This action might not be possible to undo. Are you sure you want to continue?

**This implies that there is a potential energy function V (R) that depends
**

on the relative separation R of their centres, and is given by

V (R) =

0 R > a

1

+a

2

∞ R ≤ a

1

+a

2

(8.12)

and this is sketched in Fig. 8.2.

The impact parameter b between two moving molecules is deﬁned

as the distance of closest approach that would result if the molecular

trajectories were undeﬂected by the collision. Thus for a hard-sphere

potential there is only a collision if the impact parameter b < a

1

+

a

2

. Focus on one of these molecules (let’s say the one with radius a

1

).

This is depicted in Fig. 8.3. Now imagine molecules of the other type

(with radius a

2

) nearby. A collision will only take place if the centre of

these other molecules comes inside a tube of radius a

1

+a

2

(so that the

molecule labelled A would not collide, whereas B and C would). Thus

our ﬁrst molecule can be considered to sweep out an imaginary tube of

space of cross-sectional area π(a

1

+a

2

)

2

that deﬁnes its ‘personal space’.

The area of this tube is called the collision cross-section σ and is then

given by

R

V R

a a

Fig. 8.2 The hard-sphere potential

V (R).

σ = π(a

1

+a

2

)

2

. (8.13)

If a

1

= a

2

= a, then

σ = πd

2

(8.14)

where d = 2a is the molecular diameter.

Fig. 8.3 A molecule sweeps out an

imaginary tube of space of cross-

sectional area σ = π(a

1

+ a

2

)

2

. If the

centre of another molecule enters this

tube, there will be a collision.

Is the hard-sphere potential correct? It is a good approximation at

lower temperatures,

2

but progressively worsens as the temperature in-

2

But not too low a temperature, or

quantum eﬀects become important.

creases. Molecules are not really hard spheres but slightly squashy ob-

jects, and when they move at higher speeds and plough into each other

with more momentum, you need more of a direct hit to cause a collision.

Thus as the gas is warmed, the molecules may appear to have a smaller

cross-sectional area.

3

3

Cross-sections in nuclear and particle

physics can be much larger than the size

of the object, expressing the fact that

an object (in this case a particle) can

react strongly with things a long dis-

tance away from it.

8.3 The mean free path 71

8.3 The mean free path

Having derived the mean collision time, it is tempting to derive the

mean free path as

λ = vτ =

v

nσv

(8.15)

but what should we take as v? A ﬁrst guess is to use v, but that turns

out to be not quite right. What has gone wrong?

Our picture of molecular scattering has been to focus on one molecule

as the moving one, and think of all of the others as sitting ducks, ﬁxed

in space waiting patiently for a collision to occur. The reality is quite

diﬀerent: all molecules are whizzing around. We should therefore take

v as the average relative velocity, i.e. v

r

, where

v

r

= v

1

−v

2

(8.16)

and v

1

and v

2

are the velocities of two molecules labelled 1 and 2. Now,

v

2

r

= v

2

1

+ v

2

2

−2v

1

· v

2

, (8.17)

so that

v

2

r

= v

2

1

+v

2

2

= 2v

2

, (8.18)

because v

1

· v

2

= 0 (which follows because cos θ = 0). The quantity

which we want is v

r

, but what we have an expression for is v

2

r

. If

the probability distribution is a Maxwell–Boltzmann distribution, then

the error in writing v

r

≈

v

2

r

is small,

4

so to a reasonable degree of

4

Equation 7.23 implies that

v/

p

v

2

=

q

8

3π

= 0.92, so

the error is less than 10%.

approximation we can write

v

r

≈

v

2

r

≈

√

2v (8.19)

and hence we obtain an expression for λ as follows:

λ ≈

1

√

2nσ

. (8.20)

Substitution of p = nk

B

T yields the expression

λ ≈

k

B

T

√

2pσ

. (8.21)

To increase the mean free path by a certain factor, the pressure needs

to be decreased by the same factor.

Example 8.1

Calculate the mean free path for a gas of N

2

at room temperature and

pressure. (For N

2

, take d = 0.37 nm.)

Solution:

The collision cross-section is πd

2

= 4.3 ×10

−19

m

2

. We have p ≈ 10

5

Pa

and T ≈ 300 K, so the number density is n = p/k

B

T ≈ 10

5

/(1.38 ×

10

−23

×300) ≈ 2×10

25

m

−3

. This leads to λ ≈ 1/(

√

2nσ) = 6.8×10

−8

m.

kk

kk

- 2.a.1 - Kinetic Theory of Gases
- 169
- 15TheKineticTheoryofGasesRev2
- 10 Ideal Gases
- OFIC-07_HauserThomas
- 10 Ideal Gases
- Gaussian Tutorial
- Lec7 (1)
- c4cp05096g
- su3c7 by adel khamis
- Plant Pigments
- Bochi Cchio Gaussian Train 2009
- Molecular Electronic Junctions
- Tutorial 7 Momentum
- Sergei Tretiak, Cris Middleton, Vladimir Chernyak and Shaul Mukamel- Localized and Delocalized Electronic Excitations in Biological and Artificial Antenna Complexes
- on of Substances Lab
- Amber Tools
- CH13 IMF Student
- Physics of Continuum
- Molecular Visualization in Chemistry Workshop
- The Behavior of Alkanes
- series_128_vol262_1
- BM-Notes
- Ideal Gas in a Finite Container
- physics Sample Test 1 - 2014 Past Paper
- David H. Whittum- Ultimate Gradient in Solid-State Accelerators
- Chapter 1 Introduction
- Short Questions chapter No. 3. Fsc Physics First Yeardoc
- adsorpsi
- L-BFGS
- cc

Are you sure?

This action might not be possible to undo. Are you sure you want to continue?

We've moved you to where you read on your other device.

Get the full title to continue

Get the full title to continue reading from where you left off, or restart the preview.

scribd