ENGINEERING THERMODYNAMICS

Category: Professional Core Course

(Theory and Practice)
Course code: ME234AI
Faculty: Dr P R Venkatesh, Associate Professor, Mech Dept, RVCE, Bengaluru
Room No 2, Ground Floor, Department of Mechanical Engineering, RVCE
Mob: 9620117755 Email: venkateshpr@rvce.edu.in

Dr P R Venkatesh, Mech Dept, RVCE

 Unit II
Irreversibility: Irreversibility and factors of irreversibility, Carnot cycle, Carnot
theorems.
Entropy: Clausius theorem and Inequality, Entropy-property of a system,
Principle of increase of entropy, Change of entropy for different processes,
Exergy and Anergy.

Dr P R Venkatesh, Mech Dept, RVCE

Irreversibility:
• An irreversible process is one that is carried out in such a way that the system and its
local surroundings cannot be exactly restored to their respective initial states at the end
of the reverse process, i.e. a net change occurs in the universe.
• If a process can proceed in one direction only and the reversal of the direction leads to a
violation of the second law of thermodynamics, the process is called an irreversible
process.
• If the driving force between the parts of the system or between the system and the
surroundings is finite in magnitude, the process is irreversible.

Dr P R Venkatesh, Mech Dept, RVCE

 Factors that render a process irreversible:
The following are some of the factors that make a process irreversible.
• Friction due to movement—sliding friction as well as fluid friction
• Inelastic deformation
• Spontaneous chemical reaction
• Heat transfer through a finite temperature difference
• Combustion (formation of new chemical constituents)
• Mixing of substances at different compositions
• Unrestrained expansion of a fluid (gas or liquid) to a lower pressure
• Gas seeping through a porous plug (throttling expansion)
• Magnetic hysteresis of a material
Dr P R Venkatesh, Mech Dept, RVCE
 Classification of Irreversible Process
The following are some of the types of reversibility;
(1) Mechanical irreversibility: The dissipation of work (mechanical work) into
internal energy either in a system or of a surroundings may be due to the
phenomena as viscosity (fluid friction among the molecules), friction (mechanical
friction between surfaces), inelasticity, electric resistance and magnetic
hysteresis.
(2) Thermal irreversibility: Thermal irreversibility is associated with transfer of
heat between a system and surroundings by virtue of a finite temperature
difference.
(3) Internal irreversibility: Internal irreversibility is associated with fluid friction
(rubbing of one layer of gas over the other and turbulence) and temperature
difference variations within the fluid. Combustion and diffusion cause internal
irreversibility.
Dr P R Venkatesh, Mech Dept, RVCE
(4) External irreversibility: External irreversibility is due to friction at the
bearings and between the atmosphere and rotating members. All these absorb
some work developed by the system.

(5) Irreversibility due to dissipative effect:

Irreversibility of a process may be due to dissipative effects in which work done
on a system, instead of increasing the P.E. and K.E. of the system (high grade
energies) if it increases the molecular internal energy of the system, i.e. heat
energy (considered as low grade energy) increasing the temperature of the
system, then the work is said to be dissipated.
The energy which is dissipated cannot be recovered and becomes an
unavailable energy. Dissipative effects may be due to viscosity, friction,
inelasticity, electric resistance, etc. Due to dissipative effect, work is lost.
Dr P R Venkatesh, Mech Dept, RVCE
 Carnot cycle
• The Carnot cycle is a hypothetical cycle
developed by a French engineer, Sadi Carnot in
1824 for a heat engine or for a reversed heat
engine.
• All the processes involved in the Carnot cycle are
reversible, thereby providing the best possible
device for power development purpose.
• No friction between the piston and the cylinder.
• The walls of the piston and the cylinder are
perfectly insulated.
• The cylinder head is so arranged that it can be a
perfect insulator or a perfect conductor as well.
• A source and sink with infinite quantity of heat at
high and low temperature, respectively.
• A perfect gas is used as a working medium.
Dr P R Venkatesh, Mech Dept, RVCE
Following are the four stages of Carnot cycle :
Stage 1 (Isothermal Expansion Process 1-2):
Hot energy source is applied. Heat Q1 is taken in while
the fluid expands isothermally and reversibly at
constant high temperature T1.
 V1   V1 
Isothermal Expansion work W1−2 = PV
1 1 ln   = RT1 ln   = Q1
 V2   V2 
Stage 2 (Adiabatic Expansion Process 2-3):
The cylinder becomes a perfect insulator so that no
heat flow takes place. The fluid expands adiabatically
and reversibly while temperature falls from T1 to T2.
 p V - p V   R(T1 - T2 ) 
Adiabatic Expansion work W =  2 2 3 3  =  
 γ - 1   γ - 1 

Dr P R Venkatesh, Mech Dept, RVCE

Stage 3 (Isothermal Compression Process 3-4): Cold
energy source is applied. Heat Q2 flows from the fluid
while it is compressed isothermally and reversibly at
constant lower temperature T2.
 V3   V3 
Isothermal compression work W3−4 = PV
3 3 ln   = RT2 ln   = Q2
 V4   V4 

Stage 4 (Adiabatic compression 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.
 p V - p V   R(T2 - T1 ) 
Adiabatic Compression work W4−1 =  4 4 1 1  =  
 γ -1   γ -1 

