Solution Manual For Physical Chemistry 4th Edition

PI:il~~AL
C
H
E
M
I
S
T
R
Y
, - - - - P.W. ATKINS---....... . ._
Solutions Manual for
Physical Chemistry
Fourth Edition
P. W. ATKINS
Physical Chemistry
FOURTH EDITION
P W. Atkins, 1990
All rights reserved. No part of this publication may be

reproduced, stor ed in a retrieval system, o r transmitted,
in any form or by any means, electronic, mechan ical,
photocopying, r ecording, or other wise, w itho ut the prior
permission of Oxford U niversity Press.
'Reprinted by arra ngement w ith Oxford Publishing
Limited' or 'This reprint has been authori zed by Oxford
Publishing Limited for sale in J apan only and not for
export ther efr om' together w ith the fu ll copyright line as
printed in the Work.
Preface to the fourth edition

I have reworked all the solutions in this edition from scratch and in the light of
comments received on the earlier editions. I have also adopted, within the
constraints of space to which a Solutions manual is subject, a slightly more
generous style , with more words, more details, a more open layout, and more
guidance.
The solutions have been examined in detail by Michael Fuson, of Denison
University, Granville, Ohio and by Charles Trapp, of the University of
Louisville, Louisville, Kentucky. I am greatly indebted to them both for their
good advice, which I have tried to follow, and their detailed comments. If errors
remain, they are probably at locations where I ignored what they advised.
Oxford,
April1990
P.W.A.
Contents
PA RT 1: EQU ILI B RI UM
I . Th e prope rti es o f gases
2. The first law: th e co ncepts
3. The first law: the mac hinery
4. Th e second law: the concepts
5. Th e second law: the mac hinery
6. Cha nges o f sta te : ph ysica l tra nsfo rm ati o ns of pure substa nces
7. Cha nges of state: physica l tra nsfo rm ati o ns of sim ple mixtures
8. Cha nges of sta te: the ph ase rule
9. C ha nges of state : che mi ca l reactio ns
10. Equilibrium electroch e mi st ry
1
18
40
59
78
93
108
132
147
170
PA RT 2: ST R UCTUR E
II . Qu a ntum th eory: introduct io n a nd principles
12. Q ua ntum th eory: techniq ues a nd applicati o ns
13. A to mic structure a nd ato mic spectra
14 . Mo lec ul a r structure
15 . Symme try: its de te rmin a ti o n a nd co nseque nces
16. Ro ta ti o na l a nd vibratio na l spectra
17 . E lectro nic tra nsiti o ns
18. Magnetic reso na nce
19. Statist ica l the rmod ynamics: the concepts
20 . Stati stica l the rmod yna mics: the machin e ry
2 1. Diffractio n me thods
22. T he e lectric a nd mag ne tic pro pe rties of mo lecules
23. Macromo lecul es
198
216
234
247
266
28 1
304
321
334
349
372
390
409
PA RT 3: CHA NGE
24. The kin e ti c th eo ry of gases
25. Mo lecules in mo tio n
26. T he ra tes of che mica l reactio ns
27. T he kineti cs of complex reactio ns
28 . Mo lecul ar reactio n d yna mics
29 . Processes at solid surfaces
30. D yna mic e lectroche mist ry
432
454
472
497
516
539
563
APPENDI X: Linea r regressio n
577
PART 1: EQUILIBRIUM
1. The properties of gases
Exercises
1.1
V;
Pr= Vr X p; (3]
V; = 1.0 L= 1000 cm 3 , Vr= 100 cm 3 ,p;= 1.00 atm

Pr=
1000cm 3
x 1.00 atm = 10 x 1.00 atm = 10 atm
---100 em1
1.2 (a) Find what pressure a perfect gas exerts from pV=nRT. Since the
molar mass of Xe is 131 g mol - I, the sample has n = 1.00 mol X e.
Therefore, with p = nRTIV,
p=
1.00 mol x 0.0821 L atm K -I mol - I x 298.15 K

J.OL
24atm
That is, the sample hasp= 24 atm, not 20 atm.

(b) The van der Waals equation is (1 1]:
nRT an 2
p= V-nb- V 2
For xenon, Table 1.4 gives a= 4. l 94 L2 atm mol - I and
b = 5.105 x 10- 2 L mol- 1 Since n = 1.00 mol and V= 1.0 L,
nRT
V-nb
an 2
- 2
V
l.OOmol x 0.0821LatmK - 1 mol - 1 x 298.15K

_
(1.0-0.05I)L
=25.8atm
4. 194 L2 atm mol- 1 x (1.00 mol) 2
(1.0 L) 2
Therefore,
p = 25 .8 atm- 4.194 atm = 22 atm
4.194atm
The properties of gases
Vr
1.3 p;= V Xpr [3]
I
Vr = 4.65 L, V; = 4.65 L + 2.20 L = 6.85 L

p 1 =3.78 x l0 3 Torr
Therefore
4.65 L
(a) p ; = _ LX 3.78 X !OJ Torr= 2.57 X !OJ Torr
6 85
(b) Since l atm = 760 Torr exact ly,
p; = 2.57 x JOJ Torr x
1.4
1 atm
Torr
760
3.38 atm
Vr
Tr= V X T; [5]
I
V; = l.O L, V 1 = 100 em\ T; = 298 K

100 cm 3
Tr= lOOO em' x 298 K = 30 K
Tr
1.5 Pr= T Xp; [5]
I
Internal pressure= quoted pressure+ atmospheric pressure

p ; = 24lb in - 2 + 14.7 lb in - 2 = 38.7lb in - 2
T; = 268 K (- 5 oq, Tr= 308 K (35 oq
Pr=
308 K
_
_
K X 38.7lb in - 2 = 44.5 lb in - 2
268
Therefore
p(internal) = 44 .Slb in - 2 - 14.7 lb in - 2 = 30 lb in - 2
Complications include the change in volume of the tyre, the change in rigidity
of the material from which it is made , and loss of pressure by leaks and
diffusion.
1.6
v,
T1= V
T; [5]
Vr= 1. 14 V; (a 14 per cent increase) , T; = 340 K
Therefore,
!.14 V;
Tr = -V--- X 340 K = !. 14 x 340 K = 388 K
I
V; = 2.0 m' , p; = 755 Torr , p 1 =(a) 100 Torr, (b) 10 Torr

Therefore:
(a) V1 =
755 Torr
x 2.0m 1 =15m1
IOOTorr
--
(b) V1 =
755 Torr
1
1
Torr x 2.0 m = !. 5 x 102 m
10
I.s
11
nRT
p=vliJ
0.255 g
g mol _ 1 = 1. 26 x 10 - 2 mol , T= 122 K. V = 3.00 L
20 18
.
Therefore,
1.26 x 10 - 2 mol x 0.0821 L atm K - I mol - 1 x 122 K
p=
1.9
3.00 L
4.22 x 10 - 2 atm
n 1 RT
(a)V=- - (7]
PJ
0.225 g
g mol _ 1 = 1.11 5 x 10 - 2 mol, p(Ne) = 66.5 Torr. T= 300 K
20 18
n(Ne) =
Therefore, since there is on ly o ne vo lume,

! . liS x 10- 2 mol x 62.36 L Torr K - I mol - 1 x 300 K
V=
(b) p =
66.5 Torr
nRT
n( Cl-1)4
-
[I], n = n(Cl-1 4 )
0.320 g
16.04 g mol- 1
+ n(Ar) + n(Ne)
1.995 x 10 - 2 mol
=3. 14L
n(Ar) =
0.175g
g mol _ 1 =4.380 x 10 - 2 mol
39 95
.
n = (1.995 + 4.380 + l.llS)
10- 2 mol= 7.490 X 10- 2 mol
Therefore
7.490 X 10- 2 mol X 62 .36 L Torr K - l mol - l X 300 K
p=
3.137 L
447Torr
mRT
RT
Therefore, M = - V = p p
p
p= 1.23 g L - 1, T=330 K , p = 150 Torr
Hence
1.23 g L - l X 62.36 L Torr K - l mol - 1 x 330 K
150Torr
= 169 g mol - l
M=
1.11
p=
RT
p
M = p - [Exercise 1.10]
33.5 mg
_
mL =0.1340 g L - 1, p = 152 Torr, T=298 K
250
0.1340 g L - l x 62.36 L Torr K - l mol - 1 x 298 K

M=
152 Torr
= 16.4 g mol - l
1.12
nRT
(a) p=v[1J
n = 1.0 mol , T= 273.15 K (i) or 100 K (ii)

V = 22.414 L (i) or 100 cm 3 (ii)
1.0 mol
8.206 X
(i) p =
(ii) p =
w- 2 L atm K -l mol - l X 273.15 K

22.414 L
1.0 mol
8.206 X
w-~
L atm K - l mol - l X 1000 K
0.100 L
1.0 atm
8.2 x 102 atm
From Table 1.4, a = 5.489 L2 atm mol - 2 and b = 6.380 x 10- 2 L mol - 1
T herefore ,
1.0 mol X 8.206 X 10- 2 L atm K - I mol - l X 273.15 K
nRT
(i) - - =
V- nb
(22.414 -1.0 X 6.380 X 10- 2) L
= 1.003 atm
5.489 U atm mol- 2x (1.0 mol) 2

_
V2 =
(22.414 L)2
= 1.09 x 10-2 atm
an 2
and p = 1.003 atm - 1.09 x 10- 2 atm = 0.992 atm = 1.0 atm
nRT 1.0 mol X 8.206 X 10- 2 L atm K - I mol- l X 1000 K

103
(ii) V- nb =
(0.100- 0.06380)L
= 2 27 x
atm
5.489 L 2 atm mol- 1 x (1.0 mol) 2
V2 =
(0. 100 L) 2
an 2
5.49 x 10 atm
and p = 2.2'7 x 103 atm - 5.49 x 102 atm = 1.7 x 10 3 atm
Vc= 3b(12a) = 3 X 0.0226 L mol - 1 =6.78 x 10- 2 L mol - 1

a
0. 751 L 2 atm mol - 1
2
Pc= 27b 2 (l b] = 27 X (0.0226 L mol- 1) 2 = 54 5 atm
1.13
8a
8 x 0.751 U atm mol - 1
T = - - (12c] = - - ------=---,- ----,--- - -----,c
27Rb
27 X 8.206 X 10- 2 L atm K -I mol-l X 0.0226 L mol - l
= 120K
1.14
Z=
~; (9]; for a perfect gas V~ = RTIp . Since the molar volume is 12
per cent smaller than that of a perfect gas,
RT
Vm=0.88 V~, = 0 .88 p
Therefore,
p
RT
(a) Z=RTx0.88 p =0.88
ZRT 0.88 X 8.206 X 10- 2 L atm K - I mol - l X 300 K

p
20 atm
(b) V~= - =
1.1 L
Since V"' <

1.15
v::, attractive forces dominate
pV"'
Z = RT [9], implying that Vm=
ZRT
Since Z = 0.86 , T= 300 K, p = 20 atm,

0.86 x 8.206 x l0 - 2 LatmK - 1 mol - 1 x 300K
Vm=
20 atm
_
=1.059Lmo l- 1
(a) V = n V"' = 8.2 X 10- 3 mol X 1.059 L mol - 1

=8.7mL
(b) B=Vm(':;'-1) [lOb]=Vrn(Z - 1)
= 1.059 L mol - 1 x (0.86-1) = -0.15 L mol - 1
1.16
n = n(H 2) + n(N 2) = 2.0 mol+ 1.0 mol= 3.0 mol
2.0mol
(a) x(H 2) = . mol= 0.67
30
RT 8.206 x 10- 2 LatmK- 1 moi - 1 X 273.15K
22
.4 L
= 1.00 atm mol - 1
p(H 2) = 2.0 mol x 1.00 atm mol - 1 = 2.0 atm

p(N 2) = 1.0 mol x 1.00 atm mol - 1 = 1.0 atm
(c) p = p(H 2) + p(Nz) [7]

= 2.0 atm + 1.0 atm = 3.0 atm
1.17
b= ! Vc [12a , Vc=98.7cm 3 mol - 1]

= 1 x 98.7 cm3 mol - 1 = 32.9 cm3 mol- 1
a= 27b 2pc= 3 V ~ pc [12b, Pc= 45.6 atm]

= 3 X (98.7 X 10- 3 L mo l- 1) 2 X 45.6 atm = 1.33 L 2 atm mol - 2
As b is approximate ly the volume occupied per mole of particles
b
u
1-
32.9 x
w - ~> m -' mol -
NA- 6.022x 1W' mol - l
""' -
=5.46 X 10 - "9 m 1
Then, with Vrnol = }:rrr -',
3
)
9
( 4:rr x 5.46 x l0 - " m-'
r=
11.1
=0 .24nm
From Table 1. 4, a= 6.493 L" atm mol - 2 , b = 5.622 x 10 - 1 L mol- 1 There fore ,
6.493 U atm mo l- 2
,
,
= 1.4 X JO-' K
5.622 x 10 - Lmol - 1 x8.206xlo - - La tmK - 1 mo l- 1
Tn =
b
5.622 X J0 - 5 m-' mol - 1
_
(b) As in Exa mpl e 1.1 7, V111., 1 = N A=
X _. mol _ 1
6 022 102
r=
3
)
29
( 4:rr X 9.3 X J0 - m-'
11.1
9.3X J0 - "9 m-'
= 0.28 nm
1.19 At 25 oc and 10 atm, the reduced tempe rature and pressure [Sect ion 1.5]
of hyd roge n are
T,=
p,=
298 K
_
_ K = 8 .968
33 23
1.0 atm
12 .8 at m
_
=0 .078 1
[Tc= 33 .23 K, Tabl e 1.3]

[pc= 12.8at m, Table 1.3]
Hence , the gases named will be in corresponding states at T= 8 .968 x Tc and

at p = 0.0781 x p, .
(a) For ammo ni a , Tc= 405 .5 K and Pc= 111 .3 atm [Table 1.3], so
T= 8.968 X 405.5 K = 3.64 X 10-' K

p = 0.078T x 111. 3 at m = 8.7 atm
(b) For xe non, Tc= 289.75 K and Pc= 58.0 atm, so
T= 8.968 X 289.75 K = 2.60 X JO-' K
p = 0.0781 x 58.0 atm = 4.5 atm

(c) For helium, Tc = 5.21 K and Pc = 2.26 atm, so
T = 8.968 x 5.21 K = 46.7 K
p = 0.0781 x 2.26 atm = 0.18 atm

Problems
1.1
p
Vr = ---'x V; [3] andp = pgh [Example 1.2]
Pr
Total pressure: p; = 1.0 atm

pr= 1.0 atm + pgh
pgh = 1.025 x 103 kg m- 3 x 9.81 m s- 2 x 50 m = 5.03 x 105 Pa
Hence, Pr= 1.01 x 105 Pa + 5.03 x 105 Pa = 6.04 x 105Pa
_
_ l.Oix 105Pax
3
3
Vr- 6.04 x 105 Pa 3m - 0.5 m
1.2 External pressure is p; and pressure at foot of column is Pr+ pgh . At

equilibrium the two pressures are the same, so
Pr-p;=pgh
=l.Ox10 3 kgm- 3 x9.81ms- 2 x0.15m
= 1.5 X 103 Pa ( = 1.5 X 10- 2 atm)
1.3 p V = nRT [1] implies that, with n constant,
PrVr p;V;
--Tr
T;
or
V
Vr
Tr
(r)3 X-
Pr =~ X - Xp;= ~
T;
rr
Tr
Xp;
T;
1.0 mv 253 K
2
= ( 3.0 m} X 293 Kx 1.0 atm = 3.2 X 10- atm

RT
RT
Thatis p = p - or- = ,
M' 'p M
For a real gas
nRT
RT
p= (1 + B'p+ )=p-(1+B'p+ )
V
which rearranges to
p RT RTB'
- = - + - -p + .. .
p M
M
Therefore, plot pip against p and expect a straight li ne with intercept RTI M
at p = 0. Draw up the fo llowing table:
piTorr
91.74
188.93
277.3
452.8
639.3
760.0
pl(kg m- 3)
(plp)1(105 m2 s- 3)
0.225
0.544
0.456
0.552
0.664
0.557
1.062
0.568
1.468
0.581
1.734
0.584
T he points are plotted in Fig. 1.1, and the limiting behaviour is confirmed
0.59
"'"'
_&,
"'E
057
V)
0.55
.8-
0.53
.. "
0.2
0.1.
VIJ
0.6
0.8
The intercept at p = 0 is at
~I (105 m 2 s- 2) = 0.540, or pip= 0.540 x 105 m 2 s- 2

Therefore,
RT
M=
Fig 1.1
0.540 x 105 m- s --
1.0
p/10 Po
10

8.314J K- 1 mo l- 1 x298.15 K
0.540 x 105 m 2 s- 2
=4.59
10- 2 kg mol - 1 = 45.9 g mo l- 1
p = 1.0 atm , T= 298 K
l.Oatm x JJ 3xl03 L
(a) n = 8.206 x 10 2 L atm K 1 mo l 1 x 298 K
4 62 x IO' mol
(b) m(H 2) = nM(H 2) = 4.62 X 103 mo l X 2.02 g mol - 1 = 9.33 x W g

Mass of displaced air= 113m 3 x 1.22 kg m - >= 1. 38 x I0 2 kg
Therefore, th e payload is 138 kg- 9.33 kg= 129 kg
(c) For helium, m = nM(H e) = 4.62 x 101 mo l x 4.00 g mo l- 1 = 1R kg
The payload is now 138 kg- 18 kg= 120 kg
1.6 The mass of displaced gas is pV, whe re V is the vo lum e of the bulb and p
is the density of the gas. The balance conditio n for the two gases is
m(bulb) = pV(bulb ), m(bulb) = p' V(bulb )
which implies that p = p'. however , because [Prob lem 1. 4]
pM
p= RT
the bal a nce condition is

pM=p'M'
which impli es th at
This relation is va lid in the limit of zero pressure (for a gas be having
perfectly).
In expe rim e nt l , p=423 .22To rr . p '=327. 10To rr ; hence
M' =
423 .22 Torr

lT
x 70.014 g mo l- 1 = 90.51) g mol - 1
37_7. 1( orr
11
In experiment 2, p = 427.22 Torr , p' = 293.22 Torr; hence

M' =
427 .22 Torr

_ Torr x 70.014 g mol - 1= 102.0 g mol - 1
293 22
In a proper series of experiments one should reduce the pressure (e.g. by

adjusting the balanced weight). Experiment 2 is closer to zero pressure than
experiment 1, it may be safe to conclude that M = 102 g mol - 1. The molecule
CH 2FCF3 has M = 102gmol - 1.
T
I. 7 At constant volume , p = T
x p 1 where T1 and p 1 are the temperature and
pressure of the triple point. Therefore,

274.16 K
)
_ K -1 PJ
(a) P274.1oK-P m. lr. K= (
273 16
=
1
1
_ x 50.2 Torr= 0.184 Torr
_ x p3 =
273 16
273 16
(b) For 100 oc (373 K)

p=
373 K
_ K X 50.2 Torr= 68 .6 Torr
273 16
374 K
)
68.6 Torr
(c) PJ74K-Pm K= (
K-I Pm K=
=0 . 184Torr
373
373
1.8 Draw up the fo llowing table, which is based on the reaction
N 2+ 3H 2---7 2NH 1
Initial amounts
Final amounts
Specifically
Mo le fractions
N2
H2
NH1
Total
n
0
n+n'
Jn'
0
0
1.33 mol
0.80
n + .\ n'
1.66mol
n- *n '
0.33 mol
0.20
nRT
p=--y= 1.66 mol x
8.206 X
1.00
w- 2 L atm K - I mol - l X 273.15 K

22
.4 L
12
= 1.66 atm
p(H2) = x(H2)P = Q
p(N 2) = x(N 2 )p = 0.20 x 1.66 atm = 0.33 atm
p(NH 3) = x(NH 3)p = 0.80 x 1.66 atm = 1.33 atm
1.9
RT 8.206 X 10- 2 L atm K - I mol -l X 350 K

(a) V = - = -- - - - - -- - -"'
p
2.30 atm
= 12.5Lmol- 1
RT
a
RT
(b) From p = V m_ b- V~ [11 b], we obtain V m= --a-+ b [rearrange llb]
p+
v2
m
Then , with a and b from Table 1.4,

8.206 X
w- 2 L atm K - I mol - l X 350 K
L'
I ,
6 .493 - atm mo 2.30 atm + (12.5 L mol 1)2
Von=
+5.622 x 10- 2 L mol - 1
28.72Lmol - 1
- - - - - + 5.622 X 10 - 2 L mol - 1
2.34
= 12.3 L mol -
Substitution of 12.3 L mol- 1 into the denominator of the first expression

results in V"' = 12.3 L mol - 1, so the cycle of approximation may be terminated .
8
3
=-X
40atmx160 x 10 - 3 Lmol - 1
8.206 X 10 - 2 L atm K - I mol I
1 Vc
160 X 10 - 6 m3 mol - 1
Umol = NA = 3 N A = 3 X 6.022 X 1023 mol I
b
4n
- 3 r3
Umol-
210K
8.86 X 10- 29 m3
Hence, with V, and T, from Table 1.3,

r=
3
)
29
3
( 4.nx8.86x10- m
1/3
=0.28nm
V,=2b, T,= bR (Table 1.5]

4
1.11
Hence
b = tV,=t x 118.8 cm 3 mol - 1 =59.4cm 3 mol - 1
a = 4bRT, = 2RT, V,
= 2 x 8.206 x 10- 2 L atm K - I mol - 1 x 289.75 K x 118.8 x 10- 3 L mol- 1
= 5.649 U atm mol- 2
Hence
nRT
V-nb
= - - e-na! R'TV
1.0 mol x 8.206 x 10- 2 L atm K - I mol - 1 x 298 K

l.OL-l.Omol x59.4x 10
L mol
)
1.0 mol x 5.649 L2 atm mol- 2
xexp ( - 8._2_0_6 _x_1_0__~
x_l_
. O_L_2~a-t_m_m
__o_l-~1
2 x--2-98__
=26.0 atm x e- 0231

=21 atm
RT
V m( 1 -
~) - V ~'
13
14

2
a ] -1 +b-, + .. .)
=RT(
- 1+ [ b - vm
RT VITI V;;,
Compare this expansion with
B+C
p = -RT( 1+ , + . .. ) [lOb]
Vm
V"' V;;,
and hence find

a
B=b-- and C = b 2
RT
-___:_:__:__
__
a = RT(b- B)
= 8.206 X 10- 2 X 273 L atm mol - 1 X (34.6 + 21.7) cm 3 mol - 1
= 22.40 L atm mol - l X 56 .3 X
1.13
w-} L
mol - l= 1.26 L 2 atm mol - 2
RT
p = - - e - ai RTV.,. [Table 1.5] =
vlll-b
RT
vm
(1 -vmb)
-
e - ai R TV.,.
1
Now use the expansions--= 1 +x +x 2 + and e -.r = 1- x + h 2 +
1- x
-
and obtain
2
RT{ 1+-+-,
b
b +. . . }
p=V"'
Vm V~,
1 - -a- + -1 ( -aRTV111 2 RTV"'
)2+ ... }
RT{
vm
a ) 1 ( 2 ab
a ) 1
}
l+ b- RT VITI+ b - RT+2R 2 T 2 v ~ + ...
Comparing with the virial expansion [lOb] gives

a
ab
a2
B= b -RT and C= b 2 -Rf+2Rifi
To find a and b we form
C - t B 2 = ! b2 , implying that b=(2C -8 2) 112
and then use a = RT(b-8) .
From the data:
b= (2 x 1200 cm 6 mol - 2 -471 cm 6 mol - 2) 112 = 43.9 cmJ mol - 1

a=22.40 L atm mol - l X (43.9+21.7)
= 1.47 U atm mol -
w-.1 L mol - l
1.14 For critical behaviour, show th at there is a point of inflexion with zero
slope, and identify the critical constants.
RT
p=y-- v" +v.1

m
That is,
-
RTcV~ =2BVc -3C:O

RTcV c 3BVc+6C-O
which solve to
Now use the equation of state to find Pc:

RTC
vc
v~
v~
Pc=-----:;+]
It follows that
1.15
pVm
RT = 1 + B'p+ C'p 2 + (lOa]
pV"'
B
C
- = 1 + - + -, +(lOb]
RT
Vm
V~,
15
16
whence
B 1 p+C 1p 2
vm
v~,
=-+-+
Now multiply through by Vm, replace pVm by RT{1 + (B/Vm) +},and

equate coefficients of powers of 1/V"':
8 RT+
1
BB 1 RT+ C 1 R 2 T 2
vm
+ =B+-+
von
Hence , 8 1 RT=B, implying that BI=RT

2 ,
,
, ,
C-8 2
Also , BB RT+ CIR T - = C , orB-+ C'R-T-= C , implying that C' =R2Tz
-1
Therefore, the limiting slope of a plot of pip against p is B RTf M. From Fig.
1.1, the slope is
I
B 1 RT
~=
(0.584- 0.544) x 105 m2 s- 2

(1.013- 0.122) X 105 Pa
4.5 X 10- 2 kg - 1m3
Therefore, since the intercept lies at RTf M = 0.540 x 105 m2 s- 2 [Problem 1.4]
BI
4.5 X 10- 2 kg - 1 m 3
0.540 X 105m2s-2 = 8.3 X 10 -7 Pa - 1 [1 Pa = 1 kg m - I s-2]
Hence, B I = 8.3 X 10- 7 Pa -I
1.0133 X 105 Pa atm - I = 8.4 X 10 - 2atm - 1
Since B = RTB [Problem 1.15]

1
B = 8.206 X 10- 2 L atm K - I mol - l X 298 K X 8.4 X 10 - 2 atm - 1
=2.1 Lmol- 1
1.17 Hydrostatic pressure is given by p = pgh [example 1.2]; therefore
dp = - pg dh [p decreases ash increases]
pM
Since p= RT [Problem 1.4]

dp = -
17
pMgdh .
.
dp
Mgdh
RT , 1mplymg that
=-Iff
This relation integrates to
p =Poe - M~h ! IIT

For air, M = 29 g mol - 1and at 298 K
Mg 29 X 10-1 kg mol - 1X 9.81 m s- 2
_
RT =
2.48 x 10-' Jmol -l
=1.15x10 - 4m - l [1J=1kgm2s-2]
(a) h = 15 em
p =Po X e-O.I) mx 1.1:\x 111-"m l = 0.99998po

(b) h = 1350 ft, which is equivalent to 412 m [1 inch= 2.54 em]
2. The first law: the concepts

Exercises
2.1
w = -mgh[3]
(a) w=-l.Okg x 9.81ms - 2 x 10m=-98J

(b) w =- 1.0 kg x 1.60 m s- 2 x 10m= -16 J
2.2
w= -mgh (3]
=- 65 kg x 9.81 m s- 2 x 4.0 m =- 2.6 k~
2.3
w=
-pcx ~V
(5]
Pcx = 1.0 atm X 1.013 X 105 Pa atm - I= l.Ol X 10 5 Pa

~ V=
100 em 2 x 10 em= 1.0 x 10 3 em 3 = 1.0 x
w-> m 3
w = -l.Ol X 105 Pa X 1.0 X 10- 3 m 3 =- 1.0 X 102 ]
as 1 Pa m3 = 1 J .
2.4
(a)
w = -p 0 ~V[5]
Pcx=200Torr X 133.3 Pa Torr - 1 = 2.666 X 104 Pa

~V=3.3L = 3.3x 10- 3 m 3
Therefore, w =- 2.666 X 104 Pa X 3.3 X 10- 3 m3 =- 88 J

Vr
(b) w= -nRTin V (7]

I
4.50 g
~
n = 16.04g mol-l= 0.280) mol
RT=2.577kJmol - 1, V;=l2.7L. Vr=16.0L
_
w =- 0.2805 mol x 2.577 kJ mol - 1 x In
2.5
Vr
w= -nRTin V [7]
I
16.0L
. L = -167 J
12 7
The first law: the concepts
nRT= 52.0 X w-] mol X 8.314 J K- 1 mol - l X 260 K

= 1. 124 X 10 2 J
2
w =- 1.124 X 10 J X In
t = + 124 J
w= -pc,t-.V[5]
2.6
Pcx =95bar=95X 10 5 Pa
!-. V =- 0.450 LX 0.67 =- 0.302 L =- 0.302 x 10- 1 m '
Therefore,
w= + 95 X 105 PaX 0.302 X 10- ' m1 = + 2.9 kJ
w=-pcxl-.V[5]
2.7
Mg(s) + 2HCI(aq)--> H 2(g) + MgCI 2(aq) , M(Mg) = 24 .31 g mol - 1
nRT
V;=O , Vr= - -, pi=Pcx
Pr
nRT
w=- pc.x(Vr- V;) =- PcxX--=- nRT
Pcx
n=
15 g
1
. g mol _ 1 = 0.617 mol, RT= 2.479 kJ mol 24 31
Hence , w = - 0.617 mol x 2.479 kJ mol - 1 = - 1.5 kJ
t-.H /f,, =2.60 kJ mol - 1 [Table 2.2].
2.8
750 x 10' g
n
22 .99 g mol - 1
q=nl-.H /f,, =
750x 101 g
_ 1 X 2.60 kJ mol - 1 =8.5 x 104 kJ
22. 99 g mo 1
q
.
229 J
C=- [Sect1on 2 SJ = -- =89 8J K- 1
!-. T
2.55 K
.
29
.
The molar heat capacity (at constant pressure) is the refore

C1 =
'
89 .8JK - 1
3.0mol
= 30 J K- 1 mol - 1
19
20
For a pefect gas,

C" - Cv= R [16, molar quantities]
Hence
Cv= C"- R = (30- 8.3) J K- 1mol - 1=22 J K- 1mol - 1
2.10
q= C!).T, C = nC" , V=75 m3
pV
l.Oatm x 75xl03 L
n=-=
2
RT 8.206 X
L atm K- 1mol -l
w-
_
1
= 3.07 x lO"mol
X 298 K
1
1
q=3.07 x 10 mol x 21 J K- mol - x 10 K=6.4 x 10 2 kJ
1
Since q = P x t, where Pis the power of the heater and tis the time for which
it operates,
6.4 X 105 J
,
.
t=-p = l.O x 103J s _1= 6.4 X 10- s (about 11 mm)
q
In practice, the walls and furniture of a room are also heated.

q = -1.2 kJ [energy leaves the sample]
2.11
!).H= -1.2 kJ [!).H=q at constant pressure]

q
1.2 kJ
C = !).T= 15 K =80J K- 1
2.12
q=C!).T=nC,,!).T
=3.0 mol x 29.4J K- 1mol - 1x 25 K = +2.2 kJ

!).H=q [lOa] = +2.2 kJ
!). U = !).H- !).(p V) (9] = !).H- !).(nRT)
= !).H- nR!).T
= 2.2 kJ- 3.0 mol x 8.314 J K- 1mol - 1x 25 K
= 2.2 kJ - 0.62 kJ = + 1.6 kJ

2.13
q=0.50 mol x 26.0 kJ mol - 1= + 13 kJ
(5] = - Pcx V(g) (V(g) ~ V(/)]

nRT
= pc xX - - = -nRT
Pcx
Therefore, w = -0.50 mol x 8.3141 K - I mol - 1x250 K= -1.0 kJ
!).H = q [lOa] = + 13 kJ
W
= - Pcx/). V
!).U=q+ w= +13 kJ -1.0 kJ = +12 kJ
21
CfiHsCzHs(l) + 0 2(g) ~ 8C0 2(g) + 5H 20(l)
2.14
11H'! = 811H f((C0 2 , g)~ 5!1Hf((H 20 , l)- !1Hf (eb, l) [eb = ethylbenzene]
= 8(- 393.51) + 5(- 285.83)- ( -12 .5) kJ mol - 1

=-4564.7kJmol - 1
2.15
11H'! =- 4003 kJ mol - 1
C6 Hdl) + 90 2 (g)~6C0 2 (g) + 6H 20(l)
11H'! =- 4163 kJ mol - 1
C6 H 14(l) + Jf0 2(g) ~6C0 2 (g) + 7H 20(l)

The difference of these two reactions is
C6H1 2(l) + H 2 0(l)~ C1,H 14(l) + f0 2(g)
!1H 9 = + 160 kJ mol- 1
To replace the H 20 by H 2 we subtract

H 2 0(l)~
H 2(g) +
!1H 9 =- !1H 9 (H 20, /) = + 285 .83 kJ mol- 1
~ 0 2 (g)
Giving
CfiH12(/) + H2(g)~CoH 14 (/)
!1H 9 = -126 kJ mol - 1
2.16
3C(s) + 3H 2(g) + 0 2 (g)~CH 3 COOCH 3 (/)
/!,. U =
!1H- !1nMRT (11),
!1H f( =- 442 kJ mol - 1
!1nM= - 4 mol
!1nMRT=- 4 mol x 2.479 kJ mol - 1= - 9.916 kJ
Therefore
!1U f = -442 kJ mol - 1+9.9 kJ mol - 1= -432 kJ mol - 1
The reverse reaction is

10C0 2(g) + 4H 2 0(l)~ C 10Hx(s) + 1202(g)
!1H 9 = + 5157 kJ mol - 1
The C0 2 and H 20 can be replaced by adding the following two reactions [and
using !!,.Hf((C0 2) and !!,.H f((HzO), Tab le 2.10]:
10C(s) + 100 2 (g)~ 10C02(g) !1H 9 =- 3935 kJ mol - 1
4H 2(g) +20 2 (g)~4Hz0(l) !1H 9 = -1143 kJ mol - 1
Thus overall:
lOC(s) + 4H 2 (g)~ CwHx(s)
!!,.H 9
+ 5157-3935-1143 kJ mol - 1= + 79 kJ mol - 1
22
2.18
C= ~qTand q = /Vt [section 2.5]
Hence
3.20 A X 12.0 V X 27.0 s
C
=
1.617 K
641JK - 1
because 1 A V s = 1 J.
2.19
q=n~H ~, ~H ~ =
-5157 kJ mol - 1 [Table 2.9]
Therefore ,
120 x w-Jg
lql=
_ X5157Jmol - 1 =4.83kJ
128 .1 8 g mo 1 1
4.83 kJ
q
C = - = - - = 1.58 kJ K -l
~T
3.05 K
When phenol is used, since ~H ~ = -3054 kJ mol - 1 [Table 2.9],
100 x w-3 g
_
lql
_1 x 3054 kJ mol - 1 = 3.245 kJ
94 .1 2 gmo 1
Therefore,
q
3.24SkJ
58 kJ K_ 1 =2 .05 K
~T=c= 1.
2.20
C~T
MC~T
q=C~T, I~Hcl=-=--=--[m: massof sample]
Therefore, since M = 180.16 g mol - 1,

180.16 g mol - 1 X 641 J K- 1 X 7.793 K
_
I~Hcl=
_
g
=2802kJmol - 1
0 3212
Therefore, since the combustion is exothermic,
~He=
-2.80 MJ mol - 1
The combustion reaction is

C~H 1 2 0~(s)
Hence
+ 60 2(g)--76C0 2(g) + 6H 20(l)
~Uc = ~He;
therefore
~Uc =-
~n~ =
2.80 MJ mol - 1
For the enthalpy of formation we combine

6C0 2(g) + 6H 20(l)--7 C~H 1 2 06 (s) + 60 2(g)
6C(s) + 60 2(g)--76C0 2(g)
6H 2(g) + 30 2(g)--7 6H 20(l)
~H=
+2.8 MJ mol - 1
~H =~H=
2.36 MJ mol - 1
-1.72 MJ mol - 1

The sum of the three is
6C(s) + 6H 2(g) + 30"(g)---.,> ChH I20h(s)
!1H1 = 2.80- 2.36- 1. 72 MJ mol - 1 = - 1.28 MJ mol - 1

2.21
AgCI(s)-,> Ag+(aq) + Cl - (aq)
!1H 6 = !:l.H f'(Ag +, aq) + !:l.Hf'(CI - , aq)- !:l.Hf'(AgCI, s)

= 105.58 + ( -167.16)- ( -127.07) kJ mol - 1
=+65.49kJmol - 1
NH >+ S0 2-,> NH 3S0 2
!1H 6
=-
40 kJ mol - 1
!1Hf'(NH 3S0 2, s) = !1H )"(NH 3 , g)+ !1H f'(S0 2, g)- 40 kJ mol - 1

=- 46 .11-296.83-40 kJ mol - 1 =- 383 kJ mol - 1
2.23
C(gr) + 0 2(g)-,>C0 2(g)

C( d) + 0 2(g)---.,> C02(g)
!1H 6 =- 393.51 kJ mol - 1

!1H 6
=-
395.41 kJ mol - 1
The difference is
C(gr)---.,> C( d)
2.24
!:l.H f}. =- 393.51- ( - 395.41) kJ mol - 1 =- 1.90 kJ mol - 1
q = n!:l.H 'ji
1.5g
1
. g mol _ 1 x ( - 5645 kJ mol - ) = -25 kJ
342 3
Effective work available =25 kJ x 0.25 = 6.25 kJ

Since w = mgh, with m = 65 kg
h=
6.25 X W J
,
65kg x 9.81ms-
2.25
9.8m
t;.H'j
Ml f'(8)
C>Hx(l) + 50"(g)~C> H x(g) + 50"(g)~3CO"(g) + 4H"O(I)
(a) !:l.H 'ji(l) = !:l.H?.,P+ !:l.H'ji(g)

= 15 kJ mol - 1 - 2220 kJ mol - 1 =- 2205 kJ mol - 1
(b) !:l.n g= - 2 [50 2 replaced by 3C0 2]
23
24
Therefore D. U f((l) = D.H f((l)- (- 2)Rl'

=- 2205 kJ mol - 1 + 2 x 2.479 kJ mol - 1
=- 2200 kJ mol - 1
2.26 D.H 9 > 0 indicates an endothermic reaction and D.H 9 < 0 an exothermic
reaction. Therefore, (a) is exothermic, (b) and (c) are endothermic.
2.27 0 =
L vJSJ; hence
J
(a) 0=C0 2 +2H 20-CH4-20 2

v(C0 2) = + 1, v(H 20) = + 2, v(CH 4) = -1, v(0 2) = - 2
(b)
0=~H 2 -2C - H 2
v(~H 2 )
= + 1, v(C) = - 2, v(H 2) = -1
(c) 0= Na +(aq) + Cl-(aq)- NaCI(s)

v(Na+) = + 1, v(Cl-) = + 1, v(NaCl) = -1
(a) D.H 9 = D.H f3(N 2 0 4 , g)- 2D.H f3(N0 2 , g)
2.28
= 9.16-2 x 33.18 kJ mol- 1 = - 57.20 kJ mol - 1

(b) D.H 9 = D.Hf3(NH 4Cl, s)- D.Hf3(NH 3 , g)- D.H f3(HC1 , g)
=- 314.43- (- 46.11)- (92.31) kJ mol - 1 = -176.01 kJ mol- 1
(c) D.H 9 = D.H f3(propane , g)- D.Hf3(cyclopropane , g)
=20.42-53 .30 kJ mol - 1 = -32.88 kJ mol - 1
(d) The net ionic reaction is obtained from
and is
H +(aq)
+ OH - (aq)~ H 20(/)
D.H 9 = D.H f3(H 20, l)- D.H f3(H+, aq)- D.Hf3(0H- , aq) .
= - 285.83-0 - (- 229.99) kJ mol - 1 =- 55 .84 kJ mol - 1
The sum of the three reactions is
2.29
1:1H 9 /( k1 mol - 1)
2NO(g) + 0 2(g) ~ 2N0ig)
-114.1
! 0 2(g) + 2N02(g) ~ N20 5(g)
t(- 110.2)
N2(g) +
0 2 (g)~
2NO(g)
180.5
N2(g)+ t0ig)~N20 s(g)
+11.3
Hence, 1:1Hf (N 20 5 , g)=+ 11.3 k1 mol - 1

1:1H 9 /(k1mol - 1)
2.30 (a)
K(s) + 1 Cllg)~ KCl(s)
-436.75
KCl(s) + tOz(g)~ KClOls)
H89.4)
-392.1
Hence , 1:1H f (KC10 3 , s) =- 392.1 k1 mol - 1
(b)
Na(s) + t 0 2(q) + !H 2 (g)~ NaOH(s)
-425.61
NaOH(s) + COig)~ NaHC0 3(s)

C(s) +
02(g)~C02(g)
-393.51
Na(s) + C(s) + t Hig) + t0 2 (g) ~ NaHCOJ(s)

Hence, 1:1H f (NaHC0 3 , s) =- 946.6 k1 mol (c)
tN 2 (g) + t0 2 (g)~NO(g)
- !(75.5)
! N2(g) + iO(g) + tC12(g) ~ NOCl(g)
2.31
-946.6
+90 .25
NO(g) + tCllg)~ NOCl(g)
Hence, 1:1Hf (NOCl , g)=52.5 k1 mol -
-127.5
+ 52.5
1
1:1H 9 (T2) = 1:1H 9 (T1) + 1:1C,I:1 T (Example 2.12]
1:1C,, = C"(N 20 4 , g)- 2C,(N0 2, g)

=77.28-2 x 37.201 K- 1 mol - 1 = +2.881 K- 1 mol - 1
1:1H 9 (373 K) = 1:1H 9 (298 K) + 1:1CPI:1 T
= -57 .20 k1 mol - 1 +2.88 1 K- 1 x 75 K
= -57 .20+0.22 k1 mol - 1 = -56.98 k1 mol - 1
25
26

Mg 2+(g)+ 2 Cl(g)+ 2e-
24 1.6
Mg 2+(g)+ Cl 2(g)+ 2e-
15.035 eV = 1450.7
3.78 eV = 729.4
Mg 2+(g) + 2 Cl - (g)
383.7 = 767.4
Mg(g)+CI 2(g)+ e-
7.646 eV = 737.7
Mg(g) + Cl2(g)
Mg 2 (g) + 2 Cl - (aq)
167.2
D.Hhvd (Mg 2+) =
Mg(s) + Cl 2 (g)
-x
641.32
MgCI2(s)
I 150.5
MgCI2 (aq)
2.32
Distance up on left= distance down on right.
Therefore,
150.5 + 641.32 + 167.2 + 737.7 + 1450.7 + 241.6 = X+ 767.4 + 729.4
Solving to x = 1822.2, implying that t..H ~<J(Mg 2 + ) = -1822.2 kJ mol- 1
Problems
2. 1 (a) w = -p ,t..V [5]
0
V; = 100 em'= 1.00 X w -~ m', p = 1. 0 atm = 1.013 X 105 Pa
nRT
VI=-- =
8.206xl0- 2 LatmK- 1 mo l- 1 x 293K
5.0g
44 .01 gmo l- 1
X - -- - - - - - - - - - - -
l.Oatm
w-' m'
=2.73L=2.73 x
Therefore, w =- l .OTI X 10 5 PaX (2.73 X w- - 1.00 X w - ~) m'

= -267Pa m' = - 0.27 kJ
Vr
(b) w = -nRT inV [7]
I
-5.0g
44. 0 1 g mo l
_ 1 x8. 314JK- 1 mol- 1 X293 K x ln
= -277 J X In 27.3= -0 .92 kJ
2.i3xio- ' m'

_~
,
100
. x 10 m

2.2
= -
27
Pexll V [5]
nRT
Vr= -- ~
Pcx
V;; so ilV= Vr
nRT
Hence w= - pc,X-- = -nRT
Pcx
= - 1.0 mol x 8.314 J K- 1 mol - 1 x 1073 K
= - 8.9kJ
Even if there is no physical piston, the gas drives back the atmosphere, so the
work is also - 8. 9 kJ
2.3
Since the volume is fixed, w = 0.
Since ilU=q at constant volume , ilU= +2.35 kJ
ilH = ilU + il(pV) = ilU + V Llp as il V = 0. From the van der Waals equation
[Table 1.5],
RT
a
p= vm - b - V m2
RilT
Llp = V _ b [Ll V m = 0 at constant volume]
m
Therefore,
From the data,

15.0 L
Vm = _ mol= 7.5 L mol - '
20
vm- b=7 .5 -
4.3 X
w- zL mol - l =7.46 L mol-l

1
RVilT 8.314 J K- mol - 1 x 15.0 L x 41 K

0.68 kJ
7.46 L mol 1
vm - b
Therefore,
ilH = 2.35 kJ + 0.68 kJ = + 3.03 kJ

2.4
w= -
ri p d v =
B)
n JrRT(
i vlll 1 + vm
d vm
28
The fi rst law: the concepts

1
1)
=- nRTln -V +nBRT( - 1 - V;
Vmr Vm;
From the data ,

nRT = 70 X 10- 3 mol x 8.3141 K - l mol- 1 X 373 K = 2171
5.25 cm 3
6.29 cm 3
1
3
Vm; = 0mmol = 75.0cm mol- , Vmr= 70mmol
7
89.9cm mol-
and so
s(
:mr - :m) = - 28.7 cmJ mol - l x

= - 6.34 x
(75.0c~J mol-l
89.9
w- 2
Therefore,
6.29
w = - 2171 In _ - 2171
5 25
6.34 X 10- 2
= - 39.21-13.81 =-53 1
Since tl.U = q + w
~nd
tl.U=+83.51 ,
q = tl.U- w = 83.5 +53 1 = + 1361
:J
:J
tl.H = tl.U + tl.(pV) with pV= nRT ( 1 +
tl.(p V)
= nRTB!l. ( : = nRTB( :mr= 2171 X
( -
as !!.. T = 0
6.34 X 10- 2) = -13.81
Therefore,
tl.H = 83.51-13.81 = 69 .71
2.5
tl.H = q [constant pressure] = + 22.2 k1
q 18.02 g mol - 1
tl.Hvar =-=
10
x22.2k1 = +40k1mol- 1
n
g
c~J mol-l)

Hence f':...U = 22.2 kJ - 0 .555 mol x 8.3141 K- 1 mol- 1 x 373 K
= 22.2 kJ - 1.72 kJ = + 20 .5 kJ
w=q- !!..U [as !!..U=q+ w] = 22.2 kJ - 20.5 kJ = 1.7 kJ

2.6
q = ltV = 0.232 A X 12.0 V X 650 s = 1.81 kJ
!!..H = q + l.81 kJ
!!..H 102 g mol- 1

f':...Hvap=----;;-= 1.
g Xl.81kJ = 98.7 kJmol- 1
871
f':...Vvap = f':...Hvap-RT [f':...n8 = + 1]
= 98.7 kJ mol- 1 - 8.314 J K- 1 mol- 1 x 351 K = 95.8 kJ mol- 1
2.7
q = nf':...Hvap,son = Hq withf':...Hvap = 8.18kJmol - 1 [Table2.2]

/),. vap
The volume occupied by the gas at a pressure p is V = nRT!p; therefore
qRT
V=-p!!..Hvap
32.5 kJ
8.314 J K- 1 mol- 1 X 112 K
1.013 X 105 PaX 8.18 kJ mol
= 3.65 X 10- 2 m 3 = 36.5 L

2.8
2C(s) +
3H 2 (g)~C2H6(g)
!!..Hf7(T2) = !!..Hf7(T1) +
!!..CP dT [17]
!!..CP = CP(C2H 6) - 2Cp(C)- 3CP(H2)

0.1272
Cp(C2H 6)/(J K- 1 mol- 1) = 14 . 73+~T
Cp(C,s)/(JK- 1 mol- 1) = 16.86+
4.77 x 10- 3
8.54 x 105 K2
K
T - - -y""""2 - -
Cp(H 2, g)I(J K- 1 mol- 1) = 27.28+
3.26 X 10- 3
0.50 X 10 5 K2
K
T+-- y""""2- -
29
30
=-
100.83 X 52 K + t
-1.56 X 106 X
Therefore
= - 2.65 X
0.1079 X (35<f- 2982) K
3~ 0 - 2~ 8) K
103 K
L\CP dT =- 2.65 kJ mol- 1
Hence L\Hf'(350 K) = L\Hf'(298 K) - 2.65 kJ mol- 1

= - 84.68
kJ mol- 1 - 2.65 kJ mol- 1
= - 87.33
kJ mol- 1
2.9 (a) q = L\H'( at constant pressure. Therefore, the heat outputs per mole
are:
Butane
pentane
octane
3537
5471
(b) The heat outputs per gram are IL\Hcl/ M, and are:
Ml(g mol- 1)
(L\HciM)I(kJ g- 1)
2.10
58.13
49.51
72.15
49.02
114.23
47.89
L\H". - L\U,,. = L\(pVm) = pL\Vm
M
Vm =- where pis the density; therefore:
( 1
1 )
L\H,,. - L\U,,. = pML\p = pM p(d) - p(gr)
x(3.52:cm- 3 2.27:cm- 3)
=- 9.39 x 10 10 Pa cm 3 mol- 1
=- 9.39 x 104 Pa m3 mol- 1=- 9.39 x 104 J mol- 1
= - 93.9 kJ mol- 1
2.11
C5H 100 5(s) + 50 2 (s)~ 5C0 2(g) + 5H20(/),
~n 8 =
For benzoic acid

~U =
Since
0.825 g
_ g mol_ 1x (- 3251 kJ mol- 1) =- 21.96 kJ
122 12
~T =
1.940 K,
lql 21.96kJ
C = ~T = 1.940 K = 11.32 kJ K-1
For 0 -ribose,
~U= - C~T= - 11.32kJ K- 1x 0.910 K
Therefore,
~U
~U, =--;;- =
- 11 .32 kJ K- 1x0.910Kx
150.13 g mol- 1
_ g
0 727
=- 2127 kJ mol- 1
~H,= ~U,[~n 8 = 0]
= -2130 kJ mol- 1
The standard enthalpy of formation is obtained from the sum

~H/(kJ
5COz(g) + 5Hz0(1)~ C5 Hw0 5(s) + 50 2(g)
2130
5C(s) + 50z(g)~5C0 2 (g)
5X
(-
393.51)
5Hz(g) + tOz(g) ~ 5H20( I)
5X
(-
285.83)
5C(s) + 5Hz(g) + t0 2 (g) ~ CsHwOs(s)

Hence, ~H? = -1267 kJ mol- 1
2.12
mol- 1)
Cr(C 6 H 6 )z(s)~ Cr(s)
~H, = ~U,+2RT
+ 2C6H 6 (g),
-1267
~n 8 =
+2mol
31
32
= 8.0 kJ mol- 1 + 2 x 8.314 J K- 1 mol- 1 x 583 K = + 17.7 kJ mol- 1

11H'( (583 K) = 211H'((C6H 6 , g, 583 K) - 17.7 kJ mol- 1
The enthalpy of formation of benzene gas at 583 K is related to its value at
298 K by
/1Hf'(benzene, 583 K) = /1Hf'(benzene, 298 K) + (Tb- 298 K)Cp(l)
+ (583 K- Tb)Cp(g) + 11H?,r
- 6(583 K- 298 K)Cp(graphite)
- 3(583 K - 298 K)Cp(H 2 , g)
where Tb is the boiling temperature of benzene (353 K). We shall assume that
the heat capacities of graphite and hydrogen are approximately constant in the
range of interest, and use their values from Table 2.10:
11H'((583 K) = 49 .0 kJ mol- 1 + (353 - 298)K x 140 J K- 1 mol- 1
+ (583- 353)K x 28 J K- 1 mol- 1 + 30.8 kJ mol- 1
- 6(583 -298)K x 8.53 J K- 1 mol- 1
- 3(583 - 298)K X 28.82 J K- 1 mol- 1
= 49.0 + 7.70 + 6.44+ 30.8 + 14.59 + 24.64 kJ mol- 1
= + 54.7 kJ mol- 1
Therefore, for the metallocene,
11H'((583 K) = 2 x 54.7 - 17.7 kJ mol- 1 = + 91.7 kJ mol- 1
C 12 H 22 0
2.13
!1H 9 =
11
+ H 2 0~4CH 3 CH(OH)COOH
4/1Hf'(lactic acid) - 11H'((sucrose) -11H'((H 20, l)
= 4 x (- 694.0)- (- 2222)- (- 285.8) kJ mol- 1

= - 268 kJ mol- 1
11H~ =
Therefore,
reaction.
2.14
11H~
- 5645 kJ mol - 1
is more exothermic by 5376 kJ mol- 1 than the hydrolysis
(a) KF, C=4.168 kJ mol- 1
ml(mol KF/kg CH 3COOH)
0.184
0.590
0.821
1.208
11TIK
1.592
4.501
5.909
8.115
q =- CI1T/kJ
11H!(kJ mol-
1
)
-6.635
-34.2
-18.76
-24.63
-33.82
- 31.8
-30.0
-28 .0
Plot t'!.H against m (Fig. 2.1a) and find the best straight line , or else do a
least-squares best fit (Appendix):
t'!.HI(kJ mol - 1) =- 35.4 + 6.2m/(mol KF/kg CH 3COOH)
(a)
(b)
-28
46
,/
In
-30
I
-<:]
-36
0
Av ...... ,.,......
~ -32
-34
..... ~
.A:. ~
02
42
t>
'"'
..,..,... v
v.
v
Fig2.1
38
c...
'
3-4
Ot.
06
Therefore, the limiting value (at
m~O)
OB
10
12
30
is t'!.H =- 35.4 kJ mol - 1
(b) KF CH 3COOH, C=4.203 kJ K- 1

0.280
0.504
0.910
1.190
t'!.T/K
-0.227
-0.432
-0.866
-1.189
q =- Ct'!.T/kJ
+ 0.954
1.816
3.64
5.00
t'!.HI(kJ mol- 1)
+3.4
m/(mol KF/kg CH 3COOH)
+3.6
+4.0
+4.2
Plot t'!.H against m (Fig. 2.1b) or make a least-squares best fit:

t'!.HI( kJ mol - 1) = 3.15 + 0.9m/(mol kF/kg CH 3COOH)
Therefore, the limiting value (at
m~O)
is t'!.H = + 3.15 kJ mol - 1
See the original reference for further details.

2.15
Draw up the following thermodynamic cycle:
33
34
K+ (g)
+ F- (g) + CH:JCOOH (g)

x= -ll.H""'ot F H formation
20.8
K+(g) + F- (g)
+ CH 3COOH (/)
K +(g) + F HOOCCH 3(g)
821 [Table 2.11]
734
KF CH3COOH(s)
3.1
KF (CH 3COOH)
35.2
KF (s) + CH 3COOH (/)
Since distance up on left= distance up on right ,

821 +20.8=x+734+3.1 +35.2, so x=69.5
Therefore, !:!.H 9
w =-
2.16
w= -F
= -70 kJ mol - 1
Fdz [Section 2.3], F(z)=Fsin nz!a
nz
Fa(
nz?
nz 1)
sin - dz = - cos-- -cosa
n
a
a
1
(a) z 2 =a,z 1 =0
Fa
w=- (cosn-cosO) = -2Fa!n
n
(b) The force opposes extension only up to z =a, and no work needs to be
done from z=a to z=za; hence the work is -2Fa!n. If, however , the
external force is balanced against the internal (so that the overall extension is
reversible), then the system does work in the region from a to 2a, and overall
w=O.
2.17
w= -
Therefore,
p dV [6]
W=-nRT
J
(1v
2
2 - +nB
-2 +n-C
+ ) dV
3
I
For argon, n = 1.0 mol, and
nRT= 1.0 mol X 8.3141 K- 1 mol- 1 x 273 K = 2.il kJ

From Table 1.2, B = -21.7 cm 3 mol- 1, C= 1200 cm 6 mol- 2, so
n 2BRT= 1.0 mol x (- 21.7 cm 3 mol-') x 2.27 kJ =- 49.3 kJ cm 3

t n 3CRT=t(l .Omol) 2X (1200cm 6 mol- 2) x 2.27kJ= + 1362 kJ cm6
Therefore,
- kJ ( 1 - 1)
(a) w =- 2.27- kJ In 2-49.3 kJ ( 1 - 1) + 1362
2
10002 500
1000 500
= -1.57 + o.049- 4.1 x 10-J kJ
= -1.52 kJ= -1.5 kJ
(b) For a perfect gas, only the first term contributes , so w- = 1.57 kJ =
-1.6 kJ
2
2.18
w =J
nRT n~
p dV with p = V _ nb -lfZ [Table 1.5]
Therefore ,
w= -nRT
2 dV
J2 dV
'V-nb +n2a ' V2
1 1)
V 2- nb)
=-nRTin ( - -n 2a ( - - V,-nb
V2 V,
Suppose
nb ~ V,
nb)
nb
then ln( V-nb) =ln V+ln 1-V = In V-V.
(
35
36
Then
where W 0 is the perfect gas value. In a reversible compression , V2 < V1, and so
w < W 0 if bRT <a but w > W 0 if bRT> a. If attractions dominate repulsions
(bRT < a), we should expect less work to be done on compression and w < w0 ,
as found.
w= - nRT
2.19
In(~~ = ::) -na( ~2 - ~)[Problem 2.18]

2
Vc= 3nb [Table 1.5]
T, = T ,
c
(V,_
28na
w = -27b T,ln V,_1 -
t)
t
1 1)
na(
-3b V,_ 2 -~
3bw
Define w, = - , then
a
1) ( 1 1)
2w, = - t nT,In -v,-( V,. I - -1 - n v,. 2 v,_1
Along the critical isotherm, T,= 1 and V,_ 1 = 1, V,. 2 =x. Hence :
3x-1) 1
wln=ll9 in -2- --+1
r
X
(
2.20
(a) (ap)
= (
aT v
37
a_rnRT)) = nR = I!_
aJ\ v
v v
T
Equal
ap)
nR
( na )( nRT)
( aT v=V - nbe-na!RTV + RT2V V - nb e - na!RTV
nR ) ( 1+ RTV
na ) e - na/RTV= ( 1+RTV
na ) T
p
= ( V - nb
_ap) = -nRT e - na/RTV + ( __

na ) ( _nRT)
_ _ e-na/RTV
( av T (V-nb) 2
RTV 2 V-nb
nRT) ( na
1 )
( v - nb RTV 2- v- nb e-na!RTV
-na- - - V- )p
( RTV V - nb V
a~:T= (aav(!~) J
T=
= ( aav
~) /
(aav(
( aav(
+ R;)
Rn~ ~))
~)
38
(a
2
ap
(ap) )
avaT = aT av T v =
(a (
nap
p ))
aT RTV 2- v - nb v
R; 2 (!~)v- R;;V 2 -V~nb(!~) v

n2a2p
2
R T V
p
T(V- nb)
nap
2
RT V(V- nb)
a2p
a2p
Hence, avaT= aTav
Llc
LlCP = Lla + LlbT + T 2 where Lla =
L v ah etc.
1
Hence,
ilH(T2) = ilH(T1)+
r(
ila+ilbT+
ilH(Tt) + 6.a(T2- Tt) +
~~) dT
tilb(n- TD - ilc( ~ - ~)
For the reaction

ilHf'(l) = -285.83 kJ mol- 1
we need [Table 2.16]
1
a!(J K- mol-
1
)
K- 2
1)
b!(J
mol -
c/(J K mol- 1)
H 2 0(l)
H 2 (g)
75.29
27.28
3.26 x w-
0.50 X lOS
Lla=75.29 - 27.28 -
t x 29 .961 K-
0 2 (g)
29 .96
4.18 x w- 3
-1.67 X lOS
1
mol- = 33.03 J K- 1 mol- 1
Llb = 0 - 3.26 X 10- 3 -tx 4.18 X 10- 3 J K- 2 mol- 1 = - 5.35
10- 3 J K- 2 mol- 1
Llc= 0 - 0.50 X lOS + t x 1.67 x 105 1 K mol- 1 = 0.34 X 105 1 K mol- 1

ilH}3(373.15 K = 285.83 k1 mol- 1 + 33.031 K- 1 mol- 1 X 75.00 K
- ~X
5.35 X 10- 3 1 K- 2 mol- 1 X {(373.15 K)2 - (298.15 K)2 }
- 0.34 X 1051 K mol-l X
373\5 K- 298\5
= ( -285.83 +2.36) k1 mol- 1

=- 283.47 k1 mol- 1
If instead we use [Table 2.10]
Cp(H 20) =75 .29 1 K- 1 mol- 1, Cp(H 2) =28 .82 1 K- 1 mol-l, and Cp(0 2) =
29.361 K- 1 mol- 1 (the values at 298.15 K),
ilH}3(373 K) = ilH}3(298 K) + 31.791 K- 1 mol- 1 x (373.15 K- 298 K)
= (- 285.83 +2.38) k1 mol- 1

= - 283.45 k1 mol- 1
which is the same to the stated number of significant figures.
39
3. The first law: the machinery

Exercises
ay
a2
3.1 Show that ax ay = ay ax [Box 3.1]
a2t
a2t
a2t
(a) ay ax= ay (2xy) = 2x

- - = - ( x 2 +6y)=2x
axay ax
(b) ay ax= ay (cosxy - xy sinxy) = -x sinxy -x sin xy -x 2y cosxy
=
-2x sinxy -x 2y cosxy
a2t
a2t
ax ay =ax ( - x 2 sinxy) = - 2x sinxy -x 2y cosxy
(c) - = - (2t+e')=e'
as at as
ay
atas
a
(tes+2s) = es
at
-=-
because (aU/aV)T=O for a perfect gas [Section 3.1]

3.3 H= U+pV
(:8p
1 +p(5)p
(!~) p= (:~)p/ (:~) p [Box 3.1]= (!~)p (aav(U+pV)) p

=
(!~)J (!~\ +p}
The first law: the machinery

dV = (
3.4
We use
din
~)
dp + (
a = ~(~~)
~)
dT
[4] and JC=
-~e~
V =2_dV =2_(a~ dp+2_(a~

v
v ap} r
v aT} p
[7] and obtain
dT =-JCdp+adT
(:~ r = (aavGnRT) r =Q
3.5
H= U+pV = U+nRT [pV=nRT]
(!~ = (!~ +(a:~~

T
a = ~(:~
3.6
=0+0=Q
[4]
V = V' {0.75 + 3.9 x 10- 4 TIK + 1.48 x 10- 6 (T/K) 2}
0.974
=0.97 x 1.3 x
= 1.3 x
w- 3 K -
JC=-2.(a~
v ap Jr
3.7
dV
w- 3 K -
-JC dp [at constant T]
dp = ~ d (~) = _ V d'V = _ dV = 1C dp
p m
v
vv
41
42
bp
Therefore - = Kbp
p
For bpi p = 0.08 X 10- 2 = 8 X 10- 4

8 x 10- 4
bp
(~!f)
3.8
8 x 10- 4
7.35 X 10 7 atm
= -11-cp
l.l x 103 atm
[10]
= - 0.25 K atm- 1 x 29 J K -I mol- 1 = -7 .2 J atm- 1 mol- 1
q =-
(~!f)
bp =7.2J atm- 1 mol- 1 x 15 mol x 75 atm =8.1 kJ
q = Q[adiabatic process]
3.9
w = - pex
~ V=
- 600Torr X
1.013 X 105 Pa
760Torr
40 X 10- 3 m3= -3.2 kJ
- 3.2x103J
15
~T= - ~ [ ] = 4.0 mol x 21.1 J K 1 mol
Pex~V
~U=q+
= - 38 K
w = 0-3.2 kJ = -3.2 kJ
~H = ~U+~(pV)=~U+nR ~T
= -3.2 kJ + 4.0 mol x 8.314 J K- 1 mol- 1 x -38 K

= -1.9 kJ
3.10
q = Q [adiabatic process]
~U= Cv~T =
3.0 mol x 27.5 J K- 1 mol- 1 x 50 K= +4.1 kJ
w= ~U-q=4.1 kJ -0= +4.1 kJ

~H = ~U+nRT~T
= 4.1 kJ + 3.0 mol x 8.314 J K- 1 mol - 1 x 50 K = +5.4 kJ
nRT; 3.0 mol X 8.206 X 10- 2 L atm K -I mol V;=--=

p;
2.0 atm
200 K
= 24.6L

200 K)J.J l
V1 = 24.6Lx (
K
=11.8L
250
nRTr 3.0 mol X 8.206 X 10 - 2 L atm K - I mol - l X 250 K
Pr=-y;-=
11.8 L
=5.2 atm
nRT; 1.0 mol X 8.206 X w-z L atm K - I mol - l X 310 K
V;= - =
=7.83 L
p;
3.25 atm
3.11
CP Cv+R (20.8+8.31)JK - 1 mol- 1

y = Cv = ~=
20 .81 K - 1 mol- 1
= 1.4
lly=0.714
V 1=V;
p;)
(p;
l tr
[21]=7 .83L x
(3.25 a:tm)o.7J4
_
=9.44L
_ 0atm
25
PrVr
2.50 atm x 9.44L
Tr= nR = 1.0 mol X 8.206 X w-z L atm K - 1 mol-l
_
288
w= Cv(T1 - T;) [15] = 20.8 J K - I mol - 1 x 1.0 mol x (288 K-310 K)

=
-0.46 kJ
3.12
~v=(:~b ~T=aV~T[4]
(a) Mercury, a= 1.82 X 10- 4 K - I ,

~V= 1.82X 10- 4 K- 1 X l.Ocm 3 x5 K
= 9.l X 10- 4cm 3 = 0.9 mm 3
(b) Diamond, a= 0.03 x 10- 4 K - I
~T=0.03 X 10- 4 K -I X 1.0 cm 3 X 5 K =0.02 mm 3
3.13
For
~-t=
~T=
~p =
(aT)
ap
-
, so
fl
~T
~p = -
~-t
-5.0 K,
-5.0K
K
1 .2 atm
= -4.2 atm
43
44
3.14
11 = (aT)
ap
(~T)
=lim
H
op-0
Draw up the following table:

p/atm
opl atm
oTIK
(oT/op)!(K atm- 1)
32
-31
-22
0.71
24
-23
-18
0.78
18
-17
-15
0.88
11
-10
-10
1.00
8
-7
-7.4
1.06
5
-4
-4.6
1.15
Plot oT!op against op (Fig. 3.1) and extrapolate to op=O. Hence we find that
f.1 = 1.3Katm- 1
14
Fig 31
:~
1\.
~
r-..._
~
f;;::
06
3.15
w= CvTi{
10
t-.~.a
20
-opjatm
30
(~;)lie -1} [18]
Cv 37 .11-8.31
.
c=R=
[Cp-Cv=R , Cp from Table 2.10]
8 31
=3.47
nRTi
V. = '
Pi
2.0 mol X 8.206 X 10- 2 L atm K - I mol-l
298 K
10 atm
= 4.89 L = 4.89 x 103 cm 3

Vr = Vi+ 20 em x 10 cm 2 = 4.89 x 103 cm 3 + 200 cm 3 = 5.09 x 103 cm 3

w=2.0 mol x 298 K X 28.80J K- 1 mol - 1
X
4.89)
{(5.09
1/3.47
--
-200 J
--
q = 0 [adiabatic process]
11 u = q + w = -200 J
Tr= (
v:
V)l tc
4.89)
(
= -5.09
T; [17b]
1/3.47
X298K =295K
------
11H= !1U + ll(pV) = 11U + nRT !1T, !1T= -3 K
= -200 J + 2.0 mol x 8.314 J K- 1 mol- 1 X ( -3 K)

=
-2501
3.16 (a) T1 = (
v:
V) ltc
Pr)
(p;
Hence T 1 = -
x T; [17b] and
11
<r
Cv
R
v: = (Pr)
p; ltr [19]
C
Cv
C
R
x T cy =- x2=_.!!.
"
CP=20.79J K - 1 mol- 1 [Table 2.10], so cy=2.501

1.00 atm) 1t2.so1
T1 = ( .OO atm
X 298 K = -----226 K
2
!1V
(b) 11T= -pcx Cv [16]
(Tr T;)
Pcx
Pex
Tr- T;= --(Vr- V;) = --nR ---Cv
Cv
Pr p;
That is, since Pcx = pr,

nR) _
nRT;Pex
_1+nRpe,ICvp;
( 1+Cv Tr-T;+ C vP; orTr- l +n RIC v xT;
63.09 g
45
46
and Cv= CP-R= (20.79- 8.314) J K- 1 mol- 1= 12.48 J K- 1 mol- 1

and obtain
nRpex
-Cvp;
0.495 mol X 8.314 J K - 1mol- 1X 1.00 atm

=0.333
0.595 mol x 12.48J K- 1mol- 1x2.00 atm
nR 8.314J K- 1 mol- 1
Cv =12.48JK- 1mol_ 1= 0. 666
1 +0.333
Therefore, Tr = + 0.
x 298 K = 238 K
1
666
Problems
3.1
2.3 x 10- 6
~e=2.3x10- 6 atm =---
atm
2.3 x 10- 6
1.013 X 105 Pa = 2.3 X 10-11 Pa-l
~v=GnT ~p= -~eV~p. ~p=pgh

~p
= 1.03 x 1frl kg m- 3 x 9.81 m s- 2 x 1000 m = 1.010 x 107 Pa
Consequently' since
~ V=
v = 1000 cm 3 = 1.0 X 10- 3 m\
-2.3 X 10-ll Pa-l X 1.0 X 10- 3 m3 X 1.010 X 107 Pa
= -2.3 x 10- 7 m\ or -0. 23 cm 3

For the change of volume with temperature, we use
a=~(:~P
~v=(:~P ~T=aV~T
= 8.61
10- 5K -I
1.0 X 10- 3 m3 X (- 30 K)
= -2.6 X 10- 6 m3 , or - 2.6 cm 3

Overall,
~V= - 2.8cm 3
47
For molar quantities interpret V as V m and use
M
p
V m = - where p is the density and M the molar mass.
Then
(a) For copper, a = 0.501 X 10- 4 K - I and 1( = 7.35 X 10- 7 atm- 1 = 7.26 X
10- 12 Pa- 1 (Table 3.1 and Problem 3.1]. Also,
p= 8.960 g cm- 3 = 8.960 x 103 kg m- 3 , M = 63.54 g mol- 1
Hence,
cp -
(0.501 X 10- 4 K- 1) 2 X 298.15 K X 63 .54 X 10- 3 kg mol- 1

Cv=
7.26 X 10- 12 Pa-l X 8.960 X 103 kg m- 3
= 0.731 J K- 1 mol- 1
(b) For ethanol, a = 1.12 X 10- 3 K -I'
1( =
7.68 X 10- 5 atm ""' 1 = 7.58 X 10- 10 Pa-l'
p=0.789 x 103 kg m- 3 , M =46.06 g mol- 1 Hence

3
1 2
3
1
)
=...:...__ _ _ ___:__ _ _ _ _ _ _ _-..,.-_ _
c -c
P
(1.12 X 10- K - X 298.15 K X 46.06X 10- kg mol7.58 X 10- 10 Pa- 1 X 7.89 X 102 kg m- 3
=28.81 K- 1 mol- 1
The difference in energy required as heat is
Therefore, for copper

l'l.q
500 g
_ X0 .731J K- 1 mol - 1 X50K =0.29kJ
. 4gmol 1
- -635
For ethanol,
l'l.q =
500g
_ g mol_ 1 x 28.8 J K - 1 mol- 1 x 50 K= 16 kJ
46 06
48
3.3
tiUm=
(au"')
aT PtiT
G~P =Cv+aVm(~~) T [5]=Cv +anTVm

Since
cp-
Cv =a v m(P + nT) [12], we know that
Cp-Cv
nT = -----;;v- - p
and hence that
(au"')
aT
(CP-
Cv
)
=Cv+aVm -----;;v--p =CP-apVm
CP=75.291 K- 1 mol - 1 [Table 2.10], a=2.1 x 10- 4 K - 1 [Table 3.1] and Vm=
18.07 X 10- 6 m3 mol - 1. Therefore
(:~
=75.29 1 K - 1 mol - 1 -2.1 X 10 - 4 K - 1 X 1.013 X 105 Pa

X
18.07 X 10- 6 m3 moJ - I
= 75 .291 K - 1 mol - 1 - 3.8 X 10- 4 1 K - I mol - l
=75.29 1 K - 1 mol - 1
Therefore, tiU=75.29 1 K - 1 mol - 1 x 10 K=0.75 k1 mol - 1
(b) tiHm =
aT ) PtiT= CPtiT=0 .75 k1 mol (aH"'
The difference is
tiHm- tiUm = apV"' tiT= 3.8 m1 mol - 1
which is the change in energy as a result of doing expansion work .

