CHAPTER

The Second Law of

Thermodynamics
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A process must satisfy the first law to occur

However, does it ensure that the process will actually take place?

potential energy lost = kinetic energy gained kinetic energy lost = potential energy gained
(satisfies the first law) (satisfies the first law – VIOLATES the 2nd LAW!)
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Transferring heat to a paddle Transferring heat to a

A cup of hot coffee does wheel will not cause it to wire will not generate
not get hotter in a cooler rotate. electricity.
room.

It is clear from the above examples that processes take place in a certain direction
and not in the reverse direction. First law alone is not enough to determine if a
process will actually occur.

Another principle is needed: Second law of Thermodynamics

 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
4
the theoretical limits for the performance of commonly used
 THERMAL ENERGY RESERVOIRS

A source
supplies
energy in
the form of
Bodies with relatively large
heat, and a
thermal masses can be
sink
modeled as thermal energy
absorbs it.
reservoirs.
• 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.
 HEAT ENGINES

The devices that convert

heat to work.
1. They receive heat from a
high- temperature source
(solar energy, oil furnace,
Work can nuclear reactor, etc.).
always be 2. They convert part of this
converted to heat to work (usually in the
heat directly form of a rotating shaft.)
and completely,
but the reverse 3. They reject the remaining
is not true. waste heat to a low-
temperature sink (the
atmosphere, rivers, etc.).
Heat engines and other cyclic
4. They operate
devices usually on a cycle.
involve a fluid to
Part of the heat and from which heat is
received by a heat transferred while undergoing a
engine is cycle. This fluid is called the
converted to work, working fluid.
while the rest is 6
rejected to a sink.
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HEAT ENGINES:
are thermodynamic systems operating in a cycle to which net heat is transferred
and from which net work is delivered.

Solar
energy Oil
furnace
Nuclear reactor

or QH : heat transfer between cyclic device and high temp. medium at TH

Rotating shaft

or QL : heat transfer between cyclic device and high temp. medium at TH

The atmosphere
Rivers
Sea
A steam power plant

A portion of the work

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

8
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DEFINITION of PERFORMANCE for any device

Desired output What I Get
In general : performance =
= required input What I pay for

In heat engines: the desired output = net work output = Wnet ,out

the required input = heat supplied to system = Qin

Thermal efficiency Wnet,out Q  Qout Q

th   in  1 out
 Qin Qin
or th Qin
 QH QH
Wnet,out QL
  1
Thermal efficiency

Schematic
of a heat
engine.

Some heat engines perform

Even the
better than others (convert
most efficient
more of the heat they receive
heat engines
to work).
reject almost
one-half of
the energy
they receive
as waste
heat. 10
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
A heat-engine cycle cannot be completed no for the simple
without rejecting some heat to a low- reason that without a
temperature sink. heat rejection process
Every heat engine must waste some in a condenser, the
energy by transferring it to a low- cycle cannot be
completed.
temperature reservoir in order to
complete the cycle, even under
11
idealized conditions.
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
must exchange heat with the the Kelvin–Planck
environment as well as the furnace. statement of the second
The impossibility of having a 100% law.
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.
12
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 where heat is
absorbed by the refrigerant serves
Basic components of a as the evaporator, and the coils
refrigeration system and usually behind the refrigerator where
typical operating heat is dissipated to the kitchen air13
serve as the condenser.
 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 Can the value of COPR

is to remove QL from the be greater than unity?
cooled space.
14
 The
Heat Pumps
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. Can the value of
COPHP be lower than
unity?
for fixed values of QL and
QH What does 15
COPHP=1
 • 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
When installed
whose refrigerated space is a room or a
backward, an air
building instead of the food compartment.
conditioner functions
as a heat pump. • The COP of a refrigerator decreases
with decreasing refrigeration
Energy efficiency rating (EER):temperature.
The amount
of heat removed from the •cooled space it
Therefore, inis not economical to
Btu’s for 1 Wh (watthour) of electricity
refrigerate to a lower temperature than 16
consumed. needed.
The Second Law of
Thermodynamics: 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.

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
To date,body to a warmerhas
no experiment one.
been
A refrigerator that
conducted that contradicts the second
violates the Clausius
law, and this should be taken as sufficient
statement of the
proof of its validity.
second law.
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 18
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Example 1:
Heat is transferred to a heat engine from a furnace at a rate of 75MW. If waste heat
rejection to a nearby river is 48MW, determine the power output and the thermal
efficiency for this heat engine.

