BASIC THERMODYNAMICS

Course no. ME21202

Section 4
Dr. Sourav Mitra
RAC Lab(first floor)
Department of Mechanical Engineering

1
THERMODYNAMICS:
Second Law of
Thermodynamics

2
 Motivation
• Zeroth law: Thermal equilibrium (defined “Temperature”)

• First law: Conservation of energy (defined “Internal energy”)

Boundary energy transfer  change in internal energy of the
system

• Second law: Direction of a process, limits the efficiency of a cycle

3
 Heat Engine
• Heat Engine: Device that converts heat to work undergoing a
thermodynamic cycle

4
 Heat Engine
• Heat Engine: Device that converts heat to work undergoing a
thermodynamic cycle

• Heat engine is often used in a

broader sense to include work
producing devices that do not
operate in a thermodynamic
cycle.

• E.g. internal combustion such as

gas turbines and car engines

• These devices operate in a

mechanical cycle but not in a
thermodynamic cycle (purging of
exhaust gases). Rankine Cycle (Steam power plant)

5
 Thermal reservoir
• Thermal reservoir: Hypothetical body
with a relatively large thermal
capacity (mass x sp. heat capacity)
which can provide/absorb thermal
energy without any change in
temperature
Thermal
reservoirs
• E.g.: Atmosphere, Large water bodies
• E.g.: Large two-phase system

A reservoir that supplies energy in the form of heat is

called a source, and one that absorbs energy in the
form of heat is called a sink

6
 Heat Engine
Thermal efficiency:
Qin: magnitude of heat supplied to the
working fluid by the source

Wout: Amount of work developed by the

turbine

Qout: magnitude of heat rejected to the sink

(wasted)

Win: Amount of work needed for the cycle to

operate (compression work)
Wnet = Wout - Win
From first law: Wnet = Qin - Qout

Efficiency, ηth = desired output/input = net work produced/heat input

Wnet Qout
ηth = ηth = 1 −
Qin Qin
7
 Heat Engine
QL
Thermal efficiency: ηth = 1 −
QH

QH: Heat input (magnitude) to the cyclic device from high

temperature medium

QL: Heat rejected (magnitude) by the cyclic device to a low

temperature medium

Note: QH , QL: only magnitude in the above equation

Can we avoid the heat loss (QL) at TL ?

If yes, we can increase the efficiency of the cycle !!!

8
 Heat Engine

Simple heat engine to lift weight. Working fluid initially at 30°C

Heat supplied from a reservoir at 100°C to eventually heat the gas and lift the weight

Can we bring back the gas to initial state without cooling ?

NO
We need another reservoir with temperature less than or equal to 30°C
9
 Heat Pump (Refrigerator)
• Heat Pump: Device that pumps heat from lower temperature
reservoir to higher temperature reservoir and consumes work
while undergoing the thermodynamic cycle

10
 Heat Pump (Refrigerator)
Coefficient of performance (COP):
QL: magnitude of heat supplied to the cyclic device by the
lower temperature source

Win: Amount of work needed as input

QH: Magnitude of heat rejected by the cyclic device to the

sink at higher temperature
Wnet = QL - QH
COPR = desired output/input = useful cooling/work input

QL
COPR =
Wnet ,in

QL
COPR =
QH − QL
11
 Heat Pump (Refrigerator)
Coefficient of performance (COP):
QL: magnitude of heat supplied to the cyclic device by the
lower temperature source

Win: Amount of work needed as input

QH: Magnitude of heat rejected by the cyclic device to the

sink at higher temperature
Wnet = QL - QH
COPH = desired output/input = useful heating/work input
QH
COPH =
Wnet ,in

QH
COPH = =
COP COPR + 1
QH − QL
H

12
Heat Pump (Refrigerator)

13
Only cooling Heating & cooling
 Second Law statements
The Kelvin-Planck statement
It is impossible for any system to operate in a thermodynamic cycle and
deliver a net amount of energy by work to its surroundings while
receiving energy by heat transfer from a single thermal reservoir.
TH

QH
System undergoes
Not possible !!
thermodynamic cycle
Wnet

QH = Wnet Doesn’t violate first law

For the cycle to deliver a net amount of energy by work to its surroundings there needs to
be another thermal reservoir at lower temperature

Thermal efficiency of a heat engine can never be 100 %

14
 Second Law statements
The Clausius statement
It is impossible for any system to operate in such a way that the “sole
result” would be an energy transfer by heat from a cooler to a hotter
body.
TH > TL
TH TH
QH QH

Ok !! Not possible !!

QL QL
TL TL

QH = QL Doesn’t violate first law

When heat transfer from a cooler body to a hotter body occurs, there must be some
“other effect” associated with this heat transfer
15
 Equivalence of the two statements
Violation of Kelvin-Planck statement
Lets say we have a heat engine which violates Kelvin-Planck statement
and has 100% thermal efficiency. Then we can use this work produced to
run a heat pump

Violation of Clausius
statement

16
 Reversible & Irreversible process
A reversible process is defined as a process that can be reversed without
leaving any trace on the surroundings.

