CONI'ENTS

Preface •• . ... . . . . . . . . . .. ... . i

CRA.PI'ER l: Introduction to Statistical Methods. .. .. . 1

CRA.PI'ER 2: Statistical Description of Systems of Particles •• ll

CRA.PI'ER 3: Statistical Thermodynamics 16

CRA.PI'ER 4: Macroscopic Parameters and their Measurement 18
CRA.PI'ER 5: Simple Applications of Macroscopic Thermodynamics. 20
CRA.PI'ER 6: :Ba.sic Methods and Results of Statistical Mechanics. 32
CRA.PI'ER 7: Silllple Applications of Statistical Mechanics • • • 41
CRA.PI'ER 8: Equilibrium between Phases and Chemical Species •• 54
CHAPrER 9: Quantum Statistics of Ideal Gases • • • • • • 64
CHAPrER l0: Systems of Interacting Particles ••••• 84
CRAPI'ER 11: Magnetism and Low Temperatures •• 90
CHAPI'ER l2: Elementary Theory of Transport Processes. 93
CRAPI'ER 13: Transport Theory using the Rel.axation-Time Approximation 99
®.Pl'ER l4: Near-Exact Formulation of Transport Theory ••••• l07
CRAPI'ER 15: Irreversible Processes and Fluctuations • • • • • • • 117
 PREFACE

This manual contains solutions to the problems in Fundamentals of Statistical and Thermal

Physics, by F. Reif. The problems have been solved using only the ideas explicitly presented

in this text and in the way a student encountering this material for the first tillle would

probab]_y approach them. Certain topics which have implications far beyond those called for in

the statement of the problems are not developed further here. The reader can refer to the

numerous treatments of these subjects. Except when new symbols are defined, the notation

conforms to that of the text.

It is a pleasure to thar,k Dr. Reif for the help and encouragement be freely gave as this

work was progressing, but he has not read all of this material and is in no way responsible for

its shortcomings. Sincere thanks are also due to Miss Beverly West for patiently typing the

entire manuscript.

I would great]_y appreciate your calling errors or omissions to my attention.

R. F, Knacke
 CHAP.PER 1
Introduction to Statistical Methods

1.1

There are 6-6-6 = 216 ways to roll three dice. The throws giving a sum less than or equal to 6

are
Throw 1,1,1 1,1,2 1,1,3 1,1,4 1,2,2 1,2,3 2,2,2
No. of
Permutatiom l 3 3 3 3 6 l

Since there are a total of 20 permutations, the probability is ~~G = -k

1.2

(a) Probability of obtaining one ace= (probability of an ace for one of the dice) x (probabil-
1 1 5 6!
ity that the other dice do not shov an ace) x (number of permutations)= (b)(l - '6') (5!1!)
5 5
= (5) = .4o2 •
(b) The probability of obtaining at least one ace is one minus the probability of obtaining

none, or
56
1 - (;-) = .667
(c) By the same reasoning as in (a) ve have

l 2 2 4 6!
(b) ('6') 5!2! = .04o

1.3

The probability of a particular sequence of digits such that five are greater than 5 and five are
1 5 1 5
less than 5 is (
2) (2). Then multip:cying by the number of permutations gives the probability

irrespective of order.

1.4

(a) To return to the origin, the drunk must take the same number of steps to the left as to the
right. Thus the probability is
N N.I l N
W (-2) = --------- (-2)
C!) ! <J) !
where N is even.

(b) The drunk cannot return to the lamp post in an odd number of steps.
1.5

th
(b) (Probability of being shot on the N trial)= (probability of surviving N-1 trials) x
th 5 N-l l
(probability of shooting onesel.f on the N trial)= (b) (b).
(c) 6

1.6

m= m3 = O since these are odd moments. Using n

r cl
= (p clp) (p+q)
r N

2
m = (2n - N)
2
= 4n
2 - 4nN
- + W--
~2
and

4
m =

we find m2 = N and ";f+ = 3lf - 2N.

1.7

The probability of n successes out of N trials is given by the sum

2 2
w(n) = E E 'W
m
i=l j=l

with the restriction that the sum is taken only over terms involving w1 n times.
2 2
Then W(n) = E w. E v. If ve sum over all i ••• m, each sum contributes
. i=l i m=l m
(vi-1~2 ) and
W' (n) = (w + w
1 2
l
N N! n N-n
W' (n) = E .....,...,,.._.__..,.. v w by the binomial theorem •
n=O n!(N-n)! 1 2

Applying the restriction that w must occur n times we have

1
N! n N-n
W(n) = n!(N-n)! "W'l w2

'We consider the relative motion of the two drunks. With each sillr..i.ltaneous step, they have a

probability of 1/4 of decreasing their separation, 1/4 of increasing it,and 1/ 2 of maintaining

it O'J taking steps in the same direction. Let the number of times each case occurs be n , n ,
1 2
and n , respectively. steps is
3

2
The drunks meet if n = n • Then the probability that they meet after N steps irrespective of
1 2
the number of steps

vhere we have inserted a parameter x which cancels if ~=n • We then perfonn the unrestricted
2
sum over n n n and choose the term in which x cancels. By the binomial expansion,
1 2 3
1 1 1 N 1 2N 1/2 -1/ 2 2N
pr= (4 x + 4X + 2) = (2) (x + x )

l 2N 2N 2N ! 1/ 2 n -1/ 2 2U-n
Expansion yields P' = (2) ~ n! 2N- ! (x ) (x )

Since x must cancel we choose the terms where n = 2N-n or n = N

Thus

1.9

(a) 1n (1-p)N-n ~ -p (N-n) ~ -Np n << N thus (1-p )N-n ~ e -Np

N!
(b) (N-n)! = N(N-1) • • • (N - n+l) ~ 1f if n << N

(c) N! n (
W(n) = n!(N-n)! P 1-p
)N-n n -Np "'n -A
~ n! p e = n! e
r
1.10

(a)
0)

E "'n!n = e -t. e"' = 1

n=O
= n ->..
(b) - =
ll "L., n >.. eI
-"
n=v n.

(c) n2 = n~ n~n e ->-. = e ->-. (~) 2 L. ~~ = >-.2 + >-.

-- 2 -2
(.6n) = n
...!;)
- n- = >-.

1.11

(a) The mean number of misprints per page is l.

>-.n ->-. e -l
Thus W(n) = -,
n.
e
= n!

-1
and W(O) = e = .37

3
 2 -1
{b) P =1 - 2: ~ = .08
n:::() n.

1.12

(a) Dividing the time interval t into small intervals ~t ve have again the binomial distribution

for n successes in N = t/~t trials

N! n ( )N-n
W( n ) = n., (N -n ) •, P 1-p

-,.._n "-
In the lilllit ~t ~ o, W(n} ~ n! e as in problem 1.9 vhere )... = ~ , the mean number of disintegra-

tions in the interval of time.

4n -4 n 0 1 2 3 4 5 6 7 8
(b) W(n) =-,
n. e W(n) . 019 .(176 .148 .203 .203 .158 .105 .()51 .003

1.13
2 2
We divide the plate into areas of size b. Since b is much less than the area of the plate,

the probability of an atom hitting a particular element is much less than one. Clearzy n << N

so we may use the Poisson distribution

6n -6
W(n) =,
n. e

1..1.4

We use the Gaussian approDJDation to the binomial distribution.

(21.5-2COr
W(n) =_ _;l.;;;..__ e- 2(400/4 = .013

J;;¥f
J..1.5

The probability that a line is in use at e:n:y instant is 1/30. We vant N lines such that the

probability that N+l or more lines are occupied is less than .01 vhen there are 2000 trials
during the hour.

•01 = l. - r.N ___,;;;..__

1
e
n=O~ cr

-n = 20CO
30 = 66.67,
vhere

4
The sum may be approxilllated by an integral

N¥z° l - 2 2
.99 =
J1 --
,Ji;' a
exp [-(n-n) /2a ] dn

(n-n+½;& 1 _ 2
.99 =
J -1
(-n- 2)/cr
~
- e y 12 dy afier a change of' integration variable.

The lower limit may be replaced by -eo with negligible error and the integral f'ound f'rcan the

tables of' error functions.

- l
We f'ind N-n~ = 2. 33
a

N = 66.67 + (2.33)(8.02) - .5 ::: 85

1.16

{a) The probability f'or N molecules in Vis given by the binomial distribution
N-N
N ! V N V o
W(N) = N!(No-N)! (-) (1 - -)
0 Vo Vo

V
Thus N=NP=N
0 ov- 0
V
NoV
- V )
(1 - -V
(N-i)2 0 0
(b) =
Ff- i

l
(c) If V << V,
0
:::-
N

(d) ~o

1.17

Since O <<; <<land since N0 is large, we may use a Gaussian distribution.

0

exp [-(N-N}2/2 d] dN

5
1.18
N N A

R = L.i r.
-:1.
= tr_i -:i.
~- (S. 's are unit vectors)
-:1.

R•R = .f..2 !
i
S
i
2 2
+ .f.. £I £ ~-• ~. = m,2 + .f..2 L. I L. cos
i j -:i. -J i j
e.j
:i.

2 2
The second te:rm is O because the directions are randcm. Hence R = Nt •

1.19
N
The total volt age i s V = L. v. ; hence the mean square i s
i l.

- N - N N
v2=L.v .
2 +r. L.V. V.
i l. i f j l. J

where v . = vp and v .
2 = v 2 p.
J. J.

Hence P = v2 /R = ( f f/R ) i [l+(l-p) /:N'p]

1.20

(a) The antennas add in phase so that the total amplitude is E = NE, and since the intensity
t
is proportional to Et2, It= ~I-

(b) To find the mean intensity, we must calculate the mean square amplitude. Since amplitudes

may be added vectorially

2 -- --2N2 --2
Et ~·:!<!. = ~ L.
= -., §.i +~ L.i L. §_1. •Sj
-., i / j -

where the -J.

S . 's are unit vectors. The phases are random. so the second term is O and

1.21

a
n.
J

Since ani = O, the second term on the right is O and

_.!. 1 _ .!.
(An2)2 = N-2 (a 2)2 = N.!.2 lv
-~
as
n
_ .!.
but (An2)2 = As = Nas

:Equating these expressions we find N = 106 •

6
1.22
N N
(a) x=I'.s.,
• J..
but since s. =t, x =L t =
l
Nt
i i

N N N
2 2
(b) (x-x) = L, (s.-t) + L, L. (s,-t)(sj-t)
i J.. i Jj ~

2
Since (s.-t)
J..
=t - t = O, the second term is O and (x-x) =L.N cr2 = Ncr2 •
i

1.23
N N
(a) The mean step length is t. x = I:i si = V.-: Nt
i

2 N 2 N N - - . - ----....
(b) ( x-x) = L, ( s . - t) + I: I: ( s . - t )( s . - t ) ' ( s . -t) = t -t = 0
i J.. j Ji J.. J J..

2
To find the dispersion (si-t) , we note that the probability that the step length is between

sands+ ds in the range t - b tot+ bis:~.

-fn.b (s. -t )2 ds. b2

Hence (s
i
-t) 2 =
1 t-b
J.
2b
J.. = -
3

2 N b2 Nb2
(x-x) = L, 3 = 3
i

1.24

(a) w(e) de = de
2JT

2
w(e) de= 2JT a si~ e de sine de
(b) 2
4n a

1.25

(a) He find the probability that the proton is in e and e + de and thus the probability for the

resulting field.

From problem 1.24 w(e) de= sin/ de

Since b = L (3 cos 2 e-1) we have !dbl = 6µ cos e sine

a3 de 83

and

7
(b) If the spin is anti-parallel to the field,

Then if either orientation is possible, we add the probabilities and renormalize

a3 ,J;' db

12/µ 2 -µ a%'

W(b)db = ( 83~ ' + a3 ,.;-:; ,} db

12Jµ2-µ a% 12 Jµ 2 -i-µa %

a
3 Ji db
12 Jµ2-i-µa%'
(b)

b
-2µ/a -µ/a3 2µ/a 3

Q(k) =
L
oo
ds e
iks
W( s) = =Im
b
~ ds
~
11
eiks
-
s2+b2

Q may be evaluated by contour integration. For k > O, the integral. is eval.uated on the path

-kb
residue (ib) = ~ i

:Fork< O

kb
-residue (-ib) = ~ Q(k) = e kb

8
Thus Q(k) = e
-lklb

<?(x) = 1
2rr L"° 1
dk e - ikx QN(k) =2rr L 0
dke -ikx e Nkb. +2rr
1 J"°
0
dke -ikx e -Nkb

= -1
'IT
1"°
0
dk e -Nkb COS k X

This integral may be found from tables.

Nb dx
C?{x) dx = !
7T' 2 _2.. 2
X + Irb
c,>(x) does not become Gaussian because the moments sn diverge.
1.27

From equation (1.10.6) and (1.10.8) we see that

(? (x) = 12rr L"° dk e - ikx Q (k) •• -~(k)

1
(1)

where

We expand Q. (k).,
J.

- 1 2 2
Q. ( k ) = exp [i s.k - - (6s. ) k ]
J. J. 2 J.

thus fran (1), ~

v-(x) = 2rr
1L 00

dk exp(i{L. s.-x)k -
i J.
N_
2 L.i (.6.s.)
J.
lN 2 2
k]

This integral -may be evaluated by the methods of section l.ll. We find

@(x) = &' exp [-(x-µ) 2/20]

2

N
where µ = L.
i
s.
J.

1.28

The probability that the total displacement lies in the range! to!+ dE after N steps is

@(r) d\: = J~- J W(~1 ) W{2.2 ) ••• W(~) d\1

(d3r)
where the integral is evaluated with the restriction
N
r < L. s. < r + dr
- i=l -i - -

9
We remove the restriction on the limits by introducing a delta f'unction

In three dimensions

or (? (r) = -l -
3
Leo d
3k e -i.k•r
- - QN(k)
(2rr) . - -

1.29

For displacements of uniform length but of random direction W(~) = 5 (s-~), in spherical
lii7rs
coordinates..W(s) is a properly normalized probability density since

1 27T'J7T'Jc:o s 2 sin e ds de dq> 5 (s-t) = 47rf

2
c:o 5 (4,ii--t) =1
0 0 0 !i,,r s O

We find the Fourier transform Q(!).

Q(~ =JJJ a 3~ e~·~ w(~ =J2rr1Jc:o

0 0 0
s
2
sin e ds de dcp 5 (s-t) ei.ks cos
47r s
2
e

_~17T' sin4rre de
- t:Cll e
i.k-t cos e =
0

From

we have, for N = 3
(?(r) - _ l _
- (2rr)3 102zr11c:o
0 0
k2 sine dk de dcp e-i.kr cos e

The angular integrations are trivial and

To evaluate the integral, we use the identities

3
sin k-t Sin kr -_ -l s i n kr sin
. k·D cl-COS 2 k-f~
:'v ~)
k2 k2 2

lO
 1
= [cos k{r-l)-cos k{r+t][1-cos 2kt]
4k2
1
=
2 [3 cos k(r-t)-3 cos k(r+t) + cos k(r+-3-t)- cos k(r-3-t)]
8k
The integral of the first two terms in the last identity is
3 lco cos k(r-t)-cos k(r+t) dk = 3
4
1= sin2 !(r+t)-sin2 !(r-t) dk
E o k2 o k2

On making the substitutions x = !<r+t) and y = ~(r-t), it follows that

3
Ji:
lco Ir+tj
0
2
2
sin x
x2
dx _ 3
4
J
0
00
Ir-tl
2
2
sin y dy _ 3rr ( Ir+tl _ Ir-tl)
y2 - Io
The third and fourth tenns may be evaluated in the same way.

; Jco
0 0
cos k{r+¼)-cos k(r-3-t) dk =
~
-g,..
~
(lr-3tl-lr+3-tl)

Ccmbining these results, we have

1
O<r<t
8rr .t,3

G>{r) = 1 3 (3-l-r) t<r<3-t

16ir-f;r

0 r >3-l

CHAPrER 2

Statistical Description 2! Systems~ Particles

p = ~ op = ~ o E

Hatched areas are accessible to the particle.

L X

2.2

Since p/ + P/ = 2mE, the radius in

p space is .,;;;;;;- •

11
(a) The probability oi' displacement x is the probability that cp assumes the required value in

the expression x = A cos (wt+ cp).

-w-(cp)dcp = ~ .and P(x)dx = 2v(cp) dtp = ~

7I'

vhere the i'actor oi' 2 is introduced because tvo values oi' <p give the same x.

Since

ve have

(b) We take the ratio oi' the occupied volume, av,

in phase space vb.en the oscillator is in the
p
range x to x + dx and E to E + 6E, to the total accessible

volume, v.

ov/2
E - P2 + m ,ix2
Since - 2m 2 (J.)

ve have Ae = 7r ~
,./mw2
r- = ~E , and v = 2:° 6E •

Hence P(x)dx = 6v = 2 6:p 6x

V 2rr 6E
(a)

For arr:, x, p ~ = 6E
m
P(x)dx = ~ dx = ~ dx
7r p 7r / 2 2 2'
"V2mE - mW X

.:here ve have used (1). From (1) and x = A cos (wt + cp), it i'ollows that E = ½w2mA.2 •
Thus P(x)dx = ! dx
7I' '22
VA~-x~

2.4
(a) The number of wey-s that N spins can be arranged such that ~ are parallel. and n are anti-
2
parallel. to the fie1d is

and

J.2
Since ve have n.. = -1. (N - -E ) , n = -1. {N + -E)
.l. 2 µH 2 2 2µH

N! 6E
Thus n(E) = N E 2
<2 - 2µH)! (~ + 2~)! µH

(b) Using Stirling's approximation, 1n n! = n 1n n-n, ve have

1n n(E) = - .±(N _ ~) 1n .±(1. _ l ) _ .±(N + ~) 1n .±(1. + l ) + 1n 6E

2 µH 2 NµII 2 µII 2 NµH 2µII

N! -
( c) We expand 1n f(~) = 1n ~ ! (N-~) ! about the maximum, n1

where

From (1.)

ftni_) is eval.uated by noticing that the integral. of f(nJ.) over all n must equal. the total. number
1
of permutations of spin directions,~-

-
n
1
is found :frcm the maximum condition

d 1n f(n )
1

and --
1.
---
1.
..,
N-~-
~ = N/2
Substituting these expressions into (2), we have

1.3
Since and 1 E ) it f'ollws that
n..J. = -2 (N - -µH '

2
2 E 6E
O(E) exp [ - N <2µH) J 2µH

2.5
{a)
If cl. f is an exact differential,

Since second deri-va.tives are equal,

{b) If 71. f is e:x:a.ct, lB -a. f = f(B) - f(A) = 0 if A= B

2.6
2
o2f' o r
(a) not ex.act dX oy I eydX

2 J,2 2 l 2 2 J,2 10 J,2 2 J,2 7

(b)
J,1 ay + 1 {x -2) dx =
3, J,1 {x -l)dx + 1 2dx =3 , 1 (x -x)dx + 1 x dx = 3
(c) exact
2,2 [ ] (2,2)
(d) J,1,1 71.f= x+Z
X (1,1)
=l for all :paths

{a) The particle in a state vith energy E does vork, 71.w, vhen the length of the box is changed

to L
X
+ dLX • This vork is done at the expense of the energy, i.e., "d. W = -dE. Since cl. W = F dL ,
X X
it follows that Fx = - ~~ •
X 2rr2~2
(b) The energy levels are given by E = - -
m

Fx l
:P = L L = - 'E"'"'L
y z y z
2
p = 4ms.2 ( ~ ) vhere V = LX L
mV L 2 y LZ
X

I f Lx = ~ = Lz, by symmetry
2 2 2
nx = ny = nz, and using the expression for Ewe have

14
2.8

~ ~ ~
h 2
pdv + ~
l
pdv = J C
p dv

2.9
From the definition of the Young's modulus, the force is

dF-YA dL
- L
F2
W= -
1 F
l
L
F - dF = -
YA
L
2AY
(F
l
2
- F )
2
2

2.10

2.11

p=a v-5/ 3, a may be found by evaluating this expression at a point on the curve. In units of

10
6 d:ynes/m2 and 103cm3, a= 32. For the adiabatic process,
8
AE = ~ - EA = - J,
32V- 5/3 <N = -36 =-36oo joules
1
Since energy is a state :function, this is the energy cba.Dge for all paths.
8
(a) W = 321 <N = 22,400 joules

Q = AE +W = -36oo + 22, 4CO = ll,8CO joules

31
(b) P = 32 - 7 (V-1)
W=
8
fi f
[ 32 - 3 (V-1)] = ll,550 joules

Q = ll,550 - 3600 = 7 , 95C joules

(c) W = l 8
(1) dV = 700 joules

Q = 700 - 36:::,0 = -29(X) joules

15
 CHAPl'.ER 3
Statistical Thermodynamics

(a) In equilibrium., the densities on both sides of the box are the same. Thus, in the larger

volume, the mean number of Ne molecules is 750 and the mean number of' He molecules is 75.
lCXX) 100 l8
(b) P =
3
(4) Cf) = io- 5

3.2
From problem 2.4 (b)

{a) l
1n O(E) = - -(N - -E ) ln -(l
1 - -E) - -(N
l + -E ) ln -(
l 1 +E-)
2 µH 2 NµH 2 µH 2 :;·; µH

where we have neglected the small term ln ~ .

