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PHY 418: Statistical Mechanics I
Prof. S. Teitel stte@pas.rochester.edu  Spring 2013
Problem Set 5
Due Wednesday, April 3, in lecture
 Problem 1 [15 points total]
Consider a system of particles in the grand canonical ensemble, with μ the chemical potential and z=exp(βμ) the fugacity. If < N> is the average number of particles, and <E> is the average total energy,
a) show that,
1 T 
(
 ∂<E> ∂μ 
)_{T,V} 
= 
1 k_{B}T^{2} 
[ 
<EN>  <E><N> 
] 
b) show that,
(
 ∂<N> ∂T 
)_{z,V} 
= 
1 T 
(
 ∂<E> ∂μ 
)_{T,V} 
Note, on the left hand side the derivative is taken at constant fugacity z, rather than constant chemical potential μ.
 Problem 2 [15 points total]
Consider a classical gas of N noninteracting, indistingushable, particles in the grand canonical ensemble with fugacity z=exp(βμ). The particles may have internal degrees of freedom such as vibrational or rotational modes.
a) Show that the probability p(N) that there are exactly N particles in the system follows a Poisson distribution,
where λ = <N> is the average number of particles. [8 points]
b) Find expressions for <N> and <N^{2}> in terms of the fugacity z and the single particle partition function Q_{1}. [7 points]
 Problem 2 [35 points total]
Consider a classical gas of very weakly interacting molecules of different species.
There are N_{i} molecules of species number i, i = 1, 2, ..., m.
The molecules of different species may have different masses and different internal degrees of freedom (such as vibrational or rotational modes), however you may assume that the molecules do not interact with each other.
The molecules of a given species are indistiguishable from each other.
(a) Show that the canonical partition function for the gas has the form
Q = Q^{(1)}Q^{(2)}....Q^{(m)}
where
Q^{(i)} = [Q_{1}^{(i)}]^{Ni}/N_{i}!
and Q_{1}^{(i)} is the single particle partition function
for molecules of species i. [5 points]
(b) Using the result in (a), show that the total pressure of the gas is the sum of the pressures that each of the species of molecule would have on its own (total pressure is the sum of the "partial pressures").
Similarly show that the total entropy of the gas is the sum of the entropies that each species would have on its own. [5 points]
(c) By taking the appropriate derivative of the total Helmholtz free energy of the gas, compute the chemical potential µ_{i} of species i.
Express your answer in terms of Q_{1}^{(i)}. [5 points]
(d) Assume that the molecules are free (i.e. not in any external potential, except for their confinement to a box of volume V).
Show that Q_{1}^{(i)} can be written as Q_{1}^{(i)} = Vq_{1}^{(i)}(T) where q_{1}^{(i)} depends only on temperature T. [5 points]
(e) Suppose that the species of molecules undergo the chemical reaction
a_{1}A_{1} + ... +
a_{j}A_{j} ↔ a_{j+1}A_{j+1} + ... +
a_{m}A_{m}
where a_{i} is the number of molecules of species A_{i} (i = 1,...,j) that combine to create a_{k} molecules of species A_{k} (k = j+1,...,m).
As discussed in lecture, the equilibrium number of molecules of each species will be determined by the condition
a_{1}µ_{1} + ... + a_{j}µ_{j}
= a_{j+1}µ_{j+1} + ... + a_{m}µ_{m}
(make sure you understand where this result comes from!).
Use the above, and the results of the previous parts, to show that the equilibrium concentrations of the species are given by
([n_{1}]^{a1} [n_{2}]^{a2}...[n_{j}]^{aj })/([n_{j+1}]^{aj+1}...[n_{m}]^{am}) = K(T)
where n_{i} is the concentration of species i, n_{i} = N_{i}/V, and K(T) is a function of temperature only.
Derive an expression for K(T) in terms of the q_{1}^{(i)}(T).
The above result is known as the "law of mass action". [5 points]
(f) Consider the reaction
A + B ↔ C
Suppose that an energy E_{o} is released when A and B combine to form C, i.e. E_{o} is the binding energy of the molecule C when compared to its separated constituents A and B.
Assume that A, B, and C are free point particles (i.e. no internal degrees of freedom are excited).
By explicitly evaluating the single particle partition function of the three species, determine the function K(T).
Remember, you must properly include the binding energy E_{o} of molecule C when you compute its partition function. [5 points]
(g) Suppose that initially there are equal concentrations of A and B, n_{A} = n_{B} = n_{o}, while the concentration of C is initially n_{C} = 0.
Find the resulting equilibrium concentrations of A, B and C, in terms of n_{o} and the function K(T). [5 points]

