 MW

QL = ?
13

= 100 MW
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Example 2
A 600 MW steam power plant, which is cooled by a nearby river, has a
thermal efficiencyy of 40 ppercent. Determine the rate of heat transfer to the
river water. Will the actual heat transfer rate be higher or lower than this
value? Why?

14

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Example 3
An automobile engine consumes fuel at a rate of 28 L/h and delivers 60kW of
ppower to the wheels. If the fuel has a heatingg value of 44,000 kJ/kgg and a
density of 0.8 g/cm3, determine the efficiency of this engine.

15

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Second Law Statements

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
Source, TH
Qini

Heat
Engine

Wnet = Qin
Thermal efficiency
of 100%

Qout = 0

no heat engine can have a thermal efficiency of 100%

16

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Heat Pumps and Refrigerators

A

heat pump/refrigerator a thermodynamic system

operating in a thermodynamic cycle that removes heat
from a low-temperature body and delivers heat to a
high temperature body
high-temperature
cannot occurs byy itself;; requires
q
external energy
gy in
the form of work or heat from the surroundings

Refrigerators

are cyclic devices

devices, and the working fluids
used in the cycles are called refrigerant.

17

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Heat Pumps and Refrigerators

Refrigerators and heat pumps are essentially the same devices;

they differ in their objectives only
Refrigerator is to maintain the refrigerated space at a low temperature
A heat pump absorbs heat from a low-temperature source and

supplies the heat to a warmer medium

WARM
environment

WARM
house
QH desired

QH

output

Win

Win
QL desired
output

COLD
refrigerated space
18

Vapor-compression refrigeration cycle

HP

REFRIGERATOR

QL
COLD
environment
HEAT PUMP

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Coefficient of Performance, COP

The

index of performance of a refrigerator or heat pump

is expressed in terms of the coefficient of performance,
COP, the ratio of desired result to input.
Desired Result
COP =
Required Input

This

measure of performance may be larger than 1

we want the COP to be as large as possible

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Coefficient of Performance, COP

For refrigerator the desired result is the heat

supplied at the low temperature and the input
is the net work into the device to make the
cycle operate.

QL
COPR =
Wnet , in

Win = Wnet , in = QH QL
20

QH

Win

QL desired
output

COLD
refrigerated space

Applying the first law to the cyclic refrigerator:

(QL QH ) (0 Win ) = U cycle = 0

WARM
environment

COPR =

REFRIGERATOR

QL
QH Q L

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Coefficient of Performance, COP

WARM
house
QH desired
output

HP

For a heat pump, the desired result is the heat

transferred to the higher temperature and the
input is the net work into the device to make the
cycle operate.

Win
QL
COLD
environment

COPHP

QH
QH
=
=
Wnet , in QH Q L

HEAT PUMP

Under the same operating conditions the COPHP and COPR are related by

COPHP = COPR + 1
Most HP have seasonally averaged COPHP of 2 to 3
21

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 Most existingg heat ppumps

p 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.
Air conditioners are basically refrigerators whose refrigerated space is a
room or a building instead of the food compartment.
The
Th COP off a refrigerator
fi
ddecreases with
i h ddecreasing
i refrigeration
fi
i
temperature.
It is
i nott economical
i l to
t refrigerate
fi
t to
t a lower
l
temperature
t
t than
th
needed.

22

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Heat Pump and Air Conditioner Ratings

HP and AC are rated using the EER system (energy efficiency

rating)
the amount of heating (cooling) on a seasonal basis in Btu/hr per unit
rate of power expended in watts, W.

The heat transfer rate is often given in terms of tons of heating

or cooling.
cooling One ton equals 12,000
12 000 Btu/hr = 211 kJ/min
kJ/min.

Relationship between EER and COPR

EER = 3.412 COPR

23

Mostt airi conditioners

M
diti
have
h
an EER between
b t
8 to
t 12 (COP off 22.33
to 3.5)
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Example 4
A food refrigerator is to provide a 15,000 kJ/h cooling effect while rejecting
22,000 kJ/h of heat. Calculate the COP of this refrigerator.
g
Reservoir
22,000 kJ/h

Win
15,000 kJ/h
Reservoir

24

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Example 5
A heat pump is used to maintain a house at a constant temperature of 23oC.
C The heat
is losing heat to the outside air through the walls and the windows at a rate of 60,000
kJ/h while the energy generated within the house from people, lights and appliances
amounts to 4000
000 kJ/h.
/ For a CO
COP off 22.5, determine the required power input to the
heat pump.