~ = ~ ln O(E)
= ..1.... ln ½<1 - ~)
2µH l - ~(l -
2
l )
NµR

Consequently E = -NµH tanb ~

(b) T < 0 if E > 0

(c) M =µ(n -n ) = µ(2n -N) where~ is the number of' spins alligned parallel to H.
1 2 1
l
~
>i'
Since ~ = 2 (N - ~) frcm problem 2.4 (a), M = µ(N - - N)
µH

M = Nµ tanb .I:!!
kT

3.3
(a) for system A, we have f'rom 2.4 (c) ln O(E) = (1)

where we have neglected the term ln oE

2µH

In equilibrium, Hence E E 1

µ~ = µ'~'

(b) Since energy is conserved, E + E' = bNµH + b'N'µH

Substituting from (a) we find E = µ~(bNµH + b'N'µ 'H) (2)
µ~ + µ'~'
2 2
(c) Q= E- bNµH = NN'H ( b'µ'µ - bµ' µ) from (2)
µ~ + µ'2N'
(d) P(E) a: n(E) n' (E -E) where E0 is the total. energy, E0 = bNµII + b 'N'µ 'H.
0

From (l) P(E) a: exp [_

[ 2µ H2N
f
]

This expression may be rewritten in terms of the most probable energy E, equation (2).
2
P(E)dE = C exp t(E~!1 ] dE

where

The constant C is determined by the normalization requirement

co - 2
!-co C exp [- (::~) ] dE = 1

2
Thus P(E)d.E = - 1- exp [- (E-E) ] dE where cr is given above.
J;;'cr 2cr2 '
(e)
(3)

(:f) Fram equation (3), N' >> N

E- µ N(bµHN + b'µ'N'H) -b' Nµ~ N' >> N

- µ~ + µ'~' - µ'

hence l\*EI = _µ_.a;;;.~-:F-N-

3.4
The entropy change of the heat reservoir is 68 1 = - ~' and for the entropy change of the entire
Q
system, AS + AS' = AS - T' ~ o., by the second law.

Hence /\es~
'->,;) -v
Q

3.5
(a) In section 2.5 it is shown tba.t n(E)a: yN'X(E), where Vis the volume and X (E) is independent
of volume. Then for two non-interacting species with total energy E0
N +N
n(E) = C nl(E) n2(Eo-E) = CV l 2 Xi(E) x2(E)

17
2 atmospheres.

CRAPI'ER 4
Macroscopic Parameters and their Measurement

4.1
373
(a) ~ =me
1273
dT
T
= 4180 l.n fil
273
= 1310 jou1es;°K

Since ~s = -~

DB
res
= - ~
T .
= - ~
T
(373-273) = -1120 jou1es;°K

D.stot = ~ + D.sres = 190 jou1es/K

(b) The heat given off by either reservoir is Q = mc(50) = 2.09 X 105 joules. Since the

entropy cha.llge of the water is the same as in (a) ve have

(c) There vill be no entropy cha.llge if' the system is brought to its final temperature by inter-

action vith a succession of heat reservoirs differing ini'initesima~ in temperature.

4.2

(a) The final. temperature is found by relating the heats, Q, exchanged in the system. The heat

required for melting the ice is mi.f, vbere mi is the mass of the ice. Since for the other compo-

nents of the system, Q = mct.T, where m is mass and c is the specific beat, we have

mi.i + Q(melted ice) + Q(original water) + Q(cal.orimeter) = O

(30)(333) + (30)(4.18)(Tf-273)+(200)(4.18)(Tf-293)+(750)(.418)(Tf-293) = 0

Tf = 283°K

(b) The change in entropy when the ice melts is

m/
T• For the other components
T
f dT Tf
DB = me
1Ti
T = me l.n T
1

Hence
- m/ g§3_ g§3_ ~
A,
DB - 273 + mwc l.n 293 + mic l.n 273 + mccc l.n 293 = 1 • 6 jouJ.es, r-..

18
(c) The vork required is the 8l!IOUD.t of heat it vould. take to raise the water to this temperature.

W = lllr/\v (Tf-Ti) + mccc (Tf-Ti)

= [(750)(.418) + (230)(4.18)](293-283) = 12,750 joules

EQ=cd.T+pcIV by the first lav

RI'
= c dT + V dV Since pV = RI'

l::,S = 1 cl 1·Tf
i
f
T
Q =
T
c dT +
T
r Vf RdV
Jv V
i 1
Tf Vf
= c ln - + R ln - independent of process
Ti Vi
4.4
The spins becane rand~ oriented in the limit of high temperatures. Since each spin bas 2

available states, for N spins ve have

S(T -+ m) =k ln n = k ln ~ = Nk 1n 2 (1)
But since S(T)-s(o) =JT Q!tl. dT
o T
T
ve have S(T -+m) r
= JJ
1
2T
c 1 (T - 1)
dT
T = c (l-ln 2) (2)
1
ffe'1 1

where we have set s(o) = 0 by the third law. From (1) and (2) Nk 1n 2 = c (1-ln 2)
1

Nk 1n 2
cl =1 - 1n 2 = 2 • 27 Nk

4.5
T£.CT1
The entropy at temperature Tis found by evaluating S(T) - s(o) =

undiluted and diluted systems by u and d, ve have

J 0
T- d.T. Labeling the

T
dT
su(T1) - s (o) =
u 1 ffe'l
l
c
1
T
(2 - - 1) -
Tl T
= c (1-ln
1
2)

T
sd(Tl) - sd(o)
r
= J1
2 T dT
c2 TT= c2
i'r1 2
sio) = Su(o) by the third lav. Since there are oncy- io as maey magnetic atoms in the diluted

case as in the other, we must have Sd(T ) =

1
.7 8tJ(T1 ). Hence

19
 CHAPl'ER 5
Simple Applications of Macroscopic Thermodynamics

5.1
(a) pV7 = constant for an adiabatic quasistatic process. substituting pV = v Rr ve have
V l-7
or Tf = Ti ( ...!.
vi )

(b) The entropy change of an ideal gas in a process taking it from T1 ,vi to Tf,Vf vas found in

problem 4.3

t:,S = O for an adiabatic quasistatic process.

and since 1n 1 = O, it follows that

V l-7
Ti' = Ti ...!..1 )
(V

5.2
(a) W = J p a;, = area enclosed by curve = 314 joules

(b) Since the energy of an ideal gas is only a function of the temperature and since pV = Rr,
3 PcVc PAVA
AE = ~ 6T = 2 R (~ - -R-)

= ¾(6-2) x 1a9 ergs= 6co joules

( c) Q = AE + W vhere AE is calculated in (b) since the energy change is independent of path.

Again the vork is the area under the curve.

1
Q = 600 + [ 4CO + ~ ] = 1157 joules

5.3
(a)

(b) W J
= p a!-/ = area under curve = 1300 joules

(c) To find the heat, Q, ve first find the energy change in going from A to c. This, of
course, is independent of the path.

t:.E = c.p = i R(Tc-TA) = i (PcVc - PAVA) = 1500 joules

20
Then since Q = .6E + W

Q = 1500 + 1300 = 2800 joules

(d) From problem 4.3

= ~ R 1n l2
6
X
X
lO~/R + R 1n
10 /R
3 X
1
;a3 = 2.84 R = 23.6 joules/°K

5.4
(a} The total system, i.e., water and gases, does not exchange energy with the environment, so

its energy remains the same af'ter the expansion. Since the water cannot do vork, its energy

change is given by the heat it absorbs, 6E = Q = G,_,fT, where ~ is the heat capacity. The

energy of the two ideal gases is, of course, dependent o~ on temperature, .6E = C6T, where C is

the heat capacity.

6E(vater) + 6E(He) + 6E(A) = O

'1l(Tf-Ti) + CHe(Tf-Ti) + CA(Tf-Ti) = O

Thus Tf = Ti, no temperature change.

(b) Let -l be the distance from the left and v the number of moles.

Renee, in equilibrium -l = 3(80-f..), -l = 60 cm.

vr
(c) Since there is no temperature change, the entropy change is vR 1n V..
J.

R 20 6o p
~ = ~A + ~He =
3 1n
50 + R 1n 30 = 3.24 joules; K.

5.5
(a) The temperature decreases. The gas does work at the expense of its internal energy.

(b) The entropy of the gas increases since the process is irreversible.

(c) The system is isolated, Q = O, and from the first law

6E = -W =- T (Vf-Vo)
The internal energy of the gas is o~ a i'unction of temperature, .6E = vcv(Tf-T 0 )

Thus vey(Tf-To) = - T (vf-vo) (1)

In equilibrium p = T and since pVf = vRrf , ve have

21
Substitution in (1) yields

The equation of motion is mx=pA-mg-pA

0
(1)
Since the process is approximately adiabatic

pV7 =constant= (p 0 + r) V
0
7

AV 7
0
and mx = (p + !!!:8.) - - - mg - p A (2)
o A (Ax)7 o

The displacements from the equilibrium position,:, are small so ve can introduce the coor-
V V
dinate cbange x = Ao + 'I} and expand about : •

!_ = -""""'1~ - = (~)
xr V r V0
7
(1 - ill +
V0
... )
(:+'I})
We keep onzy the first and second terms and substitute into (2).
•• 2
m11 = -(p
o
+ 5)
A
UV 'I}
0

This is the equation for harmonic motion and the frequency may be determined by inspection.
Hence ½
V = !_
21T
[ (p
o
+ !!!:8.)
A
A2z]
Vm
0

5.7
p(z+dz)A
The volume element of atmosphere shown must be in
equilibrium under the forces (pressure) x (area) and
z
gravity. Then if n is the number of particles per unit p(z)A
volume, m the mass per particle, and g the acceleration
of gravity,
p(z+dz)A-p(z)A = -n(Adz)mg

~ dz = - ~ dz, where
dz NA

22
Since p = nkT, (1)
vRT
(b) pV 7 = constant. Substit uting V = - we obtain
p '

Thus

3.E_ _ ...L dT (2)

p - r -1 T

(c) From (1) and (2)

dT _ .Ll:::zl (3)
dz - rR µg

dT
For N , µ = 28 and letting , = 1.4, dz= -9.4 degrees/kilometer.
2

(d) Integrating (l) with constant T we have

p = p0 exp [-µgz/RT]

{e) From (3) T = T0 - (; ;l) µgz

Thus
1 Po
P~
p'
=
f 0
z __-__.µc..g...,_d_z_'..---..,....-
R(T
o
-
r ~
Ii:ll R
)

5.8

AP I A{P+6P
I

Consider the element shown. 6x is its initial width. The wave disturbance causes the left face

to move a distance s and the right a distance g-ti:i.s. Let P and p be tb.e equilibr i um pressure
0

and density, and p = P-P is the departure from the equilibrium pressure .
0

At:.5
tts
=
- vJ. 6.V
P:P-
0
= -
J.
Ex P

or

23
vhere we have neglected the pressure difference D.p across the slab. The displacement is found

from the equation of motion.

025
m = PA - (P+l:i.P) A = -b.PA
ot2
Since
oP
t::,.p "' dX L:ix and m = p A/::,x

we have
cP cp _ P o2g
di= di= ot2

Then

but since the order of differentiation is immaterial,

i =l - ~
~ i
ot KsP ox2
2

5.9
(a) For an adiabatic process pV7 = const.

oV
v1 ®
oV
V 1
Hence dp = and Ks
,P = -

(b) U = {p KS) ~ = ( 1) 1
vRl' - ~ , we find
Substituting P = V and P - V
1

u = (zI?-)2
1
(c) u c: T2 , independent of pressure

(d) u = 354 meters/ sec.

5.10

Substituting the given values into the equation

2
cp - cV =
vr2a
-K-

we :find
-1 -1
Cy= 24.6 joules mole deg 1 1 = l.14

5.ll
When the solid, of dimensions x:yz, expands an increment iN, ve have

24
 v+av = (x+dx)(y+ay)(z+dz)
To first order

V +av = V + yzdx + xzdy + :xydz

Therefore

For the adiabatic, quasistatic process

dS = (~ )
p
dT + (~!)T dp = 0
cc~\
_/ov_\p' ve have
Using ( ~cri)\ p -- ~T and the Maxwell relation dl') T = \"2ff)

l (''v_\
vhere a = V %:r)
p

C
o.T = ...E_
Thus D.T = -pc D.1'
~
where C
p pV
p

5.13
From the first law cp = T(~)P
W/2=•a,;/2~~\ =·C~\C:/2
Substituting the Maxwell relation (~)T = {i)p and the definition a= - ¼(t)p we have

~~~)T = -T (~) P rrT =

2
a vr - vr :

5.14
(a) TdS = dE - FdL (1)
(b) From (1) we may read off the Maxwell relation

(~)T = - (l)L (2)

Since F = aT2 (L-L)

0
(3)

(~)T = -2aT (L-L0

)

T
=1
r
(c) bT dT' = b(T-T )
T' 0
To

25
 S(L,T) - S(L0 ,T) =I'r,L (~)T dL =I'r,L -2aT(L'-L0 )dL' = -aT(L-L0 )2
0 0

Hence S (L,T) = S (L0 ,T0 ) + b(T-T 0 ) - aT(L-L0 )2

(d) In the quasistatic adiabatic process DB = 0

2
S(T 0 ,L)
0
+ b(Tf-T)
0
- aTi(L~-L
~ 0
) = S(T0 ,L)
0
+ b(Ti-T)
O
-aTf (Lf -L0 )2

b-a(L -L )2
Hence T = T i o
f i b-a(L -L ) 2
f 0
Thus if L? Live bave Tf > Ti, i.e. the temperature increases.
(e) Fram the first law

Substituting (2) and (3) ve find

~~~T = -2aT (L-L 0)

Hence CL(L,T) = C(L0 ,T) + I'r,L ~~~)T d[, = bT - aT(L-L0 )

0

(f) S(L,T )-S(L ,T ) = fL (~) dL' = fL --2a To{L'-Lo) dL' = -aTo(L-Lo)2

o o o JL T JL
0
T C dT
1
0
1T bT' - aT
1
(L-L )
2

S(L,T) - S(L,T )
o
=
1T
0
~
T
=
T
0
T1
o dT'

= b(T-T) -a(L-L0 ) 2 (T-T)

0 0
2
'!'bus S(L,T) = S(T
0
,L)
0
+ b{T-T) - eT(L-L )
0 0
5.15

(a) cf. Q = TdS = dE - 2cr t dx (1)

dE 2ot
(b) From (1) dS = T -T dx

Hence o~\ dx + cos\ ! co~\ ! co~\ <fr - 2ot ax

( di)T ~/x: d.T =
T ax)T
dx +
T af)x T
Equating coefficients, we have

26
Fran (1), ve ca.n read off the Maxwell relation

Since cr = cr -ctr,
0

If' the :film is stretched at constant temperature

E(x) - E{o) = 2-to- 0 X

(c) W (0 --t x) = - J F dx = - Jx0

2ot dx' = -2otx

By the first law dS =

dE
T +
zfY
T
dv (1)

Hence (i)T dv + (l)v dT = ¥(i)T dv + ~ ( ~),, dT + zf;{' dv

Equating c oefficients, we have

From (1), we mey- read off the Maxwell relation

Thus

If' one mole is produced

5.17
By equation (5.8.12)

substituting p = n kT (1 + B2 (T) n] we find

~
\oV)T
- p
-
+ n~ dl32 -
dT
p = n~ dl32
dT
> 0

27
5.18
(a)

Since :f'rc:m (5.8.12)

ve have

(b) From the first law, dE = Td.S - pd.V. Hence

.
0 = T cos~ -
av)E
p and (~\
oV)E
= ~T

( c) For a van der Waals gas

2
vRI' v a
P=~- v2

Thus

5.19

(a) From (p + 't)<v-b) = RT (1)

we have ( ~
rlT>~' - -RTc + 2a3 = O
CV T (v -b)2 V
C C

J
2 D
2
2RI'
c
6a
--,;:=O
= (v -b) 3 V
T C C
9 VC
Solving, we find a = 8" RI'cvc, b =
3 ·
Rr
(b) Substituting a and bin (1) yie1ds pc= 3. _£
ff VC •

(p' ~ T'
(c)
i :, 2) (v' - ½) =

To find the inversion curve, ve must have

(l)H = ~p (~ <I) p - 1) = 0

28
or

From the van der Waal.s equation

dp = RdT + (- R:r _ 28:'\ dv

v-b (v-b)2 ,.3)

v-b V
T

thus : (v;b)2 = b

On i:>Jiminatillg v and puttillg the equation 1n tems of the dimensionless variables of problem

5.19, it follows that

T'
6-3/4

(9, 3)

p'

5.21
(a) (1)

We have

-1
a -- V (ov
""°"D -ddT..s -- a' -ddT-a
o-8 ,
p

µ = (~)H : = µ' :

Substituting these expressions into ( l) ve find

(2)

29
 r ,s a'diS'
(b) Fran (2)
1T
T~

0
T
=
J 13•'
0 l +
µ'C
~
V
r

T = TO exp Jr,s
,s a'd,S
µ, C ,
J
[ 0 l + :____,J2_
V

5.22
The system may be represented by the diagram

(a) By the second law

41 42
.6S=T - T~o
For max:IJmJm heat, the equality holds and since '½ = q ..Jfl, it follows that
1

41 Ti
w=Ti-To

(b) ql
V = 11.9

5.23
We have the system

(a) (1)

(b) "3'J the second law,

Thus

It follows that

(c) The maximum amount of vork vill be obtained vben Tf = JT T ' •

1 2

Fram (1)

30
To freeze an additional mass m of water at T0 , heat mL must be removed from the ice-water mixture

resulting in an entropy change 00 The heat rejected to the body of heat capacity C
= - ~.
1
-o { Tf dT Tf
increases its temperature to Tf With an entropy change .6.82 =C IT T = C 1n T. By the
mL Tf V O 0
second law 00 + t::.S 2 = - T + C 1n T ~ O. For min:ilnum temperature increase and thus minimum
1 0 0
heat rejection the equality holds and it follm.s that

The heat rejected is Q = C(Tf-T 0 )

5.25
The probability that the system occupies a state With energy Eis proportional to the number of

states at that energy, n(E). By the general definition of entropy, S = k ln n(E), we have for the
probability
P ex: n(E) = e 8/k (1)
To raise the weight a height x, an amount of energy, mgx, in the form of heat, Q, must be given

off by the water. The temperature change is found from

Q = C'AT = -mgx

t:il: = -mgx/c
vhere C is the heat capacity of 'Water. For a mole of liquid and x = l cm, t:iJ: is on the order of
4
10- °K. Hence we may approximate the water as a heat reservoir and find for the entropy vhen

the weight is at height x

S=S _2:.._=S
o T o
0

vhere S is the entropy at height x

0
= O. Thus (1) becomes
-mgxjkl' 0
P(x) = Ae
sjk
Here we have absorbed the te:rni e into the constant A wbich is found to be kTjmg by the

usual nomalization condition. Then the probability that the veight is raised to a height Lor

more is
co co kT -mgxjkr -mgLjkr
(? =
1L
P(x)dx =
1 L
-2 e
mg
O
dx = e 0

Substituting L = l cm and the given values yields

C? = e-1018

31
In the procesS:S a -+ b and c -+ d no heat is absorbed, so by the f'irst law 'W = -6E, and since

~ = mT, ·where C is the heat capacity, we have

wa"'b = -(¾-Ea) = -vc;, (Tb-Ta)

We~= -(Ed-Ee)= -vc;, (Td-Tc)

Hovever, in an adiabatic expansion TV?'-l = canst.

T V 7-l
Hence wa,b = -vc;, Tb (1~ = -vc;, Tb (1- <v:) )
7-l
wc,d = -vc;, Tc G: -1) = vc;, Tc (1- (:~) )
The volume is constant in :process ~c so no vo~ is :performed.

Thus

CB'.API'ER 6

Basic Methods and Results of Statistical Mechanics

6.1
(a) The :probability that the system is in a state with energy E is proportional to the Boltzman

factor e-E/kr. Hence the ratio of the :probability oi' being 1n the i'i.rst excited state to the

probability oi' being in the ground state is

e
-3~/oo
--Hw/~ =
e
(b) By the dei'ini tion of mean value

1 + 3e -iiwjkr
1 + e -15.wjkr
6.2
The mean energy per particle 1s

µ He-µR/kr - µHeµ.H/kl'
e ==
e-µifi'ki:r +eµH)\!r

Hence i'o~ N particles, E = -NµH tanh I

32
6.3
(a) The :probability that a spin is parallel to the field is

eµRjkr l
p = e -µHflci' + eµR/kT = 1 + e - 2 µR/k.T
vhich yields T = k J.n[fyl-P] (1)
For P = .75 and. H = 30,CXX) gauss, T = 3.66°K

(b) Fran (1), w"'ith µ = 1.41 x lo-23 ergs/gauss, T = 5.57 x 10-3 °K

6.4
The power absorbed is :proportional to the difference in the number of nuclei 1n the two levels.

This is,

·w'here N is the total number of nuclei. Since µR << kr, ve may expand the exponentials and keep

onzy the first two tenns.

