PHYSICAL CHEMISTRY FOR

ENGINEERS
Kinetic Theory of Gases
Dr. Nadia Adrus

-2-

Week 11-12

Course outcome

Kinetic theory of gas motion and

pressure
Distribution and effusion of gas
particles
Molecular collisions

It is expected that the

students will be able to
Discuss the translation
motion of gas particles.
Explain the gas
molecular distribution
and effusion.
Justify molecular collision
including frequency and
distance particle travel
between collisions.

-3Outline
of this Lecture

Kinetic theory of gas motion and pressure

Distribution and effusion of gas particles
Molecular collisions

-4Introduction

Previous: Macroscopic (i.e.,

behaviour of gases P, V & T.

large

quantity)

This chapter: Kinetic molecular theory of gases

attempts to explain the behaviour of gases on a
molecular level.

Consider gases at low P (ideal gas) starting point

for the discussion of its transport properties.

Ideal Gas Law

-5Ideal
Gas Law

No. of moles in the ideal gas

Temp. (K)

PV nRT
Gas constant, R
= 8.314 J/mol.K

In the kinetic model of gases assume that the only contribution

to the energy of the gas is from kinetic energies of the molecules.
Note: N, total number of molecules; NA, Avogadros number: the number of atoms, molecules, etc, in a mole of a substance: N A=6.02
x 1023/mol.

-6-

Assumptions of Kinetic Theory

The kinetic model is based on 3 assumptions:
1. The gas consists of molecules of mass m in ceaseless
random motion.
2. The size of the molecules is negligible, in the sense that
their diameters are much smaller than the average distance
travelled between collisions.
3. The molecules interact only through brief, infrequent, and
elastic collisions

Note: An elastic collision is a collision in which the total translational kinetic energy of the molecules is conserved.

Kinetic Theory of
Gas Motion &
Pressure

-8-

Pressure & Molecular Speed

From the assumptions of the kinetic model, P & V of the gas are
related by,

rms speed of
the molecules

1
PV nMc2
3
Molar mass of the
molecules, M = mNA

Note: rms, root mean square

2 12

c v

-9-

Derivation: Molecular Speed

Consider particle of mass m that is travelling with a component of
velocity vx (parallel to the x-axis)
Collides with the wall

Many molecules collide

with the wall in an
interval t
Reected

Its linear momentum changes from mvx mvx

x-comp. momentum 2mvx (y- & z-compt. unchanged)

Total change of momentum: (Product of the change in momentum of

each molecule) (No. of molecules that reach the wall during the interval)

Momentum Change

10
-

Only those close enough to the surface hit it in time t, those within the
distance vx t
Consider, wall has area A All the particles in a volume,

A vxt

will reach the wall

Number of density of particles,

Total amount of molecules
in the container

nNA/V
Avogadros constant

Number of molecules in the volume,

(nNA/V) Avxt

Total Momentum Change

11
-

Assume: surface is normal to the x-axis, half the molecules of speed vx

move toward the surface.

Average number of collisions with the wall

1 2nNA Av xt
V

Total momentum change,

Particle mass
2

nNA Av xt
nmNA Av x t nMAvx t
Momentumchange
2mvx

2V
V
V

Force & Pressure

12
-

Force,

momentumchange
t
2
nMAvx
F
V

Rate of momentumchange

Pressure

F nMvx
P
A
V

Molecules travels with

the same velocity

nM vx
V

Pressure in Terms of C
13
-

Speed of a single molecule, v

2

v2 vx vy vz

c v2

12

c v2 vx vy vz

Molecules
are
moving randomly,
c 2 3 vx

vx

substitute
P

1
PV nMc2
3

nM vx
V

1 2
c
3

Video
14
-

Video

Website: http://www.youtube.com/watch?v=YSTRa27a3BQ ; http://www.youtube.com/watch?v=iMFwuHDu8dA

