Second Law of

Thermodynamics

Example 1

Heat always flows from

high temperature to low
temperature.
So, a cup of hot coffee
does not get hotter in a
cooler room.
Yet, doing so does not
violate the first low as long
as the energy lost by air is
the same as the energy
gained by the coffee.
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Example 2
The

amount of EE is
equal to the amount of
energy transferred to
the room.

It is clear from the previous

..examples that
Processes

proceed in certain direction

and not in the reverse direction.

The

first law places no restriction on the

direction of a process.

Therefore we need another law (the

second law of thermodynamics) to

determine the direction of a process.
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Thermal Energy Reservoir

It is defined as a body to which and from

which heat can be transferred without a
change in its temperature.

If it supplies heat then it

is called a source.

If it absorbs heat then it

is called a sink.

Heat Engines

We all know that doing work on the water will

generate heat.

However transferring heat to the liquid will not

generate work.

Yet, doing so does not violate the first low as long

as the heat added to the water is the same as the
work gained by the shaft.
7

Previous example leads to the concept of

Heat Engine!.

We have seen that work always converts

directly and completely to heat, but
converting heat to work requires the use of
some special devices.

These devices are called Heat Engines and

can be characterized by the following:

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Characteristics of Heat
..Engines

They receive heat from

high-temperature source.
They convert part of this
heat to work.
They reject the remaining
waste heat to a lowtemperature sink.
They operate on (a
thermodynamic) cycle.

High-temperature
Reservoir at TH

QH
HE

QL
Low-temperature
Reservoir at TL
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Piston cylinder arrangement is

..an example of a heat engine

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Difference between Thermodynamic

and Mechanical cycles

A heat engine is a device that operates in a thermodynamic cycle

and does a certain amount of net positive work through the
transfer of heat from a high-temperature body to a lowtemperature body.

A thermodynamic cycle involves a fluid to and from which heat is

transferred while undergoing a cycle. This fluid is called the
working fluid.

Internal combustion engines operate on a mechanical cycle (the

piston returns to its starting position at the end of each
revolution) but not on a thermodynamic cycle.

However, they are still called heat engines

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Steam power plant is another

..example of a heat engine

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Thermal efficiency
Desired output
Performance
Required input

Thermal Efficiency

Qin Qout
Wnet ,out
th

Qin
Qin
Qout
1
Qin

< 100 %
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Thermal efficiency
QH= magnitude of heat transfer between the cycle
device and the H-T medium at temperature TH
QL= magnitude of heat transfer between the cycle
device and the L-T medium at temperature TL

Thermal Efficiency

th

Wnet ,out
QH

QH QL
QH
QL
1
QH

< 100 %

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thermal efficiency can not

reach 100%
Even the Most Efficient Heat
Engines Reject Most Heat as
Waste Heat

40
th
0.4
100
Automobile Engine 20%
Diesel Engine
30%
Gas Turbine
30%
Steam Power Plant 40%
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?Can we save Qout

Heat the gas (QH=100

kJ)
Load is raised=> W=15
kJ
How can you go back to
get more weights (i.e.
complete the cycle)?
By rejecting 85 kJ
Can you reject it to the
Hot reservoir? NO
What do you need?
I need cold reservoir to
reject 85 kJ

A heat- engine cycle

cannot be completed
without rejecting
some heat to a low
temperature sink.
16

Example 5-1: 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.

<Answers: 30 MW, 0.375>

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The Second Law of Thermodynamics:

Kelvin-Plank Statement (The first)

The Kelvin-Plank 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.

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It can also be expressed as:

No heat engine can have a thermal

efficiency of 100%, or as for a
power plant to operate, the working
fluid must exchange heat with the
environment as well as the furnace.
Note that 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 idealized
and the actual heat engines.

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 Example

1 at the beginning of
the notes leads to the concept of
Refrigerator and Heat Pump..

Heat can not be transferred from low

temperature body to high temperature one
except with special devices.
These devices are called Refrigerators and
Heat Pumps
Heat pumps and refrigerators differ in
their intended use. They work the same.
They are characterized by the following:

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Refrigerators
High-temperature Reservoir at TH

QH

QL = Q H - W

Ref

QL
Low-temperature Reservoir at TL
Objective
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An example of a Refrigerator
..and a Heat pump

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Coefficient of Performance of a
Refrigerator
The efficiency of a refrigerator is expressed in term of
the coefficient of performance (COPR).