(1 + ~ - 1 + ~)
Hence, n - n .., N ___
kT"'-_ ___,;;_ =
+ - 1+~+1-.@
kT kT
1
Thus the absorbed power 1s proportional. to T- •

:p(z+dz)A
_ _ _ _...__ _ _ z + dz
The volume element of at2!1osphere shown must be 1n
equilibrium under the forces o:f the pressure and ...,_--+-------~ z
mn(z)Adzg p(z)A
gra:nty. Then i:f m is the mass per :particl.e, A
the area, and g the eccel.etation of granty, we

have
p(z+dz) A - p(z)A =~dz A= - mn(z) A dzg

Substituting the equetion of state, p =~leads to

dn(z) - - 5 n(z)
dz - ~

Thus n(z) = n(O)e-mgzjkr

33
6.6
E
(a)

As T approaches O the system tends to the low energy state, while in the limit of high tempera-

tures all states became equal.ly probable. The energy goes :from the low to the high temperature

(b) The specific heat is, C.., oE)

= (~ , i.e., the slope of E.
V

(c) _N\.l ~~:~:::1

tl+e - J
+_

and

To find the temperature at which E changes limit, we

evaluate T vhere
-
E-Ne:
N e:l+e:2
[ J
- 1 +-
2 -- 2 - e :l

which yields

34
The heat capacity is

and f1v -+ 0 as T --. o, T -+ cc •

(a) The mean energy per mole is

-e;...., 2 NA e:e -e:/kT

Oe -OJ,,.m
/A.I. + 2e:e ,~
E = N
A
(l)
l + 2e -e:jkT l + 2e-e:jkT

where NA is Avogadro's number.

NA
(b) We find the molar entropy from the partition function z. Clearly, Z = ~ where
-e: .j.kT
t =~e 1 , the sum being over states of a single nucleus.
i
Thus

and s = k (1n z + ~E) (2)

(c) As T -+ O, the nucleii go to the ground stat~, and by the general definition of entropy

S=Nklnn=Nklnl=O
A A

as T -+ =, all states become equally probable, n -+ 3 and

It is easily verified that expression (2) approaches these limits.

CV
(d) From (1) we have

T
6.8
The polarization, ~ is defined a.s
N is the number of negative ions per unit volume,
e is the electronic charge, and i
N ~ where

is the vector
0
£, 0
>e

from the negative to the positive ion. Then the

0 a
0
35
aean x component of Eis

p
X
= !Pl
-
cose = Ne It!
-
lt_xl = Ne X
vhere x .nd e are shown in the diagram. The positive ion can have energy + e;a or - e~a ,

and since there are two lattice sites for each energy ve have
ela ~ _~ ~
(~) e 2 + (- ~) e 2
F = N e - - - - - - - - - - - - - - - -_ ~
2
tanh e!a
2ld'
x et'.9. ~ _~ ~
e 2 + e 2
6.9
(a) The electric field is found from Gauss's Theorem

Ia~ •£ da = lm-q
A
vhere q is the enclosed charge and£ is the vector normal to the surface, a.

By symmetry, Ea= E 2rrr L = lm-q

E(r'
- !.I
=_gs,~
rL -

The electric potential is given by

U(r) = ir ~--~ 0
=- f!l ln ~o

Since U(r) = -Vat r = R,

0
ve can evaluate q.

Thus E(r) = r ln rR
V
0
A
! , U(r) =
- ln R
V ln !,_
ro
ro
(b) The energy of an electron at position! is qU(!) = -eU(r) vhere e is the electronic

charge. Since the probability of being at! is proportional to the Boltzmen factor, ve have

for the density

= p(O)
(0
!...
r
-ev~ ln(R/r )
o

6.10
2 mw2r 2
(a) The centrifugal force mw r yields the potential energy - - 2- . Since the probability that
a molecule is at r is proportional to the Boltzmann factor, the density is
2 2
p(r) = p(O) exp [mw r /2kT) (1)
(b) Substitutingµ= NAm, the molecular veight, into (1) and evaluating this expression at r
1
and r ve have
2
6.ll
The mean separation, x, is found from the probability that the separation is between x and x+dx,
_ U(x)
P(x)dx cc e kT dx

12 6
Where u(x) = u0 [<!) X
- 2(!)
X
]

It is easily verified that the minimum of the potential is at x = a. Since departures from this

position are small, ve may expand U(x) about a to obtain

36 U0 2 252 U0
U(x) ""' -U0 + -2- (x-a) - 3 (x-a) 3
a a
vhere ve have kept only the first three terms. It follows that
2
36 U (x-a) 252 U0 (x-a) 3]
P(x)dx = C exp [ - a~o + a~ d.x

We have absorbed the irrelevent constant term, e- Uc/k'I', into the normalization constant C.
This constant is eval.uated from the usual. requirement
00
1 00
36 U0 (x-a}2] . [ 252 U0 (x-e.)3]
1co
P(x)dx = C
O
exp
[
- 2
a kT
exp
3
a.k.T
dx = l

The predominent factor in the integrand is exp t36 U0 (x-a) 2/a~] so the second factor may be
expanded in a Taylor's series as in Appendix A.6. Furthermore, the region of integration can be
extended to -co since the exponential is negligably small except near a.

Thus (1)

vhere ve neglect all but the first two terms. The first integral is evaluated in Appendix A.4
vhil.e the second is O since the integrand is an odd function.

Then
6
C=-
a
cu;1_?,._
iT kT

By definition, x= J~ x P(x) dx, and to the same approxillla.tion as in (1) we have

36 U0 2] ( 252 u0 (x-a)3)
exp [ - -a 2-kT
- (x-a) l. + -------
a 3k.T
dx

The first term in the integrand is a Gaussian times x and the integral. is just a. The second

may be eval.uated by making the substitution~= x-a

37
 -
X =a+
K u~½
-
0
7rk1'

Noting that the second integral is O since the integrand is an odd function, and evaluating the

first by Appendix A.4, we find

1 dx .15 ak .15k
Thus a= - dT = au + (.15)ald' ~ ~ since U
0
» kl'
X 0 0

6.12
(a) Let the dimensions of tl:e box be x, y, z. Then the volume and area are

V = xyz A = xy + 2yz + 2xz (1)

EJirninating x,. we have

V = yz A - 2yz
y + 2z

av av
From the conditions for an extremum, ~=oz = O, it follO'ws that
.
(A-2yz) (y+2z) - 2yz (y+2z) - y (A-2yz) = 0
(2)
(A-2yz) (y+2z) - 2yz (y+2z) -2z (A-2yz) = 0
l l
A2 A2
Subtracting these equations yields y = 2z. Then substitution in (2) gives y - - z - -
1
A2
- E ' - 2J3'
and from (1) we find x = ./3 .
(b) From equation (1), we have
dV = yz dx + xz dy + xy dz (3)
The equation of constraint is

g(x,y,z) = xy + 2yz + 2xz - A= 0 (4)

and Adg = A(y+2z) dx + A(x+2z) dy + A(2x + 2y) dz= 0 (5)

Adding (3) and (4) and noting that the differentials are nO'W independent, we have

yz + A(y+2z) = 0

xz + A(x+2z) = 0 (6)
xy + ;\.(2x+2y) = 0

We multiply the first equation by x, the second by y, and the third by z, and add.

3xyz + A(2xy + 4xz + 4yz) = 0

Substituting (4) yields
A=-~
2A
and substituting ;I.. into equations (6) gives

l - ~ (y + 2z) = 0

l - i (+ X 2z) = 0

1 - : (2x+ 2y) = 0

The first two equations show that x = y and the third yields x = ~- Then substitution in the
Alfa Alfa Alfa
first and second equations gives x = .,,/3 , Y = , z = .fj
13 2

6.)3
S + S = -k L. P (l)ln P (l) - k L. P (2)1n p ( 2)
l 2 r r s s
r s

But since L, P (l) = L. P (2 ) = l, we may write

r r s s
s + s = -k L. L. p (l)p (2)ln p (1) _ k L. L. p (2)p (l) 1n p (2)
1 2
r s rs r s r s r s

= -k L. L. p (l)p (2) 1i.n_ p (1)+ 1n p (2~

rs r s l:- r s J
= -k L. L. p (l)p (2)ln p (l)p (2)
r s r s r s

= -k L, L, p 1n p since P (l) p ( 2) = p
r s
rs rs r . s rs
6.14
From the definition, we have

S + S = -k L.P (l)ln P (l)_k L. p (l)ln p (l) (1)

1 2 r r s s
r s
SubstitutL".lg P (l) =LPrs 2
r and P ( ) =L P in (1) we have
s
s rs
r

s1 + s2 = -k r, r, P 1n P (1)_k r, r, P 1n? (2)

rs rs r rs rs s

= -k L, L, p 1n p (1)? (2) (2)

r s rs r s
For the total system, the entropy is

s = -k L, L, p 1n p (3)
r s rs rs
Then from (2) and (3)

s-(s +s )
1 2
= -k r, r, p 1n p + k r, r, P 1n P (1)p (2)
rs rs rs rs rs r s

= •k LL Prs ln
p (l)p (2) (4)
r s
r s
39
(b) Since -1.n x ~ -x + 1 or l.n x ~ x-1, we have

l.n p (l)p (2)

r s
- 1

Fran (4), s-(s1+s 2) = k Z: I: p 1n r

p (l)p (2)
P5 ~ k r, r, p
(p (l)p (2)
r s
rs rs p
rs rs rs rs

But since L. L. P (l)p ( 2 ) = 1, it follows that

·r s
r s
s-(sl+s2) 5 k r, Lo Pr(l)Ps (2)_1 = 0
r s

6.15
(a) Since S = -k L. Pr l.n Pr and So = -k Lo Pr (O)l.n Pr (O) ' we have
r r

S-S
o
=kL.
rLr r r
\_p
lnP +P lnP (O)_p lnP (O)+P (O)lnP (OJ
r r r r rJ
(l)

vhere we have added and subtracted the term k Lo P 1n P (o). We show that the sum of the last
r r
r
two tems in (1) is zero.
-,3E
Since P (0 )
r
=e r;z

1n P (O) = -f3E - 1n Z
r r
Then using Lo P = 1, ve have
r r
-!: p
r
ln p (O) = f3
r
L Pr Er + L. P ln Z =
r
~E + 1n Z
r r r

Similarzy Lop (O)ln p (O)= -13 Lo P (0)3 - Lo P (C)ln z = -p3 - 1n Z

r r r r r r r r
Addi:cg, we obtain
_z p 1n F (0) + :z ? (0)1.n p (0) = 0
r r = r r r
Thus (l) becom:::s
p (0)
s-s = k L, -P 1n p + p 1n p (O)] = k Lo p 1n _r__ (2)
[ r r r r r Pr
0 - r
P (0) P (0) •
(b) Since! 1n -f-- ~ T - J.,eq_uation (2) yields
r r ~O)
s-s o ~kl'. Pr r
P = 0
r r

consequentzy S
0
~ s.

40
 CHAPI'ER 7

Simple Applications of Statistical Mechanics

7.1
th
(a) We label the positions and momenta such that r .. and p.j refer to the j molecule of type
-iJ -1

i. There are N. molecules of species i. Then the classical partition function for the mixture
J.

of ideal gases is

ZI 1 exp[- ~l (:2.1/+. • ,+E_lNl2) • • •

The integrations over~ yield the volume, V, while the E_ integrals are identical. Since there

The term in brackets is independent of volume, consequentzy

ln Z' = (N + ••• +Nk) 1n V + 1n (constant)

1
and - lo 1
p = §" dV 1n Z' = (Nl+ ••• +~) fN

pV = (N1+ ••• +Nk)kT = (v 1 + ••• +vk) RT (1)

th
(b) For the i gas, piV = viRT, hence by (1)
p = I: p.
i l.

7.2
(a) By the equipartition theorem the average value of the kinetic energy of a particle is
-€ = 23 kT.
(b) The average potential energy is
iL mgz e -i3mgz dz

u
f 0
Le -pmgz dz

Then

On carrying out the differentiation, we find

u=kT+ mgr.
l - emgLjkr

41
7.3
{a} Before the partition is removed, we have on the left, pV = vRT, After removal the pressure

is
_2vRT_~
Pr -(1+1i)v - 1+b

(b)

Si a vR r
The initial and final entropies of the system for different gases are

N:v + i ln T+o~ + vR r~:v i + ln T+aJ

Sf a vR r (l;:lV + ~ 1n T+o~ + vR r(l;~lV + ~ 1n T+o~

Here one adds the entropies of the gases in the left and right compartments for Si while sf is
the entropy of two different gases in volume (l+b)V.

Then !::,S = S -s .
f l.
= vR
t21n V(l+b)
__.__.._ - 1n - V - 1n bV
NAV
-
NAV
J
NAV
= vR 1n
(l+b)2
b

(c) In the case of identical gases, S.l. is again the sum of the entropies of the left and right
compartments. Sf is the entropy of 2v moles in a volume (l+b)V.

sl.. = vR 11n ..,;!,__ + .11n T+cr

L NAv 2
7 + vR L!in bNVAv + .11n
~ 2
T + crl
~

2
Thus = vR 1n (14~)

7.4
(a) The system is isolated so its total energy is constant, and since the energy of an ideal gas

depends only on temperature, we have

or

The total volume is found from the equation of state

Vl RI' l V 2RI'2
V=--+--
pl P2

Thus the final pressure is =

42
(c)

7.5
We take the zero of potential energy so that if a segment is oriented parallel to the vertical

it contributes energy Wa and if antiparallel it contributes -Wa to the total energy of the rubber

band (Thus if the rubber band were ~ extended, the total energy would be -Nila). Since the

segments are non-interacting,

Since the total energy is additive,

where U is t he energy of interaction, the eq_uipartition theorem still applies and

7.7
I:f the gas is ideal, its mean energy per particle is
2 2
PX Pv
e = 2iii + 2m = :k!r
and the mean energy per mole becc:mes E = NA:k!r

Thus

43
For classical. harmonic motion the mean energy is
2
-E-L+-mw
1 2 2
- 2m
x 2

By equipartition, each of these terms contributes½ kT.

Hence
2
P"'X o:T

7.9
(a)
The mean elongation is found by equating the gravitational and restoring forces

cix. = Mg, thus

(b) By the equipartition theorem

½a (x-x)2 = !2 kT

(x-x)2 kT
or
a

(c)

or M - -Jkr a'
g
2

7.10
(a) Let the restoring force be -ax. Then the mean energy of N particles is

- 1 72 1 2 )
E = N <2 mx + 2 ax

By equipartition -E =N 1 kr + -1 kT )
(- = N kT
2 2

Thus C
oE
=?!r=Nk

(b) If the restoring force is -ax3, the mean energy per particle is

J_ 72 1 4
E:=
2 mx + 4 ax

The kinetic energy term contributes ½kT by equipartition. The mean of the potential energy is
found from

J~ exp [- ~ ] ~ dX
=

J~ exp [- ~ ] dX

44
 1 4
where we have made the substitution, y = 13 / x.

¼in 13 + 1n Jco...., e -czy /4

4
Thus
d = -
O (-
¥ 1
dy) = 4p = 4 kT
1
4

1721"""'1i'.
Hence €=
2 mx+ ax = l kT+ 1 kT= 3 kT
4 2 4 4
Then the total energy is E = NE and

7.11
Since the :probability of excitation is proportional to e - kT where n is an integer, it is

clear that the two parallel components are negligibly excited at 300° where i:iw11 >> 300 k.

The perpendicular component is excited since hw << 300 k; and since 300° is in the classical
1
region, the equipartition theorem holds and we have for the mean energy per mole
1 ~ 1 22
E = NA (2 mx + 2 mw l x ) = NA kT

Thus

(a) Consider a cube of side a. The force necessary to decrease the length of a side by .6a is
K !::,;a. and therefore the pressure is t::,.p = K 6a/a2 • The change in volume is !:::,.V = -a2.6a.
0 0

1 a 26a ) a
Hence K = = - a3 ( - K .6a/a 2 = Ko
(1)
0
I
(b) The Einstein temperature is eE = hwjk. Since w = ~Kd1m where m is mass, we have from (1)

(2)

The length a is found by considering that the volume per atom is µ/ pi-IA whereµ is the atomic

weight, p the density, and NA is Avogadro's number.

1/3 63 •5 1/3
Thus a=(_H._) =( ) =2.3Xl0-8cm
pNA (8.9)(6X1023 )

Substitution of m = µ/NA and the given values yields

GE"'"' l50°K

45
7.13
'We have Mz = Ng µ
0 0
J B/71). By equation 7.8.14, ~ (71) for J =½becomes

B_21(71) =2 (coth 71 - 12 coth ~2) = 2 sinh

cash n -
71
cash
sinh
t~f~1
2 2
= 2 cosh ({/2) + sinh (//2) cosh
2 sinh 71/2) cosh (71 2) sinh

sinh
2 ( /2)
sinh (71J2) cosh (71/2)
Thus

-
The energy of the magnetic moment in the field His

E = -1:_•1! = -µH cos e

where e is the angle between the magnetic moment and the direction of the field or z-axis. Then

the probability that the magnetic moment lies in the range e toe+ de is proportional to the

Boltzmann factor and the solid a.ri..gle 2rr sine de.

Thus P(e)de « epµHcose sine de

w
·'o
J 'IT
e
SµH cos e sin e de(µ cos e)
0
and
1'1z = N0 µ Z =
J 0
n eSµH cos e sin e de

i:,µ:! -;3µH
or No
H
o
~
1n r -;re ;3µH case .
sin
e de
=
e - e
e ,., o

= No ~
~A
1n 2 sinh
~ H
~µH _
-
No
. . -... "µH
[ µHpcosn
• . ,..," µH - sinh pµH ]
H ~,-, pµ F.B SJ.Il.H ...,

We have (1)

46
 1ere by (7.8.14) B
J (Tt) = J- ll (J l
+ -)
2 coth (J + -)Tt
l
2 - -2 l l~ coth -2 Tl

I f Tl << 1 and J >> 1 in such a way that JTt >> 1, B (Tt) becomes
3

Bi Tt) = J f coth JTt - ½(~~ = coth JTt

1
JT)

-where we have used

X -X
coth x = e
X
+ e
-X
= (l + X + •••~ +
(1 + X + ••• -
?l1 -- XX ++ •••~
•••
::::: -1X for small x
e - e

whereµ= gµ J is by (7.8.2) the classical magnetic moment.

0
Then (1)
becomes
:i-,1z = N0 µ ~oth pµH - P~

,
For spin
(a) The energy of a magnetic moment in a field is E = -1:. • ~- 2 atoms

(b)

n(z )/n(z ) > 1

2 1
since n2 > :a:1 .

(c) Ii' µH << kl' we have

+ (l - µH 2.....R + !2 µ ~ ? 2,::2)
...,
and
1 2 2 2
+ (l - µHl~ + 2 µ Hl (3)

7.17
To find the fraction,;, of molecules with x component of velocity between_-:;; and v, we must

integrate the distribution between these J.illlits, i.e.,

47
 ; P,}
=f-Jti!!. (-~-/
.l -(mv 2/2kT)
s = .±
n J_-:;,
g(v )dv
X X 2rrkT
e x dv
X

m
Making the change of variable, y = ~ vx, we have,

s = -1 Jfi' e- y
(2/)
2 dy = L 1 2 2
e -(y / 2 ) = 2 erf 42
Ji;; --12 ,/~ 0

Then from tables s = .84-3.

In problem 5.9 we found that the velocity of sound is

1

u = czm)2
µ

where , = C/Cv and µ is the atomic weight. Since µ = N~,we have

1 l
u = czm) 2 = (Z:kT) 2
NAm m
.l
The most probable speed is ~ = (2kT/m) 2 • Thus

For helium, 1 = 1.66 so that u = .91 ~ and the fraction of molecules with speeds less than u is

s =
1 1°91v
n O
,.,

F(v)dv = 47!"
1
O
·91(2kT/m)
1
-
2

(;kT)
-::i
,,,!,.
2
v
2
e
mv2
- 2kT
dv

.l
Making the change of variable y = (m/ld') 2 v, we have

s =4trr~ 1.91./2 2 - 2/2

y ey dy
0
(2rr)2
a _ 2/2
This integral :rn.ay be evaluated by noticing that integration by parts of
l O
e y dy yields

/21 a + 1·a y 2 e-y2/2 dy

10
a e-y2;~~ dy = ye-y2
0 0
Since the integral on the right is the required one, we have,

The integraJ. on the right may be evaluated from tables of error functions. Thus we finds = .r,.

48
7.19

(a) V
X
= 0 by symmetry (d) (vX 3 v)
y
= vX 3 vy = 0

(b)
2
V
kl'
= - by eq_uipartition (e) (V + bv ) 2 = 2
V + 2b -V -V + b 2V 2
X m X y X X y y

(v2 V) 3 + 2 - 2 -V ) = (l+b2) kT
y VX +
(c) = (v V V = 0
X X Z X 2 m
(f) V 2 V 2 = (k'I')
X y m
7.20 2
mv
(a) TT-7vY = !n Jco r{tl dv =J"" 4n C21rm"ld')
Q V 0
3/2
ve 2kT dv
l
2m 2
By appendix A.4 we find n:Tv; = (7rkl') , a.".ld since v =

(l/v) = ~ = 1.27
(1/v) 7T

1 2 2 ~
{b) Since the energy is € =
2 mv , we have v = 2€/ m and dv = d€/ ...; 2m€. On substituting these

relations into the speed distribution F(v) dv, it follows that

3 €
- - l - -
F(€)de = 27m (nkT) 2 2
€ e kl' de

7.21

rhe most probable energy is given by the condition ~(e) = 0 or from problem 7.20b
E l €
1 1 - kl' €2 e - kl' = 0
~ e -kl'
.... 1
Thus E =2kl'
.... 1..
The most probable speed is V = (2kl'/m) 2
1 -2
Hence 2mv =kl'

7.22
V
(a) V = V
O
(1 + ~
C
) = V
0
since v = 0
X

(b) Therms freq_uency shift is given by

~
- l

(.6v) rms = =
2
v
-21
-vJ
2

But
2
'V = V
2
0 ~+ ~ x + ~

Since v = 0 and v
2 = kT/ m by equipartition, we have
X X
 l

~
2 kT 2 2 2 Vo
Thus (~v) = v O + -2v 0 -v~
rms O C
me
(c) The intensity distribution is proportional to the distribution of the x component of

velocity.
2 2
- me (v-v 0 )
I(v )dv = I 0 exp [
2
2kT Vo

where I 0 is the intensity at v=v •

0

7.23
(a) The number of molecules which leave the source slit per second is

= 1.1 x 10
18 molecules/sec

where A is the area of the slit.