11
3.4
cr X T; [Exercise 3 .16a]
Tr = ( Pr)
{;
Tr
Pr
p;
Hence cy In T = In -
49
613.85)
In ( 1522.2
= 8.3141 K- 1 mol- 1 x
=41.401 K - 1 mol - 1
248.44)
In ( 298 .1 5
3.5 Use the formula derived in Problem 3.13 :
which gives
CP Cv+A.R
A.R
y=-=
=1+Cv
Cv
Cv
In conjunction with Cv = ~ R for a monatomic, perfect gas, this gives
y= 1 + i-A.
For a van der Waals gas V, =
Vm
Vm
27RbT
-y;- = 3b, T, = T, = ~ [Table 1.5] with a=
4.194 L2 atm mol - 2 and b = 5.105 x 10- 2 L mol - 1 [Table 1.4]. Hence, at 100 oc
and l.OOatm, where Vm=RT/p=30.6Lmol - 1
30.6Lmol - 1
200
V, = 3x5.105 x 10 2 Lmol 1
27 x 8.206 x 10- 2 L atm K - I mol - 1 x 30.6 L mol - 1 x 373 K
~ = ------------8-x
--4-.1-9_4_L~
at_m__
m_o_l_~2 ----------2-
=754
Hence
3.6 For p = p(V, T),
50
dp =
(!~)T dV+ (!~)v dT
As V = V(t) and T= T(t) , divide by dt and obtain

dp (ab) dV (ap) dT
dt = av T ili + aT v ili
For a perfect gas
ap)
p (ap)
p
( av T = - V' aT v = T [Problem 2.20]
Therefore,
dp
dt
p dV
V dt
p dT
T dt
1 dp
p dt
1 dV
V dt
1 dT
T dt
-=--- +---=--- + -Hence

d In p
dt
d In V
dt
d In T
dt
--=---+-For Newtonian (exponential) cooling

T= T
e-rtTr
'
dInT
1
so - - = - dt
rT
For exponential compression

dlnp 1
V = v e - IITv so - - = '
'
dt
rT
Therefore,
d lnp
which integrates to
1 1 1
p = p; e- rtTwith -=- - rT rv
When rT = rv, p = p; independent of the time.
3.7
dp =
ap)
(av
(ap)
(!~)
dV +
2n a =~ n a (V -2nb)
(V-nb) + V 3 V-nb + V 3 V-nb
2
= -nRT
T
(!~) v dTwithp= :~:b- ~~[Table 1.5]

2
=___!!!!____=!!_+ n a
aT v V-nb T TV 2
Therefore,
-p dV n 2a
dV
p dT n2a dT
2
dp= V-nb +VJ(V- nb) V-nb +T+ 0 T
p
na
Hence T= nR (V- nb) + RV 2 (V- nb)
(~:) v =-v-:R_n_b =-(-ap_)_

aT v
For Euler's chain relation, we need to show that
Hence , in addition to (aT!ap)v and (ap/aV)r [Problem 3.7] we need

1
(:~)p
which can be found from
51
52
T
2na
= - - - -, (V - nb)
V - nb RVTherefore,
V - nb ( - nRT
2n a)
- T
2na
- R(V - nb)z+\.f"J - ~+R"VJ(V-nb)
T
2na
V - nb- RV 3 (V - nb)
=
T
2na
V-nb - RV 3 (V - nb)
- 1
, ~- ~(~n.~ v(~
ap
[Rolat;on2J
T
V 2(V - nb) 2
7
3
2n 2a [Problem 1= nRTV 3 - 2n 2a(V - nb) 2
1
V - nRT
(V - nb) 2 +\.1"3
1<:
V-nb
Then - = - R - , implying that xR = a(Vm- b)
From the chain relation,
~==
(:n T/ (:0
-1
I(!~)
/!0
[definition]
[Relation 2]
:n
=(
v [Chain relation]
V-nb
=~(Problem
3.8]
Hence, KR = a(Vm - b)
For the introduction of reduced variables, define
K,=
_.2_ (av,) = -~(a~
a,=
~r (:~:) P=~ (:~ PTc = aTe
v,
ap, r
Pc=Kpc
ap} r
Therefore' KR = a ( vm - b) becomes
PcVc 3 b 1
However, from Table 1.5, RTC =g , v< =3; therefore
81<:, = a,(3V, -1)

3.10 f.lCP =
T(:~
P-
V=--i--- V (Relation 2]
(aDP
( aV}
a~
T
2na
= V _ nb- RV 3 (V- nb) (Problem 3.8]
Hence,
2na(V- nb) 2 - nbRTV 2
f.lCp= RTV 3 -2na(V-nb) 2 XV
RTV 3
Then, introducing l; = na(V _ nb ) 2 to simplify the expression,
2
f.lCp = (
1- nbl;l~
l; _
} V [The final v~ V"' for molar quantities]
1
53
54
For xenon , Vm =24.6 L mol - 1, T=298 K, a=4.194 L 2 atm mol-Z, b = 5.105 x

10- 2 L mol - 1,
nb
vm
5.105 X 10- 2 L mol - l

3
2 08 X 10 24.6 L mol I
8.206 x 10- 2 L atm K - 1 mol - 1 x 298 K x (24 .6 L mol- 1) 3

~= 2 X 4.194 L2 atm mol - 2 X (24.6 L mol - 1 -5 .105 X 10- 2 L mol - 1) 2
=72.0
Therefore , ,uCP=
1-72.0 X 2.08 X 10- 3

1.
x 24.6Lmol - 1
7 0
= 0.294 L mol - 1
CP=20.79 J K - 1 mol - 1 [Table 2.10], so
0.294 L mol - 1
0.294 X 10- 3 m3 mol - 1
,u=20.79J K- 1 mol- 1
20.79 J K - 1 mol- 1
= 1.41 X 10 - 5 K m3 J - l = 1.41 X 10- 5 K Pa - l
= 1.41 X 10- 5 X 1.013 X 10 5 K atm = 1.43 K atm- 1
The value of ,u changes sign at T= T1 and when the sign of the numerator
1- nb~/V changes sign ( ~ -1 is positive). Hence
b~
- = 1atT=T1
vm
that is,
T = 2a ( 1 Rb
I
~) 2 = 27 T
vm
( 1c
~) 2
vm
For xenon,
2a
Rb- 8.206
X 10- 2
2 x 4.194 L2 atm mol - 2

L atm K - I mol - l X 5.105 X 10- 2 L mol-l
and so
T1 =2000K x ( 1-
5.105 x 10.
24 6
2)2
= 2000K
2000 K
The first Law: the machinery
3.11
(~~ r = (!~ r(!B r [change of variable]

=
av T(a~
ap} T[definition of H]
(a(U+pV))
={ T(!~) v-p}(!n /(a:P~ r[equation for (aV!aV)r]
J:n
T(:~)
T-p(:n / V+p(:n T
-T(ap)
aT v(a~
ap} r + v
=
=- T
3.12 #=
(:n
I(:~
+ V [chain relation]
-T(m p + v [Relation 21
(!~) H(~;) r(!:)

I
-1 [chain relation]
11#
1/Cp
Therefore,
#Cp =-
(~~ r = T(!~ v[Problem 3.11] = T(aaT ~ p
The equation of state
pV
nB
nRT= 1 +V
P-
55
56
converts to
nRT
4pB)
-p-) V2 - V - nB = 0, so V = - { 1+ ( 1+
- 112}
( nRT
2p
RT
Write
~=
nR
4pB) 112
, then
( 1 + RT
- =. - (1+~)
T 2p
Hence ,
#Cp=
If
n;2(aaT~)p
4pBIRT~ l, ~ = 1 and #Cp= nT
(aaT
~) P
and for molar heat capacities,

2
# = c;
(aiiil'B)
For argon at 25 C , using the virial coefficients from Table 1.2

B
B
-4.2 cm 3 mol - 1 -21.7 cm 3 mol - 1
373
273
373 K
aT'!_T)P= 373 K 273 K

373 K-273 K
(a
273 K
lOOK
= 6.8x 10- cm K- mol - 1

CP = 20.78 J K - I mol - 1 [Table 2.10]. Therefore ,
(298 K) 2 x (6 .8 x 10- 10 m3 K - 2 mol - 1)
_
#=
20.78JK - Imol - l
2.91 x 10-6 KPa - 1
4
= 2.91 X w- 6 x 1.013 X 105 K atm- 1= 0.29 K atm - 1

We can check that 4pBIRT ~ l by substituting B = -4.4cm 3 mol- 1, which
gives 4pB/ RT= 7 X w - ~ 1.
4
3.13
(ap)
a TV
Cp-Cv = K- [13]=aTV aT v [the line above 13]
(ap)
nR
aT v = V _ nb [Problem 3.8]
av~ (:~, - (:~,

a~
( av}
T
2na
= V _ nb - RV 3 (V - nb) [Problem 3.8]
nRTI(V - nb)
TI(V - nb)- (2na / RV )(V - nb)
~~--~~~~~~~~=
nAR
3
For molar quantities ,
Now introduce the reduced variables and use Tc = 8a/27Rb, Vc = 3b:

2a(Vm - b?
(3V, - 1) 2
RTV~
4Ty;
Hence,
For xenon, Vm=2.46Lmol - 1, Vc=ll8 .8cm 3mol- 1 , Tc = 289.8K

Hence , V, = 20.7 and T, = 1. 03; therefore
1
(62.1-1)2
):"= 1 - 4 X 1.03 X 20.73
..
0.90, glVlng A= 1.1
and
CP - Cv= 1.1R = 9.2 J K - I mol- 1
3.14
dH = Vdp, so 11H =
Vdp
57
58
For a reversible, adiabatic change , pVY= const(A), so V = A/p 11Y

!lH=A
dp
iplly=
) {
1 )
1 }
pl/y-1
IPi
Pr
yA ( Pr
Pi )
1 p;'r-1 - pf'r- 1 = y - 1 p/'Y- pf'r
y )
= y-
yA (
= y-
11-t
nRy
(prVr - PYi)=y_ (T1 -Ti)

1
y
1
1
cp
cp
y-1 = - -1 =~= cp - Cv =R
1 --
1-cp
Hence, !lH = nCP(T1 - Ti)

RTy) 112
RT
RT p
3.15 c, = ( M
,p = pM, soM =p
Hence c, = (
yp)l/2
For argon, y =
so
- (8.314JK- 1 mol- 1 x298Kx j-)I'z _

_
322 m S 1
c, 39.95 X 10- 3 kg mol- 1
-
4. The second law: the concepts

Exercises
4.1
!'!.S=
q;v [4b]
25 X 103 1
(b) !'!.S= 373.15 K 671 K - 1
T,
4.2
!'!.Sm = Cv In T~ [8b], Cv= 12.481 K - 1 mol - 1
Sm (500 K) = 146.221 K- 1mol - 1+ 12.481 K - l mol - 1X In
500
298
= 146.22+6.461 K - 1mol - 1= 152.681 K -l mol - 1

4.3
r r
For CP=a+bT [Table 2.16]
Heat extracted=
=
CP dT=
(a+ bT) dT
a(T2- Tl) + -!b(n- TD
=20.67 X (300-265) + 1 X 12.38 X 10- 3 (3002 -265 2 ) 1 mol - 1

=845 .91mol - 1
Therefore, q =
l.75x10 3 g
_
_
_ g mol _ 1 x 845.91 mol - 1 =54.9 k1
26 98
.
265
=20.67 1 K- 1mol - 1ln
-12.38 x 10- 31 K- 1mol - 1x (300-265)
300
= -3.001 K- 1 mol - 1
60
The second law: the concepts
Therefore, for the stated amount ,

ilS=
4.4
1.75 X 103 g
. g mol_ 1x ( -3.00 J K- 1mol - 1) = -195 J K- 1
26 98
p;
ilS= nR In- [7 and pV= nRT]

Pr
25 g
18.5 atm
_1X8 .314JK - 1mol - 1Xln
160
. 4gmo 1
25
. atm
4.5
+26JK- 1
Vr
ilS = nR In V [7]
I
p;V;
nR = T
1.00 atm X 15.0 L

250K
LM3 X lOS Pa X 15.0 X w-3 m3

250K
=6.08J K-1
Vr ilS -5.01 K- 1
_
In V; = nR = 6.08 J K -1 = -0.823
Hence
Vr = V; e- 0 823 = 15.0 L x 0.439 = 6.6 L
4.6 Find the common final temperature Tr by noting that the heat lost by the
hot sample is gained by the cold sample:
n;Cp(Tr- T; 1) = n 2 Cp(Tr- T;2)
Hence, Tr
n;T;1 + n2T;2
n1 +n2
Since n/n2= t ,
Tr = t(353 K + 2 x 283 K) = 306 K
The total change in entropy is therefore
Tr
Tr
ilS= ilS 1+ ilS2 =n 1CP In -T +n2 Cp In -T
il
i2
50 g
( 306
306)
= 18.02 g mol - lx 75 .5 J K - 1mol - ' x In 353 + 2ln 283
=2.8JK- 1

4. 7
f..Svap =
f..Hvap 29.4 X lfrl 1 mol ---y;=

_ K
334 88
61
= +87 .81 K _,mol-'
Since the vaporization occurs reversibly , f..S 101 =0 so f..Ssurr= - 87.81 K- 1 mol- 1
4.8
(a) f..S 9 = 2S 9 (CH 3COOH, /)- 2S 9 (CH 3CHO, g)- S 9 (0 2 , g)

= 2 x 159.8-2 x 250.3-205.141 K- 1 mol - 1 = -386.11 K- 1 mol - '
(b) f..S 9 = 2S 9 (AgBr, s) + S 9 (Cl 2 , g)- 2S 9 (AgCl, s)- S 9 (Br 2 ,

1
= 2 X 107.1 +223 .07 -2 X 96.2-152.231 K- mol -
/)
+92.61 K - 1 mol - 1
(c) f..S 9 = S 9 (HgC12 , s)- S 9 (Hg, I)- S 9 (Cl 2 , g)

= 146.0-76.02-223 .071 K- 1 mol- 1 = -153.11 K _, mol- 1
(d) f..S 9 = S 9 (Zn 2+ , aq) + S 9 (Cu, s)- S 9 (Zn, s)- S 9 (Cu 2 + , aq)
= -112.1 +33.15 -41.63 + 99.61 K- 1 mol- 1 = -21.01 K _, mol- 1
(e) f..S 9 = 12S 9 (C0 2 , g)+ 11S 9 (H 20, /) - S 9 (C 12H 22 0
11 ,
s) -125 9 (0 2 , g)
= 12 X 213.74 + 11 X 69.91 - 360.2 - 12 X 205.141 K- 1 mol - 1

=+ 512.01K- 1 mol - 1
4.9
(a)
t..G 9 = t..H 9
f..H 9 =
T t..s e
2t>.Hf (CH 3COOH, I)- 2t>.Hf(CH3CHO, g)
= 2 x ( -484 .5)- 2 x ( -166.19) k1 mol- 1 = - 636.62 k1 mol - 1

f..G 9 = -636.62 k1 mol - 1 -298.15 K x ( - 386.11 K- 1 mol - ')
= -521.5 k1 mol- 1
(b) f..H 9 = 2t>.Hf (AgBr, s) - 2t>.Hf( AgCI, s)
= 2 x ( -100.37)- 2 x ( -127.07) k1 mol- 1 = +53.40 k1 mol-'
f..G 9 = +53.40 k1 mol - 1 - 298.15 K x 92 .61 K- 1 mol- 1
= +25.8 k1 mol- 1
(c) f..H 9 = t>.Hf (HgC1 2 , s) = -224.3 k1 mol- 1
f..G 9 = - 224.3 k1 mol - 1 - 298.15 K x ( -153.11 K- 1 mol - ')
= -178.7 k1 mol - 1
(d) f..H 9
t>.Hf (Zn 2 +, aq)- t>.Hf (Cu 2 + , aq)
= +153 .89- 64.77 k1 mol - 1 = -218.66 k1 mol- '
62
!:l.G 6 = -218.66 kJ mol - 1 - 298.15 K x ( -21.0 J K - I mol - 1)

= -212.40 kJ mol- 1
(e) !:l.H 6 = !:l.Hf( = -5645 kJ mol- 1
!:l.G 6 = -5645 kJ mol- 1 -298.15 K x 512 .0 J K- 1 mol - 1
= -5798 kJ mol- 1
(a) !:l.G 6 = 2!:l.G f (CH 3COOH, l)- 2!:l.Gf (CH 3CHO , g)
4.10
= 2 x ( -389.9) - 2 x ( -128.86) kJ mol - 1 = -522.1 kJ mol - 1

(b) !:l.G 6 = 2/:iG f (AgBr, s)- 2/:iG f (AgCl , s)
=2 X ( -96.90)- 2 x ( -109.79) kJ mol - 1 = + 25.78 kJ mol - 1
(c) !:l.G 6 = !:l.G f (HgC1 2 , s) = -178.6 kJ mol - 1
(d) !:l.G 6 = !:l.Gf (Zn 2 +, aq)- !:l.Gf (Cu 2 +)
= -147 .06-65.49 kJ mol- 1 = -212.55 kJ mol - 1
(e) !:l.G 6 = 12!:l.G f (C0 2, g)+ ll!:l.G f (H20 , l)- !:l.G f(CI 2 H 22 0 1 ~> s)
= 12 x ( -394.36) + 11 x ( - 237.13)- ( -1543) kJ mol - 1
= -5798 kJ mol - 1
6C(s) + 3H2(g) + f 02(g)~ C6HsOH(s)
4.11
!:l.S 6
= S 6 (C6H 50H, s)- 6S 6 (C, s)- 3S 6 (H2 , q)- t S 6 (0 2, g)

= 144.0-6 X 5.740-3 X 130.68 - 1 X 205.14= -385.05 J K- 1 mol - 1
C6H 50H(s) + 70ig)~6C0 2 (g) + 3H 20(l)

!:l.H f( = 6!:l.Hf (C0 2 , g)+ 3!:l.Hf (H 20, l)- !:l.Hf (C6H 50H , s)
Hence ,
!:l.Hf (C6H 50H , s) = 6!:l.Hf (C0 2, g)+ 3!:l.Hf (H 20 , l ) - !:l.H f(
= 6 x ( -393.51) + 3( -285 .83)- ( - 305.4) kJ mol - 1
= -164.55 kJ mol - 1
Hence
!:l.G f = -164.55 kJ mol - 1 - 298.15 K x ( -385.05 J K - I mol - 1)
= -49.SkJ mol- 1

4.12
63
Vr
(a) dS(gas) = nR In V
I
14 g
-::-::---:-:-----,----;1
28.02 g mol
x 8.314 J K - I mol - 1 x In 2
= +2.9 J K - 1
AS( surroundings) = -2. 9 J K - I [overall zero entropy production]
dS( total) = Q
(b) dS(gas) = +2. 9 J K - I [Sa state function]
dS(surroundings) = Q[Section 4.4]

dS(total) = +2.9 J K -
(c) dS(gas)=O [qrcv= OJ

dS(surroundings) = 0 and dS (total)= 0
4.13 The same final state is attained if the change takes place in two stages ,
one isothermal compression :
Vr
dS 1 =nRln v=nR In t = -nRin2
I
and the second, heating at constant volume:

Tr
dS2 =n Cvln T= nCv In 2
I
the overall entropy change is therefore
dS = -nR In 2+nCv In 2
=n(Cv- R) In 2
4.14
2.9]
CH 4 (g) +20 2 (g)~C0 2 (g) + 2H 20(/), dG 9 = -817.90 kJ mol - 1 [Table
Therefore, the maximum non-expansion work is 817 .90 kJ mol - 1 [since

lwei= ldGIJ .
4.15
Tc
t: = 1 - - [11]
Th
64
(a) t:= 1 -
333K
K = 0.11 (11 per cent efficiency)
373
(b) t: = 1 -
353 K
K = 0.38 (38 per cent efficiency)
573
4.16
!::.H,,. + 1.9 kJ mol - 1

1
1
!::.S,,. = T,,. =
000K
=+0.95JK- mol 2
4.17
(a) No work need be done because the cooling is spontaneous.
Tc
295 K
(b) t:=Th-Tc[ 15] = 303K-295K
36 9
= 20kJ
qh Th
qc c
4.18 - = T, therefore
w=~ = (Th;cTc) Xq (13 , 15)
4.19
200K - 80K
80K
----,--- X
4.20
Tc
c = Th _ Tc [15]
(a) c =
273K
K = 14
20
(b) c=
263K
K = 8.8
30
2.10 kJ =3.15 kJ

4 _21
w = lf. = (Th-Tc) x!:J.H=(293K - 273K)

c
Tc
273 K
250g
18.02 g mol- 1
x 6.01 kJ mol- 1
= 6.11 kJ
This amount of work can be done in
Problems
T
4.1
(a) !:J.S",(t~s, T) = !:J.S",(l~s, Tr) - !:J.CP!n Tr
with !:J.CP = Cp(l ) - CP(s) = + 37.3 J K- 1 mol- 1

Therefore ,
- 6.01 x 103 J mol- 1

268
-37.3 J K- 1 mol- 1 x In
K
273
273
= - 21.3 J K- 1 mol- 1
!:J.S( surroundings)
!:J.Hrus(T)
T
!:J.Hrus(Tr)
(T- Tr)
T
+!:J.CP
T
6.01kJmol- 1
268 - 273
268K . + 37.3JK -I mol- l x
268
= + 21. 7 J K- 1 mol- 1
!:J.S(total) = 21.7-21.3 J K - I mol- 1 = +0.4 J K -I mol- 1
Since !:J.S(total) > 0, the transition
z~s
is spontaneous at - 5 ac.
T
(b) !:J.S",(l~g, T) = !:J.S,rs(l~g, Tb)+!:J.CP!n Tb
65
66

T
I:J.Hvap
=~+ I:J.C, In Tb' I:J.C,= -41.9 J. K
I:J.S",(l~g, T)=
-1
mol
-1
40.7 kJ mol - 1
368
K
-41.9JK- 1 moi - 1 X In
373
373
= +109.7 J K - 1 mol - 1
!:J.S(surroundings) =
- I:J.Hvap(T)
T
- I:J.Hvap(Tb)
!:J.CP(T- Tb)
-40.7 kJ mol - 1
378 K
( -41.9 J K -I mol-l) X
368-373
368
= -111.21 K - 1 mol - 1
!:J.S(total) = 109.7-111 .2 J K- 1 mol - 1 = -1.5 J K - 1 mol - 1
Since !:J.S(total) < 0, the reverse tra nsition,
4.2 !:J.S=
r r
C,
d; =
g~ l ,
is spontaneous at 95 oc.
(a+:T) dT
=91.47 J K - 1 moi - 1 Jn
300K
K+0 .075J K - 1 mol - 1 X27K
273
=10.7JK - 1 mol - 1
Therefore, for l.OOmol , I:J.S=+llJK - 1
At 298 K, S 6 (NH 3 , g)= 192.45 J K - I mol - 1. Therefore ,
=200.7 1 K - I mol- 1
(b) S 9 (773 K) = 192.451 K - I mol- 1 + 29 .751 K - I mol - 1 1n
+25.10x
773
298
w-) 1 K - 2 mol- l X475 K
= 232.01 K - 1 mol - 1
4.4
!::iS depends on only the initial and final states, so we can use
Tr
!::iS = nCP In T
I
Since q = nC/Tr- Ti),
/ 2Rt
Tr= Tj+-= Tj+- [q = ltV = l 2Rt]

nCP
nCP
That is,
2
I Rt)
!::iS = nCP In ( 1 + nCpTi
Since n =
500 g
_ g mol
63 6
7.86 mol ,
!::iS=7.86 mol x 24.41 K- 1 mol - 1

x ln
(1
(1.00 A) 2 X 1000 Q X 15.0 s)

+ 7.86x24.41K- 1 x293K
= 1921 K - 1 x In 1.27 = + 45.41 K - 1

For the second experiment,
67
68
dqrev(net) = 0; therefore dS = 0 and .!lS = 0.

However, for the water
LlS =
Jd~ev
q;v= f
:t
(1.00 A) 2 X 1000 Q
15.0 s
293K
+51.2JK- 1
[1J=1A Vs=1A 2 Q s]
4.5
C(s) + t0 2 (g)+2H 2 (g)~CH3 0H(l), Lln 8 = -2.5mol
M e = .!lG 9
il(p V) = .!lG 9
iln(RT) = .!lG 9 + 2.5RT
= - 166.27 + 2.5 X 2.479 kJ mol - 1

= -160.07 kJ mol- 1
4.6
Calculate the final temperature as in Exercise 4.6:
Tr
Tr
.!lS=n 1CPin T; +n 2Cpln T;z

1
=n 1CP In T; T;z [n 1 =n2]

1
200 g
3182
18.02 g mol-l x 75.5 J K-1 mol- l x In 273 x 363
+17.01 K - 1
(b) Heat required for melting= n 1 ilHrus = 11.1 mol X 6.01 kJ mol - 1
= 66. 8 kJ
The decrease in temperature of the hot water as a result of its causing the
. .
q .
66.8 kJ
meltmg IS ilT= nCP= 11.1 mol x 75 .5 J K-1 mol-l =79.6 K
At this stage the system consists of 200 g water at 0 oc and 200 g water at
90 oc -79.6 oc = 10 oc (283 K). The entropy change so far is therefore
n ilHrus
283 K
.!lS =----;:;;- + nCP In 363 K

11.1 mol x 6.01 k1 mol- 1
273
+ 11.1 mol x 75.51 K - I mol - 1 ln
283 K
363
= 244 1 K- 1 - 208.6 1 K- 1 = +35.7 1 K - 1

The final temperature is Tr= t(273 K + 283 K) = 278 K, and the entropy
change in this step is
~S = nCP In T;JTi2 = 11.1 X 75 .51 K- ln

1
278 2
X
273 283
+0.27 1 K- 1
Therefore, overall, ~S = 35.71 K - I+ 0.271 K -I = +36 1 K - I

4.7 We need ~G and ~A under the stated conditions, and begin by
calculating ~G for the transition l--"'s :
~G(T)
= ~H(T) - T ~S(T)
~H(Tr)- ~Cp(T- Tr) -
~H(Tr)- ~ ~H(Tr) - ~cP{ T- Tr- Tin~}
=(
T{
~S(Tr)- ~CP In ~}
~ -1) ~Hrus(Tr) - ~cP{ T- Tr- Tin~}
T=268 K, Tr=273 K, ~Hrus =6.01 k1 mol - 1, ~CP = +37.3 1 K - 1 mol - 1:

~G(268
K) = 268 -1 ) x 6.01 k1 mol - 1

( 273
-37.31mol - 1 x 268-273 - 268ln 268}
{
273
= - 0.11 k1 mol - 1
For
~A
we use
~A = ~G-~(pV)=~G-p ~V
=~G - pM ~(lip)
= -0.11 k1 mol - l- 1.013 X 10 5 Pa X 18.02 X w-) kg mol - l
69
70
x (917
k~ m -
999
k~ m -
= - 0.11 k1 mol - 1
Therefore:
(a) Maximum work is 0.11 k1 mol - 1
(b) Maximum non-expansion work is also 0.11 k1 mol - 1
From the data , draw up the following table :

T IK
TIK
10
15
20
25
30
50
0.284
0.47
0.540
0.564
0.550
0.428
70
100
150
200
250
298
0.333
0.245
0.169
0.129
0.105
0.089
Plot CPIT against T (Fig. 4.1). This has been done on two scales. The region 0
to 10 K has been constructed using CP= aT 3 fitted to the point at T= 10 K , at
which CP=2.8 1 K - 1 mol - 1, so a = 2.8 x 10- 3 1 K - 4 mol- 1 The area can be
determined (primitively) by counting squares, which gives area A=
38.281 K - 1 mol - \ area B (up to 0 C)=25 .601K - 1 mol - 1, area B (up to
25 oq = 27.801 K - 1 mol - 1 Hence:
Sm(273 K) =Sm(O) +63.88 1 K - 1 mol - 1
Sm(298 K) = Sm(O) + 66.081 K - I mol - 1
Th- Tc 1200 K
4.9
e = ~=
2273 K=0.53
w=mgh, w = eq , q=nflHc
oo
Fig4.1
I 1'\.
I
05
'
~
~
I'.
r-.... ........,
01
'
l8
0
20
1.0
~ t-..,
Etra cia on
60
80
100
200
300
TjK
Eq
Hence h = - = 0.53 x
mg
3 X 103 g
114.2 g mol
5512 X 103 J mol - 1

x -:-:,.-::--c----::-:-----::;2
1000 kg x 9.81 m s
=7.8km
4.10
t.G 9 = t.H 9
T t.S 9 = 26.120 kJ mol - 1
t.H 9 = +55.000 kJ mol- 1
Hence t.S 9 =
(55.000-26.120) kJ mol - 1
_ K
= +96.864 J K - I mol - 1
298 15
t.S 9 = 4S 9 (K + , aq) + S 9 ([Fe(CN) 6] 4 -, aq) + 3S 9 (H 20, /)

- S 9 (K 4 [Fe(CN) 6] 3H 20, s)
Therefore,
r-, aq) = t.S
S 9 ([Fe(CN) 6
9 -
4S 9 (K +, aq)- 3S 9 (H 20, /)
+ S 9 (K 4 [Fe(CN) 6] 3H 20, s)
= 96.864-4 X 102.5-3 X 69.9 + 599.7] K - I mol - 1
=+76.9JK - 1 mol - 1
4.11 Draw up the following table:
71
72
TIK
10
20
30
40
50
60
(Cp!T)!
(J K - 1 mol- 1)
0.209
0.722
1.215
1.564
1.741
1.850
TIK
70
80
90
100
110
120
(CPIT)I
(J K - 1 mol - 1)
1.877
1.868
1.837
1.796
1.753
1.708
TIK
130
140
150
160
170
180
1.665
1.624
1.584
1.546
1.508
1.473
TIK
190
200
(Cp! T)!
(J K- 1 mol- 1)
1.437
1.402
(C/T)/
(J K - 1 mol - 1)
Plot CPIT against T (Fig. 4.2a). Extrapolate to T= 0 using CP = aT 3 fitted to

the point at T = 10 K, which gives a = 2.09 mJ K - 2 mol- 1 Determine the area
under the graph up to each T and plot Sm against T (Fig. 4.2b).
(a)
2 0
ie-.
300 (b)
Fig4.2
-...
_E 200
~
~
'0
100
\!2.
I
l1
0
~
;;::::
IT
50
200
50
73
TIK
25
50
75
100
125
150
175
200
{Sm- Sm(O)}/
(J K- 1 mol- 1)
9.25
43.50
88.50
135.00
178.25
219.0
257.3
293.5
4.12 Draw up the following table and proceed as in Problem 4.11:
TIK
14.14
16.33
20.03 31.15 44.08 64.81
(Cp!T)I
(JK- 2 mol- 1)
0.671
0.778
0.908 1.045
1.063
TIK
183.59
225.10
262.99
298.06
(C/T)/
(J K- 2 mol- 1)
0.787
0.727
0.685
0.659
100.90 140.86
1.024 0.942
0.861
Plot CP against T (Fig. 4.3a) and CP/T against T (Fig. 4.3b), extrapolating to
Fig4 .3
(b) 10
Ia)
200
"'~ ......
,., ........
__..,....
I 150
0
\.:: 100
,.
v-
,-
..........
li
II
:i,
(j
50
0'2
f
~
0
0
100
T/K
200
300
100
T/K
200
300
T= 0 with CP = aT 3 fitted at T= 14.14 K, which gives a= 3.36 mJ K - 3 mol - 1 It

then follows that
74
298 K
CPdT=34.4 kJ mol - 1, so H m(298 K) = Hm(O) + 34 .4 kJ mol - 1
298 K
C dT
.
--T- = 243 J K - 1 mol- 1, so Sm(298 K) =Sm(O) +243 J K - 1 mol - 1
c=
4.13
Tc
r
1 h
nCP!'!.T
T , w = -=
c
Th = 1.20 K, (Tc)mcan= t (l.lO K + 0.10 K) = 0.60 K

0.60K
c = 1.20 K- 0.60 K
l.OO
1.0 g
3.9 X 10 - 5 J K -I mol - 1 X 1.00 K
1.00
=0. 6 l.uJ
w = 63 .54gmol_ 1 x
For the more realistic calculation ,
= -n
=n
=
r(AT~ +B) ( Th-Tc)dTc
(AT~ - AThT~ + BTC-
BTh) dTc
n{tA(T1 - T;) - j-A (Ti - Tf)Th +
ts(n - n)- B(Tr-1i).Th}
We evaluate this expression with n = 0.016 mol , A = 4.82 x w-s J K - 4 mol - 1,

B = 6.88 x 10- 4 JK - 2 mol - 1, Th =1. 20K , Ti=l.lOK , Tr=0.10K:
W
= 0.016 mol.
4.21
10- 4 J mol - 1 = 6.7 ttl
4.14 The four episodes of heat transfer are
qh
VB
-=nRlnTh
VA
(b) 0 [adiabatic]
Vo
(c) qc= nRTc In Vc
75
(d) 0 [adiabatic]
Therefore
Therefore
rJ.dqT = 0
dq qh qc
VaVo
- =- +- = nR In - T Th Tc
VAVC
If the first stage is replaced by isothermal , irreversible expansion,
w= -pc.(V 8 - VA), implying that q=pc.(V8 - VA) [as t..U=O]

Therefore,
Va
However , Pcx(V 8 - VA) < nRTh InVA
because less work is done in the irreversible expansion, so
rJ. Tdq <nR In VVA +nR In VVc =0

J.dq
That is, r T < O
8
4.15 The isotherms correspond to T= constant , and the reversibly traversed

adiabats correspond to S =constant. Thus we can represent the cycle as in Fig.
4.4.
v v/ v/ v VY
v v v v/ v/
10v/ v v Vv
/
v/
L7/
/ / /V
Fig4.4
Entropy
76
The area within the rectangle is

Area =
TdS= (Th- Tc) x (S2- S 1) = (Th- Tc) t':iS
= (Th- Tc)nR In
V:v
[isothermal expansion]
Therefore, the area is equal to the work done.

4.16
Tr
Tr
t':iS = nCPIn Th + nCPIn Tc [Tr is the final temperature, Tr= +( Th + Tc)]
(Th+ Tc)2
= nCP In ThTc= nCPIn 4ThTc
In the present case, Tr = 375 K.
500
3752
AS g 1 24 4 J K - I
1- 1 X I
u
-63.54gml _ x
mo
n500 x 250
= +22 .61 K - 1
4.17 g=f+yz
dg= df + y dz+z dy
= a dx-z dy+ y dz+z dy
= a dx+ y dz
dw = _d_q_ = _-_c..!:._P_d_T
c(Tc)
c(Tc)
The second law: th e concepts
Therefore ,
=CP{Tr- Ti- ThIn~}

w = w( cooling) + w( freezing)
.
lw(coohng)l =
250g
{
273}
. g mol _ 1 x 75 .5 J K - l mol - 1 X -20 K - 293 KIn
293
18 02
=0.72 kJ
.
n f'..Hrus
250 g
20
lw(freezmg)l=-=
_1 X6 .01kJmol- 1 x c0
1802
. g mo 1
27 3
= 6.11 kJ
Therefore, the total work is
w=0.72 kJ +6 .11 kJ = 6.83 kJ
If the initial temperature were 25 C, no additional work would be needed
because cooling from 25 oc to 20 oc is spontaneous.
77
5. The second law: the machinery

Exercises
Vi
Pr
tlG = nRTln - [ll]=nRTin V

Pi
r
5.1
3.0 x 10- 3 mol x 8.314 J K -I mol- 1 x 300 KIn
-3.81
t1S =
5.2
(a
atlTG) p [6] = - aaT ( -85.401 + 36.51 x
-36 .5 J K- 1
m
tlG = Vtlp [10], p=v
5.3
Therefore,
m tlp 35 g X 2999 X 1.013 X 105 Pa

p= tlG =
12x103 J
Vr
Pi
tlS = nR In -= nR In-
5.4
Vi
Pr
Hence,
Pr = Pi e-t;.SinR = 3.50 atm X e-(-25.01 K - l)i(2.00x8.3!4J K - 1)

=
3.50 atm x e1. 5o= 15.7 atm

Pr
tlG = nRTln - [11] = -T tlS

Pi
=
- 330 K
X (-
25.0 J K- 1) = +8 .25 kJ
36
60
f)
The second law: the machinery
5.5
~11 =
Pr
RT!n- [14]
Pi
29 .5
= 8.3141 K - 1 mol - 1 x 313 K x ln - = +7.3 k1 mol- 1
1. 8
5.6 11 - 11 = RTin [15 minus 14]
= RT!n y = 8.3141 K - 1 mol - 1 x 200 K x In 0.72

=
- 0.55 k1 mol - 1
= -2.63 x 10- 8 Pa - 1
y = e 8 'p+ [Above Example 5.7]

=
5.8
e -2.63x JO - HPa - l x 50 x L013 x I(J.I Pa
~G = V ~P
[10]
= 1.0 X 10- 3 m 3 X 99 X 1.013 X 105 Pa

= 10 kPa m 3 = + 10 k1
5.9
~Gm=
Problems
0
100.0
RT!n--: (11 ] = 8.3141 K - 1 mol- 1 x 298 K X In - O
1.
p,
+ 11 k1 mol - 1
79
80
and so
I:!..G 9 (T)
= ~!!.G 9(l') + (1 - ~ I:!.H 9 (l')
= -r !!.G 9 (l') + (1 + -r) !!.H 9 (l')

-r = Til'
For the reaction
2CO(g) + 0 2 (g)~ 2COz(g)
!!.G 9 (l') =2!!.G /"(C0 2 , g) -21:!..G /"(CO , g)
= 2 X ( -394 .36) - 2 x ( - 137.17) kJ mol - 1 = - 514.38 kJ mol - 1
9
!!.H (l') = 2!!.H /"(C0 2 , g) -21:!..H/"(CO , g)
=2 x ( - 393 .51) - 2 x ( -110.53) kJ mol- 1 = -565 .96 kJ mol- 1
Therefore, since -r = 3751298.15 = 1.258
I:!..G 9 (375 K) = 1.258 X ( -514.38) + (1-1.258) X ( -565.96 kJ mol- 1)
= - 501 kJ mol- 1
5.2 For the reaction
N2(g) + 3Hz(g)~ 2NHJ(g)
I:!..G 9 = 21:!..G /"(NH 3 , g)
9
9
[Problem 5.1 , -r= Til'}
(a) I:!..G (500 K) = -r !!.G (l') + (1- -r) !!.H 9 (l')
500K
(
500 K )
= 298.15 Kx 2 x ( -16.45 kJ moL- l)+ 1- 298.15 K
x 2 x ( -46.11 kJ mol- 1)
= - 55.0 + 62.43 kJ mol- 1 = +7.26 kJ mol - 1
(b) I:!..G e (1000 K) =
1000 K
(
1000 K )
_ x 2 x ( -16.45 kJ mol- 1) + 1_ K
298 15
298 15
x 2 x ( - 46.11 kJ mol- 1)
= - 110.35 + 217.09 kJ mol- 1 = + 106.74 kJ mol - 1
5.3 !!.G 9 (37C) = -r !!.G 9 (l') + (1 - -r) !!.H 9 (l') [Problem 5.1, -r= Til']
310K
(
310K )
= 298.15 K x (- 5798 kJ mol-l)+ 1 -298.15 K
x (-5645 kJ mol- 1)
= - 5804 kJ mol - 1
81
The difference is
!:J.G 6 (37 oq- !:J.G 6 (l'J = -5804- ( -5798) kJ mol - 1 = -6 kJ mol- 1
Therefore, an additional 6 kJ mol - 1 of non-expansion work may be done at
the higher temperature.
5.4 lny=
(Z-1)
-p-
dp (17]
We draw up the following table:
p/atm
103 (
1
) /atm- 1
10
40
70
100
-2.99
-3.01
-3.03
-3.04
-3.17
-3.19
-3.13
The points are plotted in Fig. 5.1. The shaded area is -0.313, so at 100 atm
y=e- 0313 = 0.73
and the fugacity of oxygen is 100 atm x 0.73 = 73 atm
Fig 5. 1
20
!.0
60
p/afm
80
700
5.5 At constant volume, dU=C 11 dT. Moreover, dS=dq,cJT=CvdTIT.

Therefore,
82
(~~ v = CvdTI(CvdT/T) = T
We can ensure that the entropy in constant by considering a reversible
adiabatic change . Then
dU= -pdV
Hence(!~
= -p
5
5.6 There are two routes. Either use H(p, S) is a state function, and A(V, T)
is a state function, and proceed as in Section 5.1:
dH=dU+p dV+ Vdp=(TdS-p dV)+p dV+ Vdp
=
Vdp+ TdS
But as dH is exact,
Similarly , dA = -S dT- p dV, and is exact.

Therefore,
Alternatively
(!~)T
= (:;)
J!~)
I (:n
= +1
5 7
(:~) v = - (
=(
:n
!~)
=-
(!~ p(!~)
v [chain relation]= (
s=
I(!~) J~~
Tl (!~)
[?]
:~) v [inversion]
[Maxwell , chain relation]
[inversion]
(:~)vi (!~) v(!~ v[Maxwell]
(!~ ,(~~) ,/ (~~)
aVT
=c
[(aH/aS)p= T,
[inversion]
by analogy with
(aU!aS)v= T]
_P_
(~~) (:~) v[Problem 5.6] = (ooTC~~) v= n:
5.8
T=
dV
Therefore dS = nR- = nR d In V
Hence, Srx.nR ln V
5.9
dH= TdS+ Vdp
dH= (~~" dS+ (~;}~ dp [H= H(p, S)]

Thus,
(~~),=T, (~~ s =V
Furthermore,
(~H)
ap
[dHexact]
(aH) (as) + (aH)

as , ap
ap
(Relation 1, Box 3.1]

s
83
84

=
T(as)
+v
ap
T
=-T(mp +v
[Maxwell]
(a) For pV=nRT
(:~P = :R, hence(~~
= -:RT + V=Q
nRT an 2
(b) For p = V _ nb- V2 [Table 1.5]
T=
p(V- nb) na(V- nb)

nR
+ RV 2
( oV
a~=!!_
na _2na(V-nb)
nR + RV 2
RV 3
Therefore
(~~
= -T/
(!~
+ V [inversion]
-T
-----:----:-::-c:----:-:-
p
na 2na(V-nb)
nR + RV 2 RV3
+v
nb- (2na/ RT)}.. 2

nb
~- (2na!RTVW ' }..= 1
-v
When b/Vm ~ 1, }.. = 1 and

2na 2na 1 2na p
2pa
RTV= RT.
RT nRT= R2 T 2
v=
Therefore,
a!!\
nb- 2na/ RT
( ap T = 1 - (2pa/ R 2 T 2)
For argon , a= 1.345 L2 atm mol - 2 , b=3 .219 x 10- 2 L mol - 1,

2na
2 X 10.0 atm x 1.345 U atm mol - 2
RT=8.206x10 2 LatmK 'mol 1 x 298K
O.llL

2pa
2 X 1.0 mol x 1.345 L2atm mol - 2
-2 =
0045
R T 2 (8.206 x 10 2 L atm K 1 mol 1 X 298 K) 2
Hence ,
aH)
( ap
=(3.22xl0-2-0.ll)L
I-0.045
!'iH=(af!:\
l'ip=-8.2Jatm ap }T
-0.083L =-8.4Jatm - I
x 1atm=-8J
--
nT=T(!~)v-p[4]
5.10
RT
BRT
Vm
V;;,
p=-+ - ,- [given]
Hence,
p2 l'iB
ForV =RT!p n1= - m
'
R !'iT
From the data, l'iB= -15 .6- ( -28.0) cm 3 mol - 1 = +12.4 cm 3 mol - 1
( 1.0 atm) 2 X (12.4 X 10- 3 L mol - 1)
Hence, (a)
nT= 8 .206 x 1o-?- L atm K I mo I I x 50 K = 3.0 X
w-J atm
85
86
Since CP=Cv+R
acp) = (acv)
ax for p Or
(fu
a
(anr)
av = aTav= aT [above]
(acv)
T
(b)
X=
~ (:~)
2
= (aaT
v [Problem 5.10]
2R7T(aB) + R~ (a ~)
V;, aT v V m aT v
= RT
2
Vm
(a aT(BT))
2
~1 = (:~ u' Cv= (:~ v
5.12
~1Cv = (:~ J:~ v = -1 I(:~
[chain relation]
= - (:~) }inversion]=p-T(:~) }41
(!~)
v = -1
I(!~
p(
Therefore
~ 1 Cv= p-
aTher
:n
r [chain relation]

nRT
p=--e-antRTV [Table 1.5]
V-nb
ap)
nRT
na
nRT
T ( ar v = v- nb e-an!RTV + RTV. v- nb e - an!RTV
nap
=p+--
RTV
nap
Hence, nr=RTV
nr~ 0 asp~ 0,
V ~ oo. a~ 0, T ~ oo. The fact that nr > 0 (because a> 0) is

consistent with a representing attractive contributions, since it implies that
(aU/aV)r>O and the internal energy rises as the gas expands (so decreasing
the average attractive interactions).
s . I4
dG=
( a~
ap)
(ac)
ap r
dp= Vdp
= -xrV (given), sod In V= -xdp

T
Hence, the volume varies with pressure as
din V =- xr
dp
or
V = V0 e -r<P-P;) [ V = V 0 when p = p;]
Hence
dG =
Jv
dp = Vo
I:~ e-r(p-p;) dp
1-e-r(Pr-P;)
G(pr) = G(p;) + V0
1-e-r !!.r
G(p;) + V o - - -
Kr
If
KT
~p ;
1, 1 - e -
Kri!.P
= 1- (1 -
Hence
G' = G + Vo ~p(1 - txr ~p)
KT
Kr
~p
+ tx} ~p
)=
KT
~P-
tx} ~p 2
87
88
For the compression of copper, the change in molar Gibbs function is
63.54 g mol- 1
= . X 106 g m 3 X 500 X 1.013 X 105 Pa X (1- +KT~p)
8 93
= 360.4 J X (1 - +KT ~p)
If we take KT = 0 (incompressible) ,
+KT~p = +
~Gm =
+360 J . For its actual value
X 0.8 X 10- atm- X 500 atm=2 X 10- 4

6
1 - +1CT ~p = 0.9998
Hence
cent) .
~Gm
differs from the simpler version by only 2 parts in 10- 4 (0.02 per
T'
~G' = r~G+
=r
(b)
~G +
~H(T")
(1-r)
~G ' _~G __
T'
T =
(l-TT')
~H
~H(T)
~H
~H
with r = T ' IT
+ (T" - T)
~CP
[given]
JrdT" _
JT"(T"-T)dT"
T" z ~CP
T" z
T
1-1)
( T' T
T' -T~C (
~H - ~C ln P
T
P
- 1 - -1)
T'
Therefore, with r = T ' IT

~G'
=r
~G+
(1-r)
=r
~G +
(1 -
~H -
r)(~H -
T'
~CP
In r- T ~CP(1-r)
T ~CP)- T'
~CP
In r
The second la w: the machinery

5.16
Ks= -~(a~ =
v ap) s
1jv(ap)
av s
For a reversible adiabatic change, p Vl' = const ,
ap) = (!____ const) = _ const = -yp

( av s av vr s y v)+ l v
Therefore ,
- 1
1
Ks= - - -
v(-~)
YP
Hence , YPKs = -1
5.17
dS=
TdS =
(!~) v dT+ (!~)
T(!~) v dT+ T(!~)
dV [S=S(V, T) ]
dV
Now,(!~) v = (!~) v(:~ v = ~X Cv

(
:~)
=(
:~) v [Maxwell]
Hence, TdS= CvdT+ T(tf) v dV

For a reversible, isothermal expansion, T dS = dqrcv ; therefore
qrev =nRT
5.18
r dV
J
i
(Vr-
nb)
V -nb =nRT!n ~
dS=(:~)PdT+(!~)Tdp [S = S(p. T)]
89
90
TdS=
T(!~)
Use (
!~)
(:;) T
=(
dT+
T(:;)
dp
:~) :~ = ~ x
P(
CP
= - (:B P [Maxwell]
Hence TdS= cp dT- T(:B pdp= c p dT- a TV dp

For reversible, isothermal compression, TdS=dq,cv, dT=O; hence
dqrcv=-a TV dp
qrcv =-a TV l'l.p if the substance is incompressible.
For mercury,
qrcv = -1.82 X 10- 4 K -I
=
5.19
273 K X 1.00 X 10 - 4 m3 X 1.0 X 108 Pa
-0.50 kJ
G'=G+
J:
Vdp
J:
G + V0
G + p * V0 (1- e - pip" )
e-plp" dp
Since e - pl~ < 1 if p > 0, G' > G . Therefore, when the pressure is relaxed , the
spontaneous direction of change is expansion .
5.20
In y=
J
P
(Z-1)
- p - dp
Z= 1 + - + - = 1+B'p+C'p 2 +
v"' v~
B
C- 8
with B' = RT' C' = R 2 T 2 [Problem 1.15]

Z-1
--=B'+C'p+
p
Therefore ,
In y =
J:
J:
8' dp+
C'p dp+
=8'p+ -i C'p 2 +
8p (C-8 2)p 2
=RT+ 2R 2T 2 + ...
For argon,
-21.13 X 10- 3 L mol - l X 1.00 atm
RT- 8.206 X w- 2 L atm K - I mol - l X 273 K
8p
-9.43 x w-4
(C- 8 2)p 2 {1.054 x 10 - 3 L2 mol - 2 - ( - 21.13 x 10- 3 L mol - 1) 2} x 1.00 atm

2 X (8 .206 X w-zL atm K - I mol - l X 273 K) 2
2R 2T 2
= 6.05 x
w- 7
Therefore,
tn y = -9.43 x
w- + 6.05 x w- = -9.42 x w4
y=0 .9991
Hence f= 1.00 atm x 0.9998 = 0.9991 atm

The equation of state
5.21
pVm
8T
RT = 1 +Vm
4p8)"2}
P 1+ ( 1+R
vm = RT{
2
solves to
so
28/R
4p8) 112
1+ ( 1+R
(z-1)
lny=
28
- p- dp=R
Jp
dp
4p8)"z
01+ 1+ R
(
91
92
=
4pB)lt2
(a-1)
- - da
z
a
a=1+ ( 1+R
=a-2-lnta
1(
4pB)lt2
4pB)I t2
-1-ln- 1 + R
2
R
= ( 1+Hence
2e(l+4pBI R)IILJ
y= 1 + (1 +4pB!R) 112
This function is plotted in Fig. 5.2. When
4pBIR~1,
Fig5.2
y 12
01
10
....
001
10
0 01
08
01
v
7 0
4p ~H
ex=1+x, (1+x) 112 = 1+ tx, and (1+xt 1 =1-x. Then

pB
r=1+R
6. Changes of state: physical

transformations of pure substances
Exercises
p*
ln-=C
p
1 1
R
p*
-=-+--lnT T* D.Hvap
p
1
8.314JK- 1 mol - 1
=
297.25 K
28.7 x 10 3 J mol- 1
400Torr
ln-500Torr
=3.300x10- 3 K- 1
Hence T= 303 K
dp
6.2
I::!.Sm
dT= 1::!. V (4]

m
I::!.Srus = 1::!. V mX
:~) = (163.3 -161.0)
10- 6 m3 mol- 1
(100 -1) X 1.013 X 105 Pa

(351.26-350.75) K
= +45.23 J K -I mol- 1
I::!.Hrus = Tr I::!.S= 350.75 K x 45.23 J K - I mol - 1
= +16 kJ mol- 1
94
Changes of state: physical transformations of pure substances
dIn p
2501.8
2501.8 K
dT
T /K
T2
- -=2
Therefore,
t::.Hvap = 2501.8 K X R
= 2501.8 K x 8.3141 K- 1 mol- 1 = +20. 80 k1 mol- 1
6.4
w=y t::.a (10]
= 7.20 X 10- 2 N m-I X (2500 -150) X 10 - 4 m2 (Table 6.1]

= 16.9 m1
6.5
y = t hpgr (15]
= +X 1.20 X 10- 2 m X 871 kg m- 3 X 9.81 m S - 2 X 4.0 X 10- 4 m

=2.05x
6.6 p = p *
w-2 N m- 1
e 2Y Vml rRT
(1 N = 1 kg m s- 2]
(13a]
r= 2yVm (tni._) - I = 2yM (tni._) - I

RT
p*
pRT
p*
=
2 X 2.70 X w- 2 N m - IX 153.81 X w-3 kg mol - l ( 87.95 Torr) - I

ln-----1600 kg m - 3x 8.3141 K - 1mol -Ix 293 K
87.05 Torr
=207 nm
6.7 t::.T =
!::.Vrus
AS
U
t::.p
(4]
fus
Tr!::.Vrus
= t::.H
Tr!::.pM
xt::.p= t::.H
t::.(llp)
fus
fus
278.6 K X 999 X 1.013 X 105 PaX 78.12 X 10- 3 kg mol- 1

= ------------~10~.~59~x
~1~03~1~m--ol~
1 ------------
x(879k~m 891k~m- 3)
3
= 3.18 K
Therefore , at lOOOatm , Tr = 278.6+3 .18=281.8K (8 .7 C)
6.8
dn
dqldt
95
1.2 x 103 W m- 2 x 50m 2

44.0 x 103 J mol - 1
= 1.4 mol s- 1
dm
-d = 1.4 mol s- 1 x 18.02 g mol - 1 =25 g s- 1

t
- -6.9
pV
m
n = - n =- V = 75 m3
RT'
M'
pVM
m = RT
24 Torr x 75 x 103 L3 x 18.02 g mol - 1
(a) m = 62.364L TorrK- 1 mol - 1 x 298.15K 1. 7 kg
(b) m =
(c)m=
98 Torr x 75 x 103 U x 78.11 g mol - 1

=31 kg
62.364 L Torr K - I mol - 1 x 298.15 K - 1.7 X 10- 3 Torr X 75 X 10 3 U X 200.59 g mol - 1
62.364LTorrK - 1 mol - 1 X298.15K
= 1.4kg
--
[The mercury is assumed to be present as a monatomic vapor.]

6.10 The vapor pressure of ice at -5 oc is 3.9 X 10- 3 atm , or 3 Torr.
Therefore , the first will sublime. A partial pressure of 3 Torr or more will
ensure that the frost remains.
6.11 The volume decreases as the vapor is cooled from 400 K to 373 K. At the
latter temperature the vapor condenses to a liquid and (if 1 atm pressure is
maintained) there is a large decrease in volume. The liquid cools with only a
small decrease in volume until the temperature reaches 273 K, when it freezes .
The direction of the slope of the solid/liquid curve shows that the volume of
the sample will then increase if the pressure is maintained. Ice remains at
260 K. There will be a pause in the rate of cooling at 373 K (about 40 kJ mol - 1
of energy is released as heat) and a pause at 273 K (when about 6 kJ mol - 1 is
released) .
6.12 Cooling from 400 K will cause the contraction of the gaseous sample
until 273 .16 K is reached, when the volume decreases by a large amount and
solid ice is formed directly; liquid water may also form in equilibrium with the
vapor and the solid.
96
6.13 See Fig. 6.1. (a) The gas expands. (b) The sample contracts but remains
gaseous because 320 K is greater than the critical temperature. (c) The gas
contracts and forms a liquid without the appearance of a discernable surface.
(d) The volume increases as the pressure on the liquid is reduced. (e) The
liquid cools, then freezes, contracting as it does so. (f) The solid expands
slightly as the pressure is reduced and sublimes when the pressure reaches
about 5 atm . (g) The gas expands as it is heated at constant pressure.
Fig6.1
Llq id
Sold
I
II
e -I
r<- -l't~d
I
~
I v
,r StG t
~ - rr I
I
I
I
71
Ga
Temperature
6.14 p = p*
e2yVmlrRT
[13a)
= p*
e2yMi rpRT
[Vm=M/p)
2 X 2.9 X 10- 2 N m- 1 X 78.11 g mol- 1
2yM
pRT 0.879xl06 gm
x8.314JK
mol
= 2.08 X 10- 9 m
2.08 X 10- 9 m
_
(a) rpRT= lOxlO 6m =2.08x10-4
2yM
P = p* ez.oii x w- = 1.0002p*
(b)
2.08 X 10- 9 m
rpRT - 0.10 X 10- 6 m
2yM
P = p* eo.ozos = l.0 2p*
0.0208
X298 .15K
Problems
14.4x 103 1 mol - 1

= 180 K X (14.5 X 10- 3- 1.15 X 10 - 4) m Jmol-1 = +5 .56 kPa K- 1
(8a, dlnp = dplp]
14.4 x 1031 mol - 1x 1.013 x 10 5 Pa
8.3141 K - 1mol - 1x (180 K) 2
+ 5.42 kPa K - 1
The percentage error is 2.5 per cent

6.2
(a)
a11(l)) (a11 (s ))
(aT aT
P-
-6 .01 k1 mol - 1
am(g))
( ----aT
= -f":..Svap=
p-
.
= - Sm(l) + Sm(s) (Section 6.5]
-22.01 K - 1mol - 1
273.15 K
(b)
(am(l))
----;;[
= - Sm(g) + Sm(l)
-/':..Hvap
Th
-40 .6 k1 mol - 1
373.15 K
-109.01 K - 1mol - 1
f":..J.t = (:;), t:..T= -Smt:..T [1]

f":..J.t(l) - f":..J.t(S) = J.t(/ , 5 C} - J.t(l , 0 C} -J.t(S, -5 C} + J.t(S, 0 C}
=J.t(l, - 5 C} -J.t(S , -5 C}[J.t(l, 0 C} =J.t(S , 0 C)]
= - {Sm(l) - Sm(s)} /':.. T = f":..Srus /':.. T
=
-5 K x -22 .01 K - 1mol - 1= +llOJ mol - 1
97
98
Since ,u(l, - 5 oq > ,u(s, -5 oq,

6.3
(a)
th~re
is a thermodynamic tendency to freeze.
(a~;l))T- c:;s))T=Vm(l) - vm(s) [2)
= M !'1 G) = 18.02 g mol - l x
C.ooo ~ cm -3
0.917 cm-3)
= -1.63 cm 3mol - 1
(b) c~;g)) T- c:;l)) T= Vm(g)- Vm(f)

-I- ~03 -I)
= 18.02 g mol-l
X (
0.5981g L
0.958 x
gL
= +30.1 L mol - 1
At 1.0 atm and 100 oc, ,u(l) = ,u(g); therefore , at 1.2 atm and 100 oc
,u(g) - ,u(l) = !'1 Vvap !'iT= [as in Problem 6.2] 30.1 X 10 - 3m3 mol- 1 X 0.2 X
1.013 X 105 Pa
= +0.6 kJ mol - 1
Since ,u(g) > ,u(l), the gas tends to condense into a liquid.
Therefore,
!'iT =
Tpgh !'1 V
!'lH
234.3 K X 13.6 X 103kg m- 3X 9.81 m S- 2 X 10m X 0.517 X 10 - 6 m 3 mol - 1
2.292 x 103J mol - 1
=0.070K
Therefore, the freezing point changes to 234.4 K
6 .5 AteqUit
Tb num,n
.
p 1V
H vap,
1 =RT ' q = -nl!'l
!'l
T =-c
q
"
99
Therefore ,
tiT=
-piV tiHvap
RTC
p
-23.8 Torr x 50.0 L x 44.0 x 103 J mol - 1

62.364 L Torr K -I mol- 1 x 298.15 K x 75.5 J K -I mol - 1 X
250g
g mol - l
18 02
.
= -2.7 K
The final temperature will be about 22 oc

d lnp
6.6
d"T=
tiHvap
RT 2 [Sa],
tiHvap
In p =constant- RT
Therefore, plot lnp against liT and identify -tiHva/R as its slope. Construct
the following table:
ere
20
40
50
70
80
90
100
TIK
273
293
313
323
343
353
363
373
1000 KIT
3.66
3.41
3.19
3.10
2.92
2.83
2.75
2.68
In p/Torr
2.67
3.87
4.89
5.34
6.15
6.51
6.84
7.16
The points are plotted in Fig. 6.2. The slope is -4546, so

75
...
Fig 6.2
......
.......
......,
~
""
2 5
~6
'r-...
.......
~8
30
32
(103/ TiK
3~
3~
3~
100
- !"J.Hvap
R
_
-1
- 4546 , or !"J.Hvap - +37 .8 kJ mol
the normal boiling point is reached at p = 760 Torr, which occurs at

1000 KIT = 2.80, so Tb = 357 K (84 C).
[Alternatively, do a least-squares fit of In p to 11 Tusing the procedure
outlined in the Appendix.]
6. 7 Adapt the procedure in Problem 6.6, but note that Tb = 227 .5 oc is
obvious from the raw data. Draw up the following table:
ere
57.4
100.4
133.0
157.3
203 .5
227.5
TIK
330.6
373.6
406.2
430.5
476.7
500.7
1000 KIT
3.02
2.68
2.46
2.32
2.10
2.00
lnpiTorr
0.00
2.30
3.69
4.61
5.99
6.63
The points are plotted in Fig. 6.3. The slope is -6.6 x 103 , so
- 6.6 X 103 K, implying that !"J.Hvap= +55 kJ mol- 1
Fig 6.3
6 1'..
..........
'
~
~
.........
0
20
6.8
!'-..
22
24
26
(1rftTJK
(a) Solid-liquid boundary:
!"J.Hrus
T
p=p * + !"J.V In T * (6a)
fus
(b) liquid- vapor boundary:
28
30
- !"J.Hvap
(c) solid-vapor boundary
We need !).Hsuh= !).Hrus + !).Hvap=41.4 kJ mol - 1

1
1 )
!).Vrus=M ( p(l)- p(s)
78.11 g mol gcm- 3
1
(
1
1 )
0.879-0.891
=+1.197cm 3 mol- 1
10.6xl03 Jmol - 1
T
(a) p=p*+l.197xl0- 6 m3 mol _ 1 lnT*
= p* + 8.855 x 109 PaIn T *

T
= p* + 6.64 x 107 Torr In T* [1 Torr= 133.322 Pa]

This line is plotted as a in Fig. 6.4, starting at (p * , T * ) = (36 Torr, 5.50 oc
[278.65 K]).
100
Fig 6.4
a
80
SA
/_..;A
_.d Vb
.s 40
20
~ .-<
-10
.--: ~ F"""
-s
--
p~ *)
10
15
101
102

1
= 30.8 x 10 J mol (b) C 8.314JK- 1 mol - 1
X(!_ __!_)
T
T*
- (1 1)
=3705 Kx - - T T*
The points are plotted as line bin Fig. 6.4, starting from (p *, T * ) = (36 Torr,
5.50 oc (278.65 K]).
1
41.4x10 Jmol (1
1)
_
(1
1)
(c) C=8.314JK - 1 mol _1 x T-T * = 498 K x T-T *
These points are plotted as line c in Fig. 6.4, starting at (36Torr, 5.50C).
6.9 For a droplet of radius a, the surface area is 4.na 2 and the volume is f .na 3 .
The area occupied by a molecule of radius r is .nr 2 and the volume it occupies
is f .nr 3 . The total number on the surface is therefore 4.na 2/.nr 2 =4a 2 /r 2 , and
the total number in the droplet is f.na 3/f .nr 3 = a 3/r 3 . Hence
4a 2/r 2 4r
a 3/r 3 a
Number on surface
Number in droplet
4 x 120pm
4.8xl0- 10 m
(a) a= 10- 5 mm , ratio
4.8 X 10- IOm

_ m = 5 X 10- 2 (1 in 20)
10 8
(b) a= 10- 2 mm , ratio =
4.8 x l0 - 10 m
_ m = 5 X 10- 5 (1 in 20 000)
10 5
(c) a= 1 mm, ratio

6.10
~A=
4.8 X 10- IOm

_ m = 5 X 10- 7 (1 in 2 million)
10 3
y ~a (11]
m
Initial volume =- with m= 100 g and p = 0.88 g cm- 3 . The volume of theN
p
droplets is N x f .nr 3 , so
m
3m
N x f .nr 3 =- , implying that N = 4.npr 3

p
103
3m
Surface area of droplets= N x 4nr 2 = pr
Surface area of initial sample is negligible. Therefore tw =3m/ pr, so
3my
~A=-
pr
3 X 100 g X 2.8 X 10- 2 N m - 1

0.88x10 6 gm- 3 xl.Ox10- 6 m
9 51
The minimum work required to achieve dispersal is w =~A, or 9.5 J.

