THERMODYNAMICS

THE SECOND LAW OF THERMODYNAMICS

Lecture 06

Thermodynamics: An Engineering Approach, 8th Edition

Yunus A. Cengel, Michael A. Boles McGraw-Hill, 2015

by Dr. Yucelen
INTRODUCTION TO THE SECOND LAW
These processes cannot occur even though they aren’t in violation of the 1st law.

Transferring heat to a paddle

wheel will not cause it to rotate.

A cup of hot coffee does not

get hotter in a cooler room.

Transferring heat to a wire

will not generate electricity. 1
 Processes occur in a certain direction, A process must satisfy both the first and second
and not in the reverse direction. laws of thermodynamics to proceed.

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.

2
THERMAL ENERGY RESERVOIRS
Bodies with relatively large
thermal masses (e.g., oceans,
lakes, and rivers) can be
modeled as thermal energy
reservoirs.

A source supplies energy in

the form 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.
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.
3
HEAT ENGINES
Work can be converted to heat directly and completely, but converting heat to
work requires the use of some special devices. These devices are called heat
engines.

Work can always be converted to heat

directly and completely, but the reverse is
not true.

4
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.
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. Part of the heat received by a
heat engine is converted to work,
while the rest is rejected to a
sink.

5
A steam power plant https://www.youtube.com/watch?v=je7I_dassXU

A portion of the work output of a heat

engine is consumed internally to maintain
continuous operation.

𝑊#D;,9:; = 𝑊9:; − 𝑊"# (kJ)

𝑊#D;,9:; = 𝑄"# − 𝑄9:; (kJ)

𝑄"# = amount of heat supplied to steam in boiler from a high − temperature source
𝑄9:; = amount of heat rejected from steam in condenser to a low − temperature sink
𝑊"# = amount of work required to compress water to boiler pressure
𝑊9:; = amount of work delivered by steam as it expands in turbine 6
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.

Network output
Thermal efficiency =
Total heat input

𝑊#D;,9:;
𝜂;L =
𝑄"#
𝑄9:;
𝜂;L = 1 − since 𝑊#D;,9:; = 𝑄"# − 𝑄9:;
𝑄"#

Some heat engines perform

better than others (convert more
of the heat they receive to work).

7
 To bring uniformity to the treatment of heat
Schematic of a heat engine.
engines, refrigerators, and heat pumps, we
define two quantities:

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

Net work output for any heat engine:

𝑊#D;,9:; = 𝑄N − 𝑄O
Thermal efficiency of a heat engine: 𝑊#D;,9:;
𝜂;L =
𝑄N
𝑄O
𝜂;L = 1 −
𝑄N

The thermal efficiency of a heat engine is always less than unity

since both 𝑄𝑯 and 𝑄𝑳 are defined as positive quantities. 8
Thermal efficiency of automobile engines ⇒ 25%
Thermal efficiency of large turbine plants ⇒ 40 – 60 %

Almost half of the energy supplied ends in the

rivers, lakes, or the atmosphere as waste or
useless energy.

Engineers:

• Increase efficiency heat → work

• Less fuel consumption → less pollution

Even the most efficient heat engines

reject almost one half of the energy they
receive as waste heat.
9
Can we save Qout (waste energy)?

A heat-engine cycle cannot be completed without rejecting some heat to a low-temperature sink.

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

temperature reservoir in order to complete the cycle.
10
Example – Net power production of a heat engine
Heat is transferred to a heat engine from a furnace at a rate of 80 MW. If the
rate of waste heat rejection to a nearby river is 50 MW, determine the net
power output and the thermal efficiency for this heat engine.

11
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.
A heat engine that violates the Kelvin–
Planck statement of the 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.
https://www.ohio.edu/mechanical/thermo/Intro/Chapt.1_6/Chapter5.html
12
REFRIGERATORS

Low temperature Q High temperature

medium medium
REFRIGERATORS

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. 4 main components:
• A compressor
• A condenser
• An expansion valve
• An evaporator
13
Condenser ⇒ cools down and condenses
heat is rejected to the surrounding medium

Compressor ⇒ increases the pressure

increases the temperature
involves work input

vapor

Basic components of
a refrigeration system
and typical operating
conditions. 14
Pressure and temperature
drop due to throttling
effect. ⟸

