Entropy

Clausius Theorem
A system is taken from equilibrium state i to another equilibrium state f following the reversible path

i-f.

A reversible adiabatic path i-a is drawn through i and also another b-f through f. Then a reversible

isotherm is drawn in such a way that the area under i-a-b-f is equal to the are under i-f.

Applying 1st law,

For process i-f,

Qi-f = Uf - Ui + Wif

For process i-a-b-f,

Qi-a-b-f = Uf - Ui + Wiabf

Since, Wif = Wiabf, Qi-f = Qi-a-b-f

Figure 1 Replacement of a reversible path
by two adiabatics and an isotherm
or, Qi-f = Qia + Qab + Qbf

Now, Qia = Qbf = 0

Therefore, Qi-f = Qbf

So, heat transferred in process i-f is equal to the heat heat transferred in isothermal process a-b.

Thus any reversible path can be substituted by a reversible zigzag path, between the same end states,

consisting of a reversible adiabatic. Such that

the heat transferred during the isothermal

process is the same as that transferred during

the original process.

The smooth closed curve represents a

reversible cycle.

Let the closed cycle be divided into large

Figure 2: Reversible cycle broken into large
number of strips by means of reversible number of Carnot cycles
adiabatics. Each strip may be closed at the top and bottom by reversible isotherms. The original

closed cycle is thus replaced by a zigzag closed path consisting of alternate adiabatic and isothermal

processes, such that the heat transferred during the isothermal processes is equal to the heat

transferred in the original cycle. Thus the original cycle is replaced by a large number of Carnot

cycles. If the adiabatics are close to one another and the number of Carnot cycles are large, the saw-

toothed zigzag line will coincide with the original cycle.

For the elemental cycle abcd dQ 1 heat is absorbed reversibly at T 1 and dQ2 heat is rejected reversibly

at T2.

d Q1 d Q2
=
T1 T2
Heat supplied is posetive, heat rejected is negative .
d Q dQ
∴ 1 + 2 =0
T1 T2
Similarly, for elemental cycle efgh,
d Q3 dQ 4
+ =0
T3 T4
Thus, for the whole cycle,
d Q1 dQ2 d Q3 dQ 4
+ + + +. ..... ..=0
T1 T2 T3 T4
dQ
⇒∮ =0
R T
dQ
The cyclic integral of for a reversible cycle is equal to zero . This is known as Clausius Theorem .
T The

Property of Entropy

R1 and R2 together constitutes a reversible

cycle.

From Clausius Theorem,

dQ
∮T =0
R1 R2
f i
dQ dQ
∴∫ +∫ =0
R iT
1
R2 f T
f i Figure 3: Entropy not path function
dQ dQ
⇒∫ =− ∫
R iT 1
R2 f T
 f
∫ dTQ
Since R1, R2 represents any two reversible paths, Ri is independent of the reversible path

connecting i and f. Therefore, there exists a property of a system whose value at the final state f minus

f
∫ dTQ
i
its value at the initial state i is equal to . This

property is called entropy and is denoted by S.

f
dQ
∴∫ =S f −S i
Ri T

When the two equilibrium states are infinitesimally near

d QR Figure 4: Entropy change during irreversible

=dS process
T

dS is an exact differential because S is a point function and a property.

Entropy From Greek word 'trope' means transformation.

Since entropy is a point or state function, and the entropy change is independent of the path followed,

the non reversible path is to be replaced by a reversible path to integrate for the evaluation of entropy

change in the irreversible process.

f
d Qrev
S f −S i =∫ = ( ΔS )irrev . path
i T

Integration can be performed along reversible

path.

Temprature - Entropy Plot

Figure 5: Area underTs diagram represents heat transfer

Figure 6: Isothermal process on T-s diagram

 f
dQrev
dS= , If {dQrev=0,theproces is reversibleand adiabatic ¿∴ dS=0 or S=constant (Isentropic proces )¿Again, {d¿Qrev=TdS¿∴Qrev=∫TdS=T (Sf−Si)¿
T i

Figure 7: Reversible adiabatic process on Ts diagram

Figure 8: Carnot cycle on Ts diagram

Carnot cycle - Area 1234 represents the net work output per cycle and the area under 4-1 indicates the

quantity of heat added to the system Q1.