6.11
h=~[15]
pgr
2 X 2.189 X 10- 2 N m- 1
0.780 X 10 3 kg m- 3 X 9.81 m s- 2 X 0.10 X 10- 3 m
= 5.i2 X 10- 2 m= 5.7 em
2y
Pressure = - [12]
r
2x2.189xl0- 2 Nm- 1
0.10x10
0.44 kPa (3.3 Torr)
6.12 The surface is curved only in the radial direction, the circumferential
direction being essentially flat (Fig. 6.5). Hence the pressure difference is y/r
in place of 2y!r, where 2r is the width of the separation of rod and tube.
104
Hence
y
h = - , r=5.0 x 10
pgr
-3
cm
0.998 X 103 kg m - 3 X 9.81 m S - 2 X 5.0 X 10 - 5 m

= 0.15m = 15cm
Therefore, if V11 = Va ,
~A
is independent of pressure.
6.14 dH = CP dT+ V dp , implying that d ~H= ~CP dT+ ~V dp
However, along a phase boundary dp and dT are related by

~H
dp
dT = T~V[S]
Therefore ,
Then, since
~ (~H)
dT
2_ d~H _ ~H = 2_ (d~H _ ~H)

T dT
T2
dT
substituting the first result gives

d (~~
- = -~cp
dT
Therefore, d
(T}
~!!\
~cp dT
=-T-= ~CP d
In T
PV
m
6.15 Amount of gas = RT' amount of vapor= M
105
m/M
Mole fraction of vapor = m/ M + PVI RT

Partial pressure of vapor= p =
m!M
m 1M+PVIRT
xP
P(mRTIPVM)
(mRTI PVM) + 1
mPA
RT
= rnA+ 1' A= PVM
For geraniol, M = 154.2 g mol - 1, T = 383 K, V= 5.00 L, P= 1.00 atm, and m =

0.32 g, so
8.206 X 10- 2 L atm K -I mol - l X 383 K
A=
1.00 atm X 5.00 LX 154.2 X 10- 3 kg mol- 1
40.76 kg - 1
Therefore,
0.32 g X 760 Torr X 40.76 kg- 1
9.8 Torr
p=
0.32gx40.76kg 1 +1
6.16
P = P0 e-MghtRT [Problem 1.17]
C = fl.Hvap
R
p = p*e- c
(~ _ _
1 )
T
T*
[8b]
let T* = Tb, the normal boiling point; then p* = 1 atm. Let T= T,, the boiling
point at the altitude h. Take P0 = 1 atm . The vapor pressure (p) is equal to the
ambient pressure when p(T) = P(h), and when this is so, T = T,. Therefore,
since P0 = p * , p(T) = P(h) implies that
e-MghtRT=exp
vap ( __
1 _1 ) }
_fl.H
__
R
T, Tb
It follows that
1
1
Mgh
-=- +--T,
Tb
T tl.Hvap
where T is the ambient temperature and M the molar mass of the air.
For water at 3000 m, using M = 29 g mol-:
106
1
1
29x10- 3 kgmol- 1 X9.81ms- 2 x 3.000x103 m
Th = 373K+
293Kx40.7x103 Jmol 1
1
=
373 K + 1.397 X 104 K
6.17 (a) From trigonometry and Fig. 6.6,

Fig 6.6
/
I
I
'
'\
I
I
r
r
-R = sin(90o- e) = cos e, implying that R = - cos 8
Use this R in the Laplace equation for the pressure (2y/ R), and by repetition
of the argument in the text [Section 6.8], arrive at
h =-
2y
pgR
2y cos
pgr
=- --
(b) The force upward on the liquid is 2nry cos e (since y is the force per unit
length, 'her is the circumference of the liquid-tube contact, and cos e the
component of force vertically). The force downward is nr 2h x pg (since nr 2h is
the volume of the liquid in the capillary and pis its density). Hence, when the
two forces are in equilibrium,
2nry cos e = nr 2hpg
which solves to
2ycos e
pgr
h= - --
107
as before.
<t = -SdT+yda + Vdp
= V dp + y do if Tis constant.
Therefore, since d,u is an exact differential ,
6.18
(~)p.T (~)
=
a, T
For a spherical droplet, V = j-nr 3 and a = 4nr 2 . Hence,

dV = dV X dr =
do dr do
(d~ / (da) = 4nr

dr }
dr
8n
=tr
Therefore,
( :y) = t r, implying that dy = tr dp
'P a, T
which integrates to
I (
.
Iymg
. t hat 'Pin - Pout=2y
y = zr
Pin- Pout ) , Imp
r
6.19 dt(mu) = F [Newton's second Jaw). Both m and F depend on the time,
and we can write

m = volume x density= (nr 2o) x p
F = 2 x circumference x surface tension= 4nry
Hence,
d
d 2
4ry
2
dt (nr opu) = 4nry, or dt (r u) = po
If we neglect acceleration ,
d
dr
4ry
-(r 2u)=2ru - = 2ru 2 = dt
dt
po
Therefore, u = (
2y)I/2
bP
When y=2 .6x 10- 2 N m- 1 , estimating a = 0.01 mm, and p = 1 g cm - 3

2 x 2.6 x 10- 2Nm - 1
)112
u=
=2ms - 1
3
3
3
( 0.01 X 10- m X 1 X 10 kg m--
7. Changes of state: physical

transformations of simple mixtures
Exercises
7.1 Let A denotes acetone and C chloroform. Then
(a)
nAMA+ncMc=m
where m is the mass of the sample . We also know that
and hence that

(b)
On solving (a) and (b), we find
Since xc = 0.4693, xA = 1- Xc = 0.5307,

0.4693 X 1000 g
nc= (0.5307 X 58.08 + 0.4693 x 119.37) g mol- 1 = 5 .44 mol
0.5307
nA = 0.4
x 5.404 = 6.111 mol
693
The total volume, V = nA VA+ n 8V 6 , is therefore
V=6.111 mol x74.166 cm 3 mol- 1 +5.404 x 80.235 cm 3 mol- 1
= 886.8 cm 3
7.2 Check whether p 8 /x 8 is equal to a constant (K 8 ):
X
0.005
p/x
6 X 103
0.012
6.4
X 103
Hence, K 6 = 6.4 x 103 kPa
0.019
6.4 X 103 kPa
Changes of state: physical transformations of simple mixtures
109
7.3 m(GeC1 4 ) = 1000 g, corresponding to

n(GeCI4) =
1000 g
_ g mol _1 = 4.664 mol , n(HCI) = 0.10 mol
214 39
0.10 mol
Therefore , x = 0.10 mol+ 4 _664 mol
0.0210
and from K = 6.4 kPa (Exercise 7 .2) ,

p = 0.0210 X 6.4 kPa =
134 Pa
p = p A +ps= xA p ~ + x 8 p ~ = xA p ~ +(1-xA )P~
7.4
[20b], hence
p - p~
XA
P *A- PB*
For boiling under 0.50 atm (380 Torr) pressure , the combined vapor pressure
must be 380 Torr , hence
XA
380 - 150
_
400 150
0.920, X 8 = 0.080
The composition of the vapor is given by [21b]:
y =
A
XA P ~
p~ + (p ~ - p~)XA
0.920 X 400
= 0 968
150+ (400-150) X 0.920 - -
and y 8 = 1-0.968 = 0.032
8.314 J K - l mol - 1 x (349. 9 K) 2 x 153.81 g mol - 1

30.0 x 10 3 Jmol - 1
= 5.22 K/(mol kg - 1)
RT * 2M
Kr = - --
!'l.Hrus
8.314 J K - l mol - 1 x (250.3 K) 2 x 153.81 x 10 - 3 kg mol - 1

2.47 x 10 3 J mol - 1
= 32 K/(mol kg - 1)
110
7.6 Let B denote the benzene and A the solute, then

ns
Ps = x 8 p~ and x 8 = - - nA +ns
nsp~
Hence p 8 = - - nA +ns
which solves to
Then, since nA = mAl MA, where rnA is the mass of A present,

MA=
mApB
mAMBpB
ms(P s- Ps)
ms(P~- Ps)
From the data,
19.0 g x 78.11 g mol- 1 x 386 Torr

500 g X ( 400- 386) Torr
=82 g mol- 1
7.7
-11Hrus (1
lnx 8 = - Ry.- T*1) [17]
Therefore, with x 8 =0.905, T * =278.65 K, and 11Hrus= +10.59 kJ mol - 1,

1
8.3141 K- 1 mol - 1
T= 278.65 K - 10.59 X 103 1 mol - 1 x In
1
905
=272.70K (-0.45aC)
7.8
11T= Krms [16b]

.
m 8 [molahty of B]
11 T =
100 g
0.1333
g =~
750
Mx
0.1333 Kr
0.1333 Kr
M
, implying that M =
l1 T
Then, since Kr= 30 K/(mol kg - 1) = 30 K kg mol- 1 [Table 8.2],

M=
=
0.1333 x 30 K kg mol- 1
_ K
0.381kgmol- 1
10 5
381 g mol- 1
7.9 llV = naRT (19a] with

103 kg m- 3
na1 V~map 6
for dilute solutions, with p 6 =
!l.T = Krma (16b]~Kr x RTpe
Therefore, with Kr = 1.86 K/(mol kg- 1) = 1.86 K kg mol- 1 [Table 8.2]

1.86 K kg mol- 1 x 120 x 103 Pa
Therefore, the solution will freeze at about - 0.09 oc
7.10 PA =YAP = 0.350p = xApj._ =xA x 575 Torr
Pa = YaP = (1 - YA)p = 0.650p = xap~ = (1-xA)

Therefore,
YaP
XaP~
Hence
0.350
575xA
0.650
390(1 - xA)
which solves to
XA = 0.268, Xa = 1- XA = 0.732
and
0.350p = xApj._
.
.
1mphes p
xApj._
= 0 _350 =
0.268 x 575 Torr

_
0 350
440 Torr
390Torr
111
112
7.11
LlGm;x=nRT{xAinxA+x 8 1nx8 } [7]
xA=x 8 =0.5, n=pVIRT

Therefore ,
LlGmix =pVX H In t + t In t }= -pVIn 2
= -1.0 X 1.013 X 10 5 PaX 5.0 X w-) m3 X In 2
= - 3.5 X 10 2 1 = -0.35 k1
-0.35 k1
298K
+1.21 K - 1
Therefore, for molar amounts,

LlSmix = - R
2:
X1
In X 1
= -R(0.7821n 0.782+0.2091n 0.209

+ 0.009 In 0.009 + 0.0003 In 0.0003)
=0.564R= +4.7 1 K - 1 mol- 1
7.13
LlGmix = nRT
2: x In
1
X1
[7]
g
_ 500
g mol
5.802 mol
1
86 17
g
_
500
n(Hep) = - - -_- -g-m-- _-..,1 4.990 mol
100 20
01
n(Hex) =
Hence x(Hex) =
5.802mol
_ mol= 0.538
10 792
j
n = 10.792 mol
113
4.990 mol
x(Hep) = 10.792 mol= 0.4 62
Therefore ,
~Gmix = 10.792 mol X 8.314 J K - I mol - 1 X 298.15 K
x (0.538 In 0.538 + 0.462ln 0.462)

= -18.5 kJ
+ 18.46 kJ
~Sm;, = 298.15K =+61.9JK - I
7.14 The greatest enthalpy of mixing occurs for xA = x 11 = i [Examp le 7.4] .
Therefore, mix equal mole fractions , or masses in the ratio
86.17 g mol - 1
0 8600
100.20 g mol - 1 =
m(Hex) M(Hex)
m(Hep)- M(Hep)
7.15
x=
p=xK[l2],K=l.25 x lO" Torr

n(C0 2)
n(C0 1 ) + n(H 20)
""'
n(C0 1 )
n(H 20)
Therefore,
Hence
10 3 g
p
n(CO,) ""'
x - - - - -6, - 1
- 18.02gmol 1.26 x l0 Torr
""' 4.4 X 10 - 5 mol
(p/Torr)
(a) p=0.10atm=76Torr ,
hence n(C0 2) = 4.4 X 10 - 5 mol
3.4 mmol kg- 1 in C0 2
76 = 3.4 X 10 - 3 mol. The solution is therefore
(b) p= l.Oatm; since n rx p, the solution is 34mmol kg - 1 in C0 2

7.16 K(N 2 )=6.51 x 107 Torr and K(0 2)=3.30 x 10 7 Torr. Therefore, as in
Exercise 7. 15 , the amount of dissolved gas in 1 kg of water is
114
103 g
n(N 2) -18.02 g mol
p(Nz)
6.51 x 107 Torr
8.52 X 10- 7 mol X (p/Torr)
For p(N 2) = xp and p = 760 Torr

n(N 2) = 8.52 X 10- 7 mol X X X 760 = 6.48x X 10- 4 mol
and with x=0 .782,
n(N 2 ) =0.782 X 6.48 X 10- 4 mo1=5 .1 X 10- 4 mol
=0.51 mmol
The molality of the solution is therefore approximately 5.1 x 10- 4 mol kg - 1
Similarly, for oxygen,
103 g
p(02)
n(O,) =
X
- 18.02 g mol- 1 3.30 x 107 Torr
1.68 X 10- 6 mol X (p/Torr)
For p(0 2) = xp and p = 760 Torr

n(0 2 ) = 1.68 X 10- 6 mol X X X 760 = 1.28 mmol X X
and when x = 0.209, n(0 2)
0.27 mmol kg- 1 in 0 2
= 0.27 mmol.
Hence the solution will be
7.17 Use the result established in Example 7.14 that the amount of C0 2 in
1 kg of water is given by
n(C0 2) = 4.4 X 10- 5 mol X (p/Torr)

and substitute p = 5.0 x 760 Torr= 3.8 x 103 Torr , to give
n(C0 2) =4.4 x 10- 5 mol x 3. 8 x 103 =0.17 mol
Hence , the molality of the solution is about 0.17 mol kg- 1 and the molar
concentration about 0.17 M .
7.18
~T=K1m 8 =1.86Kkgmol - x
7.5g
342 . 3 gmol _ 1
0.25kg
=0.16 K
Hence , the freezing point will be approximately -0.16 oc
7.19
~Hrus (
lnx 8 =~
1 1)
T * -T [17; B , the solute , is anthracene]

3
28.8 x l0 Jmol (
1
1
)
= 8.314 J K 1 mol 1 x 490.15 K- 298.15 K
= - 4.55
Therefore, x 8 = e- 4 55 = 0.0106
Since x 8 ~ 1, x( anthracene)
n( anthracene)
(b
)
n enzene
Therefore , in 1 kg of benzene,
n( anthr.) = x( anthr.) x
lOOOg
78 .11 gmo 1
=0.0106 x 12.80 mol =0.136 mol

The molality of the solution is therefore 0.136 mol kg- 1 Since M =
178 g mol - 1, 0.136 mol corresponds to 24 g anthracene in 1 kg of benzene .
7.20
!:l.Hrus(T1* -y.1) [17; B, the solute, is lead]
ln x 8 = ~
5.2 x 10 Jmol (
1
1 )
8.314JK - 1 mol 1 x 600K - 553K
= - 0.0886, implying that x 8 = 0.92
n(Pb)
x 8 n(Bi)
x 8 = n(Pb) + n(Bi), 1mplymg that n(Pb) = 1 _X a
.
.
For 1 kg of b1smuth , n(B1) =
1000 g
_ g mol
208 98
= 4.785 mol
Hence , the amount of lead that dissolves in 1 kg of bismuth is

n(Pb)=
0.92 x 4.785 mol

_ _
= 55 mol , or 11 kg
1 0 92
n = pgh [hydrostatic pressure], so

h=
(!!.._)c
pgM
115
116
Hence, plot h against c and identify the slope as RT!pgM. Fig. 7.1 shows the
plot of the data. The slope of the line is 0.29, so
30
..)
,/
Fig 7.1
./
1-0
/'
./
12
RT
pgM
0.29 em
gL I
-,----,,...-=
Therefore, M =
0.29 em L g-l = 0.29 X

RT
pgx 0 .29 x 10
_2
w-
m4 kg-l
k _
m4 g 1
8.3141 K - I mol- 1 X 298.15 K

10 3 kg m - 3 X 9.81 m S- 2 X 0.29 X 10- 2 m4 kg - 1
1.004 X
= 87 kg mol- 1
7.22 Proceed as in Exercise 7.21. The data are plotted in Fig. 7.2, and the
slope of the line is 1. 78. Therefore
12
I..3
v
4
,/
IY
5
-3
C/mg em
Fig 7.2
117
8.314J K- 1 mol - 1 x293.15 K

10 kg m X 9.81 m S- X 1.78 X 10- m kg-
M=~~--~--~------~--------~~~
3
3
2
2 4
1
1.000 X
14 kg mol - 1
7.23 The data are plotted in Fig. 7.3. From the graph, the vapor in
equilibrium with a liquid of composition (a) xT= 0.25 has YT = 0.36, (b) x 0 =
0.25 has YT= 0.82
126
122
Fig 7.3
'-l'-.
1\. \,
- :...
""'(
118
~~
['- ~
114
.......
b
100
0
02
04
(}6
08
....
1{)
mole fraction of toluene
Problems
7.1 PA =YAP and p 8 = y 8 p [Dalton's law]. Hence, draw up the following
table:
pA/kPa 0 1.399
XA
YA
XB
5.044
6.996
7.940
9.211
0 0.0898 0 .2476 0.3577 0.5194 0.6036 0.7188

0 0.0410 0.1154 0.1762 0.2772 0.3393 0.4450
p 8 /kPa 0 4.209
Ya
3.566
8.487
0 0 .0895 0.1981
0 0.2716 0.4565
11.487
0.2812
0.5550
15.462
0.3964
0.6607
18.243
0.4806
0.7228
23 .582
0.6423
0.8238
10.105
0.8019
0.5435
27.334
0 .7524
0.8846
11.287
12.295
0.9105
0.7284
32.722
0 .9102
0 .9590
The data are plotted in Fig . 7.4. The Henry's law constants are given by
36.066
118

36
"" '""'
24
Rg 7.4
.....
r--...
0....
12
~ f.--
....
rw
0.2
~..-
~
...- ~
0.6
0.4
.-"
""
0.8
1.0 XA
KA =PA
= 15 .58 kPa from the point at xA = 0.0898
XA
K8 = Ps = 47 .03 kPa from the point at x 8 = 0.0895
Xs
7.2
VA =(::) n = (!:) n(HzO) molA
1
with m=m/(mol kg- )
= (16.62 + ~ x 1.77 x m 112+ 2 x 0.12m) cm3 mol- 1

= 17.5 cm 3 mol- 1 when m = 0.100
For a solution consisting of 0.100 mol NaCl and 1.00 kg of water,
corresponding to 55.49 mol H 20, the total volume is given both by
V = 1003 + 16.62 X 0.100 X 1. 77 X (0.100) 312 + 0.12 X (0.100) 2 cm 3
= 1004.7 cm 3
and by
V=n(NaCl)VNaCI + n(H20)VHzO
= 0.100 mol x 17.5 cm 3 mol - 1+ 55.49 mol x VH2o
Therefore,
1004.7 cm 3 -1.75 cm 3
V Hzo =
.4 mol
55 9
7.3
Vsalt=
(::t
18.1 cm mol -
mol- 1 [Problem 7.2]

20
119
69.38(m - 0.07) cm 3 mol- 1 with m==m/(mol kg- 1)
Therefore , at m = 0.050 mol kg- 1, V,. 11 = - 1.4 cm 3 mol - 1

The total volume at this molality is
V = 1000.21 + 34.69 x (0.02? cm 3 = 1001.20 cm 3

Hence, as in Problem 7 .2,
1001.20 cm 3 - 0.050 mol X ( -1.4 cm 3 mol- 1)
V(HzO) =
55.49 mol
=
18.04 cm 3 mol - 1
7.4 Rework the derivation in the Further Information section of Chapter 7

with
100m 8
The procedure runs as follows:
VA =(::) =(::J MA
ns
Therefore,
MA
a 1
- wM - P
Aaw P
V =A
and hence
~ = VA+w~(~)
p
MA
dw
Therefore, plot 11 p against w and extrapolate the tangent to w = 0 to obtain

VA / MA. For the actual procedure, draw up the following table:
120
2.162
pl(g cm- 3)
ll(p!g cm- 3)
1.01
0.990
62.64
p!(g cm- 3)
ll(p!g cm- 3)
10.98
20.80
1.06
0.943
1.12
0.893
71.57
1.38
0.725
82.33
1.42
0.704
1.46
0.685
30.00
39.2
1.18
0.847
51.68
1.24
0.806
93.40
1.32
0.758
99.60
1.49
0.671
1.51
0.662
The graph of 11 p against w is shown in Fig. 7.5. Tangents have been drawn at
(a)
(b)
Fig 7.5
f':
09
"~ ~
f'
r-.....
r---...: ~
F:::::: t--... ~
~ ~L..
/
)
""-...
06
""'
0-2
o4
j...-,
II
~~ ~
04
/v
06
w(HN0 )
3
08
';:::
1-o
02
06
w(HN0 )
3
04
08
10
four values of w, and V AI MA (with A denoting H 2 0) read off from the

intercepts at w = 0 and V 8 / M 8 (with B denoting HN0 3) from the intercepts at
w = 100. We can then draw up the following table using M A= 18.02 g mol- 1
and M 8 = 63.02 g mol- 1:
w
20
40
60
80
(VA/MA)gcm 3
CVsiMs)gcm 3
VA/(cm 3 mol- 1)
V8 /(cm 3 mol- 1)
0.975
0.535
17.6
33.7
0.965
0.565
17.4
35.6
0.900
0.620
16.2
39.1
0.825
0.655
14.9
41.3
121
The partial molar volume of HN0 3 (the value of V8 ) is plotted in Fig. 7.5b.
7.5 Use the same procedure as in Problem 7.4 , and begin by drawing up the
following table:
10
p!(g cm - 3)
1/(p/g cm- 3)
1.051
0.951
15
1.107
0.903
20
1.167
0.857
1.230
0.813
The values of 11 p are plotted against w in Fig. 7 .6. The intercept at w = 100 is
10
....
Fig 7.6
""""'
"'
""""'!'\..
"'
0
20
40
60
80
100
W/%
the value of V(CuS0 4 )/M(CuS0 4 ); within the precision of the plot, all four
intercepts are coincident at 0.075, and so
V(CuS0 4) = 0.075 g- 1 cm 3 x 159.6 g mol- 1 = 12.0 cm 3 mol- 1
7.6
Let E denote ethanol and W denote water; then
V = nEVE+nwVw
For a 50 per cent mixture by mass, mE = mw, implying that
nEME
nEME =nwMw, or nw= Mw
Hence,
122
V = nEVE+
nEMEVw
Mw
which solves to
v
nE =
MEVw
VE+ Mw
Furthermore,
nE
1
xE = - -- = - - nE+nw
ME
1+ Mw
Since ME= 46 .07 g mol- 1 and Mw= 18.02 g mol- 1, ME/Mw= 2.557. Therefore
XE = 0.2811, Xw = 1-XE = 0.7189.
At this composition
VE = 56.0 cm 3 mol- 1
Vw= 17.5 cm 3 mol- 1 [Fig. 7.1 of the text]
Therefore,
nE = 56.0cm 3 mol
+2.557 x 17.5cm3 mol
= 0 993 mol
nw = 2.557 X 0. 993 mol= 2.54 mol
These two amounts correspond to 45.7 g ethanol and 45 .7 g water. In terms of

volumes of the pure liquids , mix 57.6 cm 3 of ethanol and 45. 7 cm 3 of water.
The change in volume on add.ing a virtually infinitesimal amount of ethanol
is
1.00 cm3 x 0.789 g cm - 3
3
1
~V= VE ~nE= 56.0 cm mol- x
. g mol_ 1
46 07
= 0.96cm 3
7.7 Proceed as explained in the Further Information section. Plot Vm against
xc , extrapolate the tangents , and obtain Vc from the intercept at xc = 1 and
VA from the intercept at xc = O. The volumes are plotted in Fig. 7.7a and the
intercepts are as follows:
Xc
VA/(cm 3 mol - 1)
V8 / (cm 3 mol - 1)
0.0
0.2
0.4
0.6
0.8
1.0
73.99
80.85
74.03
80.53
74.11
80.31
73.96
80.37
73 .50
80.60
72.74
80.66

Fig 7.7
(b)
A
(a)
74
82
80
72
'\.
1\.
1\
\
XI 1015
,....... V"
OfJ
c\
./
123
~""
72
02
04
1\
xrcl6
08
10
\
02
'\
Ot.
\ ....._v
04
x(C)
06
0-8
1{)
These points are plotted in Fig. 7.7b .

7.8 We find a seq uence of changes that achieve the overall change specified in
the questions , viz:
(1) Expansion of nitrogen to the same pressure as the hydrogen .
(2) Mixing.
(3) Compression of mixture to the original volume.
1.0 atm
(I) G(N 2 , 1.0 atm) = G(N 1, 3.0 atm) + n(N1)RTln _ at m
30
(2) 6.G 111 ;x = nRT{x(N 1 ) In x( N 2 )
= nRT{i In
+ x(H 2) In x(H 2)}
i + { In ~-}= -0.562nRT
(3) Sincepr=2.0atm ,
G(mixture, 2.0 atm) = G(mixture, 1.0 atm) + nRT In 2
The overal l change is therefore
6.G = n(N 1 )RT In
i-- 0.562nRT + nRT In 2
The amounts are obtained from the perfect gas law:
124
Therefore,
ft..G = Pi(N 2 ) Vi In
t - 0.562p V + p V In 2
= -pi(N 2)Vi In 3 +(In 2- 0.562)pV

= -3 .0 X 1.013 X 105 PaX 2.5 X 10- 3 m3 X In 3
+(In 2- 0.562) X 2.0 X 1.013 X 105 Pa X 5.0 X 10- 3 m3
= -835 1 + 1331 = -0.70 k1
7.9 f't..T=Krm 8 withKr=40K/(molkg- 1)
M(CF3(CF2) 3CF3) = 288.05 g mol- 1, M(CFJ(CF2) 4CF3) = 338.06 g mol - 1
The amounts corresponding to 1.00 g are therefore
n(CFJ(CF2) 3CF3) = 3.472 mmol, n(CFJ(CF2) 4CF3) = 2.958 mmol
The molalities of the solutions formed by dissolving these amounts in 100.0 g
of solvent (camphor) are therefore
m(CF3(CF2) 3CF3) = 34.72 mmol kg- 1, m(CF3(CF 2) 4CF3) = 29.58 mmol kg - 1
The resulting freezing point depressions are therefore
ft.. T= 34.72 mmol kg- 1 x 40 K/(mol kg - 1) = 1.4 K
f't..T = 29.58 mmol kg- 1 x 40 K/(mol kg - 1) = 1.2 K
The temperature measurement must therefore be able to distinguish between

these two depressions, which suggests a precision of no less than +0.05 K
Rrfx 8
7.10
nB
f't..T= f't..Hrus [16a],xs=n(CH3COOH)
n 8 MRTf
Hence ft.. T= U.AHfus X 1000 g
=m 8
m 8 MRTf
AH
U.
fus
nsM(CH3COOfi)
1000g
[m 8 : molality of solution]
60.05 g mol - 1 X 8.3141 K -l mol - 1 x (290 K) 2

11.4 x 103 1 mol - 1
= 3.68 K X m 8 /(mol kg - 1)
where m 8 is the apparent molality , which we write vm~ where v is the number
of ions per formula unit. We can draw up the following table from the data.
ft.. TIK
ml(mol kg- 1)
v=mlmo
0.015
0.037
0.077
0.295
0.602
0.115
0.0312
2.1
0.295
0.0802
2.2
0.470
0.128
1.7
1.381
0.375
1.3
2.67
0.726
1.2
125
See the original reference for further information about the interpretation of
the data.
1"1 T
7.11
0.0703 K
ms=K;= 1. 86 K/(mol kg - 1) =0.0378 mol kg -
Since the solution molality is nominally 0.0096 mol kg- 1 in Th(N0 3 ) 4 , each
formula unit supplies 0.0378/0.0096 = 4 ions. (More careful data , as described
in the original reference gives v = 5 to 6.)
7.12 On a Raoult's law b"asis, a=plp*, a=yx, and y=plxp*. On a Henry's
law basis, a= pi K, andy= plxK. Therefore, plot the data and extrapolate the
low concentration data to determine K. The data are plotted in Fig. 7.8 ,
50']
A""
0
" "'
~300
a.
~'
200
100
K Fig 7.8
I
~v
"
/ ~
~ ~ K:
t/
I"-
~ ~~
"~
02
'
-......::
ol/
0
p""
I
....v
06
04
08
~
10
x(I}
which gives K1= 465 Torr. Then draw up the following table:
X1
p/Torr
pA/Torr
Y1(R)
YA(R)
Y1(H)
0
280t
1.000
1.000
0.2
92
230
1.303
1.027
0.929
0.4
0.6
0.8
165
185
1.169
1.101
0.887
230
135
1.086
1.205
0.824
290
80
1.027
1.429
0.780
t The value of p'A; :j: the value of pj.
1.0
353 ~
0
1.000 [p/x1pt]
[p AfXAp';._]
0.759 [p/x 1KJ]
126
7.13 The data are plotted in Fig. 7.9. The regions where the vapor pressure
curves showed approximate straight lines are denoted R for Raoult and H for
Henry . A and B denote acetic acid and benzene respectively. As in Problem
300
[\ rfrciJ ola'e
'
'-'\
R'\
200
~"
\h ~;
~
Rae
100
1\..
/ ~
-=
02
I'. \ . / v
""
v
v .....
-'-l~n ty
H r--,..
Fig 7.9
lA
,......
1--'
\ ..\
"'\ ~
A~
nv< run
RH
06
08
04
"'\
10
7.12, we need to form YA = pAixAp";. and y8 =p 8 1x 8 p; for the Raoult's law

activity coefficients and y 8 = p 8 /x 8 K for the activity coefficient of benzene on a
Henry's law basis, with K determined by extrapolation. We use p ~ =55 Torr,
pt = 264 Torr, and K 8 = 600 Torr to draw up the following table:
XA
pAITorr
p 8 1Torr
aA(R)
a 8 (R)
YA(R)
Ys(R)
a 8 (H)
Ys(H)
0.2
0.4
0.6
0.8
0
264
0
1.00
20
228
0.36
0.86
1.82
1.08
0.38
0.48
30
190
0.55
0.72
1.36
1.20
0.32
0.53
38
150
0.69
0.57
1.15
1.42
0.25
0.63
50
93
0.91
0.35
1.14
1.76
0.16
0.78
1.00
0.44
0.44
1.0
55
0
l.QQ
[p Aip ";. ]
[Psi Pal
l.QO [pAIXA p~]
[pslxsp;]
0
[psi Ks]
1.00 [p 8 1xsKs]
Since G E = RT(xA In YA + x 8 In y 8 ) [as in eqn 14] we can draw up the following

table from the information above and RT=2.48 kJ mol - 1:
xA In YA
Xs In Ys
GE/(kJ mol- 1)
7.14
0.2
0.4
0.6
0.8
1.0
0
0
0
0.12
0.06
0.45
0.12
0.08
0.14
0.55
0.10
0.11
0
0
0
0.11
0.57
0.52
GE = RTx(1- x){0.4857- 0.1077(2x -1) + 0.0191(2x -1) 2}
with x=0.25 gives GE=0.1021RT. Therefore,

!:J.Gmix= nRT(xA In xA +x 8 In x 8 ) + nGE
= nRT(0 .25 In 0.25 + 0.75 In 0.75) + nGE
=
-0.562nRT + 0.1021nRT= - 0.460nRT
Since n = 4 mol and RT= 8.314 J K- 1 mol - 1 x 303 .15 K =2 .52 kJ mol - 1 ,
!:J.Gmix = - 0.460 X 4 mol
2.52 kJ mol- 1 = -4.6 kJ
(!~) = fA.~+ (a:
7.15 fA.A =
"B
[fA.~ from ideal value]
(nG E))
A
"D
anGE) = GE + n (acE)
( anA
an A "B
liB
= gRTxA(1- xA) + (1- xA)gRT(l- 2xA)

=gRT(l-xS = gRTx~
Therefore, fA.A =fA.i>+ RTin xA + gRTx~

7.16 xAdfA.A+x 6 dfA. 8 =0[6]
Therefore,
amA)
xA ( -a
XA
and so
p. T
127
+x 6 (ams)
=0 [divide through by dxA]
ax A p. T
128
which implies that

amA
-)
( a In XA
ama
= (-)
p. T
aIn X a
Then, since 11 = 11 6
[dlnx=dxlx]
p. T
+ RTinf/p 6 ,
(a lnf~)
a InfA)
( ~ p.T= ~ p.T
On replacingfby p,
(a Inps)
a InpA)
( a In XA p . T = a In Xs p. T
If A satisfies Raoult's law, we can write PA =xAp~, which implies that

