ENTROPY

The second law of thermodynamics often leads to expressions that involve

inequalities. An irreversible (i.e., actual) heat engine, for example, is less efficient
than a reversible one operating between the same two thermal energy reservoirs.
Likewise, an irreversible refrigerator or a heat pump has a lower coefficient of
performance (COP) than a reversible one operating between the same
temperature limits. Another important inequality that has major consequences in
thermodynamics is the Clausius Inequality. It was first stated by the German
physicist R. J. E. Clausius (1822–1888), one of the founders of thermodynamics,
and is expressed as
𝜹𝑸
ර ≤𝟎
𝑻
𝛿𝑄
That is, the cyclic integral of is always less than or equal to zero. This
𝑇
inequality is valid for all cycles, reversible or irreversible. The symbol
‫( ׯ‬integral symbol with a circle in the middle) is used to indicate that the
integration is to be performed over the entire cycle. Any heat transfer to or from a
system can be considered to consist of differential amounts of heat transfer. Then
𝛿𝑄
the cyclic integral of can be viewed as the sum of all these differential
𝑇
amounts of heat transfer divided by the temperature at the boundary
 Inequality of Clausius
High Temperature Reservoir 𝑇𝐻
To demonstrate the validity of
Clausius Inequality consider a two
heat engines Reversible and 𝑄𝐻 𝑄𝐻
Irreversible, both operating
between a high temperature
reservoir 𝑻𝑯 and low temperature
reservoir 𝑻𝑳 and producing a 𝑊𝑟𝑒𝑣 𝑊𝑖𝑟𝑟𝑒𝑣
work done 𝑾𝒓𝒆𝒗 and 𝑾𝒊𝒓𝒓𝒆𝒗 Rev Irrev
respectively. HE HE

𝑄𝐿 𝑄𝐿,𝑖𝑟𝑟𝑒𝑣

Low Temperature Reservoir 𝑇𝐿

Two heat engines ( reversible and irreversible)

operating between two same temperature limits
For the reversible heat engine , heat transfer 𝑄𝐻 and 𝑄𝐿 , constant
temperature 𝑇𝐻 and 𝑇𝐿 .

Now, for Reversible Engine,

𝛿𝑄 𝛿𝑄𝐻 𝛿𝑄𝐿
ර න න
𝑇 𝑟𝑒𝑣 = 𝑇𝐻 - 𝑇𝐿
1 1
= 𝑇𝐻
‫ 𝐻𝑄𝛿 ׬‬− 𝑇𝐿
‫𝐿𝑄𝛿 ׬‬

𝑄𝐻 𝑄𝐿 𝑄𝐻 𝑇𝐻
= − For Reversible Heat Engine, =
𝑇𝐻 𝑇𝐿 𝑄𝐿 𝑇𝐿

𝛿𝑄 𝑄𝐻
=
𝑄𝐿
ර =0 ∴ 𝑇𝐻 𝑇𝐿
𝑇 𝑟𝑒𝑣
Now consider for Irreversible Heat Engine
For the irreversible heat engine , heat transfer 𝑄𝐻 and 𝑄𝐿,𝑖𝑟𝑟𝑒𝑣 , constant
temperature 𝑇𝐻 and 𝑇𝐿,𝑖𝑟𝑟𝑒𝑣 .

We know

𝜂𝑖𝑟𝑟𝑒𝑣 < 𝜂𝑟𝑒𝑣

𝑊𝑖𝑟𝑟𝑒𝑣 𝑊𝑟𝑒𝑣 For Same value

<
𝑄𝐻 𝑄𝐻 of 𝑄𝐻
𝑊𝑖𝑟𝑟𝑒𝑣 < 𝑊𝑟𝑒𝑣
𝑊𝑖𝑟𝑟𝑒𝑣 < 𝑊𝑟𝑒𝑣 :- means that the heat
𝑄𝐿,𝑖𝑟𝑟𝑒𝑣 > 𝑄𝐿,𝑟𝑒𝑣 rejection 𝑄𝐿,𝑖𝑟𝑟𝑒𝑣 is more as compare to
the 𝑄𝐿,𝑟𝑒𝑣
𝑄𝐿,𝑖𝑟𝑟𝑒𝑣 = 𝑄𝐿,𝑟𝑒𝑣 + 𝑄𝑑𝑖𝑓𝑓
Now
For Reversible Process
𝛿𝑄 𝛿𝑄𝐻 𝛿𝑄𝐿,𝑖𝑟𝑟𝑒𝑣
‫ׯ‬ = ‫׬‬ −‫׬‬
𝑇 𝑖𝑟𝑟𝑒𝑣 𝑇𝐻 𝑇𝐿
𝛿𝑄
ර =0
1 1 𝑇 𝑟𝑒𝑣
= 𝑇 ‫ 𝐻𝛿 ׬‬− 𝑇𝐿
‫𝐿𝑄𝛿 ׬‬,𝑖𝑟𝑟𝑒𝑣
𝐻

𝑄𝐻 𝑄𝐿,𝑖𝑟𝑟𝑒𝑣 For Irreversible Process

= −
𝑇𝐻 𝑇𝐿
𝜹𝑸
‫ׯ‬ <0
𝑄𝐻 𝑄𝐿,𝑟𝑒𝑣 𝑄𝑑𝑖𝑓𝑓 𝑻 𝒊𝒓𝒓𝒆𝒗
= − −
𝑇𝐻 𝑇𝐿 𝑇𝐿
𝑄𝑑𝑖𝑓𝑓
Thus the Clausius Inequality
𝛿𝑄
‫ׯ‬ =− ≠0
𝑇 𝑖𝑟𝑟𝑒𝑣 𝑇𝐿
𝜹𝑸
ර ≤𝟎
𝜹𝑸 𝑻
‫ׯ‬ <0
𝑻 𝒊𝒓𝒓𝒆𝒗
From Clausius Inequality we have a quantity whose cyclic integral is zero. We know
that cyclic integral of any property is zero as state function not a path function.
𝛿𝑄
Therefore the quantity must represent a property and this property is
𝑇 𝑟𝑒𝑣
named as ENTROPY.
𝜹𝑸
It is designated as S and is defined as 𝒅S= unit as kJ/ K
𝑻 𝒓𝒆𝒗

