MODULE THREE: SECOND LAW

OF THERMODYNAMICS
Objectives
1. To introduce second law of
thermodynamics
2. To consider corollaries of the second
law of thermodynamics
3. To consider applications of the
second law of thermodynamics

Introduction
It
is
a
matter
of
everyday
experience that there is a definite
direction
for
spontaneous
processes
Spontaneous processes are
natural
occurrence processes with the
tendency
of attaining equilibrium

Examples of Spontaneous
Processes
An hot object at temperature Ti placed in an
environment of temperature To get cools to a
Temperature T and eventually has a temperature
To.
In conformity with the conservation of energy
principle, internal energy lost by the object equals
the internal energy gained by the environment.
Inverse
process
would
not
take
place
spontaneously
i.e Internal energy of the
environment would not decrease
spontaneously, while the object
warmed from To to Ti

Examples of Spontaneous Processes

Air having high pressure Pi in a closed

container would flow spontaneously to
the lower pressure Po of the surrounding,
once the container is opened.
Flow of air ceases once the air pressure
equals the pressure of the surroundings.
Inverse process would not take place
spontaneously
i.e air would not flow spontaneously
from the
surrounding at Po into the

Examples of Spontaneous
Processes

A mass suspended by a cable at

elevation Zi would fall when released.
When it comes to rest, initial potential
energy lost by the mass equals internal
energy gained by both the mass and the
surroundings.
Inverse process would not take place
spontaneously
i.e the mass would not return
spontaneously to its
initial elevation, while its internal
energy or that

Examples of Spontaneous
Processes
In each case described above, initial
condition of the system could be
restored, but not in a spontaneous
process.
Auxiliary devices would be required.
These devices would required energy
input to perform, resulting into
permanent change in the condition of

Introduction
Spontaneous processes can proceed only in
a particular direction. The first law of
thermodynamics gives no information
about direction; it states only that when
one form of energy is converted into
another, identical quantities of energy are
involved regardless of the feasibility of the
process.
First law fails to address both the direction
of the process and the extent of change of
energy from one form to another. Hence,
another general principle is required.

Introduction
Can one form of energy be
completely converted to another
form? In practice, when energy is
transferred from one form to
another,
there
is
often
a
degradation of the supplied energy
into a less useful form.
Second Law of Thermodynamics
addresses
some
of
these
difficulties

Commonly Used Terms

Heat (thermal) reservoir is a sufficiently
large system in stable equilibrium to which
and from which finite amounts of heat can be
transferred without any change in its
temperature.
A high temperature heat reservoir from which
heat is transferred is sometimes called a
heat source (eg. furnace).
A low temperature heat reservoir
from which heat is transferred is
sometimes called a heat sink (eg.
atmosphere).

Commonly Used Terms

Work reservoir is a sufficiently large
system in stable equilibrium to which and
from which finite amounts of work can be
transferred
adiabatically
without
any
change in its pressure.
Thermodynamic cycle: A system has
completed a thermodynamic cycle when the
system undergoes a series of processes and
then returns to its original state, so that the
properties of the system at the end of the
cycle are the same as at its beginning.

Commonly Used Terms

A reversible process is one in which both the
system and its environment can be returned to
exactly the states they were in before the
process occurred.
Heat Engine: A device or machine that
produce work from heat in a cyclic process. E.g.
Steam power plant in which the working fluid
(H O) periodically returns to its original state.
A thermodynamic system operating in a
thermodynamic cycle to which net heat is
transferred and from which net work is delivered.
2

Commonly Used Terms

Working substance of the engine is
the material within the engine that
actually does the work.
Examples include steam in steam
power plant
and the gasoline-air
mixture in an automobile engine.

Statements of the Second Law of

rmodynamics
Statement
1
No
apparatus
can operate in
such a way that
its only effect (in
system
and
surroundings) is
to convert heat
absorbed by a
system
completely into
work done by

Statement 2
No process is
possible solely in
the transfer of
heat from one
temperature
level to a higher
one.

Statement 1 can be expressed in

another form as:

Statement 1a
It is impossible by a cyclic process
to convert the heat absorbed by
a system completely into work
done by the system

Second Law of Thermodynamics

Clausius says
It will arouse other changes
while the heat is transferred from
the low temperature object to the
high temperature one
Kelvin says
It will arouse other changes while
the heat from the single thermal
source is taken out and is totally
changed into work.

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%.
For a power plant to operate, the
working fluid must exchange heat
with the environment as well as
the furnace.

Heat Engine
Work can be easily converted completely to other forms
of energy
Converting other forms of energy to work is not that
easy
Work can be converted to heat directly and completely
Heat can be converted to work directly, but not
completely
Converting heat to work requires the use of a device
called a heat engine
Heat engines come in many forms, pure heat engines
(steam power plants) and semi heat engines
(gas turbines)
Each heat engine operates by using
a working substance (fluid).