alnpA) = ainxA+ ainp~=l+Q
( ainXA p.T alnXA ainXA
Therefore,
a lnps)
_
( a In Xs p. T 1
which is satisfied if p 8 = x 6 p8 [by integration]. Hence, if A satisfies Raoult's
law, then so does B.
7.17
nA dVA +n 8 dV 6 =0 (6)
Hence
Therefore,
Vs(xA, Xs) = Vs(O, 1) +
VA(x")xAdVA
VA(O}
XA
We should now plot xA/(1 - xA) against VA and estimate the integral. For the
present purpose we integrate up to VA(0.5,0.5)=74.06cm 3 mol - 1 [Fig. 7.7],
and use the data in Problem 7. 7 to construct the following table:
74.11
73 .96
73.50
0.60
1.50
0.40
0.67
0.20
0.25
129
72.74
0
0
The points are plotted in Fig. 7.10 , and the area required is 0.30. Hence ,
Frg 7.10
15
10
I
!::.
"" OS
~0
~~~
72
73
74
75
V. /cm3mor 1
Am
V(CHCI 3 ; 0.5 , 0.5) = 80.66 cm 3 mol - 1 - 0.30 cm 3 mol - 1

= 80.36 em ' mol -
7.18
-~Crus
lnxA =~
[Section 7.5]
(I 1)
~Hrus
lnx =--- --A
T*
The approximations In x A= - x 8 and T = T * then lead to eqns 15 and 16 , as in

the text.
130
7.19
In aA
=- r
(a)
1
1
Therefore , d = - - d In aA+ ---zln aAdr
r
r
1
d In aA= -In aAdr - r d
r
(b)
From the Gibbs-Duhem equation, xA d,uA+ x 8 d,u 8 = 0, which implies that

(since ,u = ,u 9 + RT In a)
xA
dIn aA
dlna 8 = - - d lnaA= - - x8
= ---:; In
r-
aA dr + d
1
= - dr+d
r
[from (b)]
[from (a)]
= d lnr+d
Subtract dIn r from both sides, to obtain
as
(-1)
d In- = (- 1) d In r + d = - - dr + d
r
Then, by integration ,
8
In a = - (0)+
I'
(-1)
- r - dr
7.20 As in the argument leading to eqn 18 of the text, at equilibrium

,u ~ (p) =,u A(x A, p
+ TI)
which implies that , with ,u = ,u* + RT In a for a real solution ,

,u~(p) = ,u~(p + TI)
+ RT In aA
=,u~(p)+ J:+nVmdp+RTinaA
and hence that
J:+nVm dp
-RT!n aA
For an incompressible solution, the integral evaluates to
OV"' = -RT!n aA
In terms of the osmotic coefficient [Problem 7 .19]
Xn
nn
r=-=xA nA
For a dilute solution,
Hence
OV=nnRT
and therefore , with [B] = n 8 /V
0=[B]RT
nv"" so
131
8. Changes of state: the phase rule

Exercises
8.1 (a)
Salt,water;C=~
(b) Na +, H+, H 2P04, HPO~-,

also three equilibria, namely
H2P04 ~ H + +
Po~-,
H 20, OH - giving 7 species. There are
HPO~
HPO~- ~H + +PO~
H + +oH-~H2 0
(These could all be written as Bn~nsted equilibria without changing the

conclusions.) There are also two conditions of electrical neutrality , namely
[Na +] =[phosphates], [H +] = [OH - ] +[phosphates]
where [phosphates]= [H 2P04] + 2[HPo~- ] + 3[Po~ - ]
Hence , the number of independent components is
c = 7- (3 + 2) = ~
(c) Al 3 +, H +, AICI 3 , Al(OH) 3 , OH- , Cl - , H 20 giving 7 species. There are
also three equilibria:
AICI 3 + 3H 20
AICI 3 ~At +
3
~ Al(OH) 3 +
3HCI
+3Cl-
H20~H + +oH -
and one condition of electrical neutrality:
Hence, the number of independent components is
c = 7- (3 + 1) = 1
8.2 CuS0 4 5H 2 0(s)~CuSOis) + 5H 20(g)
We must specify 'H 20' for the gas phase and 'CuS0 4 5H 20' for the solid
phase ; CuSO~ is then fixed by the equilibrium. Hence C=2 and P=2
(s and g).
Changes of state: the phase rule
133
8.3 NH 4Cl(s) ~ NH 3 (g) + HCl(g).

For this system C = 1 (Section 8.1J and P = 2 (s and g). If ammonia is added
before heating, C = 2 (because NH 4Cl , NH 3 are now independent] and P = 2
(sand g).
8.4 The two components are Na 2S0 4 and H 20 (proton transfer equi libri a to
give HS04 etc. do not change the number of independent components
(Exercise 8.1]) so C = 2. There are three phases present (solid salt, liquid
solution, vapor), so P=3. The variance is
F=C-?+2 = 2-3+2=1
If the pressure is changed, the temperature must be changed to maintain the
equilibrium.
8.5 Still C = 2 (Na 2S0 4 , H 20) but now there is no solid phase present, so
P = 2 (liquid solution , vapor) and the variance is F = 2-2 + 2 = ~ We are free
to change the amount of dissolved salt and the pressure , but the temperature
must be changed to maintain equilibrium between the two phases.
8.6 See Fig. 8.1.
+10
-10
Liquid
(_) -30
0
;;:,
- 50
17
Fig 8.1
Liquid N,H
J
-70
...... [7
NH,N,H.,_
8. 7 Refer to Fig. 8.8 of the text. At b 3 there are two phases with compositions
xA = 0.18 and xA = 0.70; their abundances are in the ratio 0.13 (lever rule].
Since C=2 and P=2 we have F=2 (such asp and x). On heating , the phases
merge, and the single-phase region is encountered . Then F= 3 (such asp, T ,
and x). The liquid comes into equilibrium with its vapor when the isopleth
134
cuts the phase line. At this temperature, and for all points up to b 1, C = 2 and
P=2, implying that F=2 (for example p, x). The whole sample is a vapor
above b 1
8.8 The phase diagram should be labeled as in Fig. 8.2. (a) Solid Ag with
(a)
Sn
(b)
Time
dissolved Sn begins to precipitate at a~> and the sample solidifies completely at

a 2 (b) So[jd Ag with dissolved Sn begins to precipitate at b 1 , and the liquid
becomes richer in Sn. The peritectic reaction occurs at b2 , and as cooling
continues Ag 3Sn is precipitated and the liquid becomes richer in Sn. At b3 the
system has its eutectic composition (e) and freezes without further change.
8.9 The incongruent melting point [Section 8.5] is marked as 8, in Fig . 8.2a
(8, = 460 C). The composition of the eutectic is e, and corresponds to 4 per
cent by mass of silver. It melts at 8c = 215 oc_
8.10 The cooling curves are shown in Fig. 8.2b . Note the eutectic halt for the
isopleth b.
8.11 Refer to Fig. 8.2a.

(a) The solubility of silver in tin at 800 oc is determined by the point c 1 [at
higher proportions of silver, the system separates into two phases]. The point
c 1 corresponds to 80 per cent si lver by mass.
(b) See point c2 . The compound Ag3Sn decomposes at this temperat ure.
(c) The solubility of Ag 3Sn in silver is given by point c3 at 300 oc_ _

1000
it'-.
i\
135
Fig8.3
"'-..,
900
"
BOO
"
VJ
)'-..._
//
I'..
""'"I""'
700
0
x(ZrF~)
8.12 The phase diagram is shown in Fig. 8.3. A solid solution with x(ZrF4 ) =
0.21 appears at 875 oc. The solid so lution continues to form, and its ZrF4
content increases until it reaches x(ZrF4 ) = 0.40 at 820 oc. At that
temperature, the entire sample is solid.
95
Fig 8.4
93
17
Liquid
91
1\
'
~ 89
87
v
I
1\
Two phase liquid
1\
85
IV
Solid CH, and CF,
83
(CF,)
8.13 The phase diagram is drawn in Fig. 8.4 .

140
........
130
)'..,
1\..L
120
I--"
Fig 8.5
........ !'-..
\
\
110
\/
100
90
0
136
8.14 The phase diagram is shown in Fig. 8.5. The solid compound begins to
crystallize at 120 K. The liquid becomes progressively richer in diborane until
the liquid composition reaches 0.90 at 104 K. At that point the liquid
disappears as heat is removed. Below 104 K the system is a mixture of solid
compound and solid diborane.
Rg8.6
140
130
r\
\
120
;::::
\
"'-
:.::
r--
\...
'
\ F"'
- r-.
-\
\
110
1'-
100
' - 1--
90
Time
8.15 The cooling curves are sketched in Fig. 8.6.

23.0
(ne
iqud
Fig 8.7
1\.
22.5
r\
I
22.0
wo iqu/ps
II
1\
21.5
0.2
0.3
0.4
x(CsF,.)
0.5
8.16 The phase diagram is sketched in Fig. 8.7. (a) The mixture has a single
liquid phase at all compositions . (b) When the composition reaches x(C6 F 14 ) =
0.25 the mixture separates into two liquid phases of compositions x = 0.25 and
0.48. The relative amounts of the two phases change until the composition
reaches x = 0.48. At all mole fractions greater than 0.48 in C6 F 14 the mixture
forms a single liq uid phase.
137
8.17 The features are plotted in Fig. 8.8 using the instructions given in
Section 8.7 [see Example 8.5].
8.18 We first convert the mass percentage compositions to mole fractions
using M(NaC1)=58.4gmol - 1, M(H 20)=18.0gmol - 1, and
M(Na 2S0 4 10H 20) = 322.2 g mol - 1 Thus, in a sample of total mass 100 g,
n(NaCl) =
0.25 X 100 g
.4 g mol _, 0.43 mol
58
0.50 X 100 g
n(HzO) = 18.0 g mol - 1 2.8mol
0.25 X 100 g
n(Na 2S04 10H 20) = 322 .2 g mol 1 O.D78 mol
(a) These amounts corresponds to the mole fractions
x(NaCI) = 0.13, x(H 20) = 0.85, x(Na 2S0 4 10H 20) = 0.024
and corresponds to the point din Fig. 8.8 where A= NaCl, B = H 20 , and
C = N a2S0 4 1OH 20. (b) In this calculation, the 'water' apex is the one
marked B; hence the line labeled e is followed as water is added.
8.19 The composition (W , C, A)= (2.3 g, 9.2 g, 3.1 g) corresponds to
(0.128mol, 0.077mol, 0.052mol) [using M=18.02, 119.4, and 60.5gmol - 1
respectively]. The mole fractions corresponding to this composition are
138
therefore (0.50, 0.30, 0.20). The point lies at q in Fig. 8.17 of the text , the
intersection of the broken line and the third tie-line. The point q lies in the
two-phase region of the diagram. The two phases have compositions given by
the points at the ends of the tie-lines, namely (0.06, 0.82 , 0.12) and
(0.62, 0.16, 0.22). Their relative abundances are given by the level rule as
0.27 . (c) When water is added , the composition moves along the line joining
the point q to theW apex . When x(H 20) =0 .79, the system enters the
single-phase region . (b) When acetic acid is added to the original mixture, it
becomes a single-phase system when x(CH 3COOH) = 0.35 , the point a3 in the
diagram.
8.20 The positions of the four points are shown in Fig. 8.9 , which is a
reproduction of Fig. 8.18 of the text. (a) The point corresponds to a twophase system consisting of solid (NH 4)zS0 4 and liquid of compos"ition a 1 (b) A
three-phase system, consisting of solid NH 4CI , solid (NH 4) 2S0 4, and liquid of
composition d. (c) A single-phase system. (d) An invariant point: the system
consists of the saturated solution of composition d.
8.21 Refer to Fig. 8.9. Solubi li ties are given by the compositions at which
binary system just fails to become a two-phase system. These are the po in ts
(a) s 1, corresponding to x(NH 4 CI) =0 .26 and (b) s2 , corresponding to
x((NH4)zS04) = 0.30. Convert to mol kg - 1 by taking n(H 20) = 55.45 mol and
noting that M (N H 4CI) =53 .49 g mol - 1 and M ( (N H 4hS0 4) = 132. 14 g mol - 1
Since x(s) = n(s) l {n(s) + n(S)},
x(s)n(S)
n(s)= I -x(s)
139
Therefore,
(a) n(NH 4 CI)=19.5mol , (b) n((NH 4 hS0 4 )=23.8mol
and the solubilities of the chloride and the sulfate are 19 .5 mol kg - 1 and
23.8 mol kg- 1 respectively.
8.22 Refer to Fig. 8. 9.
(a) Initially the system is at s 3 (for example). It consists of a saturated
solution of composition s 1 and excess chloride. Addition of sulfate leads to a
single-phase system when the composition reaches (J. The sulfate continues to
dissolve until t } is reached; after that , the two-phase region is reached a nd
further sulfate remains undissolved.
(b) The composition consists of 0.47 mol NH 4 CI and 0.55 mol (NH 4 hS0 4 ,
with mole fractions 0.45 and 0.55 respectively . This composition corresponds
to the point s4 . Addition of water moves the system along the line s4 , t 4 Three
phases (solid chloride, solid sulfate, and unsaturated solution d) survive until
s4 is passed. Then the two-phase region is entered and there are present the
solid sulfate and a liquid of composition that changes from d toward t~. For
instance, when the overall composition is t~, the liquid composition is a 1 At t~
the single-phase region is entered and .the solution from then on becomes
progressively more dilute.
8.23 The phase diagram is shown in Fig. 8.10.
Problems
8.1 F = C-P+2, with C= 1. At the transition point P=3 (s, I, and g) for
melting and P = 3 (l, I', and g) at the transition. Hence, F= 1-3 + 2 = Q for
both.
140
8.2 The data are plotted in Fig. 8.11. (a) Atx(Mg0)=0.3, solid and liquid
are in equilibrium at 2150 oc. (b) From the tie-line at 2200 C, the liquid
2800
./
c'f""" /
./
2400
1_,
- --
v v
/"
k"
-?
Fig8.11
7r; "\.
I /
200vv
0-3
10
x(MgO)
composition is y(MgO) = 0.18 and the solid x(MgO) = 0.35. The proportions
of the two phases are given by the lever rule , and solid/liquid= 0.42. (c)
Solidification begins at point c, corresponding to 2650 oc.
8.3 The temperature-composition lines can be calculated from the formula

for the depression of freezing point (Chapter 7) :
RT*2x 8
!J.T=-!J.Hrus
For bismuth
RT*2
8.314 J K - I mol - 1 X (544.5 K/

10.88 X 103 J mol - 1
227K
For cadmi um
RT* 2 8.314 J K - I mo l- 1 x (594 K/
--=
=483K
/J.Hrus
6.07 X 10 3 J mol I
We can use these constants to construct the following tables:

x(Cd)
0.1
0.2
0.3
0.4
!J. TIK
Tr!K
22.7
522
45.4
499
68.1
476
90 .8 (!J. T=x(Cd) x 227 KJ

454 [Tr= Tt - !J.T]
141
x(Bi)
0.1
0.2
0.3
0.4
!:lTIK
48 .3
546
96.6
497
145
449
193 (!:l T= x(Bi) X 483 K]

401 [Tr= T1- !:l T]
Tr
These points are plotted in Fig. 8.12a.

(b)
(a)
600
'
~
~
a "'
an"
0
Bi
"""'
'
\
So id t i L
400
a'
Liq id
1\..
so
Fig8.12
\a'
r-..
jSOii , U:lL
Sol ~p ecip fates
lj
;".
x(Cd)
E_u ect c halt
a"
1
Cd
Time
1/
'
Liquid at a cools without separation of a solid until a' is reached (at 475 K).
Solid Bi then separates, and the liquid becomes richer in Cd . At a"' (400 K)
the composition is pure solid Bi +liquid of composition x(B i) = 0.4 . The whole
mass then solidifies to solid Bi +solid Cd. (a) At 460 K (point a"), liquid/
solid= 2_ [lever rule]. (b) At 350 K (point a"') there is no liquid. The cooling
curve is shown in Fig. 8.12b .
8.4 The data are plotted in Fig. 8.13. From the upper and lower extremes of
the two-phase region we find Tuc = 122 oc and T1c = 8 C. According to the
phase diagram, miscibility is complete up to point a. Therefore , before that
point is reached , P= 1, C=2, implying that F=3 (p, T, and x). Two phases
occur at a corresponding to w(toluidine) = 0.18 and 0.84 . At that point, P = 2,
C= 2, and F= 2 (p, or x or T). At the point a' there are two phases of
composition w = 0.18 and 0.84. They are present in the ratio
(a"- a' )I (a' -a)= 2 with the former dominant. At a" there are still two
phases with those compositions, but the former ( w = 0.18) is present only as a
trace. One more drop takes the system into the one-phase region .
142

Tuc
120
1/
100
i\.
Fig8.13
80
(.)
60
t.O
I)
20
1\..
Ttc
,.../
02
Glvcerol
()1,
06
08
10
m-Toluidine
8.5 The phase diagram is drawn in Fig. 8.14. The composition points fall on
the dotted line. The first solid to appear in (NH4 ) 2SiF6 When the water
content reaches 70.4 per cent by mass, both (NH 4) 2SiF6 and the double salt
crystallize as more water is removed. The solution concentration remains
constant until the H 20 disappears.
lA) Li, SiF;.
8.6 The information has been used to construct the phase diagram in Fig.
8.15a. In MgCu 2 the mass percentage of Mg is 100 x 24.3/(24.3 + 127) = 16,
and in Mg2Cu it is 100 x 48.6/(48 .6 + 63.5) = 43 . The initial point is a 1,
corresponding to a liquid single-phase system. At a 2 (at 770 oq MgCu 2 begins

(a)
143
(b)
1200
to come out of solution and the liquid becomes richer in Mg, moving toward
e2 At a3 there is solid MgCu 2 +liquid of composition e2 (33 per cent by mass
of Mg) . This solution freezes without further change . The cooling curve will
resemble that shown in Fig. 8.15b.
M
8.7 The points are plotted in Fig. 8.16. Note that addition of M preserves the
E/W ratio . The composition (M , E , W) = (5 g, 30 g, 50 g) corresponds to
(0.156 mol, 0.405 mol , 2.775 mol) since the mo lar masses are (32.04 , 74.12,
18.02) g mol - 1 The mole fraction composition is therefore (0.047, 0.121,
0.832), which is point a in Fig. 8.16. This point lies in the two-phase region.
The line w- a corresponds to constant M/E ratio. When either point a 1 or a2
is reached, the single-phase region is entered . These two points correspond to
the compositions a1 = (0.02, 0.05, 0.93) and a2 = (0 .20 , 0.52, 0.28) . Since nE
144
and nM remains constant at 0.156 mol and 0.405 mol respectively , we require
nw=7.3 mol, or 131 g. Hence , 81 g of water must be added.
800
' \.
Fig 8.17
L1quid
1\
\
600
./
1\
\
400
/
........
KCt .. K~FeCI,._
Liquid
... /(ct
Li uia +FeC&_
/
KFeC~+~Ia
K,f ioc4+
KA C/3
0.2
0.6
0.4
0.8
1.0
x (FeCI2l
8.8 The data are plotted in Fig. 8.17. At 360 C , K 2FeCl 4 (s) appears. The
solution becomes richer in FeCl 2 until the temperature reaches 351 oc, at
which point KFeCl 3(s) also appears. Below 351 oc the system is a mixture of
K2 FeCl 4 (s) and KFeCl 3(s).
145
8.9 (a) The phase diagram is shown in Fig. 8 .1 8. (b) The triangular area
enclosed by the two dotted lines is spanned by x(C 2H,N0 2) = 0.29 and 0.83 ,
and cannot be left by adding DEC since all composition points move toward
the DEC apex as DEC is added .
8.10 Let a and f3 co nstitute an isolated system, but be in thermal contact with
each other. When an amount of energy dq flows from a to f3 the change in
entropy is
dq
dq
Ta
Tp
dS=---=0 only if Ta= T1!

Consider an isolated system divided internally by a partition. The condition
for eq uilibrium overall is (dU )s. v = 0. The total contribution to dU at constant
e ntropy (only work being exchanged) and constant overall volume (only
internal motion of the partition) is
8.11 Refer to Fig. 8. 19 . From the properties of sim il ar triangles (using - to
denote similarity)
a a'
AA'C- AA"C" implying that-=--;
c c
146
a
c
and hence ---; =---;
a c
b b'
AB'C' - AB"C" implying that-=-,
and hence
t/ = 2
a
It follows that -;;: = t/, implying that
a'
b= b'
9. Changes of state: chemical reactions

Exercises
9.1
I'!G e = - RTin K [Sa]

= -8.314 J K - 1 mol- 1 x 400 K x In 2.07
= -2.42 kJ mol - 1
9.2
K=e-t-.c
I RT
[Sa]
= e + 3.67 x 101 1 moJ - IiX.3 14J K -
1 mo J- 1X400 K
3.01
l'!c e I'!G e
( 1 1)
9.3 - - - - - =!'!H e - - - [Gibbs-Helmholtz]
T'
T
T' T
and
1-T1) [llb]
!'!He (
InK' -InK=-~ T'
K' = 1 implies In K' = 0, which implies that !'!G e' = 0, which occurs when
-l'!c e =!'!He (~ - !_)

T
T' T
or
1 1
!'!G e
1(
I'!G e )
T' =T- T I'!H e =T 1 - !'!H e
1
33kJmol - )
4
1
=1 280K l-224kJmol - 1 = 6 66 xl0 - K 1
He nce, T' = 1SOO K

9.4
1088 K l.Sl x 105 K 2

lnK=-1.04--T-+
T2
dInK -!'! H e
d(l!T) =-R- [llb]
148
Changes of state: chemical reactions
Therefore ,
-D..H 9
2 X 1.51 X 105 K2
- R - = -1088 K + _ _ _T_ __
Therefore, at 400 K
5
D..H 9 = ( 1088K-
3.02 X 10 K
00K
4
X8 .314JK - 1 mo l- 1
= +2.77 kJ mol - 1
D..G 9 = -RT!n K
5
_
(
1088K _ 1.51 x 10 K
- RTx 1.04+ T
T2
2
)
1088 K 1.51 x 10 5 K 2)
1
=RT x ( 1.04+ 400K- (400K) 2
=+9.37kJmol = D..H 9 = T D..S 9
Therefore,
D..H 9 - D..G 9
D..S e = - - - -
2.77 kJ mol - 1 -9.37 kJ mol - 1
400K
= -16.5 J K - 1 mol - 1
9.5 p 8 = x 8 p [B denotes borneol]
0.15 mol
= 0 _15 mol+ 0 _30 mol x 600 Torr= 200 Torr
P1 = p- p 8 [I denotes isoborneol] = 400 Torr
Q=~=2 . 00
Ps
D..G,= D..G 9 + RT!n Q [4]

= +9.4 kJ mol - 1 + 8.314 J K - I mol- 1 x 503 K x In 2.00
= +12.3 kJ mol - 1
9.6
U(s) +tH 2 (g)~UHJ(s)
InK= ln(p/p 9 ) - 312 =- t In plp 9
1.04 Torr
= 4 x 8.314 J K - 1 mol- 1 x 500 K x In
[p 6 = 1 bar = 1 atm]
750 Torr
= -41.0 kJ mol - 1
9 7 K X ex: p - ,. [ 1OJ
(a) v = 1 + 1 - 1 = 1, so
K; = t K ,
(b) v = 1+1 -1-1 =0 , soK>K,
1
1
Hence,x 6 =l+K=l+O.I06
X1
0.904
= 0.096
The initial amounts of the isomers are

7.50g
n6=
140g
21.50g
--;;_;r-, n1 = M , n = ----;;;r-
The totai amount remains the same, but at equilibrium

n6
21.50 g
--;:;-- = x 6 = 0. 904, n 8 = 0. 904 X
----;;;r-
The mass of borneol at equilibrium is therefore

m6 = n 6
M=0.904
21.50 g= 19.4 g
and the mass of isoborneol is

m 1 = n 1M=0.096x21.50g=2 .1 g
9.9 Determine whether
~G 6 < 0
at 298 K:
(a)
~G 6 /(kJ
mol - 1) = -202.87- ( -95.30 -16.45) = -9 1.12
(b)
~G 6/(kJ
mol - 1) = 3 x ( -856.64)- 2 x ( - 1582.3) = +594.7
(c)
~G 6/(kJ
mol - 1) = -100.4- ( -33.56) = -66 .8
(d)
~G 6 /(kJ
mol - 1) = 2 x ( -33.56)- ( -166.9) = +99.8
(e)
~G 6 /(kJ
mol - 1) = - 744.53 - ( -27.83)- 2 x ( - 120.35) = - 476.00
149
150
Therefore, (a) , (c) , and (e) have K> 1 at 298 K.

9.10 Determine whether !1H 6 > 0 at 298 K using !1H f' values from Table
2.10.
(a) !1H 6 /(kJ mol - 1) = - 314.43- ( - 46.11- 92.31) = -176 .01
(b) !1H 6 /(kJ mol - 1) = 3 x ( - 910 .94) - 2 x ( -1675.7) = +618.6
(c) !1H 6 /(kJ mol - 1) = -100.0- ( - 20.63) = - 79.4
(d) !1H 6 /(kJ mol - 1) = 2 x ( -20.63)- ( -178.2) = + 136.9
(e) !1H 6 /(kJ mol - 1) = - 909.27 - ( - 39.7)- 2 x ( -187.78) = - 494.0
Since (a) , (c), and (e) are exothermic, an increase in temperature favors the
reactants ; (b) and (d) are endothermic, and an increase in temperature favors
the products.
6
911
K' =!1H- (1
1) (12]
In--K
R
T T'
Therefore, !1H 6 =
R In K'/K
T T'
T' = 308 K, hence, with K 'I K = x
!1H 6
8.3141 K - 1 mol - 1 x In x
=
1
- - --
298 K
= 76 kJ mol - 1 x In x
308 K
Therefore
(a) x = 2, !1H 6 = 76 kJ mol - 1 x In 2 = +53 kJ mol - 1
(b) x = t, !1H 6 =76 kJ mol - 1 x In t = -53 kJ mol - 1

9.12
!1G 6
- RTln K
The percentage error, g , is
_
(!1G e - !1G 6 ' ) _ 100 In Kl K'
g - lOOx
!1Ge
InK

Suppose K' = K + t.K, then
In~= -InK+ t.K

K'
-In (1 +
!'.~ = ~t.K
K)
Hence
100t.K
- -=-glnK
K
and the percentage error in K, k, is

k = -gIn K = 10% x In K
9.13
t.G, = t.G 9 +RTln Q [4] for ! N 2 (g)+ t H 2 (g) ~ NH 3 (g)
p(NH1)/p 9
p(NH 3)p 9
Q = (p(N z)l p e) lt2(p(Hz)/ p 9 )3' 2 p(Nz) lt2p(Hz)" 2
4.0
4.0
= (3.0) 1' 2(1.0) 3' 2= V3.0
Therefore,
t.G, = -16.45 kJ mol - 1 + RT In
4.0
y _
30
= -16.45 kJ mol - 1 +2 .07 kJ mol - 1 = -14.38 kJ mol - 1

Since t.G, < 0, the spontaneous direction of reaction is toward products.
9.14
NH 4 CI(s)~NH 3 (g)
+ HCI(g)
p = p(NH 3) + p(HCI) = 2p(NH 3) [p(NH 3) = p(HCI)]

2
_ p(NH 3) p(HCI) _ p(NH 3) _ ~
2
(a) KP- p e x p e - p e2 -4 p e
(.!!.._)
At 427 oc (700 K) , KP=
4x
(608 kPa) 2
100 kPa = 9.24
1 (1115 kPa) z
At 459 oc (732 K), KP= 4X 100 kPa = 31.08
(b) t.G 9 = - RTln KP
= -8.314 J K - 1 mol - 1 X 700 K X In 9. 24

= - 12.9 kJ mol - l (at 427 C)
151
152

R In K'IK
(c) D.H 9 =
[12, as in Exercise 9.11]
T T'
8.3141 K - 1 mol - 1 x In
31.08
.
9 24
= - -- - - - - - - -
1
1
----700 K 732 K
D.H 9 - D.G 9
(d) D.S 9 = - - - T
= + 161 k1 mol - 1
161 k1 mol - 1 -
- 12.9 k1 mol - 1)
700K
= +2481 K - 1 mol- 1
9.15
D.H 9 =
R In K'/K
1
T
1
T'
[12, as in Exercise 9.11]
2.303RlgK'IK
2.303R(pKw-pK~)
T'
T T'
2.303
8.3141 K - I mol - 1 X (14.17 -13.84)

1
293 K
303 K
= +56 .1 k1 mol - 1
9.16
D.G 9 = D.H 9
T D.S 9 = 0 when D.H 9 = T D.S 9
Therefore , the decomposition temperature (when K = J) is
D. H e
T= D.S e
(a) CaC0 3(s)--7 CaO(s) + C0 2(g)
D.H 9 = -635.09 - 393.51- ( -1206.9) k1 mol - 1 = + 178.3 k1 mol - 1

D.S 9 = 39 .75+213.74-92.91 K - 1 mol - 1 = +160.61 K - 1 mol - 1
178.3 x 103 1 mol - 1

T = 160.61K - Imol - l =1110K(8400C)
153
(b) CuS0 4 5H 20(s) :;:::=CuSOb) + 5H 20(g)
11H 9 = -771.36 + 5 x (- 241.82)- ( -2279.7) k1 mol - 1 = +299.2 k1 mol - 1

115 9 = 109+5 x 188.83 -300.41 K - 1 mol - 1 =752.21 K - 1 mol - 1
Therefore,
299.2 x 10 3 1 mol - 1
T= 752.21K - 1 mol - 1 = 397 K
9.17
!1G 9 (T) = !1H 9 (0) + T !1<1> 11 (T) [14a]
11G 9 (T) = 11H 9 (0) + l' 11<1> 0(T)

11G 9 (T) -11G 9 (T) = T 11<1>o(T) -l' 11<1>o(T)
Therefore,
!1G 9 (f) = !1G 9 (T) + T 11<1> 0(T)- T 11<1>0(l')
(a) N 2(g) + 3H 2(g)--7 2NH1(g) at 1000 K
11<1> 0(1000 K) = 2 X 203.5-197.9-3 X 137.01 K - I mol - 1 = +201.9 1 K -I mol - 1
I1<1> 0 (T)=2x 159.0-162.4-3 x 102.21 K - 1 mol - 1 = +151.01 K - 1 mol - 1
11G 9 (T) = 2!1G f'(NH 3 , T) = 2 x ( -16.45 k1 mol - 1) = -32.90 k1 mol - 1
Therefore ,
11G 9 (T) = -32 .90 k1 mol - 1 + 1000 K x 201.91 K - 1 mol - 1
-298.15 K x 151.0 J K - I mo l- 1 = + 124.0 k1 mol - 1
-11G 9 (T)
lnK=
RT
-124.10 3 1 mol - 1
8.314x103 1mol _ 1 = - 14 91
Therefore, K = e - 1491 = 3.3 x 10 - 7 at 1000 K
(b) CO(g) + H 20(g)--7 H 2(g) + C0 2(g) at 500 K and 2000 K

11G 9 (l') = !1G f'(C0 2, g) -11G f'(CO, g) -11G f'(H 20 , g)
= -394.36- ( -137.17)- ( -228.57) kJ mo l- 1 = -28.62 k1 mol - 1
11<1>o(T) = <l>o(H2, T) + <l>o(C02, T)- <l>o(CO, T)- <l>o(H20, T)
11<1> 11 (500 K) = -116.9-199.5 + 183.5 + 172.8 J K - I mol - 1 = +39 .9 1 K - I mol - 1
11<1> 0 (2000 K) = -157.6-258.8-225.9 + 223.1 J K - I mol - 1 = +65.5 1 K - I mol- 1
11<1> 0 (T) = -102 .2- 182.3 + 168.4 + 155.5 1 K - I mol - 1 = +39.4 J K - I mol - 1
154
Therefore,
t.G 9 (500 K) = -28.62 kJ mol- 1 + 500 K + 39.9 J K- 1 mol- 1
-298.15 K x 39.4 J K - I mol - 1 = -20.42 kJ mol - 1
t.G 9 (2000 K) = -28.62 kJ mol- 1 +2000 K x 65.5 J K - 1 mol - 1
-298.15 K X 39.4 J K - 1 mol - 1 = +90.63 kJ mol - 1
Hence, at 500 K
-t.G 9
+20.42xl0 3 Jmol - 1
lnK=---;rr:-=8.314JK - 1 mol - 1 x 500K
+ 4 91 ' K=l3 6
and at 2000 K
-90.63 x 103 J mol - 1
-t.G 9
InK=~= 8.314J K I mol I x2000 K = - 5 .45 , K= 4 3 X
w-J
9.18 When [Acid]= [Salt], pK. =pH (24]
Hence, pK,. = 5.40 and K. = w -s.40 = 4.0 X 10- 6

When the solution is [Acid]= 0.015 M
pH= t pK,.- f lg[Acid]
= J2
X 5.40-
[Example 9.7]
t X ( -1.82) = 3.61
In water, the NHt acts as an acid in the Br(l!nsted equilibrium
Since [NH 3 ] = (H 30 +], because the water autoprotolysis can be ignored in the
presence of a weak acid (NH:); therefore ,
(HJO +f
K.= [NH:J
[H30 +]2
S
where Sis the nominal concentration of the salt. Therefore,

[HJO +j = (SKa) 112
and pH =f pKa- f lgS

=t X 9.25 - t lg 0.10= 5.13
The CH 3COi ion acts as a weak base:

CH3COi (aq) + H 2 0(/)~CH 3 COOH(aq) + OH - (aq)
Kb =
[CH3COOH][OH - ]
[CH 3C02]
Then, since [CH 3COOH] = [OH - ] and [CH 3C0i]=S, the nominal
concentration of the salt ,
Therefore, pOH = 1- pKh - t lg S

However, pH+pOH=pKw , so pH=pKw-pOH
pK .. +pKb=pKw, so pKb=pKw-pK"
Therefore,
pH= pKw-t(pKw- pK .. ) + t lg S= tpK.v+ 1-pK.. + t lg S
=t
14.00 + t
(c) CH 3COOH(aq) +
K" =
4.75 + t
lg 0.10= 8.88
H 2 0(/)~H 3 0 + (aq)
+ CH 3COi (aq)
[H 30 +][CH 3C0i ]
[CHJCOOH]
Since we can ignore the water autoprotolysis , [H 30+] = [CH 3CO;-], so
K..
[H3o +p
A
where A= [CH 3COOH], the nominal acid concentration [the ionization is

small]. Therefore,
[H 30 +] = (AK .. ) 112 , implying that pH = }pK.. -
! lg A
Hence,
pH = t
4.75 -t lg 0.100 = 2.88
9.20 The pH of a solution in which the nominal salt concentration is S is
pH= 1PKw+ ~- pK .. + -~ lgS
[Exercise 9.19b]
The volume of the solution at the eq uivalence point is
155
156
0.100 M
V= 25 .00 mL + 25 .00 mL X _ M=41.67 mL
0 150
and the concentration of salt is
S = 0.100(M)
25.00 mL
1. mL
4 67
0.0600(M)
Hence, with pK. = 3.86,
pH = t
14.00+ t
3.86 + t
lg 0.0600= 8.3
9.21 One procedure is to plot eqn 22 , as in Fig. 9.6 of the text. An alternative
procedure is to estimate some of the points using the expressions given in Fig.
9.7 of the text. In itially only the salt is present , and we use eqn 25a [as in
Exercise 9.20]:
pH = t pK.+ t pKw+ t lgS, lgS = -1.00
= ~ (4.75
+ 14.00 - 1.00) = 8.88
(a)
When A =S, use the Henderson-Hasselbalch equation (eqn 24):
pH = pK.- lgs = 4.75 -lg _

0 10
(b)
=3 .75 - lgA.
When so much acid has been added that A li> S, use the 'weak acid alone'
formula, eqn 23:
(a)
pH = t pK. - t lgA
We can draw up the following table :
0.06
0.08
0.10
0.12
0.14
0.6
0.8
1.0
pH
8.88
4.97
4.85
4.75
4.67
4.60
2.49
2.43
2.33
Formula
(a)
(b)
(c)
The results are plotted in Fig. 9.1.

9.22 We require pKa=pH(buffer) [Example 9.12]. Therefore , (a) for
pH = 2.2 use Na 2 HP0 4 + H 3 P0 4 since
H 3 P0 4 +H 2 0;:::'::H 30 + +H 2 P04
pK., = 2.12
(b) for pH =7 use NaH 2P0 4 + Na 2HP0 4 since

H 2 P04 + H 2 0;:::'::H 3 0 + +HPO~-
pK.,=7 .2

Fig 9.1
8
6
~,_ __
r--
r--.-.
01.
o6
o.a
mfi4/mol kg 1
02
10
Problems
9.1
U(s) + ~ H 2 (g);:=UH 3 (s)
K= (p/p e)- 312
dInK
d
!).He =RT 2 --=RT 2 - (- l.2 Jnp/p e)
r
dT
dT
d lnp
=- l. RT 2 - 2
dT
3
= _ l.RT 2 (14.64 x 10 K
Tz
= - f R(14.64
= - (2.196
9.2
5.T65)
x 103 K- 5.65T)
x 104 K- 8.48 T)R
CaCI 2 NH 3 (s);:=CaCI 2 (s)+NH 3 (g)
K=plp e
!).Ge = -RTin K= -RTinplp e

= -8.314 J K- 1 mol- 1 x 400 K
x In
12.8 Torr
0Torr [p e = 750.3 Torr]
75
= +13 .5 kJ mol - 1 at 400 K
(!_- _!__)
!).Ge(T) - !).G e(T')e

T
T'
- !).H
T
Therefore, taking T' = 400 K,
T'
(12]
157
158
t...G e (T) =
40~ K x 13.5 kJ mol - +78 kJ mol - X ( 1- 40~ K)

1
= 78kJmol- 1 +
(13.5 -78)
T
kJmoi - 1 XK
400
That is,
t...G 9 (T)/(kJ mol - ')= 78- 0.161(T!K)
9.3 CO(g) + H 2(g) ~ H 2CO(/)
t...G ~P=
p
-RTln K= - RTin p e
=-8.314JK - 1 mol - 1 X298 K x ln
1500 Torr
0Torr
75
= -1.72 kJ mol- 1
Therefore, for the reaction
CO(g) +
H 2 (g)~H 2 CO(g),
t...G 9 = +28.95 + ( - 1.72) kJ mol - 1 = + 27.23 kJ mol - 1

Hence,
K=
=
e - 27.23x I03J mol - 1/8.3 141 K - I mol- l x298 K
e -10.99 = 1.68 X
10 -5
9.4 The equilibrium we need to consider in A 2(g) ~2A(g)
Initially
At equilibrium
Mo le fraction
Partial pressure
Az
Total
0
2an
2a
n
(1- a)n
1-a
n
(1 + a)n
1+a
2ap
1+a
1+a
c-a)
l+a p
159
The equilibrium constant for the dissociation is
=(pA/p e )z ___!!l_= 4a\plp e )
PA/P 9
PA,P e
1- a 2
We also know that

pV=n, 0 13 1RT=(1+a)nRT, implying that a= ::T-1
m
and n= M
In the first experiment,

pVM
764.3 Torr X 21.45 X 10- 3 L x 120.1 g mol - 1
a=----1=
mRT
0.0519 g x 62 .364 L Torr K - I mol - 1 x 437 K
=0.392
Hence, K=
4 X 0.392 2 X (764.31750.1)
_ .
=0 .740
1 0 3922
In the second experiment

764 .3 Torr X 21.45 X 10- 3 LX 120.1 g mol- 1
-1
0.038 g x 62.364 L Torr K - I mol - 1 x 471 K
p VM
a= --- -1
mRT
=0.764
Hence,
K
4 X 0.764 2X (764.31750 .1)

1-0.7642
=5.71
The enthalpy of dissociation is

!).H 9 =
R In K'/K
[12)
T T'
R ln(5.71/0.740)
1
437 K
1
471 K
=+103kJmol- 1
The enthalpy of dimerization is the negative of this value , or -103 kJ mol - 1

(i .e. per mole of dimer) .
160
InK = Ins =2.303Igs
= + 14.7 kJ mol - 1
K)
d
980
11H"7(CO) = -2 .303R d(1/T) ( -5 .98 --T- = 2.303R X 980 K
= + 18.8 kJ mol - 1
9.6 Draw up the following table using Hlg) + I 2 (g)~2HI(g)
Initial amounts/mol
Change/mol
Equilibrium amounts/mol
Mole fraction
KP =
H2
Iz
HI
Total
0.300
-x
0.300-x
0.300-x
0.900
0.400
-x
0.400-x
0.400-x
0.900
0.200
+2x
0.200+2x
0.200+2x
0.900
0.900
(p(HI)/p 9 ) 2
(p(Hz)lp 9 ) (p(I z)l p 9 )
x(HI) 2
x(H2)x(Iz) [p(J) = XJP]
co.2oo+2xr
(0.300-x)(0.400-x)
870[given]
0.900
1
Therefore,
0.0400 + 0.800x + 4x 2 = 870 X (0.120- 0.700x + x 2 )
or 866x 2 - 610x + 104 = 0
which solves to x=0.289 [x=0.42 is excluded because x cannot exceed 0.300].
The final composition is therefore 0.011 mol H 2, 0.111 mol I2 , and
0.779 mol HI.
9. 7 Draw up the following table using the reaction stoichiometry
2A+B~3C+2D
161
Initial amounts/mo l
Stated change/mol
Implied change/mol
Equilibrium amounts/mol
Mole fractions
1.00
2.00
-0 .60
0.40
0.087
-0.30
1.70
0.370
6 2
)\p 0 /p ) = X~xt.
(p A/p e )2(pB!p e ) x:;..xs
= (p clp
0
+0.90
+0.90
0.90
0.196
Total
1.00
4.00
+0.60
1.60
0.348
4.60
l.OOT
(!_)2= K,.(!_)2
pe
. pe
0.196' x0.348 2 '

K,= 0.087 2 X 0.370 = 0 33
9.8 The equilibrium constant K and its logarithm In K are plotted against
temperature in Fig. 9.2. At 8 = 20 oc we find K = 23 300. Therefore, at this
30000
11
Fig 9.2
~
20000
10
\' ~
\
In
""
"\
K
10000
K ~
\..
~
0
10
20
30
ere
hK
~r-...
40
'
7
50
temperature ,
!'!.G 6 = -RTln K= -8 .314 J K - I mol - 1 x 293 .15 K x In 23 300
=
-24.5 kJ mol - 1
From the InK graph, at 20 oc we find

dIn K
-0.0926
dT
162
Therefore
dinK
tlH 9 = RT 2 ~= 8.3141 K - 1 mol - 1 x (293.15 K? x ( -0.0926 K - 1)
=
tlS 9 =
-66.1 k1 mol - 1
tlH 9
tlG 9
( -66.1-
( -24.5)) k1 mol - 1
293.15 K
= -1421 K- 1 mol - 1
9.9 The equilibrium 12(g);:=::2I(g) is described by the equilibrium constant
x(Ir p 4a 2(plp 9 )
K=x(lz)p e = l-a 2 [Problem9.4]
If p 0 = nRTIV, then p= (1 + a)p 0 , implying that
p-po
a=-Po
We therefore draw up the follow ing table:
p!atm
104 nl
p 0 !atm
a
K,,
973 K
1073 K
1173 K
0.06244
2.4'709
0.05757
0.08459
1.800 x w-"
0.07500
2.4555
0.06309
0.1888
1.109 x 10- 2
0.09181
2.4366
0.06844 [p 0 = n 1RT!VJ
0.3415
4.848 x w-z
dInK
(-3.027- ( -6.320))
tlH 9 = RT 2 - - = 8 3141 K - 1 mol - 1 X (1073 Kf x
dT
.
200K
"""= +158 k1 mol - 1

9.10
p(P)
K" =p(A)'
p(P) = XrPr [PP is vapor pressure of pure paraldehyde J
p(A) =xAPA [PAis vapor pressure of pure acetaldehyde]

In each case, xis the mole fraction in the liquid .
p = p(A) + p(P)
=X APA +Xppp=XAPA + (1-xA)pp
implying that
163
xA= p-pp, p(A)= (p - pr)PA

PA- Pr
PA- Pr
Similarly,
p(P) = (p- PA)Pr
Pr-P A
3
Hence K = (p-pA)Pr. (pA-Pr) =Pr(pA-p)(pA - P r)

'
p
(pp-pA) (p-pp) 3pl
pl(p-pp) 3
For the vapor pressures use

/1Hvap
In p/kPa =a- R(TIK) [g1ven]

Hence, for acetaldehyde
25.6 k1 mol - 1
3079 K
lnpA/ kPa= 15.1 - 8.3141 K - 1 mol - l X TIK = 15.1--T41.5 k1 mol - 1
4992 K
2
lnpr/kPa= 17. -8.3141 K - 1 mol - 1 x TIK = 17 2 - - T We can therefore draw up the following table :
8!C
20.0
22.0
26.0
28.0
30.0
32.0
34.0
TIK
p A/kPa
PrlkPa
p/kPa
105 K,
InK,
293 .2
98.9
1.20
23.9
7.59
-9.49
295.2
106.2
1.34
27.3
5.55
-9 .80
299.2
122. 1
1.69
36.5
2.73
-10.51
301.2
130.8
1.88
42.6
1.82
- 10.91
303.2
139.9
2.10
49.9
1.20
-11.33
305.2
149.5
2.34
56.9
0.865
-1 1.66
207 .2
159.7
2.60
65.1
0.610
-12.01
8/oC
36.0
38.0
40.0
T/K
309.2
170.4
2.89
74 .3
0.433
-12.35
311.2
181.6
3.2 1
85.0
0.301
-12.71
313.2
193.5
3.55
96.2
0.216
- 13.05
pA/kPa
pp/kPa
p/kPa
10 5 K,
InK,
164
In KP is plotted in Fig. 9.3. We then use
Tr ,dIn KP/dT= -0.185 K - I at 298 K
dinK
t:J.H e = RT 2
-9
...
-10
Fig9.3
1\.
\..
~
11
'
-12
~.
290
"\.
300 VK
"
320
310
Therefore,
t:J.H 6 = 8.314 J K -I mol- 1 x (298.15 Kr x ( -0.185 K - I) = -137 kJ mol - 1

Since t:J.G 6 = -RTin K= - 8.3141 K- 1 mol - 1 x298.15 K x (- 10.3)=
+26 kJ mol - 1
It follows that
t:J.S 6 =
t:J.H 6
t:J.G 6
( -137- 26)
kJ mol - 1
298.15K
-547 J K - 1 mol - 1
For the values in the liquid , we use

3A(l)~3A(g) t:J.H ~P =
t:J.S ~P =
t:J.S ~P
Therefore , for
3A(l)~
3 x 25.6 kJ mol - 1 = + 76.8 kJ mol- 1

3 x 25.6 kJ mol - 1
K
294
+261JK- 1 mol - 1
41.5 kJ mol - 1
= __3_9_8_K__
A 3(l)
t:J.H = 76.8-137-41.5 kJ mol- 1 = -102 kJ mol - 1

6
t:J.S 6 = 261-547-104 J K - I mol - 1 = -390 J K - 1 mol - 1
165
Therefore
( -a~
ap
=K
T
(aK,,)
y -ap
+K
T
"
(aK)
- ')
ap
=0
which implies that
) = _ (aK,) x Ky
(oKy
ap
ap K"
T
and therefore that if K, increases with pressure, K >, must decrease (because
Kyl K,, is positive].
9.12 We draw up the fo llowing table using the stoichiometry A+ 3B~ 2C and
~n = v:
Initial amount/n
Change
Equilibrium amount/ n
Mole fract ion
Total
3
-3.;
3(1-)
3(1-)
2(2- .;)
0
+2
2
-.;
1-.;
1- .;
2(2- )
Since K" is independent of the pressure
(2- ) 2
(1- ,;)4
.;
2 -.;
2(2- .;)
1
166
Therefore
(2- s)s =a
(;e)
(1- s) 2
(1 + ap/p 9 )SZ- 2(1 + ap!p 9 )s + aplp 9 = 0

which solves to
1
s-1( 1+ap/p
-
112
We choose the root with the negative sign because

The variation of
s lies between 0 and 1.
s with p is shown in Fig. 9.4.
l--
,/"
/
I
0.5
Fig 9.4
1/
I
v
0
0.1
10
apl p ""
100
1000
Since p(N0 2) 2 + p(N0 2)KP- pKP = 0

(1
p(N0 =
2)
+ 4pl Kp) 112 -1

( 2/ KP)
We choose the root with the positive sign because p must be positive.
For equal absorptions,
[p= l/12]
167
Therefore
p{(1 + 4p 11Kp) 112-1} = (1 + 4p 2K, ) 112 - 1

p(1 + 4p/ K, ) 112= p -1 + (1 + 4p / K") 112
2
p\1 + 4pl/ Kp) = (p -1) + (1 + 4p 21K") + 2(p -1)(1 + 4p 2/ K,) 112

P -1 + 2(plp2- P2)/ K" = (p-1)(1 + 4p 21K") 112
{p -1 + 2(plp2- P2)/ Kp}2= (p -1r(l + 4p21Kp)
2
(P1P 2 - P2)2/ K ~ + {(p -1)(pl P2- P2)- (p -1?pz}l KP= 0

[reinstating p 9 ]
Since p=
395 mm
_
mm =5.27
75
We can therefore draw up the following table:

Absorbance
p/Torr
p 2/Torr
p 9 KP/Torr
0.05
0.10
0.15
1.00
2.10
3.15
5.47
12.00
18.65
110.8
102.5
103.0
Mean: 105
Hence , since
9.14
p9 =
750 Torr (1 bar) , KP= 0.140
f'>..G=f'>..H-Tf'>..S
t..S I = t..S +
T'
f'>..C
_P
f'>..G ' =f'>..G+
dT
T' t..C,dT+(T - T')t..S - T' IT' f'>..C/dT

T
168

=!).G+(T-T')!).S+
J 1-TT')
r
T
!).CpdT
!).c
!).CP =/).a+ T !).b + y z
T')
/).c T' !).a
T' /). c
1 - - !).C = !).a +T!).b+ - 2 ----T'!).b- - T
P
T
T
T3
= f). a -
T' !).a !).c T' !).c

T' !).b + T !).b - - - +- - - T
yz
T3
(1 1)
T' !).c - - - T' !).a In-+

T
T T'
- i T'
/).c(;
2-
; ,, )
Therefore, !).G' = !).G + (T- T ' ) !).S +a !).a+ fJ !).b + y !).c

T'
where a = T' - T- T'lnT
fJ = t(T'' - T 2) - T ' (T' - T )
y = ~- ;, + i T' ( ;, ,-
;2)
For water ,
!).G f (T) = - 237 .13 k1 mol- 1
!).S 9 ('f)= -163 .341 K - 1 mol - 1
/).a = a(H 20) - a(H 2) - f a(Oz)
=75.48 - 27.28 - 14.981 K - 1 mol - 1 = +33.221 K - 1 mol - 1

!).b = 0-3 .26 X
w-} - 2.09 X 10 - 3 1 K - 2 mol -l = - 5.35 X 10 - 3 1 K -z mol - l
/).c=0 - 0.50 x 105 +0.83 x 105 1 K mol - 1 = +0.33 x 105 1 K mol - 1

T = 298 K, T' = 372 K, so
a = -8 .5 K, {J = -2738 K 2 , y= - 8.288 x 10- 5 K - 1

and so
~G /"(372
K) = -237.13 kJ mol- 1 + ( - 74 K) x ( -163.34 J K - I mol - 1)

+ ( -8.5 K)
+ ( -2738 K 2)
(33.22 X 10- 3 kJ K - I mol - 1)

X (-
5.53 X 10- 6 kJ K -z mol - 1)
+ ( -8.288 X 10- 5 K -
I)
(0.33 X 102 kl K mol - 1)
-237.13+ 12.09-0.28 +0 .015 -0.003 kJ mol - 1
-225.31 kJ mol - 1
Note that the f3 andy terms are not significant (for this reaction and
temperature range).
169
10. Equilibrium electrochemistry

Exercises
10.1
HgCiz(s)~Hg 2 + (aq)+2CI - (aq)
K=[Hg 2 +J[C1 - f
[CI - ] = 2 x [Hg2+ ]; therefore K = 4[Hg2 +jl

and the solubility of the salt is
S= [Hg 2+] = (.\-K) 113 M

From 6.G 9 = 6.G f'(Hg2+ ) + 26.G f'(Cn- t-.G f'(HgC12)
= + 164.40 + 2 x ( -131.23)- ( -178.6) kJ mol - 1 = +80 .54 kJ mol - 1
-80.54x10 3 Jmol - 1
lnK=~=8.314JK 1 moi 1 X298.15K
-6.G 9
32 9
.4
Hence K = 7.75 x 10- 15

and
S = 1.25 x 10- 5 M
10.2
t-.G 9 /(kJ mol - 1) [Section 10.1]
Dissociation of H 2
Ionization of H
Hydration of H +
Dissociation of X2
Electron gain by X
Hydration of x Overall
! H 2--7H
H--7H + +e H +(g)--7H +(aq)
iX"--7 X
X+e - --7x X - (g)--7 X - (aq)
+203
+ 1318
+203
+ 1318
+ 122
79
-348.7
-322
y
y'
t-.G f'(Cl - )
t-.G f"(F - )
Hence t-.G f (Cn =x + y + 1294 kJ mol - 1

D.G f (F - ) =x+ y ' + 1278 kJ mol - 1
and t-.G f'(Cn- t-.G f"(F - ) = y- y' + 16 kJ mol The ratio of hydration Gibbs functions is
D.G ff(F - )
t-.G ff(Cl - )
r(Cl - )
r(F - ) [I]
=
181 pm
pm [Example 10.3] = 1.38
131
[Table 2.5]
Equilibrium electrochemistry
171
Therefore, since LlG j'f(Cn = - 379 kJ mol - 1 (Example 10.3],

LlG j'f(F - ) = 1.38 x ( -379 kJ mol - 1) = -523 kJ mol - 1
and LlG f (Cl - )- LlG f (F - ) =- 379- ( -523) + 16 kJ mol - 1 = + 160 kJ mol - 1
Hence,
LlG f (F - ) = -131.23-160 kJ mol - 1 = - 290 kJ mol - 1
(The 'experimental' value , Table 2.10, is -278.79 kJ mol 10.3
I=!
1
.)
2: m;z1
and for an MaXh salt , m + =am, m _ = bm, so
I= t(az~ + bz2_ )m
/(KCI) =
! (1 + l)m = m
I(MgCI 2) = !(2 2 + 2 x l)m =3m

/(FeCI,)= t(Y + 3 x 1)m = 6m
/( Al 2(S0 4h) =! (2 X 32 + 3 X 22)m = 15m
/(CuS0 4) = j-(2 2 + 22)m = 4m
10.4
I= /(KCI) + I(CuS0 4 ) = m(KCI) + 4m(CuS0 4 ) [Exercise 10.3]

=0.10 + 4 x 0.20 mol kg - 1 = 0.90 mol kg - 1
10.5
I= /(K,[Fe(CN)"]) + /(KCI) + /(NaBr)

= }(3 + Y)m(K1 (Fe(CN)~>]) + m(KCI) + m(NaBr)
= 6 x 0.040 + 0.030 + 0.050 mol kg - 1 = 0.320 mol kg - 1
10.6
I= /(KNO,) = m(KN01) = 0.150 mol kg - 1
Therefore, the ionic strengths of the added salts must be 0.100 mol kg - 1
(a) /(Ca(NO,h) = 1(2 2 + 2)m =3m
Therefore, the solution should be made .\ x 0.100 mol kg - 1 = 0.0333 mol kg - 1
in Ca(NO,h The mass that should be added to 500 g of the solution is
therefore
0.500 kg x 0.0333 mol kg- 1 x 164 g mol - 1 = 2.73 g
(We are neglecting the fact that the mass of solution is slightly different from
the mass of solvent.]
172
(b) I(NaCI) = m; therefore , with m = 0.100 mol kg- 1 ,

0.500 kg x 0.100 mol kg- 1 x 58.4 g mol - 1 = 2.92 g
10.7
/(KCI) = m , I(CuS0 4 ) = 4m
For J(KCl) = /(CuS0 4 ) , m(KCl) = 4m(CuS0 4 ).

Therefore, if m(KCl) = 1.00 mol kg- 1, we require m(CuS0 4 ) = 0.25 mol kg - 1
10.8
Y =(y'~y'~ ) 11 s
s=p+q[4a]
with p = 1, q = 2, s = 3, Y+ = (y +y~.-)" 3
10.9
/(LaCI 3) = +{3 2 + 3)m = 6m = 3.000 mol kg - 1
From the limi ting law,

lg Y = -0.509lz +z_I(I/mol kg - 1) 112
= -0.509 X 3 X (3.000) 112 = -2.64S
Hence
Y = 2.3
10- 3
and the error is about 1 x 104 per cent(!).
-Aiz+z -1 1 112
10. 10
lgy =
1+81112
[7]
For HBr , f=m and lz +z_ l=1 ; so

0.509)
1
8=- ( - , +- m~ 'lg Y
[m = m!m 9 ]
Hence, draw up the following table:

5.o x
Y
8
w-'
0.930
-2.01
10.0 x
0.907
-2.01
w-'
20.0 x
0.879
-2 .02
w-)
t.G 8 = -RTln K, = -8 .314J K - I mol - l X 298.15 K X In 3.9 X

= +59.4 kJ mol -
- ll
= t.G f (CaF 2 , aq) - t.G f (CaF 2, s)

Hence.
t.G f'(CaF 2, aq) = t.G 8 + t.G 1 (CaF 2, s)
= 59 .4-1167 .3 kJ mol - 1 = - 1107. 9 kJ mol - 1
RT Y m 1
20 .0 x 0.879
=-F In-- = 25.7 mY x In O O
5 X . 930
Ym 2
=34.2 mY
10.13
8 =+1.36Y
R:
Cl2(g)+2e - ---.,;2Cl- (aq)
L:
Mn 2+(aq)+2e - - Mn(s) 8 =?
T he call corresponding to these half-reactions is

Mn iMnCI 2(aq) IC12(g)IPt
8 = 1.36 Y- 8 (Mn, Mn 2 +)
Hence , 8 (Mn , Mn 2+) = 1.36 Y- 2.54 Y = - 1.18 Y

10.14
(a) R:
L:
Overa ll (R -L):
(b)
+ 0.80 y
zn +(aq) + 2e - - Zn(s)
- 0.76 y
2Ag+(aq) + Zn(s)---.,; 2Ag(s) + Zn 2 +(aq)
R : 2H +(aq) + 2e - - H 2(g)
L:
R -L:
(c)
2Ag +(aq) + 2e - - 2Ag(s)
R:
L:
R-L:
Cd 2 +(aq) + 2e - -Cd(s)
-0.40 y
Cd(s) + 2H +(aq) -Cd 2 +(aq) + H 2(g)
+0.40 y
Cr' +(aq) + 3e - -..,.cr(s)
- 0.74
4
3[Fe(CN),J'- (aq) + 3e - - 3[Fe(CN),] - (aq)
+0.36 y
Cr'+ (aq) + 3[Fe(CN).,] - (aq)- Cr(s)

+ 3[Fe(CN),,J' - (aq)
(d)
+ 1.56 y
- 1.10 y
R:
Ag 2CrO.J(s) + 2e - - 2Ag(s) + Cro~ - (aq)
+0.45 y
L:
Cl,(g) + 2e - - 2Cqaq)
+ 1.36Y
173
174
R-L:
Ag2Cr04(s) + 2Cl-(aq)
~2Ag(s) + Cro~-(aq) + Cl 2(g)
-0.91 y
Sn +(aq) + 2e - ~ Sn +(aq)
+0.15 y
+0.77 y
R-L:
2Fe 3 +(aq) + 2e- ~ 2Fe 2 +(aq)

Sn 4+(aq) + 2Fe 2 + (aq)~ Sn 2 +(aq) + 2Fe 3 +(aq)
-0.62 y
(f) R:
Mn0 2(s) + 4H+(aq) + 2e - ~ Mn +(aq) +2H 20(/)
+ 1.23 y
Cu +(aq) + 2e- ~ Cu(s)
+0.34 y
Cu(s) + MnOb) + 4H +(aq)

~ Cu 2+(aq) + Mn 2 +(aq) + 2H 20(l)
+0.89 y
(e) R:
L:
L:
R-L:
10.15 We first identify the half-reactions , and then set up the corresponding
cell :
(a) R:
Cu 2 +(aq)+2e - ~Cu(s)
+0.34 y
L:
Zn +(aq)+2e - ~Zn(s)
-0.76 y
Hence the cell is

Zn(s) IZnS0 4(aq )IICuS04(aq) ICu(s)
(b) R:
L:
AgCI(s)+e - ~Ag(s)+Cl - (aq)
H +(aq) + e - ~!H2(g)
+1.10 y
+0.22 y
and the cell is

Ptl Hlg) IH +(aq) IAgCI(s) IAg(s)
or PtiH 2(g)IHCI(aq)IAgCI(s)IAg(s)
(c) R:
L:
0 2 (g)+4H + (aq)+4e - ~2H 2 0(l)

4H + (aq)+4e-~2H 2 (g)
+0.22 y
+ 1.23 y
0
and the cell is

PtiH2(g)IH+(aq), o-(aq)I02(g)IPt
(d) R:
L:
+ 1.23 y
2H 2 0(/)+2e -~ 2oH - (aq)+Hlg)
-0.83 y
2Na+(aq)+2e - ~2Na(s)
-2.71 y
and the cell is
175
or more simply
Na(s) IN aOH(aq) IH2(g) IPt
+0.54 v
1 2 (s)+2e - ~21 - (aq)
(e) R:
L:
2H + (aq)+2e - ~H 2 (g)
and the cell is

+0.54 v
or more simply
Ptl H 2(g) IHI(aq) II 2(s) IPt
10.16 See the solutions above, where we have used E 9 = E ft - E f!
2TI + (aq)+2e - ~2TI(s)
R:
10.17
Hg +(aq)+2e - ~Hg(/)
L:
(b) Overall: 2TI+(aq) +

a(Hg 2+)
Hg(l)~2Tl(s)
-0.34V}
0.86Y
(a) E 9 = -1.20 V
+ Hg 2 +(aq)
Q= a(TI +?' v= 2
E = E9
RT
-
vF In Q [11]
=-1.20V
25.693mV
2
0.150
Xln _
0 932
= -1.20 v + 0.023 v = -1.18 v

(a) 2Na(s)+2H 2 0(l)~2NaOH(aq)+H 2 (g)
10.18
E 9 =+1.88Y [Exercise
10.16d]
Therefore , 6.G 9 = -vf 9
= -2 x 96.485 kC mol - 1 x 1.88 V = -363 kJ mol - 1
2K(s)+2H 2 0(/)~2KOH(aq)+H 2 (g)
9
= 9 (H 20, OH - , H 2)- E 9 (K, K +) = -0.83 V- ( -2.93 Y)
(b)
=+2.10V with v=2

Therefore, 6.G 9 = - 2 x 96.485 kC mol - 1 x 2.10 V = -405 kJ mol - 1
176
S 2 0~- (aq) +2e - -72SO~- (aq)
(c) R:
+2.05 Y}
+1.51 y
12(s)+2e - -?21 - (aq)
+0.54Y
!lG 9 = -2 x 96.485 kC mol - 1 x 1.51 Y = -291 kJ mol - 1
L:
(d) Zn 2 +(aq)+2e - -7Zn(s)
-0.76Y}
9 = -0.63 y
Pb- +(aq)+2e - -?Pb(s) -0.13Y
!lG e = -2 x 96.485 kC mol - 1 x ( -0.63 Y) = + 122 kJ mol - 1
?
10.19
- !lG 9
+62.5 kJ mol - 1
(a) E e =~= 2 x 96.485 kC mol - t= +0.324 y
(b) 9 = 9 (Fe>+ , Fe 2+) - 9 (Ag , Ag 2Cr0 4 ,
Cro~- )
Therefore,
9 (Ag, Ag 2Cr0 4 , Cro~- ) = 9 (Fe>+, Fe 2+)- 9
= +0. 77 - 0.324 y = +0.45 y
10.20
R:
L:
Cd2+ (aq)+2e - -?Cd(s)

2AgBr(s) + 2e- ---7 2Ag(s) + 2Br- (aq)
Hence , overall (R- L) :

Cd 2 +(aq) + 2Ag(s) + 2Br- (aq)-7 Cd(s) + 2AgBr(s)
1
Q = a(Cd 2 +)a(Br-) 2
RT
E = 9 + - In a(Cd 2+)a(Br- )2
2F
RT
2.303RT
= 9 + F In m(Cd 2 +)m(Br- )2 +
lg Y (Cd 2 +)Y (Br - )2
F
2
Igy(Cd +) = -Aiz +z- II , /=3m=0.030mol kg - 1

= -0.509 X 2 X (0.030) 112 = -0.18
lgy(Br - ) = -A iz +z_l/ 112 , /=m=0.050mol kg - 1
= -0.509 X 1 X (0 .050t 2 = -0.11
Hence,
25.693 mY
E= -0.47 Y +
In 0.010 x 0.050 2
2
112
2.303
25.693 mY
(- 0.18+2x(-0.11))=-0.62Y
2
-0.40 y
+0.07 y
-0.47 y
Equ ilibrium electrochem istry
2Ag(s) + Fe~+ (aq)___.,.2Ag + (aq) + Fe(s)
10.21
E = (Fe 2+, Fe)- 9 (Ag +, A g)= -0.44-0.80 V = - 1.24 V

9
!'!.G 9 = 2/'!.G f (Ag +, aq)- !'!.G f>(Fe' +. aq)

=2 x 77 . 1 - ( -78 .90) kJ mo l- 1 = +223. 1 kJ mol - 1
= 2!'!.G 8 (Ag +, aq)- !'!.G ((Fe ~ + . aq)
!'!.H 9
=2
a!'!.G 9 )
-( aT
x 105.58- ( -89.1) kJ mol - 1 = +300.3 kJ mol - 1

=-!'!. 5 =
!'!.G
01
!'!.H
[!'!.G=!'!.H-T!'!. S ]
"(223.1- 300.3) kJ mol 298 . 15 K
- 0 .259 kJ mol - 1 K
Therefore, !'!.G 9 (333 K) ""'223. 1 + 5 K
- I
x ( -0 .259 K - 1) kJ mol - 1
""' +22UskJmo l- 1
10.22
C u,(P0 4 Hs) :;:::= 3Cu' +(aq) + 2P01- (aq)
K,P = a(Cu' -.- ) 1 a(Po~ - )~ ""' m(Cu 2 + )'m(P01- )2

(a) S= m(Cu,(P0 4) 2) = \m(C u 2 +)
Howeve r . m(Po ~ - ) = ~ m(Cu ~+ )
Therefore
. ,.1es t h at '(' =
K 'I' = 4,11n (C u-, +)', w h.1c h 1mp
115
x ( 'I K 'I' )
Hence ,
S= .\
xn
X 1.3 X lo- ' 7t'= 1.6 X Io- ~ [mol kg -
1
]
(b) The cell react ion is

R:
C u 2 +(aq)+2e - ___.,.Cu(s)
L:
2H+ (aq) +2e - -->H~(g )
Overall: Cu 2 +(aq)
+0.34
()
+ H 2 (g)--> Cu(s) + 2H +(aq)
From the Nernst eq uation ,
RT
E=E e - - ln Q
vF
25.693 x IW ' V
= 0 .34V -
a(H +) 2
ln a(Cu +)
+ 0 .34
177
178
25 .693 x
= 0.34 Y-
w- 3 Y
In
1
X _ x
16
w- x[m(Cu 2 +) = 35]
=0.34 y -0.22 y = +0.12 y

10.23
R:
L:
(a) Sn(s) +
Sn 4 + (aq)~2Sn 2 +(aq)
Sn 4 ++2e--?Sn 2 +(aq)
2
Sn +(aq)+2e - -?Sn(s)
+0.15Y}
-0.14 Y
9 = +0.29 y
vF 9
2 X 0.29 Y
_
In K =Iff= 25.693 my= 22.6, K = 6.5 x 109
(b) Sn(s) + 2AgCI(s)~SnCI 2 (aq) + 2Ag(s)
R:
L:
2AgCI(s)+2e - -72Ag(s)+2CI - (aq)
+0 .22Y}
Sn +(aq)+2e - -7Sn(s)
InK=
-0.14Y
2X 0.36 Y
_
_ mY= +28.0, K = 1.5 X 10 12
25 693
(c) 2Ag(s) + Cu(N01Maq) ~Cu(s) + 2AgN01(aq)

R:
Cu 2+(aq)+2e - -?Cu(s)
+0.34Yl
L:
2Ag+(aq)+2e - -?2Ag(s)
+0.80Y
InK=
-0.46 y
2 X ( -0.46 Y)
_
_ mY =-35.8,K=2. 8x i0 - 1h
25 693
(d) Sn(s) + CuSO.(aq)~Cu(s) + SnSO.(aq)
R: Cu 2 +(aq)+2e - -?Cu(s)
L:
Sn +(aq)+2e - -?Sn (s)
+0.34 Y}
+0.14
+0.48 y
2 X 0.48 Y
_
InK= 25.693 mY= +37.4, K = l.7 x IOih
(e) Cu 2+(aq) + Cu(s) ~2C u +(aq)

R:
Cu 2 +(aq)+e - -7cu +(aq)
+0. 16Y}
L:
Cu +(aq)+e--?Cu(s)
+0.52Y
InK=
-0.36 y
_ my
25 693
- 14.0, K = 8.2 x 10- 7
-0.36 y
+0.36 y
S(AgCI) = m(Ag +)
10.24
AgCI(s)~Ag+(aq)
+ Cqaq)
K,r = m(Ag +)m(Cl - )/m 6
Since m(Ag +) = m(cn
K,P = m(Ag+) 2/m 62 = S 2/m 62 = (1.34 X 10- 5) 2

= 1.80 x
w-w
S(BaS0 4) = m(Ba 2 +)
BaS0 4 (s)~Ba2+ (aq)
+ so~ - (aq)
As above, K,r=S / m e' =(9.51 x 10 - 4) 2 = 9.04 x 10 - 7

2
We can estimate the activity coefficients usi ng

lg Y = -A lz +z- 11 112 , A= 0.509
For AgCI, I=S, lz +z-1= l , and so
lg Y = -0.509 X (1.34 X 10- 5) 112 = - 1. 86 X 10- ' , Y = 0.9957
Hence , K,r=y~
X K~, [K ~,
calculated previously] = 0 . 991K~,
For BaS0 4 , /=45, lz +z- 1=4, and so

lg Y = -0.509 X 4 X (4 X 9.51 X 10 - 4 ) 112 = -0. 126, Y= 0.75
Hence K,r= y~K~,= 0.75 2 K~r=0 . 56K~r
Thus, the neglect of activity coefficients is significant for BaS0 4 .
10.25 The half-reaction is
Cr 2 0~- (aq)
+ 14H +(aq) + 6e----?2Cr'+ (aq) +7H 20(/)
The reaction quotient is

a(Cr1 +) 2
Q=
a(Cr 2 0~
)a(H +) 14
v=6
Hence,
10.26
R:
L:
2AgCI(s)+2e - ---?2Ag(s)+2CI-(aq)
0.22 v
2H +(aq)+2e - ---?H 2(g) 0
+0.22V}
179
180
Overall: 2AgCI(s) +
H 2 (g)~ 2Ag(s)
+ 2H +(aq) + 2Cqaq)
Q = a(H +)2a(Cn 2 v = 2
=a(H +) 4
[a(H +) = accnJ
Therefo re, fro m the Nernst eq uatio n,
RT
= 9 +2 X2.303 F
pH
Hence
F
pH= 2 X 2.303 R TX (-
E-0.22 V
9
)
= 0.1 183 V
0.322 v- 0.22 v
- - -- - =0.86
0.1183 v
10.27
R: AgB r(s) + e - ~ Ag(s) + Br - (aq)

L:
Ove rall :
Ag + (aq) + e - ~Ag(s)
Ag Br (s) ~
Ag+(aq) + Br - (aq)
Therefore, sin ce the cell reaction is the so lu bili ty equi li brium , fo r a sat urated
solution there is no further te ndency to dissolve and so E = 0.
+0.80
L:
Agl(s)+e - ~Ag(s)+I - (aq)
Overa ll (R-L) :
ln K=
0.9509V
.
V
25 693
v} - v
- 0.15V
Ag + (aq)+! - (aq)~Ag!(s)
+ 0.9509
v= 1
_
37 .010, K=l.l84 x 10 1fi
However, K ,r = K - I since the so lu bi li ty eq uilibrium is writte n as the reverse of

the cell reactio n. T herefore, K,P= 8.45 X 10- 17 The solubility is obtain ed fro m
m(Ag +) = m(I - ) and S= m(Ag +) , so K,r = m(Ag +)2 , im plying that
S = (K,p) 112 = (8.45 X 10- 17 ) 11 2 = 9. 19 X 10- 9 (mo l kg- 1]
Problems
10.1
R:
Hg~ SO.(s)+2e - ~2Hg(l)+SO~ - (aq)
+0.62V
L:
PbSOb)+2e - ~Pb(s)+SO~ - (aq)
-0 .36V
R- L:
Pb(s) +
Hg~SO.(s)~
PbS0 4(s) + 2Hg(/ )
+0 .9R V
He nce, a suitab le ce ll wo uld be
o r, a lte rn ati ve ly,

Pb(s) IPbSOis) IH,S04(aq)ll H ~S04(aq) IHg~ SO.(s) IHg(/)
Fo r the ce ll
Pb(s) IPbSOis) IPbS04(aq )IIHg~S04(aq) IHg~SO.(s) IHg(l )
T he electrode pote ntials ~t re
beca use K,r =a +a_ = (a _)'

T herefo re,
RT K, 11 (Hg~S0 4 ) 1 ;~
E= 0.98 V- 2F In K,"(PbS04)1 '~
RT K ,"(Hg~S0 4 )
=0. 98 V- 4F ln K (PbSO)
'P
25.693
=0.98V= 0.98
10.2
.t
IW V
6.6 X 10- 7
lnl. ox lO - x [Tab le l0.6]
v- 0 .024 v = 0.96 v
(a) H~(g)
+ lO,(g)~ H ~O(/)
t.G 0 = t.G ~'(H 2 0. /) = -237. 13 kJ mo l- 1 [Tab le 2. 10]

t.G
+237. 13 kJ mol- 1
Ee = ---=
=+ 1. 23V
vF
2 x 96.485 kC mo l- 1
181
182
(b) C4 H 111(g) + lf0lg)~4C0 2 (g) + 5H 20(/)

!l.G 9 = 4!l.G }"l(C0 2 , g)+ 5!l.G }"l(HP, /)- !l.G}"l(C4HIIl, g)
=4 x ( -394.36) +5 x ( -237.13)- ( -17.03) kJ mol - 1 (Tables 2.9 , 2.10]
= -2746.06 kJ mol- 1
To find the number of electrons transferred , note that the cathode halfreaction is the reduction of oxygen to produce 5H 20:
t Oz(g) + lOe - + 10H + (aq)~5H 2 0(!)
v= 10
Therefore ,
9
10.3
-!l.G 9
+2746 .06 kJ mol - 1

=~= 10 x 96.485 kC mol - 1 = + 2 85 y
Ptl H 2(g) IHCI(aq )J Hg 2Clz(s) IHg(l)
H2 (g) +
Hg 2 CI 2 (s)~ 2Hg(l)
+ 2HCI(aq)
v=2
a(H +) 2a(Cl - ) 2 y ~ m 2
Q= [(H2)/p 9 = flp 9
RT
RT
RT f
E= 9 --ln Q= 9 --lny m+-ln9
2F
f= yp with In y=
z;
J:: (
1
) dp
2F
(Chapter 5]
Therefore,
fl
In y=
J (5.37
10- 4 atm - 1 +3.5 X 10 -xp atm- 2 ) dp
II
= 5.37 X J0- 4 (p/atm) + 1
3.5 X 10-x(p/atm?
Hence , at 500 atm ,

lny=0.268S+0.0044=0.2729 , y=1. 314
At 0.10 mol kg- 1, y = 0. 798 (Table 10.4], so
RT
RT 500 atm x 1.314
E= 9 - - l n 0.798 x 0.10+-ln - -- -F
2F
1 bar
_
_ 25 .693 mY
In 1.314 X 500 X 1.0133
= 0.27 Y- 25.693 mY In 0.0798 +
2
183
= 0.27 y + 0.0650 y + 0.0835 y = +0.42 y

H 2(g)JHCl(aq)JCl 2(g)
10.4
RT
E=E e -2FlnQ ,
Q=
H 2(g)+Cl2(g)->2HCl(aq)
v =2
a(H +)2a(cl -}"

f(Cl2)/p e , E e =+l.36Y,f/p e =l
Form= 0.010 mol kg - 1 , Y= 0.905 [Table 10.4], a(H+)a(cn = y~ m 2

E = 1.36 Y -25 .693 mY In 0.905 2 X 0.010 2+25.693 mY In ( ;e)
= 1.602 Y + 1 X 25.693 mY In e
p
Therefore ,
f E-l.602Y
In p e = 0.0 1285 y
withp 9 = 1 bar
Hence , we can draw up the following table:

p/bar
1.000
50 .00
100.0
ElY
f!p e
y
1.5962
0.637
0.637t
1.6419
22.3
0.446
1.6451
28.6
0.286
t This seems abnormally low at this pressure .
10.5
H 2(g)JHCl(aq)JHg 2Clls)JHg(/)
E=E9
RT
-F In a(H +)a(cn
2RT
2RT
=E 9 - - l n m - - l n y
F
F
= E 9 - 0.1183 Y lg m + 0.1183 Y x Ax m 112 [Debye-Hiickel and

2 x 2.303RTI F= 0.1183 Y)
E + 0.1183 Y lg m = E 9
+ constant x m 112
Therefore, plot E + 0.1183 Y lg m against m 112 , and the intercept at m = 0 is

E 9 /Y. Draw up the following table:
184
(m/m e )ll2
EIY+0 .1183lgm
1.6077
3.0769
5.0403
7.6938
10.9474
0.04010
0.27029
0.05547
0.27109
0.07100
0.27186
0.08771
0.27260
0.1046
0.27337
The points are plotted in Fig. 10.1. The intercept is at 0.26835, so E e =

+0.26835 V. The least-squares best fit (Appendix) gives E e = +0.26838 V and
a coefficient of determination equal to 0.99895.
For the activity coefficients we form:
E e -E
m
In Y= 2RT/F -In me
m
0.26838- ElY
------ln0.05139
me
and draw up the follow ing table:

0-274
Fig 10. 1
0272
.Ql
.I
:0,.
027
Lil
/
L
02fJJ
0
(}02
004
006
008
0 10
(ml me) " 2
m/(mmol kg- 1)
1.6077
3.0769
5.0403
7.6938
10.9474
In Y
Y
-0.03562
0.9650
-0.05135
0.9500
-0.06639
0.9358
-0.08090
0.9223
-0.09597
0.9085
10.6
PtiH 2(g)iNaOH(aq), NaCl(aq)IAgCI(s)iAg(s)
H 2(g) + 2AgCl(s)---c> 2Ag(s) + 2Cl - (aq) + 2H +(aq)
E = E9
RT
F In Q, Q=a(H +)"a(cn"
2
[J!p 8 = 1]
RT
RT K,a(cn
8 - F In a(OH - )
RT
= E8 - -
v= 2
-F In a(H +)a(CI - )
= E8
185
In
Kwy +m(Cl - )
= E8
Ym(OH - )
RT K".m(Cn
- In----,--,------,F
m(OH - )
RT
RT
m(Cl - )
6
E - F In K"'-F In m(OH - )
= E
RT
RT
m(Ci- )
+2.303Fx pK"-F In m(OH - )
He nce,
pK"' =
E- 8
lnm(Cl- )/m(OH - )
2.303RTI F +
2.303
E-E 8
0 051 14
= 2.303RTI F +
We then draw up the follow ing table with E 9 = +0.2223 Y:
ere
20 .0
25.0
30.0
ElY
(2.303RTI F)!Y
pKw
1.04774
0.058 19
14.23
1. 04864
0.059 18
14 .01
1.04942
0.06018
13.79
d In Kw
6.H 8
RT
- = --2
dT
He nce,
186
=2 .303 X 8.3141 K- 1 mol - 1 X (298.15 K) 2 X
13.79-14.23
10 K
= +74.9 kJ mol - 1
t::..G 9 = -RT in Kw = 2.303RTx pKw= +80.0 kJ mo l- 1

t::..H 9 -t::..G 9
t::..S 9 =
-17 .1 J K - t mol - 1
T
See the origin al reference for a careful analysis of the precise data.
Ag(s)jAgX(s)jMX(m 1)jM,Hg(s)
10.7
Hg
R: M+(m 1) + e- -----'?M,Hg(s)
ama lga m]
L:
[Red ucti on of M + and for mation of
AgX(s)+e - ~Ag(s)+X - (m 1 )
J-Ig
Ag(s) + M+(m 1) +X - (m 1 )~MxHg(s) + AgX(s)
R- L:
v=1
a(M,Hg)
Q = a(M +)a(X -)
RT
=9 - F JnQ
For a pair of such cells back to back,
Ag(s)jAgX(s)jMX(m 1)jM,Hg(s)jMX(m 2 )jAgX(s)jAg(s)
RT
ER =
-F In QR
EL =
--
RT
RT
In QL
QL
RT
(a(M +)a(X - ))t.
F = - - In - = - In -:--:----,-.,.....-,--:-:.
F
QR
F
(a(M +)a(X ))R
2RT m 1 2RT Y( l)
=-ln-+--ln-F
m2
F
Y(2)
Take m 2 =0 .09141 mol kg - 1 (t he refe rence va lue), and write m =m 1/m 9
2RT ( In
m
E=-+In Y+
- )
F
0.0914 1
Y(ref.)
187
Form= 0.09141, the extended Debye-Hiickellaw gives

- 1.461 X (0.09141) 112
_
lg Y = 1 + 1.70 X (0.0 9141 ) 112 + 0.20 X 0.09141 = -0.2735
Y =0.5328
and
m
Y )
E=0.05139V x ( ln0.09141 +ln0.5328
In Y = 0.05139 V -In 0.09141
0.05328
We then draw up the following table:
ElY
y
0.0555
0.09141
0.1652
0.2171
1.040
1.350
-0.0220
0.572
0.0000
0.533
0.0263
0.492
0.0379
0.469
0.1156
0.444
0.1336
0.486
A more precise procedure is described in the original references for the

temperature dependence of E 8 (Ag, AgCl, Cl - ), see Problem 10.10.
10.8
H 2(g)IHCl(m)IAgCl(s)IAg(s)
t H 2(g) + AgCl(s)- HCI(aq) + Ag(s)

E= E 8
RT
2RT
2RT
-F In a(H +)a(cn = E 8 -F In m-F In Y
2RT
RT
= E 8 - F In m-2 x 2.303 F lg Y
Therefore, with 2RTI F x 2.303 = 0.1183 V,

ElY+ 0.1183lg m- 0.0602m 112 = E 8 !Y- O.J183km
hence, withy= ElY+ 0.1183lg m - 0.0602m 1' \

y = E 8 !Y - 0.1183km
[m ;; mfm 8 ]
188
We now draw up the following table:
123.8
25.63
9.138
5.619
3.215
0.2135
0.2204
0.2216
0.2218
0.2221
(a) The last three points are plotted in Fig. 10.2, and extrapolate to 0.2223 V,
02224
~
~a
Fig 10.2
02222
1\
aI
e:
.l2\ 0 2220
<'l
~
<:;' 0-2218
:::..
\
\.
02216
\
0
0004 0008 0012

m/mo/kg- 1
hence 9 = +0.2223 V.
2RT
2RT
(b) = 9 -Flnm-Flny
and so
In Y =
9 - E- 0.0514 V In m
0.0514 V
0.2223-0.3524- 0.0514ln 0.100
0.0514
= -0.2285, implying that Y = 0.796

Since a(H +)=y m/m 9 , a(H+)=0.796x0.100=0 .0796 , and hence
pH= - lg a(H +) = - lg 0.0796= 1.10
10.9 According to the Debye-Hi.ickellimiting law ,
lg Y= -0.509lz +z_ II 112 = -0.509(m/m e ) 112
189
[5]
1000m/m e
1.0
(//m e )1'2
2.0
0.032
0.964
0.9649
-0.0161
-0.0155
Y(calc)
Y(exp)
lg Y(calc)
lg Y (exp)
5.0
0.045
0.949
0.9519
- 0.0228
-0 .0214
0.071
0.920
0.9275
-0.0360
-0.0327
10.0
20.0
0.100
0.889
0.9024
-0.0509
-0.0446
0.141
0.847
0.8712
-0.0720
-0.0599
The points are plotted against I 112 in Fig. 10.3. Note that the limiting slopes of
0
Fig 10.3
r\
\.
0{)2
~
~
00
"
1\cE
heo
y~
pe imE nt
1\'I
"\
\. '\
0
004
0{)8
012
016
(//mol kg- 1) 112
the calculated and experimental curves coincide.
10.10
!:iCe =
-vFEe
At 298.15 K (25 .00 C) ,

e /V = 0.23659-4.8564 X 10- 4 X 25.00-3.4205
10- 6 X (25 .00) 2
+ 5.869 X 10- 9 X (25.00) 3 = +0.22240 V

Therefore, !:iCe = -96.485 kC mol - 1x 0.22240 V = -21.46 kJ mol - 1
c:Te) vF= vFC:Oe) ~

0
l::iS e =
[d(WC = dTIK]
190
w-9 e 2WC) 3
+ 3 x 5.869 x
(a:ee)P
I (V / C) = -4.8564
0
+ 1.7607 x
10 - 4 -6.8410 X 10- 6( e;oq
w-x(ercr
Therefore, at 25.00 C,
(a!~
and
= -6.4566 x
)
oT "= -6.4566
(aEe
w-
v;oc
10- 4 V/C X C/K = -6.4566 X 10- 4 V K -
Hence ,
t).Se = -96.485 kC mol - 1 x 6.4566 x 10- 4 V K - 1 = -62.30J K - I mol - 1
and !).H e = t).G e + T t).S e
= -21.46 kJ mol - 1 +298.15 K x ( -62.30 J K -I mol - 1)
= -40.03 kJ mol - 1
For the cell reaction
jH2(g) + AgCl(s)~ Ag(s) + HCl(aq)
t).G e = t).G f'(H +) + t).G f'(Cn- t).G f'(AgCl)
= t).G f'(Cn- t).G f (AgCl)
[t).G f (H +) =OJ
Hence
t).G f'(Cl - ) = t).G e + t).G f'(AgCl) = -21.46- 109.79 kJ mol - 1
= -131.25 kJ mol - 1
Similarly,
t).H f'(Cl - ) =!).He + t).H f'(AgCl) = -40.03-127.07 kJ mol - 1
= -167.10 kJ mol - 1
For the entropy of
o-
in solution we use
t).S e = s e (Ag) + s e (H +) + s e (cnwith s e (H +) = 0. Then,
~ s e(H 2 )-
s e (AgCl)
5 9 ( en= D,.S 9
191
S 9 (Ag) + t S 9 (H 2) + S 9 (AgCI)
= -62.30-42.55 + t x 130.68 + 96.2 = +56.8 J K - 1 mol- 1

10.11 Draw up the fol lowing table using Kr(H 20) = 1.86 K kg mol - 1 (Table
8.2]:
D,.T/K
=D,.T/2mKr
(1- )/(m/m 9 )
0.01
0.02
0.03
0.04
0.05
0.0355
0.955
4.500
0.0697
0.938
3.100
0.0343
0.925
2.500
0.137
0.922
1.950
0.172
0.926
1.480
( 1- )/ m is plotted against m in Fig. 10.4. The value of (1- )/m approaches

5
/ v\
/ v A.
/ / /\.
/ / / ~
/ / /'1/ /' >-..
/ / / v/ / ~
/ / / / / / v /. >--i/ / / / / / / / / /
v / 1/ / / 1/ / / / /
Fig 10.4
/ / / / / / / / / 7
0 01
002
003
m/mol kg-1
0 04
005
infinity as m~o, but we are confident about the validity of the Debye-Hi.ickel
limiting law in this region, and evaluate the integral analyt ically up to m =
0.010m9[See Problem 10.18 for details]:
m (
II
1 - - dm=_j_A'
3
m
I"' -dm= 1.A'm

J/1
II
m -
112
A'=2.303A
Therefore, up tom= 0.010m 9 the value of the integral is 0.0781. Above that
molality, evaluate the integral numerically. In the range from 0.010m 9 to
0.050m 9 its value is 0.106. Therefore,
In Y =0.926 - 1 - (0.106+0.0781) = -0.258
192
Hence Y = 0.77.
10.12
K '=
a
K. =
a(H+)a(A -)
a(HA)
y~m(H+)m(A -)
m(HA)
y~K~
m(H+)m(A -) a 2m
= -m(HA)
1- a
Hence,
lg K~ = lg K., - 2lg Y = lg K. + 2A(IIm e) 112
= lgK. + 2A(am) 112
[! = am]
We therefore construct the following table:
1000(am/ m 9 ) 112
105 X K~
lgK~
0.0280
0.114
0.2184
1.0283
2.414
5.9115
3.89
1.768
-4.753
6.04
1.779
-4.750
7.36
1.781
-4.749
11.3
1.799
- 4.745
14.1
1.809
-4.743
17.9
1.822
- 4.739
lg K~ is plotted against (am/m 9 ) 1' 2 in Fig. 10.5, and we see that a good
-474
-475
-476
~/
0 04
l.-"
0 08
./
.,.
012
/"
0 16
0 20
.V(<><c)
straight line is obtained.

10.13 The reduction reaction is
Sb20J(s) + 3Hz0(L) + 6e- ~ 2Sb(s) + 60H-(aq)

Q = a(OH-) 6 v = 6
Fig 10.5
Therefore,
(a) E= 9
= 9 +
RT
RT
Flna(OH - t= 9 -Flna(OH - )
6
2.303RT
F
pOH
(b) Since pOH+pH=pKw,

E= 9 +
2.303RT
(pKw- pH)
(c) The change in potential is

2.303RT
F
!).=
(pOHr- pOH;)
pOHr= -lg(0.050y) = -lg 0.050 -lg Y

= -lg 0.050 + AV(0 .050) = 1.415
pOH; = -lg(0.010y) = - lg 0.010 -lg Y
= -lg 0.010 + A V (0.010) = 2.051
Hence , !).= 59.17 mY x (1.415- 2.051) = -37.6 mY
10.14
t H 2(g) + Uup +(aq)-+ Uup(s) + H +(aq)
We draw up the following thermodynamic cycle:

H+ (g)+ Uup+(g)
13.6 eV
11 .3 eV
H(g) + Uup (g)

~X4. 5
eV
~H 2 + Uup(g)
H(aq)+ Uup (g)

5.2 eV
3.22 eV
H(aq)+ Uup(g)
~H 2 + Uup (aq)
1.5 eV
H (aq) + Uup(s)
Since the distance up on the left = distance up on the right ,

13.6 + t
4.5 + 3.22 +X = 11.3 + 5.2 + 1.5
193
194
which solves to x = -1.07 e V. Therefore:

t Hz(g) + Uup + (aq)~ Uup(s) + H +(aq)
!:!.H e =+ 1.07 eV
I:!.S e = s e (Uup, s) + s e (H +, aq) - t s e (H 2 , g) - s e (Uup +, aq)
= 0.69 + 0- 1 x 1.354-1.34 meV K - 1 = -1.33 meV K - 1

!:!.G e = !:!.H e - T !:!.S e = 1.07 eV +298 .15 K x 1.33 meV K _,
= + 1.47 e V, which corresponds to + 142 kJ mol - 1

The electrode potential is therefore -I:!.G e/vF, with v = 1, or -1.47 V
10.15
K , = a(M +)a(X - ) = m(M +)m(X - ) y ~
m(M +)=m(X - )=S

In Y= 2.303lg Y= -2.303 X 0.509 x 5 112 = -1.1725 112
Hence, KJy ~ = S 2
implying that
S = K~ '21 y , = K, eL ms''2
10.16
MX(s)~M + (aq)
+ x - (aq) , K, = m(M +)m(X - )
m(M +) = S , m(x - j = S + C
K, = S(S+C), or S 2 +CS-K, =O
which solves to
S =t( C 2 + 4K,) 112 - tC
lf4K, <;! C 2 ,
4K)''2-
S= i-C ( 1 + c
2'
tC
2K,) - t c
=t C 1+ c
((l+x) 1' 2 = l+ tx + ]
= K,IC
10.17
K, = a(M +)a(X - ) = m(M +)m(X - ) y ~
=S(S+ C ) x e-460MS I'2 [lg y = -A S ''2]

We solve
[m = m i m e ]
S 2 +SC-KJy;_=o
to give
S=1-(C 2 +4KJy ; ) 112 - j-C= KJCy ;_
[as in Problem 10.16]
Therefore, since
y;_ = e -4.h!l6AC '"
K , e +4.60MC"!
5= - ---
For t;,.T=
T1- T, d t;,.T= -dT
dIn QA -/':,.Hius -/':,.Hius

and d t;,.T = RT 2 = Rn
Therefore
dlnaA -MA
-MAd!;,.T
-d
T =-K anddlnaA=
K
/':,.
According to the Gibbs-Duhem equation [Chapter 7]

nA d,uA + n 8 d,u 0 = 0
which implies that

nA dIn aA + n 0 dIn all= 0
and hence that
[.u =,u 6
+ RTin a]
195
196
We know from the Gibbs-Duhem equation that

xA dIn aA +x 8 d lna 8 = 0
and hence that
JdIn aA= - J::dIn a
Therefore
The osmotic coefficient was defined in Problem 7.19 as
Therefore,
XAJXB- d In a
=-
xA
x8
1
=m
= -1
111
m d In a 8 = -1
m
Jill d In ym
0
Jill mdlnm+ -1 Jil mdlny=1+-1 Jil mdlny

m
From the Debye-Hi.ickellimiting law,

lny=-A'm 112
Hence
[A' = 2.303A]
dIn y= - !A 'm - 112 dm
and so
= 1+-(-!A')
Jill m
0
112
(A'm )
dm=l- f -
~m 3 12
= 1-jA'm 112
For the depression of freezing point in a 1,1-electrolyte
and hence
Therefore,
11HrusXA 11 T
11Hrus 11 T
Rx 8 T * 2
vRM 8 T * 2M A
where v = 2. Therefore , since Kr= MRT * 2111Hrus
197
PART 2: STRUCTURE
11. Quantum theory: introduction and

principles
Exercises
11.1
!Yi=aT 4 (9b)
P= aT 4 X A= 5.67 X 10- 8 W m- 2 K - 4 X (1500 K) 4 X 6.0 m 2

= 1.7MW
11.2
E=Pxt, E=Nhv
Pt
0.72 X 10- 6 W X 3.8 X 10- 3 S
v=-=
5.2x10 16 Hz
Nh 8.0 x 107 x 6.626 X 10- 34 J Hz - 1
11.3
h
p=mu and p="i (176]
Therefore,
6.626 X 10- 34 J
u=-=
mJ.. 9.109 X 10- 31 kg X 0.45 X 10
h
11.4 p=-x
(c) p=
11.5
1.6 X l0 6 ms- 1
(17b]
6.626 X 10- 34 J s
( a) p- 750 X 10 - 9 m
(b) p=
6.626 X 10- 34 J
70x10-1 2m
8.83x10- 28 kgms - 1
6.626 x 10- 34 1 s
m
19
9.5x10-24kgms - l
3.5x10- 35 kgms - 1
he
2
i-mu
=hv - 1= -),_ - 1
-
Quantum theory: introduction and principles

Hence, A.=
6.626 X 10- 34 J
he
,
1
1 + 2mv-
SX
2.998 X 108 m S- 1
= 5.06 X 10-x m = 50 .6 nm
11.6
oA. = -(1-cos e)
m cc
(16,1 8],A.c=-=2.43pm
mcc
= 2.43 pm x (1 -cos 70) = 1.60 pm

Therefore , A. 1 = 70 .78 + 1.60 pm =72.38 pm
11.7
~p = O.OlOO
per cent of p 0 , p 11 =mpv
= Po X 1.00 X 10- 4
1.055 x
w-34 1 s
= ----------~--------~--~--------~
2 X 1.673 X 10- 27 kg X 4.5 X 101 m S-
1.00 X 10- 4
= 7.0l X 10- IO m, or 70 nm
2 2
n h
) "2
Hence L = ( 8mE
nh
= (8m) 112
3 X 6.626 X 10- 34 J S
(8
6.65
10
27
kg X 2.00 X lQ
= 6.09 X 10 - 9 m, Or 6.09 nm
(L2)
112
:n:x
sinL (n=l]
24
J) 112
199
200
The wavefunction has its greatest value when
and at that location
The value of x at which lfJ 2 has 25 per cent of this value is the solution of
nx
-sin 2 - = - x -
nx
or sin 2 - =-
L 4
L
That is , x =:;arcsin = 0.17 L
[arcsin in radians]
and the location is at 0.17 L from the left or the right walls
x=0.17L
0.83L
- - or -
8X
11.11
9 X (6.626 X 10- 34 J s) 2
(2.0141 X 1.6605 X 10 27 kg) X (5.0 X 10
9 m)2
5 9 10 24
X - J
he
E=hv=;:
he= 6.62608 X 10- 34 J S X 2.99792 X 108 m S- l = 1.986 X 10- 25J m

NAhc = 6.02214 X 1023 mol - l X 1.986 X 10- 25 J m = 0.1196 J m mol-l
..:Unm
EIJ
(a)
(b)
(c)
(d)
(e)
(f)
3.31 X
3.61 X
4.97 X
9.93 X
1.32 X
1.99 X
600
550
400
200
150pm
1.00 em
10 - 1 ~
10- 19
10- 19
10- 19
10- l>
10- 23
201
El(kJ mol - 1)
p/(kgms - 1)
199
218
299
598
7.98 X 105
0.012
1.10 X 10 -27
1.20 x w- 27
1.66 x w- 27
3.31 x w- 27
4.42 X 10- 24
6.63 X 10- 32
.
h 6.626 X 10- 34 J s
11.12 p = )..=
,
; the entries are in the table above.
11.13 If a photon is absorbed, the atom acquires its momentum p. It

therefore reaches a speed u such that p = mu. We use
mH
= 1.008 U = 1.008 X 1.6605 X 10- 27 kg= 1.674 X 10- 27 kg
and draw up the following table using the information in the table above:
..:Unm
600
550
400
200
150pm
1.00 em
ul(m s- 1)
0.66
0.72
0.99
1.98
2640
3.96 X 10-s
11.14 The energy of a photon of 650 nm light is E =he/ A with A= 650 nm. The
total number of photons emitted in an interval r is
Pr PrA
=E
he
N=-
with P = 0.10 Wand r = 10 y. The total momentum emitted is
Nh PrA h Pr
=X-=A
he A c
p= -
202
The momentum is acquired by the source, and since its mass is m, and
p = mv, its final speed is

Pr
0.10Js - 1 X3.16X10 8 s
em
2.998x10 8 ms- 1 x5 .0xl0 - 3 kg
v=-=
= 21ms- 1
Note that the answer is independent of the wavelength of the radiation
emitted: the greater the wavelength ther smaller the photon momentum, but
the greater the number of photons emitted.
11.15
p
N= hv
p).
[P=power in J s- 1]= he
6.626 X 10- 34 J Hz - 1 X 2.998 X lORm s- 1

=
(P!W) x (J../nm) s- 1
1. x _ 16
=5 .03xl0 15 (P/W)x(A/nm)s - 1
99 10
(a) N = 5.03 X 10 15 X 1.0 X 550 s- 1 = 2.8 X 10 18 s- 1

(b) N=5.03xl0 15 X l00 x 550s - 1 =2.8 x l0 20 s- 1
11.16 From Wien's law,
n.,.,x= tcz= 1.44 em K [8]

Therefore ,
1.44 em K
T= 5 X 480 X 10- 7 em
11.17
600
he
+mv 2 = hv- <t> = - -
J..
<l> =2. 14 eV ~ 2.14 X 1.602 X 10- 19 J = 3.43 X 10- 19 J
(a) hc!J..=
6.626 X 10- 34 J S X 2. 998 X lQR Ill

700x 10 9 m
= 2.84 X 10 - 1'1 J < <l> ,
SO
S- 1
no ejectio n occurs
19
(b) hc/J..=6 .62 x !0- J

Hence
~ mv 2
= (6.62- 3.43) X 10 - 19 J = 3. 19 X 10- 1'1 J
2 X 3.19 X 10- 19 J) 112

u= ( 9.109 x 10 31kg
=837kms - l
11.18
oA. = A.,(1- cos 8)
[16] =A., when 8 = 90
(a) A.c = 2.43 pm [16], so oA. = 2.43 pm

h
(b) Ac= mrc
[18 , mc--7 mp]
1.673 X
6.626 x w- 34 1 s
1.32 X 10- ISm
10 27 kg X 2.998 X 10Km S- 1
Therefore, OA = 1.32 fm
h
!!.E = hv=T [T= period]
11.19
(a) !!.E=
6.626 x w- 341 s
w-1 5s
corresponding to N A
(b) !!. E =
7X
7 x 10- 19J
w-19 J = 400 kJ mol - l
6.626 x w-34 1 s
1
= 7 x 10- 20 J4
, -"O::. . :k!::.J__,_,m"-'o'-'--1-_
w - 14 s
A= - = p mu
11 .20
6.626 x 10 - 34 1 s
6.6 X 10 - 29 m
( a) A- 1.0 X 10- 3 kg X 1.0 X 10 - 2m S - I
( b) A-
- 1.0 X
(c) A.-4.003
11.21
6.626 x w-341 s
6.6 X 10 - 36 m
10 3 kg X 1.00 X 10 5 m S 1
~-mu 2 =
6.626 x w- 34J s
] .6605 X 10- 27 kg X 1000 m S
99.7 pm
2e !!.) 112
e !!., implying that u = ( ----;;;-
and
203
204
that p = mv = (2mef'... ) 112 . Therefore ,

h
A. =- =
p
h
..,...-----,--=
112
(2mef'...)
6.626 X 10- 34J S

(2x9.109 x 10 31kg x 1.602 x 10 19C x f'...) 1'2
1.226 nm
= (f'.../V) I/2 [1 J = 1 c V]
(a) /1 = 100 V, A.=
1.226 nm
10.0 = 123 pm
(b) f'...=l.OkV , A. =
1.226 nm
1.
3 6
39pm
(c) f'...=100kV , A.=
1.226 nm
.
316 2
3.88pm
11.22
f'...pf'...q~ fh , f'...p=mf'...v
1.055 X 10- 34 ] S
f'...vmin=2m f'...q = 2 X 0.500 kg X 1.0 X 10
h
6m
1.1 x 10 - 28 m s- 1
h
1.055 X 10- 34 J S
1 x 10- 27 m
f'...qmin =2m f'...u = 2 X 5.0 X 10- 3 kg X 1 X 10 - 5 m s- 1
1.055 X 10- 34 ] S
f'...pmin = 2f'...q = 2 X 100 X 10- 12 m = 5 X 10- 25 kg m S- 1
h
11.23
c
2
=hv-l v= 11.24 +mu
'"
,
A.
6.626 x 10- 34 J s x 2.998 x 108 m s- 1
l=T - ! mv =
150 X 10- 12 m
he
-f
9.109 X 10- 31kg X (2.14 X 10 7 m s- 1? = 1.12 X 10- 15J
205
Problems
11.1
8nhc (
p = ---;:s- e'"m r -1
1.439 X 10- 2 m K
he
8nhc
[12], ~au=p~A,A=652 . 5nm
2.205 X 104 K
Ak -
8n X 6.626 X 10- 34 1 S X 2. 998 X 10Hm S-
(652 .5 X 10
~au= 4.221 X 10 1 m7
X (
m)
e 22 osx
II~
KI T _
)
1
4.221 x 107 1 m - 4
5 X 10 - 9 m
0.211 1m - 3
(a) T = 298 K, ~au= e220Sx lo-'/29R-1 = 1.6 X 10-33 1 m -3
0.2111 m - 3
(b) T = 3273 K, ~au= e2.2US xlo-'/3273_1 = 2.5
11.2 AmaxT = hc/5k

he
Amax= 5k
10- 4 1 m - 3
[8, and c2 = hc!k]. Therefore
xT
and if we plot Amax against liT we can obtain h from the slope. We draw up
eloc
T/K
104 /(T/K)
Amaxfnm
1000
1500
2000
2500
3000
3500
1273
7.86
2181
1773
5.64
1600
2273
4.40
1240
2773
3.61
1035
3273
3.06
878
3773
2.65
763
The points are plotted in Fig. 11.1. From the graph, the slope is 2.83 x 10~, so
he
nm
= 2 .83 X 10- 3 m K
-5k = 2 .83 X 1061/K
and
5 X 1.38066 X 10- 23 1 K - 1 X 2.83 X 10- 3 m K
h=
2.99792 X 1QH m S I
= 6.52 X 10- 341
206

2500
2000
v.
..
E 1500
I/
Fig 11 . 1
/v
r<
1000
f
/
500
8{)
60
40
20
r ( -1)
(10000/ T}K
I>
cU = 8nhc
11.3
au =
he
1.439 X 10- 2 m K
AkT
AT
e"c/Ak T
dA
[12]
[Problem 11.1]
8nhc = 4. 992 X 10- 24 J m
For A1 = 350 nm, A2 = 600 nm

(a) OU(100C)=7.47 x 10- 29 Jm - 3
(b) OU(500 C) = 4.59 x 10- 14 J m- 3
(c) OU(700oC)=3.49xl0- 11 Jm - 3
[Using standard integration programs.]
For the classical calculation , use p = 8nkT/ A4 [10]; then
OU=
2
J2cU 8nkT ( 1 1)
J pcU=8nkT y =- M-M
1
= 8; X 1.381 X
w-n J X (T!K) X { (3 .50 X
= 2.16 x 10- 3 J m - 3 x (T!K)

Then ,
(a) OU(100 oC)=0.807 J m- 3
(b) OU(500 C)=l.67Jm- 3
(c) OU(700 C)=2.10Jm- 3
\o
-7 mr- ( 6.00 X 110 -7 mr}
207
All three classical values are very much larger than the quantum values.
Js x s- 1
hv
11.4
8E=k, (8E] = J K - 1
The Einstein formul a [14] reverts to the classical expression when kT ~ hv, or
T ~ hv/ k = eE . The criterion for classical behavior is therefore that T ~ e E
6.626 X 10 -> 4 J Hz - \ X v
11
8E=k = 1. 381 x 10-l> JK _1 =4.798 x 10- (v/Hz)K
hv
(a) For v=4.65 X 10 13 Hz, 8E=4 .798x 10 - 11 X 4.65 X 10\J K=223l K

(b) For v=7.15 X 10 12 Hz , 8E=4 .798 X 10 - \\ X 7 .15 X 10 12 K=343 K
(jE)2{ e
(T e
V 2T
11 1.,.
Cv = 3R-
}2
(14],classicalvalue=3R
-1
2231 K) 2 { e22.1 1 12 x2~x } 2

(a) Cvi3R= ( 298 K
X em ll29x_l =0 .031
4
343 K) 2 { e> J12x2<JX } 2

(b) Cvi3R = (
K x e:~4 :~ 129 x _
= 0.897
298
1
115
.
2
nx
1f' 2= -L sin 2-L
The probability that the particle will be found between a and b is
P(a,b)=fh
1f! 2 dx=~fh sin 2
= (
=
dx
Z- L
sin
2~x) I ~'
b~a- ;n(sin 2~b -sin 2~a)
L=10 .0nm
0 .1 0 1 (
2nx5.05
(a) ?(4.95 , 5 .05 ) = 10.0- n sin
lO.O
2
= 0.010 + 0 .010 = 0.020
. 2n x 4.95)
sm
.
10 0
208
0.10 1 (
2nx2.05
(b) P(l.95, 2.05) = 10.0- 2n sin 10.0
. 2n x 1.95)
10.0
sm
= 0.010-0.0031 = 0.007
2nx10.0
0.10 1 (
(c) P(9.90, 10.0) = 10.0- 2n sin 10.0
. 2nx9.90)
sm 10.0
= o.o10- o.oo9993 = 6 x 10- 6

(d) P(5.0, 10.0) = 0.5
[by symmetry]
1 1 (
4n- sin2n) =061
(e) P(J-L
3 , ~L) =--3 2n sin 3
3
_._
0
If we assume that the volume otis so small that '1/J does not vary within it , the
probability is given by
(a)
r=O:
'l/J 2 or = ~e~y =9.0 x10(b)
r= a
11.7 We look for the value of A. at which pis a maximum , using (as
appropriate) the short wavelength (high frequ~ncy) approximation,
8nhe(
p = v ehc/!.kT -1
dp
5
he ( e"cl!.kT )
dA.= -;: p+A.2kT e"ci!.kT _1 p = O
he e'"t!.kT
- 5 + A.kTe"ci!.kT -1 = 0

Hence
he
5 _ 5 e"c/U T + __ e"cll.kT = 0
J..kT
and if he/ J..kT 'P 1, we neglect the initial 5, cancel the two exponenti als , and
obtain
he= 5J..kT for A= Amax and he/ AkT'P 1

or
he
J..m .. J =Sk= 2.88 mm K, in accord with observation.
11.8 Refer to Fig. 11.2.
Fig11 2
Energy : hv;
Mommtum: h/A.;
Energy: hut
Mommtum: h/A. f
(1) Energy conservation:
hv; + mcc 2 = hvr + (p 2c 2 + m~c 4 ) 112
(2) Momentum conservation:

hv; hvr
Parallel: - =-cos
c
c
e+ p cos e
Perpendicular: 0 = hvr sin e- p si n e
From condition (2):
209
210
p 2 cos 2 8'
hv
hvr
)2
(hvr
+ p 2 sin 2 8' = ( ~-----;;cos 8 + ----;;sin 8
)2
h2
---:;-(vr + vf - 2v;vr cos 8)
c-
But from condition (1):

p 2c 2 = (hv; + mcc 2 - hvr) 2 -
4
m cC
which imp lies that
and that
V;-Vr
h
- - = - -2 ( 1 -cos 8)
V;Vr
V;-Vr
But
mcC
Ar-A;
- - =- - V;Vr
Vr
V;
--
OA
Therefore,
h
oA=-(l-cos8)
mcc
11.9 We req ui re
f 1/J *1p dr =
I , and so write 1/J = NJ and find N for the given f.
. 2mrx)
=iN-, ( x - -L s m
- - ~~-
2nJT
11
Quantum theory : introduction and principles
(c) N 2
J"' e- rt"r
2
dr
J'' sine d(:l
II
II
1
2
'
(dr = r 2 sin 8 dr d(:l d</J]
II
=N 2 (~) X2X2n=l if N=~

(d) N 2 J~ r 2 X r 2e - rlu dr
II
J'
sin'
ed(:l
II
'
cos 2 </J d</J
[x = r cos </J sin 8]
II
4
I
=N 24'a 5 X - X n=32na 5N 2 = I if N=
,
3
(32na 5) 11 -
where we have used
J cos" esin ed(:l

::r
II
= -
'
cos'
II
</J
d</J by symmetry
j'' d</J = 2n
II
11.10
(a)
x" dx
II
J""' (cos 2 </J + sin 2 </J) d</J =
with
f'
e d cos e=
- 1
j "' sin
d</J =
</J
cos"
and
J-1
1/J =N(2-~)
e - 'n ""
ao
1/J 2 =N 2 2--
r ) " e -.-~""
(
ao
1jJ 2 dr=N 2
x (
,~) e -d"" dr
4r ' ~
4r 2 --+
Uo
,(
Uo
I'
sin(:ld(:l
II
I''
d</J
II
6ai, 24a~)
=N - 4x2ai;-4 x - + -,- x 2 x 2n
a0
a,;
1 )
=32Jcai;N', hence N= ( _
32nao1
11 2
(b) 1/J=Nrsin8cose - ' 12" "
1/J
dr = N '
II
,~ e
-i2u,
dr
I"'sin ' esin I''

fidf)
II
II
2
COS </J
d</J
211
212
Quantum theory : introduction and principles
2) n=32naf/V 2 hence N= ( -1--)

=N 24'a 05 ( 2-1
.
3
32nag
"
11.11
1/ 2
d
(a) dx eikx =ik e;"-'; yes; eigenvalue= ik.
d
(b) dx cos kx = -k sin kx ; no.
d
(c) dxk = O; yes ; eigenvalue=O.
d
1
(d) dxkx =k= -;,;kx ; no (1/x is not a constant] .
d e-ax' = -2ax e- a.' ; no [ -2ax IS
. not a constant] .
(e) dx
d2
11.12
(a) dx 2 eikx = -k2 eikx ; yes; eigenvalue= -k 2
d2
(b) dx 2 cos kx =
-e cos kx ; yes; eigenval ue= -k
d2
(c) -k=O
' yes ' eigenvalue=O .
dx 2
d2
(d) dx 2 kx=O ; yes; eigenvalue=O.
Hence , (a, b, c, d) are eigenfunctions of d 2/dx 2; (b, d) are eigenfunctions of

d 2/dx 2 but not of d/dx.
11 .13
1fJ =
eikx cos x+ e - ikx sin X

(a) P = cos 2 x [since
eigenvalue +kh]
eikx
is an eigenfunction of the linear momentum with
(b) P = sin 2 x [since e- ik.r corresponds to the eigenvalue -kh]

(c) cos 2 x= 0. 90, so cos x=0.95; sin 2 x= 0.10, so sin
tjJ = 0. 95
11.14
eikx
+ 0.32 e - ik.r
(T)=N
ItfJ*(:~)tjJdr
I (f)
tfJ *
tfJ*tfJ dr
11.15
'k
dtjJ
a ) tjJ = e' ' , dx =
tfJ dr
'k
1 tjJ.
x= 0.32; hence
213
214
Hence
(p, )
=~ X ik
1/J *1/J dx
IJ
1/J *1/J dx = kh
d'f/J
(b) 1/J =cos kx , dx = -k sin kx
oo
J
d'f/J
- oo
1/J * dxdx=-k
J oo
-oo
cos kxsinkx dx=O
Therefore, (p x) = Q
2
d'f/J
'
(c) 1/J=e -ax , dx =-2axe -ax-
oo
-oo
d'f/J
1/J * dx dx=-2a
J~
-oo
x e- "'' dx=O
[by symmetry]
Therefore, (px) = Q
( Gor)
(a) 'f/J= 2-- e - ' 12" " , N= - 1- 3)
1/2
32.Jrao
[Problem 11.10]
r)
(r) = -1 - J oo r ( 2-- 2r 2 e - ' 1" 11 dr x 4.n

32.nG~
11
Go
1
= -3 (4 X 3!G~ -4 X 4!a~ + 5!G~) =6G 11
8Go
-
1
= -3 (4 x 4!-4 x 5!+6!)G~ = 42G~
8Go
1 )
32.n:G 0
(b) 1jJ=Nrsin8cose- '' 2" 11 , N = ( - -5
1/2
[Problem 11.10]

(r)---1
- 32.n:aft
1
J"' r'e-'
1011
11
4.n:
drX3
,x5!a~=5a 11
24 all
1)
(r 2) = --24 au
11.17
(V)=
I"
7
2
r~e -"""dr=--X61a
241 5 II =30a
_ _II
au
11
1 )
1./J = ( .n:a~
1/2
e -"""
1)
J (
-e
1./J* - - 7./Jdr
4.n: 11 r
[Example 11.8]
215
12. Quantum theory: techniques and

applications
Exercises
(6 .626 X 10- 34 J s?
.,----.....,-----::-::---:--:;-;-:---:-:--::---:-::--;;---:-:;
=
31
9
8x9 .109 x 10
kg x (l.O x 10
m?
6 02 X 10- 20 J
h2
(a) 2- 1 = (4 - 1) mcL 2= 3 X6.02 x l0 - 20J
8
= 18.06 x l0 - 20 J = l.81 x l0 - 19J , llOkJmol - 1, l.1eV , 9l00cm- 1
h2
llh 2
20
(b) 6- Es = (36 - 25) 8mcU = 8mcU = 11 X 6.02 X 10- J
= 6.6 x 10- 19J , 400 kJ mol- 1, 4.1 eV , 33 000 cm - 1
12.2
h2
E = (nf + n ~ +nDBmU
3h 2
9h 2
11 1= BmL2' 3111 = BmL2

Hence , we require the values of n 1, n2 , and n 3 that make
nf + n ~ + n j = 9
Therefore, (n" n 2 , n 3) = (1 , 2, 2) , (2 , 1, 2) , and (2, 2, 1) and the degeneracy is

3.
K
11 E
E
(D.9L)2 - [}
K!U
1
0. - 1 =0.23, or 23 per cent
81
Quantum theory: techniques and applications

=
12.4
cu + -t )hw,
(J)
(~r
k)J /2
Eu = t hw= t h ( ;;:;
=
12.s
1.055
f..E=hw
l0 -J4 J S X
155 N m - J ) 112
= 4.30 X 10- 21]
( 2.33 x w- 2h kg
[.,+ \-., =hwJ=h(~r
21
""')2
( 4.82 x w- 1 )2
25
Hence k = m ( h
= 1.33 x 10- kg X 1.
x _,4 J
055 10
5
=278Nm - 1 [1 J=1Nm)
12.6
he
f..E=hv = y and f..E=hw
he hw h (k)J t2
Therefore - = - = - ' }. 2n 2n m
.1.=2nc
(m) 112 =2n x2 .998 x 10xms - 1

k
27
(1.673 x
kg)
Nm-J
855
w-
= 2.63 X 10- 6 m= 2.63 ,um

112
12.7
[elementary physics)
(a) w =G)
f..= hw
[harmonic oscillator level separations)

112
1
= 1.055 X 10-' 4 J S X (
m ,) = 3.4 X 10-JS J
9.81 m s- -
(b) f..E=hv=6 .626

(c) f..= hv = 6.626
10-' 4J Hz-\
w-'
5 Hz =3.3
X w -)J
J Hz- \ X 33 X 10' Hz= 2.2 X 10- 29 J
1 12
(d)
f..E=hw=h(~)
~ = _2_+_2_ with m =m
.U
.U ml m2
1
2k) 112
( = 1.055
f..= h m
=3.14xl0- 211 J
(
X
10-34 J S X
2 X 1177 N m - I
) 112
16.00 X 1.6605 X 10- 27 kg
217
218
12.8
Since A.o::m 112 ,
Ancw =2 112A01d=2 112 X2.63,um=3.72,um
The change in wavelength is Anew- A01d= 0.09 ,urn
12.9 For rotation in a plane ,

[2h 2
E= (15 , I = mr 2]
2mr 2
2 X 1.055 X 10- 34 ]
[h
r= (2m)
112
(2 X 39.95 X 1.6605 X 10
27
kg X 2.47 X 10
23
1) 112
= 1.17 x 10 - 111 m = 117 pm
12.10 J ={I ( l + 1)} 112h

=2
1, =
o,
h =
112
o,
X h = 1.49 X 10- 34 ]
+ 1.06 x
2m(~ _ E)
2
with D = {
(21a],
w-
34
1s
and
E=
Therefore , with =0.90eV , V=2.00eV, L=0 .25nm , and m=m 0 ,
w-
34
1.055 x
1s
D= (2 X 9.109 X 10- kg X 1.10 X 1.60219 X 10- 19 J) 112 = 1. 86 X IQ -ICI m
31
E=
0.90
2.00 = 0.45
250 pm
D= 186 pm = 1. 344
(e I .J+i _ e - 1.344) 2
Hence , G = 4 x 0.45 x 0. 55
12 .90
and P=
+ 12 .90 = 0.072
12.12 The diagrams are drawn by forming a vector of le ngth {j(j + 1)} 112 with a
projection mi on the z axis (see Fig. 12.1). Each vector represe nts the edge of

(a}
(b)
(c)
219
Fig 12. 1
o~--------~2~i~49~--~
a cone around the z axis (that for mi=O represents the side view of a disk
perpendicular to z).
12.13 The cones are constructed as described in Exercise 12.12; their edges
are of length {6(6+ 1)} 112 =6.48 and their projections are mi = +6, +5, . . . ,
-6. See Fig. 12.2.
Problems
3h 2
n 2h 2
12.1
E = SmL 2,
2 -1=
SmL 2
We take m(0 2) = 32.00 X 1.6605 X 10- 27 kg , and find
220
_
34
=
3 X (6 .626 X 10- J s)
=
X
_ 39
24
1 8 X 32.00 X 1.6605 X 10- 27 kg X (5.0 X 10- 2 m) 2 1.
10 J
h2
Since 8mU = 4.13
40
10- J
for n 2 X 4.13 X 10- 40 J=tx 1.381 X 10- 23 J K -I

= 2.01 x 10- 21 J
300 K
2.07 x 10- 21J) 112

n = ( 4.13 X 10-40 J
= 2.2 X 109
we require
At this level,
= 1.8 X 10- 30 J
12.2
w=
G)
112
,
(or 1.1,uJ mol- 1)
w= 2.nv = ~c = 2.ncv
We draw up the following table using the information inside the back cover:
v/m - 1
1027m 1/kg
1027 m 21kg
ki(N m- 1)
IH35CI
1H 80Br
IHI271
12CI60
14N I60
299000
1.6735
58.066
516
265000
1.6735
134.36
412
231000
1.6735
210.72
314
217000
19.926
26.568
1900
190400
23.2521
26.568
1600
Therefore , the order of stiffness is CO > NO > HCI > HBr > HI

E 0 =0
221
[1=0]
2
h
(1.055 x 10- 34 J s) 2
E 1 - - -2 - -::-----:-::-::-::------:------:-:-::-::------:--::-:;:;-:---:-:-:---::----:--:-:;-----:-::
27
12
2
-
2mr
= 1.30 x
kg X (16.0 X 10
2 X 1.008 X 1.6605 X 10
10- 22 J
m)
(1.96x 10 11 Hz)
The minimum angular momentum is h.
12.4
E=
J(J+1)h 2
[20,I=w 2J
w
2 2
J(J + 1) X (1.055 X 10- 34 J s) 2
= 2 X 1.6605 X 10
27
kg X (160 X 10
=J(J + 1) x 1.31 x 10- 22 J
12
(
1
1 )
m) 2 1.008 + 126.90
(equivalent toJ(J + 1) x 198 GHz)
Hence the energies (and equivalent frequencies, from E = hv) are:
1=
1022 EIJ
v/GHz
0
0
2.62
396
7.86
1188
15.72
2376
({)2 {)2 {)2)
12.5
h2
- 2m ax2+ ayl + az 2 1/J = E1jJ
We try the solution 1jJ=X(x)Y(y)Z(z):
h2
--(X"YZ + XY"Z + XYZ") = EXYZ

2m
2
(X"
Z")
- h- - + Y"
- + - =E
2m X
Y
Z
X"! X depends only on x; therefore, when x changes only this term changes,
but the sum of the three terms is constant. Therefore, X" IX must also be
constant. We write
h 2 X"
- m X= Ex, with analogous terms for y , z
2
222
Hence we solve
h2
- - X"=Exx
2m
The three-dimensional equation has therefore separated into three onedimensional equations, and we can write
h (n~ n~ n ~)
E = m L~+ L~ + L~
8
2
n 1, n 2 , n 3 =1 , 2, 3, ...
_(-8)"2 . (n .n:x) . (n2.n:y) . (n .n:z)

1
1/J -
L L L
I
Sin
Sin
Sin
For a cubic box
(b) (x)=
I~ X1/J 2dx=N 2I~ xe- n dx

2
N 22!
N2
(2x/- 2K 2 - "!
12.7 Proceed as in the example, matching the amplitudes and slopes of the
wavefunctions at the interfaces of the zones.
Zone A: 1/J A= A
e;~u
+A' e - ik.r
k= (
2mh
112
2m(Vh2
)}"2
ZoneB:ljJ 8 =Be"' +B'e -Kx
K =
Zone C: 1/Jc = C eik'x + C' e- ik 'x
k , ={2m(h2
V')}"2
Quantum theory : techniques and applications

The boundary conditions are
C' = 0 [No particles from right]
1/J A(O) = 1/J 6 (0), implying that A+ A'= B + B'

1/J~(O)
= 1/J8(0), implying that ikA- ikA' = xB - xB'
1/Js(L) = 1/Jc(L), implying that B e"L + B' e-L =
eik'L
1/J 8( L) = 1/J 'c( L), implying that xB e"L- xB' e- L = ik' C eik' L
The first pair of conditions solve to
and the final pair solve to
ik') Ceik'L -KL

B=21 ( 1+~
1 ( 1- ~
ik' )
B' = 2
C eik'L +<L
Hence
1( 1()(
A = 4 1+ik
ik')
1+~
Ceik ' L -L
ik ' ) Ceik'L+L
+41 ( 1-~) ( 1 - ~
= +Ceik'L{ (1 +A.) cosh xL- i
(:-~)sinh xL}
with A.=k'lk
223
224
Hence,
P~ I~ I ' ~
{:'(~)' (~)}nh'<L
U+(l+A') cosh'<L+
4
2
2 2
(1 +l) + { 1 +l +l (
~r + (ir} sinh
KL
1+l)2
- +G
2
where
G=~{ 1 + (ir +l
=
1
16 { 1 +
Gr
2
[
1+
(~rn sinh
2
+l [ 1 +
KL
(~r]}ce<L -e-L
r
Note that
k)2 -E- - -e( -E-V

1-e
-
1(
and so
This result reduces to eqn 7 in the text when l = 1.

12.8 As in Problem 12.7, we write
Zone A:
lfJA
=A
eikx
+A
Zone B: ljJ 8 = B eik 'x + B

Zone C: l/Jc = C eikx + C
e-ikx
k = (2m/h2 ) 112
e -ik'x
k = {2m(E- V)/h 2} 112
e - ikx
k = (2mE!h 2) 112

Note that l/J is oscillatory in zone B now that E > V and k' is real. We now
write C' = 0 [no particles incident from right] and impose the boundary
conditions
l/J A(O) = lfJ 6 (0), implying that A+ A'= B + B'
l/J ~(0) = l/J ~(0), implying that kA - kA' = k' B- k' B'
l/Js(L) = l/Jc(L), implying that B eik'L + B' e - ik 'L = C eikL
l/J ~(L) = l/J 'c(L), implying that k' B eik'L- B 'k' e - ik 'L = kCeikL
These equations solve to
A=
B=
H(
1 + :) B + ( 1- : )
(1 + ~)
~ (1 + ~)
B, =
k'
k'
B'}
C ei!k-k') L
C ei!k+k')L
which give A in terms of C. Then straightforward algebra leads to

IAI 2
A. 2sin 2k' L .
V
ICI2=1+ 4<1 -.t), wtth.t=
Therefore,
ICI 2
1
.
A. 2 sin 2 k' L
P=IAI2=1+G' With G= 4(1-A.)
Note that when
v~o (A.~O), c~o
and
P~
1.
12.9 We can use the calculation in Problem 12.8 with

?(reflection)= 1- ?(transmission)
1
G
= 1 -1+G=1+G
where
(VIE? sin 2{2m(E + V)lh 2} 112 L
G=
4(1 +VIE)
We write y=EIV , so
sin 2 {[(2mVIh 2)(1 +y)jl ' 2L}
G = ---'-----:---'--'--:----'--=----4y(1 + y)
v~- V
and
225
Quantum theory : techniques and applications
226
and take V = 5.0eV, L = 100pm,
(7 )
2m~ll2
L = 49 .09(proton), 69.42(deuteron)
Note that P=O when G = O, which occurs when

(2mV/h 2) 112 L(1+y) 112 =nn, nan integer
or at
h )
y = ( 2mV
(nn)z
L -1
We find these values first (to simplify the plotting), and then calculate P for
O~y~2. The results are drawn in Fig. 12.3.
1.0
Fig 12.3
I o
0.5
1\
" ,r
I'<
(\, '\
~\
J ~ \ 'j.,}
'\'
00
0.5
Vf ~ ~ 'lc:: /:
"
h2 d2
.r.
'
dx.~ + f kx 21/J = E1/J
and we write 1/J = e - 8 ' 1 , so d1fJ/dx. =- 2gx e - gx l

2
2 2
./::
1. 5
1.0
12.10 The Schrodinger equation is - Zm
ddx.-~ = - 2g e - g.r' + 4g x
e -gx' =- 2g1/J + 4g 2x 21jJ
--
2.0
This eq uation is satisfied if

2
hg
1 (mk) 112
E=- and 2h 2g 2 = j_mk
org= - - 2
2
'
m
2 h
Therefore,
k)l/2 = t hw if w= (k)l/
2
;;:;
E= t h ;;:;
which implies that
We then use 1jJ=NHe-y 212 , and obtain

d 21jJ
, =
dy-
d2
N -, (H e -y'12 ) = N{H" - 2yH'- H + y 2H} e -y'' 2

dy-
From Table 12.1
H;:-2yH;,= -2uH,
= HtH,,+ 2 + (u + l)H.,}+ uHH, + (u -l)H.,-2}

= iH, +2 + u(u -l)H., _2 + (u + nH,
Therefore ,
227
228
(T)=
N 2(- t hw)
=
JHuf!rHu+ 2+v(v-1)H. _2-(v+ t)H.}e-Y''2dx
aN2f... - -fhw){O + 0- (v +-f)n 1 1 ~"v!}
= t( v+t)hw [
12. 12
[dx=ady]
(x") = a "(y")
= a"
(a) (x 3)oc
N~= an !2"v!' Table 12.1]

11
[Box 12.1]
ljJy"VJdx = a"+ 1 "!jJ 2y"dy
[x = ay]
J
J
(b) (x4)=as
VJ 2y 3dy=Q by symmetry
l/JY4VJdy
Y4Vl = y4NH. e-y'l2

4
y H. = iHHu+l + vH.- 1}
= y 2{t[tH.+ 2+ (v + 1)H.] + v[tH. + (v -1)Hu-2]}
= y 2{-;\Hu+2 + (v + t)Hu + v(v - 1)Hu-2}
= y{t[! H u+J + (v + 2)Hu+1] + (v + t )[t H u+ l + vHu- 1]
+ v(v -1)[tHu-l + (v - 2)Hu-3 ]}
= y{tHu+J + t(v + 1)Hu+ l + tV2Hu-l + v(v - 1)(v- 2)H._ 3}"
Only yHu+l and yH._ 1 lead to H. and contribute to the expectation value
(since H . is orthogonal to all except H. ); hence
y 4H. = ty {(v + 1)Hu+ l +2v 2Hu- l}+
= i {(v + 1)[! H u+2 + (v + 1)H. ] + 2v 2[t H. + (v -1)H.- 2]} +

= H (v+1fH. +v 2H.}+
=t{2v 2+2v+1)H.+
Therefore,
"!jJy 4"!jJ dy = t{2v 2+ 2v + 1)N 2
JH~
e-y' dy =:a (2v 2 + 2v + 1)

and so
12.13 f.J-=
J'l/Ju X'l/Judx=a J'l/Ju Y'l/Judy

2
[x=ay]
Y'l/Ju=Nu(tHu +t + vHu- 1) e -r''2 [Table 12.1)

Hence,
J(-!Hu. Hu +t + vHu.Hu_
f.J- = a 2NuNu
1)
e-r212 dy
= 0 unless v = v 1
1
(a)
=v+1
f.J-=-!a 2NuNu+t
JH~+ t
e-r' dy= -!a 2NuNu+ 1n 112 2"+ 1(v + 1)!
= a(~)"z
(b)
VI = V
12.14
- 1
V =- -
e2
1
-=axbwithb=-1
4ne 0 r
Since 2(T) = b(V)
[x-?r]
[the virial theorem , Chapter 11]
2(T)= - (V)
Therefore , (T) = - -!(V)

h d
,
(a) Iz e"" =--e'=he' ' hence]_ z_= __
+h
id
A
12.15
229
230

h d
- e- 2 i<1> = -2he- 2;<1> hence] =- 2h

(b) l z e- 2 i<1> = -id
,
l
(c) (l, )rx
J~T cos(~ d: cos) d rx-~ J~T cossind = Q
(d) (!,) = N 2 J~ (cos xei<f> +sin x e- i<P)*
d:) (cos x ei )(i cos x ei<l> -
i sin X e- icf> ) d
= hN 2 J~T cos 2 x- sin 2 x+ cos x sin x[ e2iJ) d

= hN 2(cos 2 x- sin 2 x) x 2n = 2nhN 2cos 2x
=N 2 J~T (cos 2 x+sin 2 x+cosxsinx[e 2iJ)d

1
= 2nN 2( cos 2 X+ sin 2 x) = 2nN 2 = 1 if N 2 =2n

Therefore,
(t,) = h cos 2x
For the kinetic energy, use
t = 2/
;= -
h2 d2
21
d 2
h2
h2
h2
(a) fei) = -ei<l> and hence (T) =2/
21 ,
21
2
2
'
.
h .
,.
4h
.
2h 2
(b) Te - 21<1> = - - (21? e--lcf> = - e- 21<1> and hence (T) = 2/
21
'
_I_
'
h2
h2
h2
(c) Tcos =- / -cos) = cos , and hence (T) =
2
21
21
'
(d) T(cos x el - sin x e - l<P)

~
= /cosxei<f> + sinxe- i<l> ), and hence (T) =

2
21
First, normalize the wavefunction:
Now evaluate the expectation value :
(a e-irp + b e- 2irp + c e- Ji<P)(a e;rp + 2b e2;rp + 3c e'i<P) d
hN 2
hN 22n(a 2 + 2b 2 + 3c 2)
(aa+2+
2
(b) (T) )L;)

2/
and so
J:
2b + 3c ) h
b 2+ c 2
231
232
a 2b 2 + 4a 2c 2 + b 2c 2
- (a z+bz+cz) z
Hence,
12.17 The Schrodinger equation is
h2
- - V 2ljJ=EljJ
2m
[18, with V = O]
and hence
2/E
1\?'!jJ = -
----,;r-'!fJ [19]
Then , from eqn 22

(a) A 2Y0 0 = Q [1 = 0, m 1=0], implying that E = O and angular momentum = Q
[from{/(/+ 1)}112h] .
(b) A2 Y2 __ 1 = -2(2+1)Y2 __ 1 [/=2], and hence
-2(2+ 1)Y2 _ 1 =
2/E
- ----,;r- Y
2 __ 1,
3h 2
implying that E = I

and the angular momentum is {2(2 + 1)} 112h = 6 112 h
(c) A2Y3 . 3 = -3(3 + 1)Y3 . 3 [!= 3], and hence
- 3(3 + 1) Y3.3 = -
21
h2 Y 3. 3 , implying that E =
6h 2
and the angular momentum is {3(3 + 1)} 112h = 2Y3h
I" I
12.18
=I: (
JT
Y 3. 3 Y 3 . 3 sin 8 d8 d
64)
(~) sin
(~)
8 sin 8 d8
I~ d
[Table 12 .3]
I~
2 3
= (; )
(2.n)
(1- cos 8) d cos 8
4
1
sin 2 8 = 1- cos 2 8]
35 1
=
(1-3x 2 +3x 4 -x 6 )dx [x=cos8]
32 -1
[sin 8 d8 = d cos 8,
= 35 (x-x3+~x'-~x7)
32
5
7
22.19
~~
_ I
= 35 x 32 = 1
32 35 -
From the diagram in Fig. 12.4, cos 8 = {!(! :~)}
112
Fig 12.4
m,
and hence 8 = arcos {l(l +I )} 112
For an a electron , m,= +-!. s=t and [with m 1-7m, [-7s]
112
8 = arcos ( / ) 112 = arcos v' = 5444'

3 4
The minimum angle occurs for m 1 = l :

1
lim 8min=lim arcos ({/(/ /1)}1 /2) =lim arcos-/ = arcos 1 = Q
1- 0
/-'Y.I
/- oo
233
13. Atomic structure and atomic

spectra
Exercises
(1 , ii=W.]
and hence
A.=~ - 1
H
1 1) - I =(1 09677x107 m - 1) --( 4 n2
1(
1)
16
---
- I
=486 .3 nm
and hence
That is , n=6
1
1
13.3 ~= 486.1 x 10
em
20 572 em - '
Hence , the term lies at
T=27 414 cm - 1 - 20 572 em - ' = 6842 em - '
I= hv- I m v 2 = 6 626 X 10 - 34 J Hz- 1 X

2
2.998 x lORm s- 1
----::-::----c--::-;;-58.4 x 10 9 m
- i: X 9.109 X 10- 31 kg X (1.59 X 106 m s- 1?

=
2.25
X 10- IXJ ,
corresponding to 14.0 eY
Atomic structure and atomic spectra

13.5
'f/JIX (2- p) e - pt 2 with p= r/a 0
235
[Table 13 .1]
d'f/J 1 d'f/J 1
- = - - =-( -1-1 +fp) e - P' 2 =0 when p=4
dr ao dp ao
Hence, the wavefunction has an extrem um at r = 4a11 Since 2- p < 0, 'f/1 < 0
and the extremum is a minimum (more formally: d2'f/J/dr 2 > 0 at p = 4).
13.6 Since '!fJJ.O rx 6- 6p + p 2 [Table 13.1], the radial nodes occur at
6- 6p+ p 2 = 0, or p= 3 Y3= 1.27 and 4.73

Since p = 3pa 1112 , the radial nodes occur at 101 pm and 376 pm .
13.7 Identify l and use angu lar momentum= {l(l + 1)} 112h.
(a) l = 0, so ang. mom.= 0

(b) 1= 0, so ang . mom. =0
(c) 1= 2, so ang. mom. =Y6h
(d) l=l ,soang. mom . =Y2h
(e) l= 1, so ang. mom.= Y2h
The total number of nodes is equal to n- 1 and the number of angu lar nodes
is equal to l; hence the number of radial nodes is equal to n -/- 1. We can
draw up the following table:
n, l
Angular nodes
Radial nodes
Is
3s
3d
2p
3p
1, 0
0
0
3,0
0
2
3,2
2
0
2, 1
1
0
3, 1
1
[I]
[n-/-1]
13.8 We use the Clebsch-Gordan series [13] in the form
j=l+s, l+s-1, . . . ll-sl

(a) l = 2, s =
! ; so j = t,
(b) 1=3, s=f; soj= ~ , ~
13.9 The Clebsch-Gordan series in Exercise 13. 8 with j = ~,

13.10 Use the Clebsch-Gordan series in the form
l = jl+h,jl+h - 1, . . . Jjl -
hl
'2, requires I = 2
236
Then, with j 1 = 5 and h = 3
1=8, 7, 6, 5, 4, 3, 2
hd!AH
- , and the orbital degeneracy g of an energy

n2
level of principal quantum number n is g = n 2 [Section 13.2] .
13.11 The energies are E = - -
(a) E= -h&AH implies that n = 1, so g = 1 (the 1s orbital).

(b) E=
-T
h&A
implies that n=3 , so g=9 (the 3s orbital, the three 3p
orbitals, and the five 3d orbitals).

(c) E = -
h&A
H implies that n = 5, so g = 25 (the 5s orbital, the three Sp

25
orbitals, the five Sd orbitals, the seven Sf orbitals, the nine Sg orbitals).
13.12 The letter D indicates that L = 2, the superscript 1 is the value of

2S + 1, so S = 0, and the subscript 2 is the value of 1. Hence,
L=2 , S=O, 1 = 2
13.13 The probability density varies as
1
1/1 2= - e -2rlao
.na6
Therefore , the maximum value is at r = 0 and 1jJ 2 is 50 per cent of the

maximum when
e- 2rlao = 0.50, implying that r =- t ao In 0.50 which is at r = 0.35a 0 (18 pm).
13.14 The radial distribution function varies as
The maximum value of P occurs at r = a0 since

dP ex: ( 2r - -2r
dr
2
)
ao
e - 2' 1" 0 =0 at r=a and P

0
max
P falls to a fraction f of its maximum when
4 2
= -eao
and hence we must solve
j1'2
-
r
= - e - rla0
a0
(a) !=0.50
r
0.260 =- e-"a" solves to r = 2.08a 0 = 110 pm
ao
---
(b) !=0.75:
r
0.319 =- e- rtao solves tor= 1.63a0 = 86 pm
ao
--
In each case the equation is solved numerically (or graphically).

13.15 The selection rules to apply are L'ln = any integer; L'll =
1.
(a) 2s- ds; L'll = 0, forbidden

(b)
2p~
(c)
3d~2p;
L'll= - 1, allowed
(d)
5d~2s;
L'll = -2 , forbidden
1s; L'll = -1, allowed
(e) 5p~ 3s; L'll = -1, allowed
13.16 For a given I there are 2/ + 1 values of m1 and hence 2/ + 1 orbitals.

Each orbital may be occupied by two electrons. Hence the maximum
occupancy is 2(2/ + 1). Draw up the following table:
2(2/ + 1)
(a) 1s
(b) 3p
0
1
2
6
(c) 3d
(d) 6g
2
4
10
18
237
238
13.17 We use the building-up principle with the orbitals occupied in the order
ls, 2s, 2p , 3s, 3p:
He
ls 2
H
ls 1
Li
K2si
Be
K2s2
B
K2s22p i
c
K2s22p2
N
K2s22p3
0
K2s22p4
K2s22ps
Ne
K2s22p6
p
AI
Si
s
Cl
Na
Mg
Ar
1
2
1
2
2
2
KL3s KL3s KL3s 3p KL3s 3p KL3s 23p 3 KL3s 23p 4 KL3s 23p 5 KL3s 23p 6
where K = ls 2, L = 2s 22p6.
13.18 Use the Clebsch- Gordan series in the form
S'=s 1+s2,s 1+s 2-l, .. . ls ~-s2 1

and
S=S'+s~> S'+s1-l, . .. IS'-sd
in succession. The multiplicity is 2S + 1

(a) S= t + t , t - t = ~with multiplicities~ respectively
(b) S' = 1, 0; then S= f, t and ! with multiplicities 4, 2, 2
(c) S'=l,O;thenS" = t,!,!;
then S"' = 2, 1 [from t ], 1, 0 [from tJ, 1, 0 [from ! ]
and S= t , t ; f , !; f, ! ; !; f, ! ; ! with multiplicities
2 (for S = t ) , ~(for S = t )
and~(forS = 2)
3.19 Use the Clebsch- Gordan series in the form

J = L+S, L+S-1 , . .. IL-SI
The number of states (M1 values) is 2J + 1 in each case.

(a) L = 0, S = 0; hence J = 0 and there is only 1 state (M, = 0)
(b) L= 1, S = t ; hence J= f, t eP312 , 2P 1,2) with 4, 2 states respectively .
(c) L=2 , S = 1; hence 1 = 3 , 2,1 CD3, 30 2, 30 1) with 7, 5, 3 states
respectively.
-(d) L=2, S = f ; hence!= }, t, f , t (40 712 , 40 512, 40 312, 40 112) with 8, 6, 4, 2
states respectively.
13.20 (a) Li [He]2s 1: S= !, L =0; 1= ! , so the only term is 2S112
239
i , so the terms are 2P 312 and 2P 112

L=2;1= ~ , f , so the terms are 2D 512 and 2D" 2
(b) Na [He]3p 1: S =-!, L = 1; 1 = ~ ,

(c) Sc [Ar]3d 14s 2 : S=t,
(d) Br [Ar]3d 104s 24p 5. We treat the missing electron in the 4p subshell as
equivalent to a single 'electron' with I= 1, s = t . Hence L = 1, S = L and 1 =
i; so the terms are 2P312 and 2P 112 .
f,
E = j.J. 8 Bm 1 (16b] with f.J.s = 9.273 X 10- 24 1 T - I
13.21
Hence,
2.23 x w-22 1
m, = f.J.sB = 12.0 T X 9.273 X 10- 24 1 T -I= 2 00
E
Hence, m 1= +2.
E = J1. 8 Bm 1 [16b], implying that
13.22
E.,,+ 1 - E.,, = f.J.sB and therefore that

hcv = f.J.sB
Therefore,
6.626 X 10- 34 1 S X 2.998 X 10 111 em S -
hcii
B = --;;;; =
= 2.1
9. 273 X 10
24
1T
1.0 cm - 1
T.
Problems
~ = '27tH(~-~)
111 11 2
13.1
'27t 11 =109677cm - 1
1\.
Find n 1 from the value of
Ama x ,
which arises from the transition n 1 + 1 ~ n 1:
2n 1 + 1
n~(n 1 +1) 2
n 2 (n + 1) 2
'2lt =-~-~--
-1.
max
2nl
+1
= 12 368 X JO - ~ m X 109 677 X 10 2 m- 1 = 135 .65
Since n 1 = 1, 2, 3, and 4 have already been accounted for, try 11 1 = 5, 6, ... .

With n 1 = 6 we get n~(n 1 + 1) 2/(2n 1 +I)= 136. Hence, the Humphreys series is
n 1 ~6 and the transitions are given by
240
and occur at 12 370 nm, 7503 nm, 5908 nm, 5129 nm, ... 3908 nm (at n 2 = 15),
converging to 3282 nm as n2-' co .
656.46 X 10- 9 m X 109 677 X 102 m- 1= 7.20
and hence n 1= 2. Therefore, the transitions are given by
The next line has n 2 = 7, and occurs at
The energy required to ionize the atom is obtained by letting n2-' co .

Then
1
A. ,. = 109 677 cm- 1x
(~- 0) = 27 419 cm - 1, or 3.40 eV
(The answer, 3.40 eV, is the ionization energy of an H atom that is already in
an excited state, with n=2.)
Therefore, if the formula is appropriate, we expect to find that

A. - 1(1-lln 2)- 1 is a constant (K). We therefore draw up the following table
n
A. - 1/cm-1
A. -1(1 - 1Jn2tlfcm-l
740747
987 663
877 924
987 665
925 933
987 662
241
Hence , the formula does describe the transitions, and K = 987 663 cm - 1 The
Balmer transitions lie at
~=K(~-~2)
n=3,4, ...
=987 663 cm- 1 (~- ~
2) = 137175 cm -
1
,
185187 cm- 1,
The ionization energy of the ground state ion is given by
~=K(1-2_)
n--7 oo
,
n-' '
A
and hence corresponds to
1
I= 987 663 cm- 1, or 122.5 eV
13.4 Refer to Fig. 13.1 , which shows an interpretation of the data in terms of
ts22p 2P
R
\()
ts22s 2s
the energy levels of the atoms. Since

K'
E(1s 2nd 1, 20) =--..,

n-
for the
0--7 P transition
[energies are hydrogen-like]
242
1
A.

l(1s 22p 1/
he
P)I
K'
[tiE= hv=
n2
:c]
from which we can write
1
610.36 X 10
K'
em
+- (a)
9
K'
1
460.29 X 10
413.23 X 10
em
+- (b)
16
K'
em
+- (c)
25
Then (b)-( a) solves to K' = 109 886 em - 1

(a)-(c) solves to K' = 109 910 em -
Mean= 109 920 em - 1
(b)-(c) solves to K' = 109 963 cm - 1

The binding energies are therefore
E(b22p, 2P) =-
610 36
10
_7 em
12 213 cm - 1 = -28 597 cm - 1
Therefore, the ionization energy is

/(ls 22s 1, 2S)=43505cm - 1, or5.39eV.
13.5 The ground term is [Ar]4s 1 2S 112 and the excited term is [Ar]4p 1 2P. The
latter has two levels with J = 1 + t = ~ and J = 1- t = t which are split by
spin-orbit coupling [Section 13.7]. Therefore , ascribe the transitions to 2P312 --?
2
S 112 and 2P 112 --? 2S 112 (since both are allowed). The splitting is equal to ~-A-
[Example 13.9]. Hence , since
(766.70 X 10- 7 cm) - 1 - (770.11
10- 7 cm) - 1 = 57.75 cm - 1
243
we can conclude that A = 38.50 em _,_

13.6 The Rydberg constants for 'H and 2H are related to f!ll.~ (in which the
mass of the electron occurs alone) by
f!/1. "'
f!/I.H = - - - 1 +mcfmr
where mr is the mass of the proton and md the mass of the deuteron. The two
lines in question li e at
and hence
v, ,
f!/I.H Ao
---
A.,,
0lo
iiD
Then, since
0?.1-1
1 + m)m"
0l n
1 + m ) m"
wh ich rearranges to
we can ca lculate md from
9 . 109 39 X 1W 11 kg
+ 9.109 39 X
1. 67262x
= 3 .3429
In
I11
=
IW
11
k~\ (82 259. 098 em - ')_ I
Hr 27 kg}
10 - 27 kg
'?ll. n
iin
82281.476cm - 1
0?.11
ii 11
82 259.098 em_,
1.000 272
82281.476cm- 1
244
13.7 The Rydberg constant for positronium (ffi-Ps) is given by

[8; also Problem 13.6)
=54 869 cm - 1 [ffi-oo = 109 737 cm - 1]
Hence
~=54 869 cm- X (~- ~2), n=3 , 4, . . .

1
=7621cm- 1, 10288cm- 1 , 11522cm - 1,
The binding energy of Ps is

E= -hcffi.p., corresponding to (-)54 869 cm- 1
The ionization energy is therefore 54869cm- 1, or 6.80eV.
13.8
ao
r*
=-z
[Example 13.5)
Therefore , r* =
13.9
(r) 2p
52.92 pm
126
0.420 pm
=I:
R 21rR 21r 2 dr
(~Y( 2 ~6 y
= (
~r
1
24 X
[p = 2Zr!na0 = Zr/a 0]
I:
~rI:
3 2
r p e-p dr
5
[Table n1 1
1
P e - p dp = 24
X~
5!
5a 0
=(~Y x~ x (~YI: p (2-p)

3
= ao
82
6a 0
I"'
0
( 4p3 -
e -P dp
4p4 + p5 ) e -p dp = ao (4 X 3!- 4 X 4! + 5!)

82
245
Therefore, (r)2p<(rh, , and the 2p electron is, on average, closer to the

nucleus.
13.10 The most probable point lies along the z-axis, and is where the radial
function has its maximum value (for 'f/.! 2 is also a maximum at that point).
From Table 13 .1 we know that
dR
and so dp =(1-tp)e-P12 =0 when p=2.

Therefore, r * = 2a 0 / Z, and the point of maximum probability lies at z =
2a0 /Z= 106 pm
Z e2 1
13.11 The attractive Coulomb force= - - --,
4ne0 ,-
The repulsive centrifugal force=
(angular momentum) 2
m er 3
(nh) 2
= - -3 [postulated]
mer
The total energy is
E = EK+ V
2
(angular momentum) 2 - -Ze
1
-X-
..:..._-=.__ __ __ _ _
2/
n2h2
ze2
2mcr 2 -
4neor
Z 2e4m
= -
32n 2 B~ 2 x ~
4ne0
246
13.12 (a) The trajectory is defined , which is not allowed according to

quantum mechanics. (b) The angular momentum of a three-dimensional
system is given by {!(I+ 1)} 112h, not by nh. In the Bohr model, the ground
state possesses orbital angular momentum (nh , with n = 1), but the actual
ground state has no angular momentum (1=0). Moreover, the distribution of
the electron is quite different in the two cases.
The two models can be distinguished experimentally by (a) showing that
there is zero orbital angular momentum in the ground state (by examining its
magnetic properties) and (b) examining the electron distribution (such as by
showing that the electron and the nucleus do come into contact , Chapter 18).
14. Molecular structure

Examples
14.1 Refer to Fig. 14.12 of the text for the molecular orbital energy level
diagram:
(a) Li 2 (6 electrons): 1sa ~ 1sa~2sa ~, B. 0. = 1

(b) Be 2 (8 electrons): 1sa ~ 1sa~2sa ~2sa~; B. 0. =0
(c) C2 (12 electrons): lsa ~ 1sa~2sa ~2sa~2pn ~; B. 0 . =2
14.2 Use Fig. 14.5 of the text for H}, Fig. 14.12 for N 2 and Fig. 14.10 for 0
2:
(a) H} (3 electrons): lsa ~ lsa~, B. 0. =0.5

(b) N 2 (14 electrons): lsa ~ lsa~2sa ~2sa~2pn~2pa ~, B. 0. = 3
(c) 0 2 (16 electrons): 1sa ~ 1sa~2sa~2sa~2pai2pn~2pxn~2p.vn~, B. 0. =2
14.3 Note that CO and CN - are isoelectronic with N 2 and that NO is
isoelectronic with N}; hence use Fig. 14.12 of the text, but without the parity
labels.
(a) CO (14 electrons): lsa 2 1sa* 22sa 22sa* 22pn<!zpa 2 , B. 0. = 3

(b) NO (15 electrons): 1sa 2 1sa *22sa 22sa* 22p.n 42pa 22pn* 1, B. 0. =2.5
(c) CN - (14 electrons): 1sa 2 1sa *22sa 22sa* 22pn 42pa 2 , B. 0 . = 3
14.4 The bond orders of B2 and C 2 are respectively 1 and 2; so C 2 should have
the greater bond dissociation enthalpy . The experimental valuesare
approximately 4 eV and 6 eV respectively.
14.5 Decide whether the electron added or removed increases or decreases
the bond order. The simplest procedure is to decide whether the electron
occupies or is re moved from a bonding or antibonding orbital. We can draw
up the following table, which denotes the orbital involved:
248
Molecular structure
NO
02
F2
2p:rc*
2p:rc*
2p:rc *
2pa
2pa*
2pa
N2
(a) AB-
CN
Change in
bond order
- z-
- z-
- z-
+t
- -r
+t
(b) AB +
2pa
2p:rc*
2p:rc*
2p:rc
2p:rc*
2pa
+t
+t
+t
- zI
- z-
Change in
bond order
- z-
Therefore, C 2 and CN are stabilized (have lower energy) by anion formation,

whereas NO , 0 2, and F 2 are stabilized by cation formation.
14.6 We can use a versi~n of Figs. 14.10 and 14.12 of the text, but with the
energy levels of 0 lower than those of C, and the energy levels of F lower
than those of Xe, Fig. 14.1. For CO we accommodate 14 electrons, and for
co
Xe
(a)
XeF
(b)
2s
XeF we insert 15 valence electrons (the core orbitals and the electrons they
supply may be neglected at this level of discussion). Since the bond order is
increased when XeF+ is formed from XeF (because an electron is removed
from an antibonding orbital) , XeF + will have a shorter bond length than XeF.
14.7 Refer to Fig. 14.17 of the text.
(a) :rc* is gerade, g
Molecular structure
249
(b) g, u is inapplicable to a heteronuclear molecule, for it has no center of

inversion.
oorbital (Fig. 14.2a) is gerade , g.

A o*orbital (Fig. 14.2b) is ungerade, u.
(c) A
(d)
(a) g
(g) u
14.8 Refer to Fig. 14.35 of the text. The plan view of then orbitals should be
interpreted with the shapes of the p orbitals in mind, and their nodal planes
that lie in the plane of the molecule. The a ~ orbitals are therefore g , the e 1
orbitals are g, the e2 orbitals are u, and the b 2 orbitals are g.
14.9 The left superscript is the value of 25 + 1, so 25 + 1 = 2 implies that 5 = t .
The symbol I indicates that the total orbital angular momentum around the
molecular axis is zero. The latter implies that the unpaired electron must be in
a a orbital. From Fig. 14.12 of the text, we predict the configuration of the
ion to be 1sa~1sa~2sa~2sa~2pn~2pa ~, which is in accord with the 2Ig term
symbol.
14.10 According to Hund's rule , we expect one 2pn" electron and one 2png
electron to be unpaired. Hence S = 1 and the multiplicity of the spectroscopic
term is 3. The overall parity is u x g = u since (apart from the complete core),
one electron occupies a u orbital and another occupies a g orbital.
14.11 The bond orders of NO and N 2 are 2.5 and 3 respectively (Examples
14.2 and 14.3); hence N 2 should have the shorter bond length . The
experimental values are 115 pm and 110 pm respectively.
14.12 Since the molecule has one unit of orbital angular momentum around
the axis, and since one electron is in a a orbital, the other electron must be in
250
Molecular structure
a :rc orbital. This suggests that the configuration is 1sa!2p:rc~, which is

consistent with the designation 3 IT" .
1J1 dr = +
14.13
J(s+V2p) d7:
=!
(s 2 +2p 2 +2V2sp) dr
=!(1+2+0)=1
as
Js d7: = 1, Jp d7: = 1, and J

2
14.14
1Ji dr=N
=N
spd1:=0
[orthogonality]
(lJ!A+A.lJ!ddr
J(1Ji i +A 21Ji~+2AlfiA1JiB)dr
[J
2
=N (1+ A. -2A.S)
1JIA1Jisd7:=S]
Hence, we require
1
)
N= ( 1+2A.S+A. 2
14.15
J
J
1J!(lsa)1Ji(1sa*) dr=
14.16
1/2
(lJ!A+ 1J1 8 )(1JIA-lJ!s) d1:
(1Ji i -1JI 1)d7:=l-l=Q

cos 
a2= - - -
cos - 1
[19]
cos 92.2
0 0370
=cos 92.2 - 1 =
Hence , there is 3.7 per cents character in the orbital.

14.17 (a) C0 2 is linear , either by YSEPR theory (two atoms attached to the
central atom , no lone pairs on C), or by regarding the molecule as having a a
framework and :rc bonds between the C and 0 atoms .
Molecular structure
251
(b) N0 2 is non-linear , since it is isoelectronic with C02 . The extra electron is

a 'half lone pair' and a bending agent. Alternatively, the extra electron is
accommodated by the molecule bending so as to give the lone pair some s
orbital character.
(c) NO; is linear, since it is isoelectronic with C0 2
(d) N02 is non-linear, since it has one more electron than N0 2 and a
correspondingly stronger bonding influence.
(e) S0 2 is non-linear, since it is isoelectronic with N02 (if .the core electrons
are disregarded).
(f) H 20 is non-linear , as expl ained in Fig. 14.25 of the text in connection with
the Walsh diagram of an AH 2 molecule .
(g) H 20 2+ is linear since the electron pair responsible for the bending (see
Fig. 14.25 of the text) is now absent.
14.18 The molecular orbital of the fragments and the molecular orbitals that
they form are shown in Fig. 14 .3.
Ia)
(b)
Fig 74.3
14.19 The atomic orbita l basis is lsA, lsll , lsc in each case ; in linear H 3 we
ignore A, C overlap; in triangular H 1 we include it.
(a)
a- E
(3
0
(3
a-E
(3
(3
=0
a-E
252
(b)
Molecular structure
a-E
f3
f3
f3
a-E
f3
f3
f3
a-E
=0
The symmetry-adapted combinations for (a) are A+ .AB + C, A- C, and

A - .AB + C, which factorizes the determinant; for (b) they are A + B + C and
the doubly degenerate pair A - C and A - 2B +C.]
14.20 From the molecular orbital energy level diagram in Fig. 14.35 of the
text we can write
(a) C6H6 (6 electrons):
aLeig
E = 2(a + 2{3) + 4(a + {3) = 6a + 8/3
(b) C6 Ht (5 electrons) : aLdg

E = 2(a + 2{3) + 3(a + {3) = Sa+ 7{3
Problems
14.1 lfJA = cos kx measured from A, 1/Js = cos k'(x - R) measuring x from A .
Then
1/J = cos kx + cos k'(x - R)
= cos kx + cos k' R cos k'x +sink' R sin k 'x
[cos( a - b)= cos a cos b +sin a sin b]
:rc
k'R
:rc
(a) k = k' = :rc/2R , cos -2 = 0 , sin -2= sin -2 = 1

:rex
:rex
1/J = cos 2R + sin 2R

For the mid point , x = tR, so 1fJ(tR)=cost:rc+sint:rc=V2
and there is constructive interference.
(b) k=:rc/2R, k' = 3:rc/2R; cosk'R=cos
:rex
:rex
1/J = cos R - sin R
2
2
3:rc
=o, sink'R = -1.
Molecular structure
253
For the mid point, x= t R, so 1/'(tR)=cost.n-sint.n=O and there is

destructive interference.
14.2 Draw up the following table:
Rla0 0
10
1.000 0.858 0.586 0.349 0.189 0.097 0.047 0.022 0.010 0.005 0.002
~ig.
The points are plotted in
TD
Fig 14.4
1\
(1sl1s}
08
\
\
I V',
I{
\
s
06
1/
r-....
0
0
'
~( .?p~
'1\ 1\
02
14.4.
~:'-..
.......... ~ ~
.._
10
14.3 The s orbital begins to spread into the region of negative amplitude of
the p orbital. When their centers coincide, the region of positive overlap
cancels the negative region. Draw up the following table:
Rla0 0 1
S
10
0 0.429 0.588 0.523 0.379 0.241 0.141 0.078 0.041 0.021 O.Ql
The points are plotted in Fig. 14.4. The maximum overlap occurs at R = 2.1a 0 .
14.4 1/' = 1fi 1s(A) 1f' 1s(B) [not normalized] with 1/' oc e -rlao, with r measured
from the parent nucleus. Hence
Molecular structure
254
1/J cc e -jzjlu11 e -1:- Rjla11

with z measured from A along the axis toward B. We draw up the following
table with R = 106 pm and a0 = 52.9 pm.
z/pm
-100
-80
-60
-40
-20
20
40
1/J+
1/J-
0.17
0.13
0.25
0.19
0.37
0.28
0.53
0.41
0.78
0.59
1.13
0.87
0.88
0.49
0.76
0.18
60
80
100
120
140
160
180
200
0.74
-0.10
0.83
-0.39
1.04
-0.74
0.87
-0.66
0.60
-0.45
0.41
-0.31
0.28
-0. 21
0.19
-0.15
z/pm
1/J+
1/J -
The points are plotted in Fig. 14.5. Note that neither wavefunction is
normalized.
12
1/
08
0-1.
./,
~v
v \"
loooo-4 .......
"
r"'
71!.
1\.
Fig 14.5
\.
'\
\
'll\
./'
\
-08
) /
2_
..,I.
z/pm
100
14.5 The electron densities are

2
,...
IV
-100
....... ~
~~~ 2
't'+
P+ - N +1/J +- (1218 pm) 3
~
'
~ ~~~
't'
P- = N -:_1/J-:_ = (622 pm) 3
200
Molecular structure
255
with 1/J+ and 1/J - given in Problem 14.4. The 'atomic density' is
1/JJs(A)2+ 1/JJ,(B )2
p= 9.35x10 5 pm 3 ,op =P - P
with 1jJ 2=e - 2' 1"" Draw up the following table using the information in
Problem 14.4:
-100
z/pm
P+ x 107/ pm - 3
0.19
P- X 107/pm - 3
0.44
p x 107/pm - 3
0.25
op+ X 107/pm- .l -0.06
op _ X 107/pm - 3
0.19
z/pm
- 80
-60
-20
20
. 0.42
0.92
4.19
8.61
1.89
0.93
2.03
4.34
9.00 19.6
0.53
1.13
2.40
5.11 10.9
-0.09 -0.11 -0.51 -1.01 -2.3
1.94
3.89
8.7
0.40
0.90
60
80
P+ x 107/pm -J
3.69
p _ x 107/pm - 3
0.26
p x 107/pm - 3
2.99
op+ X 107/pm - 3
0.70
op _ X 107/pm - 3 -2.73
-40
100
140
120
160
40
5.22
3.89
6.21
0.84
5.44
3.26
-0.22
0.6
0.77 -2.4
180
200
0.24
1.13
4.64
0.53
5.10
2.43
7.29
1.14
0.58
2.48
3.93 14.2
11.3
5.23
0.31
1.41
0.66
4.52
8.77
6.41
3.01
0.12 -1.48 -1 .31 -0.58 -0.28 -0.13 -0.07
0.27
2.22
- 0.59
1.07
0.48
5.4
4.9
The densities are plotted in Fig. 14.6 and the difference densities are plotted
in Fig. 14.7.
20
'\
5
~
I \.- ~
v \ .p
!J \~ -P..
~ ~
-100
~
\
Fig 14 .6
/1a
I ~~ \
//) ~ \
~~
::/1
~~
..1
z / pm
100
200
256
Molecular structure
TO
Fig 14.7
J ___. ~
6
""
!,
"'a2
_.j""
~ 0
.&_2
1/ \
/
\
/ \
IJ\
or.
).....(if'
)'
\
,.......
~ ......
- !,
-6
-TOO
z/pm
TOO
200
P = ll/J I2 dr= ll/J I2 or, or = 1.00pm 3
14.6
(a) From Problem 14.5,