25

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Second Law Statements

Clausius 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 highertemperature body

26

In other words, a refrigerator will not

operate unless its compressor is driven by
an external power source

Source (TH)

QL
Win = 0

Refrigerator

QL

Source (TL)

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Source (TH)
QH + QL

QH

Heat engine
T = 100%
QL = 0

Source (TH)
QL
Win = 0

Wnet = QH

Refrigerator
g

Equivalent

Refrigerator
g

QL

QL

Source (TL)

Source (TL)

The Kelvin-Planck and the Clausius statements are equivalent

q
in their
consequences.
Any device violates the Kelvin-Planck statement also violates the Clausius
statement and vice versa
27

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Assume that the heat engine shown is violating the Kelvin-Planck

statement by absorbing heat from a single reservoir and producing
an equal amount of work W.
The output of the engine drives a refrigerator that transfers an
amount of heat QL from the low-T reservoir and an amount of heat
QH + QL to the high-T reservoir.
The combination of the heat engine and refrigerator acts like a
heat pump that transfers heat QL from the low-T reservoir without
any external energy input.
This is a violation of the Clausius statement of the second law.
28

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Perpetual-Motion Machines
Any

device that violates the first or second law of

thermodynamics is called a perpetual
perpetual-motion
motion machine.

If the

device violates the first law, it is a perpetualmotion machine of the first kind (PMM1).
(PMM1)

If the

device violates the second law, it is a perpetualmotion

i machine
hi off the
h secondd ki
kindd (PMM2)
(PMM2).

29

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Perpetual-Motion Machines

A perpetual-motion machine that

violates the first law (PMM1). Ref. 1

A perpetual-motion machine that violates

the second law of thermodynamics
(PMM2). Ref. 1

Despite numerous attempts, no perpetual-motion machine is known to have

worked. If something
g sounds too good
g
to be true,, it p
probablyy is.
30

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31

http://en.wikipedia.org/wiki/Image:WaterScrewPerpetualMotion.png

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Reversible Processes
A reversible process a process that can be reversed
without leaving any trace on the surroundings
A

reversible process is a quasi-equilibrium, or quasistatic process

both system and surroundings are returned to their initial
states at the end of the reverse process
things happen very slowly,
slowly without any resisting force
force,
without any space limitation

32

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Reversible Processes
Reversible processes are idealizations of actual
p
processes.
We use reversible process concept because:
they
h

are easy to analyze

l
((since
i
system passes through
h
h
a series of equilibrium
q
states))

they serve

as limits (idealized models) to which the

actual
t l processes can bbe comparedd

33

reversible pprocesses deliver the most and consume the

least work

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Reversible Processes
Internally reversible

process

a quasi-equilibrium
quasi equilibrium process,
process which
which, once having taken
place, can be reversed and leave no change in the system
when the process is reversed, the system passes through
exactly the same equilibrium states while returning to its
initial state
Totally reversible

process

a quasi-equilibrium process, which, once having taken

place, can be reversed and in so doing leave no change in
the system or surroundings
34

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35

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Irreversible Process

An irreversible process is a process that is not reversible

All real processes are irreversible

irreversible. Irreversible processes
occur because of the following:

Friction
Unrestrained expansion of gases
Heat transfer through a finite temperature difference
Mixing
g of two different substances
Hysteresis effects
I2R losses in electrical circuits
Any deviation from a quasi-static process
36

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Last Monday Review

The

second law of thermodynamics

Heat

engine

Thermal

efficiency, COP

Kevin-Planck
Reversible

37

statement, Clausius statement

and irreversible processes

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Carnot Cycle
The

efficiency of a heat-engine greatly depends on how

the individual processes that make up the cycle are
executed

The

net work (or efficiency) can be maximized by using

pp limits on the
reversible pprocesses which pprovide upper
performance of real cycles

Nicolas
Ni l

Sadi
S di Carnot
C
t (1769-1832)
(1769 1832) introduced
i t d d th
the conceptt
of cyclic operation and devised a reversible cycle that is
composed of four reversible processes, two isothermals
and two adiabatics

38

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Carnot Cycle

Process 1-2 Reversible

isothermal expansion
Reversible heat transfer from the
heat source at TH to the working
fluid which is also at TH. The fluid
expands slowly, doing work on the
surroundings
di

39

Process 2-3 Reversible

adiabatic expansion
Reversible adiabatic expansion
during which the system does work.
As a result the workingg fluid
temperature decreases from TH to TL

Ref 1

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Carnot Cycle
Process 3-4 Reversible
isothermal compression:
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 Reversible adiabatic

compression:

40

A reversible adiabatic compression

process increases the working fluid
temperature from TL to TH

Ref 1

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The Carnot cycle may be reversed, in which it operates as a

refrigerator
fi
t ((counterclockwise
t l k i di
direction)
ti )

Carnot principles
(a)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

(b) The efficiencies of all reversible heat engines operating

between the same two constant-temperature
constant temperature heat reservoirs
have the same efficiency
41

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Consider the Lord Kelvin's Carnot heat engine

arrangementt
Since the thermal efficiency in general is
Q
th = 1 L
QH

For the Carnot engine, this can be written as

th = g ( TL , TH ) = 1 f ( TL , TH )
Considering engines A, B, and C
Q1 Q1 Q2
=
Q3 Q2 Q3

