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Problem Set 4

This document is a problem set for CHM322 by Dr. Arnab Ghosh, dated March 7, 2025, focusing on canonical and grand canonical ensembles in statistical mechanics. It includes various problems related to partition functions, chemical potentials, equilibrium constants, and thermodynamic properties of gases and photons. The problems require calculations and derivations related to statistical mechanics concepts and their applications.

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archi Kumar
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18 views3 pages

Problem Set 4

This document is a problem set for CHM322 by Dr. Arnab Ghosh, dated March 7, 2025, focusing on canonical and grand canonical ensembles in statistical mechanics. It includes various problems related to partition functions, chemical potentials, equilibrium constants, and thermodynamic properties of gases and photons. The problems require calculations and derivations related to statistical mechanics concepts and their applications.

Uploaded by

archi Kumar
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PDF, TXT or read online on Scribd
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Problem Set-4: Canonical and Grand Canonical

Ensembles and Related Applications


CHM322: Dr. Arnab Ghosh

March 7, 2025

1. If the partition function ZN of a gas of N indistinguishable particles is


given by ZN = Z1N /N !, where Z1 is the single particle partition function,
show that the chemical potential is given by µ = −kB T ln ZN1 .
2. The fugacity z is defined as z = eβµ . Using µ = kB T ln(nλ3th ), show that
z = nλ3th for an ideal gas. Comment on the limits z  1 and z  1.
3. Consider the ionization of atomic H, governed by chemical reaction H
p+ + e− . Explain why µH = µp + µe . Use the partition function for H-
βRH
atom Z1 = V eλ3 and µ = −kB T ln ZN1 , show that, one can recover Saha
th
equation
ne np (2πme kB T )3/2 −βRH
= e
nH h3
where, nx = Nx /V is the number density of species x.
4. Show that the equilibrium constant Kc for the gas-phase dissociation of
a diatomic molecule A2 2A, at temperature T much higher than the
molecule’s θrot = h2 /8π 2 IkB but much lower than its θvib = hν/kB and
too low for significant electronic excitation of either the molecule or ion,
is p
g2 mkB T /π −D/kB T
Kc = A e
gA2 2hR2
where D is the energy of dissociation of the molecule from its ground
vibrational state, m is the mass of the atom, R is the equilibrium inter-
nuclear distance, gA and gA2 are the degeneracies of the ground electronic
states of the atom and the molecule.

5. Calculate the equilibrium constant Kp for the dissociation of I2 2I at


800K. The ground state of the iodine atom is 2 P3/2 , hence 4-fold degener-
ate, while that of the molecule is 1Σ+
g , hence non-degenerate. The excited
electronic states of I and I2 may be neglected at 800K. For the molecule,

1
θrot = 0.054K, θvib = 308K, and the dissociation energy from the ground
vibrational state is D = 1.5417eV.
6. Calculate the molar entropy of CH4 at 25◦ C and 1 atm, as an ideal gas
and compare with the experimentally determined ∆Sexpt ≈ 44.5 cal/(mol
K). [ θrot = 7.54K and θvib = 1870K for CH4 and symmetry number is
σ = 12]
7. The equilibrium internuclear distance of N2 is 1.094Å and the vibrational
frequency of N2 is 7.07 × 1013 s−1 . The ground electronic state of N2 is
non-degenerate. Calculate the molar entropy of N2 as a hypothetical ideal
gas at 1 atm and 25◦ C. [Expt. 191.5 J/(mol K)].
8. ∗ A solution of NaCl dissolved in water, which is 0.9% by weight NaCl,
is isotonic with blood. Show that the osmotic pressure of blood is nearly
eight times atmospheric pressure.
P
9. Maximize the entropy S = −kB i Pi ln Pi , where Pi is the probability
P of
the
P i-th level beingPoccupied, subject to the constraints that i P i = 1,
i Pi Ei = U , and i Pi Ni = N , to derive the grand canonical ensemble.

10. Show that the volume of a hypersphere in d-dimension with radius ‘k’ is
given by
π d/2
Vd = Ak d where, A=
Γ(d/2 + 1)
11. Show that in d-dimension, DOS of particles with spin degeneracy g in a
volume V is given by
gV π d/2 d
g(k)dk = Bk d−1 dk, where, B=
Γ(d/2 + 1)(2π)d

12. Consider a general dispersion relation of the form:  = apα , where a and
α are constants. Using the previous question, so that DOS as a function
is energy is given by
Bd/α−1 d
g()d =
αhd ad/α
gV π d/2 d
where B = Γ(d/2+1)(2π)d
.
∗ Hence show that single particle canonical partition function
V
Z1 =
Λdth
where d-dimensional Λth is given by
 1/α  1/d
h a Γ(d/2 + 1)
Λth = √
π kB T Γ(d/α + 1)
Show that above results for 3d matches with standard result for (i) non-
relativistic case when s = 2 (iii) relativistic case with s = 1.

2
13. Show that the number of states in a gas with energies below Emax is
Z Emax 3/2

V
2mEmax
g(k)dk =
0 6π 2 ~2
p
For Emax = 32 kB T , show that this number is 6/π(V /λ3th ), where λth =
√ h is the thermal de-Broglie wavelength.
2πmk TB

14. Ignoring the zero point energy, show that the partition function Z for a
gas of photons in volume V is given by
Z ∞
V
ln Z = − 2 3 ω 2 ln(1 − eβ~ω )dω
π c 0

Hence, by integrating by parts, yields

V π 2 (kB T )3
ln Z =
45~3 c3
and other thermodynamic quantities:

4σV T 4 16σV T 3 4σV T 4 4σT 4


F =− ; S= ; U= ; p=
3c 3c c 3c
and various thermodynamic relations : pV = U/3 and S = 4U/3T . Fi-
nally, show that Cp for photon gas is infinite. What is the significance of
this result?
15. ∗ Show that the total number N of photons in blackbody radiation con-
tained in a volume V is
Z ∞  3
g(ω)dω 2ζ(3) kB T
N= = V
0 e~ω/kB T − 1 π2 ~c

Hence show that the average energy per photon

U π4
= kB T = 2.701kB T
N 30ζ(3)

and the average entropy per photon is

S 2π 4
= kB = 3.602kB
N 45ζ(3)

Compare the results with that for an ideal gas. What is physical signifi-
cance for the difference?

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