Entropy
Entropy
The first law of thermodynamics was stated in terms of cycles first and it was shown that the cyclic
integral of heat is equal to cyclic integral of heat and work.
If 1st law leads to internal energy than second law may be stated in terms or entropy.
In fact thermodynamics is the study of three’s E’s mamely Energy, Equilibrium and Entropy.
dQ
T R 0 ds 0
dQR
T S
2
Q R
1 T S2 S1
2 2 2
Q Q Q
1 A T 1 1 B T 2 1 a T 3 S2 S1
Q Q
T ?? T ?? (What is value) For irreversible Process.
Given by clausius inequadity.
Clausius Inequality
dQ (dQ) Q
T T R T 0
2 2 2
Q Q Q
1 T A 1 T B 1 T C
irrev. irrev. irrev. It is not a Point function.
Q Q Q
T T R T S
2 2 2
Q Q Q
S2 S1
1 T 1 T R 1 T
As show in figure.
Q Q Q
T 1A 2 T 1B2 T 1C2
But maximum of these value will be less than the unique value of reversible process i.e. 1-A-2, 1-B-2, 1-
C-2. (Which is define as change in entropy.
Here
Q
T ( S)gen dS
irrev
Clausis statement proof
dQ
T irr
0
WR = Q1R – Q2R To proof
W = Q1 – Q2
By Second Law
Q
1 2
Q1 R irr.
Q2R Q Q2R
1 1 2 R 1
Q1R Q1 Q1R
Q2 Q2R
irr. irrv.
Q1 Q1R
,
Q1 Q1R
Q2 Q2R rev irrev
Q1 T1 Q T
1R 1
Q2 T2 Q2R T2
Q1 Q 2
0
T1 T2
(Proved)
Now
Q
S
T R
A reversible adiabatic process
Q R 0
Q
( S) T R
0
S = 0
S = constant
Reversible adiabatic process is isentropic.
Now
Q (Q)R
T irrev T
We can show the
2 1
Q Q
1 R A T 2 RB T 0
……………….(1)
2 1
Q Q
1 RA T 2 RB T 0
irrev ………….(2)
From (1) & (2)
1 1
Q Q
RB B T 0
2 T 2
1 1
Q Q
B RB
2 T irrev 2 T (Proved)
Q
s
T irrev
We can say
Q
S
T
Q
S (S)gen.
T
( S) ( S)C (S)gen.
( S)i Change of entropy due
Change of entropy to int urnal irreversibility
due to external
irreversibility
Q
dS
If process is reversible T
Q TdS
2
Q TdS
1
Concept of an isolated system
Isolated Q 0
System W 0
( S) 0 (isolated system)
Q
( S) T
( S)gen.
dS = 0 dS ( S)i
S = constant dS > 0.
S1 = S2 = S Isentropic.
An adiabatic process can be isentropic and non isentropic. If adiabatic process is isensentropic it must
be reversible. If adiabatic process is non-isentropic it must be irreversible.
Althrough entropy is a point function.
Entropy generation is a path function.
A process with more irrecersibity has more entropy generation.
The entropy increase due to internal irreversibility is also called “Entropy generation”
Entropy transfer only associated with heat not with work transfer.
Combine 1st and 2nd law
We know
dQ = dU + Pdv, dQ = Tds
TdS = dU + Pdv It is valid for any process reversible or irreversible but close sys. Because it connect
various properties.