1.

Ideal gas of two-state atoms

Set temperature units to make k = 1.

a) The fraction of atoms in excited state after thermalization:

1
p= (1)
e/T2 +1

Energy conservation:
3 3
T1 = T2 + /T2 (2)
2 2 e +1
Expanding to order :

T2 T1 = <0 (3)
3

Temperature decreases.

b) The entropy of the two-state system:

2
 
/T
N T ln 1 + e/T = N ln 1 + e/T + N /T




S = = N ln 2 + O (4)
T e +1 T2

Alternatively, using p from (1):

2
 
S /N = p ln p (1 p) ln(1 p) = ln 2 + O , (5)
T2

The total entropy of the gas

2
 
3
S = Skin + S = N ln T + N ln 2 + O (6)
2 T2

The change in the entropy to order /T :

       
3 3 3
S2 S1 = N ln T2 + ln 2 ln T1 =N ln 1 + ln 2 = N ln 2 >0
2 2 2 3T1 2T1
(7)

Entropy increases.

1
2. van der Waals

a)
2

1.75

1.5

1.25

0.75

0.5

0.25

0.5 1 1.5 2

b) Set k = 1. From  
p T
= 2an = 0 (8)
n T (1 bn)2
we find
T = 2an(1 bn)2 (9)
and substituting (9) into the equation of state p(n, T ) we find

p = an2 2abn3 . (10)

See Figure.

c) Stability condition: (p/n)T > 0.

d) The critical point is at the maximum of the curve given by (8). Two conditions defining
the critical point: (p/n)T = 0 and ( 2 p/n2 )T = 0. The second condition gives:
 2 
p 2bT
2
= 2a = 0. (11)
n T (1 bn)3

Substituting into (11) the value of T from (9) and solving for n we find:
1
nc = . (12)
3b
Substituting this into (10) and into (9) we find, respectively:

a 8a
pc = ; Tc = (13)
27b2 27b

2
3. Maxwell relations

a) dU = f dL + T dS

b) Using the relation for the free energy: d(U T S) = f dL SdT , we find the Maxwell
relation:    
S f
= (14)
L T T L
Thus
 
f f 1.2 N
Q = T S = T L = T L = 300 K 2 102 m = 2.4 J. (15)
T L T 3K
Heat is released since Q < 0.

4. Cosmic microwave background

a)
3
d3 pV

1 2(3) kT
Z
n=2 = = 4.0 108 m3 ; N = nV = 400. (16)
(2~)3 e|p|/kT 1 2 ~c

b) The density of photons with velocities v inside an element of solid angle dv is

dv
dn = n . (17)
4
The flux of those photons is dJ = dnv. The rate at which the photons with the given
velocity are hitting a small surface element of area is

dJ = vdn (18)

The total rate from the photons with all values of v is (integrate over semisphere, use |v| = c):
dv 2 1 1
Z Z
vn = cn cos d(cos ) = cn (19)
4 4 0 4
Therefore rate per unit area is cn/4. The total rate for the area of the ball is
 3
cn 2 2(3) kT
= 4R 2
= R c 2 = 3.76 1013 s1 (20)
4 ~c

Another derivation: For the photons with velocity v the ball presents a cross section equal
to R2 . The rate at which these photons strike the ball is R2 cdn. Integrating over all v
we find = R2 cn, as before.

3
5. Ultrarelativistic Fermi gas at T = 0

a) F = and pF = F /c = /c.

b)
d3 p 1  3
Z
n=2 = . (21)
|p|<pF (2~)3 3 2 ~c

c)

d3 p 1 4
Z
~c ~c
E = V 2 3
|p|c = V 2 3
= V 2 (3 2 n)4/3 = 2 (3 2 N )4/3 V 1/3 (22)
|p|<pF (2~) 4 (~c) 4 4

where we used Eq. (21) and n = N/V .

d)
4/3
4
  
E ~c 2N 1
P = = 3 = (23)
V N 12 2 V 12 2 (~c)3

e) The condition for the reaction to be energetically allowed is

m A c 2 + > mB c 2 (24)

Thus min = (mB mA )c2 . Therefore, from (23):

1 ((mB mA )c2 )4
Pmin = (25)
12 2 (~c)3