Unit II

Unit : II Entropy
 CARNOT CYCLE
The cycle was first suggested by a French engineer Sadi Carnot in 1824 which works on
reversible cycle and is known as Carnot cycle.
Carnot cycle which is performed in an engine cylinder the head of which is supposed
alternatively to be perfect conductor or a perfect insulator of a heat.

The assumptions made for describing the working of the Carnot engine are as follows :
(i) The piston moving in a cylinder does not develop any friction during motion.
(ii) The walls of piston and cylinder are considered as perfect insulators of heat.
(iii) The cylinder head is so arranged that it can be a perfect heat conductor or perfect heat
insulator.
(iv) The transfer of heat does not affect the temperature of source or sink.
(v) Working medium is a perfect gas and has constant specific heat.
(vi) Compression and expansion are reversible.
Stage 1. (Process 1-2). Hot energy source is applied. Heat Q1 is taken in whilst the fluid
expands isothermally and reversibly at constant high temperature T1.

Stage 2. (Process 2-3). The cylinder becomes a perfect insulator so that no heat flow takes
place. The fluid expands adiabatically and reversibly whilst temperature falls from T1 to T2.

Stage 3. (Process 3-4). Cold energy source is applied. Heat Q2 flows from the fluid whilst it is
compressed isothermally and reversibly at constant lower temperature T2.

Stage 4. (Process 4-1). Cylinder head becomes a perfect insulator so that no heat flow occurs.
The compression is continued adiabatically and reversibly during which temperature is raised
from T2 to T1.
The work delivered from the system during the cycle is represented by the enclosed area of the
cycle. For a closed cycle, according to first law of the thermodynamics the work obtained is
equal to the difference between the heat supplied by the source (Q1) and the heat rejected to the
sink (Q2).

The Carnot cycle cannot be performed in practice because of the following reasons :
1. It is impossible to perform a frictionless process.
2. It is impossible to transfer the heat without temperature potential.
3. Isothermal process can be achieved only if the piston moves very slowly to
allow heat transfer so that the temperature remains constant. Adiabatic process
can be achieved only if the piston moves as fast as possible so that the heat
transfer is negligible due to very short time available.
 CARNOT’S THEOREM
“It states that of all engines operating between a given constant
temperature source and a given constant temperature sink, none
has a higher efficiency than a reversible engine”.

• The efficiency of an irreversible

heat engine is always less than
the efficiency of a reversible one
operating between the same two
reservoirs.

• The efficiencies of all reversible

heat engines operating between
the same two reservoirs are the
same.
 Clausius theorem
• It was first stated by the German physicist R. J. E. Clausius (1822–
1888), one of the founders of thermodynamics
• Consider a closed curve ABCDA
representing a reversible cycle.
• Dividing this curve into number of
strips with the help of reversible
adiabatic.
• Close the two successive reversible
adiabatic process at the top and
bottom by reversible isothermal
processes.
• Therefore original reversible cycle
is replaced by number of Carnot
cycles.
Consider the first carnot cycle
 Q1
Let, represents heat added to the cycle from heat reservoir at temp T1
T1
 Q2
during isothermal process. Also, represent heat rejected from the cycle
T2
from heat reservoir at temp T2 during isothermal process.
 Q1  Q2
For Carnot cycle  (But  Q2 is negative since it is rejected)
T1 T2
 Q1  Q2  Q1  Q2
  i.e.  0
T1 T2 T1 T2
 Q3  Q4
Simiarly for other cycles  0
T3 T4
So adding up all the equations
 Q1  Q2  Q3  Q4
   0
T1 T2 T3 T4
Q
  0
RT
 The cyclic intergral of for reversible cycle is zero.
This is know as "Clausius Theorem". Above equation
is only valid for reversible cycles.
 Clausius inequality
The thermal efficiency of a reversible Carnot engine is
 Q2 T
 =1  1  2
 Q1 T1
As per Carnot theorem the efficiency of an irreversible engine (I) cannot
be greater than reversible engine (R) when both operate between same
fixed temperature limits.
 I  R
  Q2    Q2 
1    1  
  Q1  I   Q1  R
  Q2   T2 
1    1  
  Q1  I  T1  R
Q T
 2 2
 Q1 T1
  Q2  Q1
 
T2 T1
 Q1  Q2
  0
T1 T2
 Q1   Q2 
    0 (Since  Q2 is negative)
T1  T2 
 Q1  Q2
  0
T1 T2
Q
 T 0 1