Evaporator ⇒ Refrigerant Refrigerant reenters the

evaporates by absorbing compressor and the cycle
heat from the refrigerated is completed.
space.
15
Coefficient of performance (COP) [REFRIGERATORS]
𝑄O = magnitude of the heat removed from the
refrigerated space at temperature 𝑇O
𝑄N = magnitude of the heat rejected to the warm
environment at temperature 𝑇N
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.
Desired output 𝑄O
COP^ = =
Required input 𝑊#D;,"#
𝑊#D;,"# = 𝑄N − 𝑄O (kJ)
𝑄O 1
COP^ = =
𝑄N − 𝑄O 𝑄N ⁄𝑄O − 1
The objective of a refrigerator
is to remove QL from the
Can the value of COPR be greater than unity?
cooled space.
16
HEAT PUMPS
Desired output 𝑄N
COPbc = =
Required input 𝑊#D;,"#

𝑄N 1
COPbc = =
𝑄N − 𝑄O 1 − 𝑄O ⁄𝑄N

For fixed values of QL and QH:

COPbc = COP^ + 1

Can the value of COPHP be

lower than unity? What
does COPHP=1 represent? The work supplied to a heat
The objective of a heat pump pump is used to extract energy
is to supply heat QH into the from the cold outdoors and carry
warmer space. it into the warm indoors. 17
Example – Analysis of a household refrigerator
A household refrigerator with a COP of 1.2 removes
heat from the refrigerated space at a rate of 60
kJ/min. Determine (a) the electric power consumed
by the refrigerator and (b) the rate of heat transfer
to the kitchen air.

18
Example – Heating a house with a heat pump
A heat pump is used to meet the heating
requirements of a house and maintain it at 20˚C.
On a day when the outdoor air temperature drops
to -2˚C, 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 (b) the
rate at which heat is absorbed from the cold
outdoor air.

19
The second law of thermodynamics:
Clausius statement
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 a higher-temperature body.

https://www.ohio.edu/mechanical/thermo/Intro/Chapt.1_6/Chapter5.html

Heat cannot spontaneously flow from cold regions to

hot regions without external work being performed on
A refrigerator that violates
the Clausius statement of the system. A refrigerator cannot operate unless its
the second law. compressor is driven by an electric motor.
20
Equivalence of the two statements

The Kelvin–Planck and the

Clausius statements are
equivalent in their
consequences, and either
Proof that the violation statement can be used as
of the Kelvin–Planck the expression of the second
statement leads to the
violation of the Clausius law of thermodynamics.
statement. Any device that violates the
Kelvin–Planck statement
also violates the Clausius
statement, and vice versa.

21
PERPETUAL-MOTION MACHINES

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

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.
https://www.youtube.com/watch?v=A-QgGXbDyR0 22
REVERSIBLE AND IRREVERSIBLE PROCESSES
2nd law à no heat engine can have an efficiency of 100 percent.
What is the highest efficiency that a heat engine can possible have?
We need to define an idealized process à reversible process
Why are we interested in reversible processes?
(1) They are easy to analyze
(2) They serve as idealized models (theoretical
limits) to which actual processes can be
compared.

IRREVERSIBLE PROCESS

REVERSIBLE PROCESSES All the processes occurring in nature are irreversible. 23

Irreversibilities
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.
Friction renders a process irreversible.

(a) Heat transfer through a

temperature difference is
irreversible, and (b) the
reverse process is impossible. Irreversible compression
24
and expansion processes.
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

Totally and internally reversible heat transfer processes.
internal and external irreversibilities. 25
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)
26
The Carnot cycle cannot be achieved in reality. The efficiency of actual cycles
can be improved by approximating to the 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.

P-⋁ diagram of the Carnot cycle. P-⋁ diagram of the reversed Carnot cycle.
Carnot heat engine cycle Carnot refrigeration cycle
27
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.

The Carnot principles.

28
Proof of the first Carnot principle.

29
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 the
thermodynamic temperature
scale.

All reversible heat engines

operating between the
same two reservoirs have
the same efficiency (the
second Carnot principle)
30
The thermal efficiency of reversible heat engines is a function of the reservoir
temperatures only.
𝜂;L,fDg = 𝑔 𝑇N , 𝑇O
𝑄O 𝑄N
Since 𝜂;L = 1 − ⟶ = 𝑓 𝑇N , 𝑇O
𝑄N 𝑄O
𝑄l 𝑄m 𝑄l
= 𝑓 𝑇l , 𝑇m , = 𝑓 𝑇m , 𝑇n , and = 𝑓 𝑇l , 𝑇n
𝑄m 𝑄n 𝑄n

𝑄l 𝑄l 𝑄m
=
𝑄n 𝑄m 𝑄n

𝑓 𝑇l , 𝑇n = 𝑓 𝑇l , 𝑇m o 𝑓 𝑇m , 𝑇n 𝜙 𝑇 =𝑇

𝜙 𝑇l 𝜙 𝑇m 𝑄N 𝑇N
𝑓 𝑇l , 𝑇m = and 𝑓 𝑇m , 𝑇n = =
𝜙 𝑇m 𝜙 𝑇n 𝑄O 𝑇O
fDg
𝑄l 𝜙 𝑇l 𝑄N 𝜙 𝑇N
= 𝑓 𝑇l , 𝑇n = =
𝑄n 𝜙 𝑇n 𝑄O 𝜙 𝑇O
31
 This temperature scale is
called the Kelvin scale,
and the temperatures on
this scale are called
absolute temperatures.

