Entropy

1-A-2-B-1  internally reversible cyclic process

1-A-2-C-1  another internally reversible cyclic process

Appling Clausius inequality for the processes

∮ δQ
T |1− A −2−B−1
=0

⟹∫
δQ
T | 1− A−2
+∫
δQ
T |2−B−1
=0 … (a)

∮ δQ
T |1− A −2−C −1
=0

⟹∫
δQ
T | 1− A−2
+∫
δQ
T |2−C−1
=0 …(b)

From (a) and (b):

∫ δQ
T |
2−B−1
=∫
δQ
T |2−C−1

∫ δQ
T |
internallyreversible process
→ change∈ property → change∈entropy

Integral form:

∫ δQ
T |internallyreversible process
=Δ S

Differential form:

δQ
T | internally reversible process
=dS

Entropy:
  Entropy is a property. It is a state (point) function and an exact differential.
 In differential form entropy change is represented by dS.
 For a closed system, undergoing an internally reversible process, entropy change is given by
the expression

∫ δQ
T | internallyreversible process
=Δ S

T |
δQ
=dS
internally reversible process
 For a closed system, undergoing an internally reversible process, entropy change takes
place due to entropy transfer (associated with heat transfer) only.

δQ
entropy change ⟵ Δ S=∫ → entropy transfer associated with heat transfer
T

 Since entropy is a state (point) function hence entropy change between two given states is
always same whether the path is internally reversible or internally irreversible.

Explanation:

As 2-B-1 and 2-C-1 are internally reversible process. Therefore, in these two cases entropy change
will be same.

∆ S|2−B−1=∆ S|2−C −1
As 2-B-1 and 2-C-1 are internally reversible process. Therefore, in these two cases entropy change is
equal to the entropy transfer associated with heat transfer.

∫ δQ
T |2−B−1
=∫
δQ
T |2−C−1
=Δ S

On the other-hand 2-D-1 is an internally irreversible process. So, entropy change is not equal to the
entropy transfer associated with heat transfer.

∫ δQ
T |
2−C −1
≠ ΔS

Q. then what is the relation between entropy change and entropy transfer associated with heat
transfer for internally irreversible process?
Let us consider an internally reversible closed system 1-A-2-B-1 where 1-A-2 and 2-B-1 are internally
reversible process and an internally irreversible closed system 1-A-2-D-1 where 1-A-2 is internally
reversible process but 2-D-1 is internally irreversible process.

According to Clausius Inequality:

∮ δQ
T |
1− A −2−B−1
=0

⟹∫
δQ
T |1− A−2
+∫
δQ
T |2−B−1
=0 … (a)

∮ δQ
T |
1− A −2−D−1
<0

⟹∫
δQ
T |1− A−2
+∫
δQ
T |2−D −1
<0 … (b)

From (a) and (b):

∫ δQ
T |
1−A −2
+∫
δQ
T |2−D−1
<∫
δQ
T |1− A−2
+∫
δQ
T |2−B−1

⟹∫
δQ
T |
2−D −1
<∫ |
δQ
T 2−B −1

⟹∫
δQ
T | internallyirreversible process
<∫
T |
δQ
internally reversible process

∫ δQ
T | internallyirreversible process
<∆ S

 Entropy change for a closed system undergoing internally irreversible process, is greater
than entropy transfer for the process.
 ∆ S> ∫
δQ
T |
internallyirreversible process

∆ S=∫
δQ
T |
internallyirreversible process
+ S gen

∆ S → entropy change

∫ δQ
T |
internallyirreversible process
→ entropy transfer due to heat transfer

S gen → entropy generation due to irreversibility

 Entropy generation within the system takes place only for internally irreversible process & it
is always positive.
 Entropy generation depends upon the irreversibility. Higher the irreversibility, higher will be
the entropy generation.

S gen ∝ irreversibilities→+ ve

 For a closed system undergoing internally irreversible process entropy change takes place
due to entropy transfer (associated with heat transfer) and entropy generation (associated
with Irreversibility).
 For internally reversible process, entropy generation within system is "zero".
 Different paths have different irreversibility, hence different magnitudes of entropy
generation. Entropy generation is a path function and inexact differential
 In differential form entropy generation can be written as δ S gen

∆ S=∫
δQ
T |
internallyirreversible process
+ S gen

dS=
δQ
T |
internally irreversible process
+ δ S gen

Q. The change in entropy of the system undergoing a cyclic irreversible process is:

a. Greater than zero c. equal to zero

b. less than zero d. equal to the Δ Ssurrounding

Entropy change for a closed system undergoing various internally reversible heat interactions:

for a closed system undergoing internally reversible process we can write:

δQ
dS= (always T →+ ve)
T
1. Heat addition process: δQ →+ ve dS →+ ve S↑
2. Heat rejection process: δQ →−ve dS →−ve S↓
3. Adiabatic /isentropic process: δQ=0 dS=0 S=constant
Entropy change for a closed system undergoing various internally irreversible heat interactions:

for a closed system undergoing internally irreversible process we can write:

 δQ
dS= + δ S gen ( always T →+ ve∧S gen →+ve )
T
1. Heat addition: δQ →+ ve dS →+ ve S↑
2. Heat rejection: it depends
3. Adiabatic process: δQ=0 dS=δ S gen →+ve S↑
Heat addition process Heat addition process Adiabatic process
Reversible Irreversible Reversibl Irreversible Reversible Irreversibl
e e
δQ S↑
<δ S gen
T
S↑ S↑ S↓ δQ S= S = constant S↑
=δ S gen
T constant
δQ S↓
>δ S gen
T

 In the case of a closed system undergoing internally reversible heat addition process
entropy always increases.
 In the case of a closed system undergoing adiabatic process entropy remain constant or
increase, it will never decrease.
 For a closed system, “every internally reversible adiabatic process is an isentropic process
but all isentropic process is not an internally reversible process” as some cases of internally
irreversible heat rejection process is also an example of isentropic process.
 Entropy of a closed system can increase, decrease & remains constant depending upon the
type of process (Internally reversible/Internally Irreversible) and the type of heat interaction
(heat addition/heat rejection/adiabatic process), but entropy of universe can never decrease.

Q. If a closed system is undergoing an irreversible process, the entropy of the system:

a. must increase c. must decrease

b. always remains constant d. Can increase, decrease or remain constant

Q. A system undergoes a state change from 1 to 2. According to the second law of thermodynamics,
for the process to be feasible, the entropy change, S₂-S, of the system

a. is positive or zero c. is zero

b. is negative or zero d. can be positive, negative or zero

physical meaning of entropy:

Entropy is related to the predictability of the position of the molecules. As the system molecules
becomes more disordered, the position of molecules becomes less predictable and entropy
Increases.

Entropy can be defined as the measure of molecular randomness or molecular disorderness.

Work interaction and entropy:

Work interaction is organized form of energy. Work is free from disorderness or randomness and
thus free of entropy.
Entropy of universe:

 Entropy is an extensive property.

 Entropy generation with the universe is equal to the entropy change of the universe which is
further equal to the summation of entropy change of system and entropy change of
surrounding
∆ S uni=∆ S sys +∆ S surr
¿
δQ
∆ S uni=∫ + S gen
T
∆ S uni=∫ 0+ S gen
∆ S uni=S gen ≥ 0

“Entropy transfer” for closed system undergoing constant temperature heat interactions:

 Entropy transfer for a closed system undergoing constant temperature heat interaction can
be calculated by evaluating (Q/T).
2
δQ
St =∫
1 T
2
1 Q 1−2
St = ∫ δQ=
T 1 T
 Entropy transfer to the system is taken as positive where as entropy transfer from the system
is taken as negative.
Entropy transfer ¿ the system→ heat added ¿ the system →+ve
Entropy transfer ¿ the system→ heat rejected by the system→−ve
Source Sink Plane Wall

−Q H + QL Q̇ Q̇
St = St = Ṡt = −
T T TH TL
Δ Ṡ= Ṡt + Ṡ g
For steady state
Ṡt + Ṡ g= Δ Ṡ=0
Ṡ g=− Ṡt
Ṡ g=−
( Q̇ Q̇
−
T H TL )
 Ṡ g=
( T H −T L
TH TL )
Q̇

Q. An amount of 100 kW of heat is transferred through a wall in steady state. One side of the wall is
maintained at 127°C and the other side at 27°C. The entropy generated (in W/K) due to the heat
transfer through the wall is ___

Soln:

Q̇=100 kW
T H =273+ 127=400 K

T L =273+27=300 K

Ṡ g=
( TH TL ) (
T H −T L
Q̇=
400−300
400 ×300 ) 3 W
100 × 10 =83.33( )
K

“Entropy change” for a closed system undergoing “internally reversible” constant temperature
heat interactions:

Q 1−2
Internally reversible = → S g =0 therefore, ∆ S=S t =
T
Source Sink Heat transfer between source
and sink

−Q H +Q L ∆ Ṡ sys=∆ Ṡ source + ∆ Ṡ string +∆ Ṡ sink

∆ S=S t = ∆ S=S t =
T T − Q̇ Q̇
⟹ ∆ Ṡ sys= +0+
TH TL

∆ Ṡ sys=
(
T H −T L
TH TL )Q̇

Q. A Carnot cycle operates on a working substance between two reservoirs at temperatures T1 and
T2, with T > T2. During each cycle, an amount of heat Q, is extracted from the reservoir at T, and an
amount Q is delivered to the reservoir at T2. Which of the following statements is INCORRECT?

a. work done in one cycle is Q1 – Q2

b. Q1/T1 = Q2/ T2
c. entropy of the hotter reservoir decreases

d. entropy of the universe (consisting of the working substance and the two reservoirs) increases

soln:

Q1 Q2
As Carnot engine is our matter of investigation → =
T1 T2
∆ S uni=∆ S source + ∆ S CHE + ∆ S sink

−Q1 Q2
∆ S uni= + 0+ =0
T1 T2
Tds equations (Gibbs equations):
For simple compressible stationary system under going internally reversible process:

δq=du+ pdv …(a)

For closed system undergoing internally reversible process:

δq
ds= … (b)
T
From (a) and (b):

Tds=du+ pdv
From the basic definition of enthalpy

h=u+ pv
dh=d (u+ pv )
dh=du+ pdv + vdp
dh=Tds+ vdp
Tds=dh−vdp