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THERMODYNAMICS

Therm - Heat (non-organised) Dynamics - Motion (Caused by force) Action of force on moving
Therm - Heat (non-organised)
Dynamics - Motion (Caused by force) Action of force on moving
body is ‘h’ as work.
Conversion of non-organised form of energy into organised form
of energy.
Main aim of thermodynamics is to convert heat into work.
Thermodynamics is branch of science deal with the heat and work
interaction and its effect on properties of system.
Importance of thermodynamics:
1. There is a property which distinguish this subject from other
sciences that is temperature and everything have certain
temperature. So, everything comes under consideration of
thermodynamics.
2. The subject thermodynamics is based on certain laws like law of
conservation of mass, etc. Laws are the statements which are
universally true but can’t be proved mathematically.
3. Most importantly thermodynamics tells us “what thins are not
possible”.
Example:
According to 2 nd law of thermodynamics no heat engine can give
100% efficiency.

1

HOW TO STUDY:

There are two ways to study thermodynamics 1) Microscopic view point (Statistical thermo) 2) Macroscopic
There are two ways to study thermodynamics
1) Microscopic view point (Statistical thermo)
2) Macroscopic view point.
3) Postulate thermodynamics (recent)
1) Microscopic view point:
In microscopic view point, behaviour of each & every
molecule is taken into consideration & to know the overall
behaviour we will use same statistical means. That why it is ‘k’
as statistical thermodynamics.
Only useful for low densities. This approach is used for
ramified gas (low pressure gas) (vacuum).
2) Macroscopic view point:
In macroscopic point of view, our attention is focused on
certain quantity of matter without going to the event occurring at
molecular level.
It is also known as classical thermodynamics average
behaviour at molecule taken into the consideration.
In our course, we will follow classical thermodynamics
only.

In classical thermodynamics, we will try to establish relation between measurable and non-measurable properties Measurable properties temperature, pressure, volume Non-measurable properties → enthalpy, entropy, internal energy, etc.

2

CONCEPT OF CONTINUUM:

ρ(dm/dV) dV dm Domain of Domain of Molecular effect Continumm ρ(dm/dV) ρ Volume V In
ρ(dm/dV)
dV
dm
Domain of
Domain of
Molecular effect
Continumm
ρ(dm/dV)
ρ
Volume
V
In microscopic point. of view, we always concern with a small
volume which is very large compared to molecular dimension.
Concepts of continuum give the criterion to apply macroscopic point
of view. Even the small volume contains very large no. of molecules.
We have to consider that small volume in such a way that statistical a
varying is meaningful and material can be considered as continuous.
Thermodynamic system, surrounding & boundary:
Surrounding
System
Universe
 System is defined as quantity of matter or region in a space where
our attention is focused.

Everything external to the system is surrounding.

3

The thing which separates system from surrounding is known as boundary

Thermodynamic boundary Real Imaginary Fixed moving Note: To get works from close system minimum one
Thermodynamic boundary
Real
Imaginary
Fixed
moving
Note:
To get works from close system minimum one boundary should
be moving.
Thermodynamic boundary
1. Adiabatic
(No heat transfer high thermal resistance.)
(R th → ∞)
2. Diathermal
Low thermal resistance
(R th → 0)
TYPES OF SYSTEM:
1. Closed system:
In closed system, there is no mass transfer across the
boundary. It has fixed mass ‘k’ as control mass. It is also c/a
control mass of system. Energy transfer may take place.
Example:

ⅰ) Rigid container

4

Gas m = Constant Q
Gas
m = Constant
Q
Q T For closed system minimum one boundary should be open. Here, all boundaries are
Q
T
For closed system minimum one boundary should be open.
Here, all boundaries are fixed.
∴ W = 0
ⅱ) Piston-cylinder arrangement without piston
Q
m = Constant
W
Q
W ≠ 0
(∴ One moving Boundary)
2. Open system:
In open system, mass transfer may also take place along
with energy-transfer.
Example: Turbine, pump, nozzle, compressor, radiator, etc.
Q
m 1
blades
W
m 2

Journal open system

5

For open system analysis attention is focused on certain volume in space surrounded by a surface known as control surface. Matter as well as energy can cross the control volume.

3. Isolated system: In isolated system neither mass nor energy interaction take place. Example: Thermal
3. Isolated system:
In isolated system neither mass nor energy interaction take
place.
Example:
Thermal flask which is perfectly insulated the best example
for isolated system is our universe.
THERMODYNAMIC PROPERTIES:
Properties are characteristic by which you can identify the
system.
Thermodynamic properties
1. Intensive
(Independent of mass or size of system)
Example:
Temperature, Density, Specific heat, Pressure, etc., Velocity.
2. Extensive
(Depends on mass or size of system)
Example:
Volume, Mass, Energy, Weight

6

M M M 2 2 V V V 2 2 P P P T T
M
M
M
2
2
V
V
V
2
2
P
P
P
T
T
T
ρ
ρ
ρ
Note:
 Ratios of two extensive properties are always intensive.
M
ρ =
(M → Intensive, V → Intensive, ρ → extensive)
V
 Specific properties are always intensive properties.
Specific property = extensive property = ext. prop/mass
(Per unit mass)
 Properties are independent of past history. Properties are the point
or state function.
 Properties are exact differential. If z is function o0f x & y and can
be represented as
dz = Mdx + Ndy
And z is exact differential if
∂M
(
) y = constant
∂y
∂x
) x = constant = ( ∂N
E.g. for ideal gas, function is
V
z = ∫ dT
dp
T
T
dT
V
dz =
dp
T
T

7

M =

1

T

V N = T dx = dT x = T dy = dp y =
V
N =
T
dx
= dT
x
= T
dy
= dp
y
= P
∂1
T
(
= 0
∂P ) T
( ∂(− V )
T
)
= 0 For ideal gas PV = RT
∂T
P
V
R
T =
P
( ∂(− R )
P
)
= 0
∂T
P
Hence, it is a property.
STATE OF SYSTEM:
State represents condition of system. When all properties of
system have definite value than system is said to be in state.
State of system is represented by a point in a diagram where properties
are co-ordinate.
1
P
1
P
Process
2
P
2

V 1

8

V 2 V
V 2
V

GIB’S PHASE RULE:

In a gib’s phase rule, Let there are total M number of properties of the
In a gib’s phase rule,
Let there are total M number of properties of the system in which
N are independent it means if we fix N number of independent
properties the M - N properties will automatically have fixed.
To find no. of independent properties required to identify the
gib’s phase rule is used. According to which,
P + F = C + 2
Where, P = no. of phases.
F = Degree of freedom /no of independent properties to
identify the system
C = no. of components
P
=
1
Water
C
=
1
H 2 O
F
=?
P + F = C + 2
F = 2
Two independent properties like pressure& temperature.
Example:
23°C @1atm pressure is complete description of system
Steam
Water
P = 2 C = 1 F =?
P + F = C + 2

9

F = 1

Either temperature or pressure is independent property.

Steam Water Ice P = 3 C = 1 F =? P + F =
Steam
Water
Ice
P = 3 C = 1 F =?
P + F = C + 2
F = 0 → Triple point of water
Note:
Invariable chemical composition irrespective of phase is k as pure
substance (e.g. water is pure substance.)
Air is not pure substance in liquid phase as chemical composition
changes when it is converted from air to liquid.
 At triple point of water all properties are fixed,
 T tp = 0.01℃/273.15 K
P tp = 0.006 bar
PROCESS AND PATH:
Change of state is known as process and series of
equilibrium states through which a system passes during its process is
known as path of process.
1
Equilibrium
states
2

path

10

Process

Reversible Irreversible Reversible: A process is said to be reversible if it reverses then follow
Reversible
Irreversible
Reversible:
A process is said to be reversible if it reverses then follow the
same path without leaving any effect on the system as well as
surrounding.
2
Q
1
2
Q 1
 For reversible process, it must follow same path and should not
affect system& surrounding.
Irreversible
Irreversibility mainly caused due to friction.
 All spontaneous process is irreversible. For the processes to be
reversible if friction is zero then process must be slow.
Quasi – Static process:
Quasi means almost.
Can't decide
1
exact path
P
W
2
V

So, divide block into different pieces,

11

P Actual path V Frictionless quasi static process is known as reversible process.  All
P
Actual path
V
Frictionless quasi static process is known as reversible process.
 All reversible process is quasi static but all quasi-static need not
be reversible.
THERMODYNAMIC CYCLE:
A system is said to be undergone a cycle if initial & final state
of system is same.
1
1
2
The minimum no. of process required to complete a cycle is 2.
Through no cycle has 2 no of process in practical. For a cycle, change
in property is zero. 3 step cycle --------.

12

THERMODYNAMIC EQUILIBRIUM:

A system is said to be in thermodynamic equilibrium if there is no any unbalances
A system is said to be in thermodynamic equilibrium if
there is no any unbalances potential (driving force) within the system.
To meet the condition of thermodynamic equilibrium three types of
equilibriums are required.
1) Thermal equilibrium [equality of temperature/no heat transfer]
2) Mechanical equilibrium [equality of all those properties which may
cause work transfer (or) no work transfer]
3) Chemical equilibrium [A system is said to be in chemical
equilibrium where there is no any mass transfer or chemical reaction
takes place within system.]
IDEAL GAS:
Obeys ideal gas equation. At all pressure and temperature.
PV = mRT
P → Absolute pressure (k pa)
V → Volume (m 3 )
M → Mass (kg)
R
→ Characteristic gas constant (kJ/kg k)
T
→ Absolute temperature
For air, R = 0.287 kJ/kg k.
A gas is said to be ideal gas if there are no any intermolecular forces.
Any gas can behave like ideal gas at very low pressure (or) very high
temperature.

13

Ideal gas

Perfect gas Semi-perfect gas (C p & C v Are constant) (C p & C
Perfect gas
Semi-perfect gas
(C p & C v Are constant)
(C p & C v Depends on temperature)
No. of moles = mass (m)/molecular weight M
m 1 = n M
∴ PV = nMRT
AVOGADRO’S HYPOTHESIS:
According to Avogadro’s hypothesis all gases at same
pressure, temperature and volume, no of moles are constant.
MR = Constant.
= Universal gas constant
̅
PV = nR T
̅
̅
R = 8.314 kj/kmol. k
Conservation of mass
M a
M b
m = ma + mb + mc + ⋯ ⋯ ⋯ ⋯ ⋯ ⋯
P a
P b
V
= V a = V b = V c = ⋯ ⋯
⋯ ⋯ ⋯ ⋯
V a
V b
Zeroth law of thermodynamics
T a
T b
T = T a = T b = T c = ⋯ ⋯ ⋯ ⋯ ⋯ ⋯
R a
R b
Daltons law of partial pressure
h a
h b
P = P a = P b = P c = ⋯ ⋯ ⋯ ⋯ ⋯ ⋯
PV = nR T
̅
P a V a = n a R
̅
T a
P a V =
n a R T
̅
̅

P b V = n b R T

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̅

P c V = n c R T

(P a + P b + P c + ⋯ ⋯ )V = (n a
(P a + P b + P c + ⋯ ⋯ )V
= (n a + n b + n c + ⋯ ⋯ )R T
̅
PV = ∑ nR T
̅
P = P a + P b + P c + ⋯ ⋯ ⋯ ⋯ ⋯ ⋯
∑ n = n a + n b + n c + ⋯ ⋯
Mole fraction: (x)
It is defined as ratio of number of moles of a gas to the total
number of moles in a mixture.
n a
n a
x a =
∑ n =
n a + n b + n c + ⋯⋯
n
b
n b
x b =
n =
n a + n b + n c + ⋯⋯
n c
n c
x c =
∑ n =
n a + n b + n c + ⋯⋯
(x a + x b + x c + ⋯ ⋯ ) = 1
x a + x b + x c +
⋯ ⋯ = 1
P
a V = n a R
̅
T
P i V = n i R T
̅
⋯ ⋯ for ith gas → (ⅰ)
PV = ∑ n R T
̅
→ (ⅱ)
eqn (ⅰ)
n i
=
eqn(ⅱ) = P i
P
∑ n
P i
= x i
P

15

MIXTURE OF IDEAL GASES:

Equivalent gas constant: → M e = Equivalent mass constant M 1 M 2 P
Equivalent gas constant:
→ M e = Equivalent mass constant
M 1
M 2
P
P = P 1 + P 2 + P 3 + ⋯ ⋯
1
P 2
V
→ V 1 = V 2 = V 3 = ⋯ ⋯ ⋯ ⋯ ⋯ ⋯
1
V 2
T
→ T 1
= T 2 = T 3 = ⋯ ⋯ ⋯ ⋯ ⋯ ⋯
1
T 2
R e = Equivalent gas
constant
R 1
R 2
n
→ ∑ n = n 1 + n 2 + n 3 + ⋯ ⋯
1
n 2
P
1 V =
m 1 R 1 T
P
=
m 2 R 2 T
2 V
P
3 V = m 3 R 3 T
(P 1 + P 2 + P 3 + ⋯ ⋯ )V = (m 1 R 1 + m 2 R 2 + m 3 R 3 + ⋯ ⋯ )T
→(ⅰ)
PV = ∑ m R e T
→(ⅱ)
From equate (ⅰ) & (ⅱ)
m R e = (m 1 R 1 + m 2 R 2 + m 3 R 3 + ⋯ ⋯ )
m 1 R 1 + m 2 R 2 + m 3 R 3 + ⋯⋯
=
R e
m 1 + m 2 + m 3 + ⋯⋯
Equivalent gas constant
m = n M
=
m 1
n 1 M 1
m 2 =
n 2 M 2
m 3 = n 3 M 3

(m 1 + m 2 + m 3 + ⋯ ⋯ ) = (n 1 M 1 + n 2 M 2 + n 3 M 3 + ⋯ ⋯ ) → ()

16

∑ m = ∑ n M e →(ⅱ)

n 1 M 1 + n 2 M 2 + n 3 M 3 +
n 1 M 1 + n 2 M 2 + n 3 M 3 + ⋯⋯
=
M e
n 1 + n 2 + n 3 + ⋯⋯
Equivalent molecular weight
Note:
Mass fraction (M. F) = m a
∑ m
Mass fraction = mass of molecule/total mass
Relation between mass fraction and mole fraction
P i V = m i R i T → (ⅰ)
PV = ∑ m R e T → (ⅱ)
(ⅰ) − (ⅱ)
P i
m i
R i
=
P
∑ m ×
R e
x i = M. F × R i
R
e
M. R = R
̅
R
̅
M e
(M.
F) i = x i ×
R
̅
M i
(M.
F) i = x i × M i
M
e
Problems with answers:
1. An ideal gas mixture consists of 2 kilo mole of N 2 and 6 kilo
mole CO 2 the mass fraction of CO 2 in mixture is.
N 2 = 2 kilo mole
CO 2 = 6 kilo mole
m CO 2
=

(M. F) CO 2

m N 2 + m CO 2

17

m CO 2 = n CO 2 M CO 2

= 6 × 44 = 264 Kg = n N 2 M N 2 m
= 6 × 44 = 264 Kg
= n N 2 M N 2
m N 2
= 2 × 28 = 56 Kg
(M. F) = 264/(264 + 56)
M.F = 0.825
2. An ideal gas mixture, whose apparent molar mass 36 kj/k mol
consist of N 2 and 3 other if the mole fraction of nitrogen is 0.3
then what mass fraction of is N 2 .
M = 36 KJ/K mole
No of gases = 4
x N 2 = 0.3
i
x N 2 = M. F × R e = M. F ×
( M e )
R
M
i
36
0.3 = (M. F) N 2 =
28
(M. F) N 2 = 0.23
3. An ideal gas mixture consist of 2 kilo mole of N 2 and 4 kilo
mole of CO 2 the apparent gas constant of mixture is,
n N 2 = 2
n CO 2 = 4
R e = M 1 R 1 n 1 +M 2 R 2 n 2
M 1 n 1 +M 2 n 2
(2+4) 8.314
(4×44)] = (6×8.314)
=
[(2×28) +
56 +176
KJ
R e = 0.215

Kg K

18

4. The rigid tank is divided into 2 compartments by a partition.

One compartment contains 3 k mole of N 2 at 600 K pa & other
One compartment contains 3 k mole of N 2 at 600 K pa & other
compartment contains 7 K mole of CO 2 at 200 K pa. Now the
position is removed& two gases from homogeneous mixture &
at 300 K pa. The partial pressure of N 2 in mixture is -----
n
= 3 K mole
N 2
p N 2 = 600 K pa
n CO 2 = 7 K mole
p CO 2 = 200 K pa
3×28
x i =
3×28+7×28
3
x N 2 =
3+7 = 0.3
p
i
300 = 0.3
p i = 90 Kpa
5. An 80 litre rigid tank contains an ideal gas mixture of 5gm of N 2
and 5 gm of CO 2 at specified pressure& temp. If N 2 were
separated from the mixture & stored at mixture temp. And
pressure its volume would be --------
80L
5gm
5gm
N 2
N 2
+ 5gm CO 2
T
P
T
P
5
n N 2 =
28

5

n CO 2 =

44

19

PV = n RT

p = p N 2 + p CO 2 5 p i 28 = =
p = p N 2 + p CO 2
5
p i
28
=
= 0.611
5
5
p
28
+ 44
p N 2 = 0.611 p
Now,
P N 2 V N 2 = m N 2 R N 2 T N 2
PV = m N 2 R N 2 T N 2
P
V N 2
=
V
P N 2
V N 2 = 80 × 0.611
V N 2 = 48.80 litre
ZEROTH LAW OF THERMODYNAMICS &
CONCEPT OF TEMPERATURE:
Temperature:
(Degree of hotness and coldness)
Macroscopic approach:
The temperature is property by virtue of difference of that
property heat flows.
Microscopic approach:
Temperature is defined as average kinetic energy of the molecules
of a system.
Internal energy:
Sum of kinetic energy of the molecule.

20

Zeroth law:

When two bodies are in thermal equilibrium with third body then there are in equilibrium
When two bodies are in thermal equilibrium with third body then
there are in equilibrium with each other.
equilibrium
A
B
A
equilibrium
B
C
B
A is in equilibrium with C
C
Reference Body
This is basic law used for temperature measurement.
Principle of thermometry:
In thermometry principle, a property which vary with
temperature. Is found first and with help of that property unknown
temp. Can be measured. The property which helps to find unknown
temp is known as thermometric property.
Types of thermometer
Thermometric property
Hg glass tube
thermometer
Length
Constant volume gas
thermometer
Pressure
Constant pressure gas
thermometer
Volume
Thermistor
Electric resistance

21

thermistor

R R 2
R
R 2
i G R 2 R 4 Thermocouple (based on see back effect) emf T T
i
G
R 2
R 4
Thermocouple (based on see back effect)
emf
T
T 2
1
See back effect:
If two metals from junction such that both are at different
temperature, then EMF is generated.
What is Peltier effect?
If two different metals form
Measurement of temperature:
1) Method used before 1954:
In this method, two reference points are used
a) Ice point of water (0°c)
b) Steam point of water (100°c)
T = a + b P
At ice point
T ice = a + b P ice
0 = a + b P I ……
(ⅰ)
At steam point

T steam = a + b P steam

22

100

= a + b P S ……. (ⅰⅰ)

From (ⅰ) & (ⅱ) 100P I b = 100 P I ; a P S
From (ⅰ) & (ⅱ)
100P I
b =
100 P I ; a
P S −
=
P I − P S
−100P
100
I
T =
+
−(P I − P S )
−P I × P
P S
−100P
100
T =
+
P I × P
P S − P I
P S −
2) Method used after 1954:
In this method, single reference point is used that is triple point
of water (0.1°c
or 273.15 K)
T = a P
At triple point,
273.15 = a P tp
273.15
a =
P tp
273.15
T =
× P
P tp
Note:
All temperature scales are arbitrary
Up to 130°C → Refrigeration.
Below 130°C → Cryogenic
Problems with solution:
1. The reading T A & T B of thermometer A & B agree at ice point and
2
steam
point. And related by equation, T A = l + mT B + nT B
When A reads 51°C then B reads 50°C.
Determine the reading of A When B reads 25°C.

T A = T B = 0 at ice point

23

L = 0

T A = T B = 100℃ 2 T A = l + mT B
T A = T B = 100℃
2
T A = l + mT B + nT B
100 = m × 100 + n × 100 2
1 = m + 100n ……… (ⅰ)
51 = m × 50 + n × 50 2
51 = m × 50 + n × 2500n ……. (ⅱ)
1 = m + 100n
50 = m × 50 + n × 5000n
−51 = m × 50 ± n × 2500n
−1 = (2500)n
n = −4 × 10 −4
m = 1.04
T A = 25.75℃
T B = 25℃
2. In a new temperature scale, say °P the boiling & freezing point of
water at atmosphere are 100°P and 300°P respective co-relate this
scale with centigrade scale and find the value of zero-degree P on
centigrade scale.
in °P
in °c
T B =
100°P
T B = 100℃
T F = 300°P
T F = 300℃
T = a + b P
At ice point 0 = a + b (300)

At steam point 100 = a + b (100)

24

100 = b (200)

b = -0.5 a = 150 ∴ T = 150 - 0.5P At P =
b = -0.5
a = 150
∴ T = 150 - 0.5P
At P = 0 °P
T = 150 °C
ENERGY INTERACTION:
For closed system and its surrounding, energy interaction takes
place in 2 ways.
1) Work interaction
2) Heat interaction
Work interaction:
In mechanics, action of force on moving body is known as work.
W = F × displacement.
m
W
Battery
Battery
Electrical work
Electrical work

25

m m Battery Battery No works Mechanical works In thermodynamics, the work is said to
m
m
Battery
Battery
No works
Mechanical works
In thermodynamics, the work is said to be done by system
if sole effect external to the system can be reduced to the rising
of weight.
The weight may not be actually raised but the net effect
external to the system can be reduced in form of lifting weight,
work transfer is a boundary phenomenon, it is recognised only
when it crosses the boundary of system.
At boundary if work is done by temperature difference then
it is heat transfer otherwise work transfer.
Heat
Electrical
Transfer
Work Transfer
Convection of work transfer:
 Work done by the system is +ve
 Work done on the system is –ve

26

W W Gas Gas Expansion Process Compression Process +ve work -ve work Expansion work is
W
W
Gas
Gas
Expansion Process
Compression Process
+ve work
-ve work
Expansion work is always +ve whereas compression work is always
–ve.
CLOSED SYSTEM WORK/NON-FLOW WORK:
(Displacement work/p. dv work)
1
P 2 V 2
P 1
P 1 V 1
Gas
P
System
A
P
2
P 2
V 1
dV
V 2
dx
V
Closed system reversible process
P = F/A → F = PA
dw =
F × dx
= PA × dx
dw = P dv
Total work w = ∫
2 P dv
(Closed system reversible process)
1
dA = P dv

27

Total area A =

1

2 P dv

(Closed system reversible work)

 Area under the curve when projected on volume axis gives closed system reversible work
 Area under the curve when projected on volume axis gives closed
system reversible work on P-V diagram.
1
b
a
P
2
V
Through the ends points are same for process A and B but the
work transfer is not same because area below the curve is not same.
Therefore, work transfer depends on path followed by system.
Work transfer is path function it is not a property. It is inexact
differential.
CLOSED SYSTEM WORK FOR VARIOUS
PROCESSES:
1) Constant volume process:
Gas
Q
Q
Rigid container with
all boundaries fixed
V = Constant
Ideal gas equation

28

P

1

P

2

= T 1

T 2

dv = 0 W = ∫ P dv = 0 Heat supplied 2 1 P
dv
= 0
W = ∫ P dv = 0
Heat supplied
2
1
P
Heat rejected
1
2
V
2) Constant pressure processes:
P
1
2
V 1
V 2
P = Constant
Ideal gas equation
V
1
= T 1
V ∝ T
V
T
2
2
dp
= 0
2
2
2
W = ∫
P dv = P ∫
dv = p[v] 1
1
1
W
= P (V 2 − V 1 )

29

Patm p Wt = 2 bar W W p g = 2 bar Gas p
Patm
p Wt = 2 bar
W
W
p g = 2 bar
Gas
p g = p Wt + p atm
Q
Q
Heat supplied
1
2
P
Heat rejected
2
1
V
3) Isothermal process (Constant temperature process):
Q
Q
T = Constant
Ideal gas equation
V
1
= T 1
PV = mRT
V
T
2
2
PV = C
P
1 V 1 = P 2 V 2
C
P =
V
2
2
C
W = ∫
P dv = ∫
( V ) dv = C ln
[ V 1 2 ] s
1
1
V
W
= P 1 V 1 ln V 1 2 = P 2 V 2 ln V 2
V
V
1
W
= P initial V initial ln V final
V
initial

Piston - independent

30

Pressure - dependent Isothermal expansion is possible when heat is added to system where as isothermal compression is possible if heat is rejected from the system.