(b) Approx:il!lating the slit as a point source, we have by (7.u.7), the number of molecules
with speed in the range between v and v + dv which emerge into solid angle an is

A~ (v) d3z = A[f(v)v cos e][v

2
dv an]
cos e~ 1 for molecules arriving at the detector slit; hence the total number which reach the

detector is 13Jnv2
e- - 2 -dv = (1)

where we have used the results of appendix A.4 and ps = ~. Letting L = 1m. be the disiance
2
between source and detector, the solid angle nd is approx:il!lately A/L • Substitution of the

given values into (1) then gives 1.7 x 10

11 molecules/sec arriving at the detector slit.

(c) In the steady state, the n1.nnber of molecules entering the detection chamber per second is
equal to the number being emitted. From (1) we find

or Pd
-
= Ps A
= 2. 4 x 10
-8 mm of Hg.
2
TIL

The rate of change of the number of particles in the container is given by

dN l -
dt = - cpA = - 4 nvA

50
Since the pressure is proportional to the number of particles, we have

dp vA
-=
dt - 4Y p

or p(t) = p(O) exp t*~

where p(O) is the original pressure. Hence the time required for the pressure to decrease to

p(t)/p(O) = 1/e is 4v
t -
VA

7.25

As in problem 7.24, we have

or

where p(O) is the original pressure. The mean speed, v, is for nitrogen at 300°K,

v = J~7f
k:T' =
m
.!n5 x 105 cm/sec

Thus
_ 4(4n/3)(1c?) 10-6
4007 sec
t = (.475 X 105 )(1) 1n 10-l =

1
(a) Since the rate of effusion is~= p/(27r m kT) 2 ,and the concentration is proportional to the

pressure, it follows that

(b) For the uranium separation, we have

1
238 + 6 19 )2
c'235I C'238 = c235I c238 (235 + o 19 =

The rate of change of the number of particles inside the container is

dN
dt = -
l -
4 nvA = - 4V
NA j8-rr m
k:T'
= -
;>,.:r,r
"-Jm

thus defining i... Since pressure is proportional to the number of particles, we find after

integrating
(1)
For Helium gas p/p 0 = 1/2 at t = 1 hour. Su:t,stituting we have

;>,.=~ln2 (2)

51
where ~e is the mass of the helium molecule. From (l) and (2) it follows that the ratio of the

Ne and He concentrations in terms of the initial concentrations is

~e/~e = (~/~e)
0
exp [-,. ~/.;~e' - 1 1,/m;;J ~
= (~/~e) 0 exp [-1n 2 (J~./,e' -~ ~
Since (~/~e) = 1, we have at t =1 hour,
0
I (1-J~/,e,) (1- j~/~e' )
7fe-' 11He = 2 = 2

(a) The rate of change of the number of particles in the left side of the box is

dNl(t)
dt = (no. entering/sec)-(no.escaping/sec)

Since the rate of effusion is f nvA, we have

dNl (t)
dt =
Av r ;J
Ii.il,72° LN2<t)-N1<tj =: I:
- '1
r-2N1<t2J
where N is the total number of particles. From the equation of state,
P1 (0) + P2 (o) V
and N = -----
2
-
kT
(1)

Thus

_Av t
Integrating,ve find e V

(b) Tbe initial entropy is

Si= Nl(O)k (1n 2N:(O)

In final equilibrium, N1 = N2 = ~

Sf = Nk (ln ~+~ 1n T + v0 )

52
7.29
(a) Inside the container vz =Oby symmetry.

{b) The velocity distribution, <1>(:!), of the molecules which have effused into the vacuum is

<I>(v) d 3v d 3v
- - = f(v)
- V
z

.... is the Maxwell distribution.

where f(v)
mv 2
z
J~dvxf~ dvy f f 2
00 00
- 2kT
dv <I> (v) V
dvz e V
O z z 0
z
Thus V = = 2
f dvxf"" dvy f
z 00 00
mv
dvz <l> (v) z
f
00
-co -co 0 - 2kT
dvz e V
z
0

The second equality follows because the integrations over v and v are identical in the numera-
x y
tor and denominator and therefore cancel. The integrals over vz are tabulated in appendix A.4.
3
~ (21;)2
VZ a ½(~) aJ~ 1;;'
7.30
(a) In t:i.!lle dt, molecules with velocity ccmponent v
z
which are in a cylinder of height v
z
dt

·with base at the aperture can escape from the container. Molecules of higher speed can escape

from a larger cylinder than can molecules of lower speed, and a proportionalJ.y larger share of

the fast molecules effuse. Thus the mean kinetic energy of particles in the beam is greater

than in the container.

l 2
J d3v
-
!2 mv
2
<l> (2::)
(b) EO = 2mv =
J 3
d! 9 (~)
Since <I>(_!) = :r(;:) V COS e and d3v = V2dV .
S1!1 e de dqi, we have
mv2
oolrr/2J,ro1T(v2
€0
i
=--------------------------
dv sine de d~)( 2 mv) e
1 2 - 2kT
v cos e

f f-rr/J,-rr
00

O o O
(v2 dv sin e de dcp)

mv2
-l m
2
J""-.? -
0
~ e 2kT dv
= ---------- = 2k.T
mv2
e - 2kT dv

where the integrals over v are evaluated by appendix A.4. Since the mean kinetic energy in the
the enclosure is e;i =
. - 3 4-
2 kT, it follows that e:
0
=
3
e;i.

7.31
When a molecule is scattered, it commutes momentum l:.p = 2mv to the disk. The force is
z z
l:.p / at. To find the total force, we must multiply l:.p /at by the number of molecules with
z z
velocity in the range (v,
,v
dv} which strike the disk in time dt and then integrate over all

velocities. Clearly only molecules in the cone of half-angle e = sin-l R/L will strike the
0

disk.
F Jd3~ [A~ (!) at]
= ~!z

2
= J:°"J:ei2rr(v dv sine de dcp)(A f(v) v cos e d_::)(2m ;/os 8 )

= (2mA.)(2rr)(- 1 cos 3e) le 0

I 3
J°"v4 f{v)dv
0 0

The integral can be expressed in terms of the mean square speed inside the container, i.e.,

! °"4
0
v f(v)dv =
2
~

8
Thus F 1 nm 2
=3 v A ( - 1 cos 3e) 0 = 31 nm 2
v A [ 1 - cos 3 (s-i.,..,
.,_....-1 _RL)]
3 O

But by eq_ui:i;,artition we have

1 2 =nkT=p
-
3 nmv
Hence F = pA [1 - cos 3 (sin-l f)]
CHAPI'ER 8
Equilibrium between Phases and Chemical Species

8.1
By equation (8.3.8), we have the proportionality

(?{v,T) dV dT o: exp [ -G0 (V,T)jk.r 0 ] dV dT

where V and Tare the volume and temperature of the portion of substance of mass M, and T is
0

the temperature of the surrounding medium. Expanding the Gibbs Free Energy G (V,T) about the
0

minimum at V = V1 and T = T yieldf

(1)

54
where the derivatives are evaluated at T = T and v = v. Since we are expanding about a mini.mum
. ,
the first derivatives in (1) are O. By (8.4.7)
cG
(dT 0) (2)
V
Since this is Oat T

Thus

and at T = T0 = T, ( c2GD
"T2
C:
V
From (2) we also find the mixed derivative
cG T cC
(~) = (1 - ~)(~) = 0 at T
ar v T T av
By the equation preceding (8.4.13)
cG
( "-vo) = (T-T ) (¾-)
"s
0 T O C T

)(els~ - (ffe) ----

( ~p) = To , = .....V
?,v2Jr
= (T-T = , at T V
o oV T oV T

1
By definition, K = Substitution of these results into (1) yields
VK

G (V,T) = G (V,T ) + -CV (T-T

)2 1 ..... 2
+-:::-- (V-V)
0 0 0 2T 0 0 2VK

and since V = r~/p 0 and CV = McV where ~ is the specific heat per gram, it follows that

(?(v,T)dV dT • exp t:;/ (T-Tf - 2M: k'.1'

0

0
(V - Mjp 0 )j dV dT

where we have absorbed the constant term G

0
(v, T) into the normalization factor.
0
Performing tl::e

usual normalization, we find

(?(V,T) dV dT =~~;,,:;/exp t Mc
_V_ (T-T
2.kT 2
0
o
)2

8.2
(a) For the solid, l.n p = 23.03 - 3754/T and for the liquid l.n p = 19.49 - 3(£3/T. At the
triple point, the pressures of the solid and liquid are equal.

55
hence

(b) Since 1n p = - t + constant vhere t is the latent heat, we have

t suu~lima t·ion = 3754 R = 31,220 joules/mole

tvaporization= 3c;63 R = 25,48() joules/mole

(c) tfusion = tsubl:ima.tion - tvaporization

= 31,220 - 25,48'.) = 5740 joules/mole.

The latent heat of sublimation is equal to the sum of the latent heats of melting and vapori-

zation, i.e., tS = t m + tV. Since t = T6V (dp/dT), the Clausius-Clapeyron equation,where vis

the volume per mole, it follovs that

(:)s a To(vg~s- vsol) ~o (vliq- vsol)(:)m + To(vgas- vliq)(:)J

or

8.4

Since I = ~ and l::,.S -+ 0 as T -+ 0 by the third law, it follovs that : -+ 0 as T -+ O.

8.5

(a) Q/1 moles/sec evaporate and are svept out by the pump. Then by the equation of state
Q pm"/ QRI'r
E = Rr or pm= LY
r
(b) We find the temperature at the pressure pm from the Clausius-Clapeyron e~uation

d"D L L
dT = T(vgas - vliquid) :::::s T vgas
where we have neglected vliquid since the volume per mole of the gas is much greater than that

of the liquid. Then using v = Rr/p we find

gas

1
R T
c!... - !...)
T
o m
-1
TR
o pm )
Hence T
m
= T O\
{ - T 1n ;;-
-o

56
8.6
The intensity, I, is given by

Differentiating with respect to T and dividing by I,we have

(1)
Since pis the vapor pressure, the Clausius-Clapeyron equation yields dp/d.T.

dp L L
dT = T(vgas - vliquid) ""T vgas

Substituting into (1) and using v

gas
= Rr/p gives
1 dI L 1
I dT = RI'2 - 2T

Differentiating the molar latent heat yields

(1)

(s -s ) is the molar entropy difference between the phases.

2 1

Thus
~A [os2 osl 7
(~) T = T tdP) T - (dP )~

But (os/c)p)T = -(ov,loT)P, a Maxwell relation, and since the coefficient of expansion is

a = -1/v (cv/oT) p ,it follows that

(2)

(~)J
Differentiating at constant p gives

(~P • (s 2 -s 1 ) + T ~~\ -
T(os/'oT) is the specific heat at constant pressure. Thus
p
(~
p
= ¥+ ( P2
C - c"O
-1
) (3)

Substituting (2) and (3) into (1) yields

a:-f.. = -T(a2v 2 - a1.v

d.T 1) fT +} +(cP2 - cpl )
Since

57
8.8
The bar moves because the higher pressure underneath it lowers the melting point. The vater is

then forced up along the sides to the top of the bar and refreezes under ~he lo.rer pressure.

To melt a mass dm of ice, heat -\'..am must be conduc,ced through the bar.. The heat passing through

it per unit time is

J:! = -K: (be) m
a
vhere mis the temperature drop across the bar and x: is the thermal conductivity. Letting x be

the position in the vertical direction, we have dm = p.(bc

l.
dx), and equating the rate at which
heat is conducted to the rate it is absorbed in the melting process ve have

-x: (be)~= t pi (be~) (1)

mis given by the Clausius-Clapeyron equation

d"D ll.p t
dt ""m = -T-,(-v1,-1a_t_e_r___v_i_c_e,...)

vhere v is the volume per gram or 1/p. Then since ll.p = 2 mg/be,

Substitution in (1) yields

dx
dt

From the Clausius-Clapeyron relation, dp/d.T = L/TAv we find

Ja: JD.; = dp

We know L(cp) and ti.V(cp), and we can find dp/dcp from the curve of vapor pressure vs. emf.

Jcp ~vf9co'j
Thus
J T
273.16 T
d.T', =
-
o
.
L
I
d:p
(-)
d~
dcp'

where 273.16°K is the temperature of the reference junction of the thermocouple.

Then

8.10

We divide the substance into small volume elements. Tle total entropy is just the sum of the
entropies of each of these, or

S = Z: S. (E.,N.)
il. l.l.

where Ei and Ni denote the energy and number of particles in the i th volume. If' we consider

58
 th
an interchange of energy between the i and j th volumes,we have since the entropy is stationary
els.l. 2s .
clS = 0 = ~
o~i
dE. +
l. 0i J
dE.
J

but since dE. = -dEj, we have

l.
cs.l. ;sj
2;E. = cE. or T.l. = T.J
l. J

Similarly, if we interchange particles

dS = 0

cs.
].
cs.
m.plies ~
oN.
or
dNi J

8.ll

(a) The chemical potential can be found frcr:n the free energy byµ=~:. He consider a small
0 1{

volume element at height z over which the potential energy may be considered co?J.stant. It is

clear that the addition of a constant term to- the energy does not change the entropy of the

substance in the small volume element. fu..'"Plicitly, the partition f'unction will be the free

particle f'unction times the factor e-~-rnez.

Thus 8 "~ 1n ~free e-;,mg~ + ~ (Ei'ree + mg~ " k [1n 2 free + "freJ
Hence the free energy is, letting N be the number of particles in £::.V

F = E - TS

= ¾1llcr + Nmgz - ~ ~ ~; + ¾Lri T + c J

and _ 6N
µ -
cF -_ .2. -"'..c '"'i'
+ mgz - kT
2

where we have put t::.V/N = ld'/p .

(b) Si.riceµ is independent of z,

~ a:o
dz =mg+pd; =O
kT d-o
or . ---= -
p
Integration yields
:p(z) = p(O) e

8.]2
The relative concentration remains the same. The dissociation is described by

2
nco ~ o
- -- = K (T)
nee~ n
2 2
Generally, when the number of particles is conserved, equilibrium is inde:pendent of v,
59
8.13
The intensity of the I atoms in the beam is proportional to their concentration 7: in the oven.

Since dissociation proceeds according to

We have
2
nI- n_ = K (T)
l.2 . n

K (T)
which gives = ~ = ~(T) (1)
by the e~uation of state. The total pressure is p =Pr+ Pr which yields on substitution
2
into (1)

or

Thus, if the total pressure is doubled, the ratio of final to initial intensities is

-1 +Jl + 8Kpp
-1 +Vl + 4Kp p

Sir..ce KP is small we may expand the square roots to obtain

~f -1 + 1
~-,,--"C""""-~-
+ 49 = 2
c[J_
J.
-1 + 1 + 2Kp-n

8.14
For chemical equilibrium we have

where n is the number of molecules per unit volume. Since ni = :pi/ kT it follows that
b
m
bl+b2+ ••• +b
••• "O
-m.
= (kI') m K (T)
n
= K:,:i (T)
8.15
-./
7'h · .,. s..,~ 1-,
tn••e "".:.i_ c.,r -',,
a~ = dE +p dV. Letting d(:pV) = V dp + p dV we have

-d. G, = dE + d(pv)-v dp

= d(E + pV) - Vdp

= d.H - V dp

where the last follows from th2 definition of enthalpy, H = E + pV. Then if pis constant

-a. Q = d.H

i.e., in a constant pressure process, the heat absorbed is equal to the change in enthalpy. In
a chemical reaction,Q = 6E = L b.h. since enthalpy is an extensive quantity.
i J. J.

60
8.16
B'J the e~uation preceding (8.10.25)
Lb. 1n ~- I = Lb. 1n .ni (1)
i 1 1 i 1

Substitution of ni = pijki' into (1) yields

L
i
b.
1
1n P.
1
=L
i
(b. 1n ~. , + b. ln kT)
, 1 1 1

b
or p m = K (T)
m p

where 1n ~(T) =
_
Li (b.1 1n ~-'+bi 1n kT)
1

Thus d 1n K (T) = L (b. dTd 1n ~-· + bTi)

dT p i J. . 1

€i b.
By (8.10.30) ~ 1n ~it = kT where e:i is the mean energy per molecule. Then multiplying Ti
piVi
by 1 = ILkT we have
1 b. p.V. b.h. 1
d 1 1
dT
1n K (T) = L J.2 Ci.1 + ; ) = L :t. 2
p i kT ~·i i kT

where h.' is the enthalpy per molecule. Multiplying and dividing by Avogadro's number gives
1
d b.h . .6H
dT
1n Kp(T) = L ..1:...1:. = -
i RI'2 Rl'2

where hi is the enthalpy per mole.

8.17
We let~ be the fraction of H 0 molecules which are dissociated. Since the pressure is pro-
2
portional to the number of molecules, we have
PH 2p0
2 2
=---- (1)

The total pressure is the sum of t~e partial pressures.

(2)

Substituting (1) and (2) into

we find
"Dt3
~(T) =------
2 (3)
(1-g ) (2+;)

61
8.18
In problem 8.16 it was shmm that
Lili = Rr
2 9:_ 1n K (T)
dT p

Using ~(T) from problem 8.17 would give M for the dissociation of 2 moles of ~O since the
reaction is 2H 0 -)2H2 + o • Hence for the dissoc~ation of l mole
2 2
2
M = ~ ~ 1n 1),(T)

where ~(T) is given by e~uation (3) in 8.17. Since s << 1, we have

K (T) p<3
= ___s _ _ _- P_53
P (1-s/ (2+s)- 2

2 3
Hence Lill= RT 9:_ 1n Ps =} R1'2 9:_ 1n s
2 dT 2 2 dT

is found by plotting 1n s vs. temperature using the given values and measuring the slope

of this curve at 1700°. We find ~T 1n s = .oo64. Thus at 1700°K

M = ¾(1.99)(1700) 2 (.cc.64) = 56,000 cal/mole

8.19
N
(a) The partition function is Z = ~ wheres is the partition function for a single molecule.

For a li~uid we assume a constant interaction potential-~ and that the molecule is free to move

in a volume N •
V

Thus
0
s = .l:...}' d\:i d 3r e -(f3i /2m)+j3~
h3 - -
0
where the integration is crver N,e,v and all
O
.E•

S = N,e,v0 /TJ h\ J d 3_E e-f3i/2m = N,e_ ef3~ v 0 !;'

0
thus defining s' .
Hence (1)

(b) For an ideal gas, the partition function is

The Helmholz free energy is

Fg, -kT J.n Zg a -kT ~ tg(~Ng_ J.n Ng)

= -kT ~g 1n Vg s I - Ng 1n Ng + N~

62
where we have used Sterling's approximation ln N ! ""'N ln N - N
g g g g
clF
Then µ
g
=~
oNg
= -kT (ln V
g
~' - 1n Ng)

(c) For the liquid, we have by (l)

Ft = -kT (1n [N-f., el3TJ v 0 ~ N,e_ - 1n N,e_, J 0

= -kT (N,t 1n v0 ~ 1 + N,t t,T} + N,e_)

clF,t
Therefore µp
1.;
=~
oN,t = -kT (ln V
o ~1 + t,T} + l)

(d) When the liquid is in equilibrium with the vapor, the chemical potentials are equal or

V
Thus __£ = V ef:>TJ+l
Ng o

but since pjkr = Ngl'vg we have

E.... = e-t,T}
kT ev
(2)
0

(e) We calculate the molar entropy difference from the Clausius-Clapeyron relation.

where in the second equality we have assumed that the molar volume of the liquid is much less

than that of the gas. Since pv = RI' we have

g

Then using (2) in this relation we find

&, = R (l + ~)
The molar heat of evaporation is

L = T6s = RI' (l + fu') (3)

""~=NAT} if TJ>>kT

(f) From (3) ir = l + ~ •

Taking the logaritbm of (2), we find
kT V
1.+.!J_=ln-=ln~
kT pV V
0 0

where v is the volume per molecule of the vapor.

g

63
Hence (4)

when v g and v 0 a re evaluated at Tb·.

(b) In (4) -we can take v to be the volume per mole instead of the volume per molecule since we
have the ratio vg/v 0 • To est:iJnate the order of magnitude of L/RI'b we let v ::::: 22.4 liters/mole
g
4 3 4 -8 3 23 3
and v ::::: - m- N ::::: - 'TT (. 5 x 10 ) ( 6 x 10 ) ::::: 10- liters /mole.
o 3 o A 3
L 20
Thus -:::::ln--:::::10
~ 10- 3

(h) we find L/r~ from eq. (4).