Both the system and the surroundings are returned to their initial states
at the end of the reverse process.

17
 Reversible & Irreversible process
A system can be restored to its initial state following a process,
regardless of whether the process is reversible or irreversible.
But for reversible processes, this restoration is made without leaving
any net change on the surroundings, whereas for irreversible processes,
the surroundings usually do some work on the system and therefore
does not return to their original state.

18
 Causes of Irreversibility
Dissipative forces: Friction (solid or fluid)

Actual pendulum

Frictionless pendulum

Thermodynamic in-equilibrium: Heat transfer across finite

temperature, unrestrained expansion

Irreversible

To reverse this process we need a refrigeration system

19
 Internally and Externally Irreversible
Internally irreversible: If irreversibilities occur within the boundaries of
the system during the process. E.g. non-equilibrium within the system
(sudden expansion/compression, temp. gradient).
Externally irreversible: If irreversibilities occur outside the boundaries
of the system during the process. E.g. Heat transfer across finite
temperature difference while the system has no gradient.
Phase change heat transfer
One side gas and another side
(Constant pressure and temperature internally)
vacuum separated by a membrane
inside an insulated cylinder.
Membrane is burst.

Internally
Internally reversible Totally Reversible
irreversible 20
Externally irreversible
 Carnot cycle: Reversible engine

1-2: Reversible Isothermal heat addition: slowly expand the gas which is in
contact with a heat source at TH

2-3: Reversible Adiabatic expansion: slowly expand the gas which is insulated
from the surrounding and work is extracted as the gas cool from TH to TL.

3-4: Reversible Isothermal heat rejection: slowly contract the gas which is in
contact with a heat sink at TL

4-1: Reversible Adiabatic compression: slowly compress the gas which is in

insulated from the surroundings. Some work is done on the gas as its temperature
increases from TL to TH
21
 Carnot cycle
1-2: Reversible Isothermal heat addition: slowly
expand the gas which is in contact with a heat source
at TH

2-3: Reversible Adiabatic expansion: slowly expand

the gas which is insulated from the surrounding and
work is extracted as the gas cool from TH to TL.

3-4: Reversible Isothermal heat rejection: slowly contract the gas which is in
contact with a heat sink at TL

4-1: Reversible Adiabatic compression: slowly compress the gas which is in

insulated from the surroundings. Some work is done on the gas as its temperature
increases from TL to TH
Reverse Carnot cycle  Carnot Heat Pump
All Heat Engines are denoted by clockwise cycles on thermodynamic chart
All Heat Pumps are denoted by anti-clockwise cycles on thermodynamic chart
22
 Carnot Heat pump
Similar to the thermal efficiency of Carnot Heat Engine, the COP of Carnot heat
pump will be given by:

QL 1 1
=
COPR = ⇒ COPR ,Carnot =
QH − QL  QH   TH 
  −1   −1
 QL   TL 

TL
COPR ,Carnot =
TH − TL

TH
COPH ,Carnot =
TH − TL

Thus, the above COP values provide an upper limit to the COP of real heat pump cycles

23
 Carnot cycle
Proposition 1:
It is impossible to construct an engine that operates between two given
reservoirs and is more efficient than a reversible engine operating between the
same two reservoirs.

24
 Carnot cycle
Proposition 2:
All engines that operate on the Carnot cycle between two given constant-
temperature reservoirs have the same efficiency

Higher Lower
efficiency efficiency
Carnot cycle Carnot cycle

Carnot cycle efficiency is a function of “reservoir temperatures” only

25
Real Heat Engines and Heat Pumps

ηth ≤ ηth ,Carnot COPR ≤ COPR ,Carnot

 TL   TL 
ηth ≤ 1 −  COPR ≤  
 TH   H
T − TL 

If it violates the above relation, the device is PMM 2

26
 Quality of energy
An important implication of Carnot efficiency is that “thermal energy” has a “quality”.

Higher temperature thermal energy has higher “quality”

 TL 
ηth ,Carnot= 1 − 
 TH 

Large amount of thermal energy stored at ambient temp. has 0 “work potential”

Work is higher grade energy as Work  Heat conversion can be 100% efficient
But only a fraction of Heat  Work
27
 Perpetual Motion Machines
Machines that violate either the first or the second law

PMM 2
PMM 1

28
 Example 1
TH
QH
Heat engine

W
QL
TL

a. Violates Kelvin-Planck statement

b. Possible, efficiency = 0
TH
QH
Heat pump
a. Possible with COPR = 0, COPH = 1
W b. Impossible, Violates Clausius statement

QL
TL
29
 Example 2
A cyclic machine shown in figure receives 325 kJ from a 1000 K energy reservoir. It
rejects 125 kJ to a 400 K energy reservoir and the cycle produces 200 kJ of work as
output. Is this cycle reversible, irreversible or impossible ?