Heat supplied P Heat rejected V Note: Isothermal curve on p-v diagram is rectangular hyperbola.
Heat supplied
P
Heat rejected
V
Note:
Isothermal curve on p-v diagram is rectangular hyperbola.
4) Adiabatic process:
(No heat transfer)
Ideal gas equation for adiabatic process,
PV γ = C
γ = Adiabatic index
γ = c p
c
v
W = ∫
2 P dv
1
P 1 V 1 γ = P 2 V 2 γ
2 C
W = ∫
dv
1
V γ
2
w = c [ −V γ+1
]
−γ+1
1
= c [ V 2 γ+1 − V 1 γ+1
w
]
−γ+1

31

w

= P 2 V 2 .V 2 γ+1 − P 1 V 1 .V 1 γ+1

−γ + 1 P 2 V 2 − P 1 V 1 w = −γ+1
−γ + 1
P 2 V 2 − P 1 V 1
w
=
−γ+1
P 1 V 1 − P 2 V 2
w
=
γ − 1
1
2
Expansion
P
Gas
2
Compression
1
V
Note:
 Different form of ideal gas equation for adiabatic process.
PV γ = C
P
1 V 1 γ = P 2 V 2 γ
PV V γ−1 = C
PV = mRT
TV γ−1
= C
1 V 1 γ−1 = T 2 V 2 γ−1
T
V 1 γ−1
T
2
=
V 2 γ−1
T
1
P
1
=
P
2
V 2 γ
V 1 γ
1
V
1
γ
2 = ( P 2
V
P
1 )
1 ) γ−1
T
2
γ
1 = ( P 2
T
P

32

5) Polytrophic process:

Ideal gas equation, PV n = C n → Polytrophic index. 1 < n <
Ideal gas equation,
PV n = C
n → Polytrophic index.
1 < n < γ
&
P 1 V 1 − P 2 V 2
w polytropic =
n −1
Note:
All process in p-v diagram can be represented by PV k = C where
K is dependent on type of process for constant pressure process,
K = 0
Isothermal process,
K = 1
Adiabatic, k = γ
Polytrophic, k = n
Constant volume = k = ∞
 Representation of various processes on p-v diagram.
K
= 0
P
K
= 1
K = n
K = r
K = ꝏ
Increasing
For Expansion
V
Increasing
K = ꝏ
K
= r
K = n
K = 1
K = 0
K = n K = r K = ꝏ Increasing For Expansion V Increasing K =

For Compression

33

SLOPE OF VARIOUS LINES ON P-V DIAGRAM:

1. Constant pressure line: P V θ = 0 Slope = m = 0 Slope
1. Constant pressure line:
P
V
θ = 0
Slope = m = 0
Slope = tanθ = tan0 = 0
2. Constant volume process:
P
V
θ = 90°
Slope = tan 90°
m = ∞
3. Isothermal process:
P
V
= dp
Slope = dy
dx
dv

m = − p

v

34

dp d c ) dv = dv ( v pdv + vdp = 0 dp
dp
d
c
)
dv =
dv (
v
pdv + vdp = 0
dp
= − p
dv
v
slope = − p
v
4. Adiabatic line:
PV γ = C
Pγ V γ−1 dv + V γ dp = 0
Dp
= γ (− p v )
dv
Slope of adiabatic curve = γ (− p v )
 Slope of adiabatic curve on p-v diagram
= γ (slope of isothermal curve on p − v)
Note:
 Net work done in cycle is equal to the area of closed region or
area of cycle.
 All clockwise cycle on p-v diagram are powers producing cycle.
(example: - Carnot cycle, etc.) All anticlockwise cycles on p-v
diagram are power consuming cycle.
(example: - refrigeration cycle)
W = ∫ P dv
(Closed system, reversible process & energy should cross the
boundary.)
35

Problems and Solutions:

1. An imaginary engine receive heat and perform work on slowly moving piston in such
1. An imaginary engine receive heat and perform work on slowly
moving piston in such way that cycle of operation of 1 kg of
working fluid can be represented as a circle of 10cm diameter on
p-v diagram. In which 1cm = 300k pa & 1cm = 0.1m 3 /kg find
network during a cycle.
Network = Area of circle
π
=
× (d 2 ) × 300 × 0.1
4
= 2356.1KJ/Kg
W net
2. An engine cylinder has piston area of 0.12m 2 & contains gas at
pressure of 1.5M Pa the gas expands according to a process which
is represented by a straight line on p-v diagram. the pressure is
0.15MPa calculate work done by gas on piston, if stroke is 0.3m.
A = 0.12m 2 P 1 =1.5M Pa P 2 = 0.15M Pa L = 0.3m
1.5 Mpa = 1500 kPa
P 1
0.15 Mpa = 150 kPa
P 2
Clearance
V 1
V 2
Volume
0.3 m
Stroke length
V 2 − V 1 = 0.3 × 0.12 = 0.036m 3
W net = area under the curve
1

W net = (150 × 0.3 × 0.12) − 2 [0.3 × 0.12 × (1500 − 150)]

36

W net = 29.7 KJ

P 1 3. A gas expands from pressure P 1 to P 2 (P 2
P
1
3.
A gas expands from pressure P 1 to P 2 (P 2 = 10 ). If pressure
expansion is isothermal the volume at end of expansion is
V 2 = 0.55m 3 . If process of expansion is adiabatic then volume at
expansion is?
1
P 1
pv 1.4 = c
T = C
P 2
2
2 1
V 2
0.55
V 1
P
1 V 1 = P 2 V 2
P
1
= 10
P
2
10 × V 1 = 0.55
V 1 = 0.055
Now, for adiabatic process,
P
1 V 1 γ = P 2 V 2 γ
P
1 ( V 2
2
=
P
V
1 ) γ
V
2
10 = (
) γ
0.055
γ = 1.4
1
V
2
10 γ = (
)
0.055
V
2 = 0.286m 3

37

4. The gas space above water above water in storage tank contains N 2 AT 25°C & 100K Pa the total volume is 1m 3 & there is 500kg water at 25°C and additional 500kg is now forced into tank assuming constant temperature throughout find final pressure on N 2 & work done on N 2 in the process.

25 0 C 100 kPa N 2 water P 1 = x 25 0 C
25 0 C
100 kPa
N 2
water
P 1 = x
25 0 C
P 1 = 100 kPa
V 2
4m 3
V 1
500
Volume water = V 1 =
1000 = 0.5m 3
V 2 = 0.5m 3
V 1 = 3.5 m 3
P 1N 2 = 100K Pa
P 2N 2 =?
Final volume, v 1 1 = 1m 3
v 2 1 = 3m 3
P 1N 2 V 1N 2 =
P 2N 2 V 2N 2
(100 × 3.5 =
P 2N 2 × 3)
P 2N 2 = 116.66KPa
W net = P 1 V 1 ln V 2
V
1
3
= 100 × 0.5 ln ( 3.5 ) = −53.95 KJ

Work done on N 2 = 53.95 KJ.

38

5. A piston cylinder device contains 0.05m 3 of gas initially at 200k pa at this state a linear spring which have spring constant of 15K N/m is just touching the piston is transmitted to gas causing the piston rise and compress the spring until volume inside a cylinder is double. If cross section are of piston is 0.25m 2 find final pressure inside the cylinder & work done by the gas.

F k × x P = A = A 0.05 Stroke length = = 0.2
F k × x
P =
A =
A
0.05
Stroke length =
= 0.2
0.25 × V 2 − V 1
A
150 × 0.2
P =
= 120
0.25
P 2 = P atm + P p + P s = 200 + 120
P 2 = 320 K Pa
 If there were no spring pressure will remain constant
200 kPa
P 1
P 2
V 1
V 2
P pisto
P at
n
m
200 kPa

39

P atm P piston P atm P piston P surrounding 100 kPa Work done by
P atm P piston P atm P piston P surrounding 100 kPa Work done by
P atm
P piston
P atm
P piston
P surrounding
100 kPa
Work done by gas = W @constant pressure + W spring
= W expansion + W spring
= P(V 2 − V 1 ) + 1 kx 2
2
= 200(1 − 0.05) + 1 × 150 × (0.2) 2
2
W gas = 13 KJ
Short trick to find area
2
320
1
200
0.05 0.1
W gas = A (below the curve)
= 0.05 × 200 + 0.05 × 120
W gas = 13 KJ

40

6. An insulated vertical tank contains 0.1kg of organ gas with the

help of piston as shown in fig. the mass of piston is 5 kg &
help of piston as shown in fig. the mass of piston is 5 kg & initially
at rest on the bottom of cylinder the cylinder is connected to
nitrogen cylinder the valve the valve is opened and nitrogen
slowly enter to the cylinder. During this process piston is lifted to
a height of 10cm by nitrogen. The initial pressure & temperature
of organ is 1 bar and 300k and final temperature of organ is 320k
calculates the work done by organ and by 2 . R = 0.208 KJ/Kg K
γ = 1.67 for organ
Ar = 0.1 kg
1 bar
300k
10 cm
N
2
100 bar
m
org = 0.1 Kg
For organ
PV = m RT
m
p = 5 Kg
1 × V = 0.1 × 0.208 × 300
P
1N 2 = 100 bar
V
1Ar = 6.24
x
= 10cm
γ−1
T
P
1Ar = 1 bar
2
1 = ( V 2
γ
T
V
1 )
T
1Ar = 300K
V
2 = 5.34m 3
T
2Ar = 320K
Work done by organ
P 1 V 1 − P 2 V 2
W
=
Ar
γ−1

41

mR (T 1 − T 2 )

=

γ−1 = 0.1×0.208(300 − 320) 1.67 − 1 W Ar = −0.627 KJ Now, work
γ−1
= 0.1×0.208(300 − 320)
1.67 − 1
W Ar = −0.627 KJ
Now, work done by N 2 ,
W
N 2 =
W ar + W piston
mgh
= 0.627 + (
)
1000
= 0.627 + 5×9.81×0.1
1000
W
N 2 = 0.6249 KJ
7. A sealed elevated storage tank of capacity 50m 3 initially
containing air at 1 bar & 25°C is to be pumped with water from a
lake also @ 25°C g = 9.7 m/s 2 the pump is operated until the
3
tank is 4 full and during this operation the temp of air & water do
not change the average elevation of water in tank is 35m above
the surface of lake. Take ρ water = 1000kg/m 3 & assume air as
ideal gas.
P
2
P
P
1
V 1
V 2
V
1 bar = 1.01 × 10 2 k pa
Volume of tank = 50 m 3
P air = 1 bar

42

T air = 25℃ = 298K

T water = 25℃ g = 9.7 m/s 2 ρ water = 1000 kg/m 3
T water = 25℃
g = 9.7 m/s 2
ρ water = 1000 kg/m 3
3
volume = V water = 4 × 50 = 37.5
m water = 1000 × 37.5 = 37500 kg
h = 35m
P.E = mgh
P
2
= V 1
P
1
V 2
50
P 2 = 100 × 12.5 = 400kpa
Work done = P 1 V 1 ln V 2
V
1
= 100 × 50 ln ( 12.5 )
50
= −6931.47 KJ
W pump = 6931.47 + 9.7 × 35 × 37500
1000
W pump = 6931.47 + 12731.25
W pump = 19662.7KJ
W pump = W air compressure + W p.e
HEAT
Heat is transient form of energy which transfers due to negative
temperature gradient. (High temp to low temp).
Heat has its meaning only if it is crossing the system.

Q ∝ m

43

Q ∝ ∆T Q ∝ m∆T Q = mc∆T

Q C = m∆T (Specific heat) Put m = 1 Specific heat is amount ∆T
Q
C =
m∆T
(Specific heat)
Put m = 1
Specific
heat
is
amount
∆T = 1
of
heat
∴ C = Q
required
to
increase
the
temperature of 1-unit mass of substance through 1°c temperature.
SPECIFIC HEAT OF GASES:
m
m
T i
T f
T i
T f
Q V
Q P
dv = 0
w = 0
Only intermolecular energy
dv ≠ 0
w ≠ 0
Intermolecular energy +
external energy
Q p >
mc p ∆T >
Q v
mC v ∆T
C p > C v
C
p

γ =

C v

γ > 1

44

Specific heat at constant pressure is greater than specific heat at constant volume because C p includes internal energy as well as external

work whereas C v includes only internal energy. For monatomic gases (Ar, He etc.) γ
work whereas C v includes only internal energy.
For monatomic gases (Ar, He etc.)
γ = 1.67
For diatomic gas,
γ = 1.4
For polyatomic gases,
γ = 1.33
 Specific heat of solids and liquids:
In case of solids & liquids with the applications of
pressure, change in volume is negligibly small (incompressible).
Therefore, for solid& liquid,
C p = C v = C
Note:
C
p
γ =
C v = 1 + 2
n
Where, n = Degree of freedom of module.
For monatomic molecule, n = 3
For diatomic molecule, n = 5
For triatomic molecule, n = 6
FIRST LAW OF THERMODYNAMICS:

First law of thermodynamics is based on law of conservation of energy heat & works are different form of same entity called energy which is conserved.

