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481 2013-10-14 RevolucionPlanck
481 2013-10-14 RevolucionPlanck
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
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.
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
(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
2
m = (2n - N)
2
= 4n
2 - 4nN
- + W--
~2
and
4
m =
1.7
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
'We consider the relative motion of the two drunks. With each sillr..i.ltaneous step, they have a
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 )
Thus
1.9
(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)
-- 2 -2
(.6n) = n
...!;)
- n- = >-.
1.11
-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
-,.._n "-
In the lilllit ~t ~ o, W(n} ~ n! e as in problem 1.9 vhere )... = ~ , the mean number of disintegra-
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
6n -6
W(n) =,
n. e
1..1.4
(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.
-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
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
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.
(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
1.21
a
n.
J
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
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.
and
7
(b) If the spin is anti-parallel to the field,
a3 ,J;' db
12/µ 2 -µ a%'
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
where
We expand Q. (k).,
J.
- 1 2 2
Q. ( k ) = exp [i s.k - - (6s. ) k ]
J. J. 2 J.
dk exp(i{L. s.-x)k -
i J.
N_
2 L.i (.6.s.)
J.
lN 2 2
k]
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
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
_~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
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
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)
0 r >3-l
CHAPrER 2
p = ~ op = ~ o E
2.2
11
(a) The probability oi' displacement x is the probability that cp assumes the required value in
vhere the i'actor oi' 2 is introduced because tvo values oi' <p give the same x.
Since
ve have
volume, v.
ov/2
E - P2 + m ,ix2
Since - 2m 2 (J.)
ve have Ae = 7r ~
,./mw2
r- = ~E , and v = 2:° 6E •
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
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,
2.6
2
o2f' o r
(a) not ex.act dX oy I eydX
{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
(c) W = l 8
(1) dV = 700 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
~ = ~ ln O(E)
= ..1.... ln ½<1 - ~)
2µH l - ~(l -
2
l )
NµR
(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)
In equilibrium, Hence E E 1
µ~ = µ'~'
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
2
Thus P(E)d.E = - 1- exp [- (E-E) ] dE where cr is given above.
J;;'cr 2cr2 '
(e)
(3)
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
(b) The heat given off by either reservoir is Q = mc(50) = 2.09 X 105 joules. Since the
(c) There vill be no entropy cha.llge if' the system is brought to its final temperature by inter-
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
(30)(333) + (30)(4.18)(Tf-273)+(200)(4.18)(Tf-293)+(750)(.418)(Tf-293) = 0
Tf = 283°K
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.
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
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) =
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
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
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-)
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.
= ~ 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
(b) Let -l be the distance from the left and v the number of moles.
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.
6E = -W =- T (Vf-Vo)
The internal energy of the gas is o~ a i'unction of temperature, .6E = vcv(Tf-T 0 )
21
Substitution in (1) yields
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
dT
For N , µ = 28 and letting , = 1.4, dz= -9.4 degrees/kilometer.
2
p = p0 exp [-µgz/RT]
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
we have
cP cp _ P o2g
di= di= ot2
Then
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
5.10
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
Therefore
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
5.14
(a) TdS = dE - FdL (1)
(b) From (1) we may read off the Maxwell relation
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
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
S(L,T) - S(L,T )
o
=
1T
0
~
T
=
T
0
T1
o dT'
26
Fran (1), ve ca.n read off the Maxwell relation
Since cr = cr -ctr,
0
Thus
5.17
By equation (5.8.12)
~
\oV)T
- p
-
+ n~ dl32 -
dT
p = n~ dl32
dT
> 0
27
5.18
(a)
ve have
.
0 = T cos~ -
av)E
p and (~\
oV)E
= ~T
Thus
5.19
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) =
(l)H = ~p (~ <I) p - 1) = 0
28
or
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
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' :
(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
41 Ti
w=Ti-To
(b) ql
V = 11.9
5.23
We have the system
(a) (1)
Thus
It follows that
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
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
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
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
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
Thus
CB'.API'ER 6
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
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
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
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
: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
dn(z) - - 5 n(z)
dz - ~
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
and
evaluate T vhere
-
E-Ne:
N e:l+e:2
[ J
- 1 +-
2 -- 2 - e :l
which yields
34
The heat capacity is
(c) As T -+ O, the nucleii go to the ground stat~, and by the general definition of entropy
S=Nklnn=Nklnl=O
A A
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
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.
E(r'
- !.I
=_gs,~
rL -
U(r) = ir ~--~ 0
=- f!l ln ~o
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
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
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
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
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
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 = 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
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.