1/T0 L/ T0
V V
0 g calculated experimental
water .018 liters/mole 31 liters/mole .83 cal/ gm°K 1.45 cal/ grn°K
nitrogen . 035 6.4 .37 .64
benzene .C87 29 .16 . 27

These results are remarkabzy good in view of the very simple theory considered here.

Quantum Statistics of Ideal Gases

9.1
configuration no. of states (a)
0 € 3€ M] BE FD
(b)
xx 1 1 --
xx 1 1 -- (c) ~ = e
-€13
+ e
-3€/,
+ e
-4:i,
xx 1 1 --
X X 2 1 1
,
X X 2 .J.. 1
X X 2 1 1

9.2

(a) For an FD gas, we have

-a~E 1
1n z = aN + Z:: 1n (1 + e r) and nr =
r

Hence s = k [ln z + pE] = k r

[
+ ~ 1n (1 + e
-a-pE
r) + P~
;1

64
 but since N = I: iir and E = I: nr €, we :find
r r r

S = k [r.r nr (ct+ /3€ )+

r
Lo 1n (1 + e -ct-/3~r~
r J (1)

1
Fram n = ----- it follows that
r 0:+/3€r
e +l
a+ /3€ r = 1n (1-n)
r - 1n nr (2)
-a-/3€ n
e r r (3)
= 1-l'!
r

Substituting (2) and (3) in (1) we find

s =k Gc nr ln(l-llr) - 1n :n~ :n.:.

r + r 1n (1 + 1-n r
r. ~
= -k z:: InL> 1n :nr + c1-n ) 1n (1-~ ~ (4)
r r. . r:J

(b) For the BE case

-a-/3€
1n Z = aN - Lo 1n (1-e r) and
r

The calculation of S Froceeds in exactly the same way as in (a). We quote the result.

s = -k r r. :nr 1n iir - (1+n)

r
1n (1+n)
r
(5)

(c) Fram (4) and (5) we see that in the classical limit where iir << 1

s ~ -k z::
r
:nr 1n :nr
for both FD and :BE statistics.

9.3
The partition function in sN/NI where
2
s= Lo exp [ - ~11
2m
(it
X
2+ it
y
2 +it 2]
Z
) (1)
it it it
X y Z

. The sum is over all FOSitive

xyz when we use the standing wave solution, equation (9.9.22).
it it it

The density of state is now greater than in the traveling wave case, and by (9.9.25)

If' we assume that successive terms ins differ little from each other, we can aFFrox:il!la.te (1)

with integrals.
Thus
cc
z: e
-
/31'12
2m X
=--K
2
""
io:, e
--K
/31'12
2m
·2
X
L
(~ dK)
7f X
K ::() 0
X
1
L
= (271m)2
X
by (A.3.6)
2mi 13
3
Hence s= 3 V
(2rr m kT)
2
h
vhich is identical to (9.10.7).

(a) The chemical potential can be found from the He.1Jnholtz free energy, F = -kT 1n z.
N
F = -kT 1n fi :::e -kT [N 1n s - N 1n N + N]
3
vhere ve have used Sterling's approximation, 1n NI :::e N 1n N-N ands =
V
(2rr m kT) 2 •
3
h
-:sF •
Then µ = ~ = -kT 1n .s.. (1)
oN N

(b) The partition function for a single molecule of a 2 dimensional gas vith binding energy -e:

- 1
0

is
~' =
~
L
K K
exp [- i3i'i\K 2 +tt 2 )~e: ]
.
2m X y 0
:::e
13
e e: 0 }Jcc exp
~
IL--(
13h
2m
2

X
2
y
2
K +K ) -
A
dK dK
2rr)2 X y
X y 2 2
i3e: -
vhere A is the area. Thus s' = e o s 3 vhere ve put A = -:S .
2
i3e: -
~ o. 3
Hence µ' = -kT 1n N' = -kT 1n e fi' (2)

(c) ~ eq_uilibrium µ = µ' and by (1) and (2)

2
i3E:
l - e o 1;3
N - N'

(2rr m kT)
or
N' . 2
n

Letting n' = N'/A and since pjkT = N/v, ve find

9.5
1
(a) By equation (9.9.14) if L = L = L = L = v3 we have
X y Z

66
 €
r
(v) (1)

(b) p
r
= - cc = 2rr 1S.
(_!:.)
oV
221-~
m
~ 3 (n 2 + n 2 + n 2)
3 X y Z

(2)

(c) The mean pressure is -P = I:r nr P-r where iir is the mean number of parti cles in state r.

Thus P=g_
3V
L.n
r r
€
r
=_g_3 VE

(d) The expression for pis valid for a system in which the energy of a c;_uantum state is given

by (1). For photons,

€
r =

Hence and

(e) The mean force on the wall is found by multipzying the change o::' momentum per collision,

2mv, by the number of particles which collide with the wall per unit time, 1 nvA.
- Hence the
0
pressure is
- 1(-)1- 1 -2
P = A 2mv (ti nvA) =
3 nmv
Letting -2
v ~
2
v we have

(3)

1 ?
since N(~ mv-) = E. Equation (3) is the exact result as shmm in section 7 .14.

9. 6
(a) l\·cP) 2 -- .,.,_ 2 _ :;_2 .
The dispersion is (~ µ µ .,.,ro'ol
By ! ,'= •m •
0
- ?
9 ,5! ,
.,.,-
'-
4 - 2-
- -a ~ , and,_-~--=-
s 2
• . s to ~_,_._n.d .,u.,_ •
~-?~ ~i·~
/ ~

=2 4 ,;-o-
t.., n €
2
by (2 ) in 9.5
gv r r r

--2 4 ?-? 4~
Hence (c.p) = 2 (E- - E:-) = _.2 (c.E)
9V ';3V
' --2 ~2
(b) Since E = - ~ca. 1n Z and (c.E) =
0
1n z, it follows that
,. , ot3 2

67
 4
(6p)2 = -2- l n Z =
c2
4 dE
9V orl - 9V 2 cf3
but by (2) in 9.5, -E = 3 V -P•
2

(6p)2 2 cp 2k.T2 bP
Thus = =
oT
'3"l cl~ 3V

(c) Substituting p ~ kT , W? find

-- V
--? 2 2kT2 N -2, 2
(6p)- /p = - (- kT) ~ (IT kT) = 3N
'3"l V T V

*9.7
The probability that a state of energy€ is occupied is proportional to the Boltzmann factor
-€/kT 0
e • Since the vibrational levels have a spacing large compared to kT, we see that
-€/kl' O 0
e is small and we may neglect this contribution to the specific heat. On the other hand,

the spacing between rotational levels is small so that these states are appreciably excited.

For a dumbbell molecule the rotational energy should be

where A is the moment of inertia and w the a.ngul.a.r frequency. We have neglected rotation about

the axis of the molecule because the moment of inertia is small. At room temperature, we

may use the equipartion theorem yielding €r = kT • Adding the energy of the translational
0

motion gives for the total energy

€=et+ Er= i kTO + kTO = i kTO

Thus the molar specific heat is

The reaction proceeds according to

21ID =

and the Jaw of mass action becomes

= K
n = (1)

From the results of section 9.12, we can immediately write dmm the quantities ;. In the

notation of that section,

68
 V
l t3€'
R2 ~ kr - !2 t,nwH2
[2rr(2m) kT]2 e e
~2 - h3 2
2fi
1 .
3 t3e~ ~kr - -2 f,·i\-- w_o
= y_ [2rr(2M) kTJ2 e 2 2 e 2
~D h3
2 2t?

l f,€' 1
s V
[ 2rr ( m-tM )s:r ]2 e HD
~kT
e
- 2 t3n"1m
HD - h3 112

where we have assumed that molecules are predaminantzy in the lO'W'est vibrational state and have

treated the rotational degrees of freedom classicaJJ.y.

The electronic ground state energies€' are approximatezy equal for the three species since

this quantity is altered onzy slightzy by the addition of a neutral particle to the neucleus

(to form D). Thus

(2)

Similarzy, the moments of inertia are of the form

A = !_ µ * R 2 = !_ ~m2 R 2
2 o 2 m -lill o
1 2
where R , the equilibrium distance between nuclei, depends primarizy on electromagnetic forces.
0

It is then approximatezy the same for the three species, and we have
2 2
~ ~ ~
-2
=
m M mM
<2) (2) (m+M)
- = ~4 (mmM+M) (3)
2 2
FinaJJ.y, the frequency for two masses coupled by a spring of constant K is

Again, K must be the same for the three molecules, a.~d

w =
HD

(4)

Substituting the ~'s into (l) and using the results (2), (3), and (4) yields

Since 7I = 7) , we hz.ve
2 2
or
%D
-=
N

~ l(m·+M)2l
L mM j exp

9.9
In a thermalJ.s" isolated ~uasistatic process, there is no entropy change. Hence by the first lav,

TdS=O=dE+pdV

Substituting E =Vu and p =,½u where u(T) is the energy density, we have

o -
= u dV + V du +
- l-
u oY
3

8v.!t
Thus
-l
V
3 V'
rN'
= J du
u
=
1Tf
T.:L
4 '.fr since -u
dT'
ex:
4
T.
li. Tf
Integrating, we find - .,;. 1n 8 = 4 1n -
3 Ti

Ti
or T
f = 2-

9.10
(a) By the fundamental thermodynal!lic relation

TdS=dE+pdV

Then substituting E= Vu and ii = 31u,- we have

- - 1- 4 - -
TdS=uoY+V~+ urN=ruoY+V~
3
du
But since u is onzy a function of T, du = dT dT, a.."ld. it follows that

4
dS = -3 ~ dV . y d.u dm
.L
.,. (1)
T T dT -

We also have ds = (~s ) dV + (c8 ) dT (2)

oV T 2;T V

Equati.Ilg coefficients in (1) and (2) yields

(~s)
4u
= -3 -T and (3)
oV T

2
(b) Since (c sfev 6T) = (d2S/'cT QV), it follows from (3) that

70
 or

Thus 1n T4 = 1n -u + C where C is the constant of integration. Finalzy -u ~

4
T.

The energy of the black body radiation in the dielectric is

where c' is the velocity of light in the material. c' is related to the velocity of light in

vacuum by c 1 = c/n, n being the index of refraction.

0 0

2
3 4
- 7r (kr)4 n 3 = 4cr n0 VT
Thus E =V-
15 (ct1)3 0 C

Here CJ is the Stefan Boltzmann constant, cr = n2k

4/6o c 2i'i3•
16 CJ n0 3 vr3
Hence =------
C
(1)

Substituting v, the volume per mole, for Vin (1) gives the heat capacity per mole,~'· The

classical lattice heat capacity per mole is~= 3R. The ratio of these two quantities is

c'
V
16crn 3
o
vr3
-=
CV 3Rc

For an order of magnitude calculation, we can let v = 10 cm3/mole and n 0 = 1.5. At 300°K, we

9.12
(a) The total rate of electromagnetic radiation or :pover is
2
P = @(4n r ) = 4rrr2 oT h.·
l.L
= (4n)(l02)(5.7',<10- 5)(10 ) · = 7.2xio
6 22 ergs/sec

7.2 x 1a15watts
(b) Since the total energy/sec crossing the area of a sphere of radius r' = llm must be the

same as that crossing the sphere of radius r = 10 cm, we have

or

71
 = 5.7 X 10llergs/sec c:m2 = 5.7 X 104 watts / c:m2

(c) The power spectrum bas a maximum at

tiwmax he
- kr - ---=3
-krA.
max

Thus

(a) The power given off by the sun is

4 2
P = cr T 0 (4n R)
Half the earth's surface intercepts radiation fram the sun at a:ny time. Renee the ~ower that

the earth absorbs is

The power that the earth emits is

In equilibrium, the power incident upon the earth is equal to the power it radiates, or P.= P
1 e

Thus

T = T /R
o "-J 2L (1)

(b) From Eq. (1) T = (5500)

9.14

We consider the liquid in equilibrium with its vapor (at vapor pressure p). By (7.12.13), the

flux of moJ.ecules incident on the liquid is p/ ./27r m kr' , and this must also be the flux j(
of particles escaping from the liquid. Since J{ cannot depend on the conditions outside the

liquid, this is the escaping flux at all pressures.

Thus
J{ = p
.J27r m kr'

The mass of a water molecule ism= 18/6.02•1023 = 2.99-10-23. Thus for water at 25 0 C where
4 2
P = 23.8 mm Hg = 3-17•10 dynes/cm we have
)( 3.17•10
4
= 1 _14 X
1022 molec~es
= (27rX2.99 X 10-2 3x1.38>0..0-l~ 298)½ sec•cm
At the vapor pressure p(T), the flux of molecules of the vapor incident on the 'Wire is by

(7.ll.13), cp.). = p/ ,J2rr m kr'. When the metal is in equilibrium 'With its vapor, the emitted flux

must equal the incident flux, cp = cp .• Then when the temperature is T, the number of particles
e i

emitted from the 'Wire per unit length in time t is

N = p(T) 2rrr t
-J2rr m kr 1

But N = 6M/m where liM is the mass lost per unit length and m is the mass per molecule.

Thus 6M = p(T) 2rrr t

m ,./2:rr m kr •

or p(T) = ~ ~
where ve have usedµ= mNA and R = NAk.

vX = o by symmetry.
J d
3y f(!) v}
(1)
By definition, =
J d
3
y f(:~:)

At absolute zero, the particles fill all the lowest states so that the distribution f(y) is just
2 12
a constant a.nd cancels in (1). = µ. By sylllllletry, VX =
3V
and (1) becomes

9.17
(a)
At T = O all states are filled up to the energy µ. Hence
the mean number of pa..-ticles per state is just 1 and we have
E= f 0
µ e:p (e:) d€

1 1
By (9.9.19) V (2m) 2 2
p(€)d€ =~ 3 € de;
4?T ii
where the factor 2 is introduced since electrons have two spin states.
3 3 3 5
E = v2 (2m)2
2n' ii3
Jµ €20
d€ = v(2m.)2 µ2
5rr2 ii3

73
 2
(b)
Since µ =
"tl.2
2m (3rr
2
i) 3 by (9.15.10), it follow-s that
E = i Nµ (1)

(c) Substituting the expression forµ in (1) we have

2 2

E= io (3rr2)3 ! 2
(i)
3
N (2)

As particles are added, each new particle can go only into an unfilled level of bigher energy

than the one before. Hence the energy is not proportional to N as it vould be if particles were

added to the same level.

(a) Differentiating E in 9.17 (c) gives

-
2
2 /
3 ~2 5/ 3
~E) -
p = - ( av T - ~ cu N (1)
5 m (;,)

(b) Again from 9.17 (c) we find

2 2/3 "tJ..2 N 5/ 3
"O = g! = (3rr) (-) -
- 3 V 5 m V
22 . 3
(c) For Cu metal, N/v = 8.4 X 10 electrons/cm • Substituting into (1) where m is the mass of

the electron, we find p:::::: 1r? atom. This enormous pressure shows that to confine a degenerate

electron gas, a strong containing volume such as the lattice of a solid is required even at o°K.
9.19
From the general relation TdS = cl. Q = CdT, we have that if the heat capacity is proportional to

a power of the temperature,C a: Ta

6S = J C; a: J Ta-1 dT a: Ta

Thus the entropy is proportional to the same power of the temperature as is the heat capacity.

(a) The heat capacity and entropy of conduction electrons in a metal is proportional to T.

Renee the ratio of the final and initial entropies is

sf 400
-=-=2
Si 2CQ
(b) The energy of the radiation field inside an enclosure is proportional to T4 , and the heat

capacity has a T3 dependence.

Thus
 9.20
(a) At T = O, the total number of states within a sphere of radius tt must equal the total
F
number of particles N.

Thus 2 _V_ (}± 7r tt 3) = N

(2rr)3 3 F

or

µ =
><2
~ (3rr
2
i) 3 (1)
The number of particles per cm3, N/v.,is NAp/µ -where NA is Avogadro's number, p = .95 gm/cm3,

andµ= 23. From (1) ve find the Fermi temperature TF = µ/k = 36,0C0°K.

(b) To cool 100 cm

3 or 4.13 moles of Na from 1°K to .3°K, an amount of heat Q must be removed.

-where~ is given by (9.16.23),

Thus Q = (4.14)(;
2
R)(~ ~') 1i· 3
T dT = -.0022 joules

Hence .0022/.8 = .0027 cm

3 of He 3 are evaporated. Note that a large amount of substance is

cooled by a very small amount of helium.

9.21
2
(a) If electrons obeyed MB statistics, the susceptibility -would be
m
/kT -whereµm is x.._
MB
= Nµ

the magnetic moment. In the actual case, most electrons cannot change their spin orientation

-when an external field is applied because the parallel states are already occupied. Only

electrons near the top of the distribution can turn over and thus contribute to x. We expect

then, that the correct expression for Xis \re with N replaced by the number of electrons in

this region, Neff.

-where TF is the Fermi temperature. 2

µm
Thus X = Neff kI' = (1)

(b) Since TF is on the order of 10

4 or 105, (1) yields a X per mole on the order of 10-6. If

electrons obeyed MB statistics, X -would be changed by the factor

75
 \m
-- =
X

This is on the order of lCO at room temperatures. KINETIC AND MAGNETIC

EN:::RGY
9.22 µ

When the field His turned on, the energy levels te

of the parallel spins shift by -!lmH vhile the

levels of the antiparallel spins shift by -tµmH·

The electrons fill up these states to the Fenni Density of

States
energy µ as shovn in the figure. The magnetic

moment is detennined by the number of electrons

vhich spill over from antiparallel states to

parallel states to minimize the energy. This is (µmH)p(µ ) where p(µ ) is the density of states
0 0

at the Fenni energyµ. Consequently the magnetization is

0

!:!H
V

N
where n = V

9.23
If we choose the zero of energy to be that of the electrons in the metal, the partition function

of an electron in the gas outside the metal is by (9.10.7)

s = 2v
h3
(27r m k.Ti e-vjkT
where the factor 2 occurs because electrons have two spin states. The chemical potential µ is
0

:!Ound from the Helmholtz free energy.

F = -kl' 1n Z = -k.T [N 1n ~ - N 1n N + N]

~
= ~
~
= -k.T 1n 1 = -kl' 1n 2V3
N ~
(2nm kT)~ e-vjkT

The chemical potential inside the metal is justµ= V - ~, and in equilibrium the chemical
0

potentials inside and outside are equal, i.e.,µ=µ.

0
Thus

Hence the mean number of electrons per unit volume outside the metal is
l
n = TI = g_ (271" m 'kr)2 e _q,/kl' (1)
V h3

Consider a situation in which the metal is in equilibrium with an electron gas. Then the emitted

flux is related to the incident flux by

q,e = (1-r) q,i (1)

The electron gas outside the metal may be treated as a classical ideal gas from which it follows

that the incident flux is

-l""' ]l
~
3
-2
-
1 - 1 2 _q, 8kT 2
•i - 4 nv - 4 ~3 (2mn l<T) e /l<T
where we haved used (1) of problem 9.23. The emitted flux is then given by (1). But since the

emitted flux cannot depend on the conditions outside the metal, this is also the flux where

equilibrium does not prevail. Thus the current density is

= 4"rr m e~l-r) (kT)2 e-q,jkT

h
where e is the electronic charge.

9.25
There are (27r)- 3 d 3_!t states per unit volume in the range (1t:d1t) and with a particular direction

of spin orientation. Since the mean number of electrons with one value of K is ~/3(€-µ) + ~

If we take the z direction to be the direction of emission, the number of electrons with wave

vector in the range (~:d~) and of either spin direction which strike unit area of the su....-f'ace

of the metal per unit time is

(1)

Then the total current density emitted is given by summing (1) over all values of K which will

allow the electrons to escape. That is, the part of the kinetic energy resulting from motion in
2 2
the z direction must be greater than V, or ~
0
K
Z
/2m > V0 1 where we use the notation of problem

77
9.23. In addition, we assume that a fraction r of -electrons of all energies are reflected.

