Solutions of Problems set 1

1. Electromagnetic radiation in an evacuated vessel of volume V at equi-

librium with the walls at temperature T (blackbody radiation) behaves
like a gas of photons having internal energy U = aV T 4 and pressure
P = (1/3)aT 4 , where a is the Stefans constant. (a) Plot the closed curve
in the P V plane for a Carnot cycle using blackbody radiation (b) Derive
explicitly the efficiency of a Carnot engine which uses blackbody radiation
as its working substance.

Solution

a)In general one can have

U U
dQ
= dU + P dV = dT + dV + P dV (1)
T V V T

4
= 4aV T 3 dT + aT 4 dV
dQ (2)
3
Thus, for an isothermal process dQ = 4aT 4 dV /3 and Q = 4aT 4 V /3.
For an adiabatic process,
4
= 4aV T 3 dT + aT 4 dV = 0
dQ (3)
3
so
dT 1 dV
= (4)
T 3 V
integrating the above equation we have T V 1/3 = contant and P V 4/3 =
constant. The Carnot cycle in the P V plane is
P

Th 2
1
11111
00000

4 3
Tc

b) From 1 to 2 in the Carnot cycle, Q12 = 4aTh4 (V2 V1 )/3.

From 2 to 3, for the high volume adiabatic path, Q23 = 0 and V3 =
3
V2 TThc .
From 3 to 4, for the low temperature isothermal path, Q34 = 4aTc4 (V4
V3 )/3.

1
 From 4 to 1, for the low volume adiabatic path, Q41 = 0 and V4 =
3
V1 TThc .
the total work done W = Q12 + Q34 . The efficiency is

W Q34 T 4 (V4 V3 )
= =1+ = 1 + c4 (5)
Q12 Q12 T (V2 V1 )
" h 3 #
3
Tc4 Th Th Tc
=1+ 4 V1 V2 =1 (6)
Th (V2 V1 ) Tc Tc Th

2. For a low density gas the virial expansion can be determined at first order
in the density and the equation of state is

N kB T N
P = 1 + B2 (T )
V V

where B2 (T ) is the second virial coefficient. The heat capacity will have
corrections to its ideal gas value. We can write it in the form

3 N 2 kB
CV,N = N kB F (T )
2 V
(a) Find the form that F (T ) must have in order for the two equations to
be thermodynamically consistent. (b) Find CP,N . (c) Find the entropy
and the internal energy.

Solution

a)In order for the two equations to be self-consistent, we must have

CV,N 2P
=T (7)
V T,N T 2 V,N

Note that
2
CV,N N
= kB F (T ) (8)
V T,N V
2
P N N
= kB + kB [B2 (t) + T B20 (T )] (9)
T V,N V V
and 2
2P N
= kB [2B20 (t) + T B200 (T )] (10)
T 2 V,N V

2
thus, the two equations are thermodynamically consistent if
d(T 2 B20 )
F (T ) = T [2B20 (t) + T B200 (T )] = (11)
dT

b) From the relations,

S S S V
= + (12)
T P,N T V,N V T,N T P,N

and
S P
= (13)
V T,N T V,N

we can write

P V
CP,N = CV,N + T (14)
T V,N T P,N

V
to find T P,N
use the fact that

P P
dP = dT + dV (15)
T V,N V T,N

dP P P dV
= + =0 (16)
dT T V,N V T,N dT
P
V T V,N
= P (17)
T P,N V T,N

2
P N N
= kB + kB [B2 (t) + T B20 (T )] (18)
T V,N V V

P NT N
= kB 1 + 2 B2 (T ) (19)
V T,N V2 V

" N 0
#
V V 1+ V (B2 + T B2 )
= N
(20)
T P,N T 1 + 2 V B2

Now combining all the equations

" #2
3 N 2 d(T 2 B20 ) 1+ N 0
V (B2 + T B2 )
CP,N = N kB kB + N kB (21)
2 V dT 1 + 2N
V B2

3
c)First find the internal energy. Note that

U 3 N 2 d(T 2 B20 )
= CV,N = N kB kB (22)
T V,N 2 V dT
and
2
U P N
=T P = kB T 2 B200 . (23)
V T,N T V,N V
Integrating these equations we obtain
Z
U 3 N2 2 0
dT = N kB T kB T B2 + constant (24)
T V,N 2 V