Q1 -Q 2 Q2
∴ ηCarnot = =1−
Q1 Q1
T 1 ( S1 -S 4 )−T 2 ( S2 -S3 ) T 1 -T 2 T2
= = =1−
T 1 ( S 1 -S4 ) T1 T1
W net =Q1 -Q2 =( T 1 -T 2 )( S 1 -S4 )

The Inequality of Clausius

For the cycle ABCD, AB be a general process (reversible or irreversible) while other processes in the

cycle are reversible.

Let the cycle be divided into a number of elementary cycles. For one of the elementary cycles,

d Q2
η=1−
dQ

Now, 1−
d Q2
dQ
≤ 1−
d Q2
dQ ( ) rev

⇒
dQ
≥ ( )
d Q2 d Q2
dQ rev

⇒
dQ
≤
( )
dQ
d Q2 d Q2 rev

Now,
( )
dQ
d Q2 rev
=
T
T2
dQ T dQ d Q 2
∴ ≤ ⇒ ≤ ,
d Q2 T 2 T T2
Figure 9 Clausius Inequality

For any process AB, reversible or irreversible.

For a reversible process,

dQrev d Q2
dS= =
T T2
Hence, for any process AB,
dQ
≤dS
T
dQ
Then for any cycle, ∮ ≤∮ dS
T

dQ
∮T ≤0 ( ∵ Entropy is a point function )
This is known as Clausius inequality .
dQ
If ∮ =0 , the cycle is reversible
T
∮ dT Q <0 , the cycle is irreversible
dQ
∮ T >0 , the cycle is impossible since it violates second law .
Entropy principle

For any process undergone by a system,

dQ
≤dS
T
dQ
∴dS ≥
T
dQ ¿∴dS≥0¿For a reversible process dS=0, ∴S=constant¿For a ir eversible or real process, dS>0. The entropy of an isolated system can never decrease.¿¿
If the process is reversible, dS =
T
dQ
For ir eversible process, dS >
T
For an isolated system, energy is always constant and also {dQ=0
This is known as the principle of increase of entropy.

An isolated system can always be formed by including any system and its surroundings within a

single boundary. The system and the surroundings together (are universe or the isolated system)

include everything which is affected by the process.

Entropy may decrease locally at some region within the isolated system, but it must be

compensated by a greater increase of entropy somewhere within the system so that net effect of an

irreversible process is an entropy increase of the whole system. The entropy increase of an isolated

system is the measure of the extent of irreversibility of the process undergone by the system.

Physically, entropy denotes the order of disorder. This particular property will determine whether

a process is possible or not and if possible in which direction.

Transfer of heat through a finite temperature difference

 Q
For A, ΔS A =−
T1
Q
For B, ΔS B=
T2
Q Q
ΔS univ= ΔS A +ΔS B=− +
T1 T2
Since, T1>T2, ΔS univ is positive and the process is irreversible .
If T1=T2, ΔS univ =0 , process is reversible.
If T1<T2, ΔS univ is negative and the process is not possible .

Mixing of two fluids

When the partition is removed, the two fluids mix together, and at equilibrium t f will be the final

temperature, t2<tf<t1.

m1 c 1 ( t 1 -t f )=m2 c 2 ( t f -t 2 )
m1 c 1 t 1 +m2 c 2 t 2
∴tf =
m1 c 1 +m2 c 2

Entropy change

Tf T
dQ
f
m1 c 1 dT Tf t f +273
ΔS 1 =∫ =∫ =m1 c 1 ln =m1 c 1 ln
T T T1 T T1 t 1 +273
1
Tf
m2 c2 dT Tf
ΔS 2 =∫ =m2 c 2 ln
T2
T T2
Tf Tf
∴ ΔSuniv = ΔS 1 +ΔS 2 =m1 c 1 ln +m2 c 2 ln
T1 T2
Now, if m 1 =m2 =m, c1 =c 2=c
2
Tf T +T
ΔS univ=mc ln and T f = 1 2
T 1 T2 2
 T 1 +T 2
2
ΔS univ=2 mc ln
√ T1 T 2

Which is always positive since A.M. ≥ G.M.

Maximum work obtainable from two finite bodies at temperature T1 and T2

Let us consider two identical bodies of constant heat capacity at temperature T 1 and T2 respectively

(T1>T2). If the bodies are merely bought together into thermal contact, delivering no work, the final

temperature reached would be maximum

T 1 +T 2
Tf=
2 If a heat engine is operated then we get some work.

Let Tf be the final temperature when the engine will stop.