15
-

Average Translational Kinetic Energ

1
PV nMc2
3

M mNA
c v2

1 nNA
2
P
mv
3 V

nNA N

Note: Molar mass, M = mNA; N = nNA

2 N

3 V

KE

Boltzmann constant,
kB=R/NA= 1.38 1023

3 nRT 3
KE
kB T
2 N
2

1N
m v2
3V

PV nRT

1
2
mv
2

1
1
m v2 mc2
2
2

2 N
KE
3 V

16
-

Root Mean Square Speed

If c of the molecules depends only on temp.,

PV constant

PV nRT

Boyles law (const. T)

Ideal gas

1
PV nRT nMc2
3

Expression for the mean

square speed of molecules

3RT
c

12

Conclusion: the c of the molecules of a gas is proportional to the

square root of the T and inversely proportional to the square root of
the M.
Note: Molar mass, M = mNA; N = nNA

17
-

The Maxwell Velocity Distribution

Actual gas:

Speeds of individual molecules span a wide range

Collisions in the gas continually redistribute the speeds among

the molecules.

Before a collision: a molecule may be travelling rapidly.

After a collision: it may be accelerated to a very high speed, only to

be slowed again by the next collision.

Distribution of Speed
18
-

FRACTION OF MOLECULES that have speeds in the range v to

(v + dv) is proportional to the width of the range,
Written f(v)dv

Distribution of speeds

M
f v 4

2RT

32
2

ve

Mv2 2RT

19
-

Calculate the Fraction of

Molecules
Narrow range of speed

f v v
Evaluate at the
speed on interest

Width of the range

of speeds of interest

Wide range Integrate

Fraction in the range v1 to v2 f vdv

v2

v1

20
-

Derivation: Maxwell Distribution

Speed
Const. of proportionality
(at const. T)

1
1
1
2
2
2
E mvx mvy mvz
2
2
2

ax y z axayaz f Ke E kT Ke 1 2mvx
Ke

1 2mvy2 1 2mvz 2 kT

2
mvx2 2kT mvy 2kT

mvz 2 2kT

Factorize

f f vx f vy f vz

Fraction of molecules in the velocity

range vx to dvx, vy to dvy,& vz to dvz

f vx K e
13

f vy K e
13

mvx2 2kT

mvy2 2kT

f vz K 1 3emvz

2kT

Determination of K
21
-

Note that molecule must have a velocity somewhere in the range < vx
,

f v dv

f vx K 1 3emvx

2kT

1 K

Use standard integral

13

2kT
dvx K

mvx2 2kT

eax dx

m
K

kT

32

f vx K 1 3emvx

M
f vx

RT

12

Mvx2 2RT

dvx

13

Maxwell-Boltzmann
velocity distribution

RT

2kT

32

12

Distribution of Speeds
22
-

Probability that a molecule has a velocity in the range vx to vx + dvx, vy to

vy + dv , vz to vz + dvz is

M
f vx vy vz

2RT

32

M vx2 vy2 vz 2 2kT

v2 vx vy vz

dvxdvydvz

4v2dv

Maxwell speed
distribution

M
f v 4

RT

32
2

2RT

2kT

v2eMv

or

m
f v 4

kT

32

v2eMv

c*,
cc
,
c
&
cc
rel
23
-

c*: speed at which df(v)/dv = 0

2RT
c

12

2kT

12

8RT
c

c: square root of the 2nd

moment of distribution
2 12

c v

3RT

12

3kT

*Previously discussed
Note: k=R/NA, Boltzmanns constant; , reduced mass

cc: Average value

12

12

8kT

12

ccrel: two dissimilar molecules

of masses mA & mB

8kT

crel

12

mA mB

mA mB

*Will be discussed later

Comparative Values for Speed

24Distributions
-

Some important speeds in the Maxwell speed distribution

Most
probable
speed, c*

Average
speed, cc

Root-mean
square
speed, c

Relative
mean
speed, ccrel

To compare only certain aspects of the distribution

Such as the speed at which the distribution is maximized, or
at the average speed

Comparison
of
c,
cc
,
c
25
-

Most probable speed

Average speed
Root-mean square speed

Example 1
26
-

Determine vmp, vave, and vrms for the following species at 298 K:
a) Ne

b) Kr

c) CH4

Note: J kg1 m2 s2
Example 2
Compute mp, ave, and rms for O2 at 300 and 500 K. How would
your answers change for H2?

