CLAUSIUS INEQUALITY

Rev. adiabatic

B
A

P C

dQ2 T2

Fig.2.15 Clausius inequality

Let us consider a cycle ABCD (Fig. ) let AB be a general process either reversible (or)
irreversible, TT while the other processes in the cycle are reversible. Let the cycle be divided into
a number of elementary cycles, as shown for one of these elementary cycles.
dQ2
 =1 -  2.12
dQ1
where, dQ is the heat supplied at T1 & dQ2 is the heat rejected at T2. Now the efficiency of a
general cycle will be equal to (or) less than the efficiency of a reversible cycle.
dQ2  dQ2 
1- ≤ 1    2.13
dQ1  dQ1  rev

dQ2  dQ2 
(OR)   
dQ  dQ  rev
dQ  dQ 
OR  
dQ2  dQ2  rev
 dQ  T
Since,   
 dQ2  rev T2
dQ T dQ dQ2
 OR  for any process AB, reversible (or) irreversible.
dQ2 T2 T T2
dQrev dQ2
For a reversible process = dS = 
T T2
dQ
Hence for any process AB =  ds
T
dQ
Then for any cycle =   ds
T
Since entropy is a property & the cyclic integral of any property is zero.
dQ
 0  2.14
T
This equation is known as the clausius inequality. It provides the criterion of the reversibility of a
cycle. If,
 dQ
  0 , the cycle is reversibility.
T
dQ
  0 , the cycle is irreversible and possible.
T
dQ
  0 , the cycle is impossible, since it violates the second law.
T

2.24 STATEMENT:
When a system operates on a cycle (reversible (or) irreversible) having heat interaction
with the number of heat reservoirs than the algebraic sum of quotients of heat transfer from heat
reservoirs to their respective absolute temperature is always equal to (or) less than zero.

2.25 ENTROPY
2.25.1 INTRODUCTION:
The first law of thermodynamics deals with the property energy and the conservation of
it. The second law back to the definition of a new property called Entropy. Entropy is a
somewhat abstract property and it is difficult to give a physical description of it without
considering the microscopic state of the system. Entropy is best understood and appreciated by
studying it uses in commonly encountered engineering processes and this is what we intent to do.

2.25.2 DEFINITION:
Entropy is a function of “a quantity of heat which shows the possibility of conversion of
heat into work. The increase in entropy is small when heat is added at a high temperature is
greater when heat addition is mode at a lower temperature. Thus for maximum entropy, there is
minimum availability for conversion into work and for minimum entropy there is maximum
availability for conversion into work.

2.25.3 ENTROPY – A PROPERTY OF A SYSTEM:

P A 2

1
C

Fig. 2.16

Refer figure 2.16. Let us consider a system undergoing a reversible process from state 1
to state 2 along path A and then from state 2 to the original state 1 along path B. Applying the
clausius theorem to this reversible cyclic process, we have
 dQ
 0
T  2.15
R
Hence, when the system passes through the cycle 1-A-2-B-1, we have
2 1
dQ dQ
   0
1( A ) T 2( B) T

Now, consider another reversible cycle in which the system changes from state 1 to state 2 along
path A1 but returns from state 2 to the original state 1 along a different path C. For this
2 1
dQ dQ
   0
1( A ) T 2(C ) T

subtracting equation = from equation = We have

1 1
dQ dQ
    0 OR
2( B ) T 2(C ) T
2( B ) 2(C )
dQ dQ
1 T  1 T
As no restriction is imposed on paths A & B, except that they must be reversible, the quantity
dQ
is a function of the initial and final states of the system and is independent of the path of the
T
process. Hence it represents a property of the system. This property is known as the “Entropy”.
Change in Entropy in Reversible process:
Refer figure above :
Let S1 = Entropy at the inlet state 1 and
S2 = Entropy at the final state 2.
Change in entropy is given by
2
 dQ 
S2 – S1 =     2.16
1  T  R
The above equation may be written as
 dQ 
dS =    2.17
 T R
where dS is an exact differential.
Change in entropy in Irreversible Process: P A 2

Let 1 – A – 2 = Reversible process;

1
2 – B - 1 = Irreversible process B
2 1
dS   dS 
1( A )
R   dS 
2( B )
I 0 V

Fig. 2.17
( I represents the irreversible process).
2
 dQ 
From equation  dS   
1  T R
 2 1
 dQ 
     dS I  0  (2.18)
1( A )  T  R 2( B )

Hence, the cycle forms an irreversible cycle, applying clausius equality to the above expression,
we get
2 1
dQ  dQ   dQ 
          0  (2.19)
T 1( A )  T  R 2( B )  T  I

Now subtracting equation 2.19 from equation 2.18. we get,

1 1

 dS I    dQ 
2( B ) 2( B )  T  I

which for infinitesional changes in states can be written as

dS I    dQ  
 T I
The equation represents change in entropy for irreversible process.
Generally, we can write
dQ
dS   2.20
T
Where equality sign stands for reversible process; inequality sign stands for irreversible process.