Q1 =C p ( T 1 -T f ) , Q2 =C p ( T f -T 2 )
∴ W=Q 1−Q2 =C p ( T 1 +T 2 -2T f ) -------(2 )

Entropy change,
 Tf T
dQ
f
C p dT Tf t f +273
ΔS 1 =∫ =∫ =C p ln =C p ln
T T T T T1 t 1 +273
1 1
Tf
C p dT Tf
ΔS 2 =∫ =C p ln
T2
T T2
Tf Tf T 2f
∴ ΔS univ = ΔS 1 +ΔS 2 =C p ln +C p ln =C p ln
T1 T2 T1T2
∵ ΔS univ ≥0
T 2f
∴ C p ln ≥0 -------- (3)
T 1 T2

From eqn (1), it is seem that W is maximum, when Tf is minimum.

From eqn (2), Tf to be minimum,

T 2f T 2f
c p ln =0 ⇒ ln =ln 1 ∴ T f =√ T 1 T 2
T1 T 2 T1 T 2
W to be maximum, T f will be √ T 1 T 2
2
∴ W max =c p ( T 1 +T 2 -2 √ T 1 T 2 ) =c p ( √ T 1 −√ T 2 )

T 1+ T 2
Final temperature ranges from to √ T 1 T 2 .
2

1st law and 2nd law combined

d Qrev =Tds
Second law :-
First law, for closed non flow system,
d Q=dU+pdv ∴ TdS=dU+pdv

Again, enthalpy,

H=U +pv
∴dH=dU+pdv +vdp
=TdS+vdp
∴TdS=dH-vdp

Problems on entropy Clausius inequality

Problem 1: An inventor claims to have designed a heat engine which absorbs 1500 kJ and 150 kJ

energy as heat from reservoirs at 1000K and 300K respectively and rejects 600 kJ energy as heat to

reservoir at 600K. It delivers 1050 kJ work. Justify whether the claim is acceptable or not.

Soln :

First law, ∮ δQ=∮ δW ------ ok satisfied

δQ
Clausius inequality, ∮ ≤0
T
δQ
Now, ∮ =1 , violates Clausius inequality (2nd law)
T
Hence impossible .

Problem 2: A reversible heat engine as shown in the figure absorbs 2700 kJ from a reservoir at 900K

and rejects 2500 kJ to a reservoir at 500K. Determine the heat interaction with the reservoir at 300K

and the net work delivered by the engine. (Ans :- Q=600 kJ, W=800 kJ)
Problem 3: The latent heat of vaporization of water is 2114.3 kJ/kg and 1716.2 kJ/kg at 150°C and

250°C respectively. Calculate the change in entropy associated with the vaporization process at 150°C

and 250°C. (Ans :- 4.9966 kJ/kgK, 3.2805 kJ/kgK)

Problem 4: Two kg of water at 80°C are mixed adiabatically with 3kg of water at 30°C in a constant

pressure process of 1 atmosphere. Find the increase in the entropy of the total mass of water due to the

mixing process (cp of water =4.187 kJ/kgK). (Ans : 0.0576 kJ/K)