45

Statement of closed system undergoing cycle:

First law of thermodynamic for closed system undergoing cycle: “For a closed system undergoing a
First law of thermodynamic for closed system undergoing cycle:
“For a closed system undergoing a cycle heat transfer is equal to the
network transfer”.
∑ Q = ∑ w (Valid for closed system undergoing cycle)
Result from first law of thermodynamic:
1) Heat is a path function:
c
P
b
a
V
For cycle 1a2b1
(dQ) 1a2 + (dQ) 2b1 = (dW) 1a2 + (dW) 2b1 … …
(ⅰ)
For cycle 1a2c1
(dQ) 1a2 + (dQ) 2c1 = (dW) 1a2 + (dW) 2c1 … … … (ⅱ)
Equation (ⅰ) - (ⅱ)
(dQ) 2b1 − (dQ) 2c1 = (dW) 2b1 − (dW) 2c1 … …
Work is a path function,
(dW) 2b1 ≠ (dW) 2c1
(dW) 2b1 − (dW) 2c1 ≠ 0
(dQ) 2b1 − (dQ) 2c1 ≠ 0
(dQ) 2b1 ≠ (dQ) 2c1
(A)

46

Conclusion:

Through end points are same for path b & c but heat transfer is not
Through end points are same for path b & c but heat transfer
is not same. Therefore, heat transfer is a path function.
2) From equation (A):
(dQ) 2b1 − (dQ) 2c1 = (dW) 2b1 − (dW) 2c1
(dQ − dW) 2b1 = (dQ − dW) 2c1 = dE
The quantity (dQ − dW) is same for path b & c hence, it
does not depend on the so it must be a property, this property is
known as energy.
dQ − dW = dE
(First law of thermodynamics for closed system undergoing
a process)
3) Energy of system can be divided as
1. Macroscopic
a. Kinetic energy (
2 1 mv 2 )
b. Potential energy (mgh)
2. Microscopic
a. Translational motion of molecule
b. Rotational motion of molecule
c. Vibration motion of molecule
[Internal energy [energy associated with molecules]

E = K. E + P. E + I. E dE = d(K. E) + d(P. E) + d(I. E) Neglected, change in K.E & P.E neglected. dE = dU

47

dQ = dU + dW

(First law of thermodynamics for closed system undergoing a process neglecting change in K.E &
(First law of thermodynamics for closed system undergoing
a process neglecting change in K.E & P.E of system.)
4) Energy of isolated system is constant
dQ = dE + dW
For isolates system,
dQ = 0
dW = 0
dE = 0
E = c
Energy for universe is constant.
5) Perpetual motion of 1 st kind: (PMM-1)
Perpetual motion = Continuous motion i.e. (cycle)
The word perpetual means continuous. If a system is
producing continuous work, then it must be operating on cycle
PMM-1 is a machine which give continuous work without any
energy input.
Q = 0
PMM – 1
W
For cycle, [cycle is clockwise (work)]
∴ (Power producing)
Q = ∑ w

Q = 0

48

W = 0 So, according to 1 st law PMM-1 is not possible. If such a device is developed, then it will violate 1 st law of thermodynamics. For ideal gas, dU = mc v dT ; U = f(T) only

dH = mc p dT (Joules law) ENTHALPY: (H) In thermodynamics the term U +
dH = mc p dT
(Joules law)
ENTHALPY: (H)
In thermodynamics the term U + PV appears frequently so for
our convince this term is taken as enthalpy. It is extensive property %
specific enthalpy is given as,
H = U + PV
Specific enthalpy h = U + PV (h → Intensive)
In closed system,
Internal energy is very important.
But in open system,
Enthalpy plays vital role.
PV = Flow work
U = Internal energy
Heat transfer in various non-flow/closed systems:
1) Constant volume process:

V = C dQ = dU + dW For constant volume process dW = 0 dQ = dU

49

For ideal gas, dU = mc v dT ⇒ dQ = dU = mc v dT 2) Constant pressure process:

P = Constant dw = PdV = d(PV) dQ = dU + dW = dU
P = Constant
dw = PdV = d(PV)
dQ = dU + dW = dU + d(PV)
dQ = d(U + PV)
dQ = d(H)
For ideal gas
∴ dH = mc p dT
dQ = dH = mc p dT
3) Isothermal process:
PV = C
&
T = C
dQ = dU + dW
For ideal gas
U = f(T)
If T = Constant, then U = Constant
∴ dU = 0
dQ = dW
dW = P 1 V 1 ln V 2
V
1
dQ = dW = P 1 V 1 ln V 2
V
1

50

4) Adiabatic process:

dQ = 0 dQ = dU + dW dU + dW = 0 dW =
dQ = 0
dQ = dU + dW
dU + dW = 0
dW = −dU
Note:
Show that C p − C v = R for ideal gas
H =
(U + PV)
dH = d(U + PV)
= dU + d(PV)
dH = mC p dT
dU = mC v dT
mC p dT = mC v dT
+ d(mRT)
C p − C v = R Valid for ideal gas
C
R
R
p
C v = γ & C v =
−1 , C p =
γ
γ − 1
5) Polytrophic process:
dQ = dU + dW
P 1 V 1 − P 2 V 2
=
dU +
n−1
For ideal gas,
dQ = mc v dT + P 1 V 1 − P 2 V 2
n−1
P 1 V 1 − P 2 V 2
dQ = mc v (T 2 − T 1 ) +
n−1
= mc v
mR
P 1 V 1 − P 2 V 2
(
P 2 V 2 − P 1 V 1 ) +
n−1

51

1 1 = P 2 V 2 − P 1 V 1 [ γ−1 −
1
1
= P 2 V 2 − P 1 V 1 [
γ−1 −
n−1 ]
= n−γ
1 [ P 2 V 2 − P 1 V 1
]
γ−1
n−1
P 1 V 1 − P 2 V 2
dQ = γ−n
[
]
γ−1
n−1
dQ = γ−n
W poly
γ−1
SPECIFIC HEAT FOR POLYTROPHIC
PROCESS:
P 1 V 1 − P 2 V 2
dQ = γ − n
[
]
γ
− 1
n−1
γ − n
mR (T 1 − T 2 )
= [
]
γ
− 1
n−1
n − γ
= m
c v dT
n − 1
( n − γ
n − 1
c v → C poly )
Convection of heat transfer heat supplied to system +ve heat rejected
for system -ve
n − γ
=
C poly
c γ
n − 1
γ > n > 1
C poly is always negative
C poly = −ve

52

dQ =

[ P 2 V 2 − P 1 V 1 ] − [ P 1 V 1 − P 2 V 2

γ−1

n−1

dQ = [ P 2 V 2 − P 1 V 1 ] − [ P
dQ = [ P 2 V 2 − P 1 V 1 ] − [ P

]

In polytrophic process,

system Q If we supply the heat, then also the temperature of system decreases. This
system
Q
If we supply the heat, then also the temperature of
system decreases. This is because in such a polytrophic process work
transfer is more than heat transfer and excess amount of work comes
from the internal energy of the system as there is decrease in internal
energy. Temperature of system decreases.
Note:
Show that PV γ = Constant for ideal gas undergoing adiabatic process.
For a process,
dQ = dU + dW
dQ = dU + PdV
For adiabatic process,
For
(ⅰ)

dQ = 0 ideal gas, dU = mc v dT 0 = mc v dT + PdV … … … … mc v dT = −PdV (H = U + PV) [dU + d(PV)] dH = dU + PdV + VdP dH = dU + d(PV) dH = dU + PdV + VdP

53

For ideal gas,

mc p dT = 0 + VdP … … … . (ⅱ) VdP Equation (ⅱ)/Equation
mc p dT = 0 + VdP … … … . (ⅱ)
VdP
Equation (ⅱ)/Equation (ⅰ) → c p
c v =
−PdV
dP
γ ( dv ) = −
v
v
dP
+ γ ( dv ) = 0
v
v
Integrating,
∫ dP
+ ∫ γ ( dv ) = 0
P
v
lnP + γ lnV = ln C
PV γ = C
(Ideal gas undergoing adiabatic process)
SPECIAL CASE OF WORK TRANSFER:
Electric
works by
B The system

54

1. Electric works on The system B w = −ve; V = Constant dV =
1.
Electric
works on
The system
B
w = −ve; V = Constant
dV = 0
PdV = 0
Cannot apply W = PdV as PdV is displacement work
And in this system work is electrical.
Gas
Vacuum
System → gas + vacuum
W = 0
(If partition is removed); V = constant
PdV = 0

55

2.

Gas Vacuum dV ≠ 0 (Change is volume non-zero) PdV = 0 w = 0
Gas
Vacuum
dV ≠ 0 (Change is volume non-zero)
PdV = 0
w = 0
Since, there is nothing to resist hence, work done is
zero. This condition is called as free expansion.
Free expansion is defined as the expansion against
vacuum or unrestricted expansion.
Free expansion work is zero because as the gas is
expanding against the vacuum there is no resistance offered
from surrounding and hence work is zero.
Gas
Vacuum

dQ = dU + dW dU = 0 U = Constant; U i = U f For ideal gas, U = f(T) T i = T f H = U + PV

56

For ideal gas, H = f(T) + mRT H = f(T) H i = H f

Problems with Solutions: 1. A well-sealed room contain 60kg of air at 200° k pa
Problems with Solutions:
1. A well-sealed room contain 60kg of air at 200° k pa & 25℃ ,
now solar energy enters the room at an average rate of 0.8 KJ/sec.
while a 120Watt fan is turned on to circulate the air in room. If
heat transferred through the wall is zero, the air temperature in
room after 30min.
- 0.12 kJ/sec
for air C v = 0.718 KJ/Kgk
C p = 1.005 KJ/Kgk
R = 0.287 KJ/Kgk ; γ = 1.4
m = 60kg
For air
C v = 0.718
T = 25℃
P = 200Kpa
Q = 0.8KJ/sec
P = W = 120 Watt = 0.12 KJ/sec
t = 30min

57

dQ = dW + dU 30 × 60 × 0.8 = dU − 0.12 × 30 × 60 dU = 1656 mC v dT = 1656/[60 × 0.718(T 2 − 25)] T 2 = 63.44℃ A two-kilo watt base board electric resistance heater in a vacant room is turned on & kept on for 15min. the mass of air in room at 75kg and room is perfectly sealed find the temp rise of air at end of 15min.

2. W = 2 kW P = 2Kw = 2KJ/sec m = 75kg dQ =
2.
W = 2 kW
P = 2Kw = 2KJ/sec
m = 75kg
dQ = 0
dW = dU
mC v dT
= 2 × 15 × 60
75 × 0.718 × (dT) =
2 × 15 × 60
3.

dT = 33.42℃ Room contains 60kg of air at 100 k pa & 15the room has 250watt refrigerator 120W TV, a 1 KW electric resistance & 150W fan. During cold winter day it is observed that the refrigerator & TV &fan & electric resistance heater is running continuously but air temp in room remains constant. The rate of heat loss from the room in KJ/hr.

58

dQ = dW + dU

dQ = mC v dT − (0.250 + 0.120 + 1 + 0.05) × 60
dQ = mC v dT − (0.250 + 0.120 + 1 + 0.05) × 60 × 60
dT = 0
dQ = 0 − 5112
dQ = −5112KJ/hr
Heat loss
dQ = 5112KJ/hr
4. Helium at 20 atm and 40℃ is contained in small steel cylinder
having a volume of 15cm 3 = 15 × (10 −2 ) 3 m 3 . The cylinder is
placed in large container having a volume of 1500cm 3 . The large
cylinder is perfectly evacuated and insulated by an appropriate
means helium discharged to fill the container calculate final
pressure of helium.
15cm 3
1500cm 3
20 atm
Work = 0 (free expansion)
T initial = T f
T f = 40℃
dT = 0
dU = 0
Now,

initial = T f

T

59

P i V i = P f V f

20 × 15 = P f × 1500 P f = 0.2 atm 5. A
20 × 15
= P f × 1500
P f = 0.2 atm
5. A gas undergoes a thermodynamics cycle consisting of following
processes
(ⅰ) Process 1-2 → Constant pressure
P = 1.4 bar ;
V 1 = 0.028m 3 ;
= 10.5KJ
W 1−2
(ⅱ) Process 2-3 → Compression with PV = C
U 3 = U 2
(ⅲ) Process 3-1→ Constant volume
U 1 − U 3 = −26.4 KJ
(i)
Find heat transfer & change in internal energy for 1-2
(ii)
Find heat transfer in 2-3
(iii)
Find heat transfer in 3-1
P
1
3
1.4 =
P
2
1
2
V 2
V 1
(ⅰ) W 1−2 = 10.5KJ
10.5
=
P(V 2 − V 1 )
10.5
= 1.4 × 100 × (V 2 − 0.028)
V 2 = 0.103m 3
dQ = dW + dU
dU = U 2 − U 1

