JSPM’s Rajarshi Shahu College of Engineering,Pune - 033
Department of Mechanical Engineering
Thermodynamics (ME2203T)
UNIT- 4
Second Law of Thermodynamics
Prof.A.R.Devshette
Mech. Engg. Dept.
RSCOE, Pune
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 imposible 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 contant. 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.
It was first stated by the German physicist R. J. E.
Clausius inequality Clausius (1822–1888), one of the founders of
thermodynamics, and is expressed as
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.
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.
Clausius theorem
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 system from
T1=400 K 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.
Adiabatic Process (Reversible)
This shows that there is no change in entropy
and hence it is known as isentropic process. Fig.
represents an adiabatic process. It is a vertical
line (1-2) and therefore area under this line is nil.
Hence heat supplied or rejected and entropy
change is zero.
Summary of Formulae
END OF UNIT 4
THANK YOU