We can write
42

Thermal energy
reservoir at T1

Q1

Q1

Rev. HE
A

Q2
Q2
Rev. HE
B

WA
Rev. HE
C

T2

WB

WC

Q3

Q3
Thermal energy
reservoir at T3

f ( T1 , T3 ) = f ( T1 , T2 ) f ( T2 , T3 )
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One way to define the f function is

( T2 ) ( T3 ) ( T3 )
f ( T1 , T3 ) =
=
( T1 ) ( T2 ) ( T1 )
The simplest form of is the absolute temperature itself.
itself
T3
f ( T1 , T3 ) =
T1

These form the basis for establishing an absolute temperature scale (Kelvin
scale) related to the heat transfers between a reversible device and the
high- and low
high
low-temperature
temperature heat reservoirs

QL
TL
=
QH TH
43

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 The above result is onlyy valid for heat exchange

g across a heat engine
g
operating between two constant temperature heat reservoirs.
The above result does not apply when the heat exchange is occurring
with heat sources and sinks that do not have constant temperature.
Applying for the Carnot thermal efficiency:

th , rev

TL
= 1
TH

This is the maximum possible efficiency of a heat engine operating

between two heat reservoirs at temperatures TH and TL.
Note that the temperatures are absolute temperatures.
44

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The thermal efficiencies of actual and reversible heat engines

g
operating
p
g
between the same temperature limits compare as follows:

Any heat engine

45

Carnot heat engine

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Example 6
A Carnot heat engine receives 500 kJ of heat per cycle from a hightemperature heat reservoir at 652oC and rejects heat to a low-temperature
h t reservoiri att 30oC.
heat
C Determine
D t i
(a) The thermal efficiency of this Carnot engine.
(b) The amount of heat rejected to the low
low-temperature
temperature heat reservoir.
reservoir
(a) th , rev = 1 TL

TH

( 30 + 273) K
( 652 + 273) K
= 0.672 or 67.2%

TH = 652oC

= 1

((b))

QL
T
= L
QH TH
( 30 + 273) K
= 0.328
( 652 + 273) K
Q L = 500 kJ ( 0.328)
=

46

= 164 kJ

QH

WOUT

HE

QL
TL = 30oC

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Example 7
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

th , rev

QH
WOUT

HE

QL

TL
= 1
TH
300 K
= 1
1000 K
= 0.70 or 70%

TL = 300 K

The claim is false since no heat engine may be more efficient than a Carnot
engine operating between the heat reservoirs.
reservoirs
47

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Quality of energy
Consider a Carnot heat engine working between
two thermal reservoirs TL = 300 K and TH.
The

thermal efficiency of the heat

engine
g increases as the heat source
temperature TH is increased

TH (K)
1500
1000
500
350

th (%)
80
70
40
14.3

The thermal efficiency of actual heat engine can be maximized by

Supplying heat to the engine at the highest possible temperature

(limited by material strength)

Rejecting heat to lowest possible temperature (limited by the cooling

medium temperature such as atmosphere, lake, river temperature)

48

The higher the temperature, the more thermal energy can be converted to
work higher energy quality
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Reversed Carnot Device COP

If the cycle in Carnot device is operated in reverse, a reversible

heat pump/refrigerator is created.

The COP of reversible refrigerators and heat pumps are given

as follow:
QL
1
=
QH Q L QH 1
QL
1
TL
=
=
TH TL TH 1
TL

COPR =

49

COPHP

QH
QH
QL
=
=
QH Q L QH 1
QL
TH
TH
TL
=
=
TH TL TH 1
TL
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These are the maximum possible COPs for a refrigerator or a heat pump
operating between the temperature limits of TH and TL.
The COP of actual and reversible ((such as Carnot)) refrigerators
g
operating
p
g
between the same temperature limits compare as follows:

A similar relation can be obtained for heat pumps by replacing all values of
COPR by COPHP in the above relation.
relation

50

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Example 8
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 Q L TH TL

QH
Win

QL

( 2 + 273) K
=
( 25 2 ) K
= 11.96

TL = 2oC

The claim is false since no refrigerator may have a COP larger than the COP
for the reversed Carnot device.
device
51

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Example 9
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.
temperature

Q& Lost
W&in
21 oC

Q& H
52

HP

Q& L

-5 oC

Swinburne University of Technology

The heat lost by the building has to be supplied by the heat pump.
kJ
Q& H = Q& Lost = 135000
h

Using the basic definition of the COP

COPHP

Q& H
TH
=
=
Q& H Q& L TH TL
( 21 + 273) K
=
( 21 ( 5)) K
= 11.31

COPHP

Q& H
=
W&net , in

W&net , in =

Q& H
COPHP

135,000 kJ / h 1 h 1 kW
.
1131
3600s kJ / s
= 3.316 kW

=
53

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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 principles and cycle

The Carnot heat engine
The quality of energy

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