60

= U 3 − U 1

(U 2 = U 3 )

dU = 26.4KJ dQ = 10.5 + 26.4 dQ = 36.9KJ (ⅱ) dQ = dW
dU = 26.4KJ
dQ = 10.5 + 26.4
dQ = 36.9KJ
(ⅱ) dQ = dW + dU
dU = 0
(U 2 = U 3 )
dQ = dw = P 2 V 2 ln V 2
V
1
= 1.4 × 10 2 × 0.103 × ln ( 0.103
)
0.028
dQ = −18.78KJ
(ⅲ) 3-1
dQ = dW + dU
= (U 1 − U 3 ) + 0
dQ = −26.4KJ
6. A rigid insulated tank of 3m 3 volume have two compartments. 1 st
compartment of 1m 3 contains ideal gas at 0.1MPa & 300K. while
the 2 nd compartment contains same gas 1MPa & 100K. If the
partition is removed, then determine the final temp& pressure of
gas.
1m 3
2m 3
P
f
0.1 MPa
1 MPa
T
f
1000K
300K
V 1 = 1m 3 ; V 2 = 2m 3 ; V f = 3m 3
dQ = 0

Q loss = Q gain

61

P 1 V 1 = M 1 R 1 T 1

&

P 2 V 2 = M 2 R 2 T 2

Same gas P 1 V 1 = n 1 R 1 T 1 0.1 ×
Same gas
P 1 V 1 = n 1 R 1 T 1
0.1 × 10 3 × 1 = n 1 × R × 300
n 1 = (3 × 10 −1 )/R
̅
n 1 = 0.360
P 2 V 2 =
n 2 R 2 T 2
2 × 10 3 × 1 = n 2 × R × 1000
n 2 = (2 × 10 −3 )/R
̅
n 2 = 2.40
Q loss = Q gain
m 2 (1000 − T f ) = m 1 (T f − 300)
Mn 2 (1000 − T f ) = M n 1 (T f − 300)
n 2 (1000 − T f ) =
n 1 (T f − 300)
2.4(1000 − T f ) = 0.36(T f − 300)
6.66(1000 − T f ) = T f − 300
T f =
900K
P f V f = ∑ nR f T f
P f × 3 = (2.4 × 0.36) × 0.8314 × 900
P f = 700 KPa
P f = 0.7 MPa

62

7. A gas of mass 1.5kg undergoes a quasi-static expansion which

follows the relationship P = a + bV where a & b are constant the
follows the relationship P = a + bV where a & b are constant the
initial & final pressure are 1000kg & 200kpa respectively &
corresponding volumes are 0.2m 3 & 1.2m 3 . The specific internal
energy is given as μ = 1.5 ρV − 85KJ/kg where in k pa &
ϑ = m 3 /kg. Calculate the net heat transfer & maximum internal
energy of gas during expansion.
m = 1.5kg
P = a + bV
P i = 1000KPa
1
(1000)P i
2
(200)
P i
1.2
0.2
P f = 200KPa
V i = 0.2m 3
V f = 1.2m 3
μ = 1.5;
ρV − 85 KJ/kg
P = a + bV (Linear relation)
1000 = a + b(0.2)
200 = a ± b(1.2)
800 = b(−1)

b = −800

63

a = 1000 + 800(0.2)

a = 1160 = 1.5 × (1000) × ( 0.2 1.5 ) − 85 =
a = 1160
= 1.5 × (1000) × ( 0.2
1.5 ) − 85 = 115
u i
u f = 1.5 × (200) × ( 1.2
1.5 ) − 85 = 155
dU = md(U i ) = 40 × 1.5 = 60
dQ = dU + dW
1
= 60 + (1 × 200) + 2 × 1 × 800
dQ = 660 KJ
m × U = 1.5PV × m − 85m
U = 1.5PV − 85 × 1.5
U 1 = 1.5P 1 V 1 −
8.5 × 1.5
U 2 = 1.5P 2 V 2 − 8.5 × 1.5
dU = 60 KJ
dQ = 60 + 600 = 660 KJ
U = 1.5PV − 85 × 1.5
dU
d
dV [ 1.5(a + bV) × V − 85 × 1.5]
dV =
d
=
[ 1.5(aV + bV 2 ) − 85 × 1.5]
dV
= 1.5a + 1.5 × 2 × b × V − 85 × 1.5
= 1.5 × 1160 + 1.5 × 2 × (−800) × V − 127.5
= −1600 × V + 1612.5
V = 0.725m 3
U max = 1.5 × (1160 − 800 × (0.725)) × 0.725 − 85 × 1.5

U max = 503 KJ

64

OPEN SYSTEM:

When there is mass transfer along with energy transfer across system boundary then system is
When there is mass transfer along with energy transfer
across system boundary then system is called as open system.
Steady flow:
A flow is said to be steady flow, if properties do not
change w. r. to time at given location.
Uniform flow:
A flow is said to be uniform if properties do not change
w.r.to location (space) at a given time.
Note:
In closed system we talked about fixed mass but in open
system we will talk about mass flow rate.
In open system analysis, a fixed volume is considered
known as control volume.
In control volume mass can enter or leave energy can
enter or leave but volume of system remains constant.
MASS BALANCE:
(Law of conservation of mass)
If there is no accumulation of mass (control volume).
Then, rate of mass entering is equal to rate of mass leaving.
In case of steady flow, there is no accumulation of mass.
m 1 = m 2 = m → Steady flow
m
ρ =
vol

ρAL

m

time =

time

65

m = ρAL For steady flow m 1 = m 2 ρ 1 A 1 V 1 = ρ 2 A 2 V 2 → continuty equation In case of unsteady flow, m 1 ≠ m 2

OPEN SYSTEM WORK 1) External work 2) Flow work Open system work External work Flow
OPEN SYSTEM WORK
1) External work
2) Flow work
Open system work
External work
Flow work
External Work:
The work transfer across the control volume other than due to normal
fluid force
Example: shaft work
Flow work:
It is the work involved in causing the fluid element
either enter to C.v or leave the C.v.
Flow work is analogous to “displacement work”.

66

Work:

1 dm,d v P dv = ϑdm 2 dW flow = PdV = Pvdm dW
1 dm,d
v
P
dv = ϑdm
2
dW flow = PdV = Pvdm
dW flow
= P v
dm
flow × work
= P v
mass
Total flow work = P v M
= PV
At energy, flow work = −P 1 V 1
At exit, flow work = P 2 V 2
ENERGY BALANCE:
1) Steady flow:
In steady flow there is no accumulation of mass &
energy within the system (Control volume).
Mass entering m 1 = mass leaving m 2
Energy entering E 1 = energy leaving E 2

67

P 1 V 1 W CV C 1 U 1 Z 1 M 1 P
P 1 V 1 W CV C 1 U 1 Z 1 M 1 P
P 1 V 1 W CV C 1 U 1 Z 1 M 1 P

P 1

V 1 W CV C 1 U 1 Z 1 M 1 P 2 2
V 1
W CV
C 1
U 1
Z 1
M 1
P 2
2
V 2
Q
C 2
U 2
Z 2
M 2
m 1 = m 2 = m
E 1 = E 2 = E
E 1 =
1 2 m 1 C 1 2 + m 1 gZ 1 + U 1 + Q
E 2 =
1 2 m 2 C 2 2 + m 2 gZ 2 + U 2 + W
We have
W = WC v − P 1 V 1 + P 2 V 2
For steady flow,
E 1 = E 2
1 2 m 1 C 1 2 + m 1 gZ 1 + U 1 + Q =
2 1 m 2 C 2 2 + m 2 gZ 2 + U 2 + W
m 1 =
m 2 = m ;
W
= WC v − P 1 V 1 + P 2 V 2
2
2
h 1 + C 1 2
+ gZ 1 + q = h 2 + C 2
+ gZ 2 + WC v
2
1 st law of thermodynamics for open system steady flow.
Examples of Steady flow process:
1) Nozzle:
Nozzle is a device which is used to increase the velocity
of fluid in expanse of pressure energy.
1) Nozzle: Nozzle is a device which is used to increase the velocity of fluid in

68

1 2 Q = 0; Z 1 = Z 2 W Cv = 0 2
1
2
Q = 0; Z 1 = Z 2
W Cv = 0
2
2
h 1 + C 1 2
+ gZ 1 + 0 = h 2 + C 2
+ gZ 2 + 0
2
h 1 + C 1 2
=
h 2 + C 2 2
2
2
J
C 1 2
C
→ m
;
h → KJ/Kg
1
2
Kg ;
s
Hence,
2
C
1
C 2 2
h 1 +
h 2 +
2000 =
2000
C 2 >>>> C 1
C 1 Can be neglected,
When C 1 value is net given
C 2 2
h 1 = h 2 +
2000
C 2 = √2000(h 1 − h 2 )
2) Turbine:
It is used to produce work
W = +ve
Z
1
Z
2

Q = 0

Z 1 = Z 2

69

Neglecting kinetic energy changes,

2 2 h 1 + C 1 2 + gZ 1 + q = h
2
2
h 1 + C 1 2
+ gZ 1 + q = h 2 + C 2
+ gZ 2 + w T
2
C 1 − C 2 Very small
So, it can be neglected
W T = h 1 − h 2 (Steady flow, fully insulated and change in
K.E & P.E is neglected)
3) Compressor:
1
2
It consumes work, to compress the gas.
Q = 0; Z 1 = Z 1
W C = −ve
W
C = h 2 − h 1
4) Throttling process:
Example:
a) Flow through very small opened valve.
b) Flow through very small opening.
1
2
Q = 0;
Z 1 = Z 1
W C = 0
No change in kinetic energy.
h 1 = h 2

Throttling is an Iso-Enthalpy process. It is used in refrigerator.

70

OPEN & CLOSED SYSTEMS OF REVERSIBLE WORK:

Open system reversible work W open = ∫ −vdP Closed system reversible work 1 P
Open system reversible work
W open = ∫ −vdP
Closed system reversible work
1
P
dP
2
V V
W Close = PdV
dA = vdP
Total area =∫ VdP
 Area under the curve when projected on pressure axis gives open
system reversible work.
OPEN SYSTEM WORK FOR VARIOUS
PROCESSES:
1) Constant volume process:
V = C
W open = v(P 1 − P 2 )
 Flow does not take place from high pressure to flow pressure it
takes place from high energy to low energy.

71

2) Constant pressure process:

P = C dP = 0 W open = 0 3) Isothermal pressure: Pv =
P = C
dP = 0
W open = 0
3) Isothermal pressure:
Pv = Constant
C
v =
P
C
P dP
W open = ∫ −
2
W
open = −C[ln P] 1
W open = C ln P 1
P
2
W
open = P 1 V 1 ln P 1
P
2
P
1 V 1 = P 2 V 2 ⇒ P 1
= V 2
P
2
V 1
P 1 V 1 ln V 2
W open =
V
1
= Closed system work
In isothermal process,
W open = W closed

72

Problems and solutions:

1. At nozzle inlet enthalpy of fluid passing 3000 KJ/Kg & velocity is 60m/sec at
1. At nozzle inlet enthalpy of fluid passing 3000 KJ/Kg & velocity
is 60m/sec at discharge end the enthalpy is 2762KJ/Kg. the nozzle
is horizontal & perfectly insulated
A 1 = 0.1m 2 ; V 1 = 0.187m 3 /Kg; V 2 = 0.498m 2 /Kg
a. Find the velocity at nozzle exit.
b. Find mass flow rate.
c. Exit area of nozzle.
for nozzle
V
2
V 2 2
h 1 +
1 h 2 +
2000 =
2000
2
60
3000 + 2000 = 2762 + V 2 2
2000
V 2 = 692.53 m/s
ρ 1 V 1 A 1 = A 2 ρ 2 V 2 = m
1
= V 1 A 1
ϑ
1
1
= 0.187 × 0.1 × 60
m = 32.08
V 1 A 1
A 2 V 2
=
ϑ 1
ϑ 2
0.1×60
A 2 ×692.53
=
0.187
0.498
A 2 = 0.023m 3

73

2. In test of water jacketed compressor, the shaft work required is 90KJ/Kg during compression increase in enthalpy at air is 30KJ/Kg & increase in enthalpy of circulating is 40KJ/Kg. the change in velocity is negligible the atm of heat lost from compressor by air.

dQ = dU + dW W = h 2 − h 1 Water 1 2
dQ = dU + dW
W = h 2 − h 1
Water
1
2
Water
For air,
h 1 + Q = h 2 + W
Q = (h 2 − h 1 ) + W
= 30 − 90 = −60
Heat last by air = +60
Heat loss by air = 60
= Q water + Q atm
20KJ
Q atm =

74

3. A turbine operates under steady flow condition receiving steam at following state pressure is 1.2MPa. Temperature 188°C. Enthalpy 2785 KJ/Kg velocity 33.33m/s and elevation 3m. The steam leaves the turbine at following state. Pressure 20KPa enthalpy 2512 KJ/Kg velocity 100m/s elevation 0 heat is lost to surrounding at the rate of 0.29 KJ/sec. If rate of steam flow through the turbine is 0.12 Kg/sec what is power output of turbine in KW.

