Chapter 5 The Classical Second Law of

Thermodynamics Spontaneity
A cup of hot coffee does not get hotter in a
cooler room.

The mechanical work done by the shaft is first

Transferring heat to a wire will not
generate electricity.
converted to the internal energy of the water.
This energy may then leave the water as heat.
It is known from experience that any attempt
to reverse this process will fail. That is,
transferring heat to the water does not cause
the shaft to rotate.

Some processes cannot occur even though they are not in violation with the first law.
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 Processes occur in a certain direction (not over a certain path),
and not in the reverse direction. (Way or Direction nothing to
do with nature of the process nor they do decribe the process)

A process will not occur unless it satisfies both

the first and the second laws of thermodynamics.

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, as well as predicting the degree of completion of chemical
reactions.
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 HEAT ENGINES
Work can always be converted to
heat directly and completely, but the
reverse is not true.
Part of the heat received by a heat
engine is converted to work, while the
rest is rejected to a sink.
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Heat engines are the devices that convert
heat to work and all can be characterized by
the following:
1. They receive heat (𝑄𝐻 ) from a high-
temperature source (𝑇𝐻 ) (solar energy,
coal or 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
(𝑄𝐿 ) to a low-temperature sink (𝑇𝐿 ) (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
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 A Simple Heat Engine

Why we cannot convert 𝑸𝑳 to work !?

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A Heat Engine Involving Steady–State Processes
A Steam Power Plant

A portion of the work output of a

heat engine is consumed internally
to maintain continuous operation.

Wnet  Wout  Win  WT  WP

Qnet  Qin  Qout  QH  QL
Energy equation for the cycle :   W    Q
Wnet  Qnet  QH  QL

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 Thermal Efficiency

Thermal Efficiency

NetWork Output Wnet ( Energy Sought )

thermal  th  
Total Heat Input QH ( Energy That Costs )

Wnet  Qnet  QH  QL

Some heat engines perform better Wnet

than others (convert more of the thermal 
heat they receive to work). QH
QH  QL QL
thermal   1
QH QH

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 Refrigerator & Heat Pump and Their Efficiency
Coefficient of Performance (COP or 𝜷)
The transfer of heat from a low-temperature medium body to a high-temperature body
can be done with a Refrigerator or Heat Pump. The working fluid is the refrigerant,
such as R–134a or ammonia.

Desired Result
COP 
Required Input

A Simple Vapor–Compression Refrigeration Cycle.

Refrigerator Heat pump

COPR   COPHP   '
Refrigeration Q QL Heat Output Q QH
  L  '   H 
Energy that Costs W QH  QL Energy that Costs W QH  QL
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 The Second Law of Thermodynamics

There are two classical statements of the second law, known as the Kelvin–Planck
statement and the Clausius statement.

The Kelvin–Planck Statement: It is impossible to construct a device that will operate in a

cycle and produce no effect other than the raising of a weight and the exchange of heat
with a single reservoir.

Implying that it is impossible to build a heat engine that has a thermal efficiency 100 %.

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The 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 cooler body to a warmer
body.
This statement is related to the refrigerator or heat pump. In effect, it states that it is
impossible to construct a refrigerator that operates without an input of work.
This also implies that the coefficient of performance is always less than infinity.

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Three Observations about These Two Statements

Both are negative statements.

They are equivalent:

Any device that violates the Kelvin–Planck statement also violates the Clausius
statement, and vice versa.

They state the impossibility of constructing a perpetual–motion machine of the second

kind.

PMM of the first kind would create work from nothing or create mass or energy, thus
violating the first law.
PMM of the second kind would extract heat from a source and then convert this heat
completely into other forms of energy.
PMM of the third kind would have no friction, and thus would run indefinitely but produce
no work.
PMM is a device that violates one of the basic laws of thermodynamics.
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 The Reversible Process

The question that can now logically be posed is this: If it is impossible to have a heat
engine of 100 % efficiency, what is the maximum efficiency one can have under a given
definite set of working conditions? The first step in the answer to this question is to
define an ideal process, which is called a reversible process .

