Thermodp m i c s 81

a2E
From __ - -
a2E a2s - a2s
we obtain
axaT a T a x l axaT aTax
a2E
aTax

Thus (aE/a+ = t - T(at/aT),.

Substituting the expression for t , we have (aE/az)T = 0. It follows
that (ac,/az), = 0. Integrating, we get

E ( z ,T ) = E ( T ) = 6+dE E(To)= [ gdT + E(To)

= Lr KdT + E(To)= K ( T - To)+ E(To).
From
d S = % d T + T1 [ ( aE
a,),-t]dz
T

we find after integration

S(z, 2') = K In T - A -
(;l: :)
+ - + const.
(b) For an adiabatic process dS = 0 so that

After integration we have

= 0.292AZo ,
Hence fi = TOexp(0.292Alo/K).
82 ProMema d Solutions o n Thermdynamics d Statiatieal Mechanic8

1084
Consider a gas which undergoes an adiabatic expansion (throttling
process) from a region of constant pressure p; and initial volume V i to a
region with constant pressure pf and final volume Vf (initial volume 0).

Fig. 1.27.

(a) By considering the work done by the gas in the process, show t h a t
the initial and final enthalpies of the gas are equal.
(b) What can be said about the intermediate states of the system?
(c) Show for small pressure differences Ap = pf - pi that the temper-
V
ature difference between the two regions is given by AT = -(Ta - l ) A p ,

(g)
CV

where a = -
v dTp
(
av) and cp =
P

(d) Using the above result, discuss the possibility of using the process
to cool either an ideal gas, or a more realistic gas for which p = R T / ( V - b ) .
Explain your result.
(SUNY, Buffalo)
Solution:
(a) The work done by the gas in the throttling process is pfVf - p i x ,
which is equal to a reduction of the internal energy:

ui - Uf = pfvf - piVi .
Thus Ui + pi& = Uf + pfVf, i.e., Hi = Hf.
(b) Because the process is quasi-static, the final and initial states can
be any two intermediate states. Thus the conclusion is still valid for inter-
mediate states.
(c) From d H = T d S + Vdp = 0 and
d S = ( g ) p d T + ( $ ) T d p = $ d T -C ( g ) dp,
P
 Thermodynamics a3

we obtain

Thus for a small pressure difference Ap, we have approximately

(d) For an ideal gas, we have pV = NRT and a = 1/T. Hence

A T = V ( T Q - l)Ap/c, = 0 .

As A T = 0 this process cannot be used to cool ideal gases. For a realistic

gas for which p = R T / ( V - b),a = R/Vp and V ( a T - 1) = -b. Hence
A T = -bAp/c,. As Ap < 0 for a throttling process, A T > 0, such a gas
cannot be cooled by this process either.

1085
(a) Using the equation of state pV = NRT and the specific heat per
mole C, = 3R/2 for a monatomic ideal gas, find its Helmholtz free energy
F as a function of number of moles N, V, and T.
(b) Consider a cylinder separated into two parts by an adiabatic, im-
permeable piston. Compartments a and b each contains one mole of a
monatomic ideal gas, and their initial volumes are Vai = 10 litres and
Vbi = 1 litre, respectively. The cylinder, whose walls allow heat transfer
only, is immersed in a large bath a t 0°C. The piston is now moved reversibly
so that the final volumes are Vat = 6 and Vbf = 5 litres. How much work is
delivered by (or to) the system?
(Princeton)
Solution:
(a) For an ideal gas, we have dU = NC,dT and U = NC,T + Uo,
where Uo is the internal energy of the system when T = 0. As

NCu d T
dS = -
T
+ ;dV ,
s = 3- N2 R l n T + N R l n V + S h ,
a4 Problems d Sdutiom on Thermodynamica d Statiaticd Mechanics

where S
A is a constant. Assuming the entropy of the system is SO when
T = TO,V = Vo1 we have

s =3 -N R- I n -T+ N R l n - + SVo
2 To VO

where FO= UO- T O S O .

(b) The process described is isothermal. When d T = 0 , d F = -pdV.
The work delivered by the system is

1086
A Van der Waal's gas has the equation of state

(a) Discuss the physical origin of the parameters a and b. Why is the
correction to p inversely proportional to V2?
(b) The gas undergoes an isothermal expansion from volume Vl to
volume V2. Calculate the change in the Helmholtz free energy.
(c) From the information given can you calculate the change in internal
energy? Discuss your answer.
( wisco nsifl)
Solution:
( a ) On the basis of the equation of state of an ideal gas, we introduce
the constant b when considering the volume of a real gas to allow for the
finite volumes of the molecules and we introduce the constant a to allow for
the mutual attraction between molecules of the gas. Now we discuss why
the pressure correction term is inversely proportional to V2.
 Thermodynamics 86

Each of the molecules of the gas has a certain interaction region. For
the molecules near the center of the volume, the forces on them are isotropic
because of the uniform distribution of molecules around them. For the
molecules near the walls (the distances from which are smaller than the
interaction distance of molecules), they will have a net attractive force
directing inwards because the distribution of molecules there is not uniform.
Thus the pressure on the wall must have a correction Ap. If Ak denotes the
decrease of a molecule's momentum perpendicular t o the wall due to the
net inward attractive force, these Ap = (The number of molecules colliding
with unit area of the wall in unit time) ~ 2 A k As
. k is obviously proportional
to the attractive force, the force is proportional t o the number of molecules
in unit volume, n, i.e., Ak o( n, and the number of molecules colliding with
unit area of the wall in unit time is proportional to n too, we have

Ap o( n2 o( 1/V2 .