For a cycle to be possible:

ηth ≤ ηth ,Carnot
Ans: Impossible

30
 Example 3
Calculate the amount of work input a refrigerator needs to make ice cubes
out of a tray of 0.25 kg liquid water at 10°C. Assume the refrigerator works
in a Carnot cycle between −8°C and 35°C with a motor-compressor of 750
W. How much time does it take if this is the only cooling load? (Enthalpy of
fusion is 336 kJ/kg of water and Cp of liquid water = 4.18 kJ/kg)
Ans: 15.23 kJ, 20.3 s

31
 Example 4
Two reversible cycles arranged in series each produce the
same net work Wcycle. The first cycle receives energy QH by
heat transfer from a hot reservoir at 555 K and rejects
energy Q at an unknown intermediate temperature T. The
second cycle receives energy Q by heat transfer from the
intermediate reservoir and rejects energy Qc by heat
transfer to a reservoir at 222 K. All energy transfers
mentioned here are the magnitudes. Determine
a. The intermediate temperature T
b. Thermal efficiency for each power cycle
c. The thermal efficiency of a single reversible power cycle
operating between hot and cold reservoirs at 555 K and
222 K.

Ans:
a. 388.5 K
b. η1 = 30%, η2 = 42.86%
c. η = 60%
32
 Example 5
An inventor claims to have developed a refrigerator that at steady
state requires a net power input of 0.52 kW to remove 12660 kJ/h of
energy by heat transfer from the freezer compartment at -17.8°C and
discharge energy by heat transfer to a kitchen at 21°C. Evaluate the
possibility and impossibility of this claim.

Ans: Impossible device

33
 Example 6
A car engine operates with a thermal efficiency of 35%. Assume the air conditioner has a
coefficient of performance that is one third of the theoretical maximum and it is
mechanically pulled by the engine. How much fuel energy should you spend to just operate
the AC and remove 1 kJ at 15°C from car cabin when the ambient is at 35°C?

Ans: 0.595 kJ
TH TH’ = 35°C
QH = ? QH’ 1
COPR= × COPR ,Carnot
W=?
3
Heat engine
Heat pump
ηth = 0.35 1  TL ' 
QL QL’ = 1 kJ COPR =  
3  TH ' − TL ' 
TL TL’ = 15°C

QL ' 1 W 1
=
COP = ηth = ⇒ QH =
R
W W QH ηth × COPR

34
THERMODYNAMICS:
Entropy

35
 Clausius Inequality
Second law statements:
• Only thermodynamic cycles have been analyzed.
• The directionality of “thermodynamic cycles” and limiting
efficiencies have been discussed.
• We need an equation to analyze the feasibility of a process.

For a Heat Engine let’s look at the following:

δQ QH Q
∫ =
T TH
− L
TL
Please note here we are taking the magnitude of heat
transfer with their appropriate sign.

QH QL QL,rev
For reversible H.E: − =
0
TH TL

W=
rev QH − QL
36
 Clausius Inequality
Heat Engine:
For an irreversible H.E: W
=irr QH − QL ,irr

Wirr < Wrev ⇒ QL ,irr > QL ,rev

W
Wrev
irr
For the same heat input to the engine, an irreversible
H.E will lose more heat to the sink than a reversible one
QL,irr
QH QL ,irr
⇒ − <0
TH TL
δQ QH Q
For reversible cycle: ∫ T
=
TH
− L =0
TL

δQ QH Q
For irreversible cycle: ∫ T
=
TH
− L <0
TL

δQ
Clausius Inequality: ∫ T
≤0

37
 Clausius Inequality
For a Heat Pump:
δQ QH ,rev QL
for a reversible cycle: ∫ T
=
−
TH
+
TL
=
0

For the same cooling (QL), an irreversible H.P will lose W

more heat (QH) to the sink than a reversible one
⇒ QH ,irr > QH , rev

δQ QH ,irr QL
for an irreversible cycle: ∫ T
=
−
TH
+
TL
<0

For Heat Engine: For Heat Pump:

∫ δ Q ≥ 0 = 0 when no work output <0
0 reversible H.E  0 reversible H.P 
δQ   δQ  
∫ T =  − ve irreversible H.E  ∫ T 
= − ve irreversible H.P 
+ve impossible H.E  +ve impossible H.P 
   
38
 Entropy
Clausius inequality leads to the definition of another thermodynamic property “Entropy”
 δQ  p
∫  T rev = 0
1
2
 δQ 
1
 δQ  C
∫1  T  A,rev ∫2  T C ,rev =
+ 0 B

A
 δQ   δQ 
2 1

∫1  T  B,rev ∫2  T C ,rev =

+ 0 2
v
 δQ   δQ   δQ 
2 2 2

∫1=
 
 T  A,rev
∫1  T  B,rev ⇒ ∫1  T rev is path independent
 δQ   δQ 
2
Let us define a property S such that: dS ≡  
 T rev
∫1  T rev
S 2 − S1 =

 δQ 
2
Entropy S is a state function S 2 − S1 ≠ ∫  
1  T irr 39
 Entropy balance for a closed system
Consider a closed system undergoing irreversible p
process 12 shown by “dotted path” A in the 1
figure. B, rev
Let us construct a reversible process 21 shown
by “solid path” B in the figure to complete a cycle.

