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m/2
V
T
P
Energy
Basic Concepts & Definitions (Contd)
Ability to do work.
Modes of Energy
Macroscopic: Organized form of energy. Example:
Kinetic Energy (KE), Potential Energy (PE)
Microscopic: Disorganized form of energy. Example:
Internal Energy (U)
E = KE + PE + U
Total Energy (E): Sum of all macroscopic and microscopic
modes of energy.
Steady State
If the property of a system at any specified location are
independent of time, then the system is said to be in a
steady state.
Basic Concepts & Definitions (Contd)
State
It is the condition of a system identified by its properties.
The number of properties required to fix the state of a
system is given by the state postulate.
The State Postulate
The state of a simple compressible system is
completely specified by two independent, intensive
properties.
Equilibrium
It is a concept associated with the absence of any
tendency for spontaneous changes when the system is
isolated.
In a state of equilibrium, the properties of system are
uniform and only one value can be assigned to each
property.
Basic Concepts & Definitions (Contd)
Types of Equilibrium
1. Thermal Equilibrium: Equality in temperature
2. Mechanical Equilibrium: Equality in pressure
3. Chemical Equilibrium: Equality in chemical potential
4. Thermodynamic Equilibrium: 1 + 2 + 3
Basic Concepts & Definitions (Contd)
Process
When a system changes from one equilibrium state to
another, the path of successive states through which the
system passes is called a process.
Quasi Equilibrium Process
While a system passing from one state to the next, the
deviation from equilibrium is infinitesimal, a quasi
equilibrium process occurs.
It is otherwise called quasistatic process as the process
proceeds very slowly under the influence of infinitesimal
driving forces (P, T, etc).
The system remains in infinitesimally close to an
equilibrium state at all times.
Basic Concepts & Definitions (Contd)
Nonequilibrium Process
If the system goes from one equilibrium state to another
through a series of nonequilibrium states, a
nonequilibrium process occurs.
It is represented by doted line.
Example: Combustion, free expansion of gas (sudden
expansion).
Thermodynamics gives a broad definition of
work.
Work and Heat
Work
How to define work thermodynamically?
If a battery connected to resistor circuit as
shown below, does it doing any work?
Battery
Yes, it is doing some work. How?
If the resistor is replaced by a motor
which is lifting a mass, a work is
said to be done.
Work done by a system on its surrounding is
defined as an interaction whose sole effect,
external to the system, could be reduced to the
raising of a mass through a distance.
Work and Heat Contd
Thermodynamic definition of work
F = Generalized force
Dl = Generalized displacement
dW = F dl
Mechanical Work
Generalized force = Applied Force (F)
Generalized displacement = Displacement (ds)
: where P is the absolute pressure.
Work and Heat Contd
Electrical Work
Generalized force = Applied Potential (V)
Generalized displacement = Charge (q)
Magnetic Work
Generalized force = Applied Magnetic Field Strength (B)
Generalized displacement = Magnetic Dipole Moment (m)
Moving Boundary Work
= dV P W
The area on a P-V diagram represents the work for a quasi-
equilibrium process only.
Note
Non-equilibrium Work
Work and Heat Contd
Work obtained from non-equilibrium process.
Work cannot be calculated using .
Example: Paddle wheel work, Free expansion
dV P
Notes on Work
It is not a property of the system and its
differential is not exact.
It depends on the process path.
Work interactions depend upon the choice of
the system.
Energy can cross the boundary of a closed system in the
form of heat or work.
The mode of energy transfer, which cannot be
accounted as work from a macroscopic point of view is
called heat interaction.
Energy transfer as heat occurs by virtue of temperature
difference across the boundary of the system.
It is not a property of the system and its differential is not
exact.
Work and Heat Contd
HEAT
Zeroth Law of Thermodynamics
Developed by R. H. Fowler in 1931.
This law is developed after the 1
st
and 2
nd
law of
thermodynamics.
It provides the basis for the measurement of
temperature of a system
Statement
When two bodies are in thermal equilibrium with a
third body, they are also in thermal equilibrium with
each other.
Temperature Scales
Thermometry
It is defined as the act of measuring temperature
with accuracy and precision.
Temperature measurement depends upon the
establishment of thermodynamic equilibrium between the
system and the device used to measure the temperature.
The sensing element of the device has certain physical
characteristics which change with temperature and this
effect is taken as a measure of temperature.
Thermometric Property
A property or physical characteristic which changes its
value as a function of temperature is called thermometric
property.
A substance whose property or physical characteristic
changes as a function of temperature is known as the
thermometric substance.
