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**Fig. 4.9 The ﬁnal distribution for a lat-
**

tice of size 1000×1000 with one quan-

tum of energy initially placed on each

site. The error bars are calculated by

assuming Poisson statistics and have

length

√

N, where N is the number of

sites having n quanta.

n

N

4.7 Applications of the Boltzmann

distribution

To illustrate the application of the Boltzmann distribution, we now con-

clude this chapter with some examples. These examples involve little

more than a simple application of the Boltzmann distribution, but they

have important consequences.

Before we do so, let us introduce a piece of shorthand. Since we will

often need to write the quantity 1/k

B

T, we will use the shorthand

β ≡

1

k

B

T

, (4.15)

so that the Boltzmann factor becomes simply e

−βE

. Using this short-

hand, we can also write eqn 4.7 as

β =

d ln Ω

dE

. (4.16)

Example 4.3

The two state system.

The ﬁrst example is one of the simplest one can think of. In a two-state

system, there are only two states, one with energy 0 and the other with

energy > 0. What is the average energy of the system?

4.7 Applications of the Boltzmann distribution 41

Solution:

The probability of being in the lower state is given by eqn 4.14, so we

have

Fig. 4.10 The value of E as a func-

tion of /k

B

T = β, following eqn 4.19.

As T → ∞, each energy level is equally

likely to be occupied and so E = /2.

When T → 0, only the lower level is

occupied and E = 0.

P(0) =

1

1 + e

−β

. (4.17)

Similarly, the probability of being in the upper state is

P() =

e

−β

1 + e

−β

. (4.18)

The average energy E of the system is then

E = 0 · P(0) + · P()

=

e

−β

1 + e

−β

=

e

β

+ 1

. (4.19)

This expression (plotted in Fig. 4.10) behaves as expected: when

T is very low, k

B

T , and so β 1 and E → 0 (the sys-

tem is in the ground state). When T is very high, k

B

T , and so

β 1 and E → /2 (both levels are equally occupied on average).

Example 4.4

Isothermal atmosphere:

Estimate the number of molecules in an isothermal

11

atmosphere as a

11

‘Isothermal’ means constant temper-

ature. A more sophisticated treatment

of the atmosphere is postponed until

Section 12.4; see also Chapter 37.

function of height.

Solution:

This is our ﬁrst attempt at modelling the atmosphere, where we make

the rather naive assumption that the temperature of the atmosphere is

constant. Consider a molecule in an ideal gas at temperature T in the

presence of gravity. The probability P(z) of the molecule of mass m

being at height z is given by

P(z) ∝ e

−mgz/k

B

T

, (4.20)

because its potential energy is mgz. Hence, the number density

12

of

12

Number density means number per

unit volume.

molecules n(z) at height z, which will be proportional to the probability

function P(z) of ﬁnding a molecule at height z, is given by

n(z) = n(0)e

−mgz/k

B

T

. (4.21)

This result (plotted in Fig. 4.11) agrees with a more pedestrian deriva-

tion which goes as follows: consider a layer of gas between height z and

z+dz. There are ndz molecules per unit area in this layer, and therefore

they exert a pressure (force per unit area)

dp = −ndz · mg (4.22)

42 Temperature and the Boltzmann factor

downwards (because each molecule has weight mg). We note in passing

that eqn 4.22 can be rearranged using ρ = nm to show that

dp = −ρg dz, (4.23)

which is known as the hydrostatic equation. Using the ideal gas law

(in the form derived in Chapter 6), which is p = nk

B

T, we have that

dn

n

= −

mg

k

B

T

dz, (4.24)

which is a simple diﬀerential equation yielding

ln n(z) −ln n(0) = −

mg

k

B

T

z, (4.25)

so that, again, we have

n(z) = n(0)e

−mgz/k

B

T

. (4.26)

Our prediction is that the number density falls oﬀ exponentially with

Fig. 4.11 The number density n(z) of

molecules at height z for an isothermal

atmosphere.

height, but the reality is diﬀerent. Our assumption of constant T is at

fault (the temperature falls as the altitude increases, at least initially)

and we will return to this problem in Section 12.4, and also in Chap-

ter 37.

Example 4.5

Chemical reactions:

Many chemical reactions have an activation energy E

act

which is about

1

2

eV. At T = 300 K, which is about room temperature, the probability

that a particular reaction occurs is proportional to

exp(−E

act

/(k

B

T)). (4.27)

If the temperature is increased to T + ∆T = 310 K, the probability

increases to

exp(−E

act

/(k

B

(T + ∆T)), (4.28)

which is larger by a factor

exp(−E

act

/(k

B

(T + ∆T))

exp(−E

act

/(k

B

T))

= exp

−

E

act

k

B

[(T + ∆T)

−1

−T

−1

]

≈ exp

E

act

k

B

T

∆T

T

≈ 2. (4.29)

Hence many chemical reactions roughly double in speed when the tem-

perature is increased by about 10 degrees.

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