Example 3
27
-

Compare the average speed and average kinetic energy of O2 with

that of CCl4 at 298 K.
Example 4
For N2 at 298 K, what fraction of molecules has a speed between
200 and 300 m s1? What is this fraction if the gas temperature is
500 K?

Molecular
Collisions

Intermolecular Collisions

29
-

Quantitative picture of the events that take place in a collection

of gaseous molecules.
Frequency of collisions?
Distance between successive collisions?
Rate of collisions per unit volume?
A pair of molecules will collide whenever the centers of the 2
molecules come within a distance d (collision diameter) of 1
another
d

No collision

Collision occurs

The
Collision
Cylinder
30
-

Consider the particle interest is moving & that all other molecule are
stationary
Particle of interest sweeps out a collisional cylinder
Determines the no. of collisions the particles undergoes per unit of
time
Collision occur between the particle of interest & other particles that are
positioned within the cylinder.

Relative Mean Speed, ccrel

31
-

To determine the collision frequency, Z, we have to consider

the relative speed of the colliding particles.

8RT

1/2

8RT

12

crel v rel

c v

1/2

1
1
1
with

12 M1 M2

The reduced mass, of the two identical particles is m/2 &

therefore

crel v rel v1 v2
21/2 v 2 c

2 1/2

32
-

Individual Particle Collision

Frequency
Number of collisions an individual molecule undergoes with
other collisional partners
Collisional cross section (Table 16.1)
1/2

N2 Vcyl N2 vavedt N2 8kT

z12

V dt
V
dt
V

Gas comprised of one type of particle, = m1/2

8kT
N

z11 1 2
V
m1

1/2

8RT
PN

1 A 2
RT
M1

1/2

Total Collision Frequency

33
-

Total number of collisions that occur for all gases

For gas consisting of only one type of particle is
2

1 N1 8kT

Z11

2 V m1

1/2

1 P1NA 8RT

2 RT M1

2 type of gas molecule

P1NA P2NA 8kT

RT
RT

Z12

1/2

1/2

The
Mean
Free
Path
34
Gas molecules encounter collisions with other
gas molecules & with the walls of the container.

Define as the average distance

successive molecular collisions

between

vavedt
vave

z11 z12 dt z11 z12

1 type particle,
N2 = 0 z12 = 0

vave
vave

z11 N1

2vave
V

1 RT

2 P1NA

kT
2P

Example 5
35
-

a) A standard rotary pump is capable of producing a vacuum on the

order of

103 Torr. What is the single-particle collisional

frequency and mean free path for N2 at this pressure and 298
K?
b) A cryogenic pump can produce a vacuum on the order of 1010
Torr. What is the collisional frequency and mean free path
for N2 at this pressure and 298 K?

Effusion
36
-

A gas under pressure goes (escapes) from one compartment

of a container to another by passing through a small opening.

Rate, r at which molecules pass through

a small hole of area A,

Collisional rate = dNc/dt

PN A A
PA
r Zc A

12
2RTM
2mkT 1 2
Collisional flux
Note: dNc, no. of particles that hit the wall of the container

Effusion of Gas
Particles

Effusion
Ratio
38
Grahams Law: estimate the ratio of the effusion rates for 2 different
gases.

Effusion rate of gas 1 r1.

PNA A
r1 Zc ,1A
2RTM 1 1 2

Effusion rate of gas 2 r2.

r2 Zc,2A

PNA A
2RTM 2

r2

r1

PNA A
2RTM 1

PN A A
2RTM 2 1 2

r2
M1

r1
M2

Example 6
39
-

a) How many molecules strike a 1-cm2 surface during 1 min if the

surface is exposed to O2 at 1 atm and 298 K?
b) Ultrahigh vacuum studies typically employ pressures on the order
of 1010 Torr. How many collisions will occur at this pressure at
298 K?