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Thermodynamics Problem Set 1: Ideal Gas Law

This document is a problem set for a Thermodynamics course at the University of Virginia, focusing on various topics such as the ideal gas law, electronic partition functions, and quantum mechanics. It includes five questions that require derivations and calculations related to partition functions and energy expressions. The assignment is due on February 7, 2024.

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10 views2 pages

Thermodynamics Problem Set 1: Ideal Gas Law

This document is a problem set for a Thermodynamics course at the University of Virginia, focusing on various topics such as the ideal gas law, electronic partition functions, and quantum mechanics. It includes five questions that require derivations and calculations related to partition functions and energy expressions. The assignment is due on February 7, 2024.

Uploaded by

tilewabalogun
Copyright
© All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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REKIAT BALDGUN (ROBGAP)

CHEM 3420 — Thermodynamics Problem Set 1 — Due Wednesday, Feb. 7


University of Virginia: Spring, 2024 Dr. Herbst

1 Recovery of the Ideal Gas Law


Question 1. Show that if the partition function is of the form:

[q(V, T )]N
Q(N, V, T ) = (1.1)
N!
where

T2
q(V, T ) = V (1.2)
⇠
the system will obey the ideal gas law

N kB T
hP i = (1.3)
V
Note. ⇠ in 1.2 is an arbitrary constant independent of volume and temperature.

2 Electronic Partition Functions


Question 2. Consider the atomic species Cl, which undergoes electronic motion. The electronic
ground state of Cl(g) is four-fold degenerate. The first excited electronic state is 875.4 cm 1 higher
in energy and is two-fold degenerate. Determine the value of the electronic partition functions qel at
temperatures 298 K and 1000 K.

3 A Gas on a Surface
Question 3. Consider a “gas” on a surface, which can only undergo translational motion in two
dimensions over an area A = a2 . Determine formulae for q and Q then determine the average
molecular energy h"i and the average macroscopic energy hEi.

4 The Quantum Mechanical Harmonic Oscillator


Question 4. The allowed energies of a harmonic oscillator with zero-point energy can be given by
the formula
✓ ◆
1
"= v+ h⌫ (4.1)
2
Now let x = exp( h⌫/kT ). Show that

x1/2
qvib (T ) = (4.2)
1 x
is true.

5 A Gas of Hard Spheres


Question 5. An approximate partition function for a gas of hard spheres can be obtained from the
partition function of a monatomic gas by replacing V by V-b, where b is related to the volume of the
N hard spheres. Derive expressions for the energy and pressure of this system.
✓ ◆3N/2
(V b)N 2⇡mkT
Hint: Q = ⇥ qtrans (T ) where qtrans (T ) =
N! h2

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