The Boltzmann Distribution: Association
The Boltzmann Distribution: Association
Association
The intensity of transition from one quantum state to another resulting
from the interaction of electromagnetic radiation with a molecule is
not only dependent:
The ratio of molecules at the jth level to the others at different levels
shows an exponential variation
nj exp ε j / kT
N exp - εi / kT 1.
i
N ni
i
Boltzmann.03 1
where N is the total number of molecules populated all the possible
levels, nj is the number of molecules on the jth level, k is the
Boltzmann constant, and T is the temperature in Kelvin.
n2 exp ε 2 / kT
2.
n1 n2 exp ε1 / kT exp ε2 / kT
Boltzmann.03 2
n2
exp 2 1 / kT exp ε / kT 3.
n1
ni εi ε j
exp
nj kT
The dynamic modes into which the internal energy can be distributed
are:
translation-, rotation-, vibration- and electron-energy.
ni εi ε j
ln
nj kT
We shall now work out population ratios for different kinds of energy
mode at room temperature, 25 oC (298.15 K). We calculate population
distributions for one mole. The denominator of exponent takes the
value
Boltzmann.03 3
Electronic level population
For an electronic level difference Δε is quite high. If we take a
hydrogen atom in gas phase Δε = 1000 kJmol-1. The population of the
2s excited state n2s relative to ground state, n1s is
n2 s 1000 403
exp e 0, so the number 2s H-atoms
n1s 2. 48
n2 s n1s 0
n v 1 25 10 5
exp e 5 10
nv 0 2.48
nv 1 20000 5 10 5 1
It means that one out of every 20000 molecules is found at the first
vibration excited state in a time average.
nJ 1 0.05 0.02
3 exp 3 e 2.94
nJ 0 2.48
Boltzmann.03 4
The factor of 3 in the equation above requires some explanation. It
arises because the first excited level J=1 is actually threefold
degenerate (i.e. there are 3 levels all with the same energy). This
degeneracy factor must be taken into account when assessing the
probability of finding a molecule in a given level.
Rotation
The energy difference is given in wavenumber, ~ in cm-1.
c
h h h c ~ 4.
n upper hc~
n upper hc~
n lower
9 exp 7.8 and at T2 n lower
exp 8.7
kT1 kT2
Vibration
n upper hc~
n upper hc~
n lower
exp 0.008 and at T2 n lower
exp 0.323
kT1 kT2
Boltzmann.03 5
A 40-fold increment in population inversion is caused by the increase
in temperature.
Electronic
n upper hc~
exp 1.24 10 84 and at T2
n lower kT1
n upper hc~
exp 2.34 10 20
n lower kT2
Let our system quantised with energy levels εi where i index is used to
label the levels. The nature of the levels is irrelevant. The lowest level
will be labelled with the index i =0, so that
ε0 ε1 ε2 ...εi
U n0 ε0 n1ε1 n2 ε2 ... ni εi
i
5.
Boltzmann.03 6
system. In thermodynamics, we use the expression microstate to refer
to such a state.
For simplicity, we will assume that the allowed energy levels are
between ε0… ε7, increased by increment one. E.g. ε0 contains zero
energy unit, while ε5 contains five units. Altogether, we have 8 boxes
of different energies the atoms can take up.
Table 1.
Number of boxes Number of atoms in a Number of energy
box units
Boltzmann.03 7
n0 5 0ε*5=0
n1 0
n2 0
n3 1 3ε*1=3
n4 1 4ε*1=4
n5 0
n6 0
n7 0
Σ 7 7
N!
W 7.
n0 ! n1! n 2 !...
Boltzmann.03 8
1 6 1 7
2 5 1 1 42
3 5 1 1 42
4 5 1 1 42
5 4 2 1 105
6 4 1 1 1 210
7 4 1 2 105
8 4 2 1 105
9 3 3 1 140
10 3 2 1 1 420
11 3 1 3 140
12 2 4 1 105
13 2 3 2 210
14 1 5 1 42
15 7 1
Σ 1716
n0 = 6
n1 = 0
n2 = 0
n3 = 0
n4 = 0
n5 = 0
n6 = 0
n7 = 1
N=7
7! 5040
W 7
6!0!0!0!0!0!0!1! 720
7! 5040
W 420
1!1!2!3! 12
Boltzmann.03 9
Boltzmann suggested that if one can observe such an assembly over a
long period of time, each microstate will occur with equal probability
and one will find that the number of occurrences for any particular set
of distribution is proportional to the number of microstates that
correspond to that set.
For example, in the above system, there are a total of 1716 ways or
microstates. (The sum of column W). The probability of case 1
occurring, for example, is 7 in 1716. The probability of case 2
happening is 42 in 1716. The probability that case 10 is 420 in 1716
(the highest of all).
Additional reading
Boltzmann.03 10
use Newtonian mechanics, the state of the system is characterized by
the positions and velocities of all the particles in the system. In
thermodynamics, we use the expression microstate to refer to such a
state. The prefix micro stresses the fact that we know the positions and
velocities of all the microscopic components of the system. By
contrast, we use the expression macrostate when we only specify the
values of the macroscopic parameters of the system. Of course, this
does not characterize the system completely. There may be many
possible microstates that are consistent with a given macrostate. The
number of microstates in a macrostate is called the multiplicity of the
microstate. The following analogy will clarify these concepts.
Suppose we have a set of four colored balls: red (R), blue (B), yellow
(Y) and green (G). Suppose also that we have two boxes: box 1 and
box 2, where we place the balls. A microstate of the system is defined
by specifying exactly which ball goes to which box. For a macrostate,
we only provide partial information. For example, a macrostate could
be specified by determining how many balls are in each box, without
regard of its color. Let us construct a table with the possible
combinations.
Boltzmann.03 11
Notice that the multiplicity is highest (6) for the macrostate that
specifies an equal amount of balls in the two boxes. This trend is very
strongly reinforced if the number of particles in the system is high.
Suppose for example we have 20 equal balls. There is only one
microstate with 20 balls in box 1 and no balls in box 2. Hence the
macrostate (20,0) has amultiplicity of 1. On the other hand, the
multiplicity of the macrostate (10,10) is the number of possible ways
you can put 10 balls in box 1 and 10 balls in box 2. This number is
given by
20!
184.756
10!10!
Boltzmann.03 12