Reversible Process: It is defined as a process that, once having taken place, can be
reversed and in so doing leave no change in either system or surroundings.

Irreversible Process: It is a process when reversed it will leave a sign.

• All the processes occurring in nature are irreversible to some extent. If so: Why are
we interested in reversible processes?

• (1) the resulting formulations are simpler and easier to analyze (compared with the
formulations involving irreversibilities).
• (2) they be viewed as theoretical limits for the corresponding irreversible ones.

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 Factors That Render Processes Irreversible

There are many factors that make processes irreversible and they are called as
irreversibilities: friction, unrestrained expansion, mixing of two fluids, heat transfer
across a finite temperature difference, electric resistance, inelastic deformation of solids,
and chemical reactions.
Four of those factors – friction, unrestrained expansion, heat transfer through a finite
temperature difference, and mixing of two different substances – are considered here.

Friction

Unrestrained
Expansion
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 Factors That Render Processes Irreversible

Heat Transfer Through a Finite Temperature Difference

Mixing

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 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.

Totally and internally reversible heat transfer processes.

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 The Carnot Cycle
Execution of the Carnot cycle in a closed system.

1–2 A reversible isothermal process 2–3 A reversible adiabatic process in which the
in which heat transferred to or from temperature of the working fluid decreases
the high temperature reservoir. from the high temperature to low temperature.

3–4 A reversible isothermal process
in which heat transferred to or from
the low temperature reservoir.
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4–1 A reversible adiabatic process in which the
temperature of the working fluid increases from
the low temperature to high temperature.
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 P-V diagram of the Carnot cycle. P-V diagram of the reversed Carnot
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 (or Heat Pump) Cycle.

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Example of a heat engine (and refrigerator) that operates on a Carnot cycle.

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 Two Propositions Regarding the Efficiency of a
Carnot Cycle
First Proposition
It is impossible to construct an engine that operates between two given reservoirs and is
more efficient than a reversible engine operating between the same two reservoirs.

Proposition I : any  rev

The proof is given in the textbook !

Second Proposition
All engines that operate on the Carnot cycle between two given constant–temperature
reservoirs have the same efficiency.

Proposition II : any  rev

The proof proceeds with the same line of reasoning as in the first proposition.

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 Thermodynamic Temperature Scale

The zeroth law of thermodynamics provides a basis for temperature measurement, but
that a temperature scale must be defined in terms of a particular thermometer substance
and device.
A temperature scale that is independent of any particular substance, which might be
called an absolute temperature scale

The efficiency of a Carnot cycle is independent of the working

substance and depends only on the reservoir temperatures, i.e.,
if TH and TL are the same, then, 𝜂𝑡ℎ,𝐴 = 𝜂𝑡ℎ,𝐵 .
This fact provides the basis for such an absolute temperature
scale called the thermodynamic scale. Since the efficiency of a
Carnot cycle is a function only of the temperature, it follows that
QL
thermal  1  1  (TL , TH )
QH
where ψ designates a functional relation.
There are many functional relations that could be chosen, for simplicity, the
thermodynamic scale is defined as
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There are many functional relations that could be chosen, for simplicity, the
thermodynamic scale is defined as

This temperature scale is called the Kelvin scale, and the

temperatures on this scale are called absolute
temperatures.

For reversible cycles, the heat transfer ratio QH /QL can be

replaced by the absolute temperature ratio TH /TL. Then the
efficiency of a Carnot engine becomes

QL TL
thermal  1  1
QH TH

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 Ideal versus Real Machines
 th , rev irreversible heat engine
 th real  1
QL
 1
TL
th   th , rev reversible heat engine
QH TH
 
 th , rev impossible heat engine

 COPHP or Ref , rev irreversible HP or Ref .


COPHP or Ref   COPHP or Ref , rev reversible HP or Ref .
  COP
 HP or Ref , rev impossible HP or Ref .

  COPref .   COPHP
'

QL TL QH TH
 real    '
 
QH  QL TH  TL QH  QL TH  TL
real

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