Thus the electron current density is

J = e~ = 2e(l-r)
e (
2rr
)3
1= 1= 1= dit
",./2mv )11
....,
X
....,
dit
Y
(m z/m) dit z
~11
2
2 2
1 + exp [ -;:;::-(K +K +K )
2
=i X y Z

where e is the electronic charge. The integral over K

z
is of the form

= J xe ;x -+a
2
= _ ½1n
2
[l+e -x -+a]
e-x -+a+l

Hence

Since V
0
>µand, in general, I~ (µ-V
0
)1 >> 1, we can use 1n (l+x)::,,, x to expand the logarithm

and obtain

J = 2e (1-r)
(2rr)3

F.a.ch of these integrals is

(a) Since the integrand in (9.17.9) is even, one can write

= 2

where we have integrated by parts. Since the first term on the right vanishes

I = 4r = X dx (1)
2 'J o, e X+1
(b) This expression can be evaluated by series expansion. Since e-x <lone can write
-x
~ = ~ = e-xx [l - e -x+e -2x-e -3x •. •]
ex+l l+e-x

= ~ (-l)n e-(n+l)x x dx
n=O
Hence (1) becomes
 I
2
= 4 ~ (-itf co e -(n+J.)x x dx = 4 ~ ( -J.): Jco e ""'Y y ey
n=O o n=O {n+l) o
Ti.le integral is, by appendix A.4, eg_ua.J. to unity. Thus

(c)

C' C
,
,,,·· -.......\

Fig. l Fig. 2 Fig. 3

One can use the contour C of Fig. (1) to write

J
C z
2 l
sin 71" z
dz= 27T:i.
coI:
n=l n
'-J.'n
~
2
71"
= 2i
n=l
coI: (-it
n2
(3)

or J
C z
2 dz
sin 71" z
= -2i S (4)

Here the integrand ~ 0 for z ~ co. The sum in (2) is unchanged if n ~ -n. Hence one could eg_ually
veil write the symmetric expression

J dz
2 .
C' z sin 71" z
= -2i S (5)

along the contour C' of Fig. (J.). Adding (3) and (4) one gets then

dz
J
C+c' z
2
sin nz
= -4i s (6)

But here the contour can be completed along the infinite semi-circles as shown in Fig.(~ since

the integrand vanishes as lzl~co. Except for z = O, there is no other singularity in the

enclosed area so that the contour can be shrunk down around an infinitesimal circle C surroun-
o
ding z = 0 as shown in Fig. (3). For z ~ O,
l l l l 2 2 -l
2 = 2 l ~ 3 = 3 [l - -r;rr z ••• ]
z sin 71" z z [m - 0 z ••• ] m

l 1 22 l 71"
=3 [l + b 71' z •••J =7 + 5z +
7fZ 7fZ

Hence
C
f 2 ~z
z sin m
= <-2n:i. Hl)
0

79
Thus it follows by (5) that
i-rr2
-T = -4iS

or _ ~ ( -l)n _ 7r2
S = n~l n2 - 12

9.27
(a) We expand eikx in the integral

J(k) (1)

=!~
Interchanging the sum and integral yields

(2)

(b) Putting x=z in (1) to denote a complex variable, we evaluate the integral on the closed

contour sho'Wll in the figure. Here C' is the path where z is increased by 27ri and C" is a small

circle around the singularity at i-rr. Then the integral on the complete path is zero since there

are no singularities in the region bounded by the contour.

C' I

C"

But the integral is Oat x =±cc and cancels along the imaginary axis. Hence

ikz
=J e dz
(3)

where both integrals are evaluated from left to right. Along C' vhere z = x + 27ri, we have
since ex+27ri = ex

eikx dx

80
The last integral is just J(k). Thus f'rom (3) we have

(l-e -2rrk) J
e
ikz
dz
C (ez+l)(e-z+l)
= e
ikz
dz
C" (ez+l)(e-z+l)
J (4)

To evaluate the integral around the small circle c", we put z = 7Ti + t; and expand the integrand

in tem.s oft;

e ikz dz
-7Tkf (-t;)(
ikl;
J = e
C"
e
t;) d~
I' = e-1Tkf

C"
[l+iks+- •• ) a" i'
-1; 2 ~

= e -7Tk (9+c2m) (-ik~ = 2-rrke -7Tk (5)

where we have used ex= .l+x+ ••• and the residue theorem. Then combining (4) and (5) we find

7rk
=
sinh 7r k
(6)

(c) Expanding (6), we find

2 4
7rk (1rk)"' 1(-gk)
J ( k ) = sinh 7r k = 1 - + ---r 3 0 - •••

Then com!)aring coefficients with the series in (2) we can read off the Im's. We find r2 = 1r2/3.

(a) According to equation (6.9.4), the probability of stater of the system is

-pE -aN
pr c:: e r r

Then the mean. number of particles in the states is

L. n s exp [-p(nl€1 + n2€2 + ••• )- a(n 1 +n2 + ••• )]

r
n
s = L. exp [- ~ (nl€1 + n2e2 + ••• )- a(n +n + ••• ))
1 2
r

where the sum is over all n , n , ••• withcut restriction.

1 2

Letting l = L. exp [-i,(n1 €1 + n 2€2+••• )- a(n1 +n2+ ••• )) (1)

r

we have n=
s
1
13
'a~
"'s
1nZ
where the partial denotes taking the derivative where €s occurs explicitly. Evaluating the sum

(1) in the usual way, we obtain

81
 (2)

{ 1-e -{~.l~ (- -<n"il•2i\

)} 1-e })
..
-a-Be
Thus 1n l = - L. 1n (1-e · r)
r

and

(b) Using the same argument vhich leads to ( 9 . 2 .10 ) v ith the function £. ve obtain

---=-2 1 c,n
(lms) = - 'i3' c/s
where again the differentiation is performed where es occurs explicitly. Thus
a:-lj3e
s ~ 1
"- ) 2 --
(w.u
s
-----e
a+i3e
= -ns-,.., ( 1 + -_)
(e s -1)2 n
s

= iis (1+ns )

The correction term in (9.6.18) is absent sho,n.ng that if on1~ the mean number of particles is

fixed, the dispersion is greater than if t he total number is known exactly.

(c) For FD stati stics, the sums in (2) become

l = ~ + e -(a:+i3e1J
-a-;3e
bl' = L. b. (l + e r)
r

~hus :J.
s = - -1 ~" 1-'1 l = a:+5e
1
p oes . s
e + l

V
a-lj3e
1 ens e s
and (lm)2 = --~ p oe = a-lj3e = -ns 2 cln -l
s (e s+1)2 s

= -n s (1-:n)
s

82
 We can remove the restrictions on the sum over states by inserting the Kronecker o :f'unction

where the sum is over n

r
= 0,1, ••• for each r. Letting o:
-
= o:+io:' and interchanging the sum and

integral yields

(l)

where

This sum is easily evaluated as in section 9.6 and

-a-f,€
lnt (!!) =~ 1n (1-e - r) (2)
r

To approximate (1) we eA-pand the logarithm of the integrand about o:' = 0 where it contributes

appreciably to the integral.

1n e<PT l (g) = ~+ 1n l (g)

2
= (a+ia')N + 1nZ(o:) + Bl(ia') + ½B2(ia 1
) +

1 2
- - B
2 2 o:' +

where

i(N+J\)o:'
Hence e

As in section 6.8, we optimize the a:pprox:i.mation by setting

or N + o 1n ! (o:) = 0 (4)
l:g ,2
o:N aN "":2 20:
and (3) becomes e-- [ (g) =e l, (o:) e
Substitution into (1) yields
z = e
~
o:ri ,z (
~ a
) f 7f
e
-
1 ]3 1 2
-
2 2
0:
aa' (5)
4T
-a-f3€.,..
or 1n z "" aN + bl (a) = o:N - I 1n (1-e -)
r
where we have used (2). The vo.lv.e o: is determined by (1.:.)
83
which gives

CHAPI'ER 10
Systems of Interacting Particles

10.1
2
Since cr(w) dw cc K dtt and for spin waves ro = AK 2 , it follows that

Then by (10.1.20)

Substituting the dimensionless variable x = ~1'.m we obtain

The integral is just a constant not involving~. Hence

10.2
(a) By (10.1.18)

3V 2
where 2 3 ill for ro < ~
2iT
1 C

for ill >~

But since , we find

In tenns of the dimensionless variables x = ~:,m and y = ~~, this gives

1n z
= YNn - _2li
~ y3
Jy
0
1n (1-e -x) x2 dx

This expression can be put in terms of the :function D(y) by integration by parts.

84
Thus

= 'Y ~ - 3N 1n (1-e-y) + ND(y)

~ 3N (1-e
-eJT ) + ND ( e Irr)
=
i1wD - 1n
D' ~ (1)
where keD = ~wD.
(b) The mean energy is

Thus E =

= -N71 + ~:r D(y) = -N71 + 3N kT D(eJT) (2)

(c) The entropy may be found from the relation S = k[ln Z + l3E]. Then from (1) and (2), we

have
s = Nk [-3 1n (1-e-y) + 4D(y)]
-eJT
= Nk [-3 1n (1-e ) + 4D(eJT)]

For y >> 1, the upper l.illlit in the function D(71) may be replaced by co.

D(y) = 1_
y3
!co
o
~dx
ex-1
h
The integral is shown to be 7T '/15 in tables.
4
Hence D(y) = 7T 3 y >> l
5Y
For y << 1, we can expand ex::= l+x in the denominator

D(y) =; ~7)
2
x a.x = 1 y << l

From the results of' problem J.0.2, we find for y >> 1, or T << eD when we use y = ~~ = eJT
N ......_4T3
1n z = @¾ + -"'"--
3
.<>.:.J. 5e
D
 'srr4 NkT4
E = -N~ + - 5- ~
D

4,n-4
S = - 5 Nk eD
c!-/
For y « 1 (T >> eD) we find, using ey :::::: 1 + y

1n Z = ~ - 3N 1n er111 +N

E= -IiTj + 3N 1d'

s = Nk [-3 1n er/1' + 4]
10.4

The pressure is given in terms of the partition function by the relation -p = 10oV
~ 1n Z where by

equation (1) of problem 10.2

1n Z =~ - 3N 1n (1-e
-eJT ) + ND (eJT)

-eJT
Thus - _ N £!1 + 3N kT e
P- ov -eJT
1-e

where oD(GJT)
dD(eJT)

In terms of,= -(v/eD;(deJdT), this becomes

p = N .s.!l
oV
+ 3,NkT D(e frr)
V D" ~

, 4 4
- 37T
2!1. ?' N kT
p = N 2V + -5- V e 3
D

For T » eD, D( eJT) ~ l

p _ N ,Q:! + 3?' N kT
- oV V

Comparing the expression for the energy E, equation (2) in problem 10.2, vith equation (1) in

problem 10.4, ve obtain

- on {E+Nn)
=
p -- N oV + ?' -------~-
V

86
Thus a=

10.6

(a) Fran electrostatics,

(b) The induced dipole moment in terms of the polarizability a is

(c) The energy of a dipole 12 in a field Eis

u = -g ·~ a: p E a: R-6
2 2

By equation (10.3.8) and (10.3.16), the log of the partition function is

l.n Z l.n ~! ~~ ~ + N l.n V + ½NnI (~)

where n = Njv. The first two terms are the ideal gas partition functions while the last is the

contribution of the interaction. Since the interaction is represented by an additive term in

1n z, it must also be represented by an additive term in the entropy, S = [1n k Z - ~ ~~ 1n z]

Thus the entropy per mole is
S(T,n) = S (T,n) + S'(T,n)
0

where S'(T,n) = k [½ n I(~) - t3 ~(½ n I(B_V]

and

To show that A(T) is negative, we must show that the derivative c/c~ [I(~)/S] is positive.

We have
;:,. Jo:,
(~ = c~ o

but -~ue -~u -e -~u+l = 1 _ ( ~ > 0

e
~u

since (1-+f3u) is just the first two terms in the expansion of e~u. Thus the integral is positive

and A(T) is negative.

Also
10.8
From the arguments of section 10.6 ve can write down the partition function for a two dimensional
gas
z = 4
N.
('h2/3
arm/ zU

1~
vhere 1n zu = N 1n A + 2 A I(/3)
I(/3) = J'\e -/3u_1)27rR dR
0

Denoting the film pressure by Pr, ve have

1 cl
Pr = i cA ln Z

Pr N 1 if
-
kT -- -
A- - -I
2 A2

or

l
= - -
2
I.

10.9
(a) One can write dovn the mean energy from (10.7.3) and (10.7.5)

E = -Ngµ 0 H. sj
1 Z
= -NS lcDc B (x)
S
(1)
Here N is the total number of particles. The consistency condition is

(2)

We solve this equation in the given temperature limits using Fig.(10 .7.1)

T << T
C

Here the slope, kT/ 2n JS, of the straight line is small and the intersection with B (x)
s
is at large x vhere B (x)
s
== 1. Thus (2) becomes

2n JS
or X=-w
and E = -NS kT (2nJS)(l) = -2n NS2 J (3)

T == TC

In this region kT/2n JS is large and the intersection is at small x. We cannot, however,
approx:il!late Bs(x) by the linear term ½(s+l)x {eq.10.7.12) since this vould not cross the

88
line (kT/2n JS)x. Hence ve must evaluate the second term in the expansion of B (x). For
s
small x, 3
coth x ~ x1 + 3 - 45
X x
X << 1

Substitution in Bs (x) = ½8s+½)coth (s+½)x - ½coth ½j yields

B6 (x) ~ ½{<s<½) [cs4)x + }<s<½)x -fycs<½) 1- E ~ ~~

3
½ + · }

2
Bs(x) ""½ (S+l)x - (s +s+½) (sit;) x3

2
Then (2) becomes
2~JS x = ½(s+l)x - (s +s+½) (sit~) x3

2
or
• = 52 ~<½ [½ - 2n JS~+lJ (4)

In the energy (2) we substitute Bs (x) to first order and use (4)

E = -NS kT x Bs{x) = - ts(s+l) kT x2

3kT ]
= _ 5NS(S+l)kT
s2+s+½ L-
[
2n JS(S+l~
T ""TC (5)

T >> Tc

From (4) we see that x=O at kT =kTc =} nJS(S+l), i.e., the energy becomes Oat this point,
and larger T gives imaginary x in this approx:i.:mation.

Hence E=O T >> TC (6)

(b) From equations (3), (5), and (6) we have

~o T << TC
2
C = ~
2fr
= 15N k T ~- ! ~ T ""T C
nJ(S2+s+½) 3 kT

0 T>T
C
C
( c)

89
 CHAPI'ER 11
Magnetism and Low Temperatures

11.1

The mean magnetic moment is

2'.(-oE_/oH)
- r lolnZ
M = ----"""t,E=----- =~ oH
2'.e r
r
-t,E
where Z =Le r.
r
11.2

The change in entropy per unit volume is given by

H
f;;B =f o
O (~)
oH T
dH

But from the fundamental thermodynamic relation dE = TdS - MdH, we have the Max1,ell relation
oFr
(~) = (--2)
oH T dT H

where Sand M are the entropy and magnetic moment per unit volume. Since M = XH and
0 0

X = A/(T-e) we obtain
oM AH
Cy/) =
C H -(T-e) 2
H0 H 2
Thus f;;S =
J 0 (T-e)
AH
2 dH = -
A
(T-a)-
2 ?
0

11.3

The change in the molar volume when the field is increased from H=O to H=H is
0

H "
6v =
f o o (g)
cH T
,P
dH

But from dE = TdS - p dV - MdH, we see that

where v and Mare the molar volume and magnetic moment. Since M = XH and x = A/[T-e 0 (l;ap) J
we find
AB a H
=------2 0

[T-e (l-faP) )
0

90
 H H2
and
£:;.v ={ o _A_e_0_a_Ha._H_ _ = _ __A_e"""0_a_ _..,,. 0

[T-00 (1~)] 2
2
o [T-00 (1-+a p)J 2

u.4
(a) From the relation d.E' = TdS - pdV + HdM where E' = E - v'Ff-/&r we obtain

cos) = c~M)
~ V,T aT V,H

In the normal state, M = VXH"" 0 since X"" O. Thus (oS/oH)V,T ""o. In the superconducting state,

B=H+-=0
4-rrM
V

or

Thus Mis independent of temperature and (cS/oR)V,T = 0

(b) Since the heat capacity is given by C= T(osjoT) we bave fram (11.4.18)
V dH
S-S =r.-::H-
s n Ll'1f d.T

(1)

where His the critical field.

( c) When T = TC , the critical field is o. Thus

VT dH 2
C -c = ~ (-)
s n Ll'1f d.T

11.5
2
From (1) in problem 11.4 and H=H
C
[1-(T/T ) ) we obtain
C
2 2
VH 3VH
C -C =- _c_ T + c T3
s n 27rT 2 27rT Ii.
C C

But since C ==aT + bT3 , we have

n

(1)

To satisfy the .condition Cs /T ~ 0 as T ~ 0 we must set the coefficient of T in (1) equal to 0 1

2
i.e., a= VHc /2rr Tc 2.

91
Thus

ll.6
(a) The entropy is related to the heat capacity, dS = Cd.T/T. Then since at T=Tc and T::0 the
entropy of the normal and superconducting states is the same, we have
Tc C d.T
T f + Tc C dT
s(Tc)-s(o) =
f 0
=
0

Fram which it follows that (1)

(b) Since dE = Cd.T, the energy at T=TC and T::0 for the normal and superconducting states is
Tc 7T 2
En(Tc) - En(0) = f 0
7T dT = +
T 4
+
,_,n
3
f
C u..i..

Es(Tc) - Es(0) = ctr dT =

0

But En (T)
C
= E (T) and by
S C
(1) a= 3,/1' C2•
7T 2
Thus Es (0) - En (0) = - ~
'+

ll-7
From the relation dS = CdT/1' we have for the entropy in the normal and superconducting states
T
Sn (Tc) - Sn (0) = f 0
c ,dT = )'Tc

S6 (Tc) - S (0)
s
=JTc O
ctr 3
efdT = _ c
3

Since the entropy is the same for both states at T=0 and T='rc' it follows that a=3r/l'c2 •
Hence at T=T
C

92
 CHAPl'ER 12
Elementary Theory of Transport Processes

12.1

(a) 6 (b) 6 (c) 6

12.2
(a) ,E, (b) ,E, ( C) {,

(a) The equation of motion for an ion in a field C: is

mx = e!
2
e e t
Hence and X=m 2

By ( 12. l. 10) , t2 =1= 0

t2e -t/r d.; = 2T2

and X =-T
e! 2
m

(b) The time to travel a distance xis

t = ~ ; =£ T

Thus the fraction of cases in which the ion travels a distance less than xis

,/2' -t/T dt -V2

s= f 0
T
e -
T
= 1-e = .757

12.4
The differential cross section is given by

cr(n) = -2rrs ds
d!2

where d!2 is the ele::nent of solid angle ands is

the "inpact parameter" as shown.

From the sketch, s = (a + a ) sin q>

1 2

Since q> = 90-e/2 and dn = 2rr sine' de', it follows that

-(a +a ) sin 81/2
ds 1 2
an = 47!" sin e'

93
 (a1 +a2 )
2 sin e 1 /2 cos e 1 /2
ds
Hence a(e) = -2rrs an= 2 sine'

12.5
By arguem.nts similar to those of section 12,1, one has that the probability that a molecule

travels a distance x without collision is

p = e -x/~

where t i s the mean free path. Letting P = .9 and t = (ff ncr)-l yields

-ln.9 = x ./2 no = x ./2' pajkI'

-4
Letting x =20 cm and T = 300°K gives p = 1.14 X lJ llllll Hg.

12.6
The coefficient of viscosity is

(1)

where we have used t = ( ~ n cr 0 ) -l. To determine the cross section, we not e that the volume

per molecule is A/NAp where A= 39.9 gms, the atomic weight, and p = 1.65 gm cm- 3, the density

in the solid state. T::us the radius of' the molecule is

3 A 1/ 3
r = (47r N P)
A

and 00 = 4rrr2 = 5.6 x 10-15 cm2

From (1) ,,0- 4 gm cm-l sec-1 •

we find 11 -- 1.1 x ..,_ Th
· en ·h
.., e rat·io of the ca1 cult
a e d va 1 ue ~ 11 t o
0.1.

the observed value, 11 = 2.27 X 10 - 4 gm cm -1 sec -1.

,is

12.7
l 1
The coefficient of viscosity is proportional to T2 since 11 = 'IIN/ 3 ..f2 a and v = (8kr/71Ill) 2 •
0

Thus if' the temperature increas s, the terminal velocity decreases. The velocity is independent
of pressure.

12.8
The force on the inner cylinder is the pressure p times the area A= 2rr RL,

.9- = pA = 2rrRL ''"'U

11 ~
We make the approxillla.tian that the air at the outer cylinder is moving with it, i.e., at

velocity ro(R+o) ~ cuR, and the air at the inner cylinder is stationary.

Thus

and the torque is G = ..7R

(b) The viscosity is given by Tl = mv/3 ,.[2 a • Since air is ma.inzy composed of nitrogen, we
0

let m = 28/6.02 X 1023 , the mass of a nitrogen molecule. Putting a0 ~ 10

-15 2 0
cm and T = 300 K,
we find
T) = 2 x 10-4 gm cm-l sec-l

and G = 8 dyne cm

12.9

(a) We let

wherex,y, and z are to be determined. Letting L = length, T = time, and M = mass, the

dimensional equation becomes

But since C = FRs, it has dimensions MT- 2Ls+l

Thus

which gives x+(s+l)z = 21 x+2z = 01 y + z = 0,

On solving this system of equations, we find x = 4/1-s; hence the cross section a is proportional
0
to v4/(1-s).