Equation (1) shows that the algebraic sum of quotients of heat transfer
from heat reservoirs to their respective temperatures is either equal to or
less than zero for a system undergoes a cycle. It is known as “Clausius
Inequality”
Statement of Clausius Inequality
When a system operates on a cycle (reversible or
irreversible) having heat interactions with number of heat
reservoirs then the algebraic sum of quotients of heat
transfer from heat reservoirs to their respective absolute
temperatures is always equal to or less than zero.
Q
 T 0 (For Reversible cycle)

Q
 T 0 (For Irreversible cycle)

Q
 T 0 (It is impossible for any cycle)
Entropy –A property of the system
With the help of Clausius inequality we can derive as a
consequence of second law of thermodynamics a significant
property called as “Entropy”
Consider a reversible cycle
carried out along a path A and B
between state 1 and 2 as shown
in figure.
Applying Clausius inequality
equation to reversible cycle
1A2B1.
2A 1B
 Q   Q 
 
1A 
    0
T  R 2B  T  R
(i)
Now consider another reversible cycle 1A2C1 defined between the
same end states and applying Clausius inequality we get,
2A 1C
 Q   Q 
 
1A 
    0
T  R 2C  T  R
(ii)

Substracting equation (ii) from (i)

1C 1B
 Q   Q 
 
2C 
    0
T  R 2B  T  R
1C 1B
 Q   Q 
 
2C 
    (By changing the limits)
T  R 2B  T  R
2B 2C
 Q   Q 
 
1B 
T
  
 R 1C  T

R
Since no restriction were imposed except that the paths B and C
 Q 
represents reversible processes, it follows that  
T R is the function of
end state only and it is independent of path followed.
  Q 
Hence  T  R represents a property of the system and this property is called as
Entropy and it is denoted by ‘S’. Therefore the change in entropy.
 Q 
dS  
 T R
If system undergoes a process from state 1 to 2
2 2
 Q 

1
dS 
1  T

R
2
 Q 
S 2  S1 S   Unit kJ/KgK
1  T R

From above equation it is clear that the definition of Entropy is for a change and not
for a absolute value. In order to evaluate the absolute value of entropy some datum
may be chosen to represent zero value of entropy and then numerical vale can be
assigned to the value of entropy at any other state.
Entropy is a measure of the degree of randomness of molecules comprising by
system. Higher the disorder greater is the increase of entropy.
One of the most useful application of Clausius inequality is to decide whether a cyclic
device (engine or heat pump or refrigerator) exchanging heat with more than two
reservoir is possible or not.
 ENTROPY
It may be noted that all heat is not equally valuable for converting into work. Heat
that is supplied to a substance at high temperature has a greater possibility of
conversion into work than heat supplied to a substance at a lower temperature.

“Entropy is a function of a quantity of heat which shows the possibility of conversion

of that heat into work. The increase in entropy is small when heat is added at a high
temperature and is greater when heat addition is made 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.”
Entropy—A Property of a System
Let us consider a system undergoing a reversible process from state 1 to state 2
along path L and then from state 2 to the original state 1 along path M. Applying
the Clausius theorem to this reversible cyclic process, we have

…….1

…….2
Subtracting equation 2 from 1
 Change of Entropy in a Reversible Process

…..1

if the two equilibrium states 1 and 2 are infinitesimal near to each other, the integral
sign may be omitted and S2 – S1 becomes equal to dS.

…..2

infinitesimals have been used to express the idea of objects so small that there is no
way to see them or to measure them.
 Thus, from equation 2, we find that the change of entropy in a reversible process is

Equation 2, indicates that when an inexact differential δQ is divided by an integrating

factor T during a reversible process, it becomes an exact differential.

For steam, the reference point at which the entropy is given an arbitrary value of zero
is 0°C and for refrigerants like ammonia, Freon-12, carbon dioxide etc. the reference
point is – 40°C, at which the entropy it taken as zero.

In practice we can determine the change in entropy and not the absolute value of
entropy.
 THE PRINCIPLE OF INCREASE OF ENTROPY (ENTROPY AND IRREVERSIBILITY)

…..1

Let us now find the change in entropy in an irreversible process.

Consider a closed system undergoing a change from

state 1 to state 2 by a reversible process 1-L-2 and
returns from state 2 to the initial state 1 by an
irreversible process 2-M-1 as shown in Fig on the
thermodynamic coordinates, pressure and volume.