Furnace 𝑊̇ 𝑛𝑒𝑡,𝑜𝑢𝑡 = 𝑄̇𝐻

=̇𝐿 75 − 48 MW =
−𝑄
𝑄̇𝐻 = 75 27MW
MW
𝑊̇ 𝑛𝑒𝑡,𝑜𝑢𝑡
𝜂𝑡ℎ 𝑊̇
=?
= 𝑛𝑒𝑡,𝑜𝑢𝑡
H.E. ��
��
𝑄�̇ = 48 27 M W
MW
�  75 MW 
River 0.36
or 36%
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75,000 kJ/h

𝑄̇𝐻
Example 2: Heat pump

𝐶𝑂𝑃𝐻𝑃 =
𝑊
𝑛𝑒𝑡,𝑖
𝑛
75,00
→ ̇ 𝑛𝑒𝑡,𝑖 𝑄 ̇ 0
= 𝐶𝑂 𝐻 2.
𝑊 𝑛 = COP = 𝑄̇𝐻 = 75,000
𝑃 𝑃 5 kJ/h
𝐻
2.5

 30,000 kJ h (or 8.33 kW) 𝑊̇ 𝑛𝑒𝑡,𝑖𝑛

=?
𝑄̇𝐿
𝑄̇𝐿 = 𝑄̇𝐻 − 𝑊̇ 𝑛𝑒𝑡,𝑖𝑛 = (75,000 − =?

30,000)
0
 45,000 kJ h
PERPETUAL-MOTION MACHINES

A perpetual-motion machine
A perpetual-motion machine that violates the second law
that violates the first law of thermodynamics (PMM2).
(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 21
known to have worked. If something sounds too good to be true, it
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REVERSIBLE AND IRREVERSIBLE PROCESSES:

 A process is reversible if, after it has occurred ,

both the system and the surroundings can be
returned to their original states.

 If the system can not be restored to its initial

state then the process is called irreversible.

 The reversible processes do not occur in nature.

They are only idealization of actual processes.
A pendulum could be a reversible
process if it were frictionless  Reversible processes are important because they
provide the maximum work from work-producing
devices and the minimum work input to devices that
absorb work to operate . (theoretical limitation of
performance)

 The more close we approximate a reversible

process the better.
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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.
 When designing something we try to lower the
irrevesibilities.

Friction renders a
process irreversible.
(a) Heat transfer through a
temperature difference is
irreversible, and (b) the
reverse process is impossible.
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THE CARNOT CYCLE:

 A reversible cycle, i.e. limiting case for both an engine and a refrigerator.

 The Carnot engine is the heat engine that converts heat into work with
the highest possible efficiency.

 The Carnot refrigerator is the refrigerator that uses the minimum

amount of work to cool a space

 The Canot cycle is composed of four reversible processes(two

isothermal and two adiabatic).

 Can be expected either in a closed system or a steady-flow system.

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Gas in an adiabatic piston-cylinder device:

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
T )
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P-V diagram of the reversed Carnot

P-V diagram of the Carnot cycle.
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.
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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.

Violation of
Kelvin-Plank
statement

The Carnot principles. Proof of the first Carnot principle.

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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

engines operating
between the same two
reservoirs have the
same efficiency.
The arrangement of heat engines used to develop
the thermodynamic temperature scale.
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For a reversible heat engine

operating between two
reservoirs:

QH

 (TH )
QL  (T L )

With Kelvin scale  (T ) 

T
QH
( )
TH
For reversible cycles, the QL A conceptual experimental
heat transfer ratio QH /QL TL setup to determine
can be replaced by the thermodynamic
absolute temperature ratio temperatures on the Kelvin
TH /TL. scale by measuring heat
transfers QH and QL.
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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.
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For any heat engine: th  1 

Q QH
L

For a carnot engine(i.e. any reversible heat engine):  th,rev  1 

TL TH

Carnot efficiency: This is the highest efficiency a heat engine operating

between the two reservoirs at TL and TH can have.

For a steam power plant operating between TH=750K and TL=300K

the maximum efficiency is 60%.(In practicing they are under 40%)
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The Quality of Energy:

The carnot efficiency implies that, the higher the temperature TH,
the higher the efficiency and hence the higher the quality of energy.

The higher the temperature of the

The fraction of heat that can be converted to thermal energy, the higher its
work as a function of source temperature. quality.
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THE CARNOT REFRIGERATOR AND HEAT PUMP:

1
COPH
QL
 P 1
QH

No refrigerator can have a higher COP

than a reversible refrigerator operating
between the same temperature limits.
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1
COPR
QH
 1
QL

For a carnot refrigerator: For a carnot heat pump:

QH QL replace by TL
QL replace by TH TL QH TH

1 1
 COPR,rev  COPHP,rev

TH 1  1 TL
TL TH

Highest COP between the limits TL and

TH