KMM 315E

Physical Chemistry For Chemical Engineers

Week X
Boltzmann Distribution and Partition Functions
Microstates and Configurations
There are five possible outcomes for the trial:
from no heads to all heads.
Which of these trial outcomes is most likely?
The most likely configurational outcome for a trial is the
configuration with the greatest number of associated
permutations.
Configuration: a general arrangement of total energy available
to the system
Microstate: a specific arrangement of energy that describes the
energy contained by each individual oscillator.
This definition of a configuration is equivalent to the definition of
configuration from Probability and microstates are equivalent to
permutations.

The application of probability theory to chemical systems is achieved by considering

system energy.
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Configurations and weights
The weight of a configuration is the number of ways that molecules can be distributed over the
available states.
The weight of a
configuration

The most probable distribution, that of the

greatest weight, is the Boltzmann distribution.
The Boltzmann Distribution

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The Boltzmann distribution
(to look for a dominating configuration)

Two requirements

Configuration must satisfy:

The thermodynamic
temperature (T) is the unique
parameter that governs the most
probable populations of states of
a system at thermal equilibrium
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The molecular partition function
• The molecular partition function indicates the
number of thermally accessible states of a Population of state
collection of molecules at a temperature T.
• The translational partition function is calculated
by noting that translational states form a near Molecular Partition
Function
continuum. When the energy is a sum of
contributions from independent modes of
motion, the partition function is a product of Molecular Partition
partition functions for each mode of motion. Function with
degeneracies
Example: Harmonic oscillator
Evaluate the partition function for a molecule with an infinite number of equally
spaced nondegenerate energy levels. These levels can be thought of as
the vibrational energy levels of a diatomic molecule in the harmonic approximation.

q rises from 1 to infinity as the temperature is raised.

pi VARIES WITH TEMPERATURE
For uniform ladder of states of spacing ε,

The populations of the

the fraction of molecules in the state with energy levels of the system
energy εi is shown in Fig. at different
temperatures
Calculate the partition of I2 molecules in their ground state 1st
2nd excited vibrational states at 25°C. ν is 214.6 cm-1.

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Partition Function for Translation in 1D
The partition function for a particle of mass m free to move in a one-dimensional container
of length X can be evaluated by making use of the fact that the separation of
energy levels is very small and that large numbers of states are accessible at normal
temperatures.

For a given mass and length of the box, the partition function also increases with increasing
temperature, because more states become accessible.
To calculate the translational partition function of an H2 molecule
confined to a 100 cm3 vessel at 25°C we use m = 2.016mu

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Partition Function for Translation in 3D
If the energy is a sum of contributions from independent modes of
motion, then the partition function is a product of partition functions
for each mode of motion in three dimensions.

 : the thermal wavelength has the dimensions of length

The Internal Energy

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The internal energy
• The internal energy is proportional to the derivative of the partition function with respect to
temperature.
• The parameter β = 1/kT.
The relationship between the molecular partition function to the thermodynamic internal
energy of a system of independent molecules:

OR
The Statistical Entropy
• The Boltzmann formula but may be expressed in terms of the molecular partition function.

https://www.youtube.com/watch?v=Tr_gv5CKB1Y
Calculate the entropy of a collection of N independent harmonic
oscillators, and evaluate it using vibrational data for I2 vapour at 25°C

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What is the temperature of a 2 level system of energy separation equivalent to 300
cm-1. When the population of upper state is one half that of that lower state.

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