and Z
U N2 2 0
dV = kB T B2 + constant (25)
V T,N V
The internal energy is

3 N2 2 0
U= N k B T kB T B2 + constant (26)
2 V
The entropy can be find using the relations

S CV,N 3N kB N2
= = kB (2B20 + tB200 ), (27)
T V,N T 2T V

and

S P N N 0
= = kB 1 + (B2 + T B2 ) . (28)
V T,N T V,N V V
Now integrating
Z
S 3 N2
dT = N kB ln(T ) kB (B2 + T B20 ) + constant (29)
T V,N 2 V

and
Z
S N2
dV = kB N ln(V ) kB (B2 + T B20 ) + constant (30)
V T,N V

Therefore the entropy is

N2
S = kB ln(V T 3/2 ) kB (B2 + T B20 ) + constant (31)
V

4
3. Compute the Helmholtz free energy for a van der Waals gas. Assume that
the heat capacity is CV,n = (3/2)nR. Is this a reasonable choice for the
heat capacity? Should it depend on volume?

Solution

It is easiest to work with molar quantities. Let = V /N be the molar

volume, where n is the number o fmoles and V the volume. The equation
of state is then

RT
P = (32)
a 2
Let us note the relation
2
CV,n P
=T . (33)
V T,n T 2 V,n

For the van der Waals gas,

2P
=0 (34)
T 2 V,n

so CV,n can depend only on T and n and not on V . Thus,

3
CV,n = nR (35)
2
is a reasonable choice for CV,n .
The Helmoholtz free energy F = U T S can be written in molar quantities
like f = u ts, where f = F/N and so on. Note that

s s
ds = dT + d (36)
T T
We can write
s 3R
= (37)
T 2T
and
s P R
= = (38)
T T b
Thus Z
s 3
dT = R ln(T ) + r1 (), (39)
T 2
and Z
s
d = R ln( b) + r2 () (40)
T

5
 and the molar entropy is s = 32 R ln(T ) + R ln( b) + constant. In order
to agree with the Sackur-Tetrode equation in the limit when b = 0 we can
write h i
5
s = R + R ln T 3/2 ( b) . (41)
2
Next, we have to find the internal energy

u 3
= R (42)
T 2

and
u P
=T P = (43)
T T 2
Integrating we have
Z
u 3
dT = RT + r1 (), (44)
T 2

and Z
u
d = + r2 () (45)
T
and the molar internal energy is
3
u= RT + constant. (46)
2
The Helmholtz free energy, F , is F = nu nT s. Thus,
n
F = nRT nRT ln[T 3/2 ( b)] + F0 (47)

where F0 is a constant.
4. A material is found to have a thermal expansivity p = (R/P )+(a/RT 2 )
and an isothermal compressibility T = (1/)(T f (P ) + (b/P )), where
= (V /n) is the molar volume. (a) Find f (P ). (b)Find the equation of
state. (c) Under what conditions is this material stable?

Solution

a)Note that

1

P = (48)

T P

1
T = (49)
P T

6
Then

R
= + (50)
T P P RT 2

b
= T f (P ) (51)
P T P
Using the condition that d is an exact differential


= , (52)
P T P T T P T P
and

R
= (53)
P T P T
P2


= f (P ). (54)
T P T P

We can find that

R
f (P ) = (55)
P2
b)To obtain the equation of state, we integrate


d = dT + dP (56)
T P P T
To obtain
Z Z
RT b RT
dP = + dP = b ln(P ) + f1 (T ), (57)
P T P2 P P
and
Z Z
R a RT a
dT = + dT = + f2 (P ), (58)
T P P RT 2 P RT
Thus the equation of state is

RT a
= b ln(P ) + constant. (59)
P RT
c) This material is stable if

1 RT b
T = + > 0. (60)
P2 P
Thus the material is stable for all b > 0 and for negative values of b which
satisfy

RT
+b>0 (61)
P