From Clausius inequality (as the cycle is

irreversible): 2
v
 δQ   δQ   δQ 
2 1

∫  T  < 0 ⇒ ∫
1
 + ∫   <0
T irr 2  T rev

 δQ 
1
From definition of entropy change: S1 − S 2 ≡ ∫  
2  rev
T
 δQ 
2
⇒ ∫  + ( S1 − S 2 ) < 0
1
T irr

 δQ   δQ 
2

( S2 − S1 ) > ∫   dS >  
1
T irr  T irr 40
 Entropy balance for a closed system
P
Entropy change equation for closed system undergoing
any process: 1

 δ Q  Equality for reversible process

2

( S2 − S1 ) ≥ ∫   Inequality for irreversible process

1
T 
We can remove the inequality by introducing a term 𝝈𝝈𝒈𝒈𝒈𝒈𝒈𝒈 A
2
Thus, for a closed system undergoing “any” v
thermodynamic process we can write:
 δQ 
2

( S2 −=
S1 ) ∫1  T  + σgen
 Entropy generation:
Entropy change
of the system
  Entropy
generation 𝝈𝝈𝒈𝒈𝒈𝒈𝒈𝒈 takes into account all
Entropy transfer
from surrounding
irreversibilities occurring during the
process (both internal and external)
For irreversible process: σ gen > 0
For reversible process: σ gen = 0

Not possible: σ gen <0

41
 Property Relationship
Specific entropy: Specific entropy is an intensive property

How to evaluate this property for any pure substance ??

Join two state points by any reversible process (closed system)

Q dU + δ W (for any process in closed system)

First law: δ=

δ Qrev =dU + δ Wrev =dU + PdV (for obtaining an equation for dS)

= dU + PdV (Clausius equality for this reversible process)

TdS

= du + Pdv
Specific properties: Tds = dh − vdP
Tds

• These are property relationships are always applicable between two state
points.
• One can use these relationships to determine specific entropy change of any
pure substance.
Note that: δ Qirr ≠ TdS δ Wirr ≠ PdV 42
Entropy of Pure Substance (Ideal Gas)
Specific entropy: Specific entropy is an intensive property
du Pdv
Calculating entropy change for ideal gas: ds
= +
T T
cv dT RTdv
⇒ ds= +
T Tv
2 2 2
C dT Rdv
⇒ ∫ ds
= ∫ v +∫
1 1
T 1
v

 T2   v2 
⇒ s= − s c ln   + R ln  
• No charts available for
2 1 v
 1
T  v1 
Ideal Gas
• You need to carry out
this calculation
 T2   P2 
⇒=
s2 − s1 cP ln   − R ln  
 T1   P1 

43
 Entropy of Pure substance (Real Fluids)
Specific entropy: Specific entropy is an intensive property

Calculating specific entropy change for real fluids:

du Pdv dh vdP
=
ds + =
ds −
T T T T
• Requires Real Gas Properties
• Values already available in charts

Calculating entropy change during two-phase region:

(1 x ) s f + xsg
s =−

(Values of sf and sg already available in charts)

HOW ABOUT SOLIDS ?

44
Heat transfer across finite temperature difference
A solid block of specific heat capacity C at initial temperature Ti transfers heat to a thermal
reservoir at a temperature To. Taking the block as the system, evaluate the entropy
generation during the heat transfer process as the block comes in equilibrium with the
thermal reservoir.
Entropy balance for closed system

 δQ 
Tf

(S f − =
Si ) ∫   + σ gen Ti T f = To
Ti 
To 
LHS: property of the block
 To 
To
 CdT 
Si ) ∫  =
( S f −=  C ln   δQ
Ti    Ti 
T
RHS: Heat transfer from a constant temperature reservoir
To
 δQ   CdT   To − Ti 
To To

∫T  To 
= ∫T  To   To 
= C
i i

 δQ   To   To − Ti 
Tf

σ gen = ( S f − Si ) − ∫   = C ln  −C  σgen

Ti 
To b  Ti   o 
T Ti =To
 Ti  T 
σ gen
= C − 1 − C ln  i  σ gen ≥ 0
 To   To  Ti
 Unrestrained expansion
An ideal gas with gas constant R at initial pressure P
and temperature T suddenly expands against vacuum
to twice its initial volume in an adiabatic chamber.
Calculate the specific entropy generated in this
process.
First law: δ qirr= du + δ wirr
T
δq 
2
Second law: ( s2 − s1 ) =
∫1  T  + σ gen 1 2
From property relations we know:
 T2   v2  v
cv ln   + R ln  
s2 − s1 =
 T1   v1 
v 
s2 − s1= σ gen= R ln  2 = R ln 2
 v1 