Dr P R Venkatesh, Mech Dept, RVCE

Net work done during the cycle W = W1−2 +W2−3 +W3−4 +W4−1
 V1  R(T1 - T2 )  V3  R(T2 - T1 )
W = RT1 ln   + + RT2 ln   +
 V2  γ -1  V4  γ -1
 −1
 V1   V3  V2  T2 
W = RT1 ln   + RT2 ln   For the adiabatic process 2-3, = 
 V2   V4  V3  T1 
 −1
V4  T1  V2 V1  V1   V4 
For the adiabatic process 4-1, =   = or   =  
V1  T2  V3 V4  V2   V3 
 V1   V1   V1 
Hence,the net work is W = RT1 ln   − RT2 ln   = R ln   T1 − T2 
 V2   V2   V2 
 V1 
R ln   T1 − T2 
Net Work done W  V2   T1 − T2   T2 
Thermal efficiency is ηth = = = =  = 1- 
Heat input Q1  V1   T1   T1 
RT1 ln  
Dr P R Venkatesh, Mech Dept, RVCE  V2 
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. The isothermal and adiabatic processes
take place during the same stroke therefore the piston has to move very slowly for
part of the stroke and it has to move very fast during remaining stroke. This variation
of motion of the piston during the same stroke is not possible.
Dr P R Venkatesh, Mech Dept, RVCE
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”.
Corollary of Carnot’s theorem:
‘‘The efficiency of all reversible heat engines operating between the same temperature levels
is the same”.

W ( Q1 − Q2 )  Q2   T2 
Reversible Heat engine : thermal = = = 1 −  = 1 − 
Q1 Q1  Q1   T1 
Q1 Q1 T1
Reversible Heat pump : COPheat pump = = =
W (Q1 − Q2 ) (T1 − T2 )
Q2 Q2 T2
Reversible Refrigerator : COPref = = =
W (Q1 − Q2 ) (T1 − T2 )
Dr P R Venkatesh, Mech Dept, RVCE
Numerical problems on Carnot cycle

Dr P R Venkatesh, Mech Dept, RVCE

 Problem 1
A cyclic heat engine operates between a source temperature of 8000C and a
sink temperature of 300C. What is the least rate of heat rejection per kW net
output of the engine?

Data : T1 = 8000 C = (800 + 273) = 1073K , T2 = 300 C = (30 + 273) = 303K , Q2 = ? for W = 1 kW
 T2   303 
Solution : The efficiency of a reversible heat engine is;th =  1 −  =  1 −  = 0.718
 T1   1073 
W  1  1 
Also, for a heat engine,th =  0.718 =   or Q1 =   = 1.394 kW
Q1  Q1   0.718 
For a reversible heat engine,W = (Q1 − Q2 )  1 = (1.394 − Q2 ) or Q2 =0.394 kW
The least rate of heat rejection is Q2 = 0.394 kW
Dr P R Venkatesh, Mech Dept, RVCE
 Problem 2
An inventor claims that his engine has the following data;
Power developed = 30 kW Fuel consumed = 4 kg/hr, Calorific value = 45000
kJ/kg, Operating temperature limits = 750°C, 30°C. Is his claim justified?

Data : T1 = 7500 C = (750 + 273) = 1023K , T2 = 300 C = (30 + 273) = 303K , CV = 45000 kJ / kg
 4  −3
W = 30 kW, Mass of the fuel consumed m f = 4 kg / hr =   = 1.111  10 kg / sec
 3600 
 T2   303 
Solution : The efficiency of a reversible heat engine is;th =  1 −  =  1 −  = 0.704
 T1   1023 
W W  30 
Also, for a heat engine,th = = = −3  = 0.6 < th ,rev
Q1 m f  CV  1.111  10  45000 
Thermal efficiency of heat engine is less than thermal efficiency of reversible heat engine.
Hence, his claim is justified.
Dr P R Venkatesh, Mech Dept, RVCE
 Problem 3
A refrigerator working between 270C and -130C is driven by an electric motor
rated at 1.5 kW. What quantity of ice at 00C can be obtained from water at 200C
in 10 hours. Take cp of ice =2.1 kJ/kg-K, cp of water =4.2 kJ/kg-K.

Data : T1 = 270 C = (27 + 273) = 300 K , T2 = −130 C = ( −13 + 273) = 260 K

W = 1.5 kW, Temperature of ice t1 = 00 C , Temperature of water t2 = 200 C
Time taken for conversion of water into ice t = 10 hrs, mass of ice produced m = ?

Dr P R Venkatesh, Mech Dept, RVCE

  T2   260 
Solution : The efficiency of a reversible refrigerator is; COP =  =  = 6.5
 T1 − T2   300 − 260 
Q2 Q2
Also, for a refrigerator, COP =  6.5 = Q2 = 9.75 kW = 9.75 kJ / sec
W 1.5
Heat removed from water at 200C , to convert into ice at 00C is;
Q = Heat rejected by water from 200C to 00C + Latent heat of fusion of ice
Q = mc p (t2 − t1 ) + mL  9.75 = m[4.18(20 − 0) + 334] or m = 0.02335 kg / sec

[Latent heat of fusion of ice = 334 kJ / kg, Specific heat of water c p = 4.18 kJ / kg − 0 C ]
In 10 hours, amount of ice formed is m = (0.02335  10  3600) = 840.52 kg