P 1 = 1.2MPa T 1 = 188℃ V 1 = 33.33m/sec h 1 =
P 1 = 1.2MPa
T 1 = 188℃ V 1 = 33.33m/sec
h 1 = 2785 KJ/Kg ; Z 1 = 3m
h 2 = 2512 KJ/Kg ; V 2 = 100m/s
Z 2 = 0
Q lost(surrounding) = 0.29 KJ/sec
m = 0.42Kg/sec; P =?
V 1 2
m[h 1 +
+ gZ 1 ] + q = m[h 2 + V 2 2
+ gZ 2 ] + W T
2
2
9.81
0.42 [2785 + (33.33) 2
+ 1000 × 3] + 0.29
2000
2 9.81
= 0.42[2512 + (100)
+
× 0] + W T
2000
1000
W T = 112.5 KJ/sec

75

STEADY FLOW ENERGY EQUATION FOR MULTI STREAM FLOW:

m 1 m 3 W m 2 m 4 Q Steady flow equation (energy balance
m 1
m 3
W
m 2
m 4
Q
Steady flow equation (energy balance equation)
2
C 1 2
2
m ̇ [h 1
+
+ gZ 1 ] + m ̇
[h 2 + C 2
+ gZ 2 ] + Q
1
2
2
2
3
= m ̇
[h 3 + C 2
+ gZ 3 ] + m ̇
[h 4 + C 4 2
+ gZ 4 ] + W C v
3
4
2
Mass balance equation:
m ̇
m ̇
2 = m ̇
̇
1 +
3 + m 4
Problems with solutions:
1. The steam supply to the engine comprise two stream which mix
before enetering engine one steam is at rate of 0.01Kg/sec with
enthalpy 2952KJ/Kg and velocity 20m/s. the other steam is
supplied at 0.1Kg/sec with enthalpy 2569KJ/Kg and velocity
120m/s at the exit from the engine fluid leaves at 2 stream one of
water at rate of 0.001Kg/sec with enthalpy 420KJ/Kg and other
of a stream the fluid velocity at the exit is neglegibly small the
engine develoip shaft power of 25KW heat transfer is negligible

evaluate the enthalpy of second exit stream & mass flow rate.

76

m ̇

1 = 0.01Kg/sec; h 1 = 2952KJ/Kg; C 1 = 20m/s

m ̇ = 0.1Kg/sec; h 2 = 2569KJ/Kg; C 2 = 120m/s 2 m ̇
m ̇ = 0.1Kg/sec; h 2 = 2569KJ/Kg; C 2 = 120m/s
2
m ̇ = 0.001Kg/sec; h 3 = 420KJ/Kg; W C v = 25KW; Q = 0
3
Mass balance equation
m ̇
1 + m ̇
2 = m ̇
̇
3 + m 4
m ̇
4 = 0.109Kg/sec
Effect of Z is negligible
Hence,
gZ 1 = gZ 2 = gZ 3 = gZ 4 = 0
C 1 2
m ̇
1 [h 1 +
+ gZ 1 ] +
m ̇
[h 2 + C 2 2
+
gZ 2 ] + Q
̇
2
2
2
= m ̇
[h 3 + C 3 2
+ gZ 3 ] +
m ̇
[h 4 + C 4 2
+ gZ 4 ] + W C v
3
4
2
2
2
2
C
C
1
2
m ̇
[h 1 + 2000 + 0] + m ̇
[h 2 + 2000 + 0] + Q
̇
1
2
2
2
C
C
3
4
= m ̇
[h 3 + 2000 + 0] + m ̇
[h 4 + 2000 + 0] + W C v
3
4
0.01 [2952 + (20) 2 ] + 0.1 [2569 + (120) 2 ] + 0
2000
2000
2
(0)
= 0.001 [420 + 2000 ] + 0.109[h 4 ] + 25
h 4 = 2401 KJ/Kg
2. The stream of air & gasoline vapour in ratio of 14:1 by mass enter
in a gasoline engine at temperature 30°C & leave as combustion
product and temperature of 190°C. the engine has specific fuel
consumption 0.3 Kg/Kwhr. The net heat transfer rate from the
fuel air stream to the jacketed cooling water & to the surrounding

is 35Kw. The shaft power delivered by the engine is 26Kw

77

compute the increase in specific enthalpy of fuel air stream

assuming the changes in K.E & P.E is negligibley small. 14 m a m g
assuming the changes in K.E & P.E is negligibley small.
14
m a
m g =
1
SFC = 0.3 Kg/Kwhr
Q = 35 Kw
W = 26Kw
m a = m 1
&
m g = m 2
Air
m
Gasoline
ṁ (h 1 ) + Q = ṁ (h 2 ) + W C v
ṁ (h 2 − h 1 ) = −35 − 26
61
h 2 − h 1 = −
m
Specific fuel consumption is defined for output power
(SFC = To produce specific power how much fuel consumption
is required.)
SFC = 0.3Kg/Kwhr
0.3×26
=
Kg/sec
3600
m ̇
g = m 2 =
2.16 × 10 −3 Kg/sec
m air = m 1 = 14 × 0.0021 = 0.03Kg/sec
ṁ = m ̇
̇
g + m a
ṁ = 0.321Kg/sec
−61
∴ ∆h =
= −1877KJ
m

78

UNSTEADY FLOW:

Many flow problems such as filling up & evacuated cylinder are not steady in unsteady
Many flow problems such as filling up & evacuated cylinder
are not steady in unsteady state the rate at which the mass of fluid
within control volume is accumulated is equal to the net rate of mass
flow across the control volume.
M
i
M
e
I = Condition of fluid at inlet
E = Condition of fluid at outlet1
1 = Initial condition of system
2 = Final condition of system (C.V)
Mass balance,
Rate of accumulation of mass within system
= Rate of mass entering - Rate of mass leaving
m i = Mass entering
m e = Mass leaving
Mass balance:
The Rate of accumulation of mass within system
= Rate of mass entering - Rate of mass leaving.
dm
(
)
= Mass accumulation within control volume
dt
C v

79

dm ( ) C v = ( dm i ) − ( dm e )
dm
(
) C v =
( dm i ) − ( dm e )
dt
dt
dt
dm
(
)
= m i − m e
dt
C v
This is mass balance for unsteady state flow.
Energy balance:
E i = Energy of fluid at inlet
2
C
i
E i = m i h i +
+ m i gz i + Q
m i
2
E e = Energy of fluid at outlet
2
C
e
E i = m e h e + m e
+
m e gz e + W C v
2
A/c to energy balance equation for unsteady state flow:
The rate of energy accumulated within the control volume is equal to
difference between rate of energy entering to rate of energy leaving.
dE
(
) C v = ( dE i ) − ( dE e )
dt
dt
dt
dE
d
(
=
dt [E i − E e ]
dt
) C
v
2
d
C
C i 2
e
=
dt [(m i h i + m i
+ m i gz i + Q) − (m e h e + m e
+
m e gz e +
2
2
W C v )]
Now neglecting K.E & P.E changes
Energy = K.E + P.E + I.E
E = I.E
dU
d
(
)
=
dt [m i h i + Q − m e h e − W C v ]
̇
dt
C v
dU
d
d
(
)
=
dt (m i h i ) + Q − dt (m e h e ) − W C v
̇
̇
dt
C v

h i & h e Are constant with respect to time.

80

dU d d ( ) = h i dt (m i ) + Q −
dU
d
d
(
)
= h i dt (m i ) + Q −
̇
h e dt (m e ) − W C v
̇
dt
C v
dU
(
)
= m ̇ h i + Q − m ̇ h e − W C v (Energy balance)
̇
̇
i
e
dt
C v
CHARGING OF TANK:
An insulated storage tank that is initially evacuated is connected
to a supply pipe line carrying a fluid which specific internal energy is
U i & specific enthalpy h i the valve is open & fluid flow in the tank
through supply pipe line & reaches the pressure same as pressure of
supply pipe line show that final specific internal energy of final
temperature of fluid inside the tank if fluid flowing is ideal gas and
supply line temp is T i .
U i , h i , T i , P i
M i = 0
M e = 0
Q = 0
W = 0
Mass balance,
dM
(
)
=
m ̇
− m e
̇
i
dt
C v
M 1 − M 2 = m ̇
− m e
̇
i
M 2 = m ̇ ……
(ⅰ)
i

81

Energy balance,

dM ( ) = m ̇ h i + Q − m ̇ h e
dM
(
)
= m ̇ h i + Q − m ̇
h e − W C v
̇
i
e
dt
C v
U 1 − U 2 = m i
̇
h
i
U 1 = 0
U 2 = m 2 h i
U
2
2 = h i
m
U 2 = h i …
(ⅱ)
For ideal gas
du
=
C v dT
dh =
C p dT
u 2 − u 1 =
C v (T 2 − T 1 )
T
1 → 0 u 1 → 0
u 2 = C v T 2
h i = C p T i
(h e = 0 T e = 0)
From (ⅱ)
For ideal gas,
C
v T 2 = C p T i
p
T
2 = ( C C v ) T i
T 2 = γT i
T 2 > T i
1 st
 There
no
problem
with
law
of
thermodynamics
it
is
quantitative law. Process is possible or not is not the criterion of
1 st law.

82

SECOND LAW OF THERMODYNAMICS:

 According to 1 st law of thermodynamics, energy is conserved during process or cycle
 According to 1 st law of thermodynamics, energy is conserved
during process or cycle and energy balance hold good but it does
not give any information regarding process is possible or not.
 It is the 2 nd law of thermodynamics, which provide the criterion
for possibility of any process and give the direction for particular
process through the concept of entropy. It is also known as
directional law.
 1 st law is quantitative law of energy and 2 nd law is quantitative
law of energy.
Note:
All natural spontaneous process is occurring only in one direction
(high potential to low potential)
Thermal Reservoir
Source
Sink
T 1
T 2
Q 2 (Absorb)
Q 1 (Supply)
Source:
Source thermal reservoir which can supply any amount of energy
without undergoing any temp change
Example: Sun

83

Sink:

Sink is thermal reservoir which can absorb any amount of energy without undergoing any temperature
Sink is thermal reservoir which can absorb any amount of energy
without undergoing any temperature change.
Example: Atmosphere
2 nd law given by joule mathematical representation – Clausius
2 nd law of thermodynamic for cycle:
Joules experiments demonstrated that work can be
completely converted into heat but complete conversion of law
grade energy (heat) to higher grade energy (work) is not
possible for a cycle.
KELVIN – PLANK STATEMENT OF SECOND
LAW (PMM-Ⅱ):
It is not possible to construct a device which continuously delivers
the work while exchanging heat a single reservoir.
Q
PMM-II
W
PMM-Ⅱ has 100% efficiency (i.e. not possible)

84

CONCEPT OF HEAT ENGINE:

If more than one reservoir is used, then it is possible to convert low grade
If more than one reservoir is used, then it is possible to convert
low grade energy to high grade energy.
Source
T
1
Power
Q 1
Producing
Clockwise
HE
W
Q 2
T 2
Sink
1 st law applied to system
∑ Q = ∑ QW
Q 1 − Q 2 = W
O/P
W Q 1 − Q 2
η =
=
=
I/P
Q 1
Q 1
η = 1 − Q 1 2 Valid for reversible & irreversible both.
(As no assumption mode.)
Q
CLAUSES STATEMENT OF 2 ND LAW:
It is not possible to construct a device which operates on a
cycle and transfer heat from low temperature to high temperature body
without any energy input.
Source
T 1
Q 1
HE
W
Q 2
T 2
Sink
Sink
heat from low temperature to high temperature body without any energy input. Source T 1 Q

85

Heat at low temperature → low grade energy (low significance) Heat at high temperature → high grade energy (high significance)

CONCEPT OF REFRIGERATOR: Refrigerator is a device which creates & maintains lower temperature than surrounding
CONCEPT OF REFRIGERATOR:
Refrigerator is a device which creates & maintains lower
temperature than surrounding as lower temperature is to maintain
continuously the system must operate on cycle.
1 st law,
∑ Q = ∑ QW
Q 2 − Q 1 = −W
Source
T
1
Power
Consuming
Q
1
anticlockwise
cycle
R
W
Q
2
T
2
Sink
Coefficient of performance (COP)
= Desired effect /input
= Q 2
(Valid for reversible & irreversible)
W
COP =
Q 1 Q 2 ……… (1)
Q 1 −

86

HEAT PUMP:

Heat pump is device which maintains higher temperature than surrounding. Source T 1 Q 1
Heat pump is device which maintains higher temperature than
surrounding.
Source
T
1
Q 1
HP
W
Q 2
T 2
Sink
desired effect
(COP) HP =
input
Q 1
(COP) HP =
Q 1 − Q 2
(COP) HP − (COP) R = 1
(COP) HP = 1 + (COP) R
(Valid for same temperature limit)
Note:
Clauses & Kelvin-plank statements are parallel statements of 2 nd
law of thermodynamic if we violate any one of them automatically
another is violated.