46
Irreversible adiabatic and Reversible adiabatic
T1

T2’ δ wrev

An ideal gas with gas constant R, specific heat capacities ratio of ɣ expands irreversibly
against vacuum and in another case reversibly as shown in the figure. The process starts with
an initial temperature of T1 and volume v1 and the final volume is v2. Find the final
temperature and entropy generation for both the cases. T
δ qrev= du + δ wrev 1 2
First law: δ qirr= du + δ wirr
cv dT = 0 cv dT + Pdv = 0 2’
T2 − T1 =  1 
 RdT + Pdv =
0
 0
v
T2 = T1  γ −1 
γ −1
 1  dT  R   v1 
  +   dv =
0 ⇒ T =
T1 
 γ −1  T  v 
2'
 2
v
Irreversible adiabatic and Reversible adiabatic
T1

T2’ δ wrev

Second law:
 δ qrev 
2

( s2 − s1 ) =
2
 δ qirr  ( 2' 1 ) ∫ 
s − s =  + σ gen T
∫ 1
 + σ gen
T  1
T 
1 2
( s2' − s1 ) =0 + σ gen
( s2 − s1 ) =0 + σ gen
 T2'   v2  2’
T  v  s=
2' − s1 cv ln   + R ln  
s2 − s1 = cv ln  2  + R ln  2   1
T  v1 
 T1   v1  v
R T  v 
=s2' − s1 ln  2'  + R ln  2 
 v2  γ − 1  T1   v1 
σ gen = R ln  
 v1  Substituting the value for T2’ from first law we get:
σ gen = 0
Irreversible adiabatic and Reversible adiabatic
T1 T1

T2’ δ wrev

Reversibly adiabatic is also called Isentropic process as there is “no change in

entropy” of the system:
 δQ  T
=
when σ gen 0=
&  0 1
 T  2
⇒ dS = 0 2’
Irreversible adiabatic processes are not isentropic process:
v
 δQ 
dS =   + σ gen ⇒ dS = σ gen > 0 for irreversible processes
 T 
Also note that starting from same state 1 going through “irreversible” and
“reversible” adiabatic processes led to different states (2 and 2’) !!
 Carnot cycle on T-s plot
isentropic
reversible adiabatic

From first law: ∫ δ Q = ∫ δ W

If it is a reversible cycle: ∫ TdS = ∫ PdV
Area under the T-s plot and P-v plot are equal only for a reversible cycle
50
Entropy change of any isolated system
Entropy balance equation for closed system undergoing any process:
 δQ 
2
S1 )
( S2 −= ∫1  T  + σgen

Entropy change
of the system
  Entropy
generation
Entropy transfer
from surrounding

 δQ 
2

For an isolated system: ( S 2 − S1 ) = ∫1  T  + σgen


Entropy change
of the system
  Entropy
generation
Entropy transfer

( S2 − S1 ) =
σ gen ⇒ ( S 2 − S1 ) ≥ 0
  
Entropy change Entropy Entropy change
of the system generation of the system

During a process, entropy of an “isolated” system can never decrease

Doesn’t imply that entropy of any “system” cannot decrease

51
 Example 1
A well-insulated rigid tank contains 2 kg of a saturated liquid–
vapor mixture of water at 100 kPa. Initially, three-quarters of the
mass is in the liquid phase. An electric resistance heater placed in
the tank is now turned on and kept on until all the liquid in the
tank is vaporized. Determine the “entropy change of the steam”
during this process (make the system boundary such that input
energy is accounted as work).
Ans: 8.098 kJ/K
 Example 2
A piston cylinder compresses R-410a at 200 kPa, −20°C to a pressure of 1200 kPa in a
reversible adiabatic process. Find the final temperature and the specific compression work.
Ans: 61.2°C, -48.8 kJ/kg
 Example 3
A rigid tank is divided into two equal parts by a partition. One part
of the tank contains 1.5 kg of compressed liquid water at 300 kPa
and 60°C while the other part is evacuated. The partition is now
removed, and water expands to fill the entire tank. The final
pressure in the tank is 15 kPa. Determine the following during this
process:
a) Entropy change of water during the process
b) Is this process possible if the system exchanges heat with a
thermal reservoir at temperature of 30°C ?
Ans: a) -0.1135 kJ/K
b) Yes
 Example 4
1 kg of water at 300°C expands against a piston inside a cylinder until it reaches ambient
pressure, 100 kPa, at which point the water has a quality of 90%. It may be assumed that the
expansion is reversible and adiabatic. What was the initial pressure in the cylinder and how
much work is done by water?
Ans: a) 2 MPa
b) 474.2 kJ
 Example 5
A cylinder containing R-134a at 10°C, 150 kPa, has an initial volume of 20 L. A piston
compresses the R-134a in a reversible isothermal process until it reaches the saturated
vapor state. Calculate the required work and heat transfer to accomplish this process