Dr P R Venkatesh, Mech Dept, RVCE

 Problem 4
A reversible heat engine operates between two reservoirs at temperatures
700°C and 50°C. The engine drives a reversible refrigerator which operates
between reservoirs at temperatures of 50°C and – 25°C. The heat transfer to the
engine is 2500 kJ and the net work output of the combined engine refrigerator
plant is 400 kJ.
(i) Determine the heat transfer to the refrigerant and the net heat transfer to the
reservoir at 50°C.
(ii) Reconsider (i) given that the efficiency of the heat engine and the C.O.P. of
the refrigerator are each 45 per cent of their maximum possible values.
Dr P R Venkatesh, Mech Dept, RVCE
Data : T1 = 7000 C = (600 + 273) = 973K , T2 = 500 C = (50 + 273) = 323K , T3 = −250 C = ( −25 + 273) = 248K
Heat transfer to engine Q1 = 2500 kJ, Net work output of combined plant W = (W1 -W2 ) = 400 kJ
Solution :
 T2   323 
(i) The efficiency of a reversible heat engine is;th =  1 −  =  1 −  = 0.668
 T1   973 
W1 W1
Also, for a heat engine,th =  0.668 = or W1 = 1670 kW
Q1 2500
W = (W1 -W2 )  400 = (1670 − W2 ) W2 = (1670 − 400) = 1270 kJ
 T3   248  Q4 Q4
COPref =  =
   = 3.31 Also, for a refrigerator, COP =  3.31 = ;  Q4 = 4203.7kJ
 T2 − T3   323 − 248  W2 1270

Q3 = (Q4 + W2 ) = ( 4203.7 + 1270 ) = 5473.7 kJ

Q2 = (Q1 − W1 ) = ( 2500 − 1270 ) = 830 kJ
Heat rejection to the 50°C reservoir = ( Q2 + Q3 ) = (830 + 5473.7) = 6303.7 kJ

Dr P R Venkatesh, Mech Dept, RVCE

(ii) Efficiency of actual heat engine cycle  = 0.45  rev = ( 0.45  0.668) = 0.3
W1 W
Also, for a heat engine,th =  0.3 = 1 or W1 = 750 kW
Q1 2500
W = (W1 -W2 )  400 = (750 − W2 ) W2 = (750 − 400) = 350 kJ
Q4 Q
COPact = 0.45  COPrev = 0.45  3.31 = 1.49 Also, for a refrigerator, COP =  1.49 = 4 ;  Q4 = 521.3 kJ
W2 350
Q3 = (Q4 + W2 ) = ( 521.3 + 350 ) = 871.325 kJ
Q2 = (Q1 − W1 ) = ( 2500 − 750 ) = 1750 kJ
Heat rejection to the 50°C reservoir = (Q2 + Q3 ) = (1750 + 871.325) = 2621.325 kJ

Dr P R Venkatesh, Mech Dept, RVCE

 Problem 5
A heat pump is to be used to heat a house in winter and then reversed to cool
the house in summer. The interior temperature is to be maintained at 20°C.
Heat transfer through the walls and roof is estimated to be 0.525 kJ/s per
degree temperature difference between the inside and outside. (a) If the outside
temperature in winter is 5°C, what is the minimum power required to drive the
heat pump? (b) If the power requirement is same as in part (a) above, what is
the maximum outside temperature for which the inside can be maintained at
20°C?
Dr P R Venkatesh, Mech Dept, RVCE
Data : T1 = 200 C = (200 + 273) = 293K , T2 = 50 C = (5 + 273) = 278 K , T3 = ?
Heat transfer to the room Q1 = 0.525 kJ / sec - K, Work required = ?
Solution :
(a)The minimum power required for the heat pump :
The heat transferred Q1 = 0.525  (T1 − T2 ) = 0.525  (293 − 278) = 7.875 kJ
 T1   293  Q1 7.875
COPheat pump = =
   = 19.53 Also, for a heat pump, COP =  19.53 = ; Wp = 0.403 kJ
 T1 − T2   293 − 278  Wp Wp

(b) Minimum outside temperature (T3 ) :

For the same work input,W pump = WRef = 0.403 kJ
Q4 = 0.525  (T3 − T1 ) = 0.525  (T3 − 293)
Q4 T1  0.525  (T3 − 293)  293
COPref = =   =
WR (T3 − T1 )  0.403  (T3 − 293)
T3 = 308 K

Dr P R Venkatesh, Mech Dept, RVCE

 Problem 6
A heat engine is used to drive a heat pump. The heat transfers from the heat
engine and from the heat pump are used to heat the water circulating through
the radiators of a building. The efficiency of the engine is 27% and the co-
efficient of performance of the heat pump is 4. Evaluate the ratio of the heat
transfer to the circulating water to the heat transfer to the heat engine.

Dr P R Venkatesh, Mech Dept, RVCE

Data : th = 0.27, COPheat pump = 4
W W W
Solution : th =  0.27 = or Q1 = = 3.7W
Q1 Q1 0.27
Q4 Q4
COPheat pump = 4= or Q4 = 4W , Q2 = Q1 − W = ( 3.7W − W ) = 2.7 W
W W
The ratio of the heat transfer to the circulating water to the heat transfer to the heat
Heat transferred to the circulating water  Q2 + Q4   2.7W + 4W 
engine; R = = =  = 1.81
Heat transferred to the heat engine  Q1   3.7W 

Dr P R Venkatesh, Mech Dept, RVCE

 Problem 7
A domestic food freezer maintains a temperature of –15°C. The ambient air
temperature is 30°C. If heat leaks into the freezer at the continuous of 1.75
kJ/s, what is the least power necessary to pump this out continuously?

