Engineering Thermodynamics

EMEC 3436

Chapter 6:
The Second Law of Thermodynamics

Dr. Ali Tarokh

Reference: Yunus Cengel and Michael Boles, Thermodynamics: An Engineering Approach, McGraw-Hill,9th
Edition (Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display)
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.
 6–1 Introduction to the Second Law 1

A cup of hot coffee does not Transferring heat to a wire

get hotter in a cooler room. will not generate electricity.

Transferring heat to a paddle

wheel will not cause it to rotate.

These processes cannot

occur even though they
are not in violation of the
first law.
 6–1 Introduction to the Second Law 3

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.
 6–2 Thermal Energy Reservoirs 2

A reservoir that supplies energy A source supplies energy in the

in the form of heat is called a form of heat, and a sink absorbs it.
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.
 6–3 Heat Engines 1

Heat Engınes: The devices

that convert heat to work. Work can always be converted to heat directly
and completely, but the reverse is not true.
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.
 6–3 Heat Engines 2

Heat engines and other cyclic Part of the heat received by a heat engine
devices usually involve a fluid is converted to work, while the rest is
to and from which heat is rejected to a sink.
transferred while undergoing a
cycle.
This fluid is called the working
fluid. Qin
↓
Boiler
F

Turb
Tunet =
Wout-Win

Qut
 6–3 Heat Engines 3

A steam power plant

Schematic of a steam power plant.
Q in = amount of heat supplied to
steam in boiler from a high-
temperature source (furnace)
Q out = amount of heat rejected
from steam in condenser to a low-
temperature sink (the atmosphere,
a river, etc.)
W out = amount of work delivered
by steam as it expands in turbine
W in = amount of work required to
compress water to boiler pressure
W net,out = W out − W in ( kJ )
W net,out = Q in − Q out ( kJ )
 6–3 Heat Engines 4

W net,out = W out − W in ( kJ )

A portion of the work output of a heat engine is

consumed internally to maintain continuous operation.

·
 6–3 Heat Engines 5

Thermal efficiency Some heat engines perform

better than others (convert more
Net work output
Thermalefficiency = of the heat they receive to work).
Total heat input
Wnet,out
ηth =
Qin
W net,out = Q in − Q out

Qout
η th = 1−
Qin

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.
 6–3 Heat Engines 6

QH = magnitude of heat transfer

between the cyclic device and the high- Schematic of a heat engine.
temperature medium at temperature TH
QL = magnitude of heat transfer
between the cyclic device and the low-
temperature medium at temperature TL

W net,out = Q H − QL

Wnet,out QL
ηth = or ηth = 1 −
QH QH
 6–3 Heat Engines 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, 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.
 6–3 Heat Engines 10

Example: 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.

i i i
W net,out = Q H − Q L = (80 − 50) MW = 30 MW

i
W net,out 30MW
ηth = i
= = 0.375 (or 37.5%)
QH 80MW

Winet , out = GH- @c = 100 MW-50Mw)

Inetout = 30 MW.
37 5 %
30MW 0 375 : .

Wret Out =
.

Uth
, =

- = 80 nw
Ou
 6–3 Heat Engines 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.
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.
 6–4 Refrigerators And Heat Pumps 1

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. Environment
QH Heat Rejected
into
=

frcondenser

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.
 6–4 Refrigerators And Heat Pumps 2

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.

Desired output Q
COPR = = L
Required input Wnet,in

- = QH − QL (kJ)
Wnet,out
QL 1
COPR = =
QH − QL QH QL −1

Can the value of COPR be greater than unity?

 6–4 Refrigerators And Heat Pumps 3

Heat Pumps
The objective of a heat pump is to
Desired output Q supply heat QH into the warmer space.
COPHP = = H
Required input Wnet,in
QH 1
COPHP = =
QH − QL 1 − QL QH

COPHP= COPR +1

for fixed values of QL and QH

 6–4 Refrigerators And Heat Pumps 4

Example: 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.
KJ
COPHo Ou GH
Watin
=

00 , 000 32, 000 T

-
> = = :

2 5
Wet , in
COPUr
.

Winet ,
in =
@h-Qu
= On-linet = 80 , 000 15/h -32 ,
000
& -
40 000,
with
 6–4 Refrigerators And Heat Pumps 5

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 EER ≡ 3.412 COPR
(watthour) of electricity consumed.
 6–4 Refrigerators And Heat Pumps 6

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-n 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.
 6–4 Refrigerators And Heat Pumps 7

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.
 6–5 Perpetual-motion Machines 1

A perpetual-motion machine that violates 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.
 6–5 Perpetual-motion Machines 2

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

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

worked.
If something sounds too good to be true, it probably is.
 6–6 Reversible And Irreversible Processes 1

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?
 6–6 Reversible And Irreversible Processes 3

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 Irreversible compression and expansion

processes.
Friction renders a process irreversible.
 6–6 Reversible And Irreversible Processes 4

(a) Heat transfer through a temperature difference is irreversible, and (b) the reverse
process is impossible.
 6–6 Reversible And Irreversible Processes 5

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.
 6–7 The Carnot Cycle 1

Execution of the Carnot cycle in a closed system.

I Reversible Isothermal Expansion (process 1-2, TH = constant)

2 Reversible Adiabatic Expansion (process 2-3, temperature drops from TH to TL)
3 Reversible Isothermal Compression (process 3-4, TL = constant)
& Reversible Adiabatic Compression (process 4-1, temperature rises from TL to TH)
 6–7 The Carnot Cycle 2

P-V diagram of the Carnot cycle. P-V diagram of the reversed Carnot cycle.
# identical to non-reversed
process
(Carnot)

ii
-- Const Temlive
.

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.
 6–7 The Carnot Principles 3

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.
 6–8 The Thermodynamic Temperature
Scale 1

The arrangement of heat engines used to

A temperature scale that is
develop the thermodynamic temperature scale.
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.
 6–8 The Thermodynamic Temperature Scale 2

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

TH TL T (  C) = T (K ) − 273.15

 QH 
  = TH
 Q  TL
L rev
 6–9 The Carnot Heat Engine 1

QL The Carnot heat engine is the most efficient of all

η th = 1− Any heat engine heat engines operating between the same high- and
QH
low-temperature reservoirs.

TL
η th,rev = 1− Carnot heat engine
TH

< η th,rev irreversible heat engine


η th = η th,rev reversible heat engine

 >η th,rev impossible heat engine

 6–10 The Carnot Refrigerator And Heat Pump 1

Any refrigerator or heat pump No refrigerator can have a higher COP than a
1 reversible refrigerator operating between the
COPR = same temperature limits.
QH QL −1

1
COPHP =
1− QL QH

Carnot refrigerator or heat pump

1
COPR,rev =
TH TL −1
1
COPHP,rev =
1− TL TH
 6–10 The Carnot Refrigerator And Heat Pump 2


< COPR,rev irreversible refrigerator


COPR 
= COPR,rev irreversible refrigerator



> COPR,rev impossible refrigerator


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.
 6–10 The Carnot Refrigerator And Heat Pump 3

Example: A heat pump is to be used to heat a house during the winter, as shown in the
figure. 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.

1 1
COPHP,rev = = = 11.3
1− TL TH 1− (−5 + 273K ) (21 + 273K )
i
i Q 37.5kW
W net,in = = = 3.32kW
COPHP 11.3
 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.
End of Chapter 6