Ans: a) -3.185 kJ
b) -3.837 kJ
 Example 6
Water in a piston/cylinder is at 1 MPa, 500°C. There are two stops, a lower one at which
Vmin= 1 m3 and an upper one at Vmax= 3 m3. The piston is loaded with a mass and outside
atmosphere such that it floats when the pressure is 500 kPa. This setup is now cooled to
100°C by rejecting heat to the surroundings at 20°C. Find the total entropy generated in the
process.
Ans: 26.27 kJ/K
 Example 7
One kilogram of ammonia is contained in a spring-loaded piston/cylinder, as saturated liquid
at −20°C. Heat is added from a reservoir at 100°C until a final condition of 800 kPa, 70°C is
reached. Find the work, heat transfer, and entropy generation.

P
P2

P1

v1 v2
v

Ans: 97.8 kJ
1447 kJ
1.307 kJ/K
 Example 8
A piston–cylinder device contains 1.2 kg of nitrogen gas (ideal gas) at 120 kPa and 27°C. The
gas is now compressed slowly in a polytropic process during which PVn=constant. The
process ends when the volume is reduced to one-half and the temperature is 77°C. During
the process the device also interacts with the surrounding at constant temperature of 20°C.
Determine the work of compression, entropy change of nitrogen and entropy generation
during this process. Ans: -80.11 kJ
-0.1098 kJ/K
0.01174 kJ/K
 Example 9
A 1m3 insulated, rigid tank contains air at 800 kPa, 25°C. A valve on the tank is opened, and
the pressure inside quickly drops to 150 kPa, at which point the valve is closed. Assuming
that the air “remaining inside” has undergone a reversible adiabatic expansion, calculate
the mass withdrawn during the process.

Ans: 6.52 kg

C.M
C.M
 Example 10
A rigid container with a volume of 200 L is divided into two equal volumes by a partition,
shown in Fig. Both sides contain nitrogen; one side is at 2 MPa, 200°C, while the other is at
200 kPa, 100°C. The partition ruptures, and the nitrogen comes to a uniform state at 70°C.
Assume the temperature of the surroundings to be 20°C. Determine the net entropy
generation for the process.

Ans: 0.293 kJ/K

 Example 11
There are refrigerators driven by heat and not work. Consider one such thermodynamic
cycle interacting with 3 thermal reservoirs (as shown in the figure). Determine the minimum
temperature T1 for the case shown in figure?
T2 = 100°C

T3 = 50°C

Q3

Q2 = 1 kJ

Q1 = 1 kJ

T1

62
 Example 12
A rigid tank contains 4 kg air at 200°C, 4 MPa that acts as the hot-energy reservoir for a heat
engine with its cold side at constant 20°C. Heat transfer to the heat engine cools the air
down to a final 20°C and then the engine stops. Assuming all the processes to be reversible,
find the final air pressure and the work output of the heat engine. (Cv = 0.718 kJ/kg.K)
δQ
Second Law: dS= + σ gen
Ans: 2478 kPa, 114 kJ
sys
TL
2
QL
∫ dS
1
air + ∫ dS HE =
TL
Q
mair ( s2 − s1 ) + 0 = L
TL

First Law: dU=

sys δ Q − δW
2

∫ dU
1
air + ∫ dU HE =
QL − W

mair ( u2 − u1 ) + 0 = QL − WH . E
mair ( u2 − u1 ) = QL − WH .E
QL − WH .E= mair ( u2 − u1 )

mairTL ( s2 − s1 ) − WH=
.E mair ( u2 − u1 )
=
WH .E mairTL ( s2 − s1 ) − mair ( u2 − u1 )
 Example 13
A cylinder fitted with a frictionless piston contains water, as shown in Fig. A constant
hydraulic pressure on the back face of the piston maintains a cylinder pressure of 10 MPa.
Initially, the water is at 700°C, and the volume is 100 L. The water is now cooled and
condensed to saturated liquid. The heat released during this process is the Q supply to a
cyclic heat engine that in turn rejects heat to the ambient air at 30°C. If the overall process is
reversible, what is the net work output of the heat engine? Ans: 2999 kJ
δQ
Second Law: dS=
sys + σ gen
TL
2
QL
∫ dS
1
water + ∫ dS HE =
TL
Q
mwater ( s2 − s1 ) + 0 = L
TL

First Law: dU=

sys δ Q − δW
2

∫ dU
1
water + ∫ dU HE =
QL − W

mwater ( u2 − u1 ) + 0 = QL − (WH . E + W piston )

mwater ( u2 − u1 ) = QL − WH . E − Pmwater ( v2 − v1 ) mwaterTL ( s2 − s1 ) − W
=H .E mwater [ h2 − h1 ]
WH . E mwater ( u2 − u1 ) + P ( v2 − v1 ) 
QL −= WH .E mwater TL ( s2 − s1 ) − ( h2 − h1 ) 
=
WH . E mwater ( u2 + P2 v2 ) − ( u1 + Pv
QL −= 1 1 )
  P=
2 P=
1 P