Heat Engines

They receive heat from a hightemperature source (eg. Furnace).

They convert part of this heat
to work (mostly through
rotating shaft).
They reject the waste heat to
low-temperature sink.
(eg. Atmosphere, River).
They operate on a cycle
Purposely built to convert heat
to work.

Heat Engine
Qin = amount of heat
supplies to steam in
boiler
from
high
temperature
source
(furnace)
Qout = amount of heat
rejected from steam in
condenser to a lowtemperature sink
Wout = amount of work
delivered by steam as it
expands in turbine
Win = amount of work
required to compress
water to boiler pressure

Heat Engine Efficiency

Class Work
1. Which of the following heat engine
conditions
is most preferable:
a) absorbed heat of 300 J and discarded
50 J of heat
b) absorbed heat of 350 J and 300 J of
work done
c) 400 J of work done and 100 J of heat
discarded.

Class Work
2. A Carnot engine receives 250 kJ/s of heat
from a heat-source reservour at 525 C and
rejects heat to a heat-sink reservour at 50 C.
What are the power developed and the heat
rejected?

Solution
Efficiency

of Carnot Heat Engine,

= where
= 50 C = (50 + 273) K = 323 K and
= 252 C = (252 + 273) K = 525 K
So = = = 0.3847
Efficiency of Carnot Heat Engine, =
0.3848

Exercises
1. Describe a process that would satisfy
the conservation of energy principle,
but does not actually occur in nature.
2. To increase the thermal efficiency of a
reversible power cycle operating
between thermal reservours at
temperatures TH and TC, would it be
better to increase TH or decrease TC by
equal amounts?
3. What is the thermal efficiency of an
heat engine that absorbed 374 kJ and

Exercises
4.

Obtain and

Refrigerators and Heat

Pumps
Heat
moves
in
nature
from
high
temperatures to lower temperatures, no
devices required.
The reverse process, heat from low
temperatures to high temperature, requires
special devices called refrigerators
or heat pumps.
Working fluid used in refrigeration
cycle is called a refrigerant.
The objective of refrigerator is to
remove heat from the refrigerated space

Refrigerators and Heat

Pumps

The refrigerant enters the compressor as

vapour and compressed to condenser pressure
It condenses as it flow through the coils of the
condenser by rejecting heat to
the surrounding medium
Its pressure and temp.
drop drastically as it
expands in capillary tube.
It evaporates in evaporator by absorbing heat
from the refrigerated space.

Refrigerators and Heat

Pumps

In household refrigerator, the freezer

compartment (where heat is absorbed by
the refrigerant) is the evaporator.
Coils behind the refrigerator (where heat
is dissipated to surroundings) is the
condenser.
In a refrigerator, the interior
of the unit is the cold reservour,
while the warmer exterior
is the hot reservour.

Heat Engine vs Heat

Pump

In the refrigeration process, work W is used

to remove heat QC from the cold reservoir
and deposit heat Q into the hot reservoir.

Coefficient of Performance (COP)

The index of performance of a refrigerator or

heat pump is expressed in terms of the
coefficient of performance, COP, the ratio of
desired
resultoftoPerformance,
input.
Coefficient

=
=

Coefficient of Performance of a
refrigerator can be greater than 1.
While the efficiency of a heat engine
must always be less than 1

Coefficient of Performance (COP)

Efficiency

of a Heat Pump,

=
=

The objective of a Heat Pump

is to maintain a heated space
at a high temperature, by
absorbing heat from a low
temperature source.

Exercise
Establish

a relationship between

and .

Carnot Cycle and Carnot

Law
A theoretical heat engine was designed by
a French engineer Sadi Carnot (1824), a
reversible heat engine, whose operation
was based on Carnot Cycle.
A B : Rev. Isothermal Expansion
Carnot Cycle
B C: Rev. Adiabatic Expansion
C D: Rev. Isothermal Compression
D A : Rev. Adiabatic Compression

Carnot Cycle and Carnot Law

For
any given heat reservours, no engine can
have a thermal efficiency higher than that of
Carnot engine
The thermal efficiency of a Carnot engine
depends only on the temperature levels but
not the working fluid of the engine.
Hence,
Actual heat engines are irreversible while
Carnot engine (ideal engine) is reversible.

Carnot Cycle and Carnot

Law
Corollaries of the second
law:
The thermal efficiency of an
irreversible power cycle is
always less than the thermal
efficiency of a reversible
power cycle when each
operates between the same
two thermal reservours.
All reversible power cycles
operating between the same
two thermal reservours have
the same thermal efficiency.