(b) The viscosity is given by T) = riv/3../2 a and here a

0 0
~ v4/l-s. Since velocity depends on

the square root of the temperature, we have

1 1
-2)
T) ~ T T4;tr.-s) = 'I!°C..+7hV2(s-1)

12.10
(a) Consider a disk of radius rand width t::;x. '
at the point x. There is a pressure difference
2
.C:.p across the disk giving force -rrr t:.p and a \. __,.,
\ I

. ou(x,r)
viscous retarding force 27rT t:.xT) or • Hence
~x-1~1-
the condition that the disk moves without

acceleration is

95
But since t::.p ~ - cpfx) t::.:x., where the minus sign is introduced because p(x) is a decreasing
ox
function of x, we have
2 op(x) _ 2JT 6U(r,x)
71T ox - r7J or

Assuming that the fluid in contact with the walls is at rest, it follows ihat

u(r)
f 0
du'
1
~J
::,_~/...,.\

ox
r,

a
r
r'dr'

For a liquid, ~~ The mass flowing per second across a ring of radius r' and width

dr 1 is pu(r')2rrr'dr 1 where pis the density. Then the total mass flow is

M=
f a pu(r')2rrr'dr' = li2 £.....
TJL
(p -p)
1 2
Ja 2 2
(a -r' )r'dr'
0 0

4
= ~ ~ ~ (pl-p2)
(b) For an ideal gas, the density is p(x) = (µ/RT)p(x) whereµ is the molecular weight. Thus

the mass flow is

.
Since Mis independent of x, we obtain
L
•f
M
0
ax = - -s m 1
1f µa
TJ
4

p
p2
p dp
1
4
w},..ich yields • 7r ~ a ( 2 2)
M = 16 TJRT L P1 - P2

12.ll

Let T(z,t) be the temperature at time t and position z. We consider a slab of substance of

thickness dz and area A. By conservation of energy, (the heat absorbed per unit time by the slab

is equal to (the heat entering the slab per unit time through the surface at z) minus (the heat

leaving per unit time through the surface at z+dz). Since the heat absorbed per unit time is

me oT/ot = pA dzc oTjclt, where c is the specific heat per unit mass and p is the density, we have
 pA dz c~ = A [Qz -Qz+dJ
• A [-• ~ - ~• ~ - • ~(~)0]
and

u.12
The wire gives off heat fR per unit time and length. In order that the temperature be indepen-
dent of time, a cylindrical shell between rand r -kir must conduct all the incident fR heat.

Thus

-1
T
T
o dT = r2R
2rrK
f a
b dr
r
2
or 6.T = T--'l' = I R 1n ~
o 27rit a

12.13
(a) The heat in.flux per cm height of the dewar across the space between the walls is

al'
Q = -2rrr K-
dr (1)
where r is the radiu.s, r ~ 10 cm.

We let oT t:1r _ 298 - 273 _ 4 oK/

°ar ~ t:.r - 10. 6 - 10 - 2 cm

by (12.4.9)

The specific heat per molecule is c = (3/2)k while cr 2 -8 ) 2 en.

2
0
= 47rR = h7r(lO The mean velocity

is v- = (8kT/ 7l!ll)-I
7~
• Choosing an intermediate te~perature T = 286 0 K, we find v = l.2 x lO 5cm/ sec.
Substitution of these values into (l) yields

Q = l.2 watts/ cm.

(b)_ The thermal conductivity remains approximately constant until the pressure is such that

the mean free path approaches the dimensions of the container, L = .6 cm. At lower pressures,

the conductivity is roug~ proportional to the number of molecules per unit volume n. Thus
the heat influx is reduced by a factor of l.O when

n = 1 ~ 14
10 molecules/cm3
l0./2 L cr0

ham p = nl!:T, we find p ~ 3 x 10-3 mm Hg.

97
(d) cr -
-
~
.frr 1'I} Jµ NJ'kT gives cr
l =
l l x io-l5 cm2 ,
•
2
cm •
3
-8 -8
(e) cr = 7T<l2gives
.
~ = l. 8 X 10 cm, d 2 = 3.0 x lO cm.

l2.l5
The gases are uniformly mixed when the mean square of the displacement is on the order of the

square of the dimensions of the container. We have, after N collisions,

2z = r.
i

since the second term is zero by statistical independence.

Then

2 22 2 22
Z = v -r N= v rt
3 3
where N = t/-:. Since -r = ,f,fo = 1/,/2 n cr v, one has on neglecting the distinction between v2
2
and v,
z2 = -~-J v kT)t = ~
3412\crp 5
kT
CTp
J~7r
kT
m
t

Substitution cf z
2 h 2
= 10 · en, cr"" lC
-l~ 2
"cm, and the given temperature and pressure yields

sec.

12.16

A molecule undergoes a momentum change of 2µv z in a collision ,.;i th the cube where µ = rnM/m+.'-1,
the reduced mass. Then the force is given by the momentum change per collision t:imes the

number of molecules which strike the cube per unit time, summed over all velocities.
r3m -V )2
,z ~ 1/2 2100 2 - -(v
2 z
dv
......:Ttot = 2µn (27r) L vz e
z
0

We may approximate the exponent since v >> V. Thus

 - ~ (v -v)2
2 z
e (1-1-f)mv v)
z

and -.5tot=2µn(2rr)
m8 1/2
L
2f°"vz2 e - f3m2 V
z
2
(1+/3mV"zV)dvz
0

The first integral is just the force on a stationary irall as in section 7.14. The resistive

force is then
f3mv 2
--
2 z
e

- 2
=µnvVL

by Appendix A.4 and 7.u.13. Since we expect M >> m, µ. ""'m, and the equation of motion becomes

M ~ =
dt
-mn v VL2

V = V O exp t~ n v l~
The velocity is reduced to half its original. value in time

M 1n 2
C = - 2
mn v L

CHAPl'ER 13

Transport Theory using the Relaxation-Time Approximation

13.1
2
By (13.4.7) 't" V
z

The value of the integral :is unchanged if v 2 or v 2 is substituted for v 2 • Hence since
X y Z
2 2
v
2
=v
X
+v
y
+ v Z 2 , we obtain

ael = - -e3
2
J a3 v
-
~e -rv2
The quantities-rand ogfc,e are functions o~ of v. Thus the substitution d 3v = v 2 dv sine de d~

yields

99
The f'u.nction g becomes the Maxwell velocity distribution
2
3/2 - mv
c~t'£!) 2kI'
e (- kr)
l

In terms of ; = (2kl'/m)1/2 ,. this is

2
~ __ -3/2 ne-(v;v)
0€ - 2rr ....5
V

Substitution into (1) of problem 13 .1 with s = v ;v yields

2
cr = ~ {-r)
m cr

where {-r)cr = 8
yJ; f 0
co
ds e -s
2
s 4 -r(vs)
"'

]3.3

Since € = ½mrf = ½n (u}+ u/ +Uz2 ), we have

og _$ o€ _$mu
~ - 0€ dUX - 0€ X

Thus T) = -mf d
3u $._ u 2 u -r = -m2
- oUX__ .z X f 3u $ u 2 u 2 -r
d
- 0€ Z X

rn· spherical coordinates, the components of velocity became

u
X
= u sine cos cp uZ = u cos e

and d3E = rrdu sin e de dcp

Therefore T) = -m
2 r
JC')
2rr
cos 2 cp dcp f
0
sin3 e cos 2 eae
1T f"" dU ~o
0 O€
u6 T

2
= -m 7T
J1r [cos e sine - cos 4e sin e]de [(X) dU fc
2
u6 -r
O

= -m
2 41r
15
f""
0
dU $
0€
u6 -r (l)

But since f 7rdcp f 2rrsin e de

0 0
= Im-, it follows that

2
TJ = - ~5 J1rdcpf ~in
0 0
edef 0
dU $
O€
u6-. =

100
Substitu+.ing the expression -J -(u;v)2
i = -2rr 2
ne

from problem 13.2 where;= (2kI'/m)1/

2 into equation (1) of 13.3 yields

T] = nkT (,)
T]
co 2
-where (' )
T]
15..f; ! 0
ds e
-s
s = u;v

13.5

Ptttting '
~ -)-1
( "le. n cr v
0
into TJ = nkI' , and using v= 1 2
(8kT/7!lll) / gives

This is larger by a factor of 1.18 than the mean free path calculation (12.3~18) and smaller

than th-2 result of the rigorous calculation (14.8.33) by a factor of l.20.

13.6
We assume the local equilibrium distribution
/3 3/2 1 2
g = n(~) exp [- 2 pmv] (1)
where the tenperature parameter /3 and the local density n are functions of z. Then in the

notation of section 13.3,

df(o) df(o)
~ = - dt =
0
-~ ~
on
on ~
- /3
0
~ 0

0n cg
dz(t)o og ~ dz(to)
= - dn 6Z dt - ~ z dt
0 0

where the last follows since dz ( t ) /dt = v z. This expression is independent of t'. Thus
0 O

(13.3.5) becomes
M
df(o)
=-w- J"" -t'/-r e dt'
0

or (2)

Using (l) this expression becomes

181
 ll on 3 ot3 mv
2
~ (3)
f = g-g v z... Ln: oz + 2p oz - 2 c1~

It remains to determine on/clz for which we use the condition

vz = l:n J 3
d v f v
- z
= 0

or
J d
3
2- g vz -
J 3
d ::. v z
2
-rg
11 on + 1.. 06 -
Ln az 2p az
mv
2
2
c)~
~ = 0

The first integral is zero since the integrand is an odd Iunction of v.

z

J d3y V/ g [¾ ~ +(¾ ½- m;
2
)~] = Q

2
where we have assumed T independent of v. By symmetr'J this equation also holds if v in the
z
2 2 2
+ vy 2 + vz , we have
2
integrand is replaced by vx or vy 2 Then since v = vX

or

on substituting (l) arid d3y = v 2 dv sine da d9, and canceling co.Cl!Ilon factors. The integrals

are tabulated in appendix A.4

l on l 05 (4)
or n dZ = ~ oz

Substitution of the equation of state n = p,!'kI' = pp yields

C:o
or -:=- = 0
c:.z

The pressure is independent of z. Then ( 3) c...'1d (r) give

c1s
f = g-gv z -r oz [~P -m;~
+ gv z -r dT l,2. _ l:_ mv-27
g
T dz l? 2 :riJ
13.7
Since there are no external forces and f is independent of time, the Boltzmann equation becomes
of of f-f(o)
V • ~ = VZ a'z = - -r

J.D2
where f(o) = g is the local Maxwell distribution of the previous problem. Letting f = g+f(l)
where f(l)<< g we have
V ~ = V ~ on + V ~~ = - f(l)
z clz z on dZ z Op dZ ..

Thus f = g-v ,.
z
rlEn$ ~oz + ~clg ~oiJ7
This is identical to equation (2) of 13.6. The ·rest of this calculation proceeds as in that

problem.

13.8
The heat flux in the z-direction is given by

=!
2
mf d 3v f v v
- z
2

where gv-r -clT

f=g+-z-
T oz
~.2._!~
2 2 kT
j
The integral over g is O since the integrand is an odd function of v. Consequentzy

~ 3;~ f
1 2 z

Qz =
m,- 1 clT
4 T dZ
1
1.:1 (27r) J
3
d Y v vz
2 2
e
- ~ r..~-t3mVJ21
We can exploit the synmietry of the integral by replacing v 2 by v 2/3. Then the onzy angular
z

- 2
de-oendence occurs in d3v = v dv sine de dcp whic.h yields 47TV dv when the integration over angles
-
2

is performed.

Qz =
Thus we obtain

'Tr !llT
3T
clT [ ~ 3/ ~
~ L(2rr) J I.L5 Jco 6 -
o dvv e
~
1 2
-;3m
Jcoo dvv8e - ~
1 J
The int2grc.ls are tabulated in appendix A.4 •

~
.
"',z
= IT m,-
3 T
oT
oz
C
E (m3) / ~ ~-~
3
J t lo
2rr 7r
2
( pm)
7 2
/ -~m 105
..., 32 1r

_2_.nk2r,,1 -:,,
oT
2 ~ ,- oz

13.9
Th~ mean free path argument has
2
4 nk T
K = -3l ncv
-
t = - - - -r
7r m
1 2
since t = v,- and v = (8kT/7TII1) / • Thus the constant relaxation time approximation yields a

103
 2
result greater than the mean free path argument by ~ = 1.96.
7T

13.10
From problems 13.4 and 13.8 we find

~ = (5/2)(nksr/m)T = 2~ = 5C
T) n kl' T 2 m 3 iii
where c = (3/ 2)k, the specific heat per molecule. The simple mean free path argument gives

C
T) m

Experiment shows that the ratio (K/ TJ)(c/ m)-l lies between 1.3 and 2.5 (see discussion after

(12.4.13)) so that the constant relaxation t:L..-ne appro::d..mation yields better agreemer.:t with
experiment than does the mean free path argument.

13.11
In the absence of a temperatur.e gradient, the eqv.ilibrium distribution of a Fermi-Dirac gas is

(1)

In the given situation, f is independent of time but ,rill depend on z because of the temperature

gradient oTfe z along the z direction. ·r his temperature gradient alone would cause the electrons

to drift, but since no current can flow, there is a redistribution so as to set up a field !(z)

to counter the effect of the temperature gradient and reduce t he mean drift velocity v to zero.
z
Thus the Boltzmann equation becomes
f-f
V
of + e C ( z) cf = 0
z dz m ovz T

We ,rill assume that the temperature gre.dient is sufficie..'ltzy small so that f ca.n be written
f = g+f(l), /l) << g whe!'e /l) !'epresents a s:::iall departure from local equi.lioriu."D. •
.,.(1)
J.
Thus (2 )
T

It is convenient to write this in terms of the dinensionless parameter

X = ~(€-µ ) = ~( 1 IllV
2 -µ ) (2)
2

Thus ~ (€-µ) ~= ~ i i
~=
clg ox 5mv og
ov z dX ~= .
z
z dX

104
Then from ( 2) we find

It remains to find C from the condition that vz = !}'d3v f·v

n - z
= 0 where f is given by (4).

The integral over g is O since the integrand is odd. Letting T = TF = const. for electrons near
the Fe!"!li level, we have

or (5)

The second integral can be expressed in terms of n, the total number of electrons per unit
~ 1 cg
volume. Since ox= ~v cv
z z

J oo
·...,, dvz v Z2 ~
00
C = -l }' dv v £5.._
d l 1
dX pm -co Z Z dV z = -/3m [v Zg] -co - -/3m
00
J' 00

g dv Z
-co

where we have integrated by parts. Since g=O at ±co, it follows that

J 3
dvv
-
clg
2 -.;;-::-:=--
z ox
1
pm
J 3 v g = -n-
d
- pm
(6)

Proceeding to the evaluation of the first integral in (5), we note that x and ogfc,x are functions
2 2 2
only of v so that we can replace v by v /3. The substitution d3v = v dv sine de d~ yields
z
2
4n v dv when the integration over angles is performed.

Thus J 3 2
d !_ v 2 x ~ = ~7T l"° 2
dv v x fx
2
Using x = 13(½ mv -µ) this becomes

~ c1-//2foo dx x(x+/3µ)3/2 ~ (7)

3 pm -co dX

From the properties of the Fermi distribution, we know that og/ox ~ 0 except where€~µ or

x ~ O. Ti e integrand contributes appreciabzy to the integral only L'l this region so we can
2
expand the factor x(x+/3µ) 3/ about x = 0 to approximate the integral. Also, the lower limit -13µ

may be replaced by -co with.negligible error.

2
x(x+pµ)3/2 ~ (t3µ)3 / 2 (x+ l2 ~)
/3µ

X
and, e
from (1)

105
Hence (7) becomes

0-,,-

3 ~:m
2 5' / 2
=.!!.(-) !co
-a,
dxx(x+pµ) l / 2 rx X
= -23/2
- - µ 3/2ml/2
5Tf2 t3fi3
[!co -co
xe X d x +3-
(eX+l)2 2/3µ
la, x2 eX dxj
-c::o(eX+l)2
(8)

These integrals are the r 1 and r 2 defined by e~uation (9.16.9). It is shown there that r1 = O
2
and r2 = 'IT / 3. Combining the results of (5), (6), and (8), we obtain

and (4) becomes

f = g-v
z
T ~
F dX (9)

Having found the distribution f, ve can nov calculate the heat flux Q.
z
2
Qz =n <vz(½ mv2 )) =½nm (vzv )

where (v v ) = -n
z
2 1
J d 3v v v
- z
2
f

The integral over g is zero since the integrand is odd,

~
2
Hence Q
Z
= - m-rF
2
1 9.§.
t3 dZ ~
d 3v v '2..2 x~ -
- dX
Z
1
3 n fi3t3
3
( 2µm ) l / f d 3v v 2 ,l~
- Z d~
7 (10)

The calculation of these integrals is similar to the steps leading to (8), Again v 2 can be
z
2 .
replaced by v /3 and the integration over angles performed to yield 41r, The first integral in

(10) becomes
4nJ=
-
3 0
dv V 6X d = -2rr (-)
~
OX 3/3m
2
7 2
/ 1= ..0:,
X (x+pµ) 5/2 ~
X
dx

The second integral in (10) is

d3V V 2V2 ~ 47Tf a, dv V6 og

J ,.. Z dX
=
3
0
dX

1c6
Here we have neglected the squared term in the expansion since it is much less than 1. The

integral is I
0
+ (5/2 ~µ) r1 = 1.

(12)

we find

Thus
-rr2 nk2.r
K =---T
3 m F

13.12
Combining the results of the previous problem and (13.4.12), we find
2 k 2
K/cr
el
= 1L_
3 e
(-) T

At 273 oK this becomes KIcrel = 7.42 X 10 -u erg cm -1 deg -1 or in more standard units
-6 -1 0
KI crel = 6 •68 x 10 watt obm deg • Experimental values at 273 Kare

element Ag Au Ql. Pb Pt Sn w Zn
6
K/crel 10X 6.31 6.42 6.09 6.74 6.85 6.88 8.30 6.31
watt ohm deg -1

CHAPrER 14

Near-Exact Formulation of Transport Theory

l4.l

The mean rate of momentum loss per unit volume due to collisions is, by (14.4.22)

(6E) = JJJ d3! d3! 1 an' ff1 vcr (v,e')(6E) (1)

! !1 n

where we assume central forces. We first perform the integration over angles by changing to

center of mass coordinates.

Thus (6p) = m (v'-v)

- - -

107
becomes, since v ~ V and v' = c +
=c +m ~ V'
- m_

(A;e_) = µ(V' -V)

mml
whereµ= - - , m being the mass of the ions and~, the mass of the heavy molecules. Since
m-tml
the mean values vx and vy are zero, it is clear that (Apx) = (Apy) = O. Hence we are left with

(Ap ) = µ(V ' - V ) and

z z z
dn' cr(V,e')(Ap ) (2)
z

V' is given in terms of V and the scattering angles. Using the coordinate system illustrated
z z
in Fig. 14.8.1, we see that

Vz' = V'cos(y' ,!) = V cos (y' ,!)

since V' = V. Inspection of Fig. 14.8.1 yields

V cos (Y',~) = v[cos(y,z) cos e'+sin e'cos ~' sin(y,z)]

= V cos e'+ V sin 0 1 cos cp' sin (y,E._)

z

and µ(V z '-V z ) = µV z (cos e'-l)+µV sin e'cos cp' sin (Y,!)

Substituting into (2) we obtain, since J~os

0
cp'dcp' = O,

For hard spheres, a is constant and

27rµVzcr J'\cos e'-l)sin e'de' = -4n µVzcr = -µVzcrt

0

where a. is the total cross section. Equation (1) then s:L~plifies t o

t.,

-(Ap z) =µat ff Vzv ffl d3! d3~1 (3)

! !1

where

Here u is the mean z component of velocity of the ions. To avoid carrying repititious constants

we let
II$ (4)
a= 2 and

l'J8
f can be simplified by making the approximation that v >> u, then
z

(5)

We again express! and !i in relative coordinates

m
1
V = C + --V v =c-~V
m+ml - -1 - m+m -
1

Thus

On completing the s~uare this yields

(oml -o;lm)
(a-+al) [ .£ + (a+a ) (m+m )
1 1

001
(a-+al) i2 + - - v2
a+al

(~ - a1m)
where K = + V (6)
-
C
(a+al) (m+ml)

Also

a1
= K
z + -
a+a Vz (7)
1
We wish to put the integral (5) in terms of y and the variable~ defined by (6). It has been

shown (14. 2 .6) that d3y1 d 3y = d3£ d3v. In terms of K we have

d3£ d\ = Jd 3~ d3y

It is easy to check from (6) that J=l. Thus (~ becoraes

i2
- (0.pz) "µat nnl c~:)
3/ 2
ff e-(~)
_1_ v2
e al->a ~+2a u Kz+2u ;:;l vJ
The first two terms in the brackets give integrations over odd functions and hence do not con-

tribute to the integral. Changing to spherical coordinates gives

-
- (6pz ) -
~
n3 at nn1
(001)5/2
(a+ai)
~
L7T
Jex, e -(a-+<-v...)x2~ J, [J°' - e
ool v2 5
a-+a1 v dv
f n 2
27T cos e sin
O 0 0

.:he integrals are found in appendix A. 4 and we obtain

109
 mml
whereµ -- - -
m-+ml. The momentum balance equation is then

ne e + (6.p ) = 0
z
which gives

Since j = neu = oel C: , we have

14.2

(a) We will assume the distribution function

f = f(o)(l+qi) (1)

where (2)

It is shmm in problem 13.6 that the condition vz = 0 yields the relation

(3)
and that the pressure is independent of z.

(b) The Boltznann eq_uatior: (ll".7.12) becomes

~Co) of CO ) cf(o) .p
DI =~ + ~ ~=""-0

:Because the situation is tir.ie indepencier:t and there are no external fo:::-ces, we are left with

or (~f3 ~;) f(o) v

2
(1 - ~;v-j ff = d3yl. dn 1 f(o)fl. (o)Vo 6~ (4)
on using (2),(3), and (J.4.7.10).
It remains to determine the :f'unction ~- The left side of (4) leads us to expect that a good

approx:i..n:.a.tion will result if we choose

110
where A and a are constants. ¢ must satisfy the restrictions (14 .7.14) to be a good approximation.