Temperature Scales Contd
Thermometric Substance
A change in dimension. e.g., mercury-in-glass
thermometer, gas thermometer, etc.
A change in electrical resistance of metals and
semiconductors. e.g., resistance thermometers,
thermistors, etc.
A thermo-electric emf for two different metals and alloys
joined together. Ex. Thermocouples.
Physical Characteristics
A change in the intensity and color of emitted radiations.
Ex. Radiation thermometer.
Fusion of materials when exposed to temperatures. Ex.
Pyrometer.
Temperature Scales Contd
t x Relationship
B Ax t + =
Linear relationship
The constants A and B can be determined from any two
fixed thermometric points, e.g., the ice point (freezing
point) and the steam point (boiling point) of water.
Note
A Fixed Point refers to an easily reproducible state of
an arbitrarily chosen standard system.
Let temperatures at ice and steam point in a scale is
represented as t
i
and t
s
and the corresponding
thermometric properties be x
i
and x
s
respectively, then
Temperature Scales Contd
B Ax t
i i
+ = B Ax t
s s
+ =
From above two equations
i s
i s
x x
t t
A
=
i
i s
i s
i
x
x x
t t
t B
=
Hence,
i s
i
i s i
x x
x x
t t t t
+ = ) (
Centigrade and Fahrenheit Scales
Temperature Scales Contd
In Centigrade scale,
t
i
= 0 C
t
s
= 100 C
Hence,
i s
i
C
x x
x x
t
=100
In Fahrenheit scale,
t
i
= 32 F
t
s
= 212 F
Hence,
Temperature Scales Contd
i s
i
F
x x
x x
t
+ = 180 32
Note
The thermometric substance used is same while
measuring temperature in Centigrade and Fahrenheit
scales.
Therefore,
180
32
100
=
F C
t t
( ) 32
9
5
=
F C
t t
\
|
=
V
v
T
u
C
|
.
|
\
|
=
It is a measure of energy storage capabilities of various
substances.
It can be specified by two independent intensive properties.
For solids and liquids
1st Law Analysis
C C C
v P
= =
2
vT
C C
v P
=
T
P
v
v
|
.
|
\
|
=
1
P
T
v
v
|
.
|
\
|
=
1
=
CS CV
Sys
A d e dV e
t dt
dE
v
| |
Sys
Sys
W Q
dt
dE
=
gz u e + + =
2
v
2
where
Work done by system
Heat transfer to the system
Shaft Power ( )
1st Law Flow Process Contd
| |
+
=
CS CV
CV
A d e dV e
t
W Q
v
as t 0, the system and the CV coincides, hence
| | | |
CV Sys
W Q W Q
=
other sh P S
W W W W W
+ + + =
S
W
=
CS
P
dA n P W v
=
CS
Sh
dA W v
........ + + =
magnetic electrical other
W W W
Rate of work done by other forces
n
F
\
|
+ +
=
CS CV
CV
other Sh S
A d
P
e dV e
t
W W W Q
| | ( )
+ +
=
CS CV
CV
other Sh S
A d Pv e dV e
t
W W W Q
v
| |
|
|
.
|
\
|
+ + +
=
CS CV
CV
other Sh S
A d gz h dV e
t
W W W Q
v
2
v
2
1st Law Flow Process Contd
| |
|
|
.
|
\
|
+ + +
=
CS
CV
CV
other Sh S
A d gz h
t
E
W W W Q
v
2
v
2
+ +
(
+ +
2
v
2
v
2 2
Condition Inlet i
Condition Exit e
=
=
where the subscripts
The state of matter at any location inside the
control volume does not change with time.
The rate of energy transfer as heat and work
across the control surface are constant.
Steady Flow Process
+
= =
CS CV
Sys
A d dV
t dt
dm
v 0
RTT for mass conservation
0 (Steady flow)
0 v = =
i e
CS
m m A d
i e
m m
=
=
|
|
.
|
\
|
+ +
|
|
.
|
\
|
+ +
2
v
2
v
2 2
For turbine, is Positive
For Compressor, is Negative
S
W
S
W
273
o
V
A =
273
t
V V V
o o t
+ =
o
o t
V
t
V V
|
.
|
\
|
=
273
1
Gay-Lussac Law
Avogadros Law
Under identical conditions of temperature
and pressure, equal volumes of all gases
have same number of molecules.
