CHM 301

SIGNIFICANCE OF THE PARTITION FUNCTION

The partition function is significant owing to the fact that it indicates the number of states which
are accessible at the desired temperature. At absolute zero, only the ground state is accessible
and q = 1; whereas at higher temperatures, almost all the states can be occupied, therefore q
approaches infinity, ∞.
If the energy levels have a constant separation, Є, an expression for evaluating the proportions of
molecules in the state with energy, Єj, is given below:
Pj = {( 1 – exp-βЄ)(exp-βЄj)}

Example
Determine the proportions of chlorine molecules in the ground, first excited, and second excited
vibrational states at 25 °C, if the energy separation is 230.5 cm s-1 ( Boltzmann’s constant is
1.381 x 10-23 J K-1, speed of light is 2.988 x 108 m s-1, Planck’s constant is 6.626 x 10-34 J s).
Solution
KT/hc = (1.381 x 10-23 J K-1 x 298 K) / (6.626 x 10-34J s x 2.988 x 1010 cm s-1)
= 4.1154 x 10-21 /1.9798 x 10-23 = 207.9 cm-1

βЄ = 230.5 cm-1 / 207.9 cm-1 = 1.109

The relative proportions are given by:
Pn = {(1 – exp-βЄ) (exp–nβЄ)}; where n is the energy level
= {(1 – exp-1.109) (exp –1.109n)}
= (1 – 0.33) (e-1.109n)
= 0.67 (exp-1.109n)
At ground state (n = 0), P0 = 0.67 (exp-1.109 x 0) = 0.67 (exp- 0) = 0.67
At first excited state (n = 1), P1 = 0.67 (exp-1.109) = 0.67 x 0.33 = 0.22
At second excited state (n = 2), P2 = 0.67 67 (exp-1.109 x 2) = 0.67 x 0.109 = 0.073
 Entropy of a Monoatomic Gas
Entropy is simply a measure of the distribution of energy. The claim that the partition function
contains all thermodynamic information can be substantiated only if it can be used to discuss the
entropy, the principal concept of the second law of thermodynamics.

The entropy of a monoatomic gas is given by the famous Sackur-Tetrode equation (1):
S = nR.ln{5/2(2πmkT/h2)3/2. V/nL} (1)
Where R is universal gas constant, n is number of moles, L is Avogadro’s number, m is mass of
molecule, T is temperature, V is volume, k is Boltzmann’s constant, h is Planck’s constant.
Since the gas is ideal, V can be replaced by nLK/P; hence equation (1) can be re-written as:
S = nR.ln{e5/2(2πmkT/h2)3/2.(kT/P)} (2)
Where P is pressure, other parameters are as defined in eqn. (1).
Note: (y)3/2 = {(y)½}3
Example
Calculate the translational entropy of hydrogen chloride gas at -10 0C and 1.2 atm (1 atomic mass
unit, amu is 1.66057 x 10-27 kg; universal gas constant is 8.314 J K-1 mol-1).
Solution
m(HCl) = 36.5 x 1.66057 x 10-27 kg = 6.061 x 10-26 kg; T = (- 10 + 273 K) = 263 K
(2πmkT/h2) = 2 x 3.14 x 6.061 x 10-26 x 1.381 x 10-23 x 263
(6.626 x 10-34)2
= 1.382 x 10-45 / 4.39 x 10-67 = 3.148 x 1021
Using eqn. (2), S = 8.314 ln (12.18 x (3.148 x 1021) 3/2 x 91.381 x 10-23 x 263)}
(1.2 x 101325)
= 8.314 ln {12.18 x 1.766 x 1032 x 2. 985 x 10-26}
= 8.314 ln (6.42 x 107) = (8.314 x 17.98) J K-l mol-l
= 149.5 J K-l mol-l

Note: 1 atm = 101325 N m-2