Entropy as a property of a system

Entropy is an extensive property of a system and sometimes is referred to as total
entropy. Entropy per unit mass, designated S, is an intensive property and has the unit
kJ/kg · K. The term entropy is generally used to refer to both total entropy and entropy
per unit mass since the context usually clarifies which one is meant. The entropy change
𝛿𝑄
of a system during a process can be determined by integrating Eq. 𝑑S= between
𝑇 𝑟𝑒𝑣
the initial and the final states:

𝟐
𝜹𝑸
𝑺𝟐 − 𝑺𝟏 = න
𝑻 𝒓𝒆𝒗
𝟏
Let us consider we have a system which is at equilibrium state 1 and system is
reaching at equilibrium state 2 by following the reversible process A. Now system is at
equilibrium state 2. Now let we have assumed that system is returning back to its
initial state i.e. state 1 from state 2 by following the process B.
Let us assume that there is one more path i.e.
process C and system is returning back to
initial state i.e. state 1 from by following the
reversible process C.
Therefore we have following processes and
thermodynamic cycle
Process 1-A-2, Reversible process
Process 2-B-1, Reversible process
Process 1-C-2, Reversible process

Thermodynamic reversible cycle, 1-A-2-B-1

Thermodynamic reversible cycle, 1-C-2-B-1
 Let us apply the concept of Clausius theorem in both the reversible cycle’s i.e.
reversible cycle 1-A-2-B-1 and reversible cycle 1-C-2-B-1.
Reversible cycle 1-A-2-B-1 Reversible cycle 1-C-2-B-1
𝛿𝑄 𝛿𝑄
ර =0 ර =0
𝑇 𝑟𝑒𝑣 𝑇 𝑟𝑒𝑣
2 1
2
𝛿𝑄 1
𝛿𝑄 𝛿𝑄 𝛿𝑄
𝑜𝑟, න +න = 0……..i 𝑜𝑟, න +න = 0 … … . ii
𝑇 𝑇 1 𝑇 𝐶 2 𝑇 𝐵
1 𝐴 2 𝐵
Subtracting the equation (ii) from (i) we get
2 2
𝛿𝑄 𝛿𝑄
න −න =0 As we are looking here that Process B and
1 𝑇 𝐴 1 𝑇 𝐶 𝜹𝑸
process C are two different processes. is
𝑻
𝟐 𝟐 basically a function of initial and final states
𝜹𝑸 𝜹𝑸
න =න and it will not be dependent over the path
𝟏 𝑻 𝑨 𝟏 𝑻 𝑪
selected by the system for completing the
cycle. Processes must be reversible processes.
So we can say that entropy is a point function
or state function.
Entropy of a pure substance
Entropy is a property, and thus the value of entropy of a system is fixed once, the
state of the system is fixed. Using a suitable reference state, the entropies of
substances are evaluated from measurable property data following rather involved
computations, and the results are tabulated in the same manner as the other
properties such as v, u, and h.
The value of entropy at a specified state is determined just like any other property.
In the compressed liquid and superheated vapor regions, it can be obtained directly
from the tables at the specified state. In the saturated mixture region, it is
determined from

𝑺 = 𝑺𝒇 + 𝐱 𝑺𝒇𝒈 kJ/kg.k

Where x is the quality and 𝑆𝑓 and 𝑆𝑓𝑔 saturated liquid and saturated liquid
vapor mixture.
 T dS Relations
The change in Entropy for a reversible process as given by its definition
𝛿𝑄
𝑑𝑆 =
𝑇 𝑟𝑒𝑣
𝑜𝑟, 𝛿𝑄 𝑟𝑒𝑣 = 𝑇 𝑑𝑆 … … … … … … 𝒊
First law applied to a closed system undergoing a process (change of states)
expressed as
𝛿𝑄𝑟𝑒𝑣 − 𝛿𝑊𝑟𝑒𝑣 = 𝑑𝐸 𝐴𝑠𝑠𝑢𝑚𝑖𝑛𝑔 𝑡ℎ𝑒 𝑑𝐾𝐸 𝑎𝑛𝑑 𝑑𝑃𝐸 𝑛𝑒𝑔𝑙𝑖𝑔𝑖𝑏𝑙𝑒 𝑎𝑛𝑑 𝑑𝐸 ≅ 𝑑𝑈

𝑜𝑟, 𝛿𝑄𝑟𝑒𝑣 = 𝑑𝑈 + 𝛿𝑊𝑟𝑒𝑣 … … … … 𝒊𝒊

𝑤ℎ𝑒𝑟𝑒, 𝛿𝑊𝑟𝑒𝑣 = 𝑃𝑑𝑉

Now equation ii can be expressed as

𝑻 𝒅𝑺 = 𝒅𝑼 + 𝑷 𝒅𝑽 … … … … … … … … . . 𝒊𝒊𝒊
Entropy equation can also be expressed in terms of enthalpy. For this let us start with the
definition of enthalpy as
𝐻 = 𝑈 + 𝑃𝑉
The change in enthalpy 𝑑𝐻 = 𝑑 𝑈 + 𝑃𝑉 during any process is then given as

𝑑𝐻 = 𝑑𝑈 + 𝑃𝑑𝑉 + 𝑉𝑑𝑃………………………………..iv
Substituting (𝑑𝑈 + 𝑃𝑑𝑉 = 𝑇𝑑𝑆) into above Equation iv,
𝑑𝐻 = 𝑇𝑑𝑆 + 𝑉𝑑𝑃
Rearranging above Equation, we can get the
expression as
𝑻𝒅𝑺 = 𝒅𝑯 − 𝑽𝒅𝑷 … … … … … … … … 𝐯
Hence, the thermodynamic property relations
involving change in entropy are:
𝑻𝒅𝑺 = 𝒅𝑼 + 𝑷𝒅𝑽
𝑻𝒅𝑺 = 𝒅𝑯 − 𝑽𝒅𝑷
And, for unit mass of working substance
𝑻𝒅𝒔 = 𝒅𝒖 + 𝑷𝒅𝒗 … … … … … 𝒗𝒊
𝑻𝒅𝒔 = 𝒅𝒉 − 𝒗𝒅𝑷 … … … … … . 𝒗𝒊𝒊
The equation T ds with the thermodynamic
relation for a working substance is know as
Gibbs Equation are extremely valuable since
they relate entropy changes of a system to
the changes in other properties.
The results obtained are valid for both
reversible and irreversible processes since
entropy is a property and the change in a
property between two states is independent
of the type of process the system undergoes.
The equation T dS are applicable whether
the change occurs in a closed or an open
system
Relations for differential changes in entropy are obtained by solving for ds in Eqs.
vi and vii