Gas 1: M
1
, P, V, T
Gas 2: M
2
, P, V, T
According to Avogadros law, each gas will contain the
same number of molecules, say n.
m
1
n M
1
= k n M
1
m
2
n M
2
= k n M
2
again
m
1
=
1
V
m
2
=
2
V
The product of molecular mass and specific volume is
constant for all ideal gases under identical conditions of
pressure and temperature.
The quantity vM is called molar volume. It represents the
volume of 1 kmol of ideal gas.
Avogadros Law
1
2
2
1
2
1
v
v
M
M
= =
Hence,
2 2 1 1
M v M v =
Constant = M v
At standard conditions of t = 0 C and p = 1.013
bar, the volume of 1 kilo mole of all gases is
equal to 22.4135 m
3
.
Avogadros Law
Molar volume = v
o
M = 22.4135 m
3
/Kmol
For molar volume of a gas, the characteristic gas
equation can be written as
T R T R M pV
u mol
= =
R
u
is called as the universal gas constant or the molar
gas constant.
Van der Waals Eqn. of State
Real gases differ from ideal ones due to
presence of the intermolecular forces and
also to the finite molecular volumes.
( ) T R b v
v
a
p
u M
M
=
|
|
.
|
\
|
+
2
v
M
= Molar volume
( ) T R b vM
M v
a
p
u
=
|
.
|
\
|
+
2 2
T R b M
m
V
M
m
V
a
p
u
=
|
.
|
\
|
|
|
|
|
.
|
\
|
+
2
2
2
where,
M
m
n =
( ) T nR nb V
V
an
p
u
=
|
|
.
|
\
|
+
2
2
Van der Waals Eqn. of State Contd
Vander Waals equation for 1 mol of real
gas is,
( ) T R b V
V
a
p
u
=
|
|
.
|
\
|
+
2
( ) 0
2 3
= + + ab aV V T R pb pV
u
At critical point all the three roots coincides.
At critical point , the isotherm has zero slope.
Van der Waals Eqn. of State Contd
Van der Waals Eqn. of State Contd
Isotherm Lines
At critical point,
Van der Waals Eqn. of State Contd
0 =
|
.
|
\
|
C
V
p
0
2
2
=
|
|
.
|
\
|
C
V
p
b V
C
3 =
u
C
bR
a
T
27
8
=
2
27b
a
p
C
=
Mixture of Gases
Total mass of gases in the cylinder is given as
Gases a, b, c, ..
Volume, V
Pressure, P
Temperature, T
........ + + + =
c b a
m m m m
........ + + + =
c b a
n n n n
Gases a, b, c, ..
Volume, V
Pressure, P
Temperature, T
Mass Fraction
. .......... , , ,
m
m
x
m
m
x
m
m
x
c
c
b
b
a
a
= = =
1 ........ = + + +
c b a
x x x
Mole Fraction
. .......... , , ,
n
n
y
n
n
y
n
n
y
c
c
b
b
a
a
= = =
1 ........ = + + +
c b a
y y y
Mixture of Gases Contd
Partial Pressure
Gases a, b, c, ..
V
P
T
Gas a
V
Gas b
V
Gas c
V
P
a
P
b
P
c T
T
T
T nR PV
u
=
T R n V P
u a a
= T R n V P
u b b
=
T R n V P
u c c
=
Mixture of Gases Contd
Partial pressure is defined as the pressure which
each individual component of a gas mixture would
exert if it alone occupied the volume of the mixture
at the same temperature.
Partial Pressure Contd
( ) ( ) PV T nR T R n n n V P P P
u u c b a c b a
= = + + + = + + + .... ....
.... + + + =
c b a
P P P P
The total pressure of a mixture of ideal gases is
equal to the sum of the partial pressures of the
individual gas components of the mixture.
Daltons Law of Partial Pressure
Remarks on Daltons Law
Specific volume ()
According to Daltons Law,
Gases a, b, c, ..
V
T
P
Gas a
V
a
= V
T
P
a
... = = = =
c b a
V V V V
... = = = =
c c b b a a
m m m m
Again,
........ + + + =
c b a
m m m m
........ + + + =
c c
c
b b
b
a a
a
v m
m
v m
m
v m
m
mv
m
Therefore,
........
1 1 1 1
+ + + =
c b a
v v v v
........ + + + =
c b a
Specific volume () Contd
Amagat-Leduc Law of Partial Volumes
The partial volume of a gas component represents the
volume that this gas component will occupy if its
temperature and pressure is kept equal to that of the gas
mixture.
Amagat-Leduc Law Contd.