(b) The equation of state can be written as

kT a
p=---
V-b V2'
In the isothermal process, the change of the Helmholtz free energy is

pdV = -k: kT V-b

a
- -dV
V2

(m) + a ($ - 4)
V2 - b
= -kTln .
( c ) We can calculate the change of internal energy in the terms of T
and V :

For the isothermal process, we have

d U = ( g ) dV.
T

The theory of thermodynamics gives

(g)T (g) =T V -Pa

86 Problems €4 Solufiona on Thermodynamics tY stati&d Mechanics

Use of the equation of state then gives

a
dU = -dV
V2
.
Integrating, we find

1087
A 100-ohm resistor is held at a constant temperature of 300 K. A
current of 10 amperes is passed through the resistor for 300 sec.
(a) What is the change in the entropy of the resistor?
(b) What is the change in the entropy of the universe?
( c ) What is the change in the internal energy of the universe?
(d) What is the change in the Helmholtz free-energy of the universe?
( Wisconsin)
Solution:
(a) As the temperature of the resistor is constant, its state does not
change. The entropy is a function of state. Hence the change in the entropy
of the resistor is zero: AS1 = 0.
(b) The heat that flows from the resistor to the external world (a heat
source of constant temperature) is

P R t = 3 x loG J

The increase of entropy of the heat source is AS, = 3 x 1OG/3O0 = lo4 J/K.
+
Thus the total change of entropy is A S = AS1 AS2 = lo4 J/K.
(c) The increase of the internal energy of the universe is

AU=3x1O6 J

(d) The increase of the free energy of the universe is

A F = AU - TAS = 0 .
 Thermodpam’cs 87

1088
Blackbody radiation.
(a) Derive the Maxwell relation

(b) From his electromagnetic theory Maxwell found that the pressure
1
p from an isotropic radiation field is equal to - the energy density u ( T ) :
3
1
p = - u ( T ) = - where V is the volume of the cavity. Using the first
3 3v
and second laws of thermodynamics together with the result obtained in
part (a) show that u obeys the equation

1 du 1
u = -T- - -U
3 dT 3

(c) Solve this equation and obtain Stefan’s law relating u and T.
( was co nsin)
Solution:
(a) From the equation of thermodynamics d F = -SdT-pdV, we know

(%)v =-s, (%) T =-p.

Noting
a2F -
-
d2F
~
we get
avaT aTav’
(b) The total energy of the radiation field is U ( T , V )= u ( T ) V . Sub-
stituting it into the second law of thermodynamics:

(!g)T (g)T ($)

= T -P=T V -P 7

T du 1
we find u = -- - -u.
3 dT 3
du
(c) The above formula can be rewritten as T - = 4u, whose solution
dT
is u = aT4, where a is the constant of integration. This is the famous
Stefan’s law of radiation for a black body.
88 Problems d Sdutiom o n Thermodynamiclr €4 Statisticd Mechanics

1089
A magnetic system of spins is at thermodynamic equilibrium at tem-
perature T . Let p be the magnetic moment of each spin; and let M be the
mean magnetization per spin, so - p < M < p . The free energy per spin,
for specified magnetization M , is F ( M ) .
( 1 ) Compute the magnetization M as a function of external magnetic
field strength B , given that

where X is a constant.
(2) Suppose, instead, that someone gives you

F ( M ) = Al(M/P)4 - (M/d2I 9

you should respond that this is unacceptable - this expression violates a

fundamental convexity principle of thermodynamics. (a) State the princi-
ple. (b) Check it against the above expression. ( c ) Discuss, by at least one
example, what would go wrong with thermodynamics if the principle is not
satisfied.
(Princeton)

Solution:
( 1 ) From dF = -SdT + H d M , we have

M
- - 5 - - 1.
LC 2
Hence
M 1
Fa,
'7
 Thermodynamics 89

(2) (a) The convexity principle of free energy says that free energy is a
concave function of T while it is a convex function of M , and if (Z>,
-

-
exists then (:;)T=.

(b) Supposing F ( M ) = X [(f)4- (f)’], we have

2X 6 M 2
(s)T= * &-l)

I Mc1 I
When - < 8,
(s) a2F
T
< 0, i.e., F is not convex.

(s)T
(c) If the convexity principle is untenable, for example if

= l/XT <0 ,

that is, (g) T

< 0, then the entropy of the equilibrium state is a mini-
mum and the equilibrium state will be unstable.

1090
A certain system is found t o have a Gibbs free energy given by

I&([
G ( p ,7’) = R T In -

where a and R are constants. Find the specific heat at constant pressure,

Solution:
The entropy is given by

S=-(g)
5
=iR-Rln
P
[ ~ (RG5j2] ’

The specific heat a.t constant pressure is