Data : T1 = 300 C = (30 + 273) = 303 K ,

T2 = −150 C = ( −15 + 273) = 258 K
Q2 = 1.75 kJ / sec
 T   258 
Solution : COPref =  2  =   = 5.733
 T1 − T2   303 − 258 
Q 1.75
Also, COPref = 2  5.733 = or W = 0.305 kW
W W

Dr P R Venkatesh, Mech Dept, RVCE

Assignment Problems:
(1) An ice plant is working on a reversed Carnot cycle. The ice at 0°C is formed
from the water at 0°C. Heat is rejected to the atmosphere at 27°C. A heat
engine drives the refrigerator. The heat engine is maintained at 227°C by
burning fuel of CV 20935 kJ/kg. The work developed by the heat engine is
7.7 kW. Calculate the fuel consumption per hour and tonnes of ice produced
in a day. Take latent heat of fusion of ice L=334.5 kJ/kg.
[Ans: 3.3 kg/hr, 20 tons of ice]

Dr P R Venkatesh, Mech Dept, RVCE

Solution to Data : T1 = (227 + 273) = 500 K , T2 = 270 C = (27 + 273) = 300 K
Assignment T3 = 00 C = (0 + 273) = 273 K , W = 7.7kW , CV fuel = 20935 kJ / kg
Problem 1:
 T3   273 
Solution : The COP of the refrigerator =  =  = 10.11
T1 = 500 K T3 = 273 K
 T2 − T3   300 − 273 
Q3 Q3
Q1 Q3 Also, the COPref =  10.11 = or Q3 = 77.86 kW
W 7.7
W= (Q1 - Q 2 ) Heat extracted = Mass of ice  Latent heat of ice
HE REF
77.86 = mice × 334.5 or mice = 0.2328 kg / sec
Q2 Q4
mice = (0.2328  3600  24) = 20111 kg / day = 20.11 tons
T2 = 300 K T2 = 300 K  T2   300 
The efficiency of a Carnot engine is th =  1 −  =  1 −  = 0.4
 T1   500 
W W  7.7 
Also, for a heat engine,th = =  0.4 = 
Q1 m f  CV  m  20935 
 f 
Hence, Mass of the fuel consumed m f = 9.195  10−4 kg / sec = 3.3 kg / hr

Dr P R Venkatesh, Mech Dept, RVCE

Assignment Problems:

(2) A Carnot heat engine operates between two reservoirs, one is at 600 K and

the other one is at T3 K. The work out from the engine is used to drive a

Carnot refrigerator, which operates between 300°K and T3 K. Calculate

(a) The temperature T3 such that heat supplied to the engine is equal to the

heat absorbed by refrigerator.

(b) The efficiency of Carnot engine and COP of Carnot refrigerator.
[Ans: 400 K, 33.33, 3]
Dr P R Venkatesh, Mech Dept, RVCE
Solution to Data : T1 = 600 K , T2 = 300 K ,
Assignment Heat transfer to engine Q1 = Heat absorbed by refrigerator Q3
Problem 2: Solution :
 T3 
The efficiency of a reversible heat engine is;th =  1 − 
 T1 
T1 = 600 K T2 = 300 K

Q1 Q3
W  T3  W1
W= (Q1 - Q 2 ) Also, for a heat engine,th =   1 −  =
HE REF Q1  T1  Q1
 T3   T1 − T3 
or W = Q1  1 −  = Q1 
Q2 Q4
 (i )
T3  T1   1 T
 T2  Q3  T2  Q3
COPref =   Also, COPref =  =
 T3 − T2  W  T3 − T2  W
T −T 
W = Q3  3 2  (ii )
 T2 
Dr P R Venkatesh, Mech Dept, RVCE
 (i) Temperature T3 when Q1 = Q3
T1 = 600 K T2 = 300 K  T1 − T3   T3 − T2 
Equating (i ) & (ii ); Q1   = Q3  
Q1 Q3  1 T  T 2 
W= (Q1 - Q 2 )
As Q1 = Q3 , they may be cancelled on both sides.
HE REF
 T1 − T3   T2 − T3   T3   T3 
 =    1 −  =  − 1 or
Q2 Q4  T1   T3   T1   T2 
 T3 T3   1 1 
 +  = 2  T3  +  = 2 T3 = 400 K
T3

 T1 T2   600 300 
(ii)The efficiency of a reversible heat engine is;
 T   400 
th =  1 − 3  =  1 −  = 0.3333 = 33.33%
 T1   600 
The COP of a Carnot refrigerator is;
 T2   300 
COPref =  = = 3
 T3 − T2   400 − 300 
Dr P R Venkatesh, Mech Dept, RVCE
 Entropy
Entropy, the measure of a system’s thermal energy per unit temperature
that is unavailable for doing useful work. Because work is obtained from
ordered molecular motion, the amount of entropy is also a measure of
the molecular disorder, or randomness, of a system.