QL − WH=
.E mwater [ h2 − h1 ]
Entropy change for an open/closed system
Rate of entropy change for closed system undergoing any process:

  δ Q 
=
dS
   + σ gen
Entropy change 
T  
of the system Entropy
generation
Entropy transfer

 δ Q k 
=
dS
 ∑ 
k  Tk 
 + σ gen

 generation
Entropy change
of the system Entropy
Multiple reservoirs

Rate of entropy change for an open system :

dSc.v.  δ Q k 
= ∑ m i si − ∑ m e se + ∑   + σ gen
dt
 k  Tk  
Entropy change  generation Entropy
of the system Entropy transfer

Sc.v. = mc.v. sc.v

65
Entropy change of single flow adiabatic SSSF system
Entropy change for single flow SSSF system :
dSc.v  δ Q k 
=(m i si − m  e se ) + ∑   + σ gen
dt k  Tk 
mi m
= =e m
 δ Q k 
 i + ∑
 e=
ms ms  + σ gen
k  Tk 
 δ qk   σ gen 
si + ∑ 
se = + 
k  Tk   m 
 δ qk   σ gen   σ gen 
If the system is adiabatic: se= si + ∑   +  se= si +  
k  T k   m   m 
⇒ se ≥ si
For an adiabatic single flow SSSF device, the fluid specific entropy at the exit is at least equal
to the inlet specific entropy.

if se = si Isentropic process for the working fluid

66
 Shaft work for an adiabatic SSSF device
Single flow SSSF device neglecting K.E. and P.E: 0 = ( hi − he ) + q − wshaft
Adiabatic device: 0 = ( hi − he ) + q − wshaft
e
⇒ wshaft =( hi − he ) ( hi − he ) =
⇒ wshaft = − ∫ dh
i
e e e e e
− ∫ du − ∫ Pdv − ∫ vdP ⇒ wshaft =
⇒ wshaft = − ∫ Tds − ∫ vdP
i i i i i
e
 δσ gen  e
⇒ wshaft −∫ T 
=  − ∫ vdP (Adiabatic device)
i  m  i
e
If reversible adiabatic ⇒ wshaft =
− vdP ∫
i
For a single flow isentropic SSSF device

Turbines: Pe<Pi wshaft > 0 Pumps and compressors: Pe>Pi wshaft < 0

Very useful for pumps where the specific volume of liquid doesn’t change significantly with
pressure: e
wpump ≈ −vliq ∫ dP ⇒ wpump ≈ −vliq ( Pe − Pi )
i
67
Isentropic efficiency of adiabatic SSSF devices
For a single flow adiabatic SSSF device Turbine
e e
− ∫ T δσ gen − ∫ vdP
⇒ wshaft =
i i
Ideal device: isentropic process
Real devices: adiabatic process (se > si)

ηturbine =
actual work o/p hi − he
ηturbine =
ideal work o/p hi − hes

ηcomp =
ideal work i/p hi − hes
actual work i/p ηcomp =
hi − he

Instead of mentioning outlet conditions one can give isentropic

efficiency to define the outlet condition Compressor

68
 Example 1
Steam at 7 MPa and 450°C is throttled in a valve to a pressure of 3 MPa during a steady-flow
process. Determine the entropy generated during this process.
Ans: 0.3706 kJ/kg.K
 Example 2
An adiabatic pump is to be used to compress saturated liquid water at 10
kPa to a pressure to 15 MPa in a reversible manner. Determine the work
input using (a) entropy data, (b) inlet specific volume and pressure values,
(c) average specific volume and pressure values. Ans: -15.1 kJ/kg
-15.14 kJ/kg
-15.1 kJ/kg
 Example 3
Steam enters an adiabatic turbine steadily at 7 MPa, 500°C, and 45 m/s, and
leaves at 100 kPa and 75 m/s. If the power output of the turbine is 5 MW and
the isentropic efficiency is 77 percent, determine:
(a) the mass flow rate of steam through the turbine Ans: 6.89 kg/s
(b) the temperature at the turbine exit 103.5°C
(c) the rate of entropy generation during this process. 4.013 kW/K
 Example 4
Saturated R-134a at −10°C is pumped/compressed to a pressure of 1.0 MPa at the rate of
0.5 kg/s in a reversible adiabatic process. Calculate the power required and the exit
temperature for the two cases of inlet state of the R-134a:
a. Quality of 0% b. Quality of 100%. Ans: -0.3 kW, -9.74°C
-16.73 kW, 45.63°C
 Example 5
A reversible and adiabatic R-22 compressor is operated in such a way that it provides a
constant pressure ratio of 3:1. Find the exit pressure and temperature when the inlet is at
100 kPa and 25°C. Ans: 76.56°C, 300 kPa