l/J~(z = 0) = P+(z = 0) = 8.6 X 10- 7 pm- 3
Therefore, the probability of finding the electron in the volume or at nucleus

A is
P = 8.6 X 10- 7 pm - 3 X 1.00 pm 3 = 8.6 X 10- 7
(b) By symmetry (or by taking z = 106 pm)
w-
P = 8.6x
(c) From Fig. 14.6,

tjJ~(+R) =
3.7 X 10- 7 pm -3, soP = 3.7 X 10- 7
(d) From Fig. 14.8, the point referred to lies at 22.4 pm from A and 86.6 pm
:>.:~
'\.
1218 pm 312
cs
&6'.6'
'?'!
~
---L..C.....------==.8
from B. Therefore,
e -22.4152.9 + e -86.6152.9
tjJ =
Fig 14.8
200pm
86-0pm
0.65 +0.19
1218 pm 312
6.97 X 10- 4 pm- 312
tjJ 2 = 4.9 X
w-
pm- 3 , so P = 4.9 X
w-
Molecular structure
257
For the antibonding orbital , we proceed similarly:

(a) tjJ2_(z = 0) = 19.6 X 10 - 7 pm - 3 (Problem 14.5) , soP= 2.0 X 10- 6
(b) By symmetry, P=2.0x 10- 6
(c) lfJ2_(t R)=O, so P=Q.
(d) We evaluate '1/J- at the point specified in Fig. 14.8:
0.65-0.19
'''
- 7 40 X 10- 4 pm -J/ 2
-r - - 622 pm312 -
ljJ2_ = 5.47 X
w-
pm - 3, soP= 5.5 X
w-
14.7 Draw up the following table using the data in the question and using
a0
e2
au
e2
e2
--=--x-=
x2
4nt:oR 4nt:olo R 4nt: 0 X (4nt:cNimce ) R
so that
Rla0
e2
4nt:oR
(V1
RH
+ V2)/RH
(E- EH)/RH
00
2.000
00
1.465
0.212
00
0.500
0.333
0.250
0.879
-0.054
0.529
-0 .059
0.342
- 0.038
0
0
The points are plotted in Fig. 14.9. The minimum occurs at R=2.5a0 , so
R = 130 pm . At that bond length
E- EH = - 0.07RH = - 1.91 eV
Hence, the dissociation energy is predicted to be about 1.9 eV and the
equilibrium bond length about 130 pm.
14.8 We proceed as in Problem 14.7, and draw up the following table:
258
Molecular structure
0 4
Fig14.9
03
'
1\
r--.. '-""'
' -..._
uo3
'
-D1
1'..
4
...........
Rla0
co
- ez- ; -R
4nE 0R
H
co
0.500
0.333
0.250
-0.007
1.049
0.067
0.338
0.131
0.132
0.158
0.055
0
0
(VI - Vz)IRH
(E- EH)/RH
00
The points are also plotted in Fig. 14.9. T he contribution V2 decreases rapidly
because it depends o n th e overlap of the two orbitals.
nmU'
h n =l ,2, . . . and 1/J,. = (2)112
L sin (nnx)
L
2 2
14.9 E,.=
Two e lectrons occupy each level (by the Pauli principle) , and so butadiene (in
which there are four n electrons) has two e lectrons in 1/J 1and two electrons in
1/Jz:
1/1 1 =
(nx)
2)1/2
( L sin L
_ (~) 112 .
1/Jz-
sm
(2nx)
L
These o rbitals are sketched in Fig. 14.10a. The minimum excitation energy is
Molecular structure
259
Fig 14.10
Compared
with
Compared
with
(a)
CH 2=CH-CH=CH-CH=CH-CH=CH 2 there are eight n electrons to

accommodate, so the HOMO will be 1/J4 and the LUMO 1/J5 . From the
particle-in-a-box solutions (Chapter 12),
h2
9h 2
6.=, -.=(25-16)--,=--,
8mcL- 8mcL-
9 X (6 .626 X J0 - :14 J s) 2
-:---::--:-::-::----c---;-;---,-----:;---:-:; =
8x9.109x 10 ' 1 kg x( 1.12 x 10 " m) 2
4 3 X J0 - 19 J
which corresponds to 2.7 eV. It follows that

he
6.626 X J0 - :1< J S X 2.998 X 10'

4.3 x w - IY J
111 S- 1
,t = - = - -- - -- - - - - , - - - - - - - -
6.
4.6 X l0 - 7 m, or 460 nm
The wavelength 460 nm corresponds to blue light ; so the molecule is likely to

appear orange in white light [since blue is subtracted]. The HOMO and
LUMO--are-
260
Molecular structure
1/J, =
(L2)
112
sin (n:rrx)
L with n = 4, 5 respectively and the two wavefunctions
are sketched in Fig. 14.10b.
14.10 Since1fJ2r = R20 Y00 =
3'2(2 v1 2 (2)
~
p)e -P' 2 X ( 1:rr)1n [Table 13.1]

4
1)1
/2 (2)3/2
=41 ( 2:rr
~
(2-p)e -pt2
2
1/J2p, = R21Y10=
1( 1 )
4 2:rr
=- -
=-1
2 ~6 (~r pe-P12 X(4~r
112(2)
3/2pe -P12 cose
a0
(2)3'
2 pe- P12 (- 3 ) 112sin8cos
-
Y6 a0
8:rr
1(1) 1/2(2) 3/2pe -P' sin8cos
=4 ~
1(1) 1/2(2)3/2
12
pe-P sin8sin
cos 8
[Table 13.1]
Molecular structure
261
Therefore,
=41 ( 1n )
6
11z(z)3'
2 {2-p-psin8cos+Y3psin8sin}e -P12
~
1( 1 )
=4 n
6
112(z)
~
312
1( 1 )
n
4 6
112(z)
~
312
12
{2-p(1+sin8cos-Y3sin8sin)}e- P
{2-p(1+[cos-Y3sin]sin8)}e- P'2
The maximum value of 1/J occurs when sine has its maximum value ( + 1) and
the term multiplying p has its maximum negative value, which is -1 when
= 120.
14.11
2
{(V 1 - V2)(1 + S) + (1- S)(V 1 + V2)}

_:__
__:::....:.__._:____:_ __:_:_.:___:_ + -2e- + 2H
(1- S)(1 + S)
4nE 0 R
2(SV2 -V 1)
2e 2
2
1- S
+ 4nEof?. + 2H
The nuclear repulsion term is always positive , and always tends to raise the
mean energy of the orbitals above EH. The contribution of the first term is
difficult to assess. Where S = O, SV2 = 0 and V1 = 0, and its contribution is
dominated by the nuclear repulsion term. Where S = 1, SV2 = V1 and once
again the nuclear repulsion term is dominant. At intermediate values of S , the
first term is negative, but of smaller magnitude than the nuclear repulsion
term.
14.12
N2
1fJ 2 dr= 1, 1/J = N(A +B) in a simplified notation .
J(A+B?dr=N J(A +B +2AB)dr=N (1+1+2S)

2
Molecular structure
262
1
2
Therefore, N = ( + S)
2 1
h2
e2
H= --\7 2 - - -
2m
e2
----
4nt:0 rA
e2
-+-- -
4nt:0 r6
4nt: 0 R
H'ljJ = E'ljJ implies that
e2
h2
e2
e2 1
4nt:0 r6
4nt:0 R
- - V ' z'ljJ ---'ljJ---'ljJ+--'ljJ=E'ljJ
4nt:0 rA
2m
Multiply through by 'ljJ *( = 'ljJ) and integrate using
h2
e2
1
--2 V' 2'1/JA--4- -'ljJA=H'lfJA
m
nt:o rA
Then:
Whence
2
EH
1
'ljJ 2 dr+ -e- 4nt:0 R
ez
'ljJ 2 dr---N
4nt: 0
'ljJ ) dr=
'ljJ ('1/J
~+~
rA
r8
and so
Then use
... J
'lfJA
~'1/JA
dr =
rs
[by symmetry] = V 1/(e 2/4nt:0)
'ljJ 6 !_'ljJ 8 dr
rA
which gives
EH = 4::
~- 1 ~ S) (V, + V
(
2)
=E
Molecular structure
or
v, + v2 e 2
4nt:u
1+5
263
E=E ~-~----+ --R
14.13 The Walsh diagram is shown in Fig. 14.11. The steep rise in energy of
Fig 14.11
2e
HAH angle
the 3a 111a;' orbita l arises from its loss of s character as the molecule becomes
planar (120). (a) In NH 3 there are 5 + 3 = 8 va lence electrons to
accommodate. This demands occupancy of the 3a 1/la2 orbital , and the lowest
energy is obtained when the molecule in nonpl anar with the configuration
2a~1 e 4 3aT. (b) C H j has only 4 + 3- 1 = 6 electrons. The 3a 11la2 orbital is not
occupied, and the lowest energy is attai ned with a planar molecule with
2
configuration 2a ; 1e ''.
264
Molecular structure
J~~~
dr=
J~ r e-
2
k'
J~ d = : 2
dr J>in e de
J~V 2~dr = J~~dd:2 (re-k')dr= J~(k2 - :)~dr

2
:rr
k
2:rr
k
:rr
k
Therefore,
h2
:rr
e2
:rr
~H~dr =- x-- - x -2
2Jl
4:rrE 0
and
h2:rr
E=
e2:rr
2Ji.k- 4:rrEok 2 h 2k 2
:rr/ k
e2k
= ---
2Jl
4:rrE0
The optimum energy is therefore

e4Jl
E =- 2:rr 2E6h 2
3
-hC!JtH, the exact value.
(b) ~=e-k' , Has before.

2
J~~~dr= J~
J~ V 2~
2 2
re- k' dr
dr = - 2
= _2
J:
sine de
J~(3k - 2k 2r 2)~
I:
I~ d=~
dr
2
24 2 2
(3kr _ 2k r ) e - k' dr
I:
(3k)
(.!!..._) 1/2- (.!!..._) 1/2}
8
2k
16
2
= -
B:rr
sin e de
3k
2k 5
I~ d
Molecular structure
265
Therefore,
3hzk
ezk 112
E =----~
2!1
co(2.n) 1/2
and the optimum energy is therefore

e 4f1
8
E = - 12.n3cYz 2 - h x he8l.H
Since 8/3.n < 1, the energy in (a) is lower than in (b), and so the exponential
wavefunction is better than the gaussian.
15. Symmetry: its determination and

consequences
Examples
15.1 Since the number of symmetry species of irreducible representations is
equal to the number of classes [end of Section 15.6], there are four classes of
-operation in the group.
15.2 The elements, other than the identity E , are a C 3 axis and three vertical
mirror planes a. The symmetry axis passes through the C-CI nuclei. The
mirror planes are defined by the three CICH planes.
15.3 A D group and a cubic group cannot possess an electric dipole moment
[Section 15.3], so of the molecules listed only (a) pyridine, (b) nitroethane,
and (c) chloromethane may be polar.
15.4 We use the procedure illustrated in Example 15 .8, and draw up the
following table of characters and their products:
J3=p,
!2=z
J1=Px
JJJ3
2C4
C2
2a.
2ad
1
1
2
2
1
1
0
0
1
1
-2
-2
1
1
0
0
1
1
0
0
The number of times that A 1 appears is 0 [since 2 0 -2 0 0 are the characters

of E itself], and so the in tegral is necessarily zero.
15.5 We proceed as in Example 15.8, considering all three components of the
electric dipole moment operator:
Component:
AI
r(.u)
A2
A 1f(.u)A 2
1
2
1
2
1
-1
1
-1
1
0
-1
0
'--or---'
1
2
1
2
1
-1
1
-1
1
0
-1
'--or---'
1
1
1
1
1
1
1
1
1
-1
-]
'-------v------
A2
Symmetry: its determination and consequences
267
Since A 1 is not present in any product, the transition dipole moment must be
zero.
15.6 We can determine the irreducible representations that contribute to the
characters using the technique adopted in Example 15.8 and expressed
formally in footnote 3 on p. 448 of the text. Thus, in this group of order 8, the
numbers of appearances of each irreducible representation is
AI: t(5+2+1+6+2)=2
A 2 : t(5 +2+1-6-2)=0
8 1: t(5 -2+1 -6+2)= 1

8 2: t(5-2+1-6+2)=0
E: t(10+0-2+0+0)= 1
That is, the orbitals span 2A 1 + 8 1 +E. One selection of atomic orbitals is
therefore
and the composition of the hybrids is p 1d 4

15.7 Under each operation the function transforms as follows:
E
c2
c.
av
y
xy
X
y
xy
1
-x
-y
xy
1
y
-x
-xy
- 1
-y
-xy
-1
ad
-y
-x
xy
1
From the C4 v character table, we see that this set of characters belongs to 8 2 .
15.8 In each case we must identify an improper rotation axis, perhaps in a
disguised form (S 1 =a, S2 = i) (Section 15 .3). Thus, D 211 contains i, C 111 contains
a 11 , T11 contains i, Td contains S4 [Refer to more extensive sets of character
tables than those provided in the text: see Further reading .)
15.9 By inspection of the outcome of successive operations we can construct
268
Symmetry : its determination and consequences
First operation :
Second
operation
Cz
C2
Cz
C2
c;
C2
Cz
c;
C2
C2
C2
Cz
C'{
C'{
C'{
C2
Cz
15.10 List the symmetry elements of the objects (the principal ones, not
necessarily all the implied ones) , then use the remarks in Section 15.2, and
Fig. 15.1
(a) Sphere: an infinite number of symmetry axes; therefore R3.

(b) Isosceles triangle: E , C2 , av, and
(c) Equilateral triangle: E , C3, C2 ,
a ~;
therefore C2v
ah
D3
'----v---'
D 3h
(d) Cylinder: E , C. , C2 ,
therefore
ah ;
D ., h
(e) Sharpened pencil: E , C.,, av; therefore C.,v

(f) Propellor: E , C3, 3C2 ; therefore D 3.
(g) Table: E, C4 , av; therefore C4 v.
(h) Person: E, av (approximately) ; therefore C, .
15.11 (a) N02 : E , Cz , av, a~ ; C2v
(b) N20: E, C.,, Cz, av ; C.,v

(c) CHCJ3: E , C3, 3av; C3v
(d) CH 2=CH2 : E , C2 , 2C:!,
ah;
D 2h
(e) cis-CHCI=CHCJ; E , C2 , av,

(f) trans-CHCI=CHCI; E, C2 ,
a ~;
ah,
15.12 (a) Naphthalene: E , C2 , C',
(b) Anthracene: E , C2 ,
(c) Dichlorobenzenes:
C2,
Czv
i; C2h
ah ; D 2h
ah; D zh

(a)
(b)
I~
(c)
I~
Fig 15. 1
~
C;,
c,
(e)
(h)
(i) 1,2-dichlorobenzene: E, C2 , av,
a~;
C2v
(ii) 1,3-dichlorobenzene: E, C2 , a,
a~;
C2v
(iii) 1,4-dichlorobenzene: E, C2 ,
c;, ah;
a,l
D 211
15.13 (a) No D or cubic point group molecule may be polar; so the only
polar molecules are N0 2 , N20, CHCI 3 , 1,2-dichlorobenzene, and 1,3-
269
270
dichlorobenzene . The trans-dichloroethene molecule is also ruled out by its a 11

plane and its inversion center. (b) All the molecules have at least one mirror
plane (a=S 1) and so none is chiral.
15.14 Refer to the C2v character table. The s orbital spans A 1 and the p
orbitals of the central N atom span A 1(p, ), B 1(p;), and B 2(py) Therefore, no
orbitals span A 2 , and hence Px(A)- Px(B) is a non bonding combination. If d
orbitals are available, we could form a molecular orbital with d xy > which is a
basis for A 2.
15.15 The electric dipole moment operator transforms as x (B 1), y(B 2), and
z(A 1) [ C2v character table] . Transitions are allowed iff 'ljJ tftl/J; dr is non-zero
[Example 15.10], and hence are forbidden unless rr x r(ft) x r ; contains A 1
Since C=A I, this requires rrxr(fi.)=AI. Since Bl X BI=AI and BzX Bz=AI,
and A 1 x A 1 =A~> x-polarized light may cause a transition to a 8 1 term,
y-polarized light to a 8 2 term , and z-polarized light to an A 1 term.
15.16 The product rrx r(fl.) X r; must contain AI [Example 15.10] . Then ,
since r; = B I, r(fl.) = r(y) = Bz [C 2v character table], we can draw up the
following table of characters:
Bz
Bl
BIB2
Cz
Ov
a'v
1
1
1
-1
-1
1
-1
1
-1
1
-1
-1
=A 2
Hence, the upper state is A 2 , because A 2 x A 2 = A 1

15.17 (a) The point group of benzene is D 611 , but we can draw conclusions by
considering the smaller group C6v because all the elements of C6v are present
in D 611 In this group the components of fl. transform as E 1(x , y) and A 1(z).
The ground term is A 1 We note that E 1 x A 1 = E 1 and A 1 x A 1 = A 1
Therefore , the upper term must be E 1 (since E 1 x E 1 contains A 1) or A 1 (since
A 1 X A 1 = A 1). In D 611 itself, fl. spans E 1u(x , y) and A 2u(z), and the ground term
is A 1g Then, using A 2uX A;g= A 2u, E 1u X A 1g= E 1u, A 2u X A 2" = A 1g, and E 1ux
E 1u= A 1g+ A 2g+ E 2g, we conclude that the upper term is either E 1u or A 2u. (b)
Naphthalene belongs to D 211 , but we can consider the simpler subgroup C2.
The ground term is A 1 so we can use the conclusions in Exercise 15.15 for the
same group. The upper terms are B 1 (x-polarized) , B2 (y-polarized) and A 1
(z-polarized). In D 211 itself, the components span B 3u(x), B 2u(y) , and B 1u(z)
271
and the ground term is A g. Hence, since A g x f =fin this group, the upper
terms are B 3" (x-polarized), B2u (y-polarized) , and B 1u (z-polarized).
15.18 We examine how the operations of the C3v group affect l, = xp,.- yp,
when applied to it. The transformation of x , y, and z , and by analogy p, , P_v ,
and p, are set out in Section 15.7:
El, =xp_v -YPx=l,

a), = -xpv+ yp,= - 1,
[(x , y , z )~(-x,y , z)]
c;t== ( - t x + t Y3y)(- t V3p, -
tP_v)- (- -}V3x- ~ y)(- t p, + t V3p,.)

[(x ,y , z)~( - ~x+ t Y3y, - t Y3x- ty, z)]
= ~ (V3xp,
+ XP_v - 3yp, - V3yp-" - V3xp, + 3xp,- YPx + V3yp-" )
=xp_v -yp, =l,

The representatives of E, a" and c; are therefore all one-dimensional
matrices with characters 1, -1, 1 respectively. It follows that I, is a basis for
A 2 [see the C3v character table].
15.19 We consider the integral
I=
f~.td2 dO= r~a sin 0 cos 0 dO
and hence draw up the following table for the effect of operations in the
group C,:
/ 1
/ 2
=sin 0
=cos 0
ah
sin 0
cos 0
-sin 0
cos 0
In terms of characters:
E
!I
!2
fd2
ah
-1
1
-1
A"
A'
A"
272
Since fJ2 does not span A', the integral must vanish. If the range of
integration is not symmetrical, the reflection ah is not a symmetry element and
the group becomes C 1, in which [ 1 and [ 2 both span A , and A X A= A; so the
integral does not necessarily vanish.
Problems
15.1 (a) Staggered CH3CH 3 : E , C3 , C2 , 3act ; D 3ct
[see Fig. 15.4 of the text]
(b) Chair C6H 12 : E , C3 , C2 , 3act; D 3ct

Boat C6H 12 : E , Cz, av ,
(c) B 2H 6 : E, C2 , 2C2, ah;
a~;
Czv
D 2h
(d) [Co(en) 3j3+: E, 2C3 , 3C2 ; D 3

(e) Crown S8 : E , C4 , C2 , 4C 2, 4ad, 2S8 ; D4d
Only boat C6H 12 may be polar, since all the others are D point groups. Only
[Co(en) 3j3+ belongs to a group without an improper rotation axis (S 1 x a) , and
hence is chiral.
15.2 The operations are illustrated in Fig. 15.2. Note that R 2 = E for all the
Fig 15.2
operations of the group, that ER = RE = R always, and that RR' = R 'R for
this group. Since C2ah = i, ahi = C2 , and iC2 = ah we can draw up the following
group multiplication table:
E
Cz
ah
c2
C2
ah
c2
ah
ah
ah
i
C2
Cz
ah
273
The trans-CHCI=CHCI molecule belongs to the group C 2".
15.3 Consider Fig. 15.3. The effect of a 11 on a point Pis to generate a"P, and
p
the effect of C2 on a11 P is to generate the point C2a1,P. The same point is
generated from P by the inversion i , so Cp"P= iP for all points P. Hence,
C2a" = i, and i must be a member of the group.
15.4 Refer to Fig. 15.3 of the text. Place orbitals h 1 and h 2 on the H atoms
and s, p,, p,, and p , on the 0 atom. The z-axis is the C~ axis; x lies
perpendicuiar to a:., y lies perpendicular to av. Then draw up the following
table of the effect of the operations on the basis:
E
Cz
av
a'v
hi
hz
s
Px
P. .
hi
hz
s
P..
P. .
hz
hi
s
hz
hi
s
Px
hi
hz
s
-p..
p,
p,
- pv
p,
p,,
p,
- p ..
- p..
p,
Express the columns headed by each operation R in the form

(new)= (originai)D(R)
where D(R) is the 6 x 6 representative of the operation R. We use the rules of
matrix multiplication set out in the Further information section of Chapter 15.
274
is reproduced by the 6 X 6 unit matri x.

(ii) C2: (hz, h,,
S,
-p-" -py, p,)~(h" hz,
S,
Pn Py, p, )
is reproduced by
0
1
0
0
0
0
1
0
0
0
0
0
0
0
0 0
0
0
0 0
1
0
0 0
D(C2 ) =
0 - 1
0 0
0 -1 0
0
0
0
0 1
(iii) av: (hz, h, , s , Pn -pY' p,)~(h 1 , h2 , s, Pn pY' p,) is reproduced by
0 1 0 0
0 0
1 0 0 0
0 0
D(av) = 0 0 1 0
0 0
0 0 0 1
0 0
0 0 0 0 -1 0
0 0 0 0
0 1
(iv) a~ : (h 1, h2 , s, -p-" pY, p,)~(h 1 , h2 , s, Pn py, p,) is reproduced by
1 0 0
0 0 0
0 1 0
0 0 0
0 0 0
0 0 1
D(a~) = 0 0 0 - 1 0 0
0 0 0
0 1 0
0 0 0
0 0
(a) To confirm the correct representation of C2av = a~ we write
D(C2)D(av) =
0 1 0
1
0
0
0
0
0
0
0
0
0
0
1
0
0
0
0
0
0
- 1
0
0
1
0
0
0
0
0
0
1
0
0
0
0
0
0
1
0
0
0
0
0
0
0
-1
0
0
0
0
- 1
0
0
0
0
0
0
0
1
0
0
0
0
1
0
0
1
0
0
0
0
0
0
0
0
0
1
0
0
0
0
0
=D(a ~)
0
0
1
0
0
0
0
0
0
1
0
0
0
0
0
0
-1
0
0
0
0
0
0
1

(b) Similarly, to confirm the correct representation of
0
1
0
0
0
0
1
0
0
0
0
0
0
0
1
0
0
0
0
1
0
0
0
0
0
0
0
0
0
0
0
-1
0
1
0
0
1
0
0
0
0
0
0
0
1
0
0
0
0
0
0
-1
0
0
1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
-1
0
1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
-1
0
0
0
0
0
0
0
0
0
1
0
av o~= C~.
275
we write
0
0
0
0
0
=D(C2)
The characters of the representatives are the sums of their diagona l elements:
(a) The characters are not those of any one irreducible representation, so the
represe ntation is reducibl e. (b) The sum of the characters of the specified sum
is
E
3A 1
81
282
3AI + 81
+28~
a~
c2
Ov
1
2
-1
-2
1
-2
3
- 1
2
wh ich is the same as the original. Therefore the representation is 3A 1 + 8 1 +

282.
15.5 Representat io n I:
D(C,)D(CJ = 1 X 1 = 1 =D(Ch)
and from the character table is either A 1 or

+ I or -1 respective ly.
A~.
Hence, either D(av) = D(ad) =
276
Representation 2:
D(C3 )D(C2 ) = 1 X ( -1) = -1 =D(C6)
and from the character table is either B 1 or B2 . Hence, either D(av) =
-D(ad) = 1 or D(av) = -D(ad) = -1 respectively.
15.6 Use the technique specified in the Comment of Example 15.4.
: All four orbitals are left unchanged, hence
x= 4
x= 1
C No orbitals are left unchanged , hence x= 0
5 No orbitals are left unchanged, hence x= 0
ad: Two orbitals are left unchanged, hence x= 2
C3 : One orbital is left unchanged, hence
2:
4:
The character set 4, 1, 0, 0, 2 spans A 1+ T 2 . Inspection of the character table

of the group Td shows that s spans A 1 and that the three p orbitals on the C
atom span T 2 Hence, the s and p orbitals of the C atom may form molecular
orbitals with the four H1s orbitals. In Td, the d orbitals of the central atom
span E+T2 [Character table , final column], and so only the T 2 set
(d,r, dY" d,x ) may contribute to molecular orbital formation with the H
orbitals.
15.7 (a) In C3v symmetry the H1s orbitals span the same irreducible
representations as in NH 3 , which is A 1+ A 1+E. There is an additional A 1
orbital because a fourth H atom lies on the C3 axis. In C3v. the d orbitals span
A 1+ E + E [see the final column of the C3v character table]. Therefore , all five
d orbitals may contribute to the bonding. (b) In Czv symmetry the H1s orbitals
span the same irreducible representations as in H 20 , but one 'H 20 ' fragment
is rotated .bY 90 with respect to the other. Therefore , whereas in H 20 the Hls
orbitals span A 1+ Bz [H 1+Hz, H 1- Hz], in the distorted CH 4 molecule they
span A 1+ 8 2 + A 1+ B 1 [H 1 + H 2 , H1- H 2 , H 3 + H4, H 3 - H4]. In C2v the d
orbitals span 2A 1+ B 1+ B2 + A z [Czv character table] ; therefore , all except
A 2(dxy) may participate in bonding.
15.8 (a) C2v . The functions x 2 , y 2 , and z z are invariant under all operations of
the group, and so z(5z 2 - 3rz) transforms as z (A 1), y(5y 2 - 3r 2 ) as y(B 2) ,
x(5x 2 - 3r 2 ) as x (B 1), and likewise for z(x z- y z), y(x 2 - z 2) , and x (z z- y z).
The function xyz transfers is 8 1x Bz x A 1= A 2 .
Therefore, in the group C2v. t~ 2A 1+ A 2 + 28 1+ 28 2 .