Desired output
COPR
Required input

QL
QL
1

W net ,in Q H Q L Q H 1
QL

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Heat Pumps

Objective

High-temperature Reservoir at TH

QH = W + Q L

QH
HP

Read to parts of
pp 259 and 260

QL
Low-temperature Reservoir at TL

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Heat Pump

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Coefficient of Performance of a
Heat Pump

The efficiency of a heat pump is expressed in term of the

coefficient of performance (COPHP).

COPHP

Desired output

Required input

QH
QH
1

W net ,in Q H Q L 1 Q L
QH
26

Relationship between Coefficient of

Performance of a Refrigerator (COPR)
and a Heat Pump (COPHP).
COPHP

COPHP

W net ,in Q L
QH
QH

W net ,in Q H Q L
QH QL

W net ,in

QL

1 COPR
QH QL QH QL

COPHP 1 COPR

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The second Law of Thermodynamics:

Clausius Statement
The Clausius statement is
expressed as follows:
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.
Both statements are negative
statements!
Read pp 262

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The second law of thermodynamics state

that no heat engine can have an efficiency of
100%.

Then one may ask, what is the highest

efficiency that a heat engine can possibly
have.

Before we answer this question, we need to

define an idealized process first, which is
called the reversible process.
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Carnots Principle
No heat engine can be more efficient than a
reversible heat engine when both engines
work between the same pair of temperature H
.and C
Isothermal Process: the temperature of the
system and the surroundings remain constant at
all times. (q=-w)
Adiabatic: a process in which no energy as heat
flows into or out of the system. (U=w)

Carnot cycle
four stage reversible sequence consisting of
isothermal expansion at high temperature T2. 1
adiabatic expansion. 2
isothermal compression at low temperature T1. 3
adiabatic compression. 4

The Carnot Cycle

Process 1-2:Reversible isothermal heat addition at high temperature, TH > TL, to the
working fluid in a piston-cylinder device that does some boundary work.
Process 2-3:Reversible adiabatic expansion during which the system does work as
the working fluid temperature decreases from TH to TL.
Process 3-4:The system is brought in contact with a heat reservoir at TL < TH and a
reversible isothermal heat exchange takes place while work of compression
is done on the system.
Process 4-1:A reversible adiabatic compression process increases the working fluid
temperature from TL to TH

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You may have observed that power cycles operate in the clockwise direction when
plotted on a process diagram. The Carnot cycle may be reversed, in which it
operates as a refrigerator. The refrigeration cycle operates in the counterclockwise
direction.

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Carnot Principles
The second law of thermodynamics puts limits on the operation of cyclic devices as
expressed by the Kelvin-Planck and Clausius statements. A heat engine cannot
operate by exchanging heat with a single heat reservoir, and a refrigerator cannot
operate without net work input from an external source.
Consider heat engines operating between two fixed temperature reservoirs at TH > TL.
We draw two conclusions about the thermal efficiency of reversible and irreversible
heat engines, known as the Carnot principles.
(a)The efficiency of an irreversible heat engine is always less than the
efficiency of a reversible one operating between the same two reservoirs.

th th , Carnot

(b) The efficiencies of all reversible heat engines operating between the
same two constant-temperature heat reservoirs have the same efficiency.
As the result of the above, Lord Kelvin in 1848 used energy as a thermodynamic
property to define temperature and devised a temperature scale that is independent
of the thermodynamic substance.
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The following is Lord Kelvin's Carnot heat engine arrangement.