For the R-22 compressor described above, a throttle is used at its exit to reduce any over-
pressure. The throttle maintains a constant outlet pressure of 300 kPa. Find the R-22
temperature at the outlet of this throttle if the inlet to the compressor is at 120 kPa and
25°C. Also determine the specific entropy generated in the throttling process.
Ans: 76.0°C, 0.01704 kJ/kg.K
 Example 6
A certain industrial process requires a steady supply of saturated vapor steam at 200 kPa at a
rate of 0.5 kg/s. Also required is a steady supply of compressed air at 500 kPa at a rate of 0.1
kg/s. Both are to be supplied by the process shown in Fig. Steam is expanded in a turbine to
supply the power needed to drive the air compressor, and the exhaust steam exits the
turbine at the “desired state”. Air into the compressor is at ambient conditions, 100 kPa and
20◦C. Give the required steam inlet pressure and temperature, assuming that both the
turbine and the compressor are reversible and adiabatic. Ans: 241.6 kPa, 138.3°C
 Example 7
A supply of 5 kg/s ammonia at 500 kPa, 20°C is needed. Two sources are available: One is
saturated liquid at 20°C, and the other is at 500 kPa, 140°C. Flows from the two sources are
fed to an insulated mixing chamber, which then produces the desired output state. Find the
two source mass flow rates and the total rate of entropy generation by this setup
Ans: 0.949 kg/s, 4.051 kg/s
0.8607 kJ/K
 Example 8
A large supply line has a steady flow of R-410a at 1000 kPa, 60°C. It is used in three different
adiabatic devices shown in Fig.: a throttle flow, a reversible nozzle, and reversible turbine.
All the exit flows are at 300 kPa. Find the exit temperature and specific entropy generation
for each device and the exit velocity of the nozzle. Ans: 49.69°C,0.1303 kJ/kg.K
5.14°C, 0 kJ/kg.K, v=279.7 m/s
5.14°C, 0 kJ/kg.K
 Example 9
A 1 m3 rigid tank contains 100 kg of R-410a at ambient temperature, 15°C, as shown in Fig. A
valve on top of the tank is opened, and saturated vapor is throttled to ambient pressure,
100 kPa, and flows to a collector system. During the process, the temperature inside the tank
remains at 15°C. The valve is closed when no more liquid remains inside. Calculate the heat
transfer to the tank and the total entropy generation in the process.
Ans: 10843 kJ, 13.38 kJ/K
o

CV
 Example 10
Horizontal insulated cylinder has a frictionless piston held against stops by an external force
of 500 kN, as shown in Fig. The piston cross sectional area is 0.5 m2, and the initial volume is
0.25 m3. Argon gas in the cylinder is at 200 kPa, 100°C. A valve is now opened to a line
flowing argon at 1.2 MPa, 200°C, and gas flows in until the cylinder pressure just balances
the external force, at which point the valve is closed. Assume Argon as ideal gas, find the
final temperature and the total entropy generation.
Ans: 371.8°C, 0.21 kJ/K
Additional Homework Problems
(For Practice)

79
 Example 1
Steam enters a turbine at a pressure of 1 MPa, a temperature of 300◦C, and a velocity of 50
m/s. The steam leaves the turbine at a pressure of 150 kPa and a velocity of 200 m/s.
Determine the work per kilogram of steam flowing through the turbine, assuming the
process to be reversible and adiabatic. Ans: 377.5 kJ/kg
 Example 2
Liquid water enters a 25-kW pump at 100 kPa and 25°C with a flow rate
of 5 kg/s. Determine the pressure of liquid water at the exit of the pump
for isentropic pump. Neglect the kinetic and potential energy changes of
water Ans: 5100 kPa
 Example 3
Steam enters an adiabatic turbine at 8 MPa and 500°C with a mass flow
rate of 3 kg/s and leaves at 30 kPa. The isentropic efficiency of the
turbine is 0.90. Neglecting the kinetic energy change of the steam,
determine (a) the temperature at the turbine exit and (b) the power
output of the turbine.
Ans: 69.1°C, 3054 kW
 Example 4
Saturated vapor R-410a enters the uninsulated compressor of a home central air
conditioning system at 5°C. The flow rate of refrigerant through the compressor is 0.08 kg/s,
and the electrical power input is 3 kW. The exit state is 65°C, 3000 kPa. Any heat transfer
from the compressor is with the ambient at 30◦C. Determine the rate of total entropy
generation for this process.
Ans: 0.00166 kW/K
 Example 5
Assume an insulated air tank has initially 40 L of 100 kPa air at ambient temperature 17°C. A
compressor is connected to this tank so that it charges the tank up to a pressure of 1000 kPa
and then it shuts off. Determine how hot the air in the tank gets and the total amount of
work required to fill the tank. Assume the entire process to be reversible and adiabatic.
Ans: 283°C, -31.9 kJ