(b) C3v . In C3v. z transforms as A ~> and hence so does z 3 . From the C3v
character table , (x 2 - y 2 ,xy) is a basis"for E , and so (xyz, z(x 2 -y 2 )) is a basis
277
for A 1x E =E. The linear combinations y(S/ - 3r 2) + 5y(x 2 - z 2) o: y and

x(5x 2 - 3r 2) + 5x(z 2 - y 2) o::x are a basis for E. Likewise, the two linear
combinations orthogonal to these are another basis for E . Hence, in the group
c )v , J-7 A1 + 3E.
(c) Td. Make the inspired guess that the f orbitals are a basis of dimension
3 + 3 + 1, suggesting the decomposition T + T +A. Is the A representation A 1
or A 2? We see from the character table that the effect of S4 discriminates
between AI and A2. 'Under s4 ' X-7 y ' Y-7- X ' Z-7- z' and so xyz-7 xyz. The
character is x= 1, and so xyz spans A 1. Likewise, (x 3 , y ', z 3)-7 (y ", -x\ -z 3)
and x= 0 + 0- 1 = -1. Hence, this trio spans T 1. Finally,
{x(z 2- y 2), y(z 2- x 2), z(x 2 - /)}-7 {y(z 2- x 2 ), - x(z 2 - / ) , - z(/- z 2)}.
resulting in
x= 1, indicating T 2. Therefore , in
Td , f-7 AI+ Tl + T 2.
(d) Oh. Anticipate an A+T+T decomposition as in the other cubic group.

Since x, y, and z all have odd parity, all the irreducible representatives will be
u. Under S4 , xyz-?xyz (as in (c)) , and so the representation is A 2" [see the
character table]. Under S4 , (x 3 ,y 3 , z 3)-?(y 3 , -x 3 , -z 3 ), as before , and x= -1 ,
indicating T 1u. In the same way, the remaining three functions span T 2u.
Hence, in Oh,j-?A2u+T1u+T2u
(The shapes of the orbitals are shown in Inorganic chemistly, D. F. Shriver, P.
W. Atkins, and C. H . Langford, Oxford University Press and W . H . Freeman
& Co (1990).]
The f orbitals will cluster into sets according to their irreducible
representations. Thus (a) f-7 A 1+ T 1+ T 2 in Td symmetry, and there is one
nondegenerate orbital and two sets of triply degenerate orbitals. (b) f-7 A 2u +
T 1u+ T 2u, and the pattern of splitting (but not the order of energies) is the
same .
15.9 (a) In Td, the dipole moment transforms as T 2 [see the character table],
and we require fr x T 2x f; to contain A 1 if the transition is to be allowed.
(i) f(d,,) = E, r(dn,) = T2 , fr X T 2 X f; = T 2 X T 2 x E
Then, since T 2 x E = (6, 0, -2, 0, 0), it follows that
T 2 X T 2 X E = (18, 0, 2, 0, 0)
The number of times that A 1 appears in this set is determined using the recipe
in Example 15.8 (and footnote 3 on p. 448 of the text), and is 1. Therefore the
transition dxy-7 d,, is not forbidden. However, closer analysis (dealing with the
representations rather than the characters) shows that the transition is not in
fact allowed.
(ii) For the transition dxy-7 J: yz we use
278
f;=T 2 , Tr=A 1 [Problem 15.8]

fr XTzX r , = A, X T zX T z=TzX Tz=A , + E+T, +Tz
Since the product contains A" the transition is allowed .
(b) In Oh the electric dipole moment operator transforms as T 1u
(i) f(d,2 ) = Eg, f(dxy ) = T 2g
But g X u X g = u; therefore the product f; x r," x fr cannot contain A 1g and so
the transition is forbidden.
(ii) [;(dxy ) = T 2g, r r(fxyz ) = A 2u [Problem 15.8]
fr X T 1u X f; = A2u X Ttu X T2g
= A2u X (A zu+ Eu + T,u +Tzu)
= A 1g + Eg+T2g + T,s
The product contains A 1g, so the transition is allowed.
15.10 (a) xyz changes sign under the inversion operation (one of the
symmetry elements of a cube) ; hence it does not span A 1g and its integral
must be zero.
(b) xyz spans A 1 in Td [Problem 15.8] and so its integral need not be zero.
(c) xyz~ -xyz under z~ - z (the ah operation in D 6h) , and so its integral
must be zero.
15.11 Refer to Fig. 15.4, and draw up the following table:
n,
1Cz
1[3
1[4
ns
1[6
1[1
1Cg
1[9
nw
X
10
0
0
2
n,
1Cz
1[3
1[4
ns
1[6
1[1
1Cg
1[9
nw
ns
1[6
1[1
1Cg
n,
1Cz
1[3
1[4
1[9
av
1[4
1[3
1Cz
n,
1Cg
1[1
1[6
ns
nw
nw
a~
1Cg
1[1
1[6
ns
1[4
1[3
1Cz
n,
1[9
1Cw
E
Cz
1[9
[xis obtained from the number of unchanged orbitals.] The character set
CT '
v
n:,
Fig15.4
n;
rr,
"TT3
1T5"
a-:_
rr,._
(10, 0, 0, 2) decomposes into 3A 1 + 2A 2 + 2B 1 + 3B 2 Now form symmetry

adapted linear combinations as explained in Section 15.9:
279
n(AI)=.n1+.n4+ns+nx [from column I]

.n(AI) = Jt2+n.1 +.n6+n1 [column 2]
.n(A1)=.nq+Jt111
[column 9)
n(Az) = Jt1 + .7ts- Jt4- .7tx
[column 1)
n(Az) =n2 +.n6- .7tJ- Jt7 [column 2]

n(81)=.nl-ns +n4-nx [column l]
.n(81)=nz-n6+.nJ -.n7 [column 2]
n(8z) = Jt1- Jts- Jt4+ .7tx [column 1]
n(8z)=nz-.7t6-.nJ+.n7 (column 2)
n(8z) = Jtq- Jt111
[column 9]
[The other columns yield the same orbitals.]

15.12 We proceed as in Problem 15.11, and begin by drawing up the
following table:
N2s
N2p,
N2p v N2p ,
02p,
02pr 02p ,
0'2p, 0'2p ,,
E N2s
N2p,
N2p, N2p,
02p,
02p,. 02p,
0'2p,
0'2p , X
0'2pr 0'2p , 10
C2 N2s -N2p, -N2p)' N2p , -0'2p, - 0'2pv 0'2p, -02p, -02p,. 02p ,
av N2s N2px -N2p.v N2p, 0'2p, -0'2p, 0'2p, 02p... -02p. 02p ,
Uv
N2s -N2p...
N2py N2p , -02p,
02py 02p , -0'2p,
0
2
0'2p, 0'2p , 4
The character set (10, 0, 2, 4) decomposes into 4A 1+ 28 1+ 38 2 + A 2 We then

form symmetry adapted linear combin ations as described in Section 15.9:
1/J(AI)=N2s
[column 1]
1/J(AI) = N2p,
(column 4]
1/J(AI) = 02p, + 0 '2p , [column 7]

1/J(AI) = 02pv- 0'2p,
[column 9]
1fJ(8 1)=N2p,
(column 2]
1/J(BI) = 02p, + 0'2py [column 5]

1/J(B 2) = N2pv
[column 3]
1/J(82) = 02pv+ 0'2py [column 6]
280
._
1/J(B 2)=02pz-0'2pz
1fJ(A2) =02p,-0'2p,
[column 7]
[columnS]
[The other columns yield the same combinations.]

15.13 We shall adapt the simpler subgroup C6v of the full D 611 point group .
The six .n-orbitals span A 1 + B 1 + E 1 + E 2, and are
1
a1 =
v 6 (.nl + .n2 + .n3 + .n4,p- .ns + .n6)
b1 =
v 6 (.nl- .n2+ .n3- .n4 + .7ts- .n6)
el =
.)
1v
e =
(2.nl- .n2- .n3 + 2.n4- .ns- .n6)

12
1
(.n2- .n3 + .ns ~ .n6)
2
1~12
(2n, + n,- n,- :"',- n, + n,)
v2 (.n2 + .n3- .7ts- .n6)
The hamiltonian transforms as A 1; therefore all integrals of the form

f 1/J 'H'f/J dr vanish unless 1/J' and 1/J belong to the same symmetry species. It
follows that the secular determinant factorizes into four determinants:
f
=~ f (.n~-.n2+
A I: Ha,a, =
B1: Hb,b,
E1: H , ,(a )e,(a)
Hence:
E2:
(.nl + ... + .n6)H(.nl + ... + .n6) dr =a+ 2/3
= a- /3,
)H(.n~-n2 + ) dr=a -
H , , (b)e,(b)
=a- /3,
,a-~-t: a-~-t:~ =0
Hence:
la+~-t: a+~-t:~ =0
0,
solves to t:=a -/3 (twice)
<l =a+ f3, H, 2(b)e2(b) =a+ f3,
H , 2(a) e2
H , ,(a)e,(b) =
2/3
He 2(a) e2(b) =
solves to t:=a+/3 (twice)
16. Rotational and vibrational spectra

Exercises
16.1
1 1
1
- = -+-
f.1
ml
m2
(Section 16.7]
We work in atomic mass units (u) and convert at the end of the calculation.
Nuclide masses are given inside the back cover of the text.
1
1
(a) f.l/U = l.00
78
1
27
.
, giving f.1 = 0.9796 U = 1.6266 X 10- kg
34 9688
1
1
1
27
(b) f.l/U = .
+ .
, giving f.1 = 1. 9044 U = 3.1624 X 10- kg
2 0141 34 9688
1
1
(c) f.l/U = l.00
1
78
36 9651
, giving f.1 = 0.9811
U=
27
1.6291 X 10- kg
In each case, the reduced mass is dominated by the lighter atom.

16.2
I= 1.1R 2 (Table 16.1)

=
,
m 1m 2
78.9183 x 80.9163 u
,
xR-=
xRm1 + m 2
78.9183 + 80 .9163
=39 .9524uxR 2
= 39.9524 X 1.6605 X 10- 27 kg X (2.28 X 10- 10 m) 2
=
3.45
10- 45 kg m2
h
16.3
B = ncl (14], implying that I= ncB

4
4
R=(-h )112
4ncB
We use
m 1m 2
126.904 X 34.9688
f.1 = m 1 + m 2 = 126.904 + 34.9688 u =
27 .4 146 u
Rotational and vibrational spectra
282
and hence obtain
R=
( 4.n X 27.4146 X 1.660 54 X
1.054 57 x 10- 34 1 s
)
27
10
1
1
10 - kg X 2.997 92 X 10 emS - X 0.1142 em -
=232 .1 pm
16.4 The wavenumber of the J = 2 ~o transition is
ii=B(J+2)(J+3)-BJ(J+1); withf=O , ii =6B

Since B = 1. 9987 em - 1 [Table 16.2], the Stokes line appears at
ii= 20 487-6 x 1.9987 cm- 1=20 475 cm - 1
16.5 In the transition, u = 1 ~o and J = 3 ~2; hence its wavenumber is
ii=ii0 +6B
[2B(J+1)=6BJ
= 2648.98 + 6 x 8.465 cm- 1 [Table 16.2] = 2699.77 cm- 1
16.6
(k)
w= ;
WI - W -
1/2
[Section 16.7]
(fl. )1/2-1
---w
11-'
7
5
3
3
_ {mCZ Na)me Cl){mCZ Na) + me Cl)}}1'2 _
1
5
3
3
- {mCZ Na) + me Cl)}mCZ Na)me 7Cl)
7
3
5
12
={me et) . mCZ Na)+me Cl)} ' _
1
5
7
3
me Cl) mCZ Na) + me et)
= {34.9688. 22.9898 + 36.9651} 1'2 -1
36.9651 22.9898 + 34.9688
= -0 .0108
Hence, the difference is 1.08 per cent.
16.7
k)1 /2
w = (;
and w = 2.nv = 2.ncii
112
283
Therefore ,
2
k =Jtw = 4n Jtc
v , Jl = fmC5Cl)
2 2
34.9688
= 4n 2 X - 2
1.660 54 X 10- 27 kg
x (2.997 924 x 10 10 ems - I x 564.9 em - 1) 2

= 328.7 N m - 1
16.8
~Gu+ l l2 =v-2(u+l)xcv+
[25b]
The transitions are therefore

~G 1 , 2 =v-2xcv
~G112 =
v- 4xcv
~Gs1 2 =
v- 6xcv
and so on. Clearly, the fundamenta l transition with the highest wavenumber is
1
~G1 ,2 = v- 2x"v = 384.3-3.0 cm- 1= 381.3 cm and the next highest is
~G 312 =
v- 4xcii = 384.3-6 .0 em - I= 378.3 em - I
16.9 The zero-point energy is
G(O) =t v-
tx v
0
[24c]
=~ (384.3- 0.75)
cm- 1= 191.8 cm - 1
and
De= Do+ f hw =Do+ G(O)
=2.153 x 8065.5 cm - 1+ 191.8 cm - 1= 1.756 x 104 cm - 1, 2.177 eY.
16.10 Use the character table for the group C2v [and see Example 16.1 OJ . The
rotations span A 2 + B 1+ B2 The translations span A 1+ B 1+ B2. Hence the
normal modes of vibration span 4A 1+ A 2+ 2B 1+ 2B 2 . (A 1, B 1, and B2 are
infrared active; a ll modes are Raman active.)
16.11 Select the polar molecules. They are (b) HCI, (d) CHCl_, , (e) CH 2Cl 2 ,
(f) Hp , (g) H 20 2 , (h) NH 3 .
284
16.12 Select those in which a vibration gives rise to a change in dipole

moment. They are (b) HCI , (c) C02, (d) H 20 , (e) CH 3CH 3 , (f) CH 4 , (g)
CH 3CI.
16.13 Select those with an anisotropic polarizability. They are (a) H 2, (b)
HCI, (d) CH3CI, (e) CH2CI 2, (f) CH3CH3.
16.14 Aobs = ( 1
+~)A
[Section 16.3, vex: 1/A.]. When using this formula , take
v > 0 for recession and u < 0 for approach. Since 50 m.p.h. corresponds to
22.4 m s- 1,
Aobs = ( 1-
2 _ 9~~:
: ss: S 1) X 660 nm = 0.999 999 925 X 660 nm
Aobs
)
(520 nm
)
v= ( ;:--1 c = 2.998 X l08 ms - 1X
0nm -1
66
= -6.36 x 10 7 m s- 1, or about 1.4 x 108 m.p.h.
[Since v = c, the relativistic expression
1- -u
)112
Vobs =
( 1+c
should really be used . It gives u= -7.02 x 107 m s- 1.]
Aobs - 1) c [Section 16.3, Exercise 16.14]
v= ( ;:-
16.15
= (706.5 nm
654.2 nm
(2kT
2A.
)112
oA.=-ln2
[llb], which implies that
7n 2
T= 2k
=
c::r
48 X 1.6605 X 10 - 27 kg
(2.998 X 108 m s- 1X 61.8 X 10 - 12 m) 2
2 x 654.2 x 10 - 9 m
2 x 1.381 x 10 - 231 K - Ix In 2
=8.4 X 105 K

5.3cm- 1
16.16
ov=-- rlps
[12b ],implying that r =
5.3 ps
~_
_
uv1em 1
5.3 ps
(a) r = --=53 ps
0.1 - 5.3 ps
(b) r = - - = 5 ps
1
(c) r =
5.3 ps x 2.998 x 10 111 em s- 1
= 2 ns
100 x 106 s- 1em
-
16.17
ov =
(a) r=1
5.31 cm - 1
r/ps
10 - 11 s=0.1 ps , implying that
(b) r= 100 X (1
16.18
[12b]
ov=50cm-i
ov =0.5 cm - 1
10- 13s) = 10 ps , implying that
N~upper~
= e -6./kT [Boltzmann distribution; Example 16.2]
N lower
= e - hcV!k T
hcv
= 1.4388 em K x 559.7 em -I
[inside front cover]
=805.3 K
N( upper) = e-sosJ K/T
N(lower)
(a) N(upper)=e -sos3129R =0.067
N(lower)
--
(b) N (upper)= e-R05 3/soo =0.20

N(lower)
-
16.19
(1:15)
(1:5)
28 = 13.10 cm- 1 [19], B= ncl

4
[14], l=fi.R 2 [Table 16.1]
285
286
1.0078 X 126.9045
f.1 = 1.0078 + 126.9045 u =
0 9999
34
57_ x_ 1.,...
0 -:-::_ ,J--s ---:-----:;:;,.....--.,---,-------,----:-)
- - - - -....,...,.,,.....---,----,1-.0:-:54-:-:= ( 4n X 2.9979 X 10 10 emS 1 X 0.9999 X 1.660 54 X 10 27 kg X t X 13.10 em 1
= 1.6044 X 10- 10 m= 160.4 pm
1.0078 X 18.9908
f.l.(HF)
= 1.0078 + 18.9908 u = 0 9570 u
f.l.(HJsCl)
1.0078 X 34.9688
1.0078 + 34.9688 u = 0.9796 u
1.0078 X 80.9163
f.l.(HsiBr) = 1.0078 + 80.9163 u = 0.9954 u
1.0078 X 126.9045
f.1.(W271) = 1.0078 + 126.9045 u = 0. 9999 u
v/cm- 1
f.l/U
k!(N m- 1)
HF
HCl
HBr
HI
4141.3
0.9570
967.1
2988 .9
0.9796
515.6
2649 .7
0.9954
411.8
2309.5
0.9999
314.2
Note the order of stiffness HF > HCl > HBr >HI.

16.21 Form
:c (~)
v = ~c = 2
112
with the values of k calculated in
Exercise 16.20 and the following reduced masses:

2.0141 X 18.9908
f.l.CZHF) = 2.0141 + 18.9908 u = 1. 8210 u
and similarly for the other halides. Then we draw up the following table:
112
ki(N m - 1)
967.1
1.8210
3002.3
/1/U
v/cm - 1
515 .6
1.9044
2143.7
287
314.2
1.9826
1640.1
411.8
1.9652
1885.9
An alternative procedure is to use

v(HX) = ( 11 CHX)) 112
vCHX)
11 (HX)
16.22
where
~Gu+ 1 12 =
~Gu+ 1 12 =
v-2(v + 1)xcv
[25b]
G(v + 1)- G(v)
Therefore , since
~Gu+ l l2 =
(1 - 2xc)v - 2vxcv
a plot of ~Gu + 1 12 against v should give a straight line which gives

(1 - 2xe)v from the intercept at v = 0 and -2xcv from the slope . We draw
up the following table:
v
G(v)/cm - 1
1481.86
2885.64
4367 .50
2781.54
7149 .04
2677.44
9826.48
2573.34
12 399 .8
~Gu+ 1 12 1cm - 1
The points are plotted in Fig. 16.1. The intercept lies at 2885.6 and the
2600
Fig16.1
~
(.)
7 2400
''
(.')
'
<l
2200
'
0
slope is -312.3/3 = -104.1; hence xcv = 52.1cm - 1 Since

v - 2xcv = 2885.6cm- 1, it follows that v = 2989.8cm - 1
288
The dissociation energy may be obtained by assuming that the molecule

is described by a Morse potential, for then
ji 2
Dclhc=-_ [combine eqns 23b and 24c]

4XeV
16.23 The separation of lines is 48 [Section 16.6], so B = 0.2438 cm - 1

Then we use
R= ( 4:n:cB)
112
[Exercise 16.19]
with /1 =tmC 5Cl) =t
34.9688 U =17.4844 U
Therefore:
R=
(
4:n X 17.4844 X 1.6605 X
= 1.989 X
1.054 s1 x w- 34 1 s
)
10 - 27 kg X 2.9979 X 10 10 em s- 1 X 0.2438 em - 1
10- 10 m = 198. 9 pm
16.24 Decide which modes correspond to (i) a changing electric dipole

moment , (ii) a changing polarizability , and take note of the exclusion
rule [Section 16.13].
(a) Nonlinear: all modes both infrared and Raman active.

(b) Linear: The symmetric stretch is infrared inactive but Raman active.
The antisymmetric stretch is infrared active and (by the exclusion rule)
Raman inactive. The two bending modes are infrared active and
therefore Raman inactive.
16.25 The molecule is centrosymmetric, and so the exclusion rule applies
[Section 16.13]. The mode is infrared inactive (symmetric breathing
leaves the molecular dipole moment unchanged at zero), and therefore
the mode may be Raman active (and is). In group theoretical terms , the
breathing mode has symmetry A 1g, and the quadratic forms x 2 + y 2 and
z 2 have this symmetry (and hence the mode is Raman active).
112
Problems
16.1
cU = ~ (2kT In 2) 112
A
[lib]
2
= 2. 998 X 10 Km S 1.237 x
IX
(2 X 1.381 X w-23 J K - I X 298 K X In 2) 1/2

(m/u) X 1.6605 X 10- 27 kg
w-'
(m/u) 112
OA
(a) For HCI, m= 1 + 35 u = 36 u, so ;:- = 2.1 x w - ~
OA
(b) For ICI, m = l27+35u=l62u , so;:-=9.7x 10- 7

For the second part of the problem, we also need
ov ov
2(2kT In 2)
--:-=-=v
v
c
OA
112
[ll a]=A
(a) For HCI, v(rotation) = 2Bc= 2 x 10.6 cm - 1 x 2.998 x 10 11 ' em s- 1

= 6.4 x 10 11 s- 1 or 6.4 x 10 11 Hz
Therefore, ov(rotation) =2.1 X
w-fi X 6.4 X 10 11 Hz= 1.3 MHz
v(vibration) =2991 cm - 1 [Table 16.2]; therefore

Ov(vibration) = 2.1
10- fi X 2991 cm - 1 = 0.0063 cm - 1
(b) For ICI, v(rotation) =2x 0.1142cm - 1 x2.998x 10 111 cm s- 1

=6 .8 x 109 Hz
ov(rotation) = 9. 7 X
w-
6.8 X 10 9 Hz = 6.6 kHz
v(vibration) = 384 cm - 1
Ov(vibration) = 9.7 X
16.2
w-
(nm)
I kT
r=-=-
4ap kT
11 2
384 em - I= 0.0004 cm - 1
289
290
For HCl , with m = 36 u,

1.381 X 10- 23 1 K - I X 298 K
r 4 X 0.30 X 10 18 m2 X 1.013 X 105 Pa
27
x ( nx36 x 1.661 x 10 - kg )112
23
1
1.381 x 10- 1 K - x 298 K
= 2.3
10- 10 S
The width of the collision broadened line is therefore approximately

1
bv = 2nr = 2n X 2.3 X 10- 10 s
700 MHz
The Doppler width is approximately 1.3 MHz [Problem 16.1]. Since the
collision width is proportional top [ oc l!r and r oc 11 p], the pressure
must be reduced by a factor of about 1.3/700 = 0.002 before Doppler
broadening begins to dominate collision broadening. Hence , the pressure
must be reduced to below 0.002 x 760 Torr = 1 Torr.
ov
16.3 Rotational line separations are 2B (in wavenumber units) and 2Bc
(in frequency units) . Hence, the transitions are separated by 596 GHz or
19.9cm- 1. We know that
h
B= - I
4JT.C _!_
.
[15b]
and from Table 16.1,

l _j_ = mAR 2(1 - cos
e)+ (m~mB) R 2(1 + 2 cos e)
rnA= 1.6735 X 10- 27 kg, ms = 2.3252 X 10- 26 kg , and m = 2.8273 X 10- 26 kg
with R = 101.4 pm and e= 10647' , which give

J_j_ = 1.6735 X 10- 27 kg X (101.4 X 10- 12 m) 2 X (1- COS 10647')
1.6735 X 10- 27 X 2.3252 X 10- 26 kg2
+
2.8273 x 10-26 kg
x(101.4x10 - 12m)z
(1 + 2 COS 10647')
= 2.8158 X 10 - 47 kg m 2
X
Therefore,
1.054 57 x 10- 34 1 s
8=----------~----~--~~---=--~
4JT. X 2.9979 X 108 m S- l X 2.8158 X 10- 47 kg m2
= 994.1 m- 1= 9. 941 em -
291
which is in accord with the data .
v2
16.4 LlGu+ ll2 =v-2(v+ l)x 0 v and De=-_
(25b and Exercise 16.22]
4X 0 V
A plot of LlGu+ 112 against v + 1 should give a straight line with intercept vat
v + 1 = 0 and slope - 2x 0 v. Draw up the following table:
v+l
LlGu+112/cm -
284.50
283 .00
281.50
The points are plotted in Fig . 16.2. The intercept is at 286.0, so v=286cm - 1
286
285
.,
E
.!2.... 284
t
~
<l
Fig 16. 2
\
\
283
1\
282
281
\
2
\
3
V+f
~ S==-C.
The slope is -1.50, so x0v=0.750cm - 1. It follows that
De=
(286 cm - 1) 2
1
X 0.
em 1 = 27 300 cm - , or 3.38 eY.
4
750
The zero-point level lies at 142.81 cm - 1, and so D 0 =3.36eY.

Since f.1. =
22.99 X 126.90
_
. +
. u = 19.464 u
22 99 126 90
292
the force constant of the molecule is

k = 4n 2,uc 2v2
=4n 2 X 19.464X 1.6605 X 10- 27 kg X (2.998 X 10 10 cm S - 1 X 286 cm - 1) 2

=93.8Nm - 1
16.5
l=,uR 2
.uC2Ci60)
12.000 X 15.9949
= 12.000 + 15.9949 u = 6.8562 u
.uC3c160)
13.0034 X 15.9949
= 13.0034 + 15.9949 u = 7.1724 u
2 16
cBC C 0)
h
1.054 57 x w-34 1 s
= 4nl = 4n x 6.8562 X 1.660 54 X 10- 27 kg x (112.82 X 10- 12 m) 2
=5.7911 x 10 10 Hz=57.911 GHz.

The first four transitions lies at 115.82 GHz , 231.64 GHz , 347.47 GHz, and
463 .29 GHz (separation 2Bc] .
Since the ratio of reduced masses is 1.0461 , the 1 (--0 transition of 13C 160 will
lie at
115.82 GHz
l.0
= 110.71 GHz
461
This differs from the 12 C 60 transition by 5.11 GHz. Hence , the equipment
must be able to resolve lines separated by 5 GHz.
16.6 The separations between neighboring lines are:
20.81 , 20.60, 20.64, 20.52, 20.34, 20.37, 20.26
mean: 20.51 cm - 1
Hence 8 = tx 20.51 cm - 1 = 10.26 cm - 1 and

h
f=--=
4nc8
R=
(~)
112
1.054 57 x w-34 1 s
=2.728 X 10- 47 kg m2
4n x 2.99793 x 10 10 cm s- 1 x 10.26cm- 1
[Table 16.1] with ,u = 1.6266 x 10- 27 kg
47
_ (2.728 X 10- kg m
1.6266 x 10 27 kg
1/2 _
-129 .5 pm
(Exercise 16.1]
293
[A more accurate value would be obtained by ascribing the variation of the

separations to centrifugal distortion, and not taking a simple average .]
Since Bcx 111 and fcx/-{ , Bcx 11/-{. Hence, the corresponding lines in 2 H 35 Cl will
lie at a factor
11- (' H 3'Cl)
~A-(H3sCl)
1. 6266
3.1624 = 0.5144
to low frequency of the 1H 35Cllines . He nce, we expect lines at 10.56, 21 . 11 ,

31.67, .. . cm - 1
16.7 It is sensible to do Problem 16.14 first, and then to use the result that
FJ = (!).Ef_I - !). r+ 1)/ he= 2Bo(21 + 1)

1
HC1
]=
/).ii~1- 1 /cm - 1
/).ii)+ 1/cm- 1
F1 /cm - 1
28 0 /cm - 1
2906.25
2843 .63
62 .62
20.87
2925.92
282 1.59
104.33
20.87
2944.99
2799.00
145.90
20 .86
2963.35
2775 .77
187.58
20.84
2981.05
2752 .01
229.04
20.82
2998.05
Hence, the mean 8 11 is 10.43 em - 1 .

2
HC1
2101.60
2069.24
32.36
10.79
2111.94
2058.02
53 .92
10.78
2122 .05
2046.58
75.47
10.78
2131.91
2034.95
93 .96
10.77
2141.53
2023.12
118.41
10.76
2150 .93
]=
!). ii ~~- /em - 1

/).ii)+ 1/cm - 1
F1 /cm - 1
28 0 /cm - 1
Hence, the mean 8 0 is 5.39cm - 1 .

Since ~A-CH 35 Cl) = 1.6266 X
16.1], we conclude that
h )
R = ( n11-cB
4
112
w-n kg and /-{eH 35 Cl) = 3.1624 X 10-
128.5 pm CH"Cl) and 128.2 pm
and hence the bond lengths are essentially equal.
27
kg [Exercise
294
[In the original reference , the effects of centrifugal distortion are taken into
account.]
16.8
h
R = ( :rr cB
4 11
)1/2 and ~v = 2cB(J + 1)
We use
11(CuBr) =
63.55 X 79.91
. + . u = 35.40 u
63 55 79 91
and draw up the following table:
13
14
15
~v/MHz
84 421.34
0.10057
90 449.25
0.100 57
96 476.72
0.100 57
B/cm- 1
[B =
~v/2c(J
+ 1))
Hence ,
R = ( 4:rr X 35.40 X 1.6605 X
) 112
1.054 57 x 10- 341 s
27
10
1
1
10- kg X 2.9979 X 10 em s- X 0.100 57 cm -
=218 pm
16.9 From Table 16.1

m(' 60)mC 2S)
m(' 2C){m(' 60)R 2+ m( 32S)R ' 2}
/('6012C32S) = m('6012C32S) (R + R ')2+
m('60 12C32S)
m(' 60)m( 34S)
m( 12 C){m(' 60)R 2+ mC4S)R ' 2}
/('6QI2C34S) = m('6012C34S) (R + R ')2+
m('60 12C34S)
m(' 60) = 15 .9949 u , m( 12C) = 12.0000 u , mC2S) = 31.9721 u , and m( 34S) =
33.9679 u. Hence,
/(' 60 12C 32 S)/u = 8.5279(R + R ') 2+ 0.20011(15.9949R 2 + 31.9721R ' 2)
/(' 60 12C 34 S)/u = 8.7684(R + R ') 2+ 0.19366(15.9949R 2+ 33.9679R ' 2)
The moments of inertia may also be obtained from the spectral data , since the
lines occur at 2cB(J + 1). The mean values are
/(' 60 12C 32S) = 1.379 98 X 10- 45 kg m2
IC 60
c'~s)
295
= 1.414 60 X 10 -~s kg m2
Therefore, after conversion of the atomic mass units to kg , the equations we

must solve are
1.379 98 X 10- 45 m2 = 1.4161
10- 26 X (R
R 1f
1.414 60 X 10- 45 m2 = 1.4560 X 10- 26 X (R + R

X 10 -26R
1
)
+ 5.3150 X l0 - 27 R 2 + 1.0624
+ 5.1437 X l0 - 27 R 2 + 1.0923
12
These two equations may be solved for R and R I. They are tedious to solve,
but straightforward. The outcome is R = 116.28 pm and R I= 155.97 pm.
1
D11 =Dc-ii with V = :\-v--!-xcii
16.10
(24c]
(a) 1HCI: iiI= 1344.8- -} x 52.05 em - 1 = 1481.8 cm - 1, or 0.184 eY

Hence, D11 =5.33-0.18=5.15eV
2f-lWXc
(b) 2HCI: -h- = a 2
[24c], so iixc <X 1/f-l as a is a constant. We also have
De= ii 2/4xcii [Exercise 16.22]; so ii 2 <X 1/f-l, implying ii <X 11f-l 112 . Reduced masses
were calculated in Exercise 16.1, and we can write
1-lCHCI)) 112
1
veHCI)= ( J-leHCI)
xvCHCI)=0.7172 x2989. 7cm = 2144.2 cm - 1
1-lCHCI)
1
XcveHCI) = J-leHcl) X XciiCHCI) = 0.5144 X 52 .05 cm =26.77 cm- 1
ii0 =
t x 2144.2- t x 26.77 cm -
= 1065.4 cm- 1, 0.132 eV
Hence,
D 0 = 5.33-0.132 eY = 5.20 eY
16.11
V(R) = De{1- e - u(R -
Rcl f
(23]
296
1.008 X 85.47
27
,u(RbH) = 1.oo + .4 u = 1.654 x 10- kg
8 85 7
v2
Dclhc=-_=
4xcv
a= 2Jrcii
(936.8 em- 1) 2
4 X 1415
. em
(2~J
112 =
2Jrcv{
15505em
2(De~hc)hc}
(1.92eV)
t/ 2
=2n x 2.998 x 10 10 em s- 1 x 936.8 em - 1

X
{ 2 X 15 505 em-
1X
1. 654 x 10- 27 kg
} 112
6.626 X 10- 34 J S X 2.998 X 10 10 em S- 1
= 9.144 x 109 m- 1 = 9.144 nm- 1 = 11(0.1094 nm)

Therefore ,
V(R) = {1- e- (R-Re)/(0. 1094nm)} 2
De
with Rc=236.7 pm. We draw up the following table:

Rlpm
50
100
200
300
400
500
600
700
800
VIDe
20.4
6.20
0.159
0.193
0.601
0.828
0.929
0.971
0.988
These points are plotted in Fig . 16.3 as the line labeled J = 0.

20
Fig 16.3
,\
1=
1\\
1\ .......
tqo 80
40
- v_,.:;::<,....
........
1= 0
-v
ll
./
200
400
600
R/pm
BOO
1000
297
For the second part , we note that B IX 1/ R 2 and write

R~
R-
V }=V+hcBJ(J+l) X -----:;
with Be the equilibrium rotational constant, B" = 3.020 em - 1 We then draw up
the following table using the values of V calculated above:
Rl pm
50
100
200
300
400
600
800
1000
ReiR
VIDe
V1ofDe
V !\ofDe
Vtoof De
4.73
20 .4
27 .5
48.7
64.5
2.37
6.20
7.99
13.3
17.2
1.18
0.159
0.606
1.93
2.91
0.79
0.193
0.392
0.979
1.42
0.59
0.601
0.713
1.043
1.29
0.39
0.929
0.979
0.30
0.988
1.016
1.099
1.16
0.24
1.000
1.016
1.069
1.11
1.13
1.24
These points are also plotted in Fig . 16.3.

16.12 The center of mass of a diatomic molecule lies at a distance x from
atom A and is such that
m Ax= m 8 (R- x)
and hence is at
ms
x=-R, m=mA+ms
m
The moment of inertia of the molecu le is
I= m Ax 2 + m 8 (R- x) 2
16.13
N, IX (2! + 1) e - hcBJ (J + l)t kT
[Boltzmann distribution]
The maximum population occurs when

d
-N
IX { 2-(21+1)2-hcB}
1
dJ
kT
e - hcBJ(J + l)l kT=O
298
which occurs at
hcB
(21+1) 2- = 2
kT
or when
kT
)1 12
]max= ( 2hcB
-2
For ICl, with kT/hc=207.22 cm - 1 (inside front cover).

207.22 cm - 1)
I max= ( 0.2284 cm - 1
112
-2= 30
For a spherical rotor ,

N, oc (21 + 1)2e -
hcBJ(J + I )Ik T
and the greatest population occurs when

dN' oc
-
{ 8J+4
dJ
hcB(21 + 1)
kT
3
}
e -hcBJ(J + I )tkT =O
which occurs when

kcB(21 + 1) 3
kT
4(21 + 1)
or at
kT)I /2
J max = ( h;;[j
1
- 2
For CH 4 ,
= (207.22 cm 5. 24 Cffi -
J max
16.14
1
) 112 _
~=
2 _
S(v , J)=G(v)+F(J)
=
s(v + 1, J
I )
(v + i
[Section 16. 9]
)v+ B,J(J + 1)
s(v, J ) = v + B" + J
I
I (
J + 1) - B ,J (J + 1)
I
For the P-branch (J = J -1):

1
~Sf= v + 8 ,+ 1(1- l)J- B,J(J + 1)

=
v- (B ,+ I+ B, )J + (B,+ I- 8 , )1 2
299
For the Q-branch (J' =1):

!!iS?= v + Bu+ }(J + 1)- B.,J(J + 1)
= V + (B u+ 1 - B.,)J(J + 1)
For the R-branch (J' =1 + 1):

!!iSf = v + B., +I(J + 1)(1 + 2)- BJ(J + 1)
= v+2B.,+ I + (3B .,+ I- B., )J + (B u+ 1 - B.,)P
Note that
/!iSf- /!iSj = 2B.,+I + (3Bu +l- Bu)J + (Bu +1+ Bu)J
= 2Bu +l + 4B u+ IJ
=2B .,+ I(21+1)

/!iSf- 1- /!iSj+1= 2B,,+ 1+ (3B.,+ 1- B.,)(J -1) + (Bu +l- Bu)(J -1) 2
- {-(B., +1+ Bu)(J + 1) + (Bu +1- Bu)(J + 1n
=2B.,(21 + 1)
Hence,
!!iSf- l!iSj
t'!iSf-1- l!iSj+l
B., +1= 2(21+1) ,B.,= 2(21+1)
1:
2925.9
2865.1
60.80
62.60
10.13
10.43
2945.0
2843.6
101.4
104.3
10.14
10.43
!!iSf/cm - 1
!!iSj !em -I
(t'!iSf-t'!iSj)/cm- 1
(!!iSf_~- !!iSj_1)/cm - 1
2906.2
Bu +/cm - 1
B)cm- 1
Hence, B0 = 10.43 cm - 1 and B1= 10.13 cm - 1. We then use

h
Ru= B
( 4n,uc .,
and obtain
)1/2with,u=l.6266x10 -
27
kg
[Exercise 16.1]
3
2963.3
2821.6
141.7
10. 12
300
For the force constant use

~S~=ii+2B v+ t with
v=O
ii = 2906.2-2 x 10.13 cm - 1 = 2885 .9 em - '

k = 4:n: 2,u.c 21i 2= 480.7 N m _,
16.15 For substitution of an atom that lies on the figure axis , the problem is
solved if we can treat the case of a linear molecule. Let an atom of mass m lie
at z from the center of mass of the molecule and another m 1 lie at z' (the
latter 'atom' may represent the remainder of the molecule). Then mz = m 1 Z 1
and I= mz 2+ m 1 z 1 2 If the separation of the two atoms is R, we also have
z + z' = R . Now Jet m be changed tom+ om but remain at the same position.
The center of mass is now determined by (m +om )i = m 1 i 1 but still i + i' =
R. The new moment of inertia is
I'= (m+om)i 2 +m'i 2

We now construct an expression for I' -I. First , note that
m
z' =m-l x z and z' = R - z
Then also
m+om
i'=--~-
X i and i=R- i '
It follows that
1
m R
m R
i= m+m'+om = M+om
=
m'
M+om
Mz
m
[M=m+m']
Mz
M+om
X -=-:--:--::-1
+ (m+om)i 2 -m Z -mz 2
(m+om) 2M 2
(m+om)M 2
m 2z 2
,
= mi(M+om) 2z 2+ (M+om) z z 2----;;;;--mz -
I' -I=m 1 i
12
12
Mom
M +om x z 2 [after some rearrangement]
We now write om=M'-M, when
1'-1=
301
(M'- M)M z z= z z !).M

M'
h
Now, B = 4nc1 and B' = 4ncl'

and so
1 1)
h (
h (B-8')
h!).8
1'- 1= 4nc
W-B =4nc ~ =4nc88'
and
z z=
h 1).8
4ncB8' !).M
Now express the quantities numerically:

,
z-=
(!).8/cm - 1)xcm
1
x- 1
1
4nx2 .9979xl010cms - 1 (B/cm- )(8'/cm- ) !).Mfu
1.05457xl0- 34 Js
1
1.6605 X 10- 27 kg
= 1.6858 X
(1).8/cm - 1)
10- 19 m2X (8/cm - I)(B' /cm-1)
1
!).M/u
But !).M/u = !).Mf(g mol- 1) if !).M is now interpreted as the molar mass (as
distinct from the molecular mass); so
1).8/cm - 1
(z/pm)z= 1.6858x lOs (8/cm - 1)(8'/cm - J)(!).M/g mol J)
[The general case is discussed in the original reference, Amer. f. Phys. 21 , 17

(1953).)
By multiplication of the right hand side by c 2/c 2 , we obtain
(zlpm? =
5.053 80 X 109(c 1).8/MHz)
--------~--...,....
1
(cB/MHz)(c8 '/MHz)(!).M/g mol - )
which we can use for the analysis of the data. Since !).v(J) = 2(1 + 1)c8, for
1 = 10 we can write
(a) cBC5Cl 12<YfeF5) =
30 711.18 MHz
1395.96 MHz
302
(b) cBC5CI 125TeF5 ) =
30 713.24 MHz
- -- 22
1396.06 MHz
(c) cBeC1 121YfeF5) =
29 990.54 MHz
22
1363.21 MHz
MC5Cl 121i'J'eF5) = 34.9688 + 125.0331 + 5 x 18.9984 = 254.9939 g mol - 1

MC 5CI 125TeF 5) = 254.0051 g mol - 1
MC7Cl 121YfeF5) = 256.9902 g mol - 1

From (a , b), c LlB/MHz=O.lO, LlM=0.9850 g mol- 1
5.053 80 X 109 X 0.10 )
z(Te) = ( 0.9850 x 1395 .96 x 1396.06
1/2
pm = 16 pm
From (a , c), c LlB/MHz = 32.75, LlM = 1.9808 g mol - 1

5.053 80 X 109 X 32.75 )
z(Cl) = ( 1. 9808 x 1396.06 x 1363.21
1/2
pm = 210 pm
Therefore, the distance between the Te and Cl atoms is 226 pm
S(u,J) = (u + ! )v + BJ(J + 1)
16.16
LlS~=v-2B(2J - 1)
(Llu=1, M=-2]
LlSJ=v+2B(2J+3)
(Llu=1, M=+2]
The transition of maximum intensity corresponds, approximately , to the

transition with the most probable value of J, which was calculated in Problem
16.13:
The peak-to-peak separation is then

LlS = LlSJ"'"' - LlS~,x = 2B(2Jmax + 3)- {-2B(2Jmax-1)}
= 8B(Jmax+ -t)
=
(__!!__)
B
2hcB
112 =
(32Bk!:\ 112
he }
To analyze the data we rearrange the relation to

hc(LlSf
B= 32kT

and convert to a bond length using
h )
R = 4:np.cB
1/2
= :rrc
(k!:\
1/2
!15 -;;}
11 /\)We can now draw up the following table:
TIK
fl/U
t:..S/cm - 1
Rlpm
HgC1 2
HgBr 2
Hgl2
555
30.13
23.8
349
565
57 .14
15.2
401
565
77.73
11.4
458
Hence , the three bond lengths are approximately 350, 400, and 460 pm.
303
17. Electronic transitions

Exercises
17.1
I'
lg/= -c[J]/
[1c]
= -855 M- 1cm- 1X 3.25
10 - 3 MX 0.25 em= -0.69S
Hence /'II= 0.20, and the reduction in intensity is 80 per cent.
17.2
1
/'
c = - [J)/lg I
[lc]
- 1
= 6.67 X 10-4M X 0.35 em lg 0.655 = 787 M- 1cm - 1
= 787 dm 3 mol- 1cm- 1= 787 x 10 3 cm 3 mol - 1cm - 1 [1 dm = 10 em)
=7 .9x10 5cm 2 mol - 1
17.4
.s4.=
-1
_ 1 _1
lg(l-0.465)=1.5mM
. em
-286 M em x 065
Jcdv
[2)
c
The absorption begins at v =I= 1.30 x 10 15Hz (at 230 nm) and extends to
1.03 x 10 15 Hz. The integral is therefore approximately

.s4.= tx 1.21 x 104 M- 1cm - 1x (1.30-1.03) x 10 15 s- 1
= 1.63 x 10 18 M- 1cm- 1s- 1 [Area of triangle= t x base x height]
Then the oscillator strength is
f= 1.44 X 10- 19 X .s4./(cm 2 mol - 1S- 1)
Electronic transitions
305
We write
.<1/. = 1.63 x 10 1x dm-' mol - 1 cm - 1 s- 1

= 1.63 x 10 1x x 10-' em-' x
w--' mmol -
em - I s- 1
= 1.63 x l0 1x cm 2 mmol- 1 s- 1
and hence obtain
For ii= 35 000 cm - 1, v= cii= 1.05 x 10 15 Hz, and

1.05
!=
10 15 Hz X (2.65 X l0 -.1o C mr
7.095xl0 - 43 Hz(Cm) 2 .
0 0104
17.6 A strong transition has f= 1. a weak transition has f = 10- -', and a
forbidden transition has f much smaller than 10- -' . Hence (a) weak, (b)
strong , (c) forbidden, (d) forbidden , (e) strong.
17.7 Conjugation of double bonds in the diene causes the absorption
characteristic of the bond [Table 17 .2] to shift to longer wavelengths [electron
in a box behavior]. Hence the absorption at 243 nm is due to the diene and
that at 192 nm to the butene.
17.8 The weak absorption at 30000cm - is typical of a carbonyl group [Table
17 .2] . The strong C=C absorption, which is typically at about 180 nm, has
been shifted to longer wavelength (213 nm) by the conjugation of the double
bond and the CO group.
1
17.9 The internuclear distance in Hi is greater tha n that in H 2 The change in

bond length and the corresponding shift in the molecul ar potential energy
curves reduces the Franck-Condon factor for transitions between the two
ground vibrational states. It creates a better overlap between u = 2 of Hi and
u = 0 of H 2 , and so increases the Franck-Condon factor of that transition.
17.10
I
I'
c;=- [:i]tlg/withl=0.20cm
We use this formula to draw up the following table:
306
0.0010
0.0050
0.0100
0.0500
0.814
447
0.356
449
0.127
448
3.0 X 10- 5
452
Hence, the molar absorption coefficient is t: = 450 M- 1 em - t.

1
I'
t: =-[J]llg/
17.11
[lc]
- 1
0.010 Mx 0.20 em Ig 0.48 = 159 M- t em - t
I'
_ = 10 I
IJJd
= 1o-o.OtOM x t59W' cm - 1x 0.40

= 10- 0 636 = 0.23, or 23 per cent
For water , [H 20]=
1.00 kg
_ gmol_ 1
18 02
L=55 .5M
and t: [l) = 55.5 MX 6.2 X 10- 5M-t cm - 1 = 3.4 X 10- 3 cm - 1

=0.34m- 1, so l!t:[1]=2.9m
I'
Hence , lim= -2.9 x lg I
(a) /'II=0.5 , l=-2.9m x lg0.5=0.9m
(b) /'/l=0.1, l=-2.9m x lg0.1=3m
17.13
.sf/. =
t:dv
[2]; refer to Fig. 17.1
From the illustration,

.sf/. =
f X Emax X 2~v 1 12
[area= f
height X base]
mean:
449
v------<~
(a) :J1=1.5x10 14 s- 1 x1x10 4 M - 1 cm - 1 =1.5 xl0 1xM- 1 cm - 1 s- 1

which is equivalent [Exercise 17.4] to 1.5 x 10 1x cm 2 mmol- 1 s- 1. Hence
f= 1.44X 10- 19 X 1.5X 10 1H=0 .2

(b) :J1=1.5xl0 14 s - 1 x5xl0 2 M - 1 cm- 1 =7.5xl0 16 M- 1 cm - 1 s- 1
which is equivalent to 7.5 x 10 111 cm 2 mmol - 1 s- 1. Therefore,
f= 1.44 X 10- 19 X 7.5 X 10 16 =0.01

Problems
-1
17.1
I'
[J =d lg/ [Ic]
Suppose I' lies in the range /" l'1/, then
1"-M
(J]max=
d lg - ,-
(J]min =
2.cl lg /" +I M
M)
1 (/"l'1[J] = (J]max- (J]min = - d lg f" + M

1
=--;,Ig
Mil") =--;/g
I (
2l'1!\
l -7')
(1l+M/1"
307
308
1
1- x
)
since-- = 1-x if x ~ 1 and - - = (1-x) 2= 1-2x.
1+x
1+x
We then use
1
-z
.
lg(1z)
=
ln(1z)
=
.
(
2 30
2 30
[z~ 1]
to write
2~~
- 2M
lg ( 1 -Y) = 2.30/"
Hence ,
2
4
2.30x275M 1cm 1x0.15cm x O.OZ = 4 x 10- M
17.2 e= Emaxe -" 212r [v=O at band center, fa constant] e= temax when v 2=
2f In 2. Therefore , the width at half height is
~v 1 12 = 2 X (2fln 2)
~vfn
11
2, implying that f =Sin
Now we carry out the integration:
.st1 =
dv = Emax
J:.,
212
e -'' r dv
[J~"' e -'2 dx=nl'2]
= emaxC2.nT)l'2
) I /2 (
)1 /2
8ln 2
= 4ln 2 Emax ~VI /2
( 2Jl'~v~
12
= Emax
Jl'
= 1.0645Emax ~Vl /2
In terms of wavenumbers,
~v 112
= c ~ii 1 12 , so
.stl = 1.0645CEmax ~V112

From Fig. 17.41 of the text we estimate Emax=9.5 M- 1cm - 1 and
4760 em - I. Then
.stl= 1.0645 x 2.998 x 10 10 em s- 1x 9.5 M- 1cm - 1x 4760 cm - 1
= 1.4 x 10 15 M- 1cm - 1s- 1
~ii 1 12 =
309
Then f = 1.44 X 10- l<J X 1.4 X 10 15 = 2.0 X 10 - 4

The area under the curve on the printed page is about 1288 mm "; each mm"
corresponds to about 190 .5 cm - 1 x 0.189 M- 1 cm - 1, and so I Edii = 4 .64 x
104 M- 1 cm - 2 Then <11 =c I Edii= 1.4 x 10 15 M- 1 cm - 1 s- 1 , corresponding to J=
2.0 x 10- 4 as before. We can conclude that the transition is forbidden.
1 1
17.3 L'1ii 112 =;:- A." where A.' and A." are the wavelengths corresponding to
f crnax on the short and long wavelength sides of the peak. From Fig. 17.42 of
the text we can estimate the following values:
280 nm peak: A.' = 260 nm , A" = 300 nm
.-:'1 ii 112 = (
2~0 - 3~0) X 10
m - I = 5. 13
Then , since Emax= 11 M- I em -
I,
10 em - I
from Problem 17.3
<11 = 1.0645ccmax f1ii 112 = 1.0645 X 2.998 X lOlllcm s- 1

x 11 M- 1 cm - 1 x 5.13 x 103 cm - 1
= 1.8 x 10 15 M- 1 cm - 1 s- 1
and
f = 1.44 x
w - l<Jx 1.8 x 10 15 =2 .6 x
w-
430 nm peak: A.' = 390 nm , A. "= 455 nm

L'1ii 1, 2 =
C~o - 4 ~ 5 ) x 10
m - = 3.66 x 10 cm -
Then, since Emax= 18M - 1 cm - 1 , from Prob lem 17.3
<11 = 1.0645 x 2.998 x lOw em s - 1 x 18 M- 1 cm - 1 x 3.66 x 103 cm - 1

=2.1
10 1s M - 1 cm - 1 S -
j= 1.44 X 10- l<J X 2.1
10 1s= 3.0 X 10- 4
For the second approach, we transfer the spectra to a wavenumber scale by

drawing up the following table:
A/nm
250
iii( 1000 cm - 1)
c/(M - 1cm - 1)
260
270
280
290
300
310
40.0
38.5
37.0
6
35.7
10
34.5
11
33.3 32.3
8
5
320
330
340
31.3
3
30.3
29.4
310
.Vnm
350
360
v/(1000 cm- 1)
t:/(M - 1 cm- 1)
28 .6
1
27 .8 27.0 26.3
3
5
8
A./nm
450
460
v/(1000cm- 1)
22.2 21.7 21.3

14
1
0
EI(M- 1 cm- 1)
370
380
390
400
410
420
430
440
25 .6
11
25.0 24.4 23 .8 23 .3 22.7

14
17
17
16
16
470
These points are plotted in Fig. 17.2. The area under the '280 nm' peak is
20
_l:Q
Fig 17.2
'
'"\
""c
b:>~
0 J
20
30
5.72 x 104 M- 1 cm- 2 and that under the '430 nm ' peak is 6.80 x 104 M - 1 cm- 2 . It
follows that
.s4.(280 nm) = 2.998 x 10 10 em s- 1 x 5.72 x 104 M- 1 cm- 2
= 1.7 x 10
15
M -
cm - 1 s- 1
.s4.(430 nm) = 2.998 x 10 10 em s- 1 x 6.80 x 104 M - 1 cm- 2

=2.0 x 10 15 M - 1 cm- 1 s- 1
These two values correspond to
311
/(280 nm) =2.5 X 10- 4 , /(430 nm) = 2.9 X 10 - 4

For the final part , we write v = cl J.. , so dv = - c dAI). 2 ; then
-I"' - I"'
d/. -
c dV-C
Ed).). 2
-CEmax
I"'
e - (.l -.lu)' l 2y
). 2
d).
II
where e -c-ol'' 2r is a gaussian centered on ). 0 with width d~termined by y:
y=
~). f"
n
81
2 [as in Problem 17.2]
The integral may be evaluated numerically , or approximated by setting ). 2 = J..6

in the denominator and extending the lower limit to - oo (neither of which
introduces much error if the lines are narrow). Then
""- =-CE2-max I"'

...II
J.. 0
e -(,( - ,(")21'-r dII.1 =
cEmax (2ny)
112
J.. 0
_"'
Therefore ,
= (2n ~J.. f/2) 112CEma x =

dl
8 In 2
= 1.0645
CE
CE max
4 In 2
J..5
ma~
(__!!___) 112
~A1 12
J.. 5
~). 1I'
For the 280 nm peak,
~A 112 =
40 nm
1.0645 X 2.998 X lORm S- l X 11 M- 1 cm - l X 60 X

.s(l =
(280 X 10- 9 m?
w-~
f = 1.44 X 10- 19 X 1.8 X 10 15 = 2.7 X 10- 4

For the 430 nm peak,
~A 1 12 = 65
nm
1.0645 X 2.998 X lORm S- 1 X 18 M- 1 cm - 1 X 65 X 10- 9 m

.s(l =
(430 X 10 - 9 m) 2
f = 1.44 X 10- 19 X 2.0 X 10 15 = 2. 9 X 10- 4

17.4 One procedure is to use the formula developed in the last part of
Problem 17.3:
312
:iJ. = 1.0645
cc
LlA. /?
rna~fi I -
From Fig. 17.43 of the text , we find LlA112 = 38 nm with A.0 = 290 nm and t:max =
235 M- 1 cm- 1; hence
1.0645 X 2.998
108 m S- 1 X 235
M-
(290 x 10
m/
cm - 1 X 38 X 10- 9 m
:il = ------------~~~~~~----------9
=3.4x
f = 1.44 X
10 16 M - 1 cm- 1 s- 1
10- 19 X 3.4 X 10 16 = 4.9 X 10- 3
The transition appears to be weakly forbidden. Since the dipole moment

components transform as A 1(z) , B 1(x) , and B 2(y), excitations from A 1 to A"
B 1, and B2 terms are allowed.
17.5 The absorbance A is defined as t: [J]l [Section 17.1]. When only Hln is
present at a concentration C
A = t:Cl where t: is the molar absorption coefficient of Hin .
When all the Hin is present as In -
A" = t:"Cl where t:" is the molar absorption coefficient if In - .

The absorbance of the mixture is
A' = t:(1- a)Cl + t:"aCl

where a is the degree of ionization of Hln. Therefore ,
A' = t:Cl + (t:"- t:)aCl

= A+a(A" -A)
which solves to
A'-A
a = A"-A
.
[In - J[H +]
Smce K . = [InH]
present]
we know that
[since [H +J is determined by any other acid
313
and so
1-a
A'-A
pH=pKa-lg-a- with a= A"-A
When A"=O,
A' 1-a
A'
a=1-- - - = - - A' a
A-A'
Hence
A'
_ = (1+
lQPH- pK"
and we can draw up the following table :

pH
A'/A
1.00
3.5
4.5
0.90
0.91
0.76
0.50
0.24
0.09
0.01
0.001
These points are plotted in Fig. 17.3 .

10
-...;;;.
Fig 17.3
!'....
1\
\
\
05
1\
\
\
0
0
[\-..
6 pH 8
From the data , E = 8.33 x 10 3 M - 1 cm - 1, E" = 18.33 x 103 M - 1 cm- 1, and A=

(1-a)CLE, A"=aCLE" . The ratios AICL and A"/CL are the effective molar
absorption coefficients of Hln and In', and we write them t and t". We draw
up the following table :
314
pH
10
tile= 1-a
a
t"/c:"=a
Average a
1
0
1
0
0.92
0.08
0.09
0.08
0.50
0.50
0.50
0.50
0.05
0.95
0.95
0.95
1.00
1.00
1.00
1.00
Then we form
pH=pK, -Ig - 1-a

pH
6.0
7.0
8.0
pKa
7.1
7.0
6.7
mean: 6.9
17.6 Use the technique described in Example 16.9 [the Birge-Sponer

extrapolation method]. Plot the differences Lliiu against v , Fig. 17.4. The
600
400
Fig 17.4
'
\.
1\
'
200
1\
\
\
12
16
20
315
separation between neighboring lines vanishes at v = 17. Each square

corresponds to 100 em - I. Therefore , since the area under the line is 68.0
squares, the dissociation energy is 6800 cm - 1 The J~:;;- ~X excitation energy
(where X denotes the ground state) to u=O is 50062 .6cm - 1, which
corresponds to 6.21 e V. The J~:;;- dissociation energy, for
OzCL:;;-)--?0+0 *
is 6800 em -
I,
0 2(X)-7 0
or 0.85 e V. Therefore, the energy of
+0 *
is 6.21 + 0.85 eV = 7.06 eV. Since 0 *--? 0 is -190 kJ mol - 1 , corresponding to

-1.97 e V, the energy of
0 2(X)-720
is 7.06 eV -1. 97 eV = 5.09 eY.
17.7 We draw up the following table :
Nz
co
Line
EK/eY
Binding
energy leY
5.6
4.5
2.4
7.2
49
1.7
15.6
16.7
18.8
14.0
16.3
19.5
Assignment
2pag
2p:n."
2sa~
2pa
2p:n.
2sa *
The spacing of the 4.5 e V lines in N 2 is 0.24 e V, or about 1940 em - 1 The

spacing of the 4.9 eV lines in CO is 0.23 eV, or about 1860 cm - 1 These are
estimates from the illustrations of the separation of the vibrational levels of
the N{ and co + ions in their excited states.
17.8 The electron configuration of NO is (2sa *)2(2p:n.) 4 (2pa) 2(2p:n. *) 1 The
data refer to the kinetic energies of the ejected electrons, and so the
ionization energies are 16.52 eV, 15.65 eY, and 9.21 eY . The 16.52 eY line
refers to ionization of a 2pa electron, and the 15.65 eY line (with its long
vibrational progression) to ionization of a 2p:n. electron. The line at 9.21 eV
refers to the ionization of the least strongly attached electron, that is 2p:n. * .
17.9 (a) Ethene (ethylene) belongs to D 211 In this group the x, y, and z
components of the dipole moment tra nsform as B311 , B 211 , and B 111 respective ly.
"2(-hf~
316
[See a more extensive set of character tables than in the text.] The n orbital is
B 1u (like z, the axis perpendicular to the plane) and n * is B 3g. Since B 3g x
B 1u = B 2u and B2u X B2u = A 18 , the transition is allowed (and is y-polarized).
(b) Regard the CO group with its attached groups as locally C2v . The dipole
moment has components that transform as A 1(z) , B 1(x) , and B 2 (y) , with the
z-axis along the C=O direction and x perpendicular to the R 2CO plane . The
n orbital is Py (in the R 2CO plane), and hence transforms as B 2. Then *
orbital is Px (perpendicular to the R 2CO plane) , and hence transforms as B 1
Since frX ri= B 1 x B 2= A 2, but no component of the dipole moment
transforms as A 2, the transition is forbidden .
17.10 (a) Vibrational energy spacings of the lower state is determined by the
of the peaks of A. From the spectrum , v = l800cm- 1 [the scale is
about 1 em~ 11745 cm - 1] . (b) Nothing can be said about the spacing of the
upper state levels (without a detailed analysis of the intensities of the lines).
For the second part of the question , we note that after some vibrational decay
the benzophenone (which does absorb near 360 nm) can transfer its energy to
naphthalene. The latter then emits the energy radiatively.
~pacing
17.11 The fluorescence spectrum gives the vibrational splitting of the lower
state . The wavelengths stated correspond to the wavenumbers 22 730 , 24 390 ,
25 640, 27 030 cm - 1, indicating spacings of 1660 , 1250 , and 1390 cm - 1 The
absorption spectrum spacing gives the separation of the vibrational levels of
the upper state. The wavenumbers of the absorption peaks are 27 800 , 29 000 ,
30 300, and 32 800 cm - 1 The vibrational spacings are therefore 1200, 1300,
and 2500 em - I .
J.lx= -e
J
L
1f!, .(x)x1f!,(x)dx , 'If!, =
2)
112
sin
(nnx)
2e
= - r,
JL xsin (nL'nx) sin (nnx)

L dx
0
!
0
ifn'=n+2
8eL
-(nz
n(n+ 1)
)(2n+1) 2 ifn'=n+l
The integral is standard , but may also be evaluated using 2 sin A sin B =
cos(A - B)- cos(A +B).
317
h2
hv= " +' - "= (2n+ 1)
8me 2.
Therefore, for the transition n + 1.,_ n,
For the transition n + 2 .,_n, f = Q.