SELECTED PROBLEMS ON ENTROPY

Problem 4. 1: A heat engine receives 1130 kW of heat from a source maintained at 292 0C and rejects
to a sink at 50C. Regarding heat rejection, the following results were reported: (a) 278 kW of heat is
rejected, (b) 834 kW of heat is rejected and (c) 556 kW of heat is rejected. In each case, examine
whether the cycle is reversible, irreversible or impossible.
Ans. (a) impossible, (b) irreversible and (c) reversible cycle
Problem 4.2: One kg of ice at -200C is exposed to the atmosphere which is at 200C. The ice melts and
comes into thermal equilibrium with the atmosphere. Calculate the entropy change of the universe.
Take latent heat of fusion of ice as 334 kJ/kg and cp of ice as 2.093 kJ/kg-K. Ans. 0.109 kJ/K
Problem 4.3: An iron block of mass 50 kg at 500 K is put into a lake which is at temperature of 285
K. Calculate the entropy changes of iron block and the lake. Also, Calculate the entropy change of the
universe. Ans. -12.65 kJ/K, 16.97 kJ/K, 4.32 kJ/K
Problem 4.4: Calculate the minimum work required to chill 2 kg of water from a temperature of 25 0C
to 20C. Take cp of water = 4.184 kJ/kg-K and ambient temperature = 250C. Ans. 7.83 kJ
Problem 4.5:1 kg of water is brought into contact with a heat reservoir at 90 0C. As a result, water
temperature becomes 900C. Calculate the entropy changes of water, the hot reservoir and the universe.
Now, if water is heated from 0 0C to 900C in two steps, first by bringing in contact with a reservoir at
400C and then with another reservoir at 900C, what will be the entropy change of the universe? What
conclusion can you draw from this observation?
Ans. 1.193 kJ/K, -1.038 kJ/K, 0.155 kJ/K,0.0842 kJ/K
Problem 4.6: During isothermal heat addition process of Carnot cycle, 800 kJ heat is added to the
working fluid from a source at 5270C. Determine the entropy changes of the source, working fluid and
the universe. Ans. -1.0 kJ/K, 1.0 kJ/kg, 0.0
Problem 4.7: The heat capacity of a particular system maintained at constant volume is given by ,
C V = A+2 BT
,where A = 0.014 J/K and B = 4.2×10-4 J/K2. The system is originally at 100 0C and a
thermal reservoir at 00C is available. What is the maximum amount of work that can be obtained as
the system is cooled down to the temperature of the reservoir? Ans. 4.508 J
Problem 4.8: If the temperature of the atmosphere is 5 0C on a winter day and if 1 kg of water at 90 0C
is available, find the maximum amount of work that can obtained. take c v of water as 4.186 kJ/kg-K
Problem 4.9: A reversible engine works between three thermal reservoirs A, B and C. The engine
absorbs equal amount of heat from the thermal reservoirs A and B kept at temperatures T A and TB
respectively, and rejects heat to a thermal reservoir C kept at temperature T C. The efficiency of the
engine is α times the efficiency of the reversible engine which works between the two reservoirs A
TA TA
= (2 α−1 ) +2 ( 1−α )
TB TC
and C. Prove that .
Problem 4.10: Ten grams of water at 200C is converted into ice at -100C at constant atmospheric
pressure. Assuming the specific heat of liquid water to remain constant at 4.2 J/gm-K and that of ice
to be half of this value, and taking the latent heat of fusion of ice at 0 0C to be 335 J/gm, calculate the
total entropy change of the system. Ans. 16.02 J/K
Problem 4.11 A thermally insulated 50-ohm resister carries a current of 1A for 1 second. The initial
temperature of the resistor is 10 0C. Its mass is 5 gm and its specific heat is 0.85 J/gm-K. Find
entropy change of the register and also that of the universe. Ans. 0.173 J/K, 0.173 J/K

Problem 4.12: Show that the minimum theoretical work input required by a refrigeration cycle to
bring two finite bodies from the same initial temperature to the final temperatures of T1 and T2 (T1<T2)
W min=mc [ 2 √ T 1 T 2 −T 1 −T 2 ]
is given by .
Problem 4.13 A gear box operating at steady state receives 0.1 kW along the input shaft and delivers
0.095 kW along the output shaft. The outer surface of the gear box is at50 0C, For the gear box,
determine the rate of heat transfer and the rate at which entropy is generated.
Ans.0.005 kW, 1.54×10-5 kW/K
Problem 4.14: An aluminium block (cp = 400 J/kg-K) with a mass of 5 kg is initially at 40 0C. It is
cooled reversibly by transferring heat to a completely reversible cyclic heat engine until the block
reaches 200C. The 200C room air serves as a constant temperature sink for the engine. Compute (i) the
change in entropy for the block, (ii) the change in entropy for the room air and the work done by the
engine. Also, calculate the entropy change of the block and the entropy change of the universe, if the
block is allowed to cool by natural convection to the room air temperature.
Ans. -132.06 J/K, 132.06 J/K, 1306 J,-132.06 J/K and 4.46 J/K
Problem 4.15: Calculate the entropy change of the universe as a result of the following processes: (i)
A copper block of 600gm mass with cp of 400 J/kg-K) at 1000C is placed in lake of 80C, (ii) The
same block at 80C is dropped from height of 100m into the lake and (iii) Two such block 100 0C and
00C are joined together. Ans. 6.63 J/K, 2.09 J/K and 3.64 J/K

Sin −Sout +S gen = ΔS system

dS system
Ṡin − Ṡout + Ṡ gen =
dt
 Qk
S gen =ΔS system −∑
Tk

Q
ΔS CV = + mi si −me s e + S gen
T

d (S CV ) Q̇
=∑ k + ∑ ṁi s i−∑ ṁe s e+ Ṡ gen
dt Tk

UNDER STEADY STATE

Q̇k
Ṡ gen =∑ ṁe s e−∑ ṁi si −∑
Tk