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 not wheel will not cause it to wire will not generate
get hotter in a cooler room. rotate. electricity.

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

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Second Law is used to:

Identify the direction of processes

Determine the quality of energy
Determine the degree of degradation of energy
Determine the theoretical limits for the performance of systems

Warm environment
Clasius statement of the 2ⁿᵈ Law:

It is impossible for any device to operate in such a QH =5kJ

manner that it produces no effect other than the
transfer of heat from one body to another body at Device
a higher temperature.
QL =5kJ

A refrigerator that violates the Cold environment

Clausius statement of the second law.
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Kelvin-Plank statement of the 2ⁿᵈ Law:

It is impossible for any device to operate in a cycle and produce work while
exchanging heat only with a single reservoir(i.e. no engine can have 100%
efficiency).

Thermal energy reservoir

Violates Kelvin-Plank Statement Q H  100kW

A heat engine that violates the Kelvin– Heat

Planck statement of the second law. engine
Wout  100kW

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.
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THERMAL ENERGY RESERVOIRS:

Or just a ‘reservoir’ is defined as a body that can supply or absorb finite

amounts of energy as heat without undergoing any change in temperature.

A source supplies energy in the form of

heat, and a sink absorbs it.
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HEAT ENGINES:
are thermodynamic systems operating in a cycle to which net heat is transferred
and from which 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
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The work producing device

that best fits into the definition
of a heat engine is the steam
power plant.

For a closed system undergoing a

cycle ΔU=0
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Thermal efficiency
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

Wnet,out Qin  Qout Qout

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

can Qout  0 ? No, because a) the cycle will not be complete!

b)violates Kelvin-Plank statement.
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Example:
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
Wnet, out  Q H  Q L
Q H  75 MW  (75  48) MW  27 MW

H.E. Wnet, out  ?

Wnet, out 27 M W
Q L  48 MW th    0.36
QH 75 M W
river

or 36%
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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.

Basic components of a refrigeration system

and typical operating conditions.
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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
For a refrigerator COPR =
Required input

QL Q L
 (or )
Wnet ,in W net ,in

Wnet,in  QH  QL ( kJ )

QL 1
COPR  
QH  QL QH 1
QL
Notice that COPR, can be greater than unity.
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Heat Pumps:

 another device that transfer heat from TL to TH.

 objective is different : maintain a heated space at high

temperature.

Desired output QH
COPHP = 
Required input Wnet,in

QH 1
COPHP  
QH  QL 1  QL
QH
The objective of a heat pump
is to supply heat QH into the
warmer space.
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75,000 kJ/h
EXAMPLE:

Q H H
Q 75,000
COPHP   Wnet,in  
Wnet,in COPHP 2.5

Wnet,in  30,000 kJ (or8.33kW ) QH  75,000 kJ

h
h COP  2.5

Q L  Q H  Wnet,in  (75,000  30,000) Wnet,in  ?

Q L  ?
 45,000 kJ
h
0
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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 TH)
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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  (TL )

With Kelvin scale  (T )  T

QH TH
( )
QL TL
For reversible cycles, the A conceptual experimental
heat transfer ratio QH /QL 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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QL
For any heat engine: th  1 
QH

TL
For a carnot engine(i.e. any reversible heat engine): th,rev  1
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
COPHP 
1  QL
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 replace by TH QL replace by TL
QL TL QH TH

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

Highest COP between the limits TL and TH