For R = 140 pm,
(2n + l)h .
v= 8m
With L = 22R
c
The highest filled orbital (the HOMO) has n = 11 [there are 22 electrons to
accommodate] , so 2n + 1 = 23. Therefore,
23h
23 X 6.626 X 10- 34 J S
v=--=
8mee
8 X 9.109 X 10- 31 kg X (22 X 140 X 10 - 12 m) 2
= 2.2
x 10 14 Hz
which corresponds to v =vic= 7400 cm- 1 This wavenumber suggests that

carotene absorbs in the infrared, which it does, but not for this reason
(infrared absorption is by vibrational excitation). In order to obtain a carrot
color (orange), we need absorption in the blue. The oscillator strength of the
12 .,_ 11 transition is
{121 X 144} =
f = (~)
3nz
233
3.1
and hence
Therefore, if we take D.v = 5000 cm - 1, corresponding to D.v = 1.5 x 10 14 Hz ,
.sa
.sa
D.v
1.5 x 10 14 s- 1
<:=- =
= 1.4 x 105 M - 1 cm - 1
Then for T = 50 per cent
318
17.13
Jcx (2n+ 1) 3
n 2(n + 1) 2
[Problem 17.12)
The value of n depends on the number of bonds: each n bond supplies two n
electrons and so n increases by 1. For large n,
n4
Jcx Sn 3 _,S and Jcx n

Therefore, for the longest wavelength transitions f increases as the chain
length is increased. The energy of the transition is proportional to (2n + 1)/ L\
but as n ex L, this energy is proportional to 11 L. Therefore , the transition
moves toward the red as L is increased and the apparent color of the dye
becomes bluer.
17.14 f.l = -e
'1/JuX'I/J udx
From Problem 12.13,
17.15 J.l= -eSR
[given)
1(R)2}
S= 1 +-R +- {
a0 3 a0
e - Rtao
[eqn 10, Section 14.4)
319
Rla0
fifo
0.737
1.376
1.093
0.573
0.233
0.08
0.02
O.Ql
These points are plotted in Fig. 17.5.
Fig 17.5
lr"\.
10
\
\
1/
1\
~
0
0
The maximum in f occurs at the maximum of RS:

d
dS
dR(RS)=S+R dR
That is,
l(R)J =0
R*- - - 1+
a0 3 a 0
320
This equation may be solved either numerically or analytically [see

Abramowitz and Stegun , Handbook of mathematical functions, Section 3.8.2],
and R * = 2.103 80a0 .
As R---'?0, the transition becomes S---'?S , which is forbidden. As R---'? oo , the
electron is confirmed to a single atom because its wavefunction does not
extend to the other.
17.16 From the work in Problem 17.5, we know that
A'=A+a(A" - A)
in the notation defined there. There exists some wavelength at which A" = A.
At that wavelength A' is independent of a . This is the isosbestic point.
17.17 Use the Clebsch-Gordan series [Chapter 13] to compound the two
resultant angular momenta , and impose the conservation of angular
momentum on the composite system.
(a) 0 2 has S = 1 [it is a spin triplet]. The configuration of an 0 atom is

[He)2s 22p 4 , which is equivalent to a Ne atom with two electron-like 'holes' .
The atom may therefore exist is a spin singlet or as a spin triplet. Since S, = 1
and S2 = 0, or S, = 1 and S2 = 1 may each combine to give a resultant with
S = 1, both may be the products of the reaction. Hence multiplicities 3 + 1 and
3 + 3 may be expected.
(b) N2 , S = O. The configuration of anN atom is [He] 2s 22p 3 . The atoms may
have S = f or t. Then we note that S, = f and S, = f can combine to give S = 0;
S, = t and S2 = t can also combine to give S = 0 (but S, = t and S2 = t cannot).
Hence, the multiplicities 4 + 4 and 2 + 2 may be expected.
18. Magnetic resonance

Exercises
= -0.4289 X 5.051
= -1.625
18.2
1~1
10- 2fi]
10- 27 1 T - 1 X 7.500 T X m 1
X m1
l-g1,uNB( -1-1)1
= 2 X 0.4036 X 5.051
=6.116x
[/ = 1, m1(max) = + 1, m 1 (min) = -1]
10- 27 ]
15.00 T
w-26 ]
6.626 X 10- 34 ] Hz - 1 X 150.0 X 106 Hz

----------::::---:--= 3.523 T
5.586 x 5.051 x l0 - 27 JT - 1
-hv
18.4
6.626 X 10- 34 ] Hz - 1
B=-=
,
g,,uN 5.0508 X 10 -7 ] T
,xg,
(v/Hz)
(v/MHz)
=1.3119 x 10- 7 - - T = 0.13119
T
g,
We can draw up the following table:
g,
322
Magnetic resonance
BIT
'H
g/
5.5857
1.4
7.05
(a) 60MHz
(b) 300MHz
3lp
0.85745
9.2
45.9
1.4046
5.6
28.0
0.40356
19.5
97.5
5.2567
1.5
7.49
2.2634
3.5
17.4
Na -Nae-t;.EikT
Na + Na e -t;.E/kT [Boltzmann distribution]
1-e-o.EikT
1+e-t;.EikT
f..E
1-(1-f...E/kT)
1+1
giflNB
= -=-2kT 2kT
That is ,
f..N giflNB 5.5857 X 5.0508 X 10- 27 ] T- 1 X B
-N- = _2_k_T_ = -2 -x-1-. 3-8-06_6_x_10__-:::23c-J-K
----,
_1,-X- 2_9_8_T
=3.43 x
w- 6BIT
(a) B = 0.3T,bNIN=1x10- 6
(b) B = 1.5T, bNIN = 5.1x10- 6
(c) B=10T, bNIN=3.4xl0- 5

18.6
B 1oc = (1- a)B
[Section 18.2]
lf...B,ocl = l(f...a)IB = l{b(CH3)- b(CHO)}IB

= 1(2.20- 9.80) 1X l0- 6B =7 .60 X l0- 6B
(a) B = 1.5 T, lf...B,ocl =7 .60 X 10- 6 X 1.5 T= llflT
(b) B=7.0T, IL1B,oc l=7.60x
18.7
IL1v l=l f...blxv 0
w- 6 x7.0T=53f1T
[46]=7.60 x10- 6v0
(a) Vo = 60 MHz, IL1vl = 7.60 X w- 6 X 60 MHz =460Hz

