School of Mechanical Sciences

Indian Institute of Technology, Bhubaneswar

E-mail: prath@iitbbs.ac.in, Tel: 2306-273
P. Rat h, Ph.D.
Asst . Pr of essor
Course Structure
Mid-semester: 30%
End-semester: 50%
Quiz & Assignments: 15%
Attendance: 5%
Reference Books
Thermodynamics: An Engineering Approach Yunus A.
Cengel and Michael A. Boles
Engineering Thermodynamics P. K. Nag
Fundamentals of Classical Thermodynamics Gordon J.
Van Wylen and Richard E. Sonntag
Thermal Science and Engineering D.S. Kumar
Essential Reading
@ My Lecture Notes
Course Outline
Fundamentals of Thermodynamics
Basic Concepts & Definitions
Zeroth Law of Thermodynamics
Thermodynamics derived from the greek words
therme means heat and dynamis means power.
Thermodynamics is the science of energy
What is Thermodynamics?
Thermodynamics is a science dealing with energy and its
transformation
It deals with equilibrium and feasibility of a process
Deals with relations between heat and work and the
properties of a system
Fundamentals of Thermodynamics
1
st
and 2
nd
laws of thermodynamics emerged
simultaneously in the 1850s.
The above laws are derived out of the works of William
Rankine, Rudolph Clausius and Lord Kelvin (formerly
William Thomson).
The term thermodynamics was first used in a
publication by Lord Kelvin in 1849.
The first textbook of thermodynamics was written in 1859
by Wiiliam Rankine, a Professor at the University of
Glasgow.
Brief History
Fundamentals of Thermodynamics
Fundamentals of Thermodynamics
What Thermodynamics tells us?
Is the proposed chemical reaction or a physical
process possible?
Does the reaction/process go to completion or
does it proceed to a certain extent only beyond
which it cannot be proceed?
How much energy is required for the process to
take place?
What is the maximum efficiency of a heat engine
or the maximum coefficient of performance of a
refrigerator?
1. Zeroth law of thermodynamics deals with thermal
equilibrium and provides a means of measuring
temperature.
2. The first law of thermodynamics tells about the conservation
of energy and introduces the concept of internal energy.
3. The second law of thermodynamics dictates the limits of
converting the internal energy into work and introduces the
concept of entropy. It also tells whether a particular process
is feasible or not.
4. The third law of thermodynamics provides a datum for the
measurement of entropy.
Fundamentals of Thermodynamics (Contd)
Principles of Thermodynamics
It consists of four laws
1. Macroscopic Approach
2. Microscopic Approach
Fundamentals of Thermodynamics (Contd)
Two approaches to study Thermodynamics
Macroscopic Approach
The structure of matter is not considered.
Only a few variables are used to describe the state of matter.
The values of these variables can be measured.
Classical thermodynamics adopts the macroscopic approach.
It is based on continuum theory.
Microscopic Approach
A knowledge of the structure of matter is essential.
A large number of variables are needed to describe
the state of matter.
The values of these variables cannot be measured.
Statistical thermodynamics adopts the microscopic approach.
Basic Concepts and Definitions
System
A definite quantity of matter bounded by some surface.
The boundary surface may be real or imaginary.
It may change in shape and size.
Sometimes the system is also referred as control mass or cv.
A system can exchange energy in the form of work and heat.
Fundamentals of Thermodynamics (Contd)
Surrounding
The combination of matter and space external to the system
constitutes the surrounding.
3 types of Systems
1. Open System (Control Volume): A properly selected region in
space that involves mass as well as energy flow across its boundary.
Ex: Compressor, turbine, nozzle.
2. Closed System (Control Mass): It consists of a fixed amount of
mass in a selected region in space and no mass can cross its
boundary. Energy can flow across the boundary. Ex: Pressure
cooker, refrigerator, cylinder fitted with a movable piston.
3. Isolated System: No mass and energy flow across the boundary of a
chosen space. Ex: Thermos flask, Universe.
Basic Concepts & Definitions (Contd)
A property is any characteristic (which can be
quantitatively evaluated) that can be used to describe
the state of a system. Ex: P, V, T, etc.
Property
Essential features of a property
It should have a definite unique value when the system
is in a particular state.
The value of the property should not depend upon the
past history of the system.
Property is a state function and not a path function.
Its differential is exact.
Basic Concepts & Definitions (Contd)
Extensive Properties: Are those whose values depend on
the size or extent of the system. Ex: Mass, Volume, Total
Energy.
Intensive Properties: Are those that are independent of the
size of a system. Ex: T, P,
Thermodynamics deals with relevant properties only.
Classification of property
1. Relevant Property: Associated with energy and its
transformation.
2. Irrelevant Property: Not associated with energy and its
transformation. Ex: Color, odor, taste
How to determine whether a property is intensive or extensive?
Basic Concepts & Definitions (Contd)
Specific Property: Extensive property per unit
mass

m
V
T
P


Extensive Property
Intensive Property
Basic Concepts & Definitions (Contd)
m/2
V
T
P