….2
Now for a reversible process, from eqn. 1, we have

….3

2, we have

…4

Again, since in eqn. 2, the processes 1-L-2 and 2-M-1 together form an irreversible
cycle, applying Clausius equality to this expression, we get

…5

Now subtracting eqn. 5 from eqn. 4, we get

….6
Eqn. 6, states that the change in entropy in an irreversible process is greater than

Combining eqns. 5 and 6, we can write the equation in the general form as

….7

where equality sign stands for the reversible process and inequality sign stands for
the irreversible process.
It may be noted here that the effect of irreversibility is always to increase the
entropy of the system.

Let us now consider an isolated system. We know that in an isolated system,

matter, work or heat cannot cross the boundary of the system. Hence according to
first law of thermodynamics, the internal energy of the system will remain
constant.

Since for an isolated system, δQ = 0, from eqn. 7, we get

….8
Eqn. 8, states that the entropy of an isolated system either increases or remains
constant. This is a corollary of the second law. It explains the principle of increase
in entropy.
 Numericals
1. A heat engine receives heat at the rate of 1500 kJ/min and gives an output of
8.2 kW. Determine :
(i) The thermal efficiency ; (ii) The rate of heat rejection.
2. Find the co-efficient of performance and heat transfer rate in the condenser of a
refrigerator in kJ/h which has a refrigeration capacity of 12000 kJ/h when power
input is 0.75 kW.
Sol.
3. A Carnot cycle operates between source and sink temperatures of 250°C and – 15°C. If
the system receives 90 kJ from the source, find :
(i) Efficiency of the system ; (ii) The net work transfer ; (iii) Heat rejected to sink.
4.
(i)A reversible heat pump is used to maintain a temperature of 0°C
in a refrigerator when it rejects the heat to the surroundings at
25°C. If the heat removal rate from the refrigerator is 1440
kJ/min, determine the C.O.P. of the machine and work input
required.

(ii) If the required input to run the pump is developed by a

reversible engine which receives heat at 380°C and rejects heat to
atmosphere, then determine the overall C.O.P. of the system.
Sol 4(i)
Sol. 4(ii)
 Clausius inequality
5. 300 kJ/s of heat is supplied at a constant fixed temperature of 290°C to a heat
engine. The heat rejection takes place at 8.5°C. The following results were obtained:
(i) 215 kJ/s are rejected.
(ii) 150 kJ/s are rejected.
(iii) 75 kJ/s are rejected.
Classify which of the result report a reversible cycle or irreversible cycle or
impossible results.
6. The heat transfer from a heat reservoir at 400 K takes place by
conduction to a heat Reservoir at 300 K. If the amount of heat
transferred is 4800 KJ, prove that the process Is irreversible with
the help of Clausius Inequality.
Q1=4800 KJ As per the sign convention, heat received by the
T1=400 K system from A heat reservoir at 300 K is positive.
i.e. if heat reservoir looses Heat it is positive and
if heat reservoir gains heat is negative
Applying Clausius inequality,
(Q1/T1) + (Q2/T2) <= 0
T2=300 K

Q2= -4800 KJ LHS = (4800/400) + (-4800/300) = -4 KJ/K

i.e. ∑(Q/T) < 0

Therefore process is irreversible

 TEMPERATURE-ENTROPY DIAGRAM (T-S Diagram)
If working fluid receives a small amount of heat dQ in an elementary portion ab of
an operation AB when temperature is T, and if dQ is represented by the shaded
area of which T is the mean ordinate, the width of the figure must be dQ/T.
.This is called ‘increment of entropy’ and is denoted by dS. The total heat received
by the operation will be given by the area under the curve AB and (SB – SA) will
be corresponding increase of entropy.

“Entropy may also be defined as the thermal

property of a substance which remains
constant when substance is expanded or
compressed adiabatically in a cylinder”.

Note. ‘s’ stands for specific entropy whereas

‘S’ means total entropy (i.e., S = ms).
Fig – Temperature –Entropy diagram
CHARACTERISTICS OF ENTROPY

1. It increases when heat is supplied irrespective of the fact whether

temperature changes or not.

2. It decrease when heat is removed whether temperature changes or not.

3. It remains unchanged in all adiabatic frictionless processes.

4. It increases if temperature of heat is lowered without work being done

as in a throttling process.