Carnot Cycle and Carnot

Law
Corollaries of the second law:
The
coefficient
of
performance
of
an
irreversible refrigerator cycle
is
always
less
than
the
coefficient of performance of
a
reversible
refrigerator
cycle when each operates
between the same two thermal
reservours.
All reversible refrigerator cycles
operating between the same two
thermal reservours have the
same coefficient of performance.

Class Work
1. The data listed below are claimed for a
power cycle operating between
reservours at 527 C and 27 C. In each
case determine if any principles of
thermodynamics would be violated
a) = 700 kJ, = 400 kJ, = 300 kJ
b) = 640 kJ, = 400 kJ, = 240 kJ
c) = 640 kJ, = 400 kJ, = 200 kJ

Solution
= 527 C = (527 + 273) K = 800 K
= 27 C = (27 + 273) K = 300 K
Principles of thermodynamics would be violated
once the efficiency is greater than that of Carnot
engine or conservation of energy principle is
violated
a) = 700 kJ, = 400 kJ, = 300 kJ

where
= = 0.625
= = = 0.5714
Since , principle of

Class Work
2. A refrigerator cycle operating between
two reservours receives energy from a
cold reservour at = 280 K and rejects
energy to a hot reservour at = 320 K.
For each of the following cases
determine whether the cycle operates
reversibly, irreversibly or is impossible:
a)
b)
c)
d)

=
=
=
=

1500 kJ, = 150 kJ.

1400 kJ, = 1600 kJ.
1600 kJ, = 400 kJ.
5.

 = 320 K

Solution

= 280 K

It is reversible, if =
It is irreversible, if <
It is impossible, if >
a) = 1500 kJ, = 150 kJ.

Class Work
3. A heat pump with Coefficient of
Performance of 2.5 supplies energy
to a house at a rate of 60,000 Btu/h.
Determine
a) the electric power drawn by the heat
pump and
b) the rate of heat absorption from the
outside air.

solution

1 J = 1 Nm = 9.486 X Btu
=
= 60,000 Btu/h
= 60,000 Btu/h X X
= 17, 569.75 J/s
a) = =
= 7027.9 J/s
b) = - = 17, 569.75 - 7027.9 =
10541.85J/s

Class Work
4.
An automobile engine consumes
fuel at a rate of 28 L/h and delivers 60
kW of power to the wheels. If the fuel
has a heating value of 44,000 kJ/kg and
a density of 0.8 g/cm, determine the
efficiency of the engine.

Solution
Volumetric

flow rate =
= x X = 7.78 X
Density =
= x X = 800
Mass flow rate = Volumetric flow rate X
Density
= 7.78 X X 800
= 0.006224

Solution

=

= = 0.24

Class Work

5.
1 kg of air as an ideal gas executes a Carnot power cycle having a
thermal efficiency of 60 %. The heat transfer to the air during the
isothermal expansion is 40 kJ. At the end of the isothermal expansion,
the pressure is 5.6 bar and the volume is 0.3 m. Determine
a) Sketch the cycle on p-v coordinates.
b) The maximum and minimum temperatures for the cycle, in K.
c) The pressure and volume at the beginning of the isothermal
expansion in bar and m, respectively.
d) The work and heat transfer for each of the four processes, in kJ.
Given: = 423.7 kJ/kg and = 167.0 kJ/kg
Molar mass of air = 28.97

solution

Given:
= 60%,
1kg of air

= 40kJ

= 0.3 m
= 5.6 bar = 5.6 X N/
a)

solution

b) For an ideal gas,

= = 585.4K
from = ,
= (1 - )
and =
Hence
= 585.4 (1 - 0.6)
= 234.2K
Max. T = 585.5K, Min. T =
234.2K

solution

c) For process 1
2 (RIE)
= 40 kJ
m( - ) = For an ideal gas isothermal system with
=,
=
Hence =
=nR
= = = 0.2382

solution
= 0.2382
= 0.24
since = (isothermal)
=
= = (5.6 0.3)/0.24 = 7 bar
d) process 2
3 (Adiabatic) = 0
= i.e = - m( - ) = m( - )
= 1(423.7 167.0)
= 256.7 kJ

solution
Process
3
4,

= (since = 0, for isothermal)
from = ,
= ,
= 16.01 kJ
Heat is removed, = - 16.01 kJ
hence
= - 16.01 kJ
process 4
1, = 0
= - m( - )
=,
= m( - )
= 1(167.0 423.7) kJ
= - 256.7 kJ

solution
summary
process
1
2
2
3
3
4
4
1
cycle
24

Q(kJ)
40
0
- 16
0
24

W(kJ)
40
256.7
- 16
- 256.7

Class Work
6. Study the given
figure and
determine:
a) The power input,
in kW.
b) The lowest
theoretical
temperature
inside the
refrigerator, in K.