𝒅𝒖 𝑷 𝒅𝒗
𝒅𝒔 = + … … … … … … … … . 𝒗𝒊𝒊𝒊
𝑻 𝑻

𝒅𝒉 𝒗 𝒅𝑷
𝒅𝒔 = − … … … … … … … … . . 𝒊𝒙
𝑻 𝑻
The entropy change during a process can be determined by integrating either of these
equations between the initial and the final states. To perform these integrations,
however, we must know the relationship between du or dh and the temperature
(such as 𝒅𝒖 = 𝒄𝒗 𝒅𝑻 𝒂𝒏𝒅 𝒅𝒉 = 𝒄𝒑 𝒅𝑻 𝑓𝑜𝑟 𝑖𝑑𝑒𝑎𝑙 𝑔𝑎𝑠) as well as the equation of
state for the substance (such as the ideal-gas equation of state Pv= RT).
Entropy Relations for an Ideal Gas
For an ideal gas, the state properties 𝑃, 𝑉 and 𝑇 are related by the equation of state as

Entropy Relations Equations

𝒅𝑺 = 𝒅𝑼/𝑻 + 𝑷𝒅𝑽/𝑻…………………..i

The change in internal energy of an ideal gas is given by

𝑑𝑈=𝑚𝑐𝑉𝑑𝑇 …………….ii
Substituting the value of P/T and dU into above entropy equation i, we get
𝑑𝑇 𝑑𝑉
𝑑𝑆 = 𝑚𝑐𝑉 + 𝑚𝑅
𝑇 𝑉
Assuming 𝒄𝑽 and 𝑅 as constants, we can get the expression for the change in entropy for
an ideal gas during any process between state 1 and state 2 in terms of temperature and
volume ratios, as
𝑻𝟐 𝑽𝟐
𝑺𝟐 − 𝑺𝟏 = 𝒎𝒄𝑽 𝒍𝒏 + 𝒎𝑹𝒍𝒏 ………………….iii
𝑻𝟏 𝑽𝟏
 Similarly, equation of state can also be rearranged as

𝑉 𝑚𝑅
= ……………iv
𝑇 𝑃
The change in enthalpy of an ideal gas is given by
𝑑𝐻=𝑚𝑐𝑃𝑑𝑇 ………v
Entropy Relations Equations
𝒅𝑯 𝑽𝒅𝑷
𝒅𝑺 = − … … … . 𝒗𝒊
𝑻 𝑻
Substituting the value of V/T and dH into entropy Equation vi, we get
𝑑𝑇 𝑑𝑃
𝑑𝑆 = 𝑚𝑐𝑃 − 𝑚𝑅
𝑇 𝑃
Assuming 𝑐𝑃 and 𝑅 as constants, we can get the expression for the change in entropy
for an ideal gas during any process between state 1 and state 2 in terms of
temperature and pressure ratios, as
𝑻𝟐 𝑷𝟐
𝑺𝟐 − 𝑺𝟏 = 𝒎𝒄𝑷 𝒍𝒏 − 𝒎𝑹𝒍𝒏 ………vii
𝑻𝟏 𝑷𝟏
Entropy Change for a Thermodynamic Process
We know that the Entropy change for the ideal gas during any process between state 1
and state 2 as
𝑻𝟐 𝑽𝟐
𝑺𝟐 − 𝑺𝟏 = 𝒎𝒄𝑽 𝒍𝒏 + 𝒎𝑹𝒍𝒏 ………………….i
𝑻𝟏 𝑽𝟏
𝑻𝟐 𝑷𝟐
𝑺𝟐 − 𝑺𝟏 = 𝒎𝒄𝑷 𝒍𝒏 − 𝒎𝑹𝒍𝒏 …………………ii
𝑻𝟏 𝑷𝟏

a. Isochoric (constant volume) process

For a constant volume process the volume remains constant i.e. 𝑉1 = 𝑉2 , and
the equation for the Entropy change for ideal gas during any process between
state 1 and state 2 is
𝑇2 𝑉2
𝑆2 − 𝑆1 = 𝑚𝑐𝑉 𝑙𝑛 + 𝑚𝑅𝑙𝑛
𝑇1 𝑉1

As volume remains constant the above equation reduces to

𝑻𝟐
𝑺𝟐 − 𝑺𝟏 = 𝒎𝒄𝑽 𝒍𝒏
𝑻𝟏
b. Isobaric (constant pressure) process
For a constant pressure process the pressure remains constant i.e. 𝑃1 = 𝑃2, and
the equation for the Entropy change for ideal gas during any process between
state 1 and state 2 is
𝑇2 𝑃2
𝑆2 − 𝑆1 = 𝑚𝑐𝑃 𝑙𝑛 − 𝑚𝑅𝑙𝑛
𝑇1 𝑃1

As pressure remains constant the above equation reduces to

𝑻𝟐
𝑺𝟐 − 𝑺𝟏 = 𝒎𝒄𝑷 𝒍𝒏
𝑻𝟏
c. Isothermal (constant temperature ) process

For a constant temperature process the temperature remains constant i.e. 𝑇1 = 𝑇2,
and the equation for the Entropy change for ideal gas during any process between
state 1 and state 2 is
𝑇2 𝑉2
𝑆2 − 𝑆1 = 𝑚𝑐𝑉 𝑙𝑛 + 𝑚𝑅𝑙𝑛 ………………….i
𝑇1 𝑉1

𝑇2 𝑃2
𝑆2 − 𝑆1 = 𝑚𝑐𝑃 𝑙𝑛 − 𝑚𝑅𝑙𝑛 …………………ii
𝑇1 𝑃1

As temperature remains constant the above equation reduces to

𝑽𝟐
𝑺𝟐 − 𝑺𝟏 = 𝒎𝑹𝒍𝒏
𝑽𝟏
𝑷𝟐 𝑷𝟏
𝑺𝟐 − 𝑺𝟏 = −𝒎𝑹𝒍𝒏 = 𝐦𝑹𝒍𝒏
𝑷𝟏 𝑷𝟐
d. Polytropic process (𝑷𝑽𝒏 = 𝑪)
We know that during a polytropic process the heat transfer is
𝛾−𝑛
𝑑𝑄 = 𝛿𝑊
𝛾−1

