Kinetic theory of Gases II

B.Sc. Ist year 2nd Semester

 Phase Space
In dynamical system theory, a phase space is a
space in which all possible states of a
system are represented, with each possible
state corresponding to one unique point in the
phase space. For mechanical system, the phase
space usually consists of all possible values
of position and momentum variables. The
combination of position space and velocity
space is known as phase space.
For example: Consider N no. of particles are
situated in static system having volume V then
there are 3N dimensions. If these particles are
situated in a dynamic system (particles are
moving) then there are three velocity co-
ordinates for all N particles. The combination
of both space gives phase space and also have
six dimensions for all n particles.
 The
The Kinetic
Kinetic Molecular
Molecular Model
Model for
for Gases
Gases
• Gas consists of large number of small
individual particles with negligible size
• Particles in constant random motion and
collisions
• No forces exerted among each other
• Kinetic energy directly proportional to
temperature in Kelvin

3
KE   R T
2
 Maxwell-Boltzmann
Maxwell-Boltzmann Velocity
Velocity Distribution
Distribution

M-B Equation gives distribution of molecules in terms of:

• Speed/Velocity, and
• Energy

One-dimensional Velocity Distribution in the x-direction:

[ 1Du-x ]

1
dN   m u x 2 / k T
 Ae 2  du x
N
 1
dN   m u x 2 / k T
 Ae 2  du x Mcad

N
0.0025

F1( u) 0.002
1
m s
0.0015
F2( u)
1
m s
0.001
F3( u)
1
m s 4
5 10

0 0
1500 1000 500 0 500 1000 1500
 1500 u 1500
1
m s
 Maxwell-Boltzmann
Maxwell-Boltzmann Distribution
Distribution
3D Velocity Distribution: [ 3Du ] , Let: a = m/2kT

 dN  a  au x 2
   e  du x
 N 1 D  u x 

 dN  a  au y 2  dN  a  au z 2
   e  du y    e  du z
 N 1 D  u y   N 1 D  u z 

Cartesian Coordinates:

3/ 2
 dN  a  a[ u x 2  u y 2  u z 2 ]
    e  du x  du y  du z
 N 3D   
 Maxwell-Boltzmann
Maxwell-Boltzmann Speed
Speed Distribution
Distribution

Re-shape box into sphere of same volume with radius u .

V = (4/3)  u3 with u2 = ux2 + uy2 + uz2
dV = dux duy duz = 4  u2 du

 dN / N  4 3/ 2 2  au 2
    a u e
 du  3D 
 3D
3D Maxwell-Boltzmann
Maxwell-Boltzmann Speed
Speed Distribution
Distribution

0.0035
Low T
0.003
F1 ( u)
1
m s

F2 ( u) 0.002
1
m s

F3 ( u)
 1 0.001
m s
High T

0
0
0 500 1000 1500 2000 2500
0 u 2500
1
m s
 3D
3D Maxwell-Boltzmann
Maxwell-Boltzmann Speed
Speed Distribution
Distribution

 dN / N  4 3/ 2 2  au 2
    a u e
 du  3D u 

Conversion of Velocity-distribution to Energy-distribution:

 = ½ m u2 ; d  = mu du

3/ 2 
 dN / N  2  1  1/ 2

        e kT
 d  3D    kT 
 Comparison
Comparison of
of Velocity
Velocity Values
Values

Ratio in terms of : kT
m

urms uavg ump

kT 8 kT kT
3  2
m  m m

1.73 1.60 1.41

Fraction
Fractionofofmolecules
moleculeswith
withEE>>Ea
Ea: : ee-Ea/RT
-Ea/RT

(Maxwell-Boltzmann
(Maxwell-BoltzmannDistribution)
Distribution)
 Different types of Velocity
Root mean square velocity: Velocity v which if possessed by
each of the n molecules of the gas leads to correct calculation
of total kinetic energy of the gas is known as root mean square
velocity.
Total kinetic energy = n1/2 m v2 .......(1)
Out of the total number of molecules n contained in the given
sample of gas, let n1, molecules have velocity v1, n2 molecules
have velocity v2 and so on then,
n= n1+n2+n3 ...................(2)
the total kinetic energy KE of the n molecules is the sum of
the kinetic energies of the individual molecules.
 Thus KE= n1 1/2 m1v12 + n2 1/2m2 v2 2 +......
½ n v2 =n1 1/2 m1 v12 +n2 1/2m2 v22 +.... ............(3)
nv2 = n1 v12 + n2 v2 2 +........ ............. (4)
v2 = (n1 v1 2 + n2 v2 2 +........)/n .............(5)
n thus 2 is the mean of squares of the velocities of all the n
molecules in the gas and is termed as mean square velocity.
So v =√[( n1v 1 2 + n2v2 2 + ......)/n] .......... (6)
Here is root of the mean of squares of velocities and is called
root mean square velocity and is often written simply as rms
velocity. Its value can be calculated as
vrms = √3RT/M .................(7)
 Average velocity
The average velocity is given by the arithmetic mean of
different velocities possessed by the molecules of the gas
at a given temperature. Suppose one molecule is moving
with velocity v1, one molecule with velocity v2, third
molecule with velocity v3 and so on. Then total velocity
will be v=v1+ v2+ v3 ...................
There are total of n molecules.
va= (v1+ v2+ v3 ......... )/n
its value can be calculated as va = (2RT/M)1/2 .......(8)
This is average velocity represented by v a
 Most probable velocity
Velocity possessed by most number of molecules
is known as most probable velocity. Most
probable velocity
mp = (8RT/πM)1/2 ....(9)
It is found that vrms > va > mp
vrms : va : mp = 1.0:0.92:0.82