These become
J 2
d 3:::: f( O) Vz (l-av ) = 0

J
r d 3v lf (o) V
- -
V
z
(1-av2 ) = 0

The first and third integrals are zero because the integrands are odd . S::..rnilarly only the v
z
component of v in the second relation will give a non -zero integral. He use this condition to

deten:iine a. That is,

2
3/2 / - ~~v
0
(:) v e dv

on USi..."lg V = V COS
z

ki'
-=-=a
m

mB
a= 5
2
and 0 = A V (1- m,5 v ) (5)
z 5
We will use the procedure of section 14.8 to evaluate the constant A. Multiplying (4) o;:; i and

(6 )

'I'he integral on the left is ee.si.l~y ev~luated. 1·le have

r
vv
d 3V .;.""" ( ::)
-
[ 2 - -2Bn
z
~- V
:;)
_ 2 V 2 + (Br.:)
z
-::-
;
2
V
z
(7)

= -n
f3m
26m
- (- 1
·-)5n(Qm)
5 ,.,
2
pm
+ (-;:-)
)
2
J 17T
0
2rrd~
0
cos 2 9 sin 9d9 r
'-' 0
co
n (2rr)
mB 3/2 8
v e dv

The int2gral o:f the second term in (7) was evaluated previously. The third term is easily shown

to be 7n/ 5pm. ~hus the integral becomes

n (1-2 + -7) - -2 -n (8)
pm 5 - 5 f3m
We split the right side of (6) into an integration over the angle n' and over~ and ~1 • We

lll
define

J = fu,an' V cr 6[vz (1- rJ v

2

Then using (8), equation (6) becomes

(9)

f"" 2- 1
To evaluate J, we express 61v (1-av )1 in center of mass coordinates (we have reintroduced
1...Z j
a= pm/5). By (14.7.11),

Using v = c + ½y_ \v1 = 5:.. - ½y_, we have

2
2 '2 L ? o:2 b 2 V
v (1-o;v ) + v 12 (1-av )=(cz + 2'z)(l-ac--o:5:..•y -
2 1 4 V )+(c 2 - 2 ,)(1-ac -+a.:::"Y.. - a 4 )

2c - 2o; c c2 - ~ c v2 - o;V z-C•V-

z z 2 z

Then c = c' and ly_l = l-y_ 1 I gives

6jv (1-av ~ =
L. z .:J
2
-a (Vz ' c•V' - V c•V)
z- -
(lC)
CaIT'Jing out the product in ( 10) •,;e find
2rr
J = -af 0
dco'
· J
f
0
7r
sin e'dB'aV 1c
[x
(V 'V '-V V )+c (V 'V '-V V )+c (V ' -v ~
z x z x y z y z y z z z
2 2
J
where the coordinate system is shown in Fig. 14.8.1. We notice that, except for constants, the

first integral is (14.8.7). The second integral involves or..ly a change of the index x toy but

is otherwise the same as the first. Consequently, by (14.8.20), these terms yield

22 o; cr
TJ
VV (c V
z xx
+ c V)
yy
(ll)

where cr is given by (14.8.21).

T)

It remains to find
J-rr sin e'de'a Ve z (v z ' 2 -vz2 )
-a
f 0
2-rr
dcp'
0
(1 ?)

fy (14.8.18)

Vz ,2_v z 2 = Vz 2cos 2 e'+2V V sin e'cos e'cos~' (A A A)2 -v 2

.S.'~A) + V2 sin2 e'cos 2~'(t·~
2 2

112
and f 0
2
z
2
z
2
2rrdcp'(V 12 -v ) = 2rr V (cos 0 1-1) +
z
-rrv2 sin2 0 1 (;·~) 2
- - (13)
To eliminate s, we write

or

and (13) becomes

The last term in J is then

(14)

and (ll) and (14) give

J =
3
2 aav
TJ
(c V V . + c V V + C V -
xxz yyz z z
?
- C
z 3
t) (15)

-- J2 a a V (V (c•V)
z - - - C
z 3
t)
TJ
We now evaluate

The evaluation of thi s integral is straightforward though tedious. In the center of mass system

3
=n 2(mS)
-27r (16)

a C v-
2
+ l V a 2
- Ea V2..v z
2 ?
v z(l-av ) = C
z
-ac
z
C
-- - 4 z
- ac z (c• V)
2 z
- 2 V
z
C - Ct2 V z c •V

.,,(o)_~ (o) is clee.:r-ly e-~.. e:; flL~Cti8:: i::

This expressicr.. is multiplied by J in the i~tegrc.nd . -'-1 C.!l

c e.nd V; hence we need keep only even terms in v (l-crv 2 )J. This yields explicitly
z

I=(f'a.3c d3v f(o)fl(o)(J2 a a V)

JJ' - - TJ
~tz 2y Z 2-ac2c Z2..v Z2_ ~
i+ Z
2v2y 2_.g
Z c.
(c
X
2y 2y
X Z
2+c
y
2y 2y
y Z
2+c
Z
2y
z4)
v- 2 + a~ 2 C 2_2
2 a 2 4 7a 2 2 ?~
-c
z 3 3 z
V + l2 C
zv + O
C
z v z --Y- (17)
Since f(o)f (o) has the si.!llple fozr.:
1
(16) all these integr~ls are the standard ones encou..>1.tered

:i..'1 this theory . We quote the result of integrating over c. In (18) the terms appear in the

ll3
order that they appear in (17)

~~
2
I = [ i a] [ n
2
(~/] [
l
(-)
~
5/2]
X

(18)
~v2 2
~O [vv 2 _ 2~
5a vv 2 _ a v3v 2 _ £ v 2v3- y_ + 5a v3 + £.... v5 + a v3v 2]
J d3v
- e
-
TJ z 4 2z 3 6~ z12 b z z

The integral becomes on subs~ituting a= ~/5,

~r vv 2 3
~ ~
J d3v e -
- TJ
[ _z -
2 bO z
V 2v3 - v
b
+ m8
60
v5]

=
! 0
00
5
V crTJe
- ~t dV 2rr
f
O
7!" (cos2e
-
__2 2
2- - bO vcos e
~ - b1 II$v2)
+ bC5""" sin e de
~v2
= ~ (-
8
3) II$
!CDv7crri e
- ~
ay
0

We let s = ½-/mi V and

= ~ (-8 m/l)(.J~y ½f ds .-s

2
"a ~) 5
7

-
102471" _l_
= - -n- (II$)3

where cr is given by (14.8.26). Substitution into (18) yields

TJ
2
I __ 32 n cr
- 25 7!"1/2(II$)3/2 TJ

and by (9)
1/2
A = _ 25 (!!!:IT) o~
32 n cr ~ dZ

_
TJ

~
To find the coefficient of thermal conductivity, we eV2luate the heat flux
t ~?
j_
25
-
ncrTJ
(!!!:IT) l / \ (l-
~ z )
v2) o~
oz

Q
z
= n (v z (12 mv2 ))

= ½n J d3y :f(o) (1+1>)vzv2= ½-n, J d3y f(o)~ vzv2

= k2 Af d3v f(o) v 2v2 (1 - II$5 v2)

- z

= ½m A G~)2-~((~~~
ll4
Thus Q =_ nksr2 A = 25 (..1L)
l/2
~
z m 32 cr !!$5 dZ
TJ

= _ 25 ~ ~7r kl' dT
32 -cr ln dZ
TJ
Therefore the coefficient of thermal conductivity is

(c) :By (14.8.32)

Renee

l4.3
(a)

(b) :By (12.4.2), the simple mean free path argument gives

l.50 -Rµ
K C
- = - =
TJ m

Hence _the Boltzmann equation gives a value for K/TJ greater than the mean free path calculation

by a factor of 2.5

(c) ~ X lQ-7erggm1aii"] Ne A Xe
TJ

Calculated l.55 .780 .237

Experimental J.. 55 .785 .250

14.4
3 2
Let t i ng f = n (:) / exp [ - ½Bmv2 ] , we have

Performing the integration over angles yields

2
= 47!Il ci) 3/2
l = 2
V dv e
- ~ [
ln n (~
3/2
- ~
2 ]

and by appendix A. 4 this is

ll5
 -
--v
N[ V
- l nN- +3
- l n T -3
2
- l n2rrk
2
3]
-m+ - r
LJ-

Comparison with (9.10.10) shows that except for a constant, this is -S/k where Sis the entropy

per unit volume of an ideal gas.

(a) Differentiating the function

H = J 3
d _!. f 1n f

yields dH =
dt J :!.. dt
d3 elf (ln f +l ) (1)

elfjdt can be found from the :Boltzmann equation. We shall assume that there are no external

forces so that the distribution :function should depend only on the velocity .and time. Then the

:Boltzmann equation becomes

elf
at =ff d3..:.J.v an' Vcr (f1 'f' - f f)
1
(2)

Substitution of (2) into (1) yields

dH =
dt JJJ a3-v d3-1
v an 'Vcr(f1 'f' -f1 f) (ln f+1) (3)

This integral is invarient under the interchange of:!.. and ~l because a is invariant under this

interchange. When the resulting expression is added to (3) we have

(4)

Similarly, this integral is invarient if the initial and final velocities are interchanged because

cr is invarient under the inverse collision, i.e.,

Thus ~
dt = !fff
2 d3-v 1
d3-1
v ' an' V'cr (f1 f-f 1 'f') (ln f 1 'f'+2)

But V=V' and by (1 4 .2. 8) , d3:!._ I d3_::1I = d3:!._ d33

1

dH =
dt
!fff
2
3
d v d v
-
3
-- 1
an' Vo (f f-f 'f' )(ln f 'f' + 2)
1 1 1
(5)

Adding (4) and (5) gives

~~ =- ½JJJ 3
d v d~ an' Vo (r1 1 r 1 -f1 f)(ln r1 'f'-ln f 1 f) (6)

116
(b) Letting f
1
'f' =y and f f
1 = x, we see that since (ln y - 1n x)(y-x);::: O, the integrand

in (6) is greater than zero wiless f 1 f 1 = f f. Hence dH/dt < 0 where the equality holds when
1 1
the integrand identica.lzy vanishes.

14.6
The equilibrium condition is

1n f = Af B mv
X X
+ B mv
y y
+ B mv
Z Z
+ c-12 mv2 (1)
This can be written in the form
2
1n f = -A'(v-v) + 1n C'
- --0

where the constants A', C' and the constant vector v contain the constants in (1).

Hence f = C' e
-A' (v-v
- --o
1
v is clearly the mean velocity which can be set equal to zero without loss of generality. To
--0

determine A', we find the mean energy of a molecule.

J d3! ½rrrlf 4n f 0
2
""v dv ½ rrN
2
e-A 'v
2

J d
3
! f

3 m
= 4 A'

Letting € = (3/2):Id', we find A' =

3/2
m/2kT. The constant CI is easily found from n = J d3! ·f which

gives C' = n(~kT) showing that f is the Maxwell distribution.

CHAPTER 15

Irreversible Processes and Fluctuations

15.1

Let the friction force depend on a, v, and T) in the manner

Then the dimensional equation where L = length, T = time, and M = mass becomes

Thus x+y-z = 1, z=l, -y-z = -2. Solution of this system of equations yieldx x=y=z=l, and
f cc T)aV

117
15.2

Since NAk = R vhere NA is Avogadro's number and R is the gas constant, we have from (15.6.11),

RI' t
or NA= 2
37111a(x)

Substituting R = 8.32 X 107 ergs mole -1 0 K-1 and the given values yields NA= 7.0 X 1023 molecules
-1
mole •

15.3
(a) The energy of an ion in the field at point z is - e Cz.

f3e! (z+a.z)
Hence ~) e
::::: 1 + f3e f. dz (1)
nfzT e
f3ei' z

(b) The flux is given by

J =-Don~ D[n(z+dz) - n(z)]

D oz - dz

Then from (1) J

D
= -nD f3e !

(c) J
µ
= nv = nµ c

( d) -nDi, e.l+nµ! = 0
µ =
J+J
D

I:!:. e
Thus
D kT

dv 1
d.t = -rv + iii F' (t) (1)

Substitution of v(t) = u(t)e-rt into (1) gives

-
au
- -l r t .,..,, ("'")
dt= -!D.e t "

Hence u = u(o) + iii

1ft . , e 1 " F'(t')dt'
0

Since u(o) = v(o) it follows that

v = voe -rt + ~ e -rt J 0
t e rt' F' ( t' ) dt' (2)

15.5

By dividing the time interval t into N successive intervals such that t = NT, we can replace the

integral in (2) of 15.4 by the sum of integrals over the intervals of length T betveen ~ and

118
 Then t' = kT + s where k is an integer and dt' = ds.

Hence v-v e
o
-rt =· e
-,NT N;l l
L,
k=O m
-
J,. e'
o
,y{k,-+s) F 1
(k,-+s) ds

=
N-l
L, e-,,- ( N-k ) ¾JT e's F'(kT+s) ds
k=O 0

In the integral, s <Tor e's< e'T~ l since,- is chosen so that T << ,-1 . It follows that

-')'T
v-v e =
0

N-l
= L, y =y
k=O k

where C\_ = lf,.

m
0
F'(k,-+s) ds.

15.7
We integrate the Langevin equation

dv l
dt = -')'V + m F' (t)
-1
over a time,- which is small compared to, but large compared to the correlation time,-* of

the random force

v(,-) - v(o) = -')'V(o),- + iiil J,.O
F'(t')dt' (1)
th
The time interval t is divided into N smaller intervals such that t = NT. Then in the k

subdivision t' = kT +sand dt' = ds. Hence (1) becomes

vk = (l-n) vk-l + ¾f ,.F'[(k-l)T+s]

0
ds

We can find the velocity at t = NT by an iterative procedure. Defining Gk as in problem 15.6 we

have
vl = (1-,,-) V0 +G0

v2 = (l-')'T) vl + Gl
(l-,,-) [(l-')'T)v0 + G]
0 + Gl
2
= (1-')'T) V0 + (l-,T) G0 + Gl
Continuing this way we see that

VN = (1-rr ) N Vo+ (l-')'T )N-1Go+ (1-,,- )N-2 Gl +••• + GN-1

N -~,- N N
Si.nee,,- << l, e-,,- = (e' ) ~ (1-rr) it follows that

ll9
or

since rr << 1. This result agrees with 15.5.

15.7
Gk = G = J(F' 0
(k+s) ) ds = 0

__ N~l _ _ N;l -rr(N-k)

Hence y - t... Yk - t... e G=O
k=O k=O
and v-ve-rt =Y=O
0

v = v 0 e-rt
Then as t ~o.,, v ~ O.
15.8

From 15. 5 we have

- N-1 - N-1 N-1
i2=I: yk2+r r y
k y
j
k=O k / j
It 'WaS shown in 15.7 that yk = O.
-y2 = N-1 - - N-1
Thus L e-27T ( N-k ) Gk 2 -_ G2 e -2rt ~~ e 21 Tk
k=O k=O
Where we have used NT= t. The sum is just the geometric series and may be easily evaluated.
21 2
y2 = a2 e -2rt ~-e ~""' G2tl-e - rtJ
1 -e 2n 2rr

2
where e 7T-l""' 27T by series expansion since )'T << 1. To find G2 ve note that

-v+
2 2 2 1-e - 2 rt
{v-v e-'v) = Y = G
o 2rr

Letting t ~o., yields, by equipartition,

2
2 kT G
V =m- = -
2)'T

120
From problem 15.5 we ~ve

and (l)

where we have changed the integration variable from s tot' to conform to the notation of the
2
text. G is independent of k allowing the choice of' k==O in (1).

2
G = \JTdt'fT{F'(t') F'(t")) 0 dt"
m o o

The integrand is the correlation :f'unction of F 'which depends only on the time difference s = t "-t' •

Making this change of' variable, we bave

- J'r
2
G = \ dt'f
-r-t'
(F'(t')F'(t'+s)) 0 ds = \
J
T T-t'
dtj K(s)ds
m o -t' m o -t'

vhere the last equality follows because (F'(t')F'(t'+s)) 0 = (F'(o)F'(s)) 0 = K(s). Since K depends
only on s, the integration overt' can be performed easily by interchanging the order of inte-

gration and reading off the limits from the figure.

G
2
~ ~2 [1_:ds L:K(s) dt' + 1:~, f-;(,) dt]
T

t'
Since T >> T* and K( s) ~ 0 for s >> -r*, s can be neglected compared
to T and the limits replaced by ± co.

Thus

121
By
2
the results of 15.8, G = 2kI' n/m. It follows that

7 = 2zDiT Jet) K(s) ds

-<C

15.ll

(a) We integrate the Iangevin equation

a..v 1
dt = --yv + m F ' ( t)
over the interval~-
v(-r) JT
J V
0
dv = -7
O
V dt' + ~JTF'(t')dt'
0

Since Tis small, ve can replace v by the initial velocity v in the first integral on the right
0

and obtain
l:::.v = v-v0 = --yv T + -l!TF'(t ')dt I
o m
0

= -rv0 -r + G (l)

and l:::.v = -1 V
0
T since G = o.
(1:::.v)2- = (7 v 0 -r)
2
- 21 v
0
T G+ a2
2
""' G = 2k.Trr/m (2)

where ve have used the result of 15.8 and kept only terms to first order in -r.

(b) Fram (1), keeping terms to lowest order in T and noting that odd moments of Gare o, ve find

(!:::.v) 3 = -3,
2
V T G
0

(!:::.v)4 = ~
2
Since G « -r, ~
G should be proportional to T.
2
Hence (!:::.v) 3 and (!:::.v)
4 are proportional to -r2 •
(c) From (2), (.6.v) 3 = - 6kr r2-r2v0 /m.
15.12

From eq. (2) of 15.4

(v(o)v(t)) = (v2(o)) e--,,t +~iol .-rti\rt• F'(t')~

=
2
(v (o)) e-
rt -rt
+ ~ (v(o))
ft (e
rt' F'(t')) dt'
. 0

But since F'(t ') is random, the second term on the right is O. By equipartition

122
Thus {v(o)v(t)) = -m e
~ -rt

and since (v(o)v(-t)) = (v(o)v(t)), we have for all t

(v(o)v(t)) = ~
m
e-,ltl

15.13
Squaring equation (2) of 15.4 yields
.,,...
v 2 (t) = v 2e-2 iv+ 2v
0 0
7-2rt It -2,t
e 1 v F'(t')dt' + ~
.,,+ I J 1 t
dt'
t
ey
(t '+t •)
F'(t')F(t")dt' 1
· o · m o o

(1)

since (F'(t')) = O. The correlation function in the integral is only a function of the time
differences= t"-t'. Ma.king this change of variable yields

tdt'f\,(t'+t") (F'(t')F'(t"))dt" =ftdtft-t~s e1 ( 2t'+s)K(s)

f 0 0 0 -t I

where K(s) = (F'(t')F '(t'+s)) = (F 1 {o)F 1 (s)). The evaluation of this integral is similar to

that of problem 15.10. Thus interchanging the order of integration and reading the limits off
the diagram of problem 15.10 with t substituted for T yields

J\tf
Q
t-t~s e'( 2t '+s)K(s)
-t I
=J -t
O
ds I t dt 'ey(2t '+s\(s)
-S
+J O
\s r t-:t 'e 1 ( 2t '+s\(s)
J0
o . ( 2rt -2ys) f t ( 2,(t-s) )
=
J-t
ds eysK(s)e -e
2 i'
I
0
ds e)' 5 K(s)e
2 )'
-l

Since K(s) is only appreciable when ys << 1, we can put e 1s ""l in the above and find

o ( 2,,-t f t 2rt
f -tt ( 2)'t 1) f a,
J
1)
ds K(s)e _ -- + ds K(s) (e -l) = ds K(s ) ~ e - ...,, ds K(s)
-t
2I o 21 21

Substitution in (1) yields

v2 (t) v/ = e-
2 (1-e -2,t)
rt + -"----,._-
la, ds K(s)
2)'m
2 -0::,

-2--
as t -'>a,, v (a,) = kl' /m by equipartition and
-2-- ~ l
v (co) = - = -
!co dsK(s)
m 2rm2 ...,,

Hence , = ~ J~ ds K(s) as in (15.8.8)

123
15.14
(a) We will denote the Fourier coefficient of F'(t) by F'(m) and that of v (t) by v (m). That
is t 1·wt
oo •

J f
co
F'(t) = eJ..lO F'(m) am and v(t) = _..,e v(w) dw (1)
~

Substitution in the Langevin equation gives

iwv(m) = -tV(m) + !m F'(m)

or ()
V ID
1
m(7+iID) F'()
ID

Denoting the spectral densities of F' and v by JF 1 (m) and Jv(m), we have from (15.15.u)

= m2 (r 2 -fo))
2
e
7T' I
v{m) 12

or JF,(co) = m2(,l-fo)2) Jv(m) (2)

(b) By (15.10.9) K(s) = (V(o)V(s)) = kT

m
e-rls l (3)

Thus JvCco) = ~ J~ K( s) e -iIDs ds

[r
• !, ~ e (-w-+, )s ds + f e (-W>-7)sds]

3v(a,) • : , [c/:;,,,j - (-7=:io,~ ":, [ x.,2J (4)

(c) Substitution of (4) into (2) gives
l
JF(w) = TI mkT y

or JF,C+)(co) = 2JF(m) = ~ mkT r

This result depends on co<< (T·;(- )- 1 , where T;: is the correlation ti.me of the fluctuation force,

since in deriving (3), one used a time scale such that -r >> ,.*. Consequentl;y', IDT ::::: 1 >> w-r*.

124