𝑇 ℃ = 𝑇 K − 273.15

𝑄N 𝑇N
=
𝑄O fDg 𝑇O

A conceptual experimental setup

For reversible cycles, the heat to determine thermodynamic
transfer ratio QH/QL can be temperatures on the Kelvin scale
replaced by the absolute by measuring heat transfers QH
temperature ratio TH /TL. and QL. 32
THE CARNOT HEAT ENGINE
The hypothetical heat engine that operates on the
reversible Carnot cycle is called the Carnot heat
engine. The thermal efficiency of any heat engine,
reversible or irreversible:
𝑄O
𝜂;L = 1 −
𝑄N
𝑄N = heat transferred to the heat engine from a high −
temperature reservoir at 𝑇N
𝑄O = heat rejected to a low − temperature reservoir at 𝑇O

𝑇O
𝐂𝐚𝐫𝐧𝐨𝐭 𝐞𝐟𝐟𝐢𝐜𝐢𝐞𝐧𝐜𝐲 ⟹ 𝜂;L,fDg = 1 −
𝑇N
The highest efficiency a heat engine operating
The Carnot heat engine is the
between the two thermal energy reservoirs at
most efficient of all heat
temperatures TL and TH can have. Note that TL and TH engines operating between
are absolute temperatures. the same high- and low-
temperature reservoirs. 33
THE CARNOT HEAT ENGINE
< 𝜂;L,fDg irreversible heat engine
𝜂;L ‚ = 𝜂;L,fDg reversible heat engine
> 𝜂;L,fDg impossible heat engine

Most work-producing devices (heat

engines) in operation today have
efficiencies under 40 percent.

The thermal efficiency of actual heat

engines can be maximized by supplying
heat to the engine at the highest
possible temperature and rejecting No heat engine can have a higher efficiency
heat from the engine at the lowest than a reversible heat engine operating
between the same high- and low-
possible temperature.
temperature reservoirs.
34
Example – Analysis of a Carnot heat engine
A Carnot heat engine receives 500 kJ of heat
per cycle from a high-temperature source at
652˚C and rejects heat to a low-temperature
sink at 30˚C. Determine (a) the thermal
efficiency of this Carnot engine and (b) the
amount of heat rejected to the sink per cycle.

35
The quality of energy
How the thermal efficiency varies with the source temperature when the sink
temperature is held constant?
More of the high-temperature thermal energy
can be converted to work. Therefore, the higher
the temperature, the higher the quality of the
energy.

The fraction of heat that can be The higher the temperature of

converted to work as a the thermal energy, the higher
function of source temperature its quality.
(for TL = 303 K). 36
THE CARNOT REFRIGERATOR AND HEAT PUMP
Any refrigerator or heat pump:

1
COP^ =
𝑄N ⁄𝑄O − 1
1
COPbc =
1 − 𝑄O ⁄𝑄N

Carnot refrigerator or heat pump:

1
COP^,fDg =
No refrigerator can have a higher COP 𝑇N ⁄𝑇O − 1
than a reversible refrigerator operating 1
between the same temperature limits. COPbc,fDg =
1 − 𝑇O ⁄𝑇N

37
 < 𝜂;L,fDg irreversible heat engine
𝜂;L ‚ = 𝜂;L,fDg reversible heat engine
> 𝜂;L,fDg impossible heat engine

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.

38
Example – Heating a house with a Carnot heat pump
A heat pump is to be used to heat a house
during the winter. The house is to be
maintained at 21˚C at all times. The house is
estimated to be losing heat at a rate of
135,000 kJ/h when the outside temperature
drops to -5˚C. Determine the minimum power
required to drive this heat pump.

39
SUMMARY
qIntroduction to the second law
qThermal energy reservoirs
qHeat engines
qRefrigerators and heat pumps
qPerpetual motion machines
qReversible and irreversible processes
qThe Carnot cycle
qThe Carnot principles
qThe Thermodynamic temperature scale
qThe Carnot heat engine
qThe Carnot refrigerator and heat pump

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