Dr P R Venkatesh, Mech Dept, RVCE

• The first law of thermodynamics was stated in terms of cycles first and it was
shown that the cyclic integral of heat is equal to the cyclic integral of work.
• When the first law was applied for thermodynamic processes, the existence
of a property, the internal energy, was found. Similarly, the second law was
also first stated in terms of cycles executed by systems.
• When applied to processes, the second law also leads to the definition of a
new property, known as entropy. If the first law is said to be the law of
internal energy, then second law may be stated to be the law of entropy.
• In fact, thermodynamics is the study of three E’s, namely, energy,
equilibrium and entropy. Dr P R Venkatesh, Mech Dept, RVCE
• 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. Dr P R Venkatesh, Mech Dept, RVCE
The efficiency of a Carnot cycle operating between two temperature limits T1 and T2 is;
 Q2   T2  Q2 T2 Q1 Q2  Q1 Q2 
thermal =  1 −  =  1 −  Hence, = or =  − =0
 Q1   T1  Q1 T1 T1 T2  T1 T2 
We know that in a Carnot cycle, heat transfer occurs only during the two isothermal
Q
processes, then the above equation can be written as,  =0
R
T
 Q 
It implies that cyclic integral of the quantity   for a reversible cycle is zero.
 T 
The above theorem is known as Clausius theorem.
 Q 
The quantity   of reversible process is a point function and it is a property of the system.
 T 
The property is called 'Entropy'.
Q
In general,   0, the equality sign applies to reversible process and the inequality sign applies
T
to irreversible process. This is known asDrClasius inequality.
P R Venkatesh, Mech Dept, RVCE
 ENTROPY; PROPERTY OF A SYSTEM
Let us consider a system undergoing a reversible process from
state 1 to state 2 along the path L and then from state 2 to the
original state 1 along path M. Applying the Clausius theorem
Q
to this reversible cyclic process, we have;  =0
R
T
When the system passes through the cycle 1 - L - 2 - M - 1, we
2
Q 1
Q
Reversible cyclic process
between two fixed end states
can write; 
1L
T
+
2M
T
=0 (i )

Now consider another reversible cycle in which the system changes

from state 1 to state 2 along the path L, but returns from state 2 to the
state 1 along a different path N. For this reversible cycle, we have;
2
Q 1
Q

1L
T
+
2N
T
=0 (ii )

Dr P R Venkatesh, Mech Dept, RVCE

 Subtracting equation (ii ) from equation (i ),
1
Q 1
Q 1
Q 1
Q

2N
T
− 
2M
T
=0  
2N
T
= 
2M
T
As no restriction is imposed on paths L and M, except that
 Q 
they must be reversible, the quantity   is a function of
 T 
the initial and final states of the system and is independent
Reversible cyclic process of the path of the process. Hence it represents a property of
between two fixed end states the system. This property is known as the entropy.

Dr P R Venkatesh, Mech Dept, RVCE

 Change of Entropy in a Reversible Process
Let S1 = Entropy at the initial state 1, and S2 = Entropy at the final state 2. Then, the change
 Q 
2
in entropy of a system, as it undergoes a change from state 1 to 2, becomes ( S2 − S1 ) =   
1  T R
Lastly, if the two equilibrium states 1 and 2 are infinitesimal near to each other, the integral sign
 Q 
may be omitted and ( S2 − S1 ) becomes equal to dS .  dS =   where dS is an exact differential.
 T R
 Q 
We find that the change of entropy in a reversible process is equal to   . This is the mathematical
 T 
formulation of the second law of thermodynamics.
 δQ 
Note : For an irreversible process, the change in entropy dS >   Hence, in general we can write;
 T 
 δQ 
dS    where equality applies to reversible process and inequality sign applies to irreversible process.
 T 
Dr P R Venkatesh, Mech Dept, RVCE
 Principle of increase of entropy
Let us 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
 δQ 
internal energy of the system will remain constant. As  Q = 0, dS     dSisolated  0
 T 
From the above equation, 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.
An example of an isolated system is the universe. Hence, dSuniverse  0
The above equation states that the process involving the interaction of a system and the surroundings
takes place only if the net entropy of the combined system increases or in the limit remains constant.
Since all natural processes are irreversible, the entropy is increasing continually.

Dr P R Venkatesh, Mech Dept, RVCE

TEMPERATURE-ENTROPY DIAGRAM (T-S diagram)
Heat change (Q)
Energy change dS =
Absolute temperature (T)

CHARACTERISTICS OF ENTROPY:
The characteristics of entropy in a summarized form
are given below :
• It increases when heat is supplied irrespective of
the fact whether temperature changes or not.
• It decrease when heat is removed whether
temperature changes or not.
• It remains unchanged in all adiabatic frictionless
processes. (as Q= 0)

