MOLECULAR

PROPERTIES OF GAS

Thermal equilibrium and temperature

-Two systems A and B are ini8ally thermally separated.

-Now they are put into thermal contact (i.e. energy can
ow through the separa8ng wall.

-A and B are in equilibrium if their thermal proper8es does
not change a@er the thermal contact is set up.



For a thermodynamic system in equilibrium, temperature is
dened as a scalar quan8ty represen8ng the thermal
property of the system. For any two systems to be in
thermal equilibrium i their temperature are equal.

How to know if two systems A and B are in equilibrium?

Zeroth Law of Thermodynamic

If A and B are each in thermal equilibrium with C, then A and B are in equilibrium.

C can be a thermometer (like a Hg column, a gas bulb, a thermocouple, and etc.)


Ideal Gas

To iden8fy a thermodynamic system:
- Pressure P [Nm-2]
- Volume V [m3]
- Temperature T [K]

Experimental nding: PV=nRT=NkT
n= number of mole of gas molecule
R= molar gas constant= 8.31 Jmol-1K-1
N= number of gas molecule=nNA
k= Boltzmann constant
NA=6.02x1023

Ideal gas model:

(1) Ideal gas is made up of par8cles in random mo8on obeying Newtons laws.
(2) The number of the gas par8cles is very large.
(3) The volume occupied by the gas par8cle is negligible as compared to the total
volume containing the gas.
(4) No intermolecular force between par8cles except during the collision.
(5) All collisions are elas8c and the period of collision is very small as compared to
the free mo8on 8me of the par8cle.

Molecular view of pressure

Consider a cubic volume having lengths of L containing
N par8cles.

Mass of each par8cle =m

Velocity of m:
!
v = v i + v j + v k
x

-Assume par8cle does not collide with other par8cle during its journey
-Assume par8cle collides with wall elas8cally


As m arrives at A1, its x-component velocity becomes vx

Momentum impact to A1 by m
=-(change of momentum of m)
=2mvx

The par8cle will then travel towards A2.

Time required to cross the distance L to arrive at A2 = L/vx

Then it collide with A2 and go back toward A1.

Total 8me required for the next collision with A1 to occur:

2L
t
=

vx


Average impulse force experience by A1 :

2mvx mvx2
Fx = t = L

As there are N iden8cal par8cles, pressure experience by A1:
1 N mvix2 m N 2
P= 2
= 3 vix
L i=1 L
L i=1
Nm " 1 N 2 %
= 3 # vix &
L $ N i=1 '
= ( vx2 )

av

= density of gas

But as v 2 = vx2 + vy2 + vz2

( v 2 ) = ( vx2 ) + ( vy2 ) + ( vz2 )
av

av

av

av

As gas particles are in random motion

( vx2 ) = ( vy2 ) = ( vz2 )
av

av

( v 2 ) = 3 ( vx2 )
av

av

av

And thus
1
P = (v2 )
av
3
(v2 ) = Mean square of particle velocity
av

Define vrms = Root mean square veolcity=

vrms =

(v )
2

av

3P
3nRT
3kT
=
=

V
m

Rela8ng a macroscopic quan8ty to a microscopic one.

Mean free path

- Gas molecule move with constant velocity before it collides with another molecule.
- The collision is elas8c and so it only changes the molecule moving direc8on but not
the speed.
- The gas molecules thus undergo zig-zag random mo8on.
- Mean free path is dened as the average distance that the par8cle travels
between two successive collisions.

m travels with v and sweeps out a cylinder. It has collision

with other molecules if there are other molecules in the
cylinder.





Equivalent to a fat molecule with diameter of 2d
sweeping out a cylinder and the other molecule become
sizeless point.

Volume of the cylinder being swept out by the fat molecule in a 8me interval t:-

Vcyl = d 2 vt

v is the average velocity of gas molecule.

No. of sizeless molecules inside the cylinder:-

N cyl = Vcyl


N

=
density
of
gas
=

V
N = Total no. of gas molecules inside the container
V = Volume of the gas container


N d 2 vt
N cyl =

V

No8ce that Ncyl is indeed the number of collisions in the 8me interval t.

The distance traveled by the moving par8cle in 8me t is :-

Lcyl = N cyl

L
V
V

= cyl = vt
=
N cyl
N d 2 vt N d 2

kT

= 2 as PV = NkT
d P


However only one molecule is moving in this model, correc8on yields:
=

kT
2 d 2 P

The distribu8on of molecule speed

- Molecules have dierent speeds following some distribu8on func8on.

Maxwell Distribu<on:-

3/2
! mv 2 $
! m $ 2
N(v) = 4 N 0 #
& v exp #
&
"
%
2

kT
2kT
"
%



- N(v)dv is the number of molecules having speed v to v+dv.
- Number of molecules having speed from v1 to v2 is:

v2
v1

N(v)dv

- Distribu8on is dependent on temperature.

Some important parameters of Maxwell Distribu8on

-The most probable speed vp (i.e. the mode)
! dN(v) $
#" dv &%v=v = 0

v p = 2kT = 2RT
m
M

M = mN A = molar mass of gas


-The average speed vav
p

vav =

vN(v)dv
N0

8kT
8RT
=
m
M

-The root mean square speed vrms

vrms = ( v

av

v 2 N(v)dv
N0

3kT
3RT
=
m
M

-Average transla8onal KE for each molecule Ktrans

K
K trans =

N0

1
1 2
m
m 2
i
mvi =
= ( v 2 ) = vrms

av
N0 i 2
2 N0
2
2

3
or K trans = kT
2

-Using Ideal Gas Law:

2
vrms
=

v
m

2
i

3RT 3P
=
M

Distribu8on of molecule energy

To obtain N(E)dE from N(v)dv
N(E)dE = N(v)dv,
N(E) = N(v)
N(E) =

dv
dE
1

1
E = mv 2
2

# E&
2N 0
1/2
E
exp
% (
3/2
$ kT '
( kT )