87

VIOLATION OF CLAUSES:

Source at (T 1 ) T 1 Q Q 1 Q 1 Q 1 1
Source
at (T 1 )
T 1
Q
Q 1
Q 1
Q 1
1
HE
HE
W = Q1 – Q2
Q
Q 2
3
Q 2
Q 3
T 2
T 2
Sink
Violation of Clausius law
Violation of Kelvin plank law
Violation of Kelvin-plank statement:
T 1
T 1
Q 3 =
Q 1 + Q 2
Q 1
Q 1
Q 1
W
W
W
W
Re
Re
Q 3
Q 2
T 2
T 2
Violation of Clausius law
Violation of Kelvin plank law
T
1
Q 3 =
Q 1 + Q 2
Q
1
W
W
HE
R
Q
2
T
2
Violation of Clausius statement

88

CARNOT CYCLE:

Q in 1 2 4 3 Q Rejected 1-2 → Isothermal expansion (heat add) 2-3
Q in
1
2
4
3
Q Rejected
1-2 → Isothermal expansion (heat add)
2-3 → Adiabatic expansion (Q = 0)
3-4 → Isothermal compression.
4-1 → Adiabatic compression.
Carnot cycle consist of two isothermal & two adiabatic process
isothermal process is very slow whereas, adiabatic vs. very fast. Hence,
the combination of these two processes in cycle is not possible.
Carnot cycle is theoretical cycle which is used for compression
of other actual cycles.
CARNOT THEOREM:
For various cycles operated between same temperature limit
non-has efficiency greater than reversible cycle.
Let us consider two engines E 1 & E 2 E 1 is a reversible engine & E 2 is
irreversible engine in same temp difference.
T 1
Q 1
Q 1
W
W
E 1
E 2
Q 3
Q 2
T 2
T 2

89

E 1 → Rev engine E 2 → Irre engine Let us assume, η irr
E 1 → Rev engine
E 2 → Irre engine
Let us assume, η irr > η rev
W
2
> W 1
(W 2 > W 1 )
Q
Q
1
2
Now reversible the direction in reversible engine,
T
1
Q
Q
Q
Q
1
1
1
1
W
W
W 1
W 2
1
2
E
E
E
E
1
2
1
2
Q
Q
3
2
Q
2
Q
3
W 2 – W 1
W net = W 2 – W 1
T
T
2
2
Violation of Kelvin-plank so our assumption is wrong,
∴ η rev
> η irr
A cycle is said to be reversible cycle if all the processes of cycle are
reversible if single cycle is irreversible, then cycle is irreversible cycle.
CLAUSIS THEOREM:
(Clausis inequality)
According to this theorem, the cyclic integral of dQ is less than or
T
equal to zero.
∮ dQ
≤ 0
T
⇒ ∮ dQ
= 0 …
Reversible cycle
T
∮ dQ
< 0 …
Irreversible cycle
T

90

If dQ > 0 …

T

Cycle is not possible

∮ dQ ≤ 0 T This is 2 nd law of thermodynamics for cycle. REVERSIBLE
∮ dQ
≤ 0
T
This is 2 nd law of thermodynamics for cycle.
REVERSIBLE HEAT ENGINE:
T 1
Q 1
HE
W
T 2
Closed system undergoing cycle.
Apply 1 st law
∑ Q = ∑ W
Q 1 - Q 2 = W
Apply 2 nd law
For reversible heat engine
∮ dQ
= 0
T
Q
1
+ ( −Q 2 ) = 0
(T is in K)
T
T
1
2
Q
1
- Q 2 = 0
T
1
T 2
Q 1
= Q 2
T 1
T 2
Q
1
= T 1
Q
2
T 2
1 + ( −Q 2 ) = 0 (T is in K) T T 1 2

91

ɳ = 1 - Q 2

Q

1

It is valid for reversible as well as irreversible For reversible, Q 1 = T
It is valid for reversible as well as irreversible
For reversible,
Q
1
= T 1
Q
2
T 2
ɳ = 1 - T 2
T
1
It is only valid for reversible.
REVERSIBLE HEAT PUMP:
T 1
System
Q 1
HP
W
T 2
Apply 1 st law
∑ Q = ∑ W
Q 2 - Q 1 = -W
∴ W = Q 1 - Q 2
Apply 2 nd law
∮ dQ
= 0 …… Reversible.
T
Q
2
- Q 1 = 0
T
2
T 1
Q
1
= T 1
Q
2
T 2
W = Q 1 - Q 2 Apply 2 nd law ∮ dQ = 0 ……

92

Q 1 1 1 Cop = = = Q 1 − Q 2 1 −
Q
1
1
1
Cop =
=
=
Q 1 − Q 2
1 − Q 2
1 − T 2
Q
T
1
1
T 1
Cop =
T 1 − T 2
It is only for reversible process
Similarly, for reversible refrigerator:
T 2
Cop =
T 1 − T 2
It is valid for reversible only.
COUPLED ENGINE:
(Engine in series)
T
1
Q
1
E
W
1
1
Q
T
Q
2
E
W
2
2
T
2
W
1 = Q 1 – Q
T
ɳ 1 = 1 -
T
1
W
2 = Q
– Q 2
ɳ 2 = 1 - T 2
T

93

a. When work from both the engine is same

W 1 = W 2 Q 1 – Q = Q – Q 2 Q
W 1 = W 2
Q 1 – Q = Q – Q 2
Q 1
– 1 = 1 - Q 2
Q
Q
T
1
– 1 = 1 - T 2
T
T
T 1
T =
T 1 + T 2
b. Efficiency of both engines are same
ɳ 1 = ɳ 2
T
1 -
1 = 1 - T 2
T
T
T = √T 1 × T 2
Note:
T
1. T 2
= T 2
×
T
T 1
T 1
(1 −
ɳ) = (1 -
ɳ 2 ) (1
- ɳ 1 )
1 −
ɳ = 1 - ɳ 1 - ɳ 2 + ɳ 1 ɳ 2
ɳ net = ɳ 1 + ɳ 2 - ɳ 1 ɳ 2
ɳ > ɳ 1
ɳ > ɳ 2
2. Two constant property line can never intersect each other.
Two adiabatic line can never intersect each other.

94

adiabatic

adiabatic isothermal P Q in V ⇒ Only one reservoir producing work. Hence violation of kelvin
adiabatic isothermal P Q in V ⇒ Only one reservoir producing work. Hence violation of kelvin
isothermal P Q in V ⇒ Only one reservoir producing work. Hence violation of kelvin
isothermal
P
Q in
V
⇒ Only one reservoir producing work. Hence violation of
kelvin planks statement
Problems with Solutions:
1. A heat engine working on Carnot cycle receive heat at 40KW
from a source of 1200K & reject it to the sink at 300K. Find
heat rejected.
T 1
Q 2
W
HE
T 2
40 = 1 - T 2
T 1
T
2
= Q 2
T
1
Q 1
40
1200 = Q 2
300
Q 2 = 10KW
2. An inventor claims that heat engine has following specification.
Power developed = 50KW. Fuel burned for hour = 3kg, heating
value of fuel = 75000kJ/kg, temperature limits = 627 & 27 0 C.
Cost = 30 Rs/kg, value of power = 5 Rs/Kwh

95

1 st Method The performance of engine, W = 50KW Q 1 = (3 × 75000) ÷ 3600 = 62.5KW

ɳ max = 1 - T 1 2 = 66.6% T 50 = W out
ɳ max = 1 - T 1 2 = 66.6%
T
50
= W out
Q in
=
ɳ actual = output input
62.5
ɳ actual = 80%
ɳ actual > ɳ max
… not possible
2 nd Method
900
K
Q ih = 62.5
HE
50
12.5
300 K
∮ dQ
62.5 12.5
=
-
T
90
300
= 0.02 (+ve)
Hence violation of 2 nd law
∴ Not possible

ɳ max = ɳ actual economical ɳ max > ɳ actual possible ɳ max < ɳ actual not possible

96

3.

If efficiency of Carnot engine is given as 0.75. if cycle direction is reversed then value of cop for Carnot refrigerator.

Q 1 0.75 = Q 1 − Q 2 1 0.75 = 1 − Q
Q 1
0.75 =
Q 1 − Q 2
1
0.75 =
1 − Q 2
Q
1
4
Q 2
1 −
⇒ Q 2
Q 1 =
= T 2
3
Q 1
T 1
1
T 2
(Cop) ref =
=
T 1 − T 2
1 − T 2
T
1
(Cop) ref = 0.33
4. In given figure E is heat engine with efficiency 0.4, and R is
refrigerator given that Q 2 + Q 4 = 3Q 1 . Then what is cop of
refrigerator.
Q 1
Q 1
E
R
Q 2
Q 3
-W in = - Q 3 + Q 4
-0.4Q 1 = - Q 3 + 2.4Q 1
Q 3 = 2Q 1
Q 1
0.4 =
Q 1 − Q 2
-0.4 Q 2 = Q 1 – 0.4 Q 1
Q 2 = 0.6Q 1

W = Q 1 - Q 2

97

W = 0.4 Q 1

Q 3 ɳ r = Q 4 − Q 3 Q 2 + Q 4
Q 3
ɳ r =
Q 4 − Q 3
Q 2 + Q 4 = 3Q 1
0.6 Q 1 + Q 4 = 3Q 1
Q 4 = 2.4 Q 1
2Q
1
(Cop) r =
= 5
2.4Q 1
− 2Q 1
5. Using the engine of 30% thermal efficiency to drive the
refrigerator having Cop = 5. What is the heat input into the
engine for each mega joule removed from cold body by
refrigerator?
T
1
Q
1
W
R
Q
2
T
2
T
1
Q
3
W
E
Q
4
T
2
ɳ = 30% = 0.03
Cop = 5
Q 2
5 =
Q 1 − Q 2

5Q 1 - 5Q 2 = Q 2

98

5Q 1 = 6Q 2

= 1.2Q 2 Q 1 0.3 = Q 3 − Q 4 Q 3 0.3Q
=
1.2Q 2
Q 1
0.3 = Q 3 − Q 4
Q 3
0.3Q 3 = Q 3 − Q 4
Q 4 = 0.7Q 3
Q 1 = 1.2 MJ
− Q 2 = Q 4 − Q 3
Q 1
1.2 MJ –
1 = Q 3 (0.3)
Q 3 = 0.66MJ
6. A heat engine is used to drive a heat pump. The heat transfers
from heat engine and from heat pump are used to heat the water,
circulating through the radiator of building the efficiency of heat
engine is 27% & COP heat pump 4. Evaluate the ratio of heat
transfer to circulating water to heat transfer to the heat engine.
T
1
Q
1
W= Q 1 - Q 2
E
Q
2
T
2
T
3
Q
3
W= Q 1 - Q 2
P
Q
4
T
4
ɳ = Q 1 − Q 2

Q

1

99

0.27 = Q 1 Q 2

Q

1

Q 2 1 = 0.73 Q Q 1 − Q 2 W in = =
Q 2
1 = 0.73
Q
Q 1 − Q 2
W in =
= 0.27 Q 1
Q 3
COP =
Q 3 − Q 4
Q 3 = 4
(Q 3 − Q 4 )
3Q 3 = Q 4
Q 4 = 3Q 3
(Q 1 − Q 2 ) + Q 4 = Q 3
0.27 Q 1 +
4Q 3 = Q 3
0.27 Q 1 = - 3Q 3
Q 2 + Q 3
= (0.73 + 1.08)Q 1
= 1.81
Q 1
Q 1
7. A house is to be maintained at temperature of 20 0 C by means of
heat pump pumping heat from atmosphere. Heat losses through
walls of house are estimated as 0.65KW per unit of temperature
difference between the inside of house & atmosphere. If
atmospheric temperature is - 10 0 C. What is minimum power
required to dry the pump.
It is proposed to use the same pump to cool the house in
summer for same room temperature, same heat loss rate and
same power input to the pump what is the maximum permissible
atmospheric temperature.