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

A temperature scale that is independent of the

properties of substance is known as the
Thermodynamic Temperature Scale.
Temperature Scales Contd
Thermodynamic Temperature Scale
Thermodynamic temperature scale in the SI is the Kelvin
scale (K).
Thermodynamic temperature scale in the English system is
the Rankine scale (R).
A temperature scale that turns out to be identical to
the Kelvin scale is the ideal gas temperature
scale.
1
st
Law Analysis
Process Path
dE W Q =

= W Q
Cyclic Process

P
V
1
2
Heat Transfer to the system
Work done by the system
Specific Heat (C)
1st Law Analysis
Specific Heat at Constant Pressure: C
P
Specific Heat at Constant Volume: C
v
Energy required to raise the temperature of a unit mass of a
substance by one degree
P
P
T
h
C
|
.
|

\
|

=
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

Properties of Pure Substance

A substance with fixed chemical composition
Pure Substance
A pure substance is not necessarily consists of a
single chemical element or compound.
A mixture of two or more phases of a pure
substance is also a pure substance as long as
the chemical composition of each phase is same.
Phase
Properties of Pure Substance Contd
A system that has distinct molecular arrangement
which is homogeneous throughout is called a
phase.
If a system contains more than one phase, they
are separated by a phase boundary.
Principal phases: Solid, liquid and gas.
There may be several phases within a principal
phase.
1
st
Law for Flow Process
From 1
st
Law of Thermodynamics

+

=
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

Machine such as a pump, a turbine, a fan or a compressor

whose shaft protrudes through the control surface and the
work transfer associated with all such devices is the shaft
power.
Work done by CV
Rate of work done by pressure forces on CV
1st Law Flow Process Contd
( )

=
CS
P
dA n P W v

Rate of work done by shear forces

=
CS
Sh
dA W v

........ + + =
magnetic electrical other
W W W

Rate of work done by other forces
n
F

The term Pv is the flow work, which is the work

associated with pushing a fluid into or out of a
control volume per unit mass.
| |


|
|
.
|

\
|
+ +

=
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

1st Law Flow Process Contd

| |
CV
CV other Sh S i
i
i i e
e
e e
E W W W Q gz h m gz h m

=
(

+ +
(

+ +
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

=

The steady state flow implies that there is no

accumulation of mass inside the control volume.
That is the rate of inflow of mass is equal to the
rate of outflow of mass.
The devices like turbines, compressors, pumps,
etc. operates at steady state conditions except
at the start up and shut down periods.
An analysis of steady state flow processes is
useful in evaluating the performance of such
devices and in the design of equipment.
Steady Flow Process Contd
Steady Flow: Applications
Turbine/Compressor
0 = Q

Adiabatic Process, i.e.

m
W
gz h gz h
S
i
i
i e
e
e

=
|
|
.
|

\
|
+ +
|
|
.
|

\
|
+ +
2
v
2
v
2 2
For turbine, is Positive
For Compressor, is Negative
S
W

S
W

Ideal Gas: Fundamentals

Properties of Ideal Gases
An ideal (or perfect) gas has no intermolecular forces of
attraction or repulsion between the particles of gas and
the particles are in a state of continuous motion.
The collision of the molecules with one another and with
the walls of the container is perfectly elastic.
It does not change its phase during a thermodynamic
process.
The volume occupied by the gas molecules is negligible
as compared to the volume of the gas.
It obeys a set of common rules governing change of its
properties.
Real gases differ from ideal ones due to presence of the
intermolecular forces and finite molecular volumes.
The equation of state for ideal gas is given
as
RT pv =
The state of zero pressure of a real gas is called
ideal state.
Under special conditions (p 0), even the real
gases behave in a similar manner. Hence,
( )
0
=
p
RT pv
Ideal Gas: Fundamentals Contd
The identical behavior of a real gas at high
temperature and low pressure is called ideal
behavior.
The internal energy u and enthalpy h are
functions of temperature alone. That is
) (
1
T f u =
) (
1
T f h =
Ideal Gas: Fundamentals Contd
Boyles Law
If the state of a perfect gas changes at constant
temperature, then the volume of a given mass of
the gas is inversely proportional to the absolute
pressure.
p
1
V
pV = Const.
Boyles law is essentially valid only at very low pressure
and at moderately high temperature.
Charless Law
If the state of a perfect gas changes at
constant pressure, then the volume of a
given mass of perfect gas varies directly as
absolute temperature.
V
T Const. =
T
V
It was found by Gay-Lussac and Regnault that at
constant pressure, the change in volume of any perfect
gas corresponding to a unit degree temperature change
is given by 1/273 of its volume at 0 C.
According to Charless Law,
Charless Law Contd
V
o
= Volume of the gas at 0 C.
V
t
= Volume of the gas at t C.
) 273 ( + = = t A AT V
t
) 273 0 ( + = A V
o

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 ......

According to Gibb-Dalton law, enthalpy of the mixture is

given as
Gibbs-Dalton Law Contd

= + + + =
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