If P and T are the pressure and the absolute
temperature of the gas mixture, then
T nR PV
u
=
For the component gases
, T R n PV
u a a
= , T R n PV
u b b
= , T R n PV
u c c
= .
( ) ( ) PV T nR T R n n n V V V P
u u c b a c b a
= = + + + = + + + .... ....
V V V V
c b a
= + + + ........
1 ........ = + + +
V
V
V
V
V
V
c b a
Fraction Volume = =
a
a
r
V
V
Amagat-Leduc Law Contd.
T nR PV
u
=
T R n V P
u i i
=
: For the gas mixture
: For a constituent of the gas mixture
n
n
P
P
i i
=
Now,
The gas equation for the partial volumes of
the gas can be written as
T R n PV
u i i
=
n
n
V
V
i i
=
Hence,
V
V
n
n
P
P
i i i
= =
Partial Pressure Ratio
Mole Fraction
Volume Fraction
Amagat-Leduc Law Contd.
R of Gas Mixture
For each constituent of the gas mixture contained
in a vessel of volume V and temperature T, we can
write
, T R m V P
a a a
= , T R m V P
b b b
= , T R m V P
c c c
=
.
( ) ( )T R m R m R m V P P P
c c b b a a c b a
.... .... + + + = + + +
Using Daltons law,
( )T R m R m R m V P
c c b b a a
.... + + + =
For the gas mixture, we have
( ) T mR T R m m m V P
m m c b a
= + + + = ....
Molecular Mass of Gas Mixture
R of Gas Mixture Contd
.... + + + =
c c b b a a m
R m R m R m mR
= = + + + =
i
i
u i i c c b b a a m
M
x
R R x R x R x R x R ....
= = + + + = =
i
i
u
i
u
i
c
u
c
b
u
b
a
u
a
m
u
m
M
x
R
M
R
x
M
R
x
M
R
x
M
R
x
M
R
R ....
= + + + =
i
i
c
c
b
b
a
a
m
M
x
M
x
M
x
M
x
M
....
1
In terms of
Mass Fraction
Molecular Mass of Gas Mixture Contd.
Gibbs-Dalton Law
........ + + + =
c b a
m m m m
........ + + + =
c c b b a a m
M n M n M n nM
........ + + + =
c c b b a a m
M y M y M y M
The internal energy, enthalpy and entropy of a gaseous mixture
are respectively equal to the sums of the internal energies, the
enthalpies and the entropies which each component of the gas
mixture would have, if each alone occupied the volume of the
mixture at the temperature of the mixture.
Gibbs-Dalton Law Contd
Internal Energy
= + + + =
i i c c b b a a
u m u m u m u m mu ......
T c m T c m T c m T c m T c m
i v i c v c b v b a v a v
= + + + =
, , , ,
......
= + + + =
i v i c v c b v b a v a v
c x c x c x c x c
, , , ,
......
= + + + =
i i c c b b a a
u x u x u x u x u ......
Specific Heats
= + + + =
i i c c b b a a
u m u m u m u m mu ......
= + + + =
i i c c b b a a
h m h m h m h m mh ......
T c m T c m T c m T c m T c m
i p i c p c b p b a p a p
= + + + =
, , , ,
......
= + + + =
i p i c p c b p b a p a p
c x c x c x c x c
, , , ,
......
Entropy
= + + + =
i i c c b b a a
s m s m s m s m ms ......
= + + + =
i i c c b b a a
s x s x s x s x s ......
Entropy Change in Mixing of Gases
Imagine a number of inert ideal gases separated from one
another by suitable partitions, all the gases being at the
same temperature T and pressure P. The total initial
entropy will be
= + + + =
k k c c b b a a i
s m s m s m s m S ......
From property relation,
vdP dT c vdP dh Tds
p
= =
The entropy of 1 kg of k
th
gas at T and P is,
k k p k
C P R T c s
k
+ = ln ln
Const. of integration
( )
+ =
k k p k i
C P R T c m S
k
ln ln
After the partitions are removed, the gases diffuse into one
another at the same temperature (T) and pressure (P).
According to Gibbs-Dalton law, the final entropy of the
mixture is the sum of the partial entropies, with each gas
exerting its respective partial pressure. Thus
Entropy Change in Mixing of Gases
( )
+ =
k k k p k f
C P R T c m S
k
ln ln
Partial pressure of k
th
gas in volume V at T
( )
= = =
k k k
k
k k k k k i f
y R m
P
P
R m P P R m S S ln ln ln ln
= = = =
k k u k k u k k k i f
y y nR y n R y R m S S S ln ln ln