Since the thermal efficiency in general is

th 1

QL
QH

For the Carnot engine, this can be written as

th g (TL , TH ) 1 f (TL , TH )
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Considering engines A, B, and C

Q1 Q1 Q2

Q3 Q2 Q3
This looks like
f ( T1 , T3 ) f ( T1 , T2 ) f ( T2 , T3 )

One way to define the f function is

f (T1 , T3 )

(T2 ) (T3 ) (T3 )

(T1 ) (T2 ) (T1 )

The simplest form of is the absolute temperature itself.

f (T1 , T3 )

T3
T1

The Carnot thermal efficiency becomes

th , rev 1

TL
TH

This is the maximum possible efficiency of a heat engine operating between two heat
reservoirs at temperatures TH and TL. Note that the temperatures are absolute
temperatures.
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These statements form the basis for establishing an absolute temperature scale, also
called the Kelvin scale, related to the heat transfers between a reversible device and
the high- and low-temperature heat reservoirs by
QL TL

QH TH
Then the QH/QL ratio can be replaced by TH/TL for reversible devices, where TH and TL
are the absolute temperatures of the high- and low-temperature heat reservoirs,
respectively. This result is only valid for heat exchange across a heat engine
operating between two constant temperature heat reservoirs. These results do not
apply when the heat exchange is occurring with heat sources and sinks that do not
have constant temperature.
The thermal efficiencies of actual and reversible heat engines operating between the
same temperature limits compare as follows:

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Reversed Carnot Device Coefficient of Performance

If the Carnot device is caused to operate in the reversed cycle, the reversible heat
pump is created. The COP of reversible refrigerators and heat pumps are given in a
similar manner to that of the Carnot heat engine as
QL
1

QH QL QH 1
QL
TL
1

TH TL TH 1
TL

COPR

COPHP

QH
QH
QL

QH QL QH 1
QL
TH
TH
TL

TH TL TH 1
TL
40

Again, these are the maximum possible COPs for a refrigerator or a heat pump
operating between the temperature limits of TH and TL.
The coefficients of performance of actual and reversible (such as Carnot) refrigerators
operating between the same temperature limits compare as follows:

A similar relation can be obtained for heat pumps by replacing all values of COPR by
COPHP in the above relation.
Example 6-2
A Carnot heat engine receives 500 kJ of heat per cycle from a high-temperature heat
reservoir at 652oC and rejects heat to a low-temperature heat reservoir at 30oC.
Determine
(a) The thermal efficiency of this Carnot engine.
(b) The amount of heat rejected to the low-temperature heat reservoir.
41

a.
TH = 652oC
QH
WOUT

HE
QL
TL = 30oC

TL
TH
( 30 273) K
1
(652 273) K
0.672 or 67.2%

th , rev 1

b.
QL TL

QH TH
(30 273) K

0.328
( 652 273) K
QL 500 kJ (0.328)
164 kJ
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Example 6-3
An inventor claims to have invented a heat engine that develops a thermal efficiency
of 80 percent when operating between two heat reservoirs at 1000 K and 300 K.
Evaluate his claim.
TH = 1000 K
QH
WOUT

HE
QL
TL = 300 K

TL
TH
300 K
1
1000 K
0.70 or 70%

th , rev 1

The claim is false since no heat engine may be more efficient than a Carnot engine
operating between the heat reservoirs.

43

Example 6-4
An inventor claims to have developed a refrigerator that maintains the refrigerated
space at 2oC while operating in a room where the temperature is 25oC and has a COP
of 13.5. Is there any truth to his claim?
TH = 25oC

COPR

QH
Win

R
QL

QL
TL

QH QL TH TL

(2 273) K
(25 2) K
1196
.

TL = 2oC

The claim is false since no refrigerator may have a COP larger than the COP for the
reversed Carnot device.

44

Example 6-5
A heat pump is to be used to heat a building during the winter. The building is to be
maintained at 21oC at all times. The building is estimated to be losing heat at a rate
of 135,000 kJ/h when the outside temperature drops to -5oC. Determine the minimum
power required to drive the heat pump unit for this outside temperature.
Q Lost

W in

21 C
o

Q H

Q L

HP
-5 oC

The heat lost by the building has to be supplied by the heat pump.

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kJ
Q H Q Lost 135000
h
Q H
TH

Q H Q L TH TL
(21 273) K

(21 ( 5)) K
1131
.

COPHP

Using the basic definition of the COP

COPHP

Q H

W net , in

W net , in

Q H
COPHP

135,000 kJ / h 1 h 1 kW
1131
.
3600s kJ / s
3.316 kW

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