Dr P R Venkatesh, Mech Dept, RVCE

 Entropy changes for a closed system
General Case for Change of Entropy of a 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 the law of conservation of energy; dQ = du + dW where;
dQ = Small change of heat, du = Small internal energy, and dW = Small change of work done
As the change in internal energy is equal to the heat added at constant volume, du = cv dT
Also, dQ = Tds, dW = pdv Substituting, Tds = cv dT + pdv Dividing both sides by T ,
 dT  pdv  p R  dT   dv 
ds = cv  + Also, pv = RT or   =   ;  ds = cv   + R 
 T  T T   v   T   v 
s2 T2
2 v
dT dv
Integrating between the states 1 & 2,  ds = cv  + R
s1 T1
T v1
v
 T2   v2 
 (s2 - s1 ) = cv loge   + Rloge   (i)
 T1   v1 
Dr P R Venkatesh, Mech Dept, RVCE
  T2   v2 
(s2 - s1 ) = cv loge   + Rloge   (i)
 T1   v1 
Alternate forms of equations of change of entropy :
p1v1 p2v2 T2 p2 v2
According to the gas equation, we have, =  = 
T1 T2 T1 p1 v1
T  p v  v 
Substituting for  2  in eqn (i), (s2 - s1 ) = cv log e  2  2  + Rlog e  2 
 T1   p1 v1   v1 
p  v  p  v 
(s2 - s1 ) = cv log e  2  +(cv + R)log e  2   (s2 - s1 ) = cv loge  2  + c p loge  2  (ii) ( c p = cv + R )
 p1   v1   p1   v1 
p1v1 p2v2 v T p 
Again, according to the gas equation, we have, =  2 = 2  1
T1 T2 v1  T1 p2 
v  T  T p  T  p 
Substituting for  2  in eqn (i), (s2 - s1 ) = cv log e  2  + Rlog e  2  2  = (cv + R)log e  2  + Rlog e  1 
 v1   T1   T1 p1   T1   p2 
 T2   p2    p1   p2  
(s2 - s1 ) = c p loge   - Rloge   (iii)  log e   = −log e   
 T1   p1   p2 
Dr PR Venkatesh, Mech Dept, RVCE
 p1  
Change of entropy for various process

Dr P R Venkatesh, Mech Dept, RVCE

Constant volume process Entropy change during constant volume process
Let 1 kg of gas be heated at constant volume and let the change in entropy and
absolute temperature be from s1 to s2 and T1 to T2 respectively. Then, Q = cv (T2 − T1 )
Differentiating dQ corresponding to small rise in temperature dT . dQ = cv dT
 dQ   dT   dT 
Dividing both sides by T, we get;   = cv   ds = cv 
 T   T   T 
 T2 
s2 T2
dT
Integrating between states 1 & 2,  ds = cv   (s2 - s1 ) = cv loge  
s1 T1
T  T1 
Entropy change during constant pressure process
Constant pressure process Let 1 kg of gas be heated at constant pressure and let the change in entropy and
absolute temperature be from s1 to s2 and T1 to T2 respectively. Then, Q = c p (T2 − T1 )
Differentiating dQ corresponding to small rise in temperature dT . dQ = c p dT
 dQ   dT   dT 
Dividing both sides by T, we get;   = c p   ds = c p 
 T   T   T 
T 
s2 T2
dT
Integrating between states 1 & 2,  ds = c p   (s2 - s1 ) = c p loge  2 
s1 T1
T  T1 
Dr P R Venkatesh, Mech Dept, RVCE
 Entropy change during isothermal Process
An isothermal expansion 1-2 at constant temperature T is shown in Fig. Entropy changes
from s1 to s2 when gas absorbs heat during expansion. The heat taken by the gas is given
by the area under the line 1-2 which also represents the work done during expansion.
s2

But, dQ = Tds  Q = T  ds = T(s2 - s1 ) Work done during isothermal process, is

s1

v  v 
Isothermal Process W = p1v1 log e  2  = RT1 log e  2  per kg of gas. Q = W for an isothermal process;
 v1   v1 
 v2   v2 
T(s2 - s1 ) = RT1 log e    (s2 - s1 ) = Rloge   ( T1 = T2 = T )
 v1   v1 
Entropy change during adiabatic process
During an adiabatic process as heat is neither supplied nor rejected, dQ = 0
 dQ 
or   = 0  ds = 0. i.e. no change in entropy and it is known as isentropic process.
 dT 
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.
Adiabatic Process Dr P R Venkatesh, Mech Dept, RVCE
Sl No Process Change of entropy /kg
1 T  v 
(s2 - s1 ) = cv log e  2  + Rlog e  2  (In terms of T and v )
 T1   v1 
General case
p  v 
(s2 - s1 ) = cv log e  2  + c plog e  2  (In terms of p and v )
 p1   v1 
T  p 
(s2 - s1 ) = c plog e  2  - Rlog e  2  (In terms of T and p )
 T1   p1 
2 Constant volume T 
cv log e  2 
 T1 
3 Constant pressure T 
c p log e  2 
 T1 
4 Isothermal process v 
Rlog e  2 
 v1 
5 Adiabatic process Zero
6 Polytropic process  −n T2
cv   e
log
 n −1  T1
Dr P R Venkatesh, Mech Dept, RVCE
 Third law of Thermodynamics
The third law of thermodynamics states that the entropy of a perfect crystal at a
temperature of zero Kelvin (absolute zero) is equal to zero.
• Entropy, denoted by ‘S’, is a measure of the disorder/randomness in a closed system. It
is directly related to the number of microstates (a fixed microscopic state that can be
occupied by a system) accessible by the system, i.e. the greater the number of
microstates the closed system can occupy, the greater its entropy.
• The microstate in which the energy of the system is at its minimum is called the ground
state of the system.
• At a temperature of zero Kelvin, the following phenomena can be observed in a closed
system:
(i) The system does not contain any heat.
(ii) All the atoms and molecules in the system are at their lowest energy points.
Therefore, a system at absolute zero has only one accessible microstate – it’s ground state.
As per the third law of thermodynamics, the entropy of such a system is exactly zero.