𝛾−𝑛
𝑑𝑄 = 𝑃. 𝑑𝑉 𝑊ℎ𝑒𝑟𝑒, 𝛿𝑊 = 𝑃. 𝑑𝑉
𝛾−1

We know that the entropy as

𝑑𝑄
𝑑𝑆 =
𝑇 𝐼𝑑𝑒𝑎𝑙 𝑔𝑎𝑠 𝑒𝑞𝑢𝑎𝑡𝑖𝑜𝑛,
𝛾−𝑛 𝑃
𝑑𝑆 = 𝑑𝑉 𝑃𝑉 = 𝑚𝑅𝑇
𝛾−1 𝑇 𝑃 𝑚𝑅
𝑜𝑟 =
𝛾−𝑛 𝑑𝑉 𝑇 𝑉
𝑜𝑟, 𝑑𝑆 = 𝑚𝑅
𝛾−1 𝑉

𝑇𝑎𝑘𝑖𝑛𝑔 𝑖𝑛𝑡𝑒𝑔𝑟𝑎𝑡𝑖𝑜𝑛 𝑠𝑡𝑎𝑡𝑒 1 𝑡𝑜 2 𝑤𝑒 ℎ𝑎𝑣𝑒

2 2
𝛾−𝑛 𝑑𝑉
න 𝑑𝑆 = 𝑚𝑅 න
1 𝛾 − 1 1 𝑉
 𝜸−𝒏 𝑽𝟐 𝐶𝑃
𝑺𝟐 − 𝑺𝟏 = 𝒎𝑹 𝒍𝒏 𝑊ℎ𝑒𝑟𝑒, 𝛾 = 𝑜𝑟, 𝐶𝑃 = 𝛾𝐶𝑉
𝜸−𝟏 𝑽𝟏 𝐶𝑣
𝑅 = 𝐶𝑃 − 𝐶𝑉
The above equation is reduced as 𝑜𝑟, 𝑅 = 𝐶𝑉 𝛾 − 1
𝑽𝟐
𝑺𝟐 − 𝑺𝟏 = 𝜸 − 𝒏 𝒎 𝑪𝑽 𝒍𝒏
𝑽𝟏
The above equation is change in entropy in a polytropic process in terms of volume
ratio
In terms of Temperature ratio
𝑤ℎ𝑒𝑟𝑒, 𝑃𝑉 𝑛 = 𝐶
𝜸−𝒏 𝑽𝟐 𝑛−1
𝑺𝟐 − 𝑺𝟏 = 𝒎𝑹 𝒍𝒏 𝑇1 𝑉2
𝜸−𝟏 𝑽𝟏 𝑜𝑟, =
𝑇2 𝑉1
1ൗ 1ൗ
𝑛−1 𝑉2 𝑇1 𝑛−1
𝛾−𝑛 𝑇1
𝑜𝑟, 𝑆2 − 𝑆1 = 𝑚𝑅 𝑙𝑛 𝑜𝑟, =
𝛾−1 𝑇2 𝑉1 𝑇2

𝛾−𝑛 1 𝑇
𝑜𝑟, 𝑆2 − 𝑆1 = 𝑚 𝐶𝑉 𝛾 − 1 𝑙𝑛 1
𝛾−1 𝑛−1 𝑇2

𝜸−𝒏 𝑻𝟏 Required equation is change in entropy

∴ 𝑺𝟐 − 𝑺𝟏 = 𝒎𝑪𝑽 𝒍𝒏
𝒏−𝟏 𝑻𝟐 in terms of temperature ratio
 In terms of pressure ratio
𝑊ℎ𝑒𝑟𝑒, 𝑃1 𝑉1 𝑛 = 𝑃2 𝑉2 𝑛
𝛾−𝑛 𝑉2 𝑛
𝑆2 − 𝑆1 = 𝑚𝑅 𝑙𝑛 𝑉2 𝑃1
𝛾−1 𝑉1 𝑜𝑟, =
𝑉1 𝑃2
1ൗ 1ൗ
𝑛 𝑛
𝛾−𝑛 𝑃1 𝑉2 𝑃1
𝑜𝑟, 𝑆2 − 𝑆1 = 𝑚 𝑅 𝑙𝑛 𝑜𝑟, =
𝛾−1 𝑃2 𝑉1 𝑃2

𝛾−𝑛 1 𝑃1
𝑜𝑟, 𝑆2 − 𝑆1 = 𝑚 𝐶𝑉 𝛾 − 1 𝑙𝑛
𝛾−1 𝑛 𝑃2

𝜸−𝒏 𝑷𝟏
∴ 𝑺𝟐 − 𝑺𝟏 = 𝒎 𝑪𝑽 𝒍𝒏
𝒏 𝑷𝟐

Required equation is change in entropy in

terms of pressure ratio
e. Isentropic process (Reversible Adiabatic Process)
The change in entropy of any system during a reversible process is given by
𝛿𝑄
𝑑𝑆 =
𝑇
If the process is reversible as well as adiabatic (𝛿𝑄 = 0), Equation reduces to
𝑑𝑆 = 0
or, 𝑆2 − 𝑆1 = 0
∴ 𝑺𝟐 = 𝑺𝟏
Hence, during a reversible and adiabatic process, entropy of the system remains and the
process is called an isentropic process.
Entropy relation for an ideal gas are,
𝑇2 𝑉2
𝑆2 − 𝑆1 = 𝑚𝑐𝑉 𝑙𝑛 + 𝑚𝑅𝑙𝑛
𝑇1 𝑉1
𝑇2 𝑃2
𝑆2 − 𝑆1 = 𝑚𝑐𝑃 𝑙𝑛 − 𝑚𝑅𝑙𝑛
𝑇1 𝑃1
Substituting 𝑆2−𝑆1=0, above Equations, we get
 𝑻𝟐 𝑽𝟐
𝟎 = 𝒎𝒄𝑽 𝒍𝒏 + 𝒎𝑹𝒍𝒏
𝑻𝟏 𝑽𝟏 …………….. 1

𝑻𝟐 𝑷𝟐
0 = 𝒎𝒄𝑷 𝒍𝒏 − 𝒎𝑹𝒍𝒏 ……………… 2
𝑻𝟏 𝑷𝟏
Simplifying Equation 1
𝑇2 𝑉2
𝑐𝑉 𝑙𝑛 = −𝑅 𝑙𝑛
𝑇1 𝑉1

𝑇2 𝑅 𝑉2
or, 𝑙𝑛 =− 𝑙𝑛
𝑇1 𝐶𝑉 𝑉1

Taking antilog on both sides, we get

𝑅 𝐶𝑃 −𝐶𝑉 𝐶𝑃
−1
or, 𝑇2 𝑉1 𝐶𝑉 𝑉1 𝐶𝑉 𝑉1 𝐶𝑉
= = =
𝑇1 𝑉2 𝑉2 𝑉2

𝜸−𝟏
𝑻𝟐 𝑽𝟏 Equation gives the temperature – volume
∴ 𝑻𝟏
=
𝑽𝟐
……………𝟑
relationship for an ideal gas undergoing an
isentropic process.
𝑖. 𝑒. 𝑻𝑽𝜸−𝟏 = 𝒄𝒐𝒏𝒔𝒕𝒂𝒏𝒕
Simplifying Equation 2
𝑇2 𝑃2
𝑐𝑃 𝑙𝑛 = 𝑅 𝑙𝑛
𝑇1 𝑃1

or, 𝑇2 𝑅 𝑃2
𝑙𝑛 = 𝑙𝑛
𝑇1 𝐶𝑃 𝑃1
Taking antilog on both sides, we get
𝑅 𝐶𝑃 −𝐶𝑉 𝐶 1
1− 𝑉 1−
𝑇2 𝑃2 𝐶𝑃 𝑃2 𝐶𝑃 𝑃2 𝐶𝑃 𝑃2 𝛾
= = = =
𝑇1 𝑃1 𝑃1 𝑃1 𝑃1

𝜸−𝟏
𝑻𝟐 𝑷𝟐 𝜸
Equation gives the temperature –
∴ = …………….𝟒
𝑻𝟏 𝑷𝟏 pressure relationship for an ideal gas
undergoing an isentropic process.
𝒊. 𝒆 𝑻𝜸 𝑷𝟏−𝜸 = 𝒄𝒐𝒏𝒔𝒕𝒂𝒏𝒕
Equating the equation 3 and 4 we have 𝜸−𝟏
𝑻𝟐 𝑽𝟏
= ……………𝟑
𝛾−1ൗ
𝑻𝟏 𝑽𝟐
𝛾−1 𝛾
𝑉1 𝑃2 𝜸−𝟏
= 𝑻𝟐 𝑷𝟐 𝜸
𝑉2 𝑃1 = …………….𝟒
𝑻𝟏 𝑷𝟏
𝛾
𝑉1 𝑃2
𝑜𝑟, =
𝑉2 𝑃1
Equation gives the pressure-volume
𝜸 𝜸
∴ 𝑷 𝟏 𝑽𝟏 = 𝑷 𝟐 𝑽𝟐 … … … … … 𝟓 relationship for an ideal gas undergoing
an isentropic process.
𝑖. 𝑒 𝑷𝑽𝜸 = 𝑪𝒐𝒏𝒔𝒕𝒂𝒏𝒕
Entropy Change in a Reversible Process
Consider the heating of a working substance by a
reversible process as shown by a curve from I to 2, on a
graph, whose base represents the entropy and the vertical
ordinate represents the absolute temperature as shown in
Fig. 6.1. This diagram is known as temperature-entropy (T-
S) diagram.
Now consider any point A on the curve 1-2. At this point,
let a small quantity of heat (𝜹Q) be supplied to the
working substance, which will increase the entropy by dS.
Let the absolute temperature at this instant be T. Then
according to the definition of entropy,

𝛿𝑄
𝑑𝑆 =
𝑇 𝑟𝑒𝑣
Fig 6.1 Temperature- Entropy diagram

𝑜𝑟, 𝛿𝑄 𝑟𝑒𝑣 = 𝑇 𝑑𝑆 … … … … … … … … … . . 𝒊
 From Fig. 6.1, we see that the term T dS represents the area under the curve during
this change of entropy. Now the total area under the curve 1-2 may be found out by
integrating the equation (i)

න 𝛿𝑄 = න 𝑇 𝑑𝑆
The total change in entropy may be obtained by integrating the above expression
from state I to state 2,
2 2
𝛿𝑄
න 𝑑𝑆 = න … … … … … … … . 𝒊𝒊
1 1 𝑇

Notes:
1. The area under the T-S diagram of any thermodynamic process represents the
heat absorbed or rejected during that process.
𝜹𝑸
2. Since‫ ׬‬is same for all reversible paths between states I and 2, so we conclude
𝑻
that this quantity is independent of a path and is a function of end states only. In
other words, the entropy is a point function and thus it is a property of the
system. The entropy maybe expressed as a function of other thermodynamic
properties of the system, such as the pressure and temperature or pressure and
volume
3. We know that according of First Law of Thermodynamics,

𝛿𝑄 = 𝑑𝑈 + 𝛿𝑊 = 𝑑𝑈 + 𝑃𝑑𝑉 … … … … … … . 𝒊𝒊𝒊 𝑊ℎ𝑒𝑟𝑒, 𝛿𝑊 = 𝑃𝑑𝑉

𝛿𝑄 = 𝑇𝑑𝑆 … … … … … … . 𝒊𝒗

From equation iii and iv we get

𝑇𝑑𝑆 = 𝑑𝑈 + 𝑃𝑑𝑉 … … … … … … … … … … … . 𝒗
Equations (iii) and (iv). 𝜹𝑸 𝒂𝒏𝒅 𝜹𝑾 are path functions, therefore these
equations are true only for reversible processes. But in equation (v)
𝒅𝑺, 𝒅𝑼 𝒂𝒏𝒅 𝒅𝑽 are point functions as they depend upon the initial and final
equilibrium stales, therefore equation (v) is true for reversible as well as
irreversible processes.

4. The entropy remains constant in a reversible cyclic process and increases in an

irreversible cyclic process
ILLUSTRATION
A Reversed Carnot Cycle that consist of four reversible process in series-
two isothermal alternated with two adiabatic process

a) Process 1-2. Isothermal Expansion in which heat is absorbed by

the system as temperature remains constant 𝑇𝐻 .Change in
𝑸
entropy during this process is given by 𝒅𝑺𝟏 = 𝟏.The system
𝑻𝟏
entropy increases. Here 𝑄1−2 = 𝑇𝐻 𝑆2 − 𝑆1 = 𝑎𝑟𝑒𝑎 1 − 2 − 𝑎
−𝑏−1

b) Process 2-3. Adiabatic expansion process in which temperature

decreases and heat transfer remains constant. Change in
entropy 𝒅𝑺𝟐 = 𝟎
𝑇𝐻
c) Process 3-4. Isothermal compression while heat transfer from
the system to the sink at constant temperature 𝑇𝐿 .Change in
𝑸
entropy𝒅𝑺𝟑 = − 𝟐. The system entropy decreases. Here 𝑄3−4
𝑻𝟐
= 𝑇𝐿 𝑆3 − 𝑆4 = 𝑎𝑟𝑒𝑎 3 − 4 − 𝑏 − 𝑎 − 3

d) Process 4-1: Adiabatic compression process in which 𝑇𝐿

temperature increases remaining heat constant. Change in
entropy 𝒅𝑺𝟒 = 𝟎 𝑏 𝑎
 Net change in entropy in carnot cyclic process is given by

𝑑𝑆 = 𝑑𝑆1 + 𝑑𝑆2 − 𝑑𝑆3 + 𝑑𝑆4

𝑄1 𝑄2
𝑜𝑟, 𝑑𝑆 = +0− +0
𝑇1 𝑇2

𝑄1 𝑄2
𝑜𝑟, 𝑑𝑆 = −
𝑇1 𝑇2
𝑤ℎ𝑒𝑟𝑒, 𝑎𝑛 𝑟𝑒𝑣𝑒𝑟𝑠𝑖𝑏𝑙𝑒 𝑐𝑎𝑟𝑛𝑜𝑡 𝑐𝑦𝑐𝑙𝑖𝑐 𝑝𝑟𝑜𝑐𝑒𝑠𝑠
𝑄𝐻 𝑄𝐿
= The net work of any cycle is equal to the
𝑇𝐻 𝑇𝐿
net heat transfer, enclosed area 1-2-3-4-1
∴ 𝒅𝑺 = 𝟎 represents the net work of the cycle. Also
the thermal efficiency of the cycle can be
Hence, change in entropy in reversible carnot expressed in terms of areas:
cyclic process is zero
𝑾𝒄𝒚𝒄𝒍𝒆 𝒂𝒓𝒆𝒂 𝟏 − 𝟐 − 𝟑 − 𝟒 − 𝟏
𝜼= =
𝑸𝟏𝟐 𝒂𝒓𝒆𝒂 𝟏 − 𝟐 − 𝒂 − 𝒃 − 𝟏
Change in Entropy in Irreversible process
Consider a cycle that is made up of two processes: process 1-2,
which is arbitrary (reversible or irreversible), and process 2-1,
which is internally reversible, as shown in Figure a. From the
Clausius inequality,
𝛿𝑄
ර ≤0
𝑇
2 1
𝛿𝑄 𝛿𝑄 Fig a A cycle composed of a reversible
න +න ≤ 0………………𝒊 and an irreversible process.

1 𝑇 2 𝑇 𝑖𝑛𝑡,𝑟𝑒𝑣 where the equality holds for an internally reversible process

and the inequality for an irreversible process. We may
The second integral in the previous relation equation 1 conclude from these equations that the entropy change of a
is recognized as the entropy change 𝑆1 − 𝑆2 . Therefore closed system during an irreversible process is greater than
𝜹𝑸
2 the integral of 𝑻 evaluated for that process. In the limiting
𝛿𝑄 case of a reversible process, these two quantities become
න + 𝑆1 − 𝑆2 ≤ 0
1 𝑇 equal. We again emphasize that T in these relations is the
thermodynamic temperature at the boundary where the
which can be rearranged as differential heat 𝜹𝑸 is transferred between the system and
the surroundings.
2
𝛿𝑄
𝑆2 − 𝑆1 ≥ න … … … … … … … . . 𝒊𝒊 The quantity ∆𝑆 = 𝑆2 − 𝑆1 represents the entropy change of
1 𝑇 the system. For a reversible process, it becomes equal
2 𝛿𝑄
It can also be expressed in differential form as to‫׬‬1 𝑇
, which represents the entropy transfer with heat.

𝜹𝑸
𝒅𝑺 ≥
𝑻
Entropy Generation
𝜹𝑸
The inequality sign in the relations 𝒅𝑺 ≥ is a constant reminder that the entropy change
𝑻
of a closed system during an irreversible process is always greater than the entropy transfer.
That is, some entropy is generated or created during an irreversible process, and this
generation is due entirely to the presence of irreversibilities. The entropy generated during a
process is called entropy generation and is denoted by 𝑺𝒈𝒆𝒏. Noting that the difference
between the entropy change of a closed system and the entropy transfer is equal to entropy
generation,Therefore,

𝟐
𝜹𝑸
∆𝑺𝒔𝒚𝒔 = 𝑺𝟐 − 𝑺𝟏 = න + 𝑺𝒈𝒆𝒏
𝟏 𝑻

Note that the entropy generation 𝑺𝒈𝒆𝒏 is always a positive quantity or zero. Its value depends
on the process, and thus it is not a property of the system. Also, in the absence of any entropy
transfer, the entropy change of a system is equal to the entropy generation.
 Lost Work

The amount of entropy generated is the measure of thermodynamic irreversibility. The

irreversibility associated with a thermodynamic process can also be quantified with
the concept know as lost work.
Mathematically
𝑊𝑙𝑜𝑠𝑡 = 𝑇𝑅 𝑆𝑔𝑒𝑛

Where,
𝑇𝑅 = 𝑟𝑒𝑓𝑒𝑟𝑒𝑛𝑐𝑒 𝑡𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒
𝑆𝑔𝑒𝑛 = 𝑒𝑛𝑡𝑟𝑜𝑝𝑦 𝑔𝑒𝑛𝑒𝑟𝑎𝑡𝑒𝑑

Lost work is always positive for all real processes

If the reference temperature is taken as the absolute temperature of the environment
𝑇0 , then the lost work is called the thermodynamic lost wok or irreversibility

𝑖. 𝑒. 𝑊0, = 𝑇0 𝑆𝑔𝑒𝑛

𝑤ℎ𝑒𝑟𝑒, 𝑊0 𝑖𝑠 𝑛𝑜𝑡ℎ𝑖𝑛𝑔 𝑏𝑢𝑡 𝑖𝑟𝑟𝑒𝑣𝑒𝑟𝑠𝑖𝑏𝑖𝑙𝑖𝑡𝑦

Increase of Entropy Principle
𝟐 𝜹𝑸
Equation 𝑺𝟐 − 𝑺𝟏 ≥ ‫𝟏׬‬ has far-reaching implications in thermodynamics. For an isolated
𝑻
system (or simply an adiabatic closed system), the heat transfer is zero, and Eq. reduces to
∆𝑺𝒊𝒔𝒐𝒍𝒂𝒕𝒆𝒅 ≥ 𝟎
The entropy of an isolated system during a process always increases or, in the limiting case of a
reversible process, remains constant. In other words, it never decreases. This is known as the
increase of entropy principle. Note that in the absence of any heat transfer, entropy change is
due to irreversibilities only, and their effect is always to increase entropy
Now, consider any system and its surrounding within a single
boundary as shown in fig b. The combination of system and
surrounding within a single boundary is called the universe.
Entropy is an extensive property, and thus the total entropy of a
system is equal to the sum of the entropies of the parts of the
system . A system and its surroundings, for example, constitute an
isolated system since both can be enclosed by a sufficiently large
arbitrary boundary across which there is no heat, work, or mass
transfer (Fig.b). Therefore, a system and its surroundings can be
viewed as the two subsystems of an isolated system, and the
entropy change of this isolated system during a process is the sum
of the entropy changes of the system and its surroundings, which is Fig b A system and its surroundings
form an isolated system
equal to the entropy generation since an isolated system involves no
entropy transfer. That is,
 𝑺𝒈𝒆𝒏 = ∆𝑺𝒕𝒐𝒕𝒂𝒍 = ∆𝑺𝒔𝒚𝒔 + ∆𝑺𝒔𝒖𝒓𝒓 ≥ 𝟎
Let us consider in the combined closed system, the heat 𝛿𝑄 is transferred from system to
surroundings

For Reversible process

−𝛿𝑄 𝛿𝑄
𝑑𝑆𝑠𝑦𝑠 = and 𝑑𝑆𝑠𝑢𝑟𝑟 =
𝑇𝑠𝑦𝑠 𝑇𝑠𝑢𝑟𝑟
Total change in entropy for the combined system,
−1 1
𝑑𝑆𝑠𝑦𝑠 + 𝑑𝑆𝑠𝑢𝑟𝑟 = 𝛿𝑄 +
𝑇𝑠𝑦𝑠 𝑇𝑠𝑢𝑟𝑟
1 1
𝑜𝑟, 𝑑𝑆𝑢𝑛𝑖𝑣𝑒𝑟𝑠𝑒 = 𝛿𝑄 −
𝑇𝑠𝑢𝑟𝑟 𝑠𝑦𝑠
Since
1 1
𝑇𝑠𝑦𝑠 > 𝑇𝑠𝑢𝑟𝑟 , 𝑡ℎ𝑒 𝑞𝑢𝑎𝑛𝑡𝑖𝑡𝑦 − 𝑖𝑠 𝑝𝑜𝑠𝑖𝑡𝑖𝑣𝑒
𝑇𝑠𝑢𝑟𝑟 𝑇𝑠𝑦𝑠
So we conclude that
𝒅𝑺𝒖𝒏𝒊𝒗𝒆𝒓𝒔𝒆 = 𝒅𝑺𝒔𝒚𝒔 + 𝒅𝑺𝒔𝒖𝒓𝒓 ≥ 𝟎
Above equation states that the process involving the
integration of a system and the surroundings, net entropy of
universe increases or remains constant.
where the equality holds for reversible processes and the inequality for irreversible ones. Note
that ∆𝑺𝒔𝒖𝒓𝒓 refers to the change in the entropy of the surroundings as a result of the occurrence of
the process under consideration. Since no actual process is truly reversible, we can conclude that
some entropy is generated during a process, and therefore the entropy of the universe, which can
be considered to be an isolated system, is continuously increasing. The more irreversible a process,
the larger the entropy generated during that process. No entropy is generated during reversible
processes (𝑺𝒈𝒆𝒏= 0).
The increase of entropy principle does not imply that the entropy of a system cannot decrease. The
entropy change of a system can be negative during a process (Fig.c), but entropy generation
cannot. The increase of entropy principle can be summarized as follows:

> 0 𝐼𝑟𝑟𝑒𝑣𝑒𝑟𝑠𝑖𝑏𝑙𝑒 𝑝𝑟𝑜𝑐𝑒𝑠𝑠

𝑆𝑔𝑒𝑛 ቐ = 0 𝑅𝑒𝑣𝑒𝑟𝑠𝑖𝑏𝑙𝑒 𝑝𝑟𝑜𝑐𝑒𝑠𝑠
< 0 𝐼𝑚𝑝𝑜𝑠𝑠𝑖𝑏𝑙𝑒 𝑝𝑟𝑜𝑐𝑒𝑠𝑠
Some Remarks about Entropy

• Processes can occur in a certain direction only, not in any direction. A process
must proceed in the direction that complies with the increase of entropy principle,
that is, 𝑆𝑔𝑒𝑛 ≥ 0. A process that violates this principle is impossible. This principle
often forces chemical reactions to come to a halt before reaching completion.

• Entropy is a non conserved property, and there is no such thing as the

conservation of entropy principle. Entropy is conserved during the idealized
reversible processes only and increases during all actual processes.

• The performance of engineering systems is degraded by the presence of

irreversibilities, and entropy generation is a measure of the magnitudes of the
irreversibilities present during that process. The greater the extent of
irreversibilities, the greater the entropy generation. Therefore, entropy generation
can be used as a quantitative measure of irreversibilities associated with a process.
It is also used to establish criteria for the performance of engineering devices.
CONCEPTS OF REVERSIBILITY,IRREVERSIBILITY, AVAILABILITY

Availability
When a new energy source, such as a geothermal well, is discovered, the first thing the
explorers do is estimate the amount of energy contained in the source. This information alone,
however, is of little value in deciding whether to build a power plant on that site. What we
really need to know is the work potential of the source—that is, the amount of energy we can
extract as useful work. The rest of the energy is eventually discarded as waste energy and is
not worthy of our consideration. Thus, it would be very desirable to have a property to enable
us to determine the useful work potential of a given amount of energy at some specified state.
This property is exergy, which is also called the availability or available energy.
The work potential of the energy contained in a system at a specified state is simply the
maximum useful work that can be obtained from the system.
The work done during a process depends on the initial state, the final state, and the process
path. That is,
Work = f(initial state, process path, final state)
In an exergy analysis,
• the initial state is specified, and thus it is not a variable.
• The work output is maximized when the process between two specified states is executed
in a reversible manner. Therefore, all the irreversibility's are disregarded in determining
the work potential.
• Finally, the system must be in the final state (dead state) at the end of the process to
maximize the work output.
A system is said to be in the dead state when it is in thermodynamic
equilibrium with the environment as in (Fig.a). At the dead state, a system
is at the temperature and pressure of its environment (in thermal and
mechanical equilibrium);
• it has no kinetic or potential energy relative to the environment (zero
velocity and zero elevation above a reference level);
• and it does not react with the environment (chemically inert).
• Also, there are no unbalanced magnetic, electrical, and surface Fig a A system that is in
equilibrium with its
tension effects between the system and its surroundings, environment is said to
• The properties of a system at the dead state are denoted by subscript be at the dead state .
zero, for example, 𝑃0 , 𝑇0 , ℎ0 , 𝑢0 , 𝑠0
• A system has zero exergy at the dead state

Therefore, we conclude that a system delivers the maximum possible work as it undergoes a
reversible process from the specified initial state to the state of its environment, that is, the
dead state.
Since availability represents the upper limit on the amount of work a device can deliver without
violating any thermodynamic laws. There will always be a difference, large or small, between
exergy and the actual work delivered by a device.
Note
That the exergy of a system at a specified state depends on the conditions of the environment
(the dead state) as well as the properties of the system. Therefore, exergy is a property of the
system–environment combination and not of the system alone.
Distinction should be made between the surroundings, immediate
surroundings, and the environment.
• surroundings are everything outside the system boundaries.
• immediate surroundings refer to the portion of the surroundings
that is affected by the process, and
• environment refers to the region beyond the immediate
surroundings whose properties are not affected by the process at
any point
Therefore, any irreversibilities during a process occur within the The immediate surroundings of a
system and its immediate surroundings, and the environment is free hot potato are simply the
temperature gradient zone of the
of any irreversibilities air next to the potato.
Reversible Work and Irreversibility
In this section, we describe two quantities that are related to the
actual initial and final states of processes and serve as valuable tools
in the thermodynamic analysis of components or systems. These
two quantities are the reversible work and irreversibility (or exergy
destruction). But first we examine the surroundings work, which is
the work done by or against the surroundings during a process.
The work done by work-producing devices is not always entirely in a
usable form. For example, when a gas in a piston–cylinder device
expands, part of the work done by the gas is used to push the Fig a As a closed system expands, some
work needs to be done to push the
atmospheric air out of the way of the piston (Fig.a). This work, which atmospheric air out of the way (𝑊𝑠𝑢𝑟𝑟 ).
cannot be recovered and utilized for any useful purpose, is equal to
the atmospheric pressure 𝑷𝟎 times the volume change of the system
𝑊𝑠𝑢𝑟𝑟 = 𝑃0 𝑉2 − 𝑉1

The difference between the actual work W and the surroundings

work 𝑾𝒔𝒖𝒓𝒓 is called the useful work 𝑾𝒖 :

𝑊𝑢 = 𝑊 − 𝑊𝑠𝑢𝑟𝑟 = 𝑊 − 𝑃0 𝑉2 − 𝑉1

When a system is expanding and doing work, part of the work done is used to overcome the
atmospheric pressure, and thus 𝑊𝑠𝑢𝑟𝑟 represents a loss. When a system is compressed,
however, the atmospheric pressure helps the compression process, and thus 𝑊𝑠𝑢𝑟𝑟 represents
a gain.
Reversible work 𝑾𝒓𝒆𝒗 is defined as the maximum amount of useful
work that can be produced (or the minimum work that needs to be
supplied) as a system undergoes a process between the specified
initial and final states. This is the useful work output (or input)
obtained (or expended) when the process between the initial and
final states is executed in a totally reversible manner. When the final
state is the dead state, the reversible work equals exergy. For
processes that require work, reversible work represents the
minimum amount of work necessary to carry out that process. For
convenience in presentation, the term work is used to denote both
work and power
Fig b The difference
between reversible work
and actual useful work is
Any difference between the reversible work 𝑊𝑟𝑒𝑣 and the useful the irreversibility.
work 𝑊𝑢 is due to the irreversibilities present during the process,
and this difference is called irreversibility I. It is expressed as (Fig. b)

𝐼 = 𝑊𝑟𝑒𝑣,𝑜𝑢𝑡 − 𝑊𝑢,𝑜𝑢𝑡 𝑜𝑟, 𝐼 = 𝑊𝑢,𝑖𝑛 − 𝑊𝑟𝑒𝑣,𝑖𝑛

The irreversibility is equivalent to the exergy destroyed. For a totally reversible process, the
actual and reversible work terms are identical, and thus the irreversibility is zero. This is
expected since totally reversible processes generate no entropy. Irreversibility is a positive
quantity for all actual (irreversible) processes since 𝑊𝑟𝑒𝑣 ≥ 𝑊𝑢 for work producing devices
and 𝑊𝑟𝑒𝑣 ≤ 𝑊𝑢 for work-consuming devices.

Irreversibility can be viewed as the wasted work potential or the lost opportunity to do
work. It represents the energy that could have been converted to work but was not. The
smaller the irreversibility associated with a process, the greater the work that is produced
(or the smaller the work that is consumed). The performance of a system can be improved
by minimizing the irreversibility associated with it.