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
= -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 = -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
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
consequentzy S
0
~ s.
40
CHAPI'ER 7
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
The integrations over~ yield the volume, V, while the E_ integrals are identical. Since there
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
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
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.
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
or
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
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
Hence
2
P"'X o:T
7.9
(a)
The mean elongation is found by equating the gravitational and restoring forces
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.
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
45
7.13
'We have Mz = Ng µ
0 0
J B/71). By equation 7.8.14, ~ (71) for J =½becomes
sinh
2 ( /2)
sinh (71J2) cosh (71/2)
Thus
-
The energy of the magnetic moment in the field His
the probability that the magnetic moment lies in the range e toe+ de is proportional to the
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
,
For spin
(a) The energy of a magnetic moment in a field is E = -1:. • ~- 2 atoms
(b)
+ (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
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
u = czm)2
µ
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
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
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
~
- 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
7.23
(a) The number of molecules which leave the source slit per second is
= 1.1 x 10
18 molecules/sec
(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
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
(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
dN l -
dt = - cpA = - 4 nvA
50
Since the pressure is proportional to the number of particles, we have
dp vA
-=
dt - 4Y p
p(t)/p(O) = 1/e is 4v
t -
VA
7.25
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
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
~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)
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
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
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
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 )
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
8.1
By equation (8.3.8), we have the proportionality
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
(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
1
By definition, K = Substitution of these results into (1) yields
VK
and since V = r~/p 0 and CV = McV where ~ is the specific heat per gram, it follows that
0
(V - Mjp 0 )j dV dT
(?(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
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
or
8.4
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
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
(1)
Since pis the vapor pressure, the Clausius-Clapeyron equation yields dp/d.T.
dp L L
dT = T(vgas - vliquid) ""T vgas
(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
(~)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)
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
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,
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'
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
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
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
~ 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.
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
~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.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
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
€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
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)
(2)
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)
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
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•
= -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)
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
(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
&, = R (l + ~)
The molar heat of evaporation is
""~=NAT} if TJ>>kT
63
Hence (4)
(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
These results are remarkabzy good in view of the very simple theory considered here.
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
64
but since N = I: iir and E = I: nr €, we :find
r r r
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
The calculation of S Froceeds in exactly the same way as in (a). We quote the result.
(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 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)
(2rr m kT)
or
N' . 2
n
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
€
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
*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.
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
= K
n = (1)
From the results of section 9.12, we can immediately write dmm the quantities ;. In the
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
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
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
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
4
dS = -3 ~ dV . y d.u dm
.L
.,. (1)
T T dT -
(~s)
4u
= -3 -T and (3)
oV T
2
(b) Since (c sfev 6T) = (d2S/'cT QV), it follows from (3) that
70
or
where c' is the velocity of light in the material. c' is related to the velocity of light in
2
3 4
- 7r (kr)4 n 3 = 4cr n0 VT
Thus E =V-
15 (ct1)3 0 C
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
or
71
= 5.7 X 10llergs/sec c:m2 = 5.7 X 104 watts / c:m2
tiwmax he
- kr - ---=3
-krA.
max
Thus
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)
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
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
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.
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)
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
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
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.
sf 400
-=-=2
Si 2CQ
(b) The energy of the radiation field inside an enclosure is proportional to T4 , and the heat
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.
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.
Thus Q = (4.14)(;
2
R)(~ ~') 1i· 3
T dT = -.0022 joules
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
75
\m
-- =
X
parallel states to minimize the energy. This is (µmH)p(µ ) where p(µ ) is the density of states
0 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
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
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
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
emitted flux cannot depend on the conditions outside the metal, this is also the flux where
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
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.
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
= 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
= 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
,
,,,·· -.......\
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
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 ~
where we have used ex= .l+x+ ••• and the residue theorem. Then combining (4) and (5) we find
7rk
=
sinh 7r k
(6)
Then com!)aring coefficients with the series in (2) we can read off the Im's. We find r2 = 1r2/3.
we have n=
s
1
13
'a~
"'s
1nZ
where the partial denotes taking the derivative where €s occurs explicitly. Evaluating the sum
81
(2)
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
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
integral yields
(l)
where
To approximate (1) we eA-pand the logarithm of the integrand about o:' = 0 where it contributes
1 2
- - B
2 2 o:' +
where
i(N+J\)o:'
Hence e
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)
10.2
(a) By (10.1.18)
3V 2
where 2 3 ill for ro < ~
2iT
1 C
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
~ 3N (1-e
-eJT ) + ND ( e Irr)
=
i1wD - 1n
D' ~ (1)
where keD = ~wD.
