Entropy
Introduction
First law when applied to the thermodynamic process it gave rise to a property called internal
energy
Similarly when second law is applied to thermodynamic process it gives rise to a property called
entropy
Clausius inequality
According to Clausius inequality the cyclic integral of factor is always less than or equal to
zero
𝑑𝑄
● ∮ 𝑇
= 0 ⇒ Reversible cycle.
𝑑𝑄
● ∮ 𝑇
< 0⇒ Irreversible and possible
𝑑𝑄
● ∮ 𝑇
> 0⇒ Impossible cycle
Entropy
It is the measure of degree of disorderness or randomness of the molecules
Entropy principle
Entropy of an isolated system can never decrease
It remains constant only for a reversible adiabatic process
According to this the entropy change of the universe which is system plus surrounding is always
greater than or equal to zero. This is known as the principle of increase of entropy or simply the
entropy principle.
System and surrounding together is universe which is an isolated system
● Irreversible device
● Reversible device
● Impossible device
Entropy change of the system
Entropy change of the system is the summation of entropy change due to internal irreversibility
and entropy change due to external interaction
𝑑𝑄
𝑑𝑆 = 𝑇
+ 𝑆𝑔𝑒𝑛
Where is entropy change of system, is entropy generated due to internal irreversibility,
is heat interaction of system and is temperature of system
If the system is internally reversible then entropy generation is zero and the entropy change of
the system is given as:
If heat is added reversibly to the system, entropy change of the system is positive
If heat is rejected reversibly by the system, entropy change of the system is negative
If the system is well insulated and the process is reversible then the value of entropy change of
the system is equal to zero i.e. isentropic process.
If the system is adiabatic and process is irreversible then
𝑑𝑆 = 𝑆𝑔𝑒𝑛
Testbook points
● Entropy change of the system may be positive, zero or negative whereas the entropy
change of the universe cannot be negative.
● If the process is reversible and adiabatic then it is said to be isentropic
● The value of entropy generation is always greater than zero
● In case internal irreversibility is compensated by decrease in external interaction than
also we can have a zero change in entropy i.e. isentropic process
● All reversible adiabatic process is isentropic but reverse may not be true due to above
case.
𝑇2
● Polytropic reversible process, ∆𝑆 = 𝑚𝐶𝑣 ( ) ln 𝑙𝑛
𝑛−𝑦
𝑛−1 𝑇1
Application of entropy principle
Transfer of heat through a finite temperature difference
Let be rate of heat transfer from reservoir A at to reservoir B at and
As so it is a irreversible process
i. Mixing of two fluid
● Let we have two system one with mass m1, c1 specific heat and T1 absolute
temperature
● Other with m2 mass, c2 specific heat and T2 absolute temperature T1>T2
● They are mixed in a insulated vessel i.e. external heat interaction is zero
Where is final temperature after mixing
● As so it is irreversible process
ii. Maximum work obtainable from two finite bodies at given temperature
● Let the bodies be at temperature respectively
● Let be heat capacity of the two bodies at constant pressure and be the final
temperature for maximum work
For maximum work process should be reversible and hence entropy change of
universe should be equal to zero
And
Combine equation of first law and second law
● From first law of thermodynamics for a closed system
For reversible process
Where is specific entropy change
is specific heat at constant volume, is final and initial absolute
temperature, are final and initial volume, is characteristic gas constant
● Now
Where symbols have usual meaning
Testbook points
● Holds good for closed system and reversible process
● It is true only for reversible process
● Holds good for any process as it contains properties only
● Holds good for any process as it contains properties only
Slope of isobaric and isochoric process on T-S graph
● for isochoric process
● for isobaric process
● As the value of so the slope of constant volume is greater than that of
constant pressure on T-S graph
Exergy
● The exergy or available energy of a system is the maximum amount of work that can
be extracted from it till it reaches the state of thermodynamic equilibrium with its
surrounding
● For any substance if pressure increases the volume decreases. Therefore in any
thermodynamic plot in p-v coordinate all process must have i.e. negative
slope
● Similarly for increase in temperature disorderness or entropy increases and hence
for any thermodynamic plot on T-s diagram i.e. positive slope
● For a system to be dead state it must have zero velocity and minimum potential
energy
● All spontaneous process in nature terminates at dead state
Exergy of heat input in a cycle
● The maximum work obtainable from a certain heat input in a cyclic heat engine is
often called the available energy (A.E.) or the available part of the exergy
● The minimum energy that has to be rejected by the second law is called the
unavailable energy (U.E.) or the unavailable part of the exergy supplied
● Let Q be the heat supplied to a reversible heat engine at temperature T and heat is
rejected to the sink at dead state
● Hence maximum work obtained is given as
Loss in AE when heat is transferred through a finite temperature
difference
● Greater the temperature difference more will be the loss of AE
● Same heat is having more importance at higher temperature in comparison to the
lower temperature
Irreversibility and Gouy-Stodola theorem
● According to this theorem the loss of available energy or irreversibility is directly
proportional to the entropy generation
I is the irreversibility
● Gibbs function (G)
● Helmontz (F)
Second law efficiency( )
● It is defined as the ratio of actual work to the reversible work. It is also called the
isentropic efficiency
● For work producing devices like turbines it is given as
● For work consuming device like compressor it is given as the ratio of reversible work
to the actual work