CHAPTER 3

THE SECOND LAW OF THERMODYNAMICS AND ITS

APPLICATIONS

➢ STATEMENT OF THE SECOND LAW

➢ ENTROPY

➢ ENTROPY – GIBBS EQUATION

➢ ENTROPY – SPECIFIC HEATS

 The Second Law of Thermodynamics

The second law of thermodynamics is a natural law

which indicates that, although the net heat
supplied in a cycle is equal to the net work done
(First law), the gross heat supplied must be greater
than the net work done.
It is impossible for a system operating in a cycle to
extract heat from a reservoir and produce an
equivalent amount of work i.e Q>W
Or
Whenever a system operates in a cycle the net work
output is less than the quantity of heat supplied
The application of the law is best illustrated by the
concept of the heat engine.
Heat engine
A heat engine is a system which when operated in a
complete cycle develops a net work from a supply of heat.
From the general implication of the second law, a source
of heat supply and a heat rejection sink are both
necessary, since some heat must be rejected by the
system. A heat engine is represented by Figure below
The heat supplied from the source = Q1
The heat rejected at sink = Q2
The work done = W
From the first law, in a complete cycle
Net heat supplied = Net work done
Using first law in Figure above,
Q1 - Q2 = W

From the second law,

Q1 >W
The thermal efficiency of a heat engine is given by
W
=
Q1
Q1 − Q2 Q2
Thus = =1−
Q1 Q1
Refrigerators
Refrigerators are devices used to transfer
heat from a low-temperature medium to
a high-temperature.
The working fluid used in the
refrigeration cycle is called a refrigerant.

The most frequently used refrigeration

cycle is the vapor-compression
refrigeration cycle, which involves four
main components: a compressor, a
condenser, an expansion valve, and an
evaporator.
Refrigerators cont’d
Coefficient of Performance (COPR):
The objective of a refrigerator is to
remove heat (QL) from the refrigerated
space. To accomplish this objective, it
requires a work input of Wnet,in. Then
the COPR of a refrigerator can be
expressed as:
Heat Pumps
Another device that transfers heat from a low-
temperature medium to a high-temperature.
The objective of a heat pump, however, is to
maintain a heated space at a high temperature.
The measure of performance of a heat pump is
also expressed in terms of
the coefficient of performance COPHP, defined
as
• Hence the second law of thermodynamics
implies that the thermal efficiency of a heat
engine must always be less than 100%
• The law can be stated in a number of ways,
depending on its implications, as follows:
 Lord Kelvin and Max Planck
The first scientists to state the
Second Law of Thermodynamics
1. Kelvin – Planck Statement of the Second laws of
Thermodynamics:
A cyclical heat engine cannot operate while receiving
heat from a single thermal-energy reservoir, i.e. Heat
engines must always reject heat to a thermal-energy
reservoir
In other words, maximum possible efficiency is less than
100%

A heat engine that violates

the Kelvin-Planck
Statement of Second law
2. Clausius Statement of the second law
No cyclical device can cause heat to transfer from
thermal-energy reservoirs at low temperature to
reservoirs at high temperature with no other effect
❑ Work is therefore required to manifest the effect
✓ It is impossible to construct a system which
will operate in a cycle, extract heat from a
reservoir and do an equivalent amount of
work on the surroundings
✓ A machine which will produce work
continuously while exchanging heat with only
a single reservoir is known as Perpetual
motion machine. This would contradict the
second law
PMM is a device that violets the first or second
law of thermodynamics
Entropy
• Entropy is a measure of the unavailability of thermal
energy to do work in a closed system.
• Heat transferred during a process may affect work transfer
and also the end state after the process
• Theoretically, the amount of heat transferred during a
process is determined by calculations if it is transferred
reversibly.
• If plotted a graph of suitable axes so that the area
underneath a process plotted on the graph gave the
quantity of heat transferred reversibly during the process.
Such a graph would be as useful as a pressure-volume graph
in determining the quantity of work done during a reversible
process

W =  dW =  pdV
Let on this new graph one axis be absolute temperature (T) and
the other axis be some new function (s) as shown. The absolute
temperature is selected because it is closely related to energy level
of a substance, notable internal energy and enthalpy

Figure for T-s

Remember that heat is that energy transfer which is
associated with temperature difference. Further the
internal energy of a substance is zero at the absolute zero
temperature. Consider an elemental strip of the T-s graph
of thickness ds at a temperature T during a process
between states 1 and 2. thus ds=elemental change in s at a
point of graph where temperature=T and entropy=s
❑Then the elemental heat transfer
reversibly=area of elemental strip
dQ=Tds
❑From this,
❑Heat transfer reversibly from state 1 to
2=total area of the graph under points 1,2
2 s=s
❑i.e  dQ =  Tds
2

1 s = s1

❑In limit as ds goes to 0

❑Heat transferred reversibly from state 1 to 2
2 s2

 dQ
1
rev =  Tds
s1
s2

Qrev =  Tds
s1
Entropy: Gibbs Equation
Differentianting, dQrev=Tds or
 dq 
ds =  
 T  reversible
Entropy (s) is a system property as a
consequence of the second law,
Useful for conducting first and second law analysis of
thermodynamic devices and systems
e.g dq=du+pdv
Tds=du+pdv
if ds=(dq/T)reversible
Tds=du+pdv
if h=u+pv dh=du+pdv+vdp Tds=du+pdv

Tds=dh-vdp Gibbs Equation

Entropy of Liquids and Solids
Recall that liquids and solids can be approximated as incompressible
substances since their specific volumes remain nearly constant during a
process (i.e. dv=0).
Tds = du + Pdv but Pdv = 0
du cdT
ds = =
T T

since cp=cv =c and du=cdT for incompressible substances.

Then the entropy change during a process is determined by

2
s2 − s1 =  Tds but ds = cdT where cavg is the average
1
2 specific heat of the
cdT
= T but cT = cavg substance over the given
1
T
temperature interval.
T2
= cavg ln (kJ / kg.K )
T1
Entropy : Using specific heats
Tds=dh-vdp Gibbs Equation Also v = RT/P dh =cpdT

Hence

Similarly, Eq. Tds=du+pdv is transformed using the

substitutions P = RT/v and du =cvdT to yield

To evaluate the entropy change in going from state

1 to state 2 state, we integrate above Eqs., that is
The second term on the right-hand side of each of
these expressions can be easily evaluated since R is
a constant, and so

In many engineering applications, an average value

of cp (or cv) over the temperature range of interest
can be used to evaluate s2-s1 with reasonable
accuracy:
• If heat is received then Qrev is positive and the
substance entropy has increased
• If heat is rejected, Qrev is negative and the entropy of
the substance has decreases
• Thus +ve and –ve changes of entropy show whether
heat has been received or rejected during a process
under consideration
 Example
• A rigid tank contains 1 kg of N2 initially at 300 K
and 1 atm. Energy is added to the gas until a
final temperature of 600 K is reached.
Calculate the entropy change of the N2
associated with this heating process.
• Solution
• Known MN2, P1, T1, T2
• Find s2-s1
 Example
• Determine the changes in the mass-specific
enthalpy and the mass-specific internal energy
for air for a process that starts at 300 K and ends
at 1000 K.
• Also show that dh-du= RT, and compare a
numerical evaluation of this with tabulated data.
• Assumption
• Air behaves as a single-component ideal gas.
• Analysis From Table, we obtain the following
values for h and u: