Ideal Gases Partition Functions Mastery of Fundamentals Questions

CH353 – Prof. Wu
Here are some questions to test your mastery of the fundamentals of ideal gases and
partition functions used in statistical mechanics. Once you’ve mastered the material, you
should be able to answer these questions without reference to your notes or textbook.

For Ideal Gases and Partition Functions:

1. Write down the equation for the partition function of an ideal gas, Q, in terms of
the molecular partition function, q. Explain why this equation has the form it
does.

Q=qN/N!, reflecting the fact that the molecules are independent, indistinguishable,
and the temperature is high enough (density low enough) to have Boltzmann
statistics.

1. Which quantum systems are used to model each degree of freedom in the
molecular partition function?

Translation: Particle-in-a-box
Rotation: Rigid Rotator
Vibration: Harmonic Oscillator
Electronic: Schroedinger’s equation for the molecule.

1. Which molecular parameters enter into the translational partition function? Into
the rotational partition function? Vibrational? Electronic?

Translation: a= box dimensions, and m = mass of molecule

Rotation: I = moment of inertia (depends on atomic masses, and bond lengths &
geometry)
Vibration: ν =frequency (depends on spring constant and reduced mass)
Electronic: energy levels given by solution to Schroedinger’s equation

1. Explain why only the translational partition function depends on volume.

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It is the only degree of freedom whose number of states is affected by the box
volume.

1. Explain qualitatively why the sum in q can be approximated by an integral for the
translational and rotational partition functions. Under which situations would this
approximation fail to be accurate?

At typical temperatures, translational and rotational energy levels are very closely
spaced, and the sum over states in the partition function can be approximated by a
continuous integral. This would fail if the energy levels get more widely spaced: very
low moment of inertia (for rotation), or very small box/low mass (for translation).
 Ideal Gases Partition Functions Mastery of Fundamentals Questions
CH353 – Prof. Wu
1. At room temperature, which degrees of freedom (translational, rotational,
vibrational and electronic) in a typical molecule will be found in an excited state?

Translational and rotational. At room temperature, a typical molecule will be in the

ground vibrational and electronic states.

1. How high does the temperature have to be before the electronic degrees of
freedom contribute significantly to the heat capacity? How about for the other
degrees of freedom (translation, rotation, vibration)?

The criteria is that the thermal energy kBT is on the order of the spacing between
energy levels. For electronic excitations, that is quite high, on the order of thousands
of degrees Kelvin; for vibrations in the hundreds to low thousands, rotations in the
tens, and translation it depends on the box size, but for typical macroscopic boxes, we
can’t see the energy gaps between translational energy states.

1. What is a vibrational temperature? A rotational temperature?

A vibrational temperature, θ vib , is that temperature at which the thermal energy is on

the order of the spacing between vibrational energy levels: kBθ vib = hν . Similarly for
h
rotation, kBθ rot = 2 .
8π I
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2. Explain why the heat capacity for an ideal gas can be decomposed into a sum of
individual contributions from translation, rotation, vibration and electronic.
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This is because the energy from each contribution is independent.

3. Explain qualitatively why the heat capacity for a monatomic ideal gas is a
constant with respect to temperature (neglecting electronic degrees of freedom),
but not for a diatomic ideal gas.

The variation of the heat capacity with temperature is due to the molecule being able
to change its internal energy with respect to temperature. For an atom, its only degree
of freedom is translation, and the energy can increase proportionally to temperature.
For polyatomic or diatomic molecules, energy can also be absorbed into rotation or
vibration, to a degree that depends on the ratio of the thermal energy to the spacing
between levels (i.e. of the temperature to the vibrational or rotational temperature).

4. Why is the vibrational partition function a product of partition functions for each
vibrational mode? How many vibrational modes are there for a molecule of N
atoms?

This is because each vibrational mode is independent. There are 3N-6 vibrational
modes for a nonlinear molecule, and 3N-5 for a linear molecule.
 Ideal Gases Partition Functions Mastery of Fundamentals Questions
CH353 – Prof. Wu

In addition, you should feel comfortable doing problems like those that have been
assigned in homework. Here are some additional problems you should feel comfortable
doing once you’ve mastered the material.

1. For a system with a finite number of states, why does the heat capacity approach
zero as the temperature goes to infinity? Why does the heat capacity approach
zero as the temperature goes to zero?

At low T, there is not enough thermal energy to populate any excited states, and so
<E> doesn’t change significantly with T: thus the heat capacity is nearly zero. At
very high T, all states are equally populated, and thus increasing T doesn’t change the
distribution in probabilities of the states either: again heat capacity is nearly zero.

2. Given a vibrational temperature or frequency, calculate the population of the

different vibrational states.

pv = e−E v / kB T /Q = e−hν / kB T /Q

3. Given a molecule, determine its symmetry number, and identify how it affects the
rotational partition function.
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The symmetry number, σ , is the number of ways a molecule can be positioned by
rigid body rotation that has the same types of atoms in the same positions. The
rotational partition function is reduced by a factor of σ
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4. Given a molecule, write down its partition function in terms of molecular
parameters such as mass, moment of inertia, vibrational frequencies, etc.
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These are listed in your textbook for different cases (e.g. diatomic, polyatomic), but
as an example for the diatomic case, we have:

q(V,T) = qtransqrot qvibqelec

 2πMkB T  3 / 2 T e−Θ vib / 2T
= 2  V⋅ ⋅ −Θ vib /T
⋅ ge1e De / kB T
 h  σΘ rot 1− e