Dr P R Venkatesh, Mech Dept, RVCE

Numerical problems on entropy

Dr P R Venkatesh, Mech Dept, RVCE

 Problem 1
An iron cube at a temperature of 400°C is dropped into an insulated bath
containing 10 kg water at 25°C. The water finally reaches a temperature of
50°C at steady state. Given that the specific heat of water is equal to 4186 J/kg
K. Find the entropy changes for the iron cube and the water. Is the process
reversible ? If so why ?

Data : Temperature of iron cube Ti = 400C = 673 K , Temperature of water Tw = 25°C = 298 K
Mass of water mi = 10 kg , Equilibrium temperature of water & iron Teq = 500 C = 323K
Specific heat of water cw = 4186 J / kg − K

Dr P R Venkatesh, Mech Dept, RVCE

Solution : Let mi and ci be the mass and specific heat of iron.
(a) Change in entropy of iron cube & water : This is a constant pressure process.
Heat lost by iron cube = Heat gained by water  mi ci (Ti − Teq ) = mwcw (Teq − Tw )
mi ci (673 − 323) = 10  4186  (323 − 298) or mi ci = 2990 J / K
  Teq    323 
Entropy change of iron siron = mi ci log e    = 2990  log e   = -2195 J / kg
  Ti    673 
  Teq    323 
Entropy change of water s water = mwcw log e    = 10  4186  log e   = 3372.2 J / kg
  Tw    298 
The net change in entropy is snet = ( siron + s water ) = ( −2195 + 3372.2 ) = 1177.2 J / kg

(b) No. As the net change in entropy is Δsnet > 0, the process is irreversible.
Dr P R Venkatesh, Mech Dept, RVCE
 Problem 2
An ideal gas is heated from temperature T1 to T2 by keeping its volume
constant. The gas is expanded back to its initial temperature according to the
law pvn = constant. If the entropy change in the two processes are equal, find
the value of n in terms of the adiabatic index γ.

Data : Entropy change for constant volume process = Entropy change for polytropic process
 T2   −n  T2    − n 
Solution : mcv log e   = mcv   log e      =1
 T1   n −1   T1   n − 1 

( − n ) = ( n − 1) or 2n = (1 +  )  n =
( 1+ γ)
2

Dr P R Venkatesh, Mech Dept, RVCE

 Problem 3
A heat engine is supplied with 278 kJ/sec of heat at a fixed temperature of
2830C and the heat rejection takes place at 50C. The following results were
received. (i) 208 kJ/sec of heat rejected (ii) 139 kJ/sec of heat rejected (iii) 70
kJ/sec of heat rejected. Classify the above as reversible, irreversible or
impossible.

Data : Q1 = 278 kJ / s, T1 = 2830 C = 556 K , T2 = 50 C = 278 K

Solution : Q1 = 278 kJ / s, (i ) Q2 = 208 kJ / s,(ii ) Q2 = 139 kJ / s (iii ) Q2 = 70 kJ / s

 Q  Q1 Q2   278 208 
(i) When Q2 = 208 kJ / s :  T =  T1 − T2  =  556 − 278  = -0.248 kJ / kg - K
Q
As   0, the cycle is irreversible.
T
Dr P R Venkatesh, Mech Dept, RVCE
  Q  Q1 Q2   278 139 
(ii) When Q2 = 139 kJ / s :  = − = −  = 0 kJ / kg - K
T  T1 T2   556 278 
Q
As  = 0, the cycle is reversible.
T

 Q  Q1 Q2   278 70 
(iii) When Q2 = 70 kJ / s :  = − = −  = 0.248 kJ / kg - K
T  T1 T2   556 278 
Q
As   0, the cycle is impossible.
T

Dr P R Venkatesh, Mech Dept, RVCE

 Problem 4
A closed system contains air at a pressure 1 bar, temperature 300 K and volume
0.018 m3. This system undergoes a thermodynamic cycle consisting of the
following three processes in series : (i) Constant volume heat addition till
pressure becomes 5 bar, (ii) Constant pressure cooling, and (iii) Isothermal
heating to initial state. Represent the cycle on T-S and p-V plots and evaluate
the change in entropy for each process.
Take cv = 0.718 kJ/kg-K and R = 0.287 kJ/kg-K.