(b) The mean energy is
Thus E =
(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
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)
, 4 4
- 37T
2!1. ?' N kT
p = N 2V + -5- V e 3
D
Comparing the expression for the energy E, equation (2) in problem 10.2, vith equation (1) in
86
Thus a=
10.6
u = -g ·~ a: p E a: R-6
2 2
where n = Njv. The first two terms are the ideal gas partition functions while the last is the
To show that A(T) is negative, we must show that the derivative c/c~ [I(~)/S] is positive.
We have
;:,. Jo:,
(~ = c~ o
since (1-+f3u) is just the first two terms in the expansion of e~u. Thus the integral is positive
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
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
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)
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.
~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
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
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
(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)
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
(1)
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
(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..
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
12.2
(a) ,E, (b) ,E, ( C) {,
mx = e!
2
e e t
Hence and X=m 2
and X =-T
e! 2
m
t = ~ ; =£ T
Thus the fraction of cases in which the ion travels a distance less than xis
12.4
The differential cross section is given by
cr(n) = -2rrs ds
d!2
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
where t i s the mean free path. Letting P = .9 and t = (ff ncr)-l yields
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
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,
velocity ro(R+o) ~ cuR, and the air at the inner cylinder is stationary.
Thus
(b) The viscosity is given by Tl = mv/3 ,.[2 a • Since air is ma.inzy composed of nitrogen, we
0
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
Thus
On solving this system of equations, we find x = 4/1-s; hence the cross section a is proportional
0
to v4/(1-s).
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
.
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.
by (12.4.9)
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
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
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
2z = r.
i
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
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
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
where {-r)cr = 8
yJ; f 0
co
ds e -s
2
s 4 -r(vs)
"'
]3.3
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
u
X
= u sine cos cp uZ = u cos e
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)
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
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
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
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)
181
ll on 3 ot3 mv
2
~ (3)
f = g-g v z... Ln: oz + 2p oz - 2 c1~
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
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
l on l 05 (4)
or n dZ = ~ oz
C:o
or -:=- = 0
c:.z
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
~ 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
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
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
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
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
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
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
~
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
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
l4.l
The mean rate of momentum loss per unit volume due to collisions is, by (14.4.22)
where we assume central forces. We first perform the integration over angles by changing to
107
becomes, since v ~ V and v' = c +
=c +m ~ V'
- m_
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
and µ(V z '-V z ) = µV z (cos e'-l)+µV sin e'cos cp' sin (Y,!)
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)
Thus
(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
d3£ d\ = Jd 3~ d3y
109
mml
whereµ -- - -
m-+ml. The momentum balance equation is then
ne e + (6.p ) = 0
z
which gives
14.2
where (2)
(3)
and that the pressure is independent of z.
:Because the situation is tir.ie indepencier:t and there are no external fo:::-ces, we are left with
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
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 )
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
lll
define
(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),
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)
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)
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
(14)
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
c e.nd V; hence we need keep only even terms in v (l-crv 2 )J. This yields explicitly
z
: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
=
! 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
-
102471" _l_
= - -n- (II$)3
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 ))
= 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
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
14.4
3 2
Let t i ng f = n (:) / exp [ - ½Bmv2 ] , we have
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
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
elf
at =ff d3..:.J.v an' Vcr (f1 'f' - f f)
1
(2)
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
(4)
Similarly, this integral is invarient if the initial and final velocities are interchanged because
Thus ~
dt = !fff
2 d3-v 1
d3-1
v ' an' V'cr (f1 f-f 1 'f') (ln f 1 'f'+2)
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)
~~ =- 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
J d3! ½rrrlf 4n f 0
2
""v dv ½ rrN
2
e-A 'v
2
J d
3
! f
3 m
= 4 A'
CHAPTER 15
15.1
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
(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)
-
au
- -l r t .,..,, ("'")
dt= -!D.e t "
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
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
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
ll9
or
15.7
Gk = G = J(F' 0
(k+s) ) ds = 0
v = v 0 e-rt
Then as t ~o.,, v ~ O.
15.8
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
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' •
- 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-
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
15.ll
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
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
(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
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
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 ...,,
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)
~
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
[r
• !, ~ e (-w-+, )s ds + f e (-W>-7)sds]
since in deriving (3), one used a time scale such that -r >> ,.*. Consequentl;y', IDT ::::: 1 >> w-r*.
124