1.

(a) Consider the single particle partition function

Z ∞
V 8πV 1
Q1 (V, T ) = 3 e−βpc d3 p = 3 3 3 .
h −∞ h β c

Identify with Q1 (V, T ) ≡ V /λ3rel we have

λrel = hc/(2π 1/3 kT ).

Also λcl = h/(2πmkT )1/2 . Alternative λrel ≡ hh/pi = hc/(2kT ) is

also valid (different within a factor).
(b) Quantum effects show up when d  λ. Consider relativistic and
classical particles at the same temperature T , then
2
mc2

λrel
∼ .
λcl kB T
For non-relativisitc object m, its rest mass is larger than its ther-
mal energy and hence λrel /λcl  1. Thus the quantum effects show
up first in the relativistic system.

2. (d is the size of each molecule.)

(a) Assume there are N+ links of 0◦ angle and N− of 180◦ . For fix
N and length 2m the configuration of a molecule is completely
determined, with the number N+ and N− determined by N+ +
N− = N and |N+ − N− | = 2m. Then N+ = (N/2) ± m and
N− = (N/2) ∓ m. The number of arrangements is N !/(N+ !N− !).
Thus
2(N !)
g(N, m) = N .
( 2 + m)!( N2 − m)!

Write " #
N N
! !
2 2
g(N, m) = g(N, 0) exp ln N −2m N +2m
2
! 2 !
and use the Stirling’s formula and put ln(1±(2m/N )) ' ±(2m/N )−
(2m/N )2 /2 to second order to get

g(N, m) ' g(N, 0) exp(−2m2 /N ).

1
 (b) Put m with L/(2d) we have

L2
 
S = kB ln g(N, m) = kB (N + 1) ln 2 − .
2N d2

3. Denote two people as A and B. Let the initial number of virus carried
by A be N0 . We hope to find NA (t) and NB (t). We have
dNA
= (NB − NA )Γ = (2N − 2NA )Γ.
dt
Then

NA (t) = N − (N − N0 )e−2Γt , NB (t) = N + (N − N0 )e−2Γt .

Denote n(t) = (N −N0 )e−2Γt . Consider the average entropy as S/2N =

−kB PA ln PA − kB PB ln PB where PA = NA /(2N ). Then

S N +n N +n N −n N −n
= −kB ln − kB ln .
2N 2N 2N 2N 2N

Alternatively one can use S = kB ln NA2N !

!NB !
to arrive at the same result.
The time evolution of the entropy is

dS N −n
= −2nkB Γ ln .
dt N +n
For the case when N0 6= N the entropy can only grow.
4. Small longitudinal motions in this system may be represented as a sum
of N independent standing waves with frequencies,
 
 kd  p
ωk = 2ω0 sin  , ω0 = κ/m,

2
where k are equidistant wave numbers separated by intervals, and l =
N d is the total length of the chain.
Each mode corresponds to a simple harmonic oscillator, with the heat
capacity  2
~ωk /2T
Ck = .
sinh (~ωk /2T )

2
 Heat capacity of the chain is
N  2
X ~ωk /2T
C=
k=1
sinh (~ωk /2T )

In the limit N → ∞, we can replace the sum by an integral (the sum

will become an integral in the first Brillouin zone with ∆k = π/N d)
Z k=π/d  2  2
N π
 Z 
~ωk /2T k ~ωk /2T
C= d = d(kd)
k=0 sinh (hωk /2T ) ∆k π 0 sinh (~ωk /2T )
Heat capacity per particle is
2
1 π
Z 
C ~ωk /2T
= d(kd)
N π 0 sinh (~ωk /2T )
For T   ~ω0 , the integrand is dominated by the frequencies at ωk =
kd 
2ω0 2 , we have

Z ∞ 2 Z ∞ 2
C 1 ~ωk /2T 2T ξ dξ
= dωk ≡
N πω0 0 sinh (~ωk /2T ) π~ω0 0 sinh2 ξ

C 2T π 2 π T
= = .
N π~ω0 6 3 ~ω0
For T  ~ω0 , Ck = 1, so we have
C
= 1,
N
consistent with the equipartition theorem.

5. (a) To draw a plot, consider dimensionless variables V ← V /2b and

T ← T /(a/(4bN )) and P ← P/(ae−2 /(4b2 )) inspired by the next
problem such that the critical points are at V = T = P = 1. (Note
that we should have V > 0.5 since the volume is of course larger
than those occupied by one mole of the molecules.) We have the
nondimensionalized equation
 
2 T −2
P =e exp .
2V − 1 TV

3
 2.00
1.80 T = 0.9
T = 1.0
1.60 T = 1.1
1.40
1.20
P 1.00
0.80
0.60
0.40
0.20
0 1 2 3 4 5 6 7 8 9 10
V

(b) At the critical point we have ∂P/∂V = 0 and ∂ 2 P/∂V 2 (inflection)

equal to zero. The anwsers are

Vc = 2b, Tc = a/(4bN ), Pc = (a/(4b2 )) exp(−2).

6. (a) For gas particles in the volume, the single particle partition func-
tion is
Q1g (V, T ) = (V /h3 )(2πmkB T )3/2 ≡ V f (T ).
For absorbed particles, let A = L2s . Then
Z
A 2 A
Q1s (A, T ) = 2 e−β(p /2m−0 ) d2 p = 2 eβ0 (2πmkB T ) ≡ Ag(T ).
h h
Model the gas particles in the volume and absorbed gas particles
separately using the grand canonical ensemble, we have
X (V f (T ))Ng
Qg (zg , V, T ) = zgNg = ezg V f (T ) .
Ng
Ng !

where zg = eβµg is the fugacity and µg the chemical potential.

Similarly
Qs (zs , A, T ) = ezs Ag(T ) .
Use the ideal gas law P V = Ng kB T for the gas particles in the
volume and the fact that the the mean gas particles Ng is related

4
 to chemical potential through Ng = zg ∂ ln Qs /∂zs = zg V f (T ) we
have
Qg = eP V /kB T .
Similarly we have Ns = zs Ag(T ) and N = Ns + Ng . Then

Qs = eN −P V /kB T .

(b) In equilibrium, we have zg = zs . The mean number of gas particles

absorbed is
∂
Ns (zs , A, T ) = zs ln Qs = zs Ag(T ).
∂zs
Similarly the mean number of gas particles in the volume is Ng =
zg V f (T ). For ideal gas we have P V = Ng kB T. Then

Ns P
zs = = = zg .
Ag(T ) kB T f (T )

Ns P g(T ) P h
= = 1/2
e0 /kB T .
A kB T f (T ) kB T (2πmkB T )