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The document outlines an assignment for CHM650, focusing on statistical mechanics and various problems related to enumerating states, noninteracting spins, equilibrium constants, and gases of electrons. It includes specific tasks such as calculating partition functions, average energy, and chemical potentials for different systems. The assignment is due on March 25, 2025, and consists of multiple parts, each requiring a detailed understanding of statistical mechanics principles.

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Assign 3

The document outlines an assignment for CHM650, focusing on statistical mechanics and various problems related to enumerating states, noninteracting spins, equilibrium constants, and gases of electrons. It includes specific tasks such as calculating partition functions, average energy, and chemical potentials for different systems. The assignment is due on March 25, 2025, and consists of multiple parts, each requiring a detailed understanding of statistical mechanics principles.

Uploaded by

palistake1
Copyright
© © All Rights Reserved
Available Formats
Download as PDF, TXT or read online on Scribd
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CHM650: Assignment 3

Due Date: March 25, 2025

1. Ennumerating states (4 points): The real challenge of statistical mechanics is


to ennumerate states and identify their relative probabilities. This requires a careful
understanding of the system under consideration. For example, let us consider a
simple two phase system Al  Ag where Al and Ag are liquid and gas phases of some
material which have established equilibrium. Now, imagine that this system is in a
box of volume V and the total number of A particles is N and temperature is T . Let
us try to ennumerate the states of the system in some special cases.
(a) Consider that the particles are classical point particles i.e. each has a momentum
and a position. In this case the N -particle phase space is the space of all states.
What is a reasonable way to ennumerate all the states in this system ? What
about the probability of a state ? Note that the interaction potential of the
system is the SAME whether it is liquid or gas since the particles are the same
(b) Now we will look at the same problem from a slightly different point of view.
Let us consider the box to be cubic with side L. Thus L3 = V . Now, imagine
that this box is divided into a lattice of cubic boxes of sides a, such that a << L.
Each box is either occupied by exactly 1 particle or not occupied. This is the
famous lattice gas model. Now, let us completely neglect the momentum degrees
of freedom. List all the possible states of this system. Again, the lattice can
represent either a liquid or a gas (or even a solid, if you wish).
(c) Now, we wish to calculate the probability of such a state. In order to write the
probability of a state, we require the energy of a state. We will consider some
models of increasing complexity. First, assume that particles at two different
sites do not interact with each other. In terms of your earlier understanding of
interparticle potentials, does this correspond to an ideal gas or a hard sphere
gas ? Explain. Finally, assume that having a particle in a box lowers the
energy by . Based on just this information, postulate a reasonable expression
for the probability of a state and calculate the canonical partition function and
the average energy and heat capacity. Calculate the chemical potential of the
system.
(d) Now consider that there is some interaction energy in this system where the
energy of two neighboring sites which are occupied is additionally lowered by δ.
This is closely related to the classic Izing model in statistical mechanics. Write
the expression for the partition function involving sums over all states. It is not
possible to evaluate this expression for a 3D system analytically.
2. Noninteracting spins in an external field(2 points): Consider a system of
noninteracting spins, such that each spin can take a value of 1/2 or -1/2. The system
is in an external field H so that the energy of a spin is equal to −sµH/2 where s is

1
the spin value which can be +1/2 or -1/2. Calculate the partition function of this
system, the average energy. Calculate the average spin hsi. Calculate the entropy of
the system. How does this behave in the limit of T → 0 ? Does this violate third law
of thermodynamics. Discuss briefly.

3. Equilibrium Constant (2 points): Calculate the equilibrium constant at 1 atm


pressure and 8000 K of the reaction

N2 ↔ 2N.

Given, for N2 : Atomic Mass = 14 amu, θv = 3400K, θr = 2.895K, Bond dissociation


energy De = 940 kJ/mol. Assume that only the ground electronic states contribute
to the partition functions.

4. Gas of electrons (2 points): Calculate the pressure exerted by a gas of electrons


at µ, V, T . This will give the pressure of the gas as a sum of logarithms. The sum is
over all states; which can be characterized by the momentum p~ which satisfies

p2
p =
2m
so that the sum over all states can be replaced by the integral over scalar momentum
α
X Z∞
→ dp4πp2
i=1 0

Express the average energy and the average number of particles in terms of integrals
above. You will not be able to evaluate the integrals but these are related to a
function called the Fermi function which you can look up in standard books (not
required here). How is the average energy related to the pressure of an ideal Fermi
gas ?

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