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1. (Debye model.) Use the Debye approximation to find the following thermodynamic functions of a solid as a function of temperature T . Express your answers in terms of the function
Z y 3
x dx
3
D(y) = 3
y 0 ex 1
and the Debye temperature D = h
D /kB = (
hv/kB )(6 2 N/L3 )1/3 .
(a) Show that the partition function of the Debye model is given by
Y
1
.
ZDebye =
1 ehn
n
(1)
In the problem, we drop the contribution of the zero-point energy for the quantum
harmonic oscillator.
(b) Show that the Helmholtz free energy F = kB T log Z is given by
F = 3N KB T log[1 exp(D /T )] N kB T D(D /T ).
(2)
R
P
Q
Hint: use log i Bi = i log Bi and integration by parts x2 log(1ex )dx = x3 /3 log(1
R
ex ) x3 /(ex 1)dx.
(c) Show that the mean energy hEi is given by
hEi = 3N kB T D(D /T ).
(3)
(4)
3. (Plant cell.) The concentration of potassium K+ ions in the internal sap of a plant cell of
a fresh water alga may exceed the concentration of potassium K + ions in the pond water in
which the alga is growing in by a factor 104 . The chemical potential of the K+ ions is higher
in the sap because their concentration n is higher there. Estimate the difference in chemical
potential at 300K and show that it is equivalent to a voltage of 0.24V across the cell wall, i.e.
0.24 eV (electron volt). Assume the system of the ions as an ideal gas.
4. (Grand partition function.)
(a) Consider a system that may be unoccupied with energy zero or occupied by one particle
in either of 2 states, 0 and . Show that the grand partition function (also known as the
Gibbs sum) for this system is
Z = 1 + + exp(),
(5)
where = exp(). We exclude the possibility of one particle in each state at the same
time.
(b) Show that the thermal average occupancy of the system is
hN i =
+ exp()
Z
(6)
(c) Show that the thermal average occupancy of the state at energy is
hN ()i =
exp()
Z
(7)
(d) Find an expression for the thermal average energy of the system.
(e) Allow the possibility that the orbital at 0 and may be occupied each by one particle
at the same time. In this case, show that
Z = 1 + + exp() + 2 exp() = [1 + ][1 + exp()].
Since Z can be factorized as shown, we have in effect, two independent system.
(8)