2.25.4 CHANGE OF ENTROPY FOR AN IDEAL GAS:

Let 1 kg of gas at a pressure P1, Volume V1, absolute temperature T1 and entropy S1, be heated
such that its final pressure, Volume, absolute temperature and entropy are P2, V2, T2 and S2
respectively. Then by law of conservation of energy.
dQ = dU + dW  2.21
where
dQ = Small change of heat;
dU = Small internal energy
dW = Small change of work done (Pdv)
dQ = (vdT + Pdv)

Dividing both sides by T, we get

dQ CvdT PdV
   2.22
T T T
dQ P R
But  dS and PV = RT = 
T T V
CvdT RdV
Hence, dS = 
T V
Integrating both sides, we get
S2 T2 V 2
dT dV
 dS = Cv   R
S1 T1
T V1
V
 S2 – S1 = Cv loge T2 + R loge V2
T1 V1
We have
P1V1 P2V2

T1 T2
T2 P2V2

T1 P1V1
Substituting the value of T2 / T1 in equation, we get
PV V
S2 – S1 = Cv loge 2 2  R log e 2
P1V1 V1
P V V
=Cv loge 2  Cv log e 2  R log e 2
P1 V1 V1
P2 V2
S2 – S1 = Cv loge  (Cv  R) log e
P1 V1
P2 V2
S2 – S1 = Cv loge  Cp log e  2.23
P1 V1
Again, we have
V2 P1T2

V1 P2T1
V2
Substituting the value of in equation
V1
T PT
S2 – S1 = Cv loge 2  R log e 1 2
T1 P2T1
T2 P1 T
=Cv loge  R loge  R log e 2
T1 P2 T1
T2 P2
= (Cv + R) loge  R loge
T1 P1
T2 P2
S2 – S1 = (Cv + R) loge  R loge
T1 P1
 2.24
2.26 ENTROPY FOR NON FLOW PROCESSES:
2.26.1 CONSTANT VOLUME PROCESS: Fig.2.18
V=C
T2 2

T1 1
Q
T

S1 S2
S
Fig. 2.18
Consider Heating process of 1 kg of gas. Then Q = Cv (T2 – T1)
Differentiating
dQ = CvdT
Divided by T.
dQ dT dT
 Cv  dS  Cv  2.25
T T T
Integrate both sides, we get
S2
dT
 dS  Cv 
S1
T
S2 – S1 = Cv loge T2 / T1  2.26

2.26.2 CONSTANT PRESSURE PROCESS: Fig.2.19

V=C P=C
Consider 1 kg of gas be heated at constant pressure.
T2 2
Q = Cp (T2 – T1)
T1 1
Q
Tn
For small increase dQ = Cp (dT)
S1 S2
Divided by T S
Fig. 2.19
dQ dT dT
 Cp  dS  Cp
T T T
Integrate both sides, we get
S2 T2
dT
 dS  Cv  T
S1 T1

S2 – S1 = Cp loge T2 / T1  2.27

1 2
T1=T2
Q
T

S1 S2
S
Fig. 2.20

2.26.3ISOTHERMALPROCESS: Fig.2.20
In constant temperature process
Q = W

Here, 1
T1
S2

Q =  TdS  T (S 2  S1 ) T2 2
S1
T
V2 V
W = P1V1 loge = RT1 loge 2 per kg of gas. S1=S2
V1 V1 S

V2 Fig. 2.21
T (S2 – S1) = R T1 loge
V1
V2
(S2 – S1) = R loge  2.28
V1
2.26.4 ADIABATIC PROCESS (REVERSIBLE) Fig. 2.21
During an adiabatic process as heat is neither supplied nor rejected.
dQ
dQ = 0 OR 0 OR dS = 0  2.29
T
This shows that there is no change in entropy and hence it is known as Isentropic process.

2.26.5 POLYTROPIC PROCESS: Figure 2.22 T1 1

The expression for entropy change in polytropic process (PVn = C) T2

2
Q
can be obtained from equation T

S1 S2
T V
(S2 – S1) = Cv loge 2  R loge 2 S
T1 V1 Fig. 2.22
 2.30

2.26.6 PRINCIPLE OF INCREASE OF ENTROPY:

Consider a cycle in which the system is taken from state 1 to 2 by an arbitrary process
(Reversible (or) irreversible) along the path A and the cycle is completed by a reversible process
by bringing the system from state 2 to 1 along the path R as shown in figure.
Applying clausius inequality,
dQ
 0
T
2A 1R
dQ dQ
i.e.   0 …. (i)
1A T 2R T
Assume that during the arbitrary process A the system absorbs heat from a heat reservoir
(surroundings) at temperature T, the entropy of surroundings will decrease by an amount given
by the equation.
2A
dQ
1A T   (S ) surr. …. (ii)
Since the process (2R) is reversible, it implies that the temperature of the system and
surroundings at any instant is same and the heat energy will be transferred from the system to the
surroundings during this process. Therefore, the entropy of the system will decrease and it is
given as,
1R
dQ
2 R T   (S ) system …. (iii)

Substituting (ii) and (iii) in (i)

- (S) surr - (S) system ≤ 0
OR
(S) surr - (S) system ≥ 0
(S) Universe ≥ 0  2.31
Above equations show that the entropy change of the system and its surroundings (i.e. for
Universe) during any process between two equilibrium states is always greater than (or) equal to
zero. This is known as “Principle of increase of entropy”.
Note: If the system is assumed to be isolated from its surroundings, then (S) Universe=0.
Reduces to (S) Isolated system ≥ 0