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. (4.17)
Similarly, the probability of being in the upper state is
P() =
e
1 + e
. (4.18)
The average energy E of the system is then
E = 0 P(0) + P()
=
e
1 + e
=
e
+ 1
. (4.19)
This expression (plotted in Fig. 4.10) behaves as expected: when
T is very low, k
B
T , and so 1 and E 0 (the sys-
tem is in the ground state). When T is very high, k
B
T , and so
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 rst 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 nding 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 = nm to show that
dp = g 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 dierential 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 o exponentially with
Fig. 4.11 The number density n(z) of
molecules at height z for an isothermal
atmosphere.
height, but the reality is dierent. 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.