Data : p1 = 1 bar, T1 = 300 K , V1 = 0.018 m 3 , p2 = 5 bar, cv = 0.718 kJ / kg − K , R = 0.287kJ / kg − K

Process 1-2 → Constant volume; Process 2-3 → Constant pressure; Process 3-1 → Isothermal

Dr P R Venkatesh, Mech Dept, RVCE

 Solution :
p1V1 100  0.018
Mass of air m = = = 0.021 kg
RT1 0.287  300
c p = (cv + R ) = (0.718 + 0.287) = 1.005 kJ / kg - K

T-S & p-V diagrams

p1 p2  p2   5
Constant volume process 1 - 2 : = ; T2 =    T1 =    300 = 1500 K
T1 T2  p1  1
 T2   1500 
Change in entropy (s2 − s1 ) = mcv log e   = 0.021  0.718  log e   = 0.0243 kJ / kg - K
 T1   300 
Constant pressure process 2 - 3 :
 T3   300 
Change in entropy (s2 − s1 ) = mc p log e   = 0.021  1.005  log e   = −0.034 kJ / kg - K
 T2   1500 
Dr P R Venkatesh, Mech Dept, RVCE
 T-S & p-V diagrams

Constant temperature process 3 - 1 : p3 = p5 = 5 bar

 p3   5
Change in entropy (s1 − s3 ) = mR log e   = 0.021  0.287  log e   = 0.0097 kJ / kg - K
 p1  1

Dr P R Venkatesh, Mech Dept, RVCE

 Problem 5
Air at 20°C and 1.05 bar occupies 0.025 m3. The air is heated at constant
volume until the pressure is 4.5 bar, and then cooled at constant pressure back
to original temperature. Calculate;
(i) The net heat flow from the air.
(ii) The net entropy change. Also, sketch the process on T-s diagram.

Data :
p1 = 1.05 bar, T1 = 200 C = 293 K , V1 = V2 = 0.025 m 3 , p2 = 4.5 bar
Process 1-2 → Constant volume; Process 2-3 → Constant pressure; Process 3-1 → Isothermal

Dr P R Venkatesh, Mech Dept, RVCE

 Solution :
p1V1 105  0.025
Mass of air m = = = 0.03122 kg
RT1 0.287  293
Constant volume process 1 - 2 :
p1 p2  p2   4.5 
= ; T2 =    T1 =    293 = 1255.7 K
T1 T2  p1   1.05 

(i) Net heat flow : It is the sum of heat added at constant volume and the heat rejected at constant pressure
Q = m  cv (T2 − T1 ) + c p (T3 − T2 )  = 0.03122  0.718  (1255.7 − 293) + 1.005  (293 − 1255.7) = - 8.63 kJ / kg - K
 V1 
(ii) Net change in entropy : s = (s2 − s1 ) + (s3 − s2 ) = (s3 − s1 ) = mR log e  
 V3 
As the process 3-1 is isothermal, p1V1 = p2V3  (1.05  0.025) = ( 4.5  V3 ) V3 = 5.833  10−3 m 3
V   0.025 
(s3 − s1 ) = mR log e  1  = 0.03122  0.287  log e  −3 
= 0.013 kJ / kg - K
 V3  5.833  10  RVCE
Dr PR Venkatesh, Mech Dept,
 Problem 6
1 kg of air initially at 8 bar pressure and 380 K expands polytropically (pv1.2 =
constant) until the pressure is reduced to one-fifth value. Calculate;
(i) Final specific volume and temperature.
(ii) Change of internal energy, work done and heat interaction.
(iii) Change in entropy. Take : R = 0.287 kJ/kg K and γ = 1.4.

1
Data : m = 1 kg, p1 = 8 bar, p2 =  8 = 1.6 bar , T1 = 380K , pv1.2 = C
5
R = 0.287 kJ / kg − K ,  = 1.4

Dr P R Venkatesh, Mech Dept, RVCE

Solution :
RT1  0.287  380 
(i) Final specific volume and temperature, v2 , T2 : p1v1 = RT1  v1 = =  = 0.1363 m 3

p1  800 
1 1
p  n
 8 
1.2
Also, for a polytropic process, p1v1n = p2v2n  v2 = v1  1  = 0.1363   = 0.521 m 3
 p2   1.6 
p2v2  160  0.521 
p2v2 = RT2  T2 = =  = 290.45 K
R  0.287 
(ii) Change of internal energy, work done and heat interaction :
R 0.287
Change of internal energy u = cv (T2 − T1 ) = (T2 − T1 ) = (290.45 − 380) = -64.25 kJ / kg
 −1 1.4 − 1
R(T1 − T2 ) 0.287  (380 − 290.45)
Work done W = = = 128.5 kJ / kg
n −1 (1.2 − 1)
Heat interaction Q = (W + u ) = (128.5 − 64.25) = 64.25 kJ / kg

Dr P R Venkatesh, Mech Dept, RVCE

  −n  1.4 − 1.2  
 Alternately, Q =   W =    128.5 = 64.25 kJ / kg 
   −1   1.4 − 1  
 T2   v2 
(iii) Change in entropy : (s2 - s1 ) = cv log e   + Rlog e  
 T1   v1 
 290.45   0.521 
(s2 - s1 ) = 0.718  log e   +0.287  log e  = 0.192 kJ / kg - K
 380   0.1363 

Dr P R Venkatesh, Mech Dept, RVCE

 Exergy and Anergy
• Exergy is the maximum useful work that could not be obtained from the
system at a given state in a specific environment.
• In other words, the exergy of a system is the maximum useful work possible
during a process that brings the system to equilibrium with a heat reservoir.
• Exergy is the energy available to be used. Therefore it is also called the
availability or available energy. After the system and surroundings reach
equilibrium, the exergy becomes zero.

• Anergy is the energy that is not utilizable and rejected to the surroundings.
It is also called unavailable energy.
• For any thermodynamics system,
Energy supplied = Work done + Heat rejected
=Available energy +Unavailable energy
= Exergy Dr P R Venkatesh,
+ Mech Dept,Anergy
RVCE