1

Boltzmann Distribution Equipartition of Energy

At a given temperature, the energy of a collection of molecule is distribution among the various modes of motion (that is, translational, rotational, vibrational, electronic, ). All distributions are equally likely; however, the particles in the distributions are indistinguishable. Therefore, some distributions are more probable than others. This principle is known as the equipartition of energy. Illustration 1: Consider the following illustration putting two balls into three different boxes. If each ball is equally likely to be in any box, what is the most likely arrangement if we examine the box after shaking it? a) Two balls in one box. b) Two balls in separate boxes. Each ball is equally likely to be in any box so lets look at all the possibilities.

By looking at all the possibilities, we see that finding the two balls in separate boxes is twice as likely finding two ball in one box. Illustration 2: Consider the following illustration putting three balls into three different boxes. If each ball is equally likely to be in any box, what is the most likely arrangement if we examine the box after shaking it? a) Three balls in one box. b) Two balls in one box and one ball is a separate box. c) Three balls in separate boxes.

2 Three balls in one box. Two balls in one box and one ball is a separate box. Three balls in separate boxes. Probability 3/27 = 11% 18/27 = 67% 6/27 = 22%

Boltzmann Distribution
As the numbers get larger, that is 1023 , the most probable distribution for a given amount of macroscopic energy among microscopic energy states is given by the Boltzmann distribution. ni e = N
j Ei kT Ej kT

ni number of molecules in the ith energy state. N total number of molecules. Ei energy of the ith energy state. k Boltzmanns constant: 1.38 10-23 J/K Note: R = kNA

Let us examine how the energy of 106 HCl molecules is distributed among the different vibrational states at T = 298 K.
1 1 % E = hc e + = ( 6.626 10 34 J s )( 2.997 1010 c m / s )( 2991cm 1 ) + 2 2 1 = ( 5.617 10 20 J ) + 2
kT = (1.381 1023 J / K ) ( 298K ) = 4.118 1021 J

0 1 2 3 4

E 2.802 10-20 J 8.425 10-20 J 1.404 10-19 J 1.966 10-19 J 2.528 10-19 J

E/kT 6.82 20.46 34.10 47.74 61.38

exp(-E/kT) 1.09 10-3 1.31 10-9 1.55 10-15 1.85 10-21 2.20 10-27

n0 n0 e 6.82 1.09 103 = 6 = 6.82 = = 1 n 0 = 106 1 = 106 20.46 34.10 47.74 61.38 3 N 10 e +e +e +e +e 1.09 10 n1 n1 e 20.46 1.3110 9 = 6 = 6.82 20.46 34.10 47.74 61.38 = = 1.21 106 3 N 10 e + e + e +e +e 1.09 10 6 6 n1 = 10 1.2110 = 1 The vibrational energy is large compared to the thermal energy; therefore, approximately 999,999 molecules out of a million are in the ground vibrational state at 298 K and 1 molecule is in the first excited state.

3 Let us consider what happens to the energy distribution at a higher temperature such as 2000 K?
kT = (1.38110 23 J / K ) ( 2000K ) = 2.762 1020 J

E kT

n = 106

E kT E kT

0 1 2 3 4 5 6

1.02 3.04 5.08 7.11 9.15 11.17 13.21

868998 113843 14911 1950 260 34 4

Role of Degeneracy in the Boltzmann Distribution

The Boltzmann distribution includes all degenerate states as equally probable as well. Therefore the more precise formulation of the Boltzmann distribution is ni g e kT = i Ej N g je kT
j Ei

gi degeneracy of the ith energy state.

Degeneracy is important when partitioning the rotational energy of sample of molecules. Remember that each rotational state J can have an M value that ranges from J, , -J. Thus each rotational state J has 2J +1 M values; thus the degeneracy for rotational energy levels is 2J +1.

4 Example: What is the distribution of rotational energy in a sample of HCl at 298 K? The rotational constant of HCl is 10.44 cm-1
E J = hcBJ ( J + 1) = ( 6.626 1034 J s )( 2.997 1010 c m / s )(10.44cm 1 ) J ( J + 1) = ( 2.073 10 22 J ) J( J+ 1)

Recall that

J 0 1 2 3 4 5 6 7 8 9 10 11

g 1 3 5 7 9 11 13 15 17 19 21 23

E 0J 4.146 10-22 J 1.244 10-21 J 2.488 10-21 J 4.146 10-21 J 6.219 10-21 J 8.707 10-21 J 1.161 10-20 J 1.493 10-20 J 1.866 10-20 J 2.283 10-20 J 2.736 10-20 J

(2J + 1) exp(EJ/kT) 1 2.713 3.696 3.826 3.288 2.430 1.569 0.895 0.493 0.205 0.083 0.030

cumulative sum 1 3.713 7.409 11.235 14.523 16.953 18.522 19.417 19.910 20.115 20.198 20.228

% of population 4.94 13.41 18.27 18.91 16.25 12.01 7.76 4.42 2.44 1.01 0.48 0.15

Most of the molecules are in the J = 3 state, with the J = 2 and J = 4 states also well populated.

5 The fact that most of our molecules are not in the rotational ground state accounts for the shape of the rotovibrational spectrum. The intensities of the lines are not the highest for the transitions involving the J = 0 state. Below is the acetylene rotovibrational spectrum. The highest intensities involve the J = 10 states. Therefore we surmise that the J = 10 states are the most populated. (The most populated states will yield the most transitions; therefore, the highest intensities.)

(Taken from L. Willard Richards, J. of Chemical Education, Vol 43, pp. 644-647 (1966))