100

T 1 = 20 0 C
T 1 = 20 0 C
Q 1 W = Q 1 - Q 2 Q 2 T 2 = 10
Q 1
W
= Q 1 - Q 2
Q 2
T 2 = 10 0 C
T 1 = 20 0 C
T 2 = −10 0 C
Q 1 = 0.65 × (T 1 - T 2 )
= 0.65 × (293 - 263)
Q 1 = 19.5 kW
T 1
= Q 1
T
2
Q 2
Q
2 = 19.5 × 263
293
Q 2 =
17.5
W power = 19.5 – 17.5 = 2 kW
T 1 = ?
Q 1
W = Q 1 - Q 2
Q 2
T 2 = 20 0 C
Q 1 − Q 2
= 2kW
Q 1 = 2 + Q 2
Q 1 = 2 + 19.5

Q 1 = 21.5

101

T 1

= Q 1

T 2

Q 2

x 21.5 20 0 = 19.5 x = 323K x = 50 0 C ∴
x 21.5
20 0 =
19.5
x
= 323K
x
= 50 0 C
∴ T 1 = 50 0 C
8. The refrigerator is maintained at 2 0 C. every time the door
opened warm material is placed inside introducing an average of
420KJ but making only a small change in temperature of
refrigerator. The door is opened 20 times in day & refrigerator
operates at 15% ideal COP. The cost of work is 32 paisa/kWhr.
What is monthly bill for refrigerator. The atmospheric
temperature 30 0 C.
T 1 = 313
Q 1
W in
R
Q 2
T 2 = 279
Q 1 = 420 × 20 × 30 = 8400
100 × 273 + 2
15
(COP) R =
= 1.47
28
(COP) R = Q 1
W
in
420 × 20 × 30
W in =
1.47

W in = 171428.57 KJ/sec

102

W in = 171428.57

KJ × hr

3600 × sec

= 47.61 KW/hr Cost = 47.61 × 0.32 = ₹15.80 ENTROPY: ∮ dQ ≤ 0
= 47.61 KW/hr
Cost = 47.61 × 0.32
= ₹15.80
ENTROPY:
∮ dQ
≤ 0 → 2 nd law for cycle.
T
Case 1: Reversible cycle,
1
c
P
b
a
2
V
For
reversible
cycle, |a 2 b|
dQ
(
)
) 2b1 = 0 …… (1)
T
T
1a 2 + ( dQ
For
reversible
|a 2 c|,
dQ
(
)
) 2c1 = 0 …… (2)
T
T
1a 2 + ( dQ
Equation (1) & (2)
dQ
(
T
T
) 2b1 - ( dQ
) 2c1 = 0
dQ
(
T
T
) 2b1 =
( dQ ) 2c1
The quantity ( dQ ) reversible is same for both the path b & c. it only
T
depends on end points. So, it must be a property.

103

1
1
c P b 2 V This property is known as entropy. Entropy (C ′ )
c
P
b
2
V
This property is known as entropy.
Entropy (C ′ ) = Entropy
Entropy is a property it does not depend upon the path.
Entropy is same if the end points are same.
Entropy depends only on end points. Hence, as long as
end points are same the entropy remain same for reversible as well as
irreversible path.
Between two end points entropy is only defined for
reversible path & same for irreversible path.
In order to find out entropy change of irreversible path it must be
replaced by reversible path between same end points.
ENTROPY CHANGE OF SYSTEM FOR
REVERSIBLE PROCESS:
Case 1:
When heat is added to the system.
ds = dQ
T

ds = + ve s 2 − s 1 = +ve The entropy of system increases when heat is added to a system.

104

ds = ( dQ ) T reversible This is 2 nd law of thermodynamics for
ds = ( dQ
)
T
reversible
This is 2 nd law of thermodynamics for process.
Irreversible cycle
1
c
P
2
V
For reversible cycle |2b|,
dQ
(
)
T
T
1a 2 + ( dQ
) 2b1 = 0
dQ
(
) 1a 2 = -( dQ
)
T
T
2b1
For
irreversible cycle |a 2 c ′ |,
dQ
(
)
T
T
1a 2 + ( dQ
) 2c ′ 1 < 0
-( dQ
T
T
) 2b1 <
( dQ ) 2c ′ 1
ds > ( dQ
T
) 2c ′ 1
ds > ( dQ
)
T
irreversible
dQ
(
T
T
) reversible > ( dQ ) irreversible
ds = Entropy
Case 2:
When heat is rejected,
ds = dQ

T

105

ds = -ve s 2 − s 1 = -ve Entropy of a system decreases
ds = -ve
s 2 − s 1 = -ve
Entropy of a system decreases when heat is rejected.
 Entropy of universe always increases
Case 3:
Reversible adiabatic process
dQ = 0
∴ ds = 0
s 2 − s 1 = 0
s 2 = s 1
In this process entropy is same hence it is called isentropic process.
For reversible process entropy of system is constant.
Note:
System entropy can increase or decrease or become
constant depending upon type of heat transfer.
ENTROPY CHANGE FOR IRREVERSIBLE
PROCESS:
ds > ( dQ
)
T
irreversible
ds = ( dQ
T
) irreversible + (δs) generation
1
d
P
c
2

106

V

For reversible process,

(δs) generation = 0 The end points are same for irreversible path c ′ &
(δs) generation = 0
The end points are same for irreversible path
c ′ & d ′ ,
The entropy change will be same but
dQ
(
T
T
) 2c ′ 1 ≠ ( dQ ) 2b ′ 1
So,
((δs) generation ) 2c ′ 1 ≠ ((δs) generation ) 2b ′ 1
So, Entropy is a property so it does not depend on the path followed
by process, but entropy generation is not a property.
It depends on path followed by the process.
(δs) generation is measure of irreversibility of a system.
In case of reversible process,
(δs) generation = 0
and if δs for 2c ′ 1 is greater than 2d ′ 1 then c ′ will be more
irreversible.
(δs) 2c ′ 1 > (δs) 2d ′ 1
For irreversible path,
ds = ( dQ
(δs) generation
T
) irreversible +
For non- adiabatic & heat rejection
dQ
(
T
) irreversible = - a
At same time (δs) generation = a
∴ ds = -a + a = 0
s 2 − s 1 = 0

107

s 2 = s 1 (Isentropic) Reversible adiabatic process is always isentropic but isentropic process
s 2 = s 1 (Isentropic)
Reversible adiabatic process is always isentropic but
isentropic process need not to be reversible adiabatic.
A Non-adiabatic irreversible process also can be isentropic.
ADIABATIC PROCESS:
1. Reversible
ds = ( dQ
)
T
reversible
ds = 0
s 2 = s 1 (Isentropic)
2. Irreversible
ds = ( dQ
) + (δs) generation
T
ds = + ve
Note:
Adiabatic process need not to be isentropic always. If
adiabatic process is reversible then only it is isentropic & if it is
reversible then it must be non-isentropic.
 During adiabatic process, system entropy never decreases.
Physical meaning of entropy:
Entropy is the measure of molecular disturbance. Greater
the disturbance greater the change in entropy.
Entropy principle:
Entropy of isolated system never decreases.
ds ≥ ( dQ )
T

108

For isolated system, dQ = 0

∴ ds ≥ 0 Universe is best example of isolated system. Hence, entropy of universe
∴ ds ≥ 0
Universe is best example of isolated system.
Hence, entropy of universe always increases.
(ds) universe ≥ 0
(ds) system + (ds) surrounding ≥ 0
Entropy of system can increase or decrease or become constant.
Entropy surrounding can increase, decrease or become constant. But
entropy of universe never decreases.
Note:
a/c to 1 st law, entropy of universe is constant and a/c to 2 nd law,
entropy of universe never decreases.
TEMPERATURE – ENTROPY DIAGRAM: (T-S
DIAGRAM)
T
S
Area of strip dA = T dS
Total area below curve,
2
A = ∫
T ds
1
ds = ( dQ
)
T
reversible
dQ = T ds → Reversible

109

Total heat transfer =

1

2 T ds

Area under the curve when projected on entropy axis on T-S diagram gives reversible heat
Area under the curve when projected on entropy axis on T-S
diagram gives reversible heat transfer.
REPRESENTATION OF CARNOT CYCLE IN T-S
DIAGRAM:
1
2
1
Q
T
in
1
P
2
T
2
4
4
3
3
Q
R
S
V
Q in = T 1 ds
Q R = T 2 ds
Q
T 2 ds
R
ɳ = 1 -
in = 1 -
Q
T 1 ds
ɳ c = 1 - T 2
T
1
 Area under T-S cycle gives net heat transfer a/c to first law
∑ Q = ∑ W. Hence, area under cycle gives network transfer.
 Area under (P-V) = Area under (T-S)
Note:
Second law is directional law with the help of entropy principle
we can determine the direction for particular process.
Isolated
Q
A
B
T
T
B
A

110

(S) Isolated

0

(∆S) A + (∆S) A ≥ 0 −Q + ≥ 0 T T A Q
(∆S) A + (∆S) A ≥ 0
−Q
+
≥ 0
T
T
A
Q B
Q [ T A − T B
] ≥ 0
T A T B
=
0
T A =
(ds) Isolated
T B
>
0
T A >
(ds) Isolated
T B
< 0
T A < T B
(ds) Isolated
The process is possible or only that direction of process is
possible in which either entropy of universe is constant or increasing.
COMBINED 1 ST & 2 ND LAW OF
THERMODYNAMICS:
dQ = dU + dW → 1 st law for all process
dW = P dV → Reversible process valid
dQ = dU + P dV → Valid for reversible process
ds = dQ → Valid for reversible process
T
dQ = T ds
T dS = dU + P dV
Valid for all process
1 st T- dS equation
This equation is valid for reversible as well irreversible process
because it connects various properties.
T ds = du + P dv
Specific form (divided by mass)

H = U + PV

111

dH = dU + P dV + V dP

(dQ = dU + P dV)

dH = dQ – V dP ⇒ dQ = dH – V dP T ds
dH = dQ – V dP
⇒ dQ = dH – V dP
T ds = dH + P dv
2 nd T- ds equation for all process.
Slope of various lines on T-S diagram
V = C
PV r = C
T
P = C
T = C
S
1. Slope of isothermal process = Tan 0 = 0
2. Slope of adiabatic line = Tan 90 = ∞
3. Slope of constant volume line:
v = C
∴ dv = 0
We know,
T ds = dU + P dV
T ds = dU
(dU = C v dT)
T ds = C v dT
dS
dT = C v
T
dT
T
v → Slope of constant volume line in T-S diagram
dS =
C

112

4. Slope of constant pressure line:

P = C We have, T ds = dh – V dP dP = 0
P = C
We have,
T ds = dh – V dP
dP = 0
∴ T ds = C p dT
∴ dT
T
p → Slope of constant pressure line in T – S diagram
dS =
C
C p > C v
∴ Slope of constant volume line on T – S diagram > Slope of
constant pressure line on T – S diagram
OPEN SYSTEM REVERSIBLE WORK:
1 st law for steady flow open system:
2
h 1 + C
2
1 + gz 1 + q = h 2 + C 2
+ gz 2 + W open
2
2
Neglecting K.E & P.E change
h 1 + q = h 2 + W open
Now,
q = (h 2 - h 1 ) + W open
dq = dh + W open
For reversible process,
T ds = dh + W open ……. (1)
Now, we have,
T ds = dh – V dP ……
(2)

From (1) & (2)

113

dW open =

- V dP

W open = - ∫ V dP Assumption made 1. Steady flow 2. Open system
W open = - ∫ V dP
Assumption made
1. Steady flow
2. Open system
3. Neglect K.E & P.E
4. Reversible system
ENTROPY CHANGE FOR IDEAL GAS:
Case 1: Temperature & volume
We know,
T ds = du + P dv
For ideal gas
T ds = C v dT + P dv
ds = C v
dT + P T dv
T
Pv = mRT
R
⇒ P
T =
V
dT
ds = C v
+ R dv
T V
Integrating
S 2 - S 1 = C v ln T 1 2 + R ln V 2
T
V
1
Change of entropy in terms of temperature & volume

114

Case 2: Temperature & pressure

T ds = dh – v dP For ideal gas T ds = C p
T ds = dh – v dP
For ideal gas
T ds = C p dT - v dP
ds = C p
dT - v T dP
T
For ideal gas
Pv = mRT
v mR
T =
P
ds = C p
dT - R P dP
T
S 2 - S 1 = C P ln T 1 2 + R ln P 2
T
P
1
Change in entropy in terms of T & P
Case 3: pressure & volume
- S 1 =
C v ln T 1 2 + R ln V 2
S 2
T
V
1
= C
ln T 1 2 + (C P −
C v ) ln V 2
v
T
V
1
= C
[ln T 2 1 −
ln V 1 2 ] + C P ln V 2
v
T
V
V
1
V 1
=
C v [ln [ T 2
×
]] + C P ln V 2
T
V
1
V 2
1
For ideal gas
P 1 V 1
T
P 2 V 2
=
1
T 2
T 2 V 1
= P 2
T 1 V 2
P 1

S 2 - S 1 = C v [ln [ P 1 2 ]] + C P ln V 2

P

V

1

115