(b) v 0 = 350 MHz , If... vi = 7.60 X 10- 6 X 350 MHz=2.66 kHz
18.8 (a) The spectrum is shown in Fig. 18.1. (b) When the frequency is
changed to 350 MHz, the separation of the CH 3 and CHO resonance increases
Magnetic resonance
29Hz
323
Fig 18.1
~~~~--- ~ ----~~--
456Hz
----._j
-v
by a factor of 5.8, the fine structure (the splitting within the groups) remains
unchanged , and the intensity increases (because oNIN increases by a factor of
5.8).
18.9
r=-
2.no
(ll] = 2.nv0(o'- o)
1
=2.n X 60 X 106 Hz X (5 .2- 4.0) X 10 - 6
2.2 ms
Therefore, the signals merge when the lifetime of each isomer is less than
about 2.2 ms, corresponding to a conversion rate of 5 x 10 2 s - 1
18.10 The four equivalent 19F nuclei (/= f ) give a single line. However , the
111
B nucleus (I= 3, 19.6 per cent abundant) results in 2 x 3 + 1 = 7 lines and the
11
B nucleus (I= f , 80.4 per cent abundant) results in 2 x i + 1 = 4 lines. The
splitting arising from the 11 B nucleus will be larger than that arising from the
111
B nucleus (since its magnetic moment is larger, by a factor of 1.5, Table
18.1). Moreover, the total intensity of the 4 lines due to the 11B nuclei will be
greater (by a factor of 80.4/19.6 = 4) than the total intensity of the 8 lines due
to the 10 B nuclei. The individual line intensities will be in the ratio 8: 1 (half
the number of lines, and four times as abundant). The spectrum is sketched in
Fig. 18.2.
18.11 The A, M , and X resonances lie in those distinctively different groups.
The A resonance is split into a 1 : 2: 1 triplet by the M nuclei, and each line of
that triplet in split into a 1:4:6:4:1 quintet by the X nuclei, (with JAM > lAx) .
The M resonance is split into a 1:3: 3: 1 quartet by the A nuclei and each line
is split into a quintet by the X nuclei (with JAM > lMx). The X resonance is
split into a quartet by the A nuclei and then each line is split into a triplet by
theM nuclei (with l Ax> lMx). The spectrum is sketched in Fig. 18 .3.
18.12 (a) If there is rapid rotation about the axis, the H nuclei are both
chemically and magnetically equivalent. (b) Since leis =I=Jirans , the H nuclei are
324
Magnetic resonance
Rg 18.2
Fig 18.3
ll
'' ''
tt
chemically but not magnetically equivalent . (c) Since all JHF are equal in this
molecule (the CH2 group is perpendicular to the CF2 group), the Hand F
nuclei are both chemically and magnetically equivalent.
18.13
hv
6.626 X 10- 34 ] Hz- 1 X 9 X 109 Hz
(a) B = - = ------------:::=-----:-g1JlN
5.5857 x 5.051 x w- 27 1 T- 1
=2 X 102 T
hv
6.626 X w-34 J Hz - I X 60 X 106 Hz
(b) B= gcJlN =
2.0023 x 9.274 x 10 24 JT 1
=2mT
18.14
hv
he
B=-=-g cJle
g eJleA
_
6.626 X 10- 34 ] S X 2.998 X 108 m s- 1
=2 x 9.274 X 10- 24 JT- 1 X 8 X 10- 3 m = 1. 3 T
Magnetic resonance
1010
18.15
n=-=
NA
1010
6 x 1023 mol- 1
2 x l0- 14 molcm - 3 .
which corresponds to 2 X 10- 14 X 103 mol dm - 3 , Or 2 X
2 X 9.274 X 10 - 24 J T - 1 X 0.3 T
2 X 1.381
10
23
JK
298 K
JO - II M
7 x 10 - 4
Therefore, the difference in population is

ON = 7 X 10- 4 X 2.5
18.17
10 14 =2 X 10 11
hv
g=/1-B 8
We shall often need the value

6.62608 X 10- 34 J Hz - 1
h
!1-B
9.27402 X 10
24
JT
7.14478 X 10 - ll T Hz- I
Then , in this case

7.14478 X w - ll T Hz - I X 9.2231
g=
329.12 x 10- 3 T
109 Hz
=2.0022
18.18 a= B(Iine 1) - B(line 2)
=357.3- 306.6 mT= 50.7 mT

18.19
a = B(Iine 3)- B(Iine 2) = B(line 2)- B(line 1)
B 3 - B2 = 334.8-332 .5 mT = 2.3 mT}

a=2.3 mT
B2 - B 1 = 332.5-330.2 mT = 2.3 mT
- -
Use the center line to calculate g:

hv
9.319 x 109 Hz
g = - = 7.14478 X w - ll T Hz - 1 X -,--:-----,---.,...-/1-BB
332.5 X 10 3 T
=2.0025
325
326
Magnetic resonance
18.20 The center of the spectrum will occur at 332.5 mT. Proton 1 splits the
line into two components with separation 2.0 mT and hence at 332.5 1.0 mT.
Proton 2 splits these two hyperfine lines into two, each with separation
2.6 mT, and hence the lines occur at 332.5 1.0 1.3 mT. The spectrum
therefore consists of four lines of equal intensity at the fields 330.2 mT,
332.2 mT, 332.8 mT, 334.8 mT.
18.21 We construct Fig. 18.4a for CH 3 and Fig. 18.4b for CD 3 .
(b)
(a)
0(1)
H(1)
0(2)
H(2)
0(3}
H(3)
18.22
Fig 18.4
1367631
hv 7.14478 X 10-ll
B = gfl.B =
2.0025
T Hz-l
= 35 .68 mT x (v/GHz)
(a) v = 9.302GHz, B = 331.9mT
(b) v = 33.67 GHz, B = 1201mT
Magnetic resonance
18.23
327
oB = Blocl- B = - aB}
(g - gc)
oB= - - B
gc
g = gc(l-a)
Therefore, oB =
2.0102 - 2.0023
2.0023
X B = 3. 9 X
w-) B
(a) oB=3.9x10- 3 x 0.34T=l.3mT

(b) oB=3.9x10- 3 x1.23T=4 .8mT
18.24
1
r 1 > nov if the lines are to be resolved.
2
r 1 = 200 ms and
1
1
--=
= 2ms
2nov 2n x 90.0 Hz
Since r1 > 2 ms, the two resonances will be resolved.
18.25 Since the number of hyperfine lines arising from a nucleus of spin I is
21 + 1, we solve 21 + 1 = 4 and find that I= l
18.26 The X nucleus produces six lines of equal intensity. The pair of H
nuclei in XH 2 split each of these lines into a 1:2: 1 triplet (Fig. 18.5a). The
pair of D nuclei (I= 1) in XD 2 split each line into a 1 : 2: 3: 2: 1 quintet (Fig.
18.5b).
Fig 18.5
111111
I0 2
d~ d[,,
i
328
Magnetic resonance
Problems
g,= - 3.8260
18.1
hv
6.626 x 10 - 34 J Hz - 1 X v
B = - - =----------=--____,
g,J1N (-) 3.8260 X 5.0508 X 10- 27 J T - 1
= 3.429 x 10- 8(v/Hz) T

Therefore , with v = 60 MHz,
8= 3.429 X 10- 8 x 60 X 106 T=2.1 T
oN
-3.8260 x 5.0508 x 10- 27 JT - 1 x 2.1 T

2kT =
2 X 1.381 X 10- 23 J K - I X 298 K
g1J1N8
N=
= -5 X 10- 6
Since g1 < 0 (as for an electron, the magnetic moment is anti parallel to its
spin), the f3 state (m1 = - i-) lies lower.
18 2
1
'CJ
= 2.nov = 2.n X (5.2- 4.0)
10
6X
60 X 106 Hz
=2.2 ms, corresponding to a rate of jumping of 450 s- 1

When v = 300 MHz
r J-
2n X (5 .2- 4.0)
300Hz
0.44 ms
corresponding to a jump rate of 2.3 x 103 s- 1 Assume an Arrhenius-like

jumping process
rate oc e - E,IRT
Then
ln{rate(T')} = -.(_!_-~)
rate(T)
R
T' T
Magnetic resonance
329
and therefore
,.=
R ln (r'/r)
I
I
T T'
2.3 X 10 3
8.3141 K - l mol - 1 x ln----:450
1
----280 K 300 K
=57 kJ mol - 1
7.14478x10 - 11 T x (v/Hz)
hv
18.3
g= f..l.aB=
7.14478 X 10- 11 T X 9.302 X 109

B
0.66461
BIT
0.66461
(a) gu= 0.33364 = 1.992
0.66461
(b) g ~ = 0.33194 = 2 002
18.4 Refer to Fig. 18.4 constructed previously. The width of the CH 3
spectrum is 3aH = 6. 9 mT. The width of the CD 3 spectrum is 6a 0 . The
spli ttings are proportional to the nuclear g values, hence
a0
0.85745
= S.S857
aH = 0.1535a 11 = 0.35 mT
Therefore, the overall width is 6a 0 = 2.1 mT

18.5 Construct the spectrum by taking into account first the two equ ivalent
N splitting (producing a 1:2 :3:2: 1 quintet) and then the splitting of each of
these lines into a I :4:6:4: 1 quintet by the four equivalent protons. The
resulting 25-line spectrum is shown in Fig. 18.6.
14
330
Magnetic resonance
Fig 18.6
5.7mT
18.6 We write P(N2s) = SS. mT
2
0.10 (10 per cent of its time)
1.3mT
P(N2pz) = .4 mT = 0.38 (38 per cent of its time) .
3
The total probability is
(a) P(N) = 0.10+0.38 = 0.48 (48 per cent of its time).
(b) P(O) = 1- P(N) =0.52 (52 per cent of its time).
The hybridization ratio is
P(N2p) 0.38
3
P(N2s) = 0.10 = 8
The unpaired electron therefore occupies an orbital that resembles an sp 3

hybrid on N, in accord with the radical's nonlinear shape .
From the discussion in Section 14.9 we can write
, 1 +cos 
a' =
n.. [eqn 20 of Section 14.9]
1- cos'
'
2
-2 cos 
b' -=1-a' = - - 1- cos 
2
b' - 2 cos 

A
A= -;z =
n.. , implying that cos = - 1 +cos -v
2 +11.1
a
Then, since A= 3.8, cos = -0.66 , so = 131 o.
Magnetic resonance
18.7 For C 6 H6, a= Qp with Q = 2.25 mT
following maps:
N0
2
o.oo5ANo2
oo16Vooo5
0.076
331
[15]. Hence , we can construct the
N0
2
N0
2
o.2ooAo. 12 1
004BVNo2
0.200
o.o5o,Ao.o5o
oo5oyo.o5o
NO
2
18.8 We use the same procedure is in Problem 18.7, and construct the
following maps:
0.850
0.430 0. 18300222 0. 164~Co2
0.057
0057 0069~,.).
18.9 Rotation about the bond modulates the hyperfine coupling from
113.1 MHz to 11.2 MHz. Then use r ~ 1/2.nov:
r~
2.nx (113.1-11.2) x 106 s- 1
1 6 ns
That is, at 115 K, it rotates around the parallel axis so as .to change from one
orientation (113 .1 MHz coupling) to the other (11.2 MHz) in about 1.6 ns.
which rearranges to
=
(glf.A.Nf.A.ll) 1/.1
4.nB
5.0508 X 10- 27 J T - 1 X 4.n X 10 - 7 T 2 J - I m 3)
4.n X 0. 715 X l0 -.1 T
= (5.5857
= (3.946 x
10 -.1o m 3)
18.11
(B) ex
J''
1.1 = 158 pm
J
2
(1- 3 cos 2 (})sin(} d(}
ex
1/J
r_ y-
"
11
3x 2) dx X 2.n
cx (x - x .1)1~ 1 =Q
[x =COS(}, dx =-sin(} d(}j
332
Magnetic resonance
ern, (1 - 3 cos 2 e) sin
18.12
)=
(B
4Jl R 3
nucl
ede
-gi!N!om,~0 _ __ _ _ _ __
Je sine de
max
The denominator is the normalization constant, and ensures that the total
probability of being between 0 and emax is 1.
If emax = :n: [complete rotation), sin emax = 0 and (Bnucl ) = 0. If emax= 30o,
sin 2 emax = 0.25, and
- 5.5857 X 5.0508 X 10- 27 J T - 1 X 4:n: X 10- 7 T 2 J- 1 m 3 X 0 .25
(Bnucl) =
4:n: X (1.58 X 10- 10 m) 3 X 2
= - 0.89!T
18.13
I(w) = Are
=Are
J:
G(t) eiwt dt
J:
coswote-tlr+iwtdt
1
= - i-Are .
.
{ 1(w 0 +w+Ih)
-
Magnetic resonance
333
When wand w 0 are similar to magnetic resonance frequencies (or higher) ,

only the second term in brackets is significant (because 1/(w0 + w) ~ 1 but
ll(w 0 -w) may be large if w = w0 ]. Therefore ,
I (w) =tA re .(
1
1
)
w0 - w + 11r
1Ar
1/r
= J- A ( w -w )'-+ 1/r z
0
1 + ( w 0 -w )'-r-'
which is a Lorentzian line centered on w 0 , of amplitude tAr and width 2/r at

half height.
18.14 We have seen [Problem 18.13] that if Gcxcosw 0t, then /(w)cx
11{1 + (w 0 - w ) 2r 2}, which peaks at w = w 0 . Therefore , if
G(t) ex a cos w 1t + b cos w2t
we can anticipate that
/(w)cx1+(w 1 -w) 2r 2 +1+(wz-w?r 2

and explicit calculation shows this to be so. Therefore, /(w) consists of two
absorption lines , one peaking at w = w 1 and the other at w = w2
19. Statistical thermodynamics: the

concepts
Exercises
19.1 From the Boltzmann distribution
N+
N_ = e-P' = 1 when
19.2
q=
=
f3 = 0,
CJt~kT) 1/2
{'hr
which occurs when T = co.
[10]
120 X 10- 3kg mol- 1X 1.381 X 10- 23 J K -l X T}3t2

6.022 x 10 23 mol - 1x (6.626 x 10 - 34 J s) 2
2.00 X 10- 6 m 3
= 4.94 X 10 23 (T/ K) 312
X
(a) T=300 K, q = 4.94 X 1023 X (300) 312 =2.57 X 1027

(b) T= 400 K, q = 4. 94 X 1023 X 1023 X ( 400) 312 = 3.95 X 1027
19.3
(a)
A = h(~mY/2 [10]=h( 2n~kTr
= 6.626 x 10- 34 J s
(m
39.95 X 1.6605 X
10 - 27~g
1.381
10 - J K - lx
276pm
(T/ K)l t2
( b) q= i\3=
23
1.00 X 10- 6 m3( T/K?' 2

4.76 X 1022 ( T/K) 312
(2 .76x 10- 10 m?
(i) T= 300 K, A = 1.59 X 10- 11 m = 15.9 pm, q = 2.47 x 1Q26

(ii) T=3000K , A=5.04pm , q=7 .82x1027 .
T)
112
Statistical thermodynamics: the concepts
q=:
19.4
3,
implying that;.= (
~Y.
q ( -m ) 3t2
However as A.oc 1/m 11 2 -=
'
'q'
m'
Therefore,
hcii 1.4388(ii/cm- 1)
j3E = kT =
TIK
Therefore,
q = 3 + e-
1.43RR x "00/ 19<KI
(inside front cover]
+ 3e -
1.43RR x 4700/ !9( KJ
= 3 +0.0706+ 0.085 = 3.156
19.6
U - U(O)
N
L
.
'
E; e -/Jr;
he~
(Section 19.3] =- L.J ii; e -fihn';

q i
he
= _ _ X (O + 3500 em 3.156
+ 3 x 4700 em - I x e =he x 204.9 em 19.7
N; e -flr;
N=q
I,
e-
J.4JRRx3SIKJt i9<XJ
J.43RRx 47JOt J9()())
corresponding to 2.45 kJ mol - 1.

N+
(6a] which implies that -N =e -/3'

-
for a two- level system (N + + N _ = N; c = 0, E+ =E) . Therefore,

1
N_
f3 = ~InN+ , which implies that T=
(N )
kin
N:
335
336
Therefore,
1.4388cmK x 540cm- 1
354 K
T = ~=
ln(0.90/0.10)
=
Inhcii/k
N+
19.8 The exact and approximate values are as follows:
x!
120
Approximation 1:
Approximation 2:
21
118
19.9
(c) =
q=
10
15
3 628 800
(3 .629 X 106)
4.54 X 105
3.599 X 106
1.307 674 X 10 12
2: e-P<;= 1 + e - * sPB
1.3395 X 10 11
1.3004 X 10 12
x! =exlnx-x
[in question]
(energies measured from lower state]
-q1 (aq)
a(3
(c)
e- x
1
We write x=2J.1 6 f3B, then =-x =--:;---2f.ls 8 1 +e
e +1
This function is plotted in Fig. 19.1. For the partition function we plot
q=1+e-x
05
1\"-
04
2.0
Fig 19. 1
.....
"' t'-. .....

t--....
1\
'1\
t- t--
1.0
1\
"
01
..........
......;;;
.......
4
0
5

The relative populations are
N+
N _ =e -',x=2J.lsf3B=
2 X 9.274 X 10 - 24 J T - 1X l.OT
1.381x10-23 JK - I xT
=1.343/(T/K)
N+
- = e-1.34314 = _._
0 72
( a) T= 4 K 'N
N
__.::. = e - 13431298 = _._
0 996
( b) T = 298 K 'N_
19.10
dq
q=:Le-lic;=1+e - '+e - 2-', x=g 1J.I.Nf3B
(/=1]
dq
d/3 = g,J.i.NB dx = -g,J.i.NB(e --' + 2e -:!x)
and so
1 dq g1J.i. NB (J + 2e --') e -'
(t:) =-qd/3=
l+e -' +e -2x
19.11
e"
k!:\
S~ = Ri n ( p 9 A 3}
(23bwithp=p 9 ]
6 .626 x w- 34 1 s
h2 ) 112
A= ( 2nmkT
= (2n X 20.18 X 1. 6605 X 10- 27 kg X 1.381 X 10- 23 J K - I T) 112
3.886 x 10 - 10 m
(T/K) It2
512
1
e X 1.38l x 10- 23 JK - T
(T) 3t2
S 9 =Rln
X 5
10
"'
1xl0 Pax (3.886 x l0
m) 3
K
= R In 28 .67 x (T/K ) 512
(a) T = 200 K, S ~ = 8.3141 K - I mol- 1X In 28.67 x (200) 512
= 138 J K - 1mol - 1
(b) T= 298 .15 K, S ~ = 8.314 J K - I mol - 1x In 28.67 x (298. 15) 512
=146JK - 1mol- 1
337
338
1.4388 em K x 560 cm- 1

hcf3V = - - -5--,.0_0_K_ __
1.611
1
Therefore, q = _ e_ 1_611 = 1.249

1
The internal energy due to vibrational excitation is
U- U(O) =
NE e-P<
_ e -P<
1
[Example 19.6]
Nhcve-"CI'P
- 1 _ e -hciip
Nhcv
_1
e"e~'P
= 1.249 x Nhc x 560 cm- 1

and hence
U - U(O)
Sm/NAk= NAkT +In q
[15]
he
=0 .249x kTx560cm- 1 +1n 1.249
0.249 X 1.4388 K em x 560 em - I
K
+In 1.249
500
= 0.401 + 0.222 = 0.623
Hence, Sm=0.623R=5 .18J K- 1 mol - 1
19.13 (a) Yes; He atoms indistinguishable and mobile. (b) Yes; CO molecules
indistinguishable and mobile. (c) No; CO molecules can be identified by their
locations. (d) Yes; H20 molecules indistinguishable and mobile. (e) No; H 2 0
molecules can be identified by their locations.
19.14
A
(a) S"' = R Inp
[23b , A constant if Tis constant]
Therefore, at constant temperature

A
A
p;
1).5 = R In-- R In-= R Inm
Pr
P;
Pr
(b) Sm = R In BT 312
[23a , B constant if Vis constant]
At constant volume
For a monatomic gas , Cv= }R, so

T,
f).Sm=Cvln T
I
in accord with thermodynamics. Similarly, at constant pressure,
Sm = R In CT 511
[23b]
T,
and 1).5 = ~ R In T
I
For a perfect gas C,,=Cv+R= ~R, so
T,
1).5= C,, In T
I
also in accord with thermodynamics.
Problems
19.1
N+
-=~ X
N_
e - 1"
-11
1
'
at therma l equilibrium
ze - IAJXXx -l 50/.11MI
[Boltzmann]
= 0.23
0.30
The observed ratio is - - = 0.43 . Hence the populations are not at
0.70
equilibrium.
339
340
v
h
19.2 q=A3 , A=( nmkT) 112
2
[10 ,{3 =1/kT]
and hence
(6.626 X 10 - 34 J s) 2
10
)
(
27
23
6
3
2n X 39.95 X 1.6605 X 10 - kg X 1.381 X 10 - J K - I 1.0 X 10- m
2/3
=3.5 x 10- 15 K
The exact partition function in one dimension is
q=
2: e
-(n'-l )h'PI8mL'
11 = 1
For an Ar atom in a cubic box of side 1.0 em ,
(6.626 X 10- 34 J s) 2
8 X 39.95 X 1.6605 X 10- 27 kg X 1.381 X 10- 23 J K - I X 3.5 X 10- 15 K
X
=0.171
Then
q=
.2: e-Ol7i (nL I)= 1.00+0.60+0.25 +0.08 +0.02+ . .. = 1.95

11 =1
The partition function for motion in three dimensions is therefore
(1.0 X 10- 2 m)
341
We use hcf3 = 1/(207 cm - 1) at 298 K and 1/(3475 cm - 1) at 5000 K . Therefore ,

(i) q = 5 + e - 4707tzo7 + 3e - 475 It 2o7 + 5e - I055wzm
= 5 + 1.3 X 10 - lll + 3.2 X 10- lll + 2.7 X 10- 22 = 5.00
(ii) q = 5 + e -4707/3475 + 3e - 475 IIJ475 + 5e - 10559/3475
5 + 0.26 + 0.76 + 0.24 = 6.25

g; e -llc; g; e - hciJ\
(b) P;=-q-=-q- [g; is the degeneracy]
=
Therefore,
5
P0 =- = 1.00 at 298 K and 0.80 at 5000 K
P2 =
P2 =
3e - 475 1/ 207
5.00
3e
6.5 x 10 - 11 at 298 K
- 475 1/3475
0.12 at 5000 K
6.25
(c) We need U- U(O), and evalu ate it by explicit summation:

Um- Um(O)
(i)
NAhc
"")
11
u - u (0)
m
NAhc
1
-{0 + 4707 cm - 1 X e - 470712117 + } = 4.32 X 10- 7 cm - 1
5.00
1
-{0 +4707 cm- 1 x e - 4711713m + } = 1178 cm - 1
6.25
Hence, at 298 K
um- Um(O) = 4.88 X 10-
J mol- l
and at 5000 K
Um- Um(O) = 14.10 kJ mol - 1
It follows that
(i) Sm =
4.88 X 10- 6 J mol - 1

K
+ 8.3144 J K - I x In 5.00
298
(ii) Sm=
=
13.38 J K - I mol- 1 (esse nti ally R In 5]

14.10 x 103 J mol - 1
000K
+8.314JK - 1 mol - 1 ln 6.25
5
18.07 J K - I mol - 1
342
19.4 We measure energies from the lower states, and write
q = 2 + 2e -hcp;; = 2 + 2e -1.4388x 121.1/(T/K)

= 2 + 2 e -174.2/(T/K)
This function is plotted in Fig. 19.2 .
_)7"
.........
Fig 19.2
II
J
2
J
0
400
200
600
T/K
800
1000
(a) At 300 K
Po=-q= 1 + e-174.21300=0.64
P, = 1- P0 = 0.36
(b) The electronic contribution to U is
U- U(O)
Nhc
121.1 em-' x e-t74.213oo

-----=-:-=-=--= 43.45 em_,
1 + e -t74.2t300
which corresponds to 0.52 kJ mol- 1.

For the electronic contribution to the molar entropy, we need
U - U(O)=
q=
300K
500K
0.518 kJ mol - '

3.120
0.599 kJ mol - '

3.412

Then we form
At300K:Sm=
518Jmol - 1
00K +8.314JK - 1mo l- 1ln3 .120
3
=11.2JK - 1mol - 1
599Jmol - 1
At500K : Sm=
+ 8.314JK - 1mol - 1ln3.412
500K
= 11.4J K - I mol - 1
At 100 K, hc,B = 1/(69.50 em - 1) and at 298 K, hc,B = 1/ (207 .22 em - 1) .

Therefore, at 100 K
(a) q = 1 + e -2 U.30/69.so+ e - 43S.39/69.so+ e - 636.27/69.so
+ e -845.93/69 so+ e - llls4.3H/69.so= 1.049
and at 298 K
(b) q = 1 + e -213.301207.22 + e -425.391207.22 + e -636 211201 22
+ e -636.27/207 22+ e - I054.3R/207.22 = 1. 56
In each case
1
P 0=-=(a) 0.953, (b) 0.641
q
e - hcf3' 1
P 1 = - - =(a) 0.044, (b) 0.230
e - Jrc{JV2
P2 = --=(a) 0.002, (b)= 0.083
For the molar entropy we need to form Um- Um(O) by explicit summation:
1
2:
q
Urn - Um(O) = -
E;
e -f3r,=q
2: hcii;
i
e - hciJv;
343
344
and find (a) 125 J mol - 1 at 100 K and (b) 1400 J mol- 1 at 298 K. It follows
from
Sm --
um - um(0)
T
+ RJ nq
125 J mol - 1
that (a) Sm=
K
+ R In 1.049= 1.65 J K - l mol- 1
100
(b) Sm =
1400Jmol- 1
298
+ R In 1.56= 8.371 K - l moi- 1

5!
[1]=5!0!=1
(b) We draw up the following table:
f.
2E
3E
4E
SE
4
3
3
2
2
1
0
0
1
0
2
1
3
5
0
0
1
0
2
1
0
0
0
1
1
0
0
0
0
1
0
0
0
0
0
1
0
0
0
0
0
0
W= N!ln 1 !n2 !
5
20
20
30
30
20
1
The most probable configurations are {2, 2, 0, 1, 0, 0} and {2, 1, 2, 0, 0, 0}

jointly.
19.7 We draw up the following table :
2E
3E
4E
5E
6E
0
I
0
0
0
2
0
0
0
0
0
0
0
I
0
0
0
3
0
0
0
0
0
0
0
0
I
0
0
0
0
I
0
0
0
0
0
0
0
I
0
0
0
1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
7
7
7
7
6
6
6
6
6
6
6
5
5
5
5
5
5
4
4
4
4
3
3
2
2
1
0
1
0
0
0
2
0
0
1
0
I
0
3
I
0
2
1
0
3
0
2
2
4
3
3
2
5
4
6
5
7
9
0
I
0
2
0
1
0
2
1
0
1
1
0
1
0
1
0
2
0
0
2
1
0
1
1
0
0
0
()
0
I
0
0
0
2
0
0
1
0
0
0
1
0
0
0
I
0
0
0
1
0
0
0
1
0
0
0
0
0
0
0
0
0
1
0
0
1
0
0
1
0
0
0
0
0
1
0
0
1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
The most probable configuration is the 'almost exponential'

{4, 2 , 2,1 , 0, 0,0,0,0 , 0}.
19.8
(a)
n
_!_
no
= e -f!ic, which implies that - j{3E = In ni- In n 11
jE
and therefore that In ni =In no- kT
()
0
0
0
0
0
0
0
0
345
9E
9
72
72
72
72
252
252
84
252
504
504
504
504
504
1512
1512
1512
1512
630
2520
1260
3780
504
2520
252
756
72
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
346
Therefore, a plot of In ni against j should be a straight line with slope -EI kT.
Alternatively, plot In Pi against j, since
We draw up the following table using the information in Problem 19.7:
2
0.69
2
0.69
1
0
[most probable configuration]
These points are plotted in Fig. 19.3 (full line) . The slope is -0.46, and since
El he= 50 em_, , the slope corresponds to a temperature
50 cm - 1 X 2.998 X 10 10 em s- 1 X 6.626 X 10- 34 J S
T =-------0-.4-6_X_1_.-38_1_X
__
10--~2 ~
___7, - - - - - - 3 J_K
=160K
[A better estimate, 104 K , is found in Problem 19.9.]
16
Fig 19.3
12 r\.
'[\.
1\ \.
06
C::......
.s
04
'\
\.
'\
'\
'\
-04
[\..
'\.
j
4
I
-<>:>
347
(b) Choose one of the weight 2520 configurations and one of the weight 504
configurations, and draw up the following table:
W = 2520
ni
4
1.39
6
1.79
3
1.10
0
1
0
1
0
lnni
W=504
ni
lnni
00
Inspection confirms that these data give very crooked lines .
19.9
dIn q
1
(a) U- U(O) = -N~ with q= _ efJ'
1
dlnq 1dq -Ee- f!c

~=q d/3= 1-e-fJ'
V- U(O)
E e- flr
aE= - - -
1-e-P< = eP' -1
1a
Hence, eP< = -+a

- , implying that
1
For a= 1, f3 = -In 2, implying that
E
1
(b) q=l-e -f!< =
1 (1 +-a1)
f3 =-In
(a )=1+a
1- l+a
1
0
00
1
0
1
0
348
(c) SINk =
U- U(O)
NkT +In q
=a(3E+ In q
=a In ( 1
+~)
ln(1 +a)
=a In (1 +a)- a In a+ In (1 +a)
=
(1 +a) In (1 +a)- a In a
When the mean energy is
E,
a = 1 and then S/ Nk = 2ln 2.
When P + > P _ it is necessary for (3 < 0. For a negative temperature to describe

a three-level system, the populations are specifically inverted as T ~- T only
if the separations E2 - E1 and E1 - Eo are equal.
20. Statistical thermodynamics:

the machinery
Exercises
Cv=t(3+v~+2vt)R
20.1
[18)
with a mode active if T > eM

(a) v~ = 2, vv=O; hence Cv=t(3+2)R=tR
[Experimental: 3.4RJ
(b) v~ = 3, vv=O; hence Cv=t(3+3)R=3R
[Experimental: 3.2R]
(c)
v~=3,
vv=O; hence Cv=H3+3)R=3R
[Experimental: 8.8R)
Some of benzene's 30 vibrational modes must be at least partly active.

20.2
0.6950
TIK
q=--x (
')
a
Blcm
0.6950 X (TIK)
10.59
[Table 20.2]
[a= 1] = 0.06563(T/K)
(a) q = 0.06563 x 298 = 19.6

(b) q=0.06563x523=34.3
20.3 Look for the rotational subgroup of the molecule (the group of the
molecule composed only of the identity and the rotational elements, and
assess its order).
(a) CO. Full group Coov; subgroup C 1; hence a= 1
(b) 0 2 Full group D oo h; subgroup C2 ; hence a=2
(c) H 2S. Full group C2v; subgroup C2 ; hence a=2
(d) SiH4 . Full group Td; subgroup T; hence a= 12
(e) CHC1 3 . Full group C3v; subgroup C3 ; hence a = 3
1.0270
(T/K) 312
20.4 q = -a-(ABC/cm 3 ) 112
2X
[Table20.2]
1.0270 X 298 312

(27.878 X 14.509 X 9.287) 112
[a=2)=43.1
350
Statistical thermodynamics:the machinery
The high temperature approximation is valid if T > (}R, where

hcB
(}R
=k
= 1.4388 em K x B
= 1.4388 K x 27 .878
[choose the 'worst case']
= 40K
Therefore, the approximation is valid so long as Tis substantially greater than
40K.
1
(a) q = :Le-P'=;:2:C21+1)2e-"cBPJ(J+I)
20.5
JMK
1.4388 K
hc8{3 =
q = _1
12
2:
5.28
7.597
= TIK, a =
( 2 J + 1)2
12
e -7.5971(1+ 1)/(T/ K)
1
= 12 (1.0000 + 8.5526 + 21.4543 + 36.0863 + . .. )
1
X 439.27 = 36 .61 at 298 K
12
Similarly, at 500 K
1
q = 12 (1.0000 + 8. 7306 + 22.8218 + 40.8335 + ... )
12
950 .06=79.17
[Note that the results are still approximate because the symmetry number is a
valid corrector only at high temperatures. To get exact values of q we should
do a detailed analysis of the rotational states allowed by the Pauli principle.]
1.0270
(T/K) 312
(b) q = -a- x (B/cm-1)3'2 [Table 20.2, A= B = C]
1.0270
=-u
(T/K) 312
_ ) = 7.054 X 10- 3X (T/K) 312
5 28 312
X (
351
At 298 K, q = 7.054 X 10- 3 X 298112 = 36.3

At 500 K, q =7.054 X 10- 3 X 500312 =78.9
For 0
2,
11 = tm(O) =
-t X 16.00 u = 8.00 u
and a= 2; therefore
q=
8n 2 X 1.381 X 10 - 23 J K - I X 300 K X 8.00 X 1.6605 X 10 - 27 kg X (1.20 X 10 - 111 m) 2
2 X (6.626 X 10- 14 J s) 2
= 71.2
1.0270
20 .7
(T!K) 312
q = - a - (ABC/em
3) 112
[Table 20.2, a= I]
1.0270 X (T!K) 312

49
(3.1752 X 0.3951 X 0.3505) 112 = 1.5
(a) q = 1.549 X 298 312 = 7.97
312
X
(T/K)
101
(b) q = 1.549 X 373 312 = 1.12 X 104
20.8
Cv!R = f,f=
fJv) (
(T 1 _ e
e -JoviT )
Ovi T
[17]
We write x = flvl T ; then
This function is plotted in Fig. 20.1. For the acetylene (ethyne)

calculation, use the expression above for each mode. We draw up the
following table using kT/ he= 207 cm - 1 at 298 K and 348 em - I at 500 K ,
and fJviT=hcv/kT.
352

10
"\
0-8
06
Fig20. 1
'\
~
<.)
\
[\
04
\
~
02
' r-.....
6
1---.
10
Cv!R
ii/cm- 1
298K
500K
298 K
500K
612
612
729
729
1974
3287
3374
2.96
2.96
3.52
3.52
9.54
15 .88
16.30
1.76
1.76
2.09
2.09
5.67
9.45
9.70
0.505
0.505
0.389
0.389
0.007
3.2 X 10- 5
3.2 X 10- 5
0.777
0.777
0.704
0.704
0.112
0.007
0.006
The heat capacity of the molecule is the sum of these contributions,

namely 1.796 at 298 K and 3.086 at 500 K.
u- U(O)
N
Nee- P<
=-"'
e e -P; =
-q L.J
l+e-fl
I
Cv=
353
(!~ v k~2 (~~ v (~;:) (1 :~~Pr)2

=-
Hence, for molar quantities

x 2 e- -'
E
Cv!R= ( 1 +e -"'? ' x={3E= kT
The three functions are drawn in Fig. 20.2.
(a)
Fig 20.2
(b) 0. 5
\
q
' '\
_\
....... .......
\
\
\
0
10
I'
(c) 0.5
r"\
0.4
I
I
0.3
ct
1\
\
() 0.2
0. 1
I
I
J
0
0
1\
i\.
........ 1--2
6
X
0.6950
20.10
q R = -0
TIK
Blcm _1 (Table 20 .2, a=2]
0.6950 X 298
265
= 2 X 0.3902 =
10
10
354
qv =
-1e-) ( 1-1e-b) \ 1-1e-c)
with a =
b=
1.4388 X 1388.2
298
[Table 20.2]
_
=6 .702
1.4388 X 667.4
298
1.4388 X 2349.2
c= ---:-::-::-298
3.222
11.34
Hence,
1
(
1 , ,
q v = 1-e-6.7o_, X 1-e-L2-
)2 1-e-1 11.34 = 1.086

X
In each case the contribution to G is given by
G- G(O) = -nRTin q
[Table 20.1]
Therefore, the rotational contribution to the molar Gibbs functions is

-RTln qR = -8.314 J K - I mol - 1X 298 K X In 265
= -13 .8 kJ mol - 1
and the vibrational contribution is
-RTln qv = -8.314 J K - I mol - 1X 298 K X In 1.086
= -0.20 kJ mol - 1
20.11
q=4+2e-fl'
[2P312 has 4 states, 2P 112 has 2]

N dq NE e-fic
U-U(O)=---=-q d/3 2+e-flc
2R ( t:/3)2 e -fir
(2 + e flc )2
Therefore, since at 500 K {3t: = 2.535

2 X 2.53S2 X e - 2535
Cvl R =
(2 + e 2535 ) 2 = 0.236
At 900 K, when f3t: = 1.408,
2x 1.4082 xe - J. 4ox
Cv!R=
0.193
I40R
(2+ e- )2
Note that Cv is smaller at 900 K than at 500 K, for then the temperature
is higher than the peak in the 'two-level' heat capacity curve.
20.12 q=3+2e - fi' [the 3L: term is triply degenerate, and the 1 ~ term is
doubly (orbitally) degenerate]
1.4388 em K x 7918.1 cm- 1
At 400 K , /3t: = - - - -- - K - - - - 28.48
400
Therefore, the contribution to G is
-RT!n q= -8.314] K - I mol - 1 x 400 K x ln(3 + 2 x e- 2x4 x)

= - 8.314 J K - I mol - 1 X 400 K
= -3.65 kJ mol -
In 3
20.13 The spin degeneracy of Co 2 + is 4 [the ion is a spin quartet], so q = 4.

The contribution to the entropy is
R In q= 8.314J K - I mol - 1 Y in 4= 11.5 J K - I mol - 1

20.14
Cv=t(3+v~+2vt,)R
[18]
with v~ = 3 and vt = 0. Hence Cv= 3R; and since C,- Cv = R, CP = 4R =

33.3 J K - I mol - 1. The experimenta l value is slightly greater, signifying a
contribution either from the excitation of molecular vibration or from gas
imperfections.
355
356
20.15 In each case Sm=Rlns
[19]. Therefore,
(a) Sm = R In 3 = l.lR = 9 J K - I mol- 1

(b) Sm= R In 5 = 1.6R= 13 J K - I mol - 1
(c) Sm=R In 6= 1.8R= 15 J K - 1 mol - 1
20.16 Use Sm = R Ins
n:
s
S",IR
[19]. Draw up the following table:
1
0
6
1.8
6
1.8
6
1.8
6
1.8
3
1.1
6
1.8
6
1.8
6
1.8
6
1.8
3
1.1
1.8
where a is the 1, 2, 3 isomer , b the 1, 2, 4 isomer, and c the 1, 3, 5 isomer.

T
~A =2 .561 x l0 - 2x (T/K) 512 x (M/gmol - 1) 312
20.17
[Table20.2]
= 2.561 X 10- 2 X (298) 512 X (28.02) 312 = 5.823 X 106

qR
=f
298
0.6950 X 1.
9987
v_
1
q - 1 _e -235BI2o7.2
qe
(Table 20.2) = 51 .81
1.00
-
Therefore, NA =5.823 x 106 x 51.81 x 1.00=3.02 x 108
Um- Um(O) = t RT + RT= t RT [T ii> (}T,
(}R]
Hence
S~ =
Urn- Um(O)
{ q~
}
T
+R lnNA+1
(Table20.1]
= i R + R{ln 3.02 x 108 + 1} = 23.03R

=191.4JK- 1 mol - 1
The difference between the experimental and calculated values is negligible ,
indicating that the residual entropy is zero.
N A= 2.561
10 -"(TIK) 512 (M!g mol - 1) 312 [Table 20.2]
q T(I2)/ N A= 2.561
10 - 2 X 1000 512 + 253.8 312 = 3.27 X 109
qT(I)/ N A= 2.561
10- 2 X 1000512 + 126.9 312 = 1.16 X 109
20.18
qT/
357
TIK
B/cm -
0.6950
a
qR(J, ) = - - X - -1
1000
= t X 0.6950 X 0.0373 = 9316

qv(I 2) =
1
v/cm - 1
[Table 20.2]
_ e - "' a= 1.4388 TIK
1
= 1 - e - -' 14 .36/695 = 3. 77
qE(l) = 4
qE(l 2) = 1
Hence K =
(q e(I)!NS
q 6 (1z)INA
e-D/ RT
[22]
(1.16 X 109 X 4) 2 e- 179

3
3.27 X 10 9 X 9316 X 3.77 = 3 2 X 10 -
20.19 We need to calculate

q 6 ( 9 Br2)q 6 (8 1Br2)
K =
e -1!. , / RT
P
q 6 ( 9Brx 1Br?
The ratio of the translational partition functions is virtually 1 [because the
masses nearly cancel; explicit calculation gives 0.999]. The same is true of the
vibrational partition functions. Although the moments of inertia cancel in the
rotational partition functions, the two homonuclear species each have a = 2 , so
qR(9Br2)qR(RIBr2)
qRCYBrxiBr)2 = 0.25
The value of !)..0 is also very small compared with RT, so
KP=0 .25
Problems
20.1
qv =
1
_e
hnVJ
[Table 20.2]
358
which rearranges to
ii = -kTln
he
{_I }
I
I- -
Therefore, if q = l.OOI ,
-500 K
ii= 1.4388 em K ln
I
}
__
I_ = 2.4 x I03 cm-1
20.2
l.OOI
q = 2 + 2e-P
x 2 e-..Therefore, Cvl R = (I + e x)2' X= {JE.

TIK
50
298
500
(kT/hc)/cm- 1
X
Cv!R
Cvi(J K -I mol - 1)
34.8
3.46
0.354
2.94
207
0.585
0.079
0.654
348
0.348
0.029
0.244
Note that the double degeneracies do not affect the results because the two
factors of 2 in q cancel when U is formed. In the range of temperatures
specified, the electronic contribution to the heat capacity decreases with
increasing temperature.
20.3
x- e-x
Cvl R = (I+ x) 2
[Problem 20.2], x = 211 8 B{J
Therefore , if B=5.0T,
2 X 9.274 X 10- 24 J T- 1 X 5.0 T
X=-------=------:---1.38I X 10- 23J K -I X T
6.72
TIK
(a) T=50 K, x=O.I34, Cv=4.47 x 10- 3 R , implying that Cv=

3. 7 x 10- 2 J K -I mol- 1. Since the equipartition value is about 3R
[v~ = 3, vt =O], the field brings about a change of about O.I per cent.
(b) T=298 K, x=2.26x 10- 2, Cv=l.3x 10- 4 R, implying that Cv=

1.1 mJ K - I mol - 1, a ch~,mge of about 4 x 10 - 3 per cent.
n1 =- 'X
f oo
=-
1 (2/kT) 112
e -m~!Jl/ 2/kT dm=- - oo
a h2
f oo
e -x:! dx
-00
= ~ (2nf~!:\ 112
a
h- }
U- U(O) =-
Cv=(a~
aT} v
Sm =
Naq
q a(3 = 2(3 = i_-NkT
[or get by equipartition]
= i.-R = 4.2JK - 1mol - 1
Um- Um(O)
T
+ R In q
[Table 20.1]
1 (2nlkT) 112
=iR+Rln- - 2
47 kgm 2X 1.381 X 10- 23 J K -I X 298)112

- (1.055x10 34 Jsf
~(2nX 5.341 X 10-
_ J.
- 2R+Rln3
= -! R+1.31R = l.81R, or 15JK - 1mol- 1

20.5
q = 1 + 5e-/lc
t: = E(J = 2) - E(J = 0) = 6hcB

U- U(O)
N
5t: e -/Jc
1 +5e-/J<
5t: 2/3 2e -/Jc

Cvl R = ( 1 + 5e -P<)2
hcB
[E= hcBJ(J + 1)]
180(hcB{3)2e- 6hcB{J
( 1 + 5e -611cB/i)2
k= 1.4388 em K x 60.864cm - 1=87.571 K

Hence,
359
360
Cvl R =
1.380 X 106e -525.4 KIT

( 1 + Se - 525.4 KI T) 2
and the draw up the following table:
TIK
50
100
150
200
250
300
350
400
450
500
Cvl R
0.02
0.68
1.40
1.35
1.04
0.76
0.56
0.42
0.32
0.26
These points are plotted in Fig. 20. 3.

Fig 20.3
15
I 1\
\
I
\
)r\.
~
I
I
II
05
"
I'-.
0
0
20.6
Sm =
2
qR= n;
Um + Um(O)
T
12
200
300
T/K
t.{XJ
500
+ R In qR [Table 20.1 , internal modes]
cl~T) c~~~Trr
=~{8n/~~ i (:~rr
=
700
[Table 20.2]
ra=12]
{8n X 2.93 X 10- 45 kg m 2 X (1.46 X 10- 45 kg m 2)2
23 K
x (1.381 x w- 1
(1.055 X 10
=9950
- I
34
x 362
sr
K) 3}1'2
Urn - Um(O)
T
=M
361
[from qR, or by equipartition]
M+ R In 9950
Therefore, Sm =
10.7R , or 89 J K - I mol- 1.
In two dimensions (rotation about one axis)

qR
kT)
=-;1 (2:rrJ
---,r11
112
~ {2:rr X 2. 93
[Problem 20.4]
w-
45
(1.055 x 10
6
=
kg m2 X 1.381
34
10 - 23 J K -
IX
362 K} 1/2
J sf
15.2
Urn - Um(O) = t R
[from
q\
or by equipartition]
Therefore, Sm = t R + R In 15.2
=3.2R , or 27 J K - 1 mol- 1
Hence, the change in rotational entropy on adsorption is
LlSm = 27- 89 J K - I mol - 1 = -62 J K - I mol - 1
The change in translational entropy on adsorption is

0
e ( hz(3 )
:rrm e
LlS~ = R In y e
V6 =
a6
1.0 mol
112
[Problem 20.13]
RT
=
pe
8.21
10- 5 m-'( T/K)
1.0 mol x 4.08 x w - lx m2 x 6.022 x 1023 mol - 1 x TIK
2.46 X 104 m 2(T/K)
[The standard state of a mobile , two-dimen sional film is defined so that the
average separation of adsorbed molecules at 273 K is the same as in a threedimensional gas at 273 K and 1 bar; see the original reference .]
2.46 x 104 m 2(T/K)
y e = 8.21 X 10- 5 m\T!K) = 3 00 X lOx m- l
a6
h 2f3 )
( 2:rrm e
112
(2:rre
78.12 X
6.626 x w-34 1 s
1.6605 X w- 27 kg X 1. 381
10- 23 J K -
I X
T) 112
362
1.20 X 10-lOm
(T/K)lt2
Therefore,
.!lS~ =
3.00 X 108 m - 1X 1.20 X 10- 10 m

362112
R In------:-:::------
= -6.3R , or -52JK- 1 mol- 1

Hence , the overall change in entropy is
.!lS"' = - 52 - 62 J K - l mol - 1= - 114 J K - l mol - 1
which is in agreement with the experimental value ( -111 J K - l mol - 1) at low
surface coverage, suggesting that the model of a mobile, single-axis roation
layer is appropriate. (However, the data cannot identify which of the
molecular axes is involved: we have assumed rotation about the figure axis.)
At higher surface coverages the change in entropy is only -52 J K - t mol - 1,
suggesting that rotation about all three axes is then possible, so that only the
translational contribution ( .!lS~ =-52 J K _,mol-') occurs.
20.7 The absorption lines are the values of {E(J + 1)- E(J)}I he for J =
0, 1, .. . . Therefore, we can reconstruct the energy levels from the data using
he
hcf3 = kT= 207.223 cm - 1
q=
L (21 + 1)
e -f3h cE(J )
1=0
= 1 + 3e - 2t.t 91207.223 + 5e -(2t. t9+42.37)t207.223+ 7e -(2t. t9+ 42.37+63.56)t207.223 + ...

= 1 +2.708+3 .679+3.790+ ... = 19.89
The ratio of translational partition functions is

qT(CHD 3)qT(DCI)
qT(CD 4)qT(HCI)
M(CHD 3)M(DCI)} 3'2

{ M(CD 4)M(HCI)
19.06 X 37.46}3/2
0 964
= { 20.07 X 36.46
=
363
The ratio of rotational partition functions is

(B(CD 4)/cm- 1) 312B(HCI)/cm - 1
qR(CD 4)qR(HCI)
a(CHD 3) (A(CHD 3)B(CHD 3) 2/cm 3) 112 B(DCI)/cm 1
12
2.63 312 X 10.59
6 24
= 3 X (2 .63 X 3.28 1) 112X 5.445 =
qR(CHD,)qR(DCI)
a(CD 4)
The ratio of vibrational partition functions is
q v( CHD 3)q v(DC I) q(2993)q(2142)q(1003 ) 3q(1291 ) 2q( 1036) 2q(2145)

q v(CD 4 )q v(HCI) q(2109)q(1092) 2q(2259) 3q(996) 3q(2991)
1
where q(x) = 1- e 1.43RSx/(TIK)
We also require !:!.E0 , which is equal to the difference in zero point energies :
!:!.E0 / he = -!{(2993 + 2142 + 3 X 1003 + 2 X 1291
+ 2 X 1036 + 2145)
- (2109 + 2 X 1092 X 3 X 2259 X 3 X 996 + 2291)} cm- 1
= -990cm- 1
Hence,
K = 0. 964 X 6.24 X Q e+ '- 4388 x9'!0/(T/K)
= 6 .02 Q e +1424/(T/K)
where Q is the ratio of vibrational partition functions. We can now evaluate K
(on a computer), and obtain the following values:
TIK
500
1000
1500
2000
2500
3000
3500
4000
4500
5000
110
34
26
23
22
22
21
21
21
21
20.9
H 20
+ DCI ;:= HDO + HCI
q9
(HDO)q 9 (HCI)
K = q e (H20)q e (DCI)
e -f3t>.Eu
The ratio of translational partition functions [Table 20.2] is

qT(HDO)qT(HCI)
qT(H 20)qT(DCI)
{M(HDO)M(HCI)}3'2
M(H 20)M(DCI)
_ {19.02 X 36.46}312 _
41
- l.0
- 18.02 X 37.46
364
The ratio of rotational partition functions is

qR(HDO)qR(HCI)
(27.88 X 14.51 X 9.29) 112 X 5.449
707
2
qR(H 20)qR(DCI) = X (23.38 X 9.102 X 6.417) 112 X 10.59 = 1.
[a = 2 for H 20 , a= 1 for the other molecules].

The ratio of vibrational partition functions is
qv(HDO)qv(HCI) q(2726.7)q(1402.2)q(3707.5)q(2991)
qv(H 20)qv(DCI) - q(3656 .7)q(1594.8)q(3755.8)q(2145)
1
where q(x) = _ e - 1.4388 xxt(T/K)
1
We also need f).0 from the difference in zero-point energies:

/).0/hc = H2726.7 + 1402.2 + 3707.5 + 2991)
- (3656.7 + 1594.8 + 3755.8 + 2145)} cm - 1

=-162cm- 1
Therefore,
K = 1.041 X 1.707 X Q X e 1. 4JSRx lb2/(T/K)

= 1.777Q e233/(T/K)
We then draw up the following table (using a computer):
TIK
100
200
300
400
500
600
700
800
900
1000
18.3
5.70
3.87
3.19
2.85
2. 65
2.51
2.41
2.34
2. 29
and specifically K = 3.89 at 298 K and 2.41 at 800 K .

21.10
<l>o=
Gm(T)- Hm(O)
qTqi
= -R In NA
Gm(T)- Gm(O)
= -
---
[Table 20.1]
where qi is the partition function for the internal modes .

(a) H 2 :
(!:)e
=0 .02561 x 10005' 2 x 2.016 312 =2.32 x 106
1 0.6950 X 1000
qR=zX
60.864
qv =
5 711
1
_
e4-lfKUY/695.3
= 1.002
1
Hence <l> jf=- R In 2.32 X 106X 5.711 X 1.002

= -R In 1.33 x 107= -136J K - l mol - 1
(b) N2 (
!]
e = 0.02561 X 1000512 X 28.02312 = 1.20 X 1QH
1 0.6950 X 1000
qR=zX
1.9987
= 173.9
1
q v = 1 _ e- 2358.o7t695.3 = 1. 035
Hence <l> jf=- R In 1.20 X 108 X 173.9 X 1.035

= - R In 2.16x 10u1 = -198J K - l mol- 1
(!:)
(c) NH 3
e = 0.02561 X 1000512 X 17.03312 = 5.69 X 107
1. 0270 X 1000312
qR = 3X (6.34 X 9.442)112 = 455
1
qv = q(3336.7)q(950.4)q(3443.8) 2q(1626.8) 2
1
where q(x) = 1- e- 1.43RR,,(TtK)
1
1 -e -x/695 .0 = 1.68
Hence
<l> jf= -R In 5.69 X 107x 455 X 1.68 = - 204 J K - l mol - 1
For the equilibrium N2+ 3H2:;:::::2NH 3 we need
~<1> 1?" = 2( -204)- ( -198)- 3 x ( -136) J K - J mol - 1
= +198JK- 1 mol - 1
Then proceed as in Section 9.4 (Example 9.6) using the data in Table 9.1.
Specifically 6.H 9 ( T) = -92.2 kJ mol - 1 and
~{Hm(T)-
Hm(0)} = 2 X 9.92 - 8.669 - 3 X 8.468 kJ mol- 1

= -14.23 kJ mol - 1
365
366
Hence
~G ;;;(T)
198 +
14.23 X 103 92.2 X 103

1000
1000 J K -I mol-l
= + 120 J K - 1 mol - 1
and
20.11
<1> 0 = -R In q and q =
2: (21 + 1) e - llcp;;,
J
since each 1 level is (21 + 1)-fold degenerate . We then draw up the following
table :
TIK.
1000
2000
3000
4000
5000
(kT/hc)/cm - 1
q
<1> 0/(J K -I mol - 1)
695
2.000
-5 .76
1391
2.000
-5.76
2085
2.002
-5.77
2780
2.014
-5 .82
3475
2.053
-5.98
20.12
q B(Na)2
Na 2 (g)~2Na(g) , K= q e (Na )NA e -
Dof RT
qT(Na)/ NA = 0.02561
1163 512 X 22.99 312 = 130 X 108
qT(Na2 )/ N A= 3.68 X 108

qR(Na 2) =
t X 0.6950 X
qE(Na) = 2.00
1163
= 2612
_
0 1547
[Problem 20.11)
(2.00 X 1.30 X 108r

X - 70.4/9.67 Hence , K- 3.68 x 108 x 2612 X 5.60 e
- 8 7
If the degree of dissociation is a at equilibnum, we have

K
)112
a= ( K+ plp e
4
[eqn9ofSection9.3]
8 7 ) 1/2
=0.83
( 8.7 + 4.0
[p=p 9 ]
Hence, at equilibrium the mole fractions are

1-a
2a
x(Na 2) = - = 0.095 , x(Na) = - = 0.905
l+a - - l+a - - -
Therefore,
2nm)
2nma
qT = ( f3hz XY= f3h2 , a=XY
Um-Um(O)=Sm=
Um- Um(O)
T
~(:;)=RT
+R(lnqm-lnNA+l)
(Table20.1]
= R + R ln(e qm!NA) = R ln(e 2qm!NA)
Since in three dimensions

2nm)
312 V }
S =Rln e 512 ~
{
( h2j3
m
NA
[Sackur-Tetrode equation J
The entropy of condensation is the difference:

2
e (2nmlh f3)(am1NA)
sm = R In e5'2(2nm/ h2/3))/2( v m/ N A)
=R tn{(avmm)
(z~mf3 e\112}
"
367
368
1
Bv
q = _ e-x' x = hw/3 = hcvf3 = T
1
20.14
[Table 20 .2]
N(aq)
d
U-U(O)=-- =-N(1-e - x) -(1e -x)-'
q af3 v
d/3
Nhw e-x
1-e-x
Nhw
e'-1
H-H(O)=U-U(O)=
S=
Nhw e-x
_ e -x
1
Nhw
e' -
U- U(O)
Nkx e-x
T
+nRlnq= _e-x -Nkln(1-e -x)
1
= Nk{-x- -ln(1- e-x) }

ex-1
A- A(O) = G- G(O) = -nRT!n q

=
NkTin (1- e-x)
The functions are plotted in Fig. 20.4.

Fig 20.4
'\
\
\
I.
100
~~
'
.....
0
01
j....A
r--. -....
X
.......
~v
......
!.,.;'
1-0
I
a'
r-....
~
I
001
'\
001
.........
~
V)2
1\
...... r
"""'
....... ...._

For several modes ,
<l>o= -R
L In qQ = R L ln(1- e-xo)
Q
At 1000K, kT/hc=695.03cm - 1 , and so

x 1 = 4.80 , x 2 = 1.37 , x 3 = 4.95 , x4 = 2.34
and
<l>o = R ln{(1- e -4 so)(1- e - u7)(1 - e -4 9s)\1- e -2.34n
= -0.518R= -4.31 J K - 1 mol- 1
20.15
N
NkT
(a) U-U(O)=--""e -e- f!c! = - q
qL.Ji
(k~2) ~ ~ eJ e-f!c;_ : ~ eie -PcY}
(k~ 2) r2~2q- k:~2
= nR{%-
2(
q2}
(!Y}
S= U- ~(O) +nR In(~+ 1) =nR{ ~+In e:}

(b) At 5000 K, kTI he= 3475 em -
I.
We form the sums
369
370
q=
L e -flri = 1 + e - 21 850I3475 + 3e- 21870I3475 + . . = 1.0167
= (-1-) {0+21850 e-21850/3475 + 3 x 21870 e-21 87013475+ .. }=0.1057

3475
= (-1-) 2{0 + 218502 e- 21850/3475 + 3 x 218702 e- 21870/3475 + .. } = 0.6719

3457
Then the electronic contributions are
Hm- Hm(O) = Urn - Um(O) = RTq
0.1057
= 8.3141 K - l mol - 1x 5000 K x = 4.32 kJ mol- 1
1. 0 167
= 8.314JK - 1 moi- 1X
<1> 0 =
0.6719 (0.1057)2}
- 1.
1.
=5.41JK- 1 mol - 1
0167
0167
-R In q
= -8.314 J K - l mol- 1x In 1.0167 = -0.14 J K - l mol - 1
M;
Since g11 6 f3B ~ 1 for normally attainab le fields,
M;
= 4+ -i(g!lsf3Br
2: M] [2: M1=o ]
M1
M1
Statisticalthermodynamics:the machinery
Therefore , if K is the actual equilibrium constant and K 0 is its value when

B = 0, we write
K
Ko =
)2
10
20
1 + 9(,usf3B)2 "'"1 + 9,u~/32B 2
For a shift of 1 per cent, we require

20
9,u ~ /3 2 B "'=0.01, or ,u 8 /3B "'= 0.067

2
Hence
0.067 kT
B"'=---
0.067 X 1.381
,Us
10- 23 1 K _ , X 1000 K
9.274 x
w-24 1 T-'
"'=lOOT
20.17
yRT) "2
CP
c, = ( M
,y=Cv' CP=Cv+R
(a) Cv= R(3+v~+2vt)= tR(3+2)= tR

Cp= t R+ R= f R
1.40R~ 112
7
= -MY= > =140hencec
. '
s
1.40RT) 112
(b) Cv= -} R(3+2)=tR , y=l.40, c, = ( ~
(c) Cv= t R(3+3)=3R
4R~II 2
CP=3R+R=4R, y=t, c, =
(3/Vi)
For air, M "'=29 g mol - 1, 1"'=298 K, y= 1.40
c,
"'"(1.40 x 2.48 k1 mol - ') 112 =

_1
29 X 10 -3 kg mol - l
350m S
371
21. Diffraction methods

Exercises
21.1 The points and planes are shown in Fig. 21.1a.
Fig 21.1
(a}
(41}
(b)
(4 1)
(41)
(41}
21.2 See Fig. 21.1b .

21.3 Draw up the following table, using the procedure set out in Section 21.2:
Original
Reciprocal
(2a , 3b , c) 9r (2 , 3, 1)
(a, b, c) or (1, 1, 1)
(6a, 3b , 3c) or (6 , 3, 3)
(2a, -3b, -3c) or (2, -3, -3)
(t, t, 1)
(1, 1, 1)
(t, t,
(t,
t)
- +,
21.4 The planes are drawn in Fig. 21.2a.

21.5 The planes are drawn in Fig. 21.2b.
- t)
Clear
fractions
Miller
indices
(3,
(1 ,
(1,
(3 ,
(326)
(111)
(122)
(322)
2, 6)
1, 1)
2, 2)
- 2, - 2)
Diffraction methods
373
Therefore,
432 pm
d,,, = 3112 = -----yn- = 249 pm

a 432 pm
d211 = 6112 =~= 176 pm
d 11lO=a=432pm
21.7
A= 2d sin 8
[2a]
=2 x 99.3 pm x sin 20.85 =70.7 pm

21.8
A
8=arcsin d
2
A1
[2a, arcsin=sin - 1]
A,
1::!.8 =arcsin d- arcsin

2
2
154.051 pm)
(154.433 pm)
= arcsin ( 2 x 77 .8 pm -arcsin 2 x 77 .8 pm = -1 .0r
= -0.0187 rad
The separation of the components is therefore 2 x 5. 74 em x 0.0187 = 0.21 em.
374
Diffraction methods
21.9
V = 651 pm x 651 pm X 934 pm = 3096 X 10- 28 m3
NM
21.10 p = - VNA
[N is the number of formul a units per unit cell]
309 X 106 g m - 3 X 634 X 784 X 516 X 10- 36 m3 X 60022 X 1023 moJ - I

1540 77 g mol 1
=309
Therefore, N = 4 and the true calculated density (in the absence of defects) is
p=
21.11
634 X 784 X
dhkt = {
={
4 x 1~4 0 77 g mol - 1
4 001 gcm- 3
516 X 10-Jo cm3 X 60032 X 1023 mol - 1 - -----'='-----
Gr Gr Grrl/2
+
[1]
(8~2r + (9~7r + ( 6~7Y}
2
-1/
pm = 190 Pm
21 .12 The plane cuts the axes at a/5 , b/2 , and c/3 , and so the intersection
distances are 240 pm, 606 pm , and 395 pm o
21.13 Since the reflection at 3206 is (220) , we know that
A.
154 pm
d220 =
2 sm
0e [2] = 2 sm0 32 6
0
and hence, since
a
d220 = (22 + 22)1/2
it follows that
a
[1] = 81/2
143 pm
Diffraction methods
375
a = 8 112 X 143 pm = 404 pm

Therefore, we can draw up the following table:
lOs csiner;
-pm2
h2+k2+ [2
(hkl )
alpm
19.4
22.5
32.6
39.4
1.86
2.47
4.90
6.80
3
4
8
11
(111)
(200)
(220)
(311)
401
402
404
402
).
The average value of a is 402 pm.

).
21.14
ehkl
= arcsin -2d
hkl
).{(h)2
= arcsin Z ~ +
(k)2
b + ([)2}1/2
~
h )2 ( k ) 2 ( l )
= arcsin 77 { ( 542 + 917 + 645
7
Therefore, 8 100 = arcsin ( : ) = 8.1
5 2
2} 1/2
8010 = arcsin ( ;: ) = 4.82

7
8 111 =arcsin 77 X ( 1 ) 2+ ( 1 ) 2+ ( 1 ) 2} 1/2

{ 542
645
917
=arcsin
77
378
= 11.75
21.15 From the discussion of systematic absences [Section 21.4] we can

conclude that the unit cell is face -centered cubic.
376
Diffraction methods
21.16 The Jines with h + k + l odd are absent; hence the cell is body-centered
cubic [Section 21.4].
21 ' 17
hk/
="' /,
L.J
e bri(hx,+ky,+ tz,l
[6]
with/;= i [each atom is shared by eight cells]. Therefore,

F,kt =
i f{1
+ ebrih + e2--rik + e2--rit + e2--ri(h+kl + e2--ri(h +tl + e2--ri(k+l) + ebri(h+k+tl}
However , e bri = 1; h, k , and l are all integers. Hence all terms are unity, and
F,kt= [_
21.18 The four values of hx + ky + lz that occur in the exponential functions in

F have the values 0, ~ 3, and f , and so
F,kt rx
1 +~" + e 6iJr +~ 7 i"= 1- 1 + 1 - 1 = Q

eill
21.19 Refer to Fig. 21.3. The hatched area is 3 112R x 2R = 2V3R 2 . The net
number of cylinders in a hatched area is 1, and the area of a cylinder's base is
nR 2 The volume of the prism (of which the hatched area is the base) is
2V3R 2L, and the volume occupied by the cylinders is nR 2L. Hence , the
packing fraction is
nR 2 L
n
!=2V3R 2 L =2v3= 0 9069
21.20
d 100 =a= 350 pm
Diffraction methods
377
NM
p= VNA' implying that
pVNA 0.53 X 106 g m - 3 X (350 X 10- 12 m)' X 6.022 X 10 23 mo] - 1

N=--= ----=----~-----':-------M
6.94 g mol - 1
= 1.97
An fcc cubic cell has N = 4 and a bee unit cell has N = 2 . Hence, lithium has a
bee unit cell.
21.21
(} khl
=arcsin
{:a
(h 2 + k 1 + !")
112
The systematic absences in an fcc structure are that (hkl) all even or all odd
are the only permitted lines [Fig. 21.12 of the text]. Since A/2a = 0.213, we
expect the following lines:
(hkl):
111
200
220
311
(}
21
25
37
45
The density is calculated from
NM
4 X 63.55 g mol - 1
p=VNA =(361pm) 3 x6 .022 x 1023 mol - 1 8 97 gcm -J
21.22 Draw points corresponding to the vectors joining each pair of atoms.
Heavier atoms give more intense contributions than light a to~Remember

that there are two vectors joining any pair of atoms (AB and AB); don 't
forget the AA zero vectors for the center point of the diagram. See Fig. 21.4
for (a) BF3 and (b) C6 H 6 .
21.23
p2
h1
(a) =2m =2m..1. 2 [p=h/..1.]
2X
(b) Write E = ! kT
(6 .626 X 10-'4 J s)"

1.675 X 10 27 kg X (70 X 10
[equipartition], then
12
20
27
m) 2 = X l0 - J
Diffraction methods
378
0 o_o~
~n1r;r;
oooo
0
2 x 2.7x10- 20 J
T=k = 1.381 X 10-23 J K 2E
21.24
3.9 X 103 K
h
h
A=-=- , which implies that
p mu
6.626 x 10- 34 1 s
u=-=
=7 9kms - 1
mA 1.675 X 10- 27 kg X 50 X 10- 12 m
.
h2
21.25 Combine E = t kT and E= mA 2 , to obtain
2
h
A= (mkT) 112
6.626 x 10- 34 1 s
27
(1.675 X 10- kg X 1.381 x 10- 23 J K - I X 300 K) 112
= 252pm
21.26
h2
E = mA 2 [Exercise 21.23] and E = e !:J.
2
Therefore ,
h2
!:J.fj) - - -2
- 2meA
= 4.6 kV
21.27
(6.626 X 10- 34 J s) 2
31
2 X 9.109 X 10- kg X 1.602 X 10- 19 C X (18 X 10- 12 m) 2
[1 J = 1 C V]
h
h
A=- = p m cu
Diffraction methods
(2
9.109 X
6.626 x w- 34 1 s
10- 31 kg X 1.602 X 1Q -
YC X
379
/1 ) 112
1.227 nm
(11/V)l/2
Problems
21.1
= 2a sin 6.0 = 0 .209a
In an NaCI unit cell (Fig. 21 .5) the number of formula units is 4 [each corner
ion is shared by 8 cells, each edge ion by 4, and each face ion by 2].
Fig21.5
380
Diffraction methods
Therefore,
(4M)lt3
NM
4M
p = VNA = a 3NA' implying that a = pNA
4 x 57.44 g mol- 1
_
) 113
5602
a = ( 2.17 X 106 g m- 3 X 6.022 X 1023 mol - 1 =
pm
and hence
A= 0.209 x 560.2 pm = 117 pm

21.2 Follow Example 21.3 . Note that since R=28.7mm , 0/deg=
(D/2R)(180/n) = Dlmm. Then proceed through the following sequence:

(1)
(2)
(3)
(4)
(5)
Convert from distance to angle using 0/deg = Dlmm.

Calculate sin2 e.
Find the common factor A= A2/4a 2 in sin 2 e = (A 2/4a 2)(h 3+ k 2+ ! 2).
Index the lines using sin 2 0/ A= h 2+ k 2 + ! 2.
Solve A = A214a 2 for a.
We therefore draw up the following table:

D/mm
14.5
20.6
25.4
29.6
33.4
37.1
44.0
0/deg
103sin 2 e
sin 2 0/A
(hkl )
14.5
62.7
1.03
(001)
20.6
124
2.03
(011)
25.4
184
3.02
(111)
29.6
244
4.00
(002)
33.4
303
4.97
(012)
37 .1
364
5.97
(112)
44.0
483
7.92
(022)
Dl mm
47 .5
50.9
54.4
58 .2
62.1
66.4
78.1
0/deg
103sin 2 e
sin 2 0/A
(hkl)
47.5
544
8.92
(003)
(122)
50.9
602
9.87
(013)
54.4
661
10.84
(113)
58.2
722
11.84
(222)
62.1
781
12.80
(023)
66.4
840
13.77
(123)
78.1
947
16.69
(004)
with A = 61.0 x 10- 3. When we compare this sequence of indexes with Fig.
21.12 of the text, we conclude that the lattice is primitive cubic.
A
154pm
a = 2A 112 = 2 X (61.0 X 10-3)112
213 pm
Diffraction methods
381
21.3 Measure the diffraction angles from the illustration, and then proceed as
in Problem 21.2.
(a)
Diem
2.2
3.0
3.6
4.4
5.0
5.8
6.7
7.7
81deg
103 sin 2 8
sin 2 81A
(hkl)
22
140
2.4
(011)
30
250
4.2
(002)
36
345
5.8
(112)
44
482
8.1
(022)
50
587
9.9
(013)
58
719
12.1
(222)
67
847
14.3
(123)
77
949
16.0
(004)
with A= 0.0594. Comparison with Fig. 21.12 of the text identifies the lattice as
body-centered cubic.
A
154pm
a= 2A lt2= 2 x 0.05941 '2= 316 pm
In a bee lattice 4R = V3a, so R = 137 pm.
(b)
Diem
2.1
2.5
3.7
4.5
4.7
5.9
6.7
7.2
81deg
103 sin 2 8
sin 2 81A
(hkl)
21
128
2.8
(111)
25
179
3.9
(002)
37
362
8.0
(022)
45
500
11.0
(113)
47
535
11.8
(222)
59
735
16.2
(004)
67
847
18.6
(133)
72
905
19.9
(204)
with A =0.0455. Comparison with Fig. 21.12 of the text identifies the lattice as
face-centered cubic.
A
154 pm
a= 2A lt2= 2 x 0.04551'2= 361 pm
For such a lattice, 4R = V2a, so R = 128 pm.
21.4
A
dt.kt =
2 Sin 8 hkt
with A= 154 pm
1
(h)2
and-=
- + (k)2
- + (')2
dt.kt
a
b
c
We find that d 100 =a=
A
.
2 Sin 8 100
154pm
2 sin 25, = 597 pm
382
Diffraction methods
154pm
do10= b = sin o 28 ,
2
3
1270 pm
Therefore, the volume of the unit cell is

V =abc= 3.29 X 10- 28 m3
and its density is
N x 271.5 g mol - 1
p = VN A= 3.29 x 10 22 cm 3 x 6.022 x 1023 mol
NM
=1.37 xNg cm - 3
However, experimentally p = 5.42gcm- 3; so N==3.97 . That is , there are
four HgC1 2 units in each unit cell.
21.5 When a very narrow X-ray beam (with a spread of wavelengths) is
directed on the center of a genuine pearl, all the crystallites are irradiated
parallel to a trigonal axis and the result is a Laue photograph with sixfold
symmetry. In a cultured pearl the narrow beam will have an arbitrary
orientation with respect to the crystallite axes (of the central core) and an
unsymmetrical Laue photograph will result . (See J. Bijvoet et al. , X -ray
analysis of crystals, Butterworth (1951).]
21.6 A= 2a sin
e!OO
as d!Oo =a
Therefore, a=
. n
2 sm o 100
a(KCI)
and a(NaCl)
sin 0 100(NaCl)
sin 0 100 (KC1)
sin 6 0'
sin 5o 23'
1.114
Therefore , a(KCl) = 1.114x 564pm =628 pm
p(KCl)
M(KCl) {a(NaC1)}3
p(NaCl) = M(NaCl) x a(KCl)
74.55 {564 pm} J
= 58.44 x 628 pm = 0 924
Experimentally,
Diffraction methods
p(KCl) 1.99 g cm - 3
0 917
p(NaC1) = 2.17gcm 3 =
and the measurements are broadly consistent.
V = abc si n /3
21.7
and the information given tells us that a= 1.377b, c = 1.436b, and
f3 = 122 49';
hence
V = 1.377 x 1.436b 3 sin 122o 49' = 1.662b 3
NM
2M
Since p = VNA = 1.662b3N~
we know that
2M
b = ( 1.662pNA
)lt3
1
= ( 1.662 X
)1'3
2 x 128.18gmol1.152 X 106 g m- 3 X 6.022 X 1023 mol- 1
=605.8 pm
Therefore, a= 834 pm, b = 606 pm , c = 870 pm .
A.
21.8
d 111
d i l l = - - .- e lll
2sm
70.8 pm
2 sin 8 44' = 233 pm
[1], so a =233 x Y3 pm =404 pm
NM
NM
p= VNA implies that NA = pV
Therefore,
N A-
2.601
4 x 25.94 g mol - 1
106 g m 3 X (404 X 10
154pm
2 x 334.5 pm
_____ X
12
m) 3
(h 2+ k 2 + [ 2 )1 12
= 0.230 X (h 2 + k 2 + / 2) 112
6.05 x 10 23 mol - 1
383
384
Diffraction methods
The indexes may vary over all integral values [Fig. 21.12 of the text], and so
lines will occur at
(100)
(hkl)
(110)
(111)
(200)
(210)
2r23'
3057'
The density is
NM
M
210gmol- 1
12
p= VNA = VNA = (334..5 x 10- m) 3x 6.022 x 1023 mol- 1
= 9.32 x 106 g m-3, or 9.32 g cm- 3
ta
The radius of each atom is = 167.3 pm. In an fcc lattice the diagonal would
be 4 x 167.3 pm = 669.0 pm [if we ignore the variation of metallic radius with
669 .0
coordination number], giving a side a'= -y pm = 473.1 pm. The density
2
would then be
4 x 210 g mol- 1
3
2
p = (473.1x10 12m?x6.022 x1023 mol 1 13 gcm21.10
0(100K) = 222'25", 0(300K)=2157'59"
sin 0(100 K) = 0.37526, sin 0(300 K) = 0.37406

sin 0(300 K)
sin 0(100 K)
a(lOO K)
0 99681
= a(300 K)
A. V3 154.062 pm X V3
a( 300 K) = 2 sin 0 =
2 X 0.37406
356 67 pm
a(100 K) = 0.99681 x 356.67 pm = 355.53 pm
oa
a
ov
356.67-355.53
355.53
3.206 x 10- 3
356.67 3-355.53 3
355.533
9.650 x 10-3
1 ov 9.650 x 10- 3
4.8 X 10- 5 K -I
avolumc =vaT=
200 K
Diffraction methods
1 oa
3.206 X 10- 3
auncar= ~ oT=
21.11
1.6 X 10- 5 K -
200 K
_L f , fsini -sR;i-
/-
. .
'
l .J
4fcfCI
_ 4.n .
s- - sm -,1e
sR;i '
A.
-
385
[8]
sin sRcCI
, sin sRclcl
R
+ 6fc1 R
S
CCI
CICI
~n
sm x
=4 x 6 x 17 xF --+ 6 x 17 2 xF
8)112
( -3 x
Gf\
[x =sRCCJ ]
sin x
sin(8/2) 112x
IIF = 408 - + 1 0 6 2 - - X
This function is plotted in Fig. 21.6. We can find
Xma x
and
Xmin
300
from the graph,
Fig 21 .6
200
"'
100
!\
} 1\ II"
1\ ["" I\
"
V'
\
\
\
~
-100
-200
-300
10
20
30
and Smax and Smin from the data. Then, since x=sRcC\ we can take the ratio xis
to find the bond length Rcet We draw up the following table:
386
Diffraction methods
Maxima
e( expt.)
s/pm- 1
x(calc.)
(x/s)/pm
3 10'
0.0284
5.0
176
Minima
522'
0.0480
8.5
177
7 54'
0.0706
12.5
177
1 46'
0.0158
2.8
177
4 6'
0.0367
6.5
177
6 10'
0.0597
10.5
176
9 10'
0.0819
14.5
177
Hence, RCCI = 177 pm and the experimental diffraction pattern is consistent

with tetrahedral geometry.
21.12 Consider, for simplicity, the two-dimensional lattice and planes shown
in Fig. 21.7. The (hk) planes cut the a and b axes at a/ h and bl k, and we have
d
hd
d
kd
sin a= (a/h)=--;;, cos a = (blk) =t;
Then , since sin 2 a+ cos2 a = 1, we can write
and therefore
The argument extends by analogy (or further trigonometry) to three

dimensions, to give
Diffraction methods
387
21.13 If the sides of the unit cell define the vectors a , b, and c, then its
volume is V=a h A c [given]. Introduce the orthogonal set of unit vectors i, j,
k so that
a = a) + a,j + a, k
b = b,i
+ b,j + b, k
c=cxi +s,j+cJ
a,
ThenV=ab A c= bx
a>"
a,
by b,
Therefore ,
vz=
a, aY a,
b, by b,
c, Cy c,
a,
b,
c,
ax aY a? ax b, c,
bx by b, ay b, Cy
c, Cy c, a, b, c,
aY a,
b, b,
c,. c,
[interchange rows and columns, no change in value]
axa, + ayav + a,a,

bxax + b,a, + b,a,
a,b, + ayby + a,b, a,c, + aYc>' + a,c,

b,b, + b,by+ b,b, bxcx + bycv + b,c,
c.,a, + c,aY+ c,a,
Cxb, + Cyby + c,b,
az
ab
ba
ca
az
C,Cr + CyCy + C,C,
b2
ac
bc
ab cosy
ab cosy
b2
cb
c-'
ac cos {3
be cos a
= a 2b 2c 2(1- cos 2 a- cos 2 {3- cos 2 y + 2 cos
ac cos {3
be cos a
cz
a cos {3 cos y) 112
Hence,
V = abc(l- cos 2 a- cos 2 {3- cos 2 y + 2 cos a cos f3 cosy) 112

For a monoclinic cell a= y = 90, and
V = abc( I - cos 2 {3) 112 =abc sin f3

For an orthorhombic cell , a=f3= y =90, and
V=abc
388
Diffraction methods
21.14
J=
NV
T
,where N is the number of atoms in each unit cell , V,, their
c
individual volumes , and Vc the volume of the unit cell itself. Refer to
Fig. 21.8.
(b) N=2 , V .. = t nR
3
,
Vc= (
~r
[body diagonal of a unit cube is V 3]
2 x-j-nR 3
nV3
!= (4R/V3)3 =-8-=0.6802
(c) N=4 , V,, = t nR 3 , Vc=(2 V 2R) 3
4 X t nR 3
JT
!= (2 V 2R) 3 3V 2 = 0 7405
For each A atom use t ! A[each A atom shared by eight cells] but use fs for
the central atom [since it contributes solely to the cell].
Fltkl = t / A{l + e 2mlt + e LTik + e LTil + e 2lri(lt+k) + e h i(lt +l) + e LTi(k+ l ) + e 2"i(lt +k+ ll}
+ f s e " i(lt+k+ l )
=fA+ ( -1 )" +k+'Js
[ h , k, I are all integers , e;" = -1]
Diffraction methods
389
(a) !A=f,Js=O; F,k,=f [no systematic absences]
(b) fs=+JA; F,k,=fA{l+t(-l)"+k +l}

Therefore, when h + k +I is odd, Fhk 1 = fA{l- t} = tfA, and when h + k +I is
even, F,k, = ffA That is , there is an alternation of intensity (I rx F 2) according
to whether h + k +I is odd or even .
(c) fA= fs = f; F,+k +f= f{l + ( -l)" +k+l} = 0 if h + k +I+ is odd.
Thus, all h + k +I odd lines are missing.
22. The electric and magnetic

properties of molecules
Exercises
C= t:,C0 [Example 22.1] = 35.5 x 6.2 pF = 220 pF
22.1
f1.
3t:oPm
a+ 3kT= NA
22.2
p.
Therefore, k
1 1)
TT'
[6a]
3t:0
= NA (P-P')
[Pat T, P' at T']
and hence
(9t:okl NA)(P - P')
p.2 = - - - - - -
T'
9 X 8.854 X 10- 12 J - I C 2 m- 1 X 1.381 X 10- 23 J K -I X (70.62- 62.47)

X 10- 6 m 3 mol- 1
6.022 X 1023 mol - l X
351~0 K
- 423\ K)
= 3.064 X 10- 59 C 2 m2
and hence
f1.
= 5.5 X 10- 30 c m, or 1.7 D.
3t:oPm
Then
p.
a=---,:;-;- __, 3kT

3 X 8.854 X 10- 12 r
C 2 m- 1 X 70.62 X 10- 6 m 3 mol - 1
6.022 x 1023 mol- 1

3.064 X 10- 59 C 2 m2
3 X 1.381 X 10- 23 J K -I X 351.0 K
= 1.01 X 10- 39 J - I C 2 m2
The electric and magnetic properties of molecules
a
corresponding to a'=--=
9.1 x 10- -' 4 em 3
4nEu
E,-1
22.3 - E,+2
1.89 g cm - 3 x 27.18 cm 3 mol - 1

92.45 g mol
pPm
M
[6b]- ---'----:-::---,-::--...,--;--1
--
=0.556
Hence,
E,
1 +2 X 0.556
_ 0.
1
556
4.8
22.4 A D 3h (trigonal planar) molecule is nonpolar; hence the second

structure (with symmetry group C2v) is more likely .
22.5 Follow Example 22.4
Rml(cm 3 mol - 1) = 10 X 1.65 + 2 X 1.20 + 2 X 1.41 = 21.72
74.12gmol- 1
_
1
3
Vm= 0.7l gcm _3 =103.6cm mol 5
_{V"' + 2R"'}"2_ {103.6+2 x 21.72}"2_
n,-
Vm-Rm
103 .6-21.72
-1. 34
The experimental value is 1.354.
22.6
3EoRm
M{n~-1}
a = - - with R"'=- - , NA
p n~+2
Therefore,
a = 3c0M {n: -1}
pNA n~+2
and a'= 1.28 x 10- 23 cm 3.
[9]
391
392
22.7 Refer to Fig. 22.2 of the text , and add moments vectorially [see
diagram 2 of the text , Section 22.1].
(a) p-xylene: the resultant is zero, so fl = Q

(b) a-xylene: fl=0.4 D cos 30 +0.4 D cos 30 =0.7 D
(c) m-xylene : 11-=0A D cos 30+0.4 D cos 60 =0 .5 D
The p-xylene molecule belongs to the group D2h , and so it is necessarily
nonpolar.
22.8 fl = (fli+fl ~ +2fllfl2 Cost9) 1 12
[Section 22.1]
= (i.5 2+ 0.80 2+ 2 X 1.5 X 0. 80 X cos 109.5) 112 D

= 1.4D
22.9 fl* = a"&
[la] = 4.7te 0a '"&
[3]
= 4.n X 8. 854 X 10- 12J - I C 2 m2 X 1.48 X 10- 30 m3 X 1.0 X 105 V m- 1

= 1.6 x 10 - 35 Cm
[IJ=lCV]
which corresponds to 4.9flD.
22.10
V
m
n, =
R:
v +2R
{ ;m _
}1'2
[10]
M 18.02gmol- 1
-18.0cm3 mol - 1
p
1.00 g cm - 3
Hence,
-{18 .0+2 x 3.8}1'2 _
n,18.0-3.8
-1. 34

Discrepancies may be due to a more complicated local field correction
than has been assumed, and vibrational contributions.
Hence,
E,
1 + 2x .
pN A (
fl )
_ x with x = EoM a + kT
1
3
3
1.173 x 10~ g m - 3 x 6.022 x 1023 mol - 1

x=
3 X 8.854 X 10- 12 J - I C 2 m 2 X 112.6 g mol - 1
X { 4.n X
8.854 X 10- 12 ]
- I
C 2 m 2 X 1.23 X J0 - 29 m 3
(1.57 X 3.336 X 10-Jo C m?

}
+ 3 X 1.381 X 10- 23 ] K - I X 298.15 K
=0 .848
Therefore ,
E,
1 + 2 X 0.848
_ _
= 18
1 0 848
22.12 (a) Rm(CaC1 2 ) = 1.19 + 2 X 9.30 cm 3 mol - 1= 19.79 cm 3 mol - 1

Vm(CaC1 2)=
111.0 g mol- 1
_ =51.6cm 3 mol - 1
2 .1 5 gem 3
_ {Vm + 2Rm}l /2_ {51.6+ 2 X 19.79}1/2_

Vm-Rm
51.6-19.79
-1. 69
n,-
(b) Rm(NaCl) =0.46+ 9.30 cm 3 mol - 1=9.76cm 3 mol - 1

Vm(NaCl)=
58.4 g mol - 1
=27 .0cm 3 mol - 1,
. gem 3
216
which gives [as above] n, = 1.64
393
394
which gives n, = 1.23

22.13
{(0)12
-;. - (a)6
-;. }
12 6a 6} 24t:{ (a)l3
12a
F = - dV
dr with V = 4t:
Therefore, F= 4t: { ~ -7
=---;;-
2 -;.
- (a)7}
-;.
The force is zero when

116
a)l3 = (a)
-;. 7, or r = 2 a
2 ( -;.
22.14
m = gc{S(S+ 1)} 112,U 8
[Section 22.11 , ge=2]
Therefore, since m = 3.8l.u 8

S(S + 1) = t x 3.81 2 = 3.63 , implying that S = 1.47
Since S = f, there must be three unpaired spins.
22.15
xM
xm=xVm [24]= p
-7.2 X 10- 7X 78.11 g mol- 1
0.879 gem 3
22.16
_
Xm- 6.3001
-6.4 X 10- 5 cm 3 mol - 1
_1
S(S+1)
[Example 22.7]
TIK em 3 mol
Since Cu(II) is a d 9 species , it has one unpaired spin , and so S = s = t .

Therefore,
Xm =
6.3001 xt x t
cm 3 mol - 1 = --'+0
cm 3 mol - 1
298
--"-'"--"016
"'--"-'"'-'-'--'-=~
Problems
22.1 The positive (H) end of the dipole will lie closer to the (negative)
anion . The potential arising from a point dipole is
-.u
= -2 [11 , V=q 2]
4nt:ur

and since the electric field is the negative gradient of the potential ,
<g =
-drp =
-2f1.
4m::or 3
dr
-2 X 1.85 X 3.34 X 10- 3C m
-1.11
10 - 19 Vm - 1 - 1.11
(r/m)
lOXV m -
(r/nm)
(a) <g = -1.1 X 108 V m- 1 when r= 1.0 nm

-1.11
(b) <g =
(c) <g =
108 V m- l
_33
4.l x l09 Vm - 1
0
-l.ll x l08 Vm - 1
_
.
= 4.1kvm - 1
303
22.2 The energy of a dipole is initially - fJ.<g and becomes zero when it is
perpendicu lar to the field. The energy of the dipole-ion pair is initially
zero (when the dipole is perpendicular to the line of approach of the
atom) but changes to -J1.ql4nE0 r 2 [11] when the dipole points toward the
ion and has zero interaction with the applied field . We need to establish
when the magnitude of the latter interaction energy exceeds that of the
former. This occurs when
M
- -, = fJ.<g , q = e
4nE0r -
and hence when
e )112
r= ( 41CEo<g
19
9.109 x l0- C
) 112
= 4n X 8.854 X 10- 12r 1 C 2 m- 1X 1.0 X 103 v m - 1
=2.9J1.m
22.3
Pm = M(E,-l)
p E,+2
rV ~, ~
=
-V =224 x l0 4 cm 3 mol - l
3r+
~,
m
Moreover,
395
396
Therefore, evaluate Pm from
the~' r
data, and plot Pm against liT: the slope
is NAJl 2!9t:0k and the intercept at liT= 0 is NAa/3t:0 (or
~.n N
a'). We
therefore draw up the following table:
ere
100
200
300
373
2.68
26.1
19.4
16.4
473
2.11
22.4
17.2
15.7
573
1.75
19.4
15.7
15.7
0
273
3.66
32 .1
23.1
17.2
T/K
1000/(T/K)
Pm(HCI)/(cm 3 mol- 1)
P m(HBr)/(cm 3 mol- 1)
Pm(HI)/(cm 3 mol- 1)
The points are plotted in Fig. 22.1. The intercepts and slopes are
35
30
25
VH:J
"'~E 20
/VH
I'
a..E
1/.
10
./
./
HI
~v
15
""'""
.) v
5
0
I1J
2J)
3.0
trif(VKJ
4D
Fig22.1
Intercept
Slope
HCI
HBr
HI
8.9
6.4 X 103
9.3
3.8 X 103
14.1
8.3 X 102
It follows that, with 4nNA /3 =2.52 x 1024 mol - 1,

a '(HCI) =
a'(HBr)=
a'(HI) =
8.9cm 3 mol - 1
4nNA /3
9.3 cm 3 mol - 1
4nNA/3
14.1 cm 3 mol- 1
4nNA/3
3.5 x 10- 24 cm 3
3.7 x 10- 24 cm 3
5.6 x 10- 24 cm 3
We also need
1-l =
c::k)
112
(slope X cm 3 mol - l KY' 2
= (9 X 8.854 X 10- 12 r 1 C 2 m- 1 X 1.381 X 10- 23 J K - l) 112

6.022 x 10 23 mol - l
x (slope x cm 3 mol- 1 K) 112
:o~)
112
= 4.275
10- 29 C X
= 4.275
10- 29 C X (slope X cm 3 m -l) 112
= 4.275
10- 29 C X (slope X 10 - 6 m 2) 112
= 4.275
10- 32 C m X (slope) 112
(slope X cm3 mol - 1 K) 112
= 1.282 X 10 - 2 D X (slope) 112

It follows that
J.l(HCI) = 1.282 X 10- 2 D x (6.4 x 103 ) 112 = 1.03 D

J.l(HBr) = 1.282 x 10- 2 D x (3.8 x 10 3) 112 = 0.80 D
!l(HI) = 1.282 x 10- 2 D x (8.3 x 10 2Y12 = 0.36 D
22.4
(E,-1)
M
Pm = p E,+ 2
4n
NAJ.l
and Pm=)NAa '+ 9EokT
397
398
Therefore, we draw up the following table (with M = 119.4 g mol- 1):
ere
-80
-70
-60
- 40
-20
20
TIK
1000/(T/K)
193
5.18
3.1
203
4.93
3.1
213
4.69
7.0
233
4.29
6.5
253
3.95
6.0
273
3.66
5.5
293
3.41
5.0
0.41
0.41
0.67
0.65
0.63
0.60
0.57
1.65
29.8
1.64
29 .9
1.64
48.5
1.61
48.0
1.57
47 .5
1.53
46.8
1.50
45.4
E:,
,-1
,+2
pl(g cm- 3)
Pm/(cm 3 mol- 1)
Pm is plotted against 11 Tin Fig. 22.2. The (dangerously unreliable) intercept is

50
-c
I
Fig 22.2
"'
~~
40
o...E
v
/
30
/
0
3
4
10~(T/K)
5
mpt.
at 30 and the slope is 4.5 x 103 . It follows that

3 x 30 cm 3 mol - 1
a
1.2 X 10- 23 cm 3
4.n X 6.022 x 1023 mol- 1
I=
and (using the conversion factor developed in Problem 22.3)

!1 = 1.282 X 10- 2 0 X (slope) 112
= 1.282 X 10- 2 0 X (4.5 X 10 3) 112 = 0.9 0
The sharp decrease in P'" occurs at the freezing point of chloroform ( -63 oq,
indicating that the dipole reorientation term no longer contributes . Note that
Pm for the solid corresponds to the extrapolated , dipole free , value of Pm, so
the extrapolation is less hazardous than it looks.
399
22 .5
The data have been corrected for the variation in methanol density , so use
p = 0.791 gem - J for all the entries. Obtain t-t and a' from the liquid range
( 8 > -95 oq results, but note that some molecular rotation occurs even below
the freezing point (thus the -l10 C value is close to the - 80 C value). Draw
up the following table using M = 32.0 g mol - 1
ere
-80
-50
-20
20
TIK
193
5.18
57
223
4.48
49
253
3.95
42
273
3.66
38
293
3.41
34
t:, -1
-t:,+2
0.949
0.941
0.932
0.925
0.917
Pml(cm 3 mol- 1)
38.5
38.1
37.4
37.7
37 .2
1000/(T/K)
E,
P m is plotted against 1/T in Fig. 22.3. The extrapolated intercept at liT= 0 is

39
Fig22.3
v.
.,/
f-"
.//
37
3.2
3.6
4.0
l .t,
4.8
5.2
7000K/ T
35.0 and the slope is 741 (from a least-squares analysis) . It fo llows that
a' =
3 x 35.0 cm 3 mol - 1
4n x 6.022 x 1023 mol
1-t = 1.282 x 10- 2 D x (741) 112
=0.35 D
1.38 x 10 - 23 cm 3
[from Problem 22.3]
400
Therefore, draw up the following table:
TIK
292.9
309.0
333.0
387.0
413.0
446.0
1000/(T/K)
p m/(cm3 mol- ')
3.42
57.57
3.24
55.01
3.00
51.22
2.58
44.99
2.42
42.51
2.24
39.59
The points are plotted in Fig. 22.4. The extrapolated (least-squares) intercept
60
/
/
Fig22.4
/
'I
50
{
/
a..E:
J(
/ .
1,0
3.0
4.0
1000K/ T
lies at 5.65, and so a '= 2.24 x 10- 24 cm 3 [see Problem 22.5 for the
conversion]. The least-sq uares slope is 1.52 x 104 , so [as in Problem 22.5],
0 = 1.58 D.
401
22.7 Consider the arrangement shown in Fig. 22.5 . The total potential energy
of interaction of the two quadrupoles is
Expand each term using
- - = 1-x+x 2 -x -'+x~-
l+x
and keep up to A. 4 [the preceding terms cancel]. The result is
Define the quadrupole moments of the two distributions as
and hence obtain
22.8
n~ - 1
n;+2
4na 'NAp
3M
M
For a gas,
Mp
p=y-= RT
Ill
[9 ]
402

Fig 22.5
~----------(----------~
Therefore,
n =
r
{11- 4.na,
+8.na'pNA/3M} ltz =
pNA/3M
{11- 4.na
+8.na'p/3kT}ltz
'p/3kT
= {( 1 8na'p) ( 1 4.na 'p)}ltz - 1 = 1+x]

+ 3kT
+ 3kT
[ 1-x
12.na 'p
}
= 1+---+ . . .
{
3kT
112
2na'p
= 1 + - - [(1+ x) 112 = 1+ t x]
kT
Hence , n, = 1 + const.
p , with constant= 2na 'I kT
From the first line above,
3M (n~ -1)
a'= 4.nNAp
3kT(n~ -1)
n~ + 2 =~ ~
22.9 The time-scale of the oscillations is about 11(0.55 GHz) = 2 x 10- 9 s for
benzene and toluene, and 2.5 x 10- 9 s for the additional oscillations in toluene.
Toluene has a permanent dipole moment , benzene does not . Both have dipole
moments induced by fluctuations in the solvent. Both have anisotropic
polarizabilities (so that the refractive index is modulated by molecular
reorientation).
22.10 The dimers should have a zero dipole moment. The strong molecular
interactions in the pure liquid probably break up the dimers and produce
hydrogen-bonded groups of molecules with a chainlike structure. In very
dilute benzene solutions, the molecules should behave much like those in the
gas and should tend to form planar dimers. Hence the relative permittivity
should decrease as the dilution increases.
403
22.11 Consider a single molecule surrounded by N - 1 ( = N) others in a

container of volume V. The number of molecules in a sphe rical shell of
thickness drat a distance r is 4.nr 2 x N/V. T herefore , the inte raction e nergy is
u=
R4.nr-x-x
, N (-C
-4.nNC6 JRdr
- - dr=
v
r6
v
r4
J
6)
where R is the radius of the container and d the molecular diameter (the
distance of closest approach). Therefore,
4.n
1 1)
-4.nNC6
u=JXV X C6 x R 3 - d 3 = 3Vd 3
because d ~ R. The mutual pairwise interaction energy of a ll N molecules is

U = JNu [the + appears beca use each pair must be counted only once; i.e. A
with B but not A with 8 and 8 with A]. Therefore,
- 2.nN 2C6
U = 3Vd 3
For a van der Waals gas ,
nv2a2 = (aa~v T
V}
and therefore a =
22 . 12
2.nN2Cb
3V 2d 3
2.nN~C6
3d 1
B=2.nNA f x {l -e - v'k1)r 2 dr
[22c]
II
_2
.1 2.nN AC,
~3.nNA d- kT
Jxdr
d7
(1 -e' = x]
2.n
2.n NAC6 I
=- N d3 ---- x 3 A
3 kT
d'
22.13 An 'exponential-6' Lennard-Janes pote ntial has the form
404
and is sketched in Fig. 22.6. The minimum occurs where
-1
,s
dVdr {-Aa
6a- } =0
-=4c - e-rta +
7
r
which occurs at the solution of
a7 A
r7 6
- = - e:-rla
Solve this equation numerically. As an example , when A= a= 1, a minimum

occurs at r= 1.63 .
22.14
B=2:rcNA f~ {1-e- VJkT}r 2 dr

=
2:rcN A
fa,r
dr + 2:rcN A
2:rc
2:rc
[22c]
fa' {1- eclkT}r

a,
3
=3- N AaI3+-N
3 A {1- ecikT}(a 2 -
a 3I )
dr

Suppose that
E~
405
kT, then
2:rc
2:rc
B = 3NAa~-3NAE(a~- ai}lkT
For the van der Waals equation,
a
B=b-RT
Hence,
22.15 Numerical evaluation of B leads to the following values:
TIK
100
110
120
150
200
300
500
4.96
11.7
17.8
22.9
26.0
B=Oat T=105K .
22.16 The number of molecules in a volume element dr is N dr/ V = N dr. The
energy of interaction of these molecules with one at a dista nce r is VN dr. The
total interaction energy, taking into account the entire sample volume , is
therefore
u=
VNdr=N
Vdr
[Visthe interaction,notthevolume]
The total interaction energy of a sample of N molecules is t Nu (the +is

included to avoid double counting), and so the cohesive energy density is
U=--+Nu
-- = - i-Nu=-+N 2
However , N
"
Vdr
N API M, where M is the molar mass; therefore
406
22.17 Refer to Fig. 22.7a. The scattering angle is (} = n- 2a if specular

reflection occurs in the collision (angle of impact equal to angle of departure
from the surface). For b ~ R 1 +R 2 , sina=b/(R 1 +R 2):
e~ {:- 2 "'";" (R,! R,)

The function is plotted in Fig. 22.7b .
(b)
(a)
180"
Fig 22 7
!'-...
.........
t-....
90
D-2
0"4
.......
:--......
06
"r-..
08
b/{R +R J
1 2
22.18 Once again [as in Problem 2.17] we can write
e( v) =
n-2arcsin{R 1 +~2 (v)} b~R 1 +R2 (v)

0
but R2 depends on v:
Rz(v) = Rz e- utu .
Therefore, with R 1 = iR 2 and b = f Rz
(a)
1
e(v) = n- 2 arcsin { 1 + 2 e-u/u }
b > R I + Rz( v)
'
10
12
407
[The restriction b ~ R 1 + Rz(u) transforms into t R2 ~1R 2 + R 2 e -utu , which is

valid for all u.] This function is plotted in Fig. 22.8a. The kinetic energy of
160
120
Fig 22.8
'~
'\.
.......
r- ...!2...
"'r-...
........
r- r-
(a}v/v and (b}E/E.c
10
approach is E = t mv 2 , and so
(b)
8()=.n-2arcsin{l+Ze~<t">' " }
withE * = t mv *' . This function is plotted in Fig. 22 .8b.
=3a6
[I
~ x"
e-ax
dx= - n! ]
a" +l
Therefore ,
Then, since Xm= NAf.1o/;
(25b, m = O]
408
22.20 If the proportion of molecules in the upper level is P, where they have
a magnetic moment 211-a, the molar susceptibility
6.3001 X S(S + 1)
Xm =
TIK
cm3 mol - 1 [Example 22.7]
is changed to
-
Xm -
6.3001 X 4 X P
25.2P
3
1-1_
3
1-1
TIK
em mo - T/K em mo
The proportion of molecules in the upper state is

e -hCI'Ik T
P = 1 + e-hcv/k T [Boltzmann distribution]
1
1 + ehcvlkT
1.4388 em K x 121 cm - 1
and hcii/kT= - - - - - - - -
174
TIK
Therefore,
25.2 cm3 mol- 1
Xm = TIK X (1 + el74/( T/K))
This function is plotted in Fig. 22.9.
Fig 22.9
..........
'
1
I
'~
........
r-
f-L
j_
0
100
200
300
T/K
1.00
500
23. Macromolecules
Exercises
(M)N=
23.1
N IM \+ N2M2
62+78
N
(5] = -- kg mol - 1
=70 kgmol(M)M=
m 1M 1 +m ,M ,
- - (19aj
n 1 Mi+n 2 M ~
Mi+M ~
n 1M 1 +n 2M2
Ml+M2
62 + 78
2
62+78
kg mol- 1 =71 kg mol- 1
RT{ 1+B-+
c
}
232TI/c==.
M
M
[1b]
Therefore, to determine M and B we need to plot TI/c against c. We draw up

the fo llowing table:
(TI!c)/(Pa/g L - 1)
1.21
2.72
5.08
6.60
111
118
129
136
The points are plotted in Fig. 23.1. A least-squares analysis gives an intercept
of 105.4 and a slope of 4.64. It follows that
RT
_
_
M =105.4 Pa g- 1 L= 105.4 Pa kg - 1 m3
and hence that
8.3141 K- 1 mol - 1 x293 K
M=
105.4Pa kg m3
23.1kgmol- 1
The slope of the graph is equal to RTBIM 2 , so

RTB
M 2 = 4.64 Pa g- 2 L 2 = 4.64 Pa kg- 2 m6
410
Macromolecules
Fig23. 1
140
'S
"'
130
:::::: 120
(J
/.
I.-'
110
./
100
Therefore,
(23.1 kg mol- 1) 2 x 4.64 Pa kg- 2 m6
8.314JK- 1 moi 1 X293K
B=
Tile= (RTf M){1 + (B! M)c}
23.3
l.02 m mol -
[1b]
n=pgh; so
h
RT
BRT
pgM
pgM
-=--+--c
2
and we should plot il/h against c. Draw up the following table:
hlcm
(h/c)/(cm 4 mg - 1)
3.2
4.8
5.7
6.88
7.94
3.11
6.22
1.30
8.40
1.47
11.73
1.70
14.90
1.90
0.97
The points are plotted in Fig. 23.2. The least-squares intercept is 0.351 and
the slope is 0.196. From the intercept
RT
- - = 0.351 cm 4 mg - 1 = 0.351 X 10- 2 m4 kg - 1

pgM
Macromolecules
2 .0
411
Fig 23.2
}
~
,~
5
8
Cp / mg cm-3
and hence
M=
=
8.314J K - I mol - 1 x 298 K

0.867
103 kg m- 3 X 9.81 m s- 2 X 0.351
10- 2 m4 kg - 1
83 kg mol - 1
23.4 We use the same procedure as in Exercise 23.3, and begin by drawing up
h/cm
(h/c)/(100 cm 4 g- 1)
0.200
0.400
0.600
0.800
1.00
0.48
2.4
1.12
2.80
1. 86
3.10
2.76
3.45
3.88
3.88
The points are plotted in Fig. 23 .3, and give a least-squares intercept at 2.043
and a slope 1.805. Therefore ,
RT
_
-M = 2.043
pg
100 cm 4 g- 1 = 2.043 X 10- 3 m4 kg - 1
and hence
8.314J K - I mol - 1 X 298 K
M = ---~--,....----~-~--c:-----:-----:4
3
1
3
0.798 x 10 kg m- 3 x 9.81 m s- 2 x 2.043 x 10 - m kg-
155 kg mol - 1
412
Macromolecules
1.0
...v
)_,..
I/
Fig23.3
2
0
02
06
DB
10
Cp / (g/ 100cm 3)
04
From the slope,

BRT
_ 100cm 4 g- 1
x
1
805
pgM 2 =
g/(100 cm 3)
1.80-5 x 104 cm 7 g- 2
= 1.805 X 10- 4 m7 kg- 2

and hence
B=
(p!~) X M X 1.805 X 10-
m7 kg- 2
155 kg mol - 1 X 1.80S X 10- 4 m7 kg - 2

2.043 X 10- 3 m 4 kg- 1
= 13.7 m3 mol- 1
23.5
R,ms = N 112l
23.6
Rg=
[Section 23.6] = 700 112 X 0.90 nm = 24 nm
N1 12l
R
N = 3 ____2
( l
23.7
V3
[constrained chains, Section 23 .6]
)2= 3 ( 7 3 nm )2 = 6. 7
X
[r;]=lim (
c~ o
0.154 nm
r;/r; * -1)
c
[16].
103
Macromolecules
413
We begin by constructing the following table using 'YJ* = 0.985 g m- 1 s- 1:
c/(g L - 1)
1.32
2.89
5.73
9.17
0.0731
0.0755
0.0771
0.0825
The points are plotted in Fig. 23 .4 . The least-squares intercept is at 0.0716 , so

[rJ] =0.0716 Lg- 1
p'
8 .2
..,
1/
/
8.0
0,
7.8
~"I
Fig 23.4
l.}
-;:::, 7.6
I
cV
j;'
:;z-
."
......
/0
7.1.
IN"
7.2
7.0
10
23.8 S= - 2 [9a]
rw
s 1 dr dIn r
Since s = dr/dt - = - - = - , r r dt
dt
and if we plot In r against t, the slope gives S through

1 dIn r
S = w2dt
The data are as follows:
c/g dm-3
414
Macrom olecules
t/min
15 .5
29.1
36.4
58 .2
r!cm
ln (r/ cm)
5.05
1.619
5.09
1.627
5.12
1.633
5.19
1.647
The points are plotted in Fig. 23 .5. The least-squares slope is 6.62 X 10- 4 ' so
1.64
~
.!::.
.s 1.62
/
P'
v
.D
P'
40
20
4.97 X
23.9 Si nce
Fig 23.5 .
/y
E"
s-- 6.62 X 10w2
J'
min -
60
t / min
6.62 X 10- X (1/60) S- -,------:---....,..-;:- (2.it x 4.5 x 10 /60 s4
1) 2
w-'3 s, or 5.0 Sv
ccce +mbw'' '
12
kT
[Sedimentation equilibrium , Section 23 .2]
mbw 2r 2
Mbw 2r 2
In c = const. +Zkr =const . +
RT
2
and a plot of Inc against r 2 should be a straight line of slope Mb/ RT. We
rlcm
5.0
5.1
5.2
5.3
5.4
c/(mg cm - 3)
0.536
25 .0
-0.624
0.284
26.0
-1.259
0.148
27.0
-1.911
0.077
28. 1
-2.564
0.039
29.2
-3.244
r 2 /cm 2
ln (c/ mg cm - 3)
Macromolecules
The points are plotted in Fig. 23 .6. The least-squares slope is -0.623.
Therefore,
M(1- pus)w 2
2RT
-0.623 em - 2 = - 0.623 x 104 m - l
It fo llows that
M=
-0 .623 X 104 m- 2 X 2 X 8.314 J K - I mol - 1 X 293 K

--------::------..,,.--..,.--------:-=
(1-1.001 g cm- 3 x 1.112 cm 3 g- 1) x (2.n x 322 s- 1) 2
= 65.6 kg mol - 1
SRT
23.10
M = bD
3.2 X
[13]
w- 13 s X 8.3141 K - I mol - l X 293 K
(1- 0.656 X 1.06) X 8.3 X 10 - ll m 2 S- l

=31 kgmol - 1
23.11 (a) Osmometry gives the number-average molar mass, so
100 g
= 17.6kg mol- 1
(b) Light-scattering gives the mass-average molar mass , so
(M)M=
m 1M 1 +m 2M 2
m1+m2
=19.5kgmol- 1
0.30x30+0.70 x 15kgmol - 1
415
416
Macromolecules
0
Fig 23.6
'c ......
1'-r
-3
.......
........
u.....
a,.
...........
-4
25
26
27
28
29
30
r;ycm 2
Hence
(Na+]R
v[P]
[Na+]L=
1
+ 2[Cl-] + v[P]
+2X
0.0010 M
6.7 X 10- 4 M
20 X 1.00 X 10- 4 M
0.0010 M+ 20 X 1.00 X 10- 4 M
where we have used

1.00 g X 10 L- 1
[P] = 100 X 103 g mol- 1 1.00 x 10- 4 g L -I
Hence, [Na+]L = 6.7 X 10- 4 M
For simplicity, write [CI-]L = L and [CI -]R = R. Then, since v = 1,
-[P]L
L - R = L+R, implying that L 2 -R 2 = -PL

Suppose an amount n mol of CI- ions migrate from the right hand
compartment to the left, L becomes nM and R changes from 0.030 M to
(2x0.030 - n)/2M [since its volume is 2L]. Therefore, at equilibrium
n 2 +Pn - (
0.060 - n)2
=0
2
with ? = 0.100
Macromolecules
This quadratic equation solves ton= 6.7 X
[Cl -)L = 6.7 mM.
417
w- 3; therefore, at equilibrium,
23.14 Since c oc eMbw'r'I ZRT [Sedimentation equilibrium, Section 23.2],
lnc=const.+
Mbw 2r 2
RT
[b=l-pu ,]
2
and the slope of In c against r 2 is equal to Mbw 2 /2RT. Therefore,

M=
2RTx slope
bw z
2 x 8.3141 K _, mol- 1 x 300 K x 729 x 10 4 m- 2
(1- 0.997 X 0.61)
(2Jr X 50000/60 s- 1) 2
=3 .39x 10 3 kgmol- 1
23.15 The force acting is F= mrw\ and by Newton's second law of motion,
F=ma,
a= rw 2 = 4.n 2rv 2
= 4.n 2 X 6.0 X 10- 2 m X (80 X 1Q3/60 s) 2
=
4.21 x 106 m s- 2
Then, since g =9.81 m s- 2 , a=4.3 x 10 5 g

23.16
4.na 3rJ
r = kT
3
[22]
(a) With rJ(H 20) =0.8909 x 10- 3 kg m- 1 s- 1 and a(SA) = 3.0 nm,
r =
4.n X (3.0 X 10- 9 m) 3 X 0.8909 X 10- 3 kg m- 1 s- 1
3 X 1.381 X 10
23
JK
298 K
2.4 X 10-R S
(b) With rJ(CCI 4) = 0.895 x 10- 3 kg m- 1 s- 1 and a(CCI 4) = 250 pm,

4.n X (2.50 X 10-IO m) 3 X 0.895 X 10- 3 kg m- 1 S- 1
r=
3xl.381x10 23 JK 1 x298K
= 1 .4x10-"s
23.17
(::) T = -Rc1T,
(31]
Since (aylac)-r > O [given], f<O, which implies that the salt tends to avoid the
surface.
418
Macromolecules
Problems
23.1
c mbw 2(r 21 - r 22 )
In__:=
c2
2kT
[14]
RT!n (c/c 2) }112

and hence v = { 2n 2M b(d _d)
8.314 J K- 1mol - 1x 298 K x In 5

=
}112
2 --~5~
2 k~g-m--o~l~1 -x~(~l--~0~.7~5~
x~1~0~
)x~(=7~.07
. 0~2~)x--1~0~4~m~2
{ ~2n~2'x~1-
=58 Hz , or 3500 rpm.

23.2
v(P](Na +]L
(Na +]L- (Na +]R = (Na +]L + (Na+]R
(6a]
Therefore, writing [Na +k = L and [Na +]R = R , and setting v = 2,

(L + R)(L- R) = 2[P]L
Suppose an amount 2n mol Na+ migrate from the left to the right hand
compartments to reach equilibrium, then L changes from 0.030 + 0.010 M to
0.040- n M and R changes from 0.030 + 0.010 M to 0.040- n M and R changes
from 0.0050 M to 0.0050 + n M. We must therefore solve
0.045 x (0.035- 2n) = 0.030 X (0.040- n)
which gives n = 6.5 x 10- 3. Therefore, the concentration of Na + ions at
equilibrium are L = 0.034 M, R = 0.012 M. The potential difference across the
membrane is therefore
8.314 J K -I mol - 1 x 300 K 0.012
E=Finz=
96.485kCmol- 1
ln0.034
RT
= -27mV
vz
23.3
ll=RT[P](1+B[P]) , B= 4(cl-]+v[P]
400
B = 4x0.020M
(4 (Ci - ] l v[P]]
[7]
Macromolecules
419
This value of B is comparable to the values calculated for nonelectrolyte

solutions (Example 23.1], and so the two effects are comparable in this case.
SRT
23.4
M = bD
(13]
4.5 x 10 - us x 8.3141 K - I mol - 1x 293 K

(1 - 0.75 X 0.998) X 6.3 X 10 - ll m 2s - 1
=69 kg mol - 1
Now combine J= 6.1ra7J
kT
6n1]D
(10] with f= kT/ D (12] :

1.381x10- 23 JK - 1X293K
a = --=-----~--,---...,---------,-,----::,-------,
6n X 1.00 X 10- 3 kg m - 1s- 1X 6.3 X 10- ll m 2 s- 1
=3.4nm
SRT
23.5
M = bD
(13]
5.01 X 10 - 13 s X 8.314] K - I mol - l X 293 K

(1-1.0023 X 0.734) X 6.97 X 10 11 m 2 S 1
=66 .3kgmol - 1
kT
1.381 X 10- 23 J K -I X 293 K
J=-D (12]=
697
o- Il ' - 1
=5 .81 x 1Q-11kgs-l
. x1
m- s
vm =Us X M = 0.734 X w-> m3 kg - 1X 66.3 kg mol - l

= 4.87 X 10- 2 m 3 mol - 1
4n
3
=-N
3 Aa
Hence,
a= (
1
mol - ) 113
4n x 6.022 x 1023 mol - 1
3Vm) 113= (3 X 4.87 Y 10- 2m

4nNA
=2.7nm
/o = 6na7J = 6n X 2. 7 X 10- 9 m X l.QQ X 10- 3 kg m - I s- 1

=5.1 x 10- 11 kgs - 1
420
f
fo
Macromolecules
5.81x10- 11 kgs- 1
5.1 X 10-ll kg s- 1
1.14
This ratio corresponds to an axial ratio of about 3.5 for a prolate ellipsoid
[Table 23 .1]. Therefore, with
a3 =a1 a"i and a 1 =3.5a j_, a=2.7 nm

we conclude that
a 1 =6.2nm, a1. =1.8nm
23.6
S= rw 2
1 dIn r
[9a] = w 2 dt [Exercise 23.8]
Therefore, a plot of In r against twill give S. We draw up the following table:
tis
300
600
900
1200
1500
1800
r/cm
6.127
1.813
6.153
1.817
6.179
1.821
6.206
1.826
6.232
1.830
6.258
1.834
6.284
1.838
ln(r/cm)
The least-squares slope is 1.408 X 10- 5 , so

1.408 x 10-s s - I
S=(2nx50x103/60s 1)2=5.14x10-13s
SRT
Then M = bD [13]
5.14 X 10- 13 s X 8.314 J K -I mol-l
X 293 K
(1-0.9981x0.728)x7.62xl0 11 m2s 1
= 60.1 kg mol- 1
To assess the shape of the molecule we proceed as in Problem 23.5:
kT 1.381 X 10- 23 J K -I x 293 K
f=v=
7.62x10 llm2s I
=5.31 x10-llkgs-l
Vm = 0.728 cm 3g- 1X 60.1 X 103 g mol- 1=43.8 X 103 cm 3 mol - 1

=4.38 X 10- 2 m3 mol - 1
Macromolecules
421
Then,
a= ( 3Vm
4nNA
113 = (3 X 4.38 X 10- 2 m3 mol - 1)

4JT. X 6.022 X 1023 mol - 1
113
=2 .59 nm
fo=6na1] =6nX 2.59 X 10- 9 m X 1.00 X 10- 3 kg m - 1s- 1
=4.89x10- 11 kgs - 1
which gives
5.31
1o = 4.89 = l.09
Therefore, the molecule is either prolate or oblate, with an axial ratio of
about 2.8 [Table 23.1].
23.7
[rJ]=lim (
c~o
1]!1] *c
1)
and[rJ]=KM"
[Table23.3]
We draw up the following table using 1] * = 0.647 X 10- 3 kg m - I s ~ I:

c/(g/100 cm 3)
0.2
0.4
0.6
0.8
1.0
1]/(10- 3 kg m- 1s- 1)
1]/1]* -1
1
c/1]*c - )
(100 cm3 g- 1)
0.647
0
0.690
0.066
0.733
0.133
0.777
0.201
0.821
0.269
0.865
0.337
0.332
0.332
0.335
0.336
0.337
The values are plotted in Fig. 23.7 , and extrapolate to 0.330.

Hence
[17] = 0.330 x 100 cm 3g- 1= 33.0 cm 3 g- 1

and
33.0cm 3g- 1 )1to.so
M = ( 83 10-2
=158x103
. x
em 3-1
g
That is, M = 158 kg mol - 1
23.8
2
R g=-"'
R2
NL... 1
j
422
Macromolecules
D-338
/.
Fig 23.7
/V'
/
/
032
0
02
04
06
08
10
Cp/(g/100 cm'3J
(a) Center of mass at center of sphere; therefore
J"4nr dr
4
f:
Ri~ .,,,d,
(b) Center of mass at center of rod; therefore
1121
r dr
R 2=----=:.--=o'--- g
Jl/2/
dr
3V )1'3 (3vM)1'3
For a sphere, a= ( 4n;;A
=
n~A
and so
=
Rg
(~) lt2 (3v.M) 1/3

5
4nNA
= (~) l/2 (3(v,/cm
3g- 1) x cm 3g- 1X (Mig mol- 1) x g mol - 1)

4n x 6.022 x 10 23mol - 1
5.690 X 10- 9(v,/cm 3g- 1) 113X (Mig mol- 1) 113 em

= 5.690 X 10-ll m X {(u,/cm 3g- 1)(Mig mol- 1)} 113
=
113
Macromolecules
423
That is,
Rglnm = 0.056 90 x {(vJc m 3 g- 1)(M/g mol - 1)} 113

When M = 100 kg mol- 1 and v, = 0.750 cm 3 g- 1,
Rginm = 0.05690 X {0. 750 X 1.00 X 105} 113 = 2.40

For a rod,
Vmol
= na 2l, so
6.022 x 10 23 mol
x 2n x (0.5 x 10
cm) 2 x V3
=4.6 x 10 - 6 cm = 46cm
23.9 Assume the solute particles are solid spheres; the n
Rg= 0.05690 x {(v,/cm 3 g- 1)(M/g mol - 1)} 113 nm
[Proble m 23.8]
SA
BSV
DNA
66x 103
10.6 x 106
4 x 106
v,/(cm 3 g- 1)
(Rgfnm)calc
(Rgf nm)cxpt
0.752
0.741
0.556
2.09
11.3
7.43
2.98
12.0
117.0
Therefore, SA and BSV rese mble solid spheres, but DNA does not.
23.10 For a rigid rod, R goc l [Problem 23.8] ocM, but for a random coil
Rg oc N 112 oc M 112 Therefore , poly(y-benzyi-L-glutamate) is rod-like whereas
polystyrene is a random coil (in butanol).
23 11
-c
f= RT
(ay)
ac
-[A] (
l]
= RT
Then we draw up the following table:
-[A] ~Y
ay )
a[A]
= RT ~[A]
424
Macromolecules
[A]/M
- (a~:]) l(mN m- [A] ( a[ay)

A]
M-
1
)
I _
1
(mN m )
10 10f/(mol cm- 2)
0.10
0.20
0.30
0.40
0.50
26.0
25.0
26.0
23.0
30.0
2.60
5.00
7.80
9.20
15.0
1.07
2.05
3.20
3.77
6.15
For the last line we have used

1
[A]( ay) mNmf = - RT a[A] TmN m- 1
1
{ ( ay)
10- Nm= -[A]
a[ A] T (mN m- ) 24371 mol
and
10- 3 Nm- 1
J mol 1 = 4.103 X 10- 7 mo) m- 2 =4.103 X 10-II mo) cm- 2
2437
The surface pressure obeys n = RTf, with n = y * - y. Therefore, we draw up

the following table using y* = 72.8 mN m- 1 and RT= 2437 J mol- 1:
[A]/M
0.10
0.20
0.30
0.40
0.50
106f!(mol m- 2)
RIT!(mN m- 1)
(y* -y)/(mN m- 1)
0
0
0
1.07
2.60
2.6
2.05
5.02
5.1
3.20
7.81
7.7
3.77
9.21
10.0
6.15
15.0
13.0
The agreement is quite good, confirming that n = RTf.
23.12
(ay)
f = - RT ac
and y = y* +(elM) ~y,
[31]
ac
(ay)
~Y
=~
Macromolecules
425
Hence,
= -(c/M)(~y/mN
m- 1) x 4.103 x 10- 11 mol cm - 2
We then draw up the following table with c = 1M:
m- 1)
l0 11 f/(mol cm - 2)
~y/(mN
23.13
KCI
NaCI
1.4
1.64
2.7
-5.7
-6.7
-11.1
dN rx. e- <M-M)'12 r dM
We write the constant of proportionality as K, and evaluate it by requiring

that f dN = N. Put M- M = (2r) 112x , so
dM = (2r) 112 dx and

N = K(2r) 112
I~ e - ' ' dx
[a=-M/(2f) 1' 2]
=K(2r) 112
I~ e-x' dx
[a = O]
=K(2fY 12 t n
2 )\12
Hence, K = ( nf
N
It then follows that
_(sr) -+1 (-
- -
n )
112{
.7r
8f
112 _ }
(2r)
_
M =M+
-
112
.7r
23 .14 The center of the spheres cannot approach more closely than 2a; hence
the excluded volume is
426
Macromolecules
Up= j-.n(2a ) 3= 8(j-.na 3) = 8umol

where Vmol is the molecular volume. Since B= t NAu r [4],
=28 m3 mol- 1
16.n
B(Hb) = 3 X 6.022 X 10- 23 mol- 1 X (3.2 X 10- 9 m) 3
= 0.33 m3 mol - 1
Since TI = RT[P] + BRT[Pf
[1a]
if we write n o= RT[P],
II- n o BRT[Pf
----rr-- RT[P]
B[P]
1.0 g
10 g L - I
For BSV , [P] =M x 10 L - I l.O? x 107g mol _ 1
= 9.35
10- 7molL - I= 9.35 X 10 - 4 mol m- 3
II- n o
and ----rr-=28 m3 moJ -I
9.35
10- 4 mol m - 3=2. 6 X 10 - 2 corresponding to
2.6 per cent.

For Hb , [P]
66.5 x 103g mol-l= 0.15 mol m-3
II- n o
and ----rr- = 0. 15 mol m- 3 x 0.33 m3 mol - 1 = 5.0 x 10 - 2
which corresponds to 5 per cent.

23.15
B= t NAur [4]
=4NAumol [Problem 23.14]
- 16.n
3 - 16.n
3 3
- 3 NAa crr - 3NAy R g [acr1 = yRg]
Macromolecules
427
(a) Rg=N 112 l!Y6 (26)

16.n
112
21
B =--y'L'N
NA = 4 22
x- 10-------'--___..!.._
mol - 1 x (lYN)'
3 X 6" 2
=4.22 X 1023 mol - l X (154 X 10- 12 m X Y4000) 3 =0. 39 m1 mol - l
(b) Rg=2 1' 2 xRg(free) [27]
B = 2312 x B(free) = 1.19 X 1024 mol - 1 x (/YN) 3
=2 312 x0 .39 m3 mol - 1 = 1.1 m3 mol- 1
which rearranges to
[Na+JE- [Na+j~ = v[PJ[Na+]L
and hence to the quadratic equation
[Na+JE- v[P][Na +]L- [Na +]k = 0
Therefore, if [Na+]R is constant,
(Na +]L = t{v[PJ (v 2[Pj2 + 4(Na +Jkt 2}
and hence
~~::~~ = 2[~:1]R ( l + { 2[~[:1]R}
112
)
We write x=v[P]/2[Na+]R , and hence obtain

(Na+)L
,
--=x+(l+x 2t[Na +]R
[Ratio= 1 when x = 0, so choose+ sign.] This function is plotted in Fig. 23.8.
10
vu
v
I/
Fig 23.8
/
005
010
428
Macromolecules
G = U- TS - tl [given]
Hence dG=dU- TdS-S dT - l dt-tdl
23.17
= T dS + t dl- T dS - S d T -l dt- t dl = - S d T - l dt
A= U - TS = G+tl
Hence dA = dG+tdl+ l dt= - S dT-l dt+t dl+l dt

=
-SdT+tdl
Since dG and dA are both exact differentials,
(~~)r=- (:~) 1 and (~Dr= (:~),
Since d U = T dS + t dl
[given],
(aa~ r = T(~~) r +t
= - T(!!__) + t
aT
[Box3.1J
[Box 3.1 , Relation 1]

[Maxwell relation, above]
23.18 Write t=aT, then
=a
( !!__)
aT
'
1
(au)
at
=t-aT [above]
=0
and the internal energy is independent of the extension. Therefore,

t=
-T(as)
at
and the tension is proportional to the variation of entropy with extension. The
extension reduces the disorder of the chains, and they tend to revert to their
disorderly (nonextended) state .
23.19 Refer to Fig. 23.9. Since R;=R 1 +h; and
2: R;=O,
,-'
Fig 23.9
Macromolecules
-N 2: h;
and hence R 1 =
1
RI.""
" " h . hI
LJ h = - NLJ
I
ij
R g2 = 2_
"" R 2 [new definition]
NLJ
I
=N L {(R
+h;) (R 1 +h;)}
=~{ NRi+ ~ hf +2R1 ~ h;}
=2.{"'
N LJ h I
-2_""
NLJ
hI .
h}
I
ij
Since h hJ = -21 (h 2 + hJ2 - h 2)

I
IJ
[cosine rule]
1{
i N
2: hf + 2N1 2: ht- 21 2: hf- 21 2: hJ }
R =
I)
[In the last two terms, the summation over the second index contributes a
factor N.]
=
1
N2
L h~
[the original definition]
ij
a
=4:rr ( :rrii2
)3x83(:rr)II2
3
~
=2a2=Nl2
429
430
Macromolecules
Hence, Rrms = IN 112

(b) Rmean =
J: f(r)rdr = 4.n(.n~12y J:
1- -2- - x-
r e-"
-- 4.n -.na112J
(
2a 4- a.n
dr
(8~ 112I
3.n
112-
)3
2 2
'
,,
df
( a
(c) -dr = 4.n -.n 1/ 2 {2r- 2a 2r 2} e-a-r-= 0 when a-r 2 = 1.
Therefore, the most probable separation is
R* = ~ = lGNr2
When N = 4000 and I= 154 pm ,
(a) Rrms= 9.74nm, (b) Rmean= 8.97nm, (c) R * =7.95nm
23.21 A simple procedure is to generate numbers in the range 1 to 8, and to
step north for 1 or 2, east for 3 or 4, south for 5 or 6, and west for 7 or 8 on a
uniform grid. One such walk is shown in Fig. 23 .10.
Fig 23.10
There are N terms in the sums for which Rii =O , 2(N-1) terms for which
Rii=l, 2(N - 2) terms for which R i =21, ... and 2(N-k) terms for which
Rii= kl. Therefore ,
1 N-l {
sin ski} 1
P((}) = - " " 2(N-k)-- - N2Li
ski
N
k=O
2
=-
JN-1-sin-ski
2 JN
-1 sinskldk--1
d k - -,0
ski
N -sl
Macromolecules
Write x =ski, dk = dxlsl, Nl = L
(the length of the rod):
2 J<N-I)st
1
2 J(N-I)st(sinx)
P(O) = - - dx- """"2""?
sin x dx-sL 0
x
s L- 0
N
=-
sL
J<N-I)st (sin
x) dx+...,.--:;{cos(N-1)sl-1}-2
1
s-L-
Since the rod is long, (N-1)sl=Nsl=sL and

Therefore, as cos(} = 1-2 sin 2te,
2
P(O)=sL
J'L (sin
- x) dx- {sin
- tsL}2
x
sL
1
2
=-Si(sL)
- {sin
-tsL}2
sL
fsL
For L = )., sL = 4.n sin te and
Si( 4.n sin te)
P(O) = 2.n sin te
{sin(2.n sin t e)} 2

2.n sin te
This function is plotted in Fig. 23.11.
1/N ~ l.
431
PART 3: CHANGE
24. The kinetic theory of gases
Exercises
24.1
c=
(::n
112
[7b]
(::n
112
= (8 x 8.314 J K- 1mol- 1x ~ 112

nx (Mig mol- 1) g mol- 1)
T/K ) 112
1
= 145.5ms- X ( M/gmol_ 1
Therefore, we can draw up the following table with M(He) = 4.00 g mol- 1 and
M(CH4 ) = 16.04 g mol- 1:
kT
24.2 A=-1,-2-
2 ap
VK
E8
1000
c(He)/m s- 1)
c(CH4 )/(m s- 1)
640
320
1260
630
2300
1150
[12b]
kT
implies that p = 21 12 aA
With A= 10 em
1.381 X 10- 23 1 K - l X 298.15 K
p = 2 112 X 0.36X 10 18 m2 X 0.10 m
0.081 Pa
This pressure corresponds to 8.0 X 10- 7 atm.
kT
24.3 p = 2112aA
[Exercise 24.2]
, with A= a 112
Hence,
P=
1.381 X 10- 23 1 K - l X 298.15 K

2 112 X (0.36 X 10- 18 m 2) 312
1.4xl07 Pa
The kinetic theory of gases

wh ich corresponds to about 130 atm.
kT
24.4 ..1.=-21
12
ap
[12b]
1.381 X 10 - 23 J K - I X 217 K
2 112 X 0.43 X 10-IR m2X 0.05 X 1.013 X 105 Pa
=970nm
= 2ll2a(8k~ 112.!!.._
nm)
kT [?b]
=(~)112 0
nmkT
(n
X
39.95
0.36 X
1.6605 X
10- k:~ 1.381

27
112
X
10 23 J
298
K)
10-IRm2 Xp
= 4.92 X 104 s- 1 X (p/Pa)
= 4.92 X 104 S- l X 1.0133 X 105 X (p/atm)

= 4.98 x 109 s- 1x (platm)
Therefore (a) z = 5 x 10 111 s- 1 when p = 10 atm, (b) z = 5 x 109 s- 1 when p =
1 atm , and (c) Z = 5 X 103 S- 1 when p = 10- 6 atm.
24.6
zp
ZAA
= kT [Example 24.4, based on eqn 10]

2
(p/atm) X 1.0133 X 10 5 Pa
2kT 2 X 1.381 X 10- 23 J K -I X 298 K = 1. 231
25 1
l0 m - X (p/atm)
and therefore
ZAA
= 1.231 x 102' m - 3 x 4.98 x 109s- 1x (p/atm) 2

=6.13x l0 34 (p/atm) 2 m- 3 s- 1
Therefore, in 1 L, the collision frequency is

3
31
2 1
ZAA X w-) m = 6.13 X 10 (p/atm) s(a) At 10 atm, there are 6.1 x 10 33 collisions per second .
(b) At 1 atm, there are 6 x 1031 collisions per second.
(c) At 1,uatm, there are 6x 10 19 collisions per second.
433
434
Note that Z cx:. p 2 .
24.7
z=
(.n~~T)
112
ap
[9 , and Exercise 24.5]
4 X 0.43 X 10 - 18 m 2 X 0.05 X 1.013 X 105 Pa

(.n X 28.02 X 1.6605 X 10 27 kg X 1.381 X 10 23 J K 1X 217 K) 112
=4 x l08 s- 1
24.8
Z AA
('!:'\
ac V} 2 [lOa]
= 21 ,2
a(~mT)
I/2 ('!:\v
,.
V} 2
=a(~:r (;;r
[N=nNA, p V =nRT]
2
4
) 112
2ap
=a ( .nk3T3m
p 2= (.nmk 3T3) I/2
112
z Aa=aC:})
(N;')
=a(.n~Z3T3r PP'
2
[nJ
For 0 2, a = .n:X (357 pm) 2=4.00 X 10- 19 m 2

For 0 2, N2 collisions, a =.n X (178 + 185 pm) 2= 4.14 X 10- 19 m 2
m(02) = 32.00 U = 5.32 X 10- 26 kg
32.00 X 28.02 U
~(02, N2) = 32.00 + 28.02 = 2.48 X 10-26 kg

p(0 2 ) = 0.210 atm
[Example 1.6]
= 21.3 kPa
p(N 2)=0.781atm
[Example l.6]
=79.1kPa
.nk3T 3 .n x (1.381 x w -23 J K - I x 298.15 K)3= 3.65 x 1061J -3

Therefore ,
1.83 X 1Q6I J -3 ) I/2
Z(02, 0 2) = 4.00 X 10- 19 m2 X ( _ X _26 kg
X (2.13 X 104 Par
5 32 10
=3 .3 x l" 33 m - 3s- 1
Z(02, N2) =4 .14 X 10-
19
3.65 X 1061J - 3) I/2

4
m X ( 2.48 X w -26 kg
X 2.13 X 10 Pa X 7.91
2
104 Pa
= 2.7 x 1034 m - 3 s- 1
X
435
2ap 2
24.9
ZAA
= (nmk 3 T 3) 112
[Exercise 24.8)
m =0.2m(0 2) +0.8m(N 2) =29 u = 4.8 x 10- 26 kg

a=4.0x 10- 19 m2 [Exercise 24.8)
Z
- 4 0 X 10- 19 m2 X
AA-
61 3
5
1.83 X 10 r ) 112 (1.2 X 1.013 X 10 Pa) 2
X
26
( 4.8 X 10 kg
760
=2.0x 1029 m- 3 s- 1
Therefore, in 1. 0 cm 3 , there are 2. 0 x 1023 collisions per second .
24.10 The average kinetic energy of one molecule is j:mc 2 , so the molar
internal energy is ~mcWA=1.m(3kT!m)NA=tRT [or by equipartition). At
300K,
Um=t X 8.3141 K - l mol- 1X 300 K=3.7 kJ mol- 1
independent of the pressure and the identity of the molecules.

24.11
kT
A.=-21/2
ap
[12b)
1.381 X 10- 23 1 K - l X 298.15 K

2 112 X 0.43 X 10- lHm2X p
6.8 X 10- 3 m
6.7 X 10-H m
(p/Pa)
p!atm
(a) When p = 10 atm, A.= 6.7 X 10- 9 m, or 6.7 nm.

(b) When p= 1 atm, A. = 67 nm.
(c) When p = 10- 6 atm, A.= 6.7 em.
:Tr
24.12 f(u) =4n(
u2
e-mu~l2kT
m
28.0 X 1.6605 X 10- 27 kg
2kT = 2 X 1.381 X 10- 23 1 K - l X 500 K
(6)
3.37 X
10-~
m - 2 S2
Therefore, at the center of the range,

3 37 X 10 -~ m- 2s2)3t2
f(295ms - 1)=4nx
n
x(295ms- 1)2
(
436
Therefore, the fraction of molecules in the specified range is
fX !:w = 9.06 X 10- 4 m- 1 S X 10m s- 1 = 9.06 X 10- 3

corresponding to 0.91 per cent.
p
Zw= (2nmkT) 112
24.13
(13b]
90Pa
(2n X 39.95 X 1.6605 X 10
27
23
kg X 1.381 X 10
= 1.7 x 10 24 m- 2 s- 1
Therefore, the number of collisions is
N = 1.7 X 1024 m - 2 s- 1 X (2.5 X 3.0 X 10- 6 m 2) X 15 s
= 1.9 X 1020
zAs=aC:~~ (N~')
1 12
24.14
2.00 X 103 Pa X 5.00 X 10- 3 m3
pV
nR
T =-- = ~~~~~--~~~~~~
1
3
1
4.50 x 10
mol x 8.314 J K
mol
=267K
d12 = t (d1 + d2)

We obtain d from each
a 12 = n
n(:)
112
+~(~)
[Table 24.2], writing

112
a=nd
=~{a 1 +a2+2V(a a2)}

1
= t{0.27 + 0.43 + 2 x (0.27 x 0.43) 112} nm 2

= 0.35 nm 2
~=
2.02 X 28.0 U
2.02x 28 .0
1.88 u =3.13 x 10- 27 kg
Therefore ,
Z = 0.35 X 10- IS m2 X
3
8 x 1.381 x 10 - 23 1
(
K-I x 267 K)
n x 3.13 x 10
27
112
kg
1.50 X 10- mol X 3.00 X 10- mol X (6.022 X 1023 mol - lr
X --------------~------~~------------~
3
3 2
)
(5.00 X 10- m
X 500 K) 112

Therefore, the number of collisions in 1.0 ns is
N= 4.0 X 1031 m- 3 s- 1 X 5.00 X 10- 3 m3 X 1.0 X 10- 3 s
= 2.0 X 10 32
24.15
kT
J..= 21120P (12b]
But at constant volume, the pressure changes as the temperature is varied,

and p = nRTIV; therefore
kTV
V
n2112aRT n2 112 aNA
).. = --:-;;:--
and ).. is independent of temperature.

24.16
L\m = ZwA 0 m L\t

=
[Example 24 .7]
pA 0 m L\t
( m )112
(2nmkT) 112 = pAo L\t 2nkT
M )112
= pAo L\t (
2nRT
From the data, with A 0 = nrZ,
L\m = 0.835 PaX TC X (1.25 X 10- 3 m) 2 X 7.20 X 103 S
) 112
260 X 10- 3kg mol- 1
1
1
(
x 2nx8.314JK- mol- X400K
=
1.04 x 10- 4 kg, or 104 mg
24.17 1, =
dT
-1(-
dz
(16]
-0.163 mJ cm- 2 s- 1
- - - - , -1- - - x (-2.5 Km- 1)
Kcm-
24.18
[Table 24.4]
0.41 mJ em - 2 s _, x cm/m
0.41 X 10- 2 mJ em - 2 S -I= 4.1 j.d em - 2 S -I
K= tMCv[A]
[20b]
437
438
8RT)It2
kT
V
c= ( nM
and A.= 21 '2ap = 21'2anNA
Hence,
A At = (8RT)112 _1_ = (4RT)It2 _1_
nM
2 112 aNA
nM
aNA
( ]
and so
K=-1- (4RT) li2Cv= _ 1_ (4RT) 1/2 X M
3aNA nM
3aNA nM
[Cv= t R]
=!:__ (4RT) 112

2a nM
1.381 X w- 23 J K -I X (4X 8.3141 K -I mol-l X273 K)l /2

2x0.0465Js - 1K -lm- 1
nx20.2x10- 3 kgmol- 1
= 5.6 X 10- 20 m\ 0.056 nm 2

The experimental value is 0.24 nm 2.
24.19
1J = tmA.cNA(A]
__ m (4RT) 112
a nM
3
Hence a=
(21]
[Exercise 24.18]
m (4RT)It2
nM
317
= 20.2x1.6605xl0- 27 kg x(4x8.314 JK - 1mol- 1x273K)It2

3x2.98x10 5 kgm 1s 1
nx20.2x10 3 kgmol 1
= 1.42 X 10- 19 m2, Or 0.142 nm 2

which rearranges to
p~ = p~ + ( 16117Po) dV
nr4
- p-2 +
-
dt
16 X 8.50 m X 1.76 X 10 - 5 kg m - 1s - 1X 1.00 X 10 5 Pa 9.5 X 10 2 m 3

X
4
Jl X (5.0 X 10- 3 m)
3600 S
= p~+ 3.22 X 10 10 Pa 2
= (1.00 X 10 5f Pa 2 + 3.22 X 10 10 Pa 2 = 4.22 X 10w Pa 2
Hence, p 1 = 205 kPa , (2.05 bar).
24.21
17 = tmA.cNA[A]
[21 ]
= m (4RT) It2
3a nM
= 29 X 1.6605 X 10- 27 kg X (4 X 8.314 J K - I mol- l X T) 1/2
3
1
3 X 0.40 X 10- 18 m 2
Jl X 29 X 10- kg mol= 7.7 X 10 - 7 kg m - Is - I X (TIK) 112
(a) At T = 273K, 1'J=l.3x10- 5 kgm- 1s- 1, or 130,uP
(b) At T = 298K, 17 = BO,uP
(c) At T = 1000K, 1'J= 240,uP
24.22 x = t A.cCv [A ]
[20b]
k (4RT) It2
= 2a nM
[Exercise 24.18]
1.381x10- 23 JK - 1
( 4X8.314JK - 1 mol- 1X300K )1/2
2
1
8
2
= 2 X (al nm ) X 10- m X Jl X (Mig mol - 1) X 10- 3 kg mol - 1
1.23x 10 - 2 1 K -lm- 1 s- 1
(alnm~ x (Mig mol - 1) 112
(a) For Ar,
1( =
1.23 X 10- 2 J K - I m- 1s- 1

5.4 mJ K - I m- 1 s- 1
0.36 X (39.95) 112
(b) For He,
439
440
7{=
1.23 X 10- 2J K - t m-t -t

0.21 x (4.00)tt2 s
29 mJ K - t m- t s-t
The rate of flow of energy as heat is

dT
KA - = 'K X 100 X 10- 4 m2 X 150 K m-l

dz
= 1.50 K m x
1<:
= 8.1 mJ s- 1 for Ar, 44 mJ s- 1 for He

dV 1
24.23 -d ex:- [2], which implies that
t
'Y/
ry(C0 2) r(C0 2) 55 S
_
0 663
ry(Ar) = r(Ar) = 83 s =
Therefore , ry(C0 2) =0.663 x ry(Ar) = 13B,uP
For the molecular diameter of C0 2 we use
m (4R~t t2
a= 'Y/ :reM}
3
[Exercise 24 .19)
K)
= 44.01 X 1.6605 X 10- 27 kg X (4 X 8.314 J - t mol- 1 X 298

3 x 1.38 x 10 - 5 kg m -ts -t
:rc x 44.01 x 10 - 3 kg mol- 1
112
= 4.7 X 10- 19 m 2
=:rcd 2 ; therefore d= ( ;
24.24
D = j-A.c
[19)
4.7 X 10- 19 m2
)l/2
= 390 pm
2__ (~T3) 112

3pa
:rem
3p X 0.36 X 10 -
i Bm
{(1.381 X 10- 23 J K - 1) 3 X (298 K) 3} 112

2X
:rc X 39.95 X 1.6605 X 10 - 27kg
1.07m2s- 1
l.06x10 - 5 m2s- 1
(p!Pa)
(p/atm)
441
Therefore , (a) at 10- 6 atm, D = ll m2 s- 1, (b) at 1 atm , D=1.1 x 10 - 5 m 2 s- 1,

and (c) at lOOatm, D=l.1 x 10- 7 m2 s- 1
-
Problems
24.1 The time for a slot to coincide with the location of a neighboring slot is
C~o)
v. If an atom passes through, it must have a speed
l.Ocm
C~o)
/v
= 180v em= 180(v/Hz) em s- 1
Hence , the distributions of the x-component of velocity are

v!Hz
20
40
80
100
200
uxf(cm s- 1)
/(40 K)
/(100 K)
3600
0.846
0.592
7200
0.513
0.485
14 400
0.069
0.217
18 000
0.015
0.119
36000
0.002
0.057
Theoretically,
f(u x) =
(~T) 112 e - mu;mT
Therefore , as J oc f , / rx
(T1)
112
(5]
e-mu;mT
Since
mu; 83.8 x 1.6605 x 10- 27 kg x {1.80(v/Hz) m s- 'f

2kT
7 x 1.381 x l0- 23 JK - 1 x T
1.63 X 10- 2(v/Hz) 2
TIK
we can write
442
fr:x

_ 1
( TIK
)"2 e-1.63 xi0-2(v/Hz)2/(TiK)
and draw up the following table, obtaining the constant of proportionality by

fitting I to the value at T= 40 K, v =80Hz:
v!Hz
20
40
80
100
120
/(40 K)
/(100 K)
0.80
0.56
0.49
0.46
(0.069)
0.209
0.016
0.116
0.003
0.057
in fair agreement with the experimental data.
24.2
(N)
N
(X) = ~
;; Xi [A1, Pi=NJNJ
(a) (u,) =
1
{40x50+62x55+ +2x70+38x(-50)
328
+59 x(-55)+ +2x(-70)}mph

= 1.8 mph East
(b) (luxl)=
328
{40x50+62x55+ +2x70+38x50
+59 X 55+ + 2 X 70} mph

=56 mph
(c) (u;) =
1
{40x502 +62x55 2 + +2x70 2} (mph) 2
328
= 3184(mph) 2
V(u;) = 56mph
[that V(u;) =(l uxl) in this case is coincidental.]
1
(a) (h)=-{5'5"+2x(5'6")+ +6'2"}=5'9! "
53
-(b) W>=
1
{(5'5") 2+2x(5 '6") 2+ +(6'2") 2}=33.54ft 2
53
vw> = s.79 ft = 5'9! "

24 .4
K'
I(; <X
(T')I/2 x -C~
T 112 C v, so-=
-T
K
Cv
At300K , Cv=iR +R= t R

At 10 K, Cv = M
[Rotation not excited]
Therefore,
K'
K
= (300) 1/2 X ~=9.1

. 10
3 dE
24.5 Rate of energy transfer:
dT
dt = KA dz
Therefore, with K=0.241 mJ cm- 2 s- 1/(K cm - 1)

dE 0.241 mJ cm- 2 s- 1
35 K
- =
x l.Ox10 4 cm 2 x - 1
dt
K cm 5.0 em
[Table 24.4]
= 17 x 10 3 mJs - 1=17Js - 1, or 17W

Therefore, a 28 W heater is required.
24.6 The pressure change follows the equation
p=p0 e- 11 ', r=
Znm)I/2V
kT
An
[Example 24.6]
Therefore, the time required for the pressure to fall from p 0 top is
Po
t=rlnp
Consequently for two different gases at the same initial and final pressures
~=~=(:J/2
443
444
and hence
M'=
x28.02ginol(f()2M= (52)2
42
=43 g mol- 1
24.7
p
Zw=( 2nmkT) 112
(13b]
(2n X 39.95 X
(50/760) X 1.013 X lOs Pa

1.6605 X 10- 27 kg X 1.381 X 10- 23 J K -I X 1273 K) 112
=7.78 x 1025 s- 1 m2
Therefore, the collision frequency is
AZw=2n X 5.0 X 10- 2 m X 1.0 X 10- 4 m X 7.78 X 1025 s- 1 m- 2
=2.4xl021 s- 1
24.8
t = rln
p, r = (2nm)
kT
p0
.
(2nM) 112 V
Smce r = - RT
I/ 2
Ao
[Example 24.6]
1
. A0
( 2n X 32.0 X 10- 3 kg mol - )

8.314 J K 1 mol 1 x 298 K
1/2
3.0 m3
x ----,----,--..,...-.,--.,.-,
n x (1.0 x 10 4 m) 2
=8.6 x lOs s
we find that
0.80
7
t= 8.6 X lOs X in 0. 0 = 1.1 X lOsS (30 h)
dN
-Ap
24.9 dt= -ZwA = (2nmkT)I tz
where pis the (constant) vapor pressure of the solid. The change in the
number of molecules inside the cell in an interval !:l.t is therefore !).N =
-ZwA /).t, and so the mass loss is
m )It2
!:l.t
( 2nkT
/).m = !).Nm = - Ap - -
)1 12
= -Ap ( 2nRT
/).t
445
Therefore, the vapor pressure. of the substance in the cell is
l:!,.m (2nR!:\ 112

AM
M)
= -
For the vapor pressure of germanium,

=
X (2n X 8.314 J - I mol-l X 1273

4.3 X 10- 8 kg
n X (5.0 X 10- 4 m) 2 X 7200 S
72.5 X 10- 3 kg mol- 1
K)
1/2
=7.3 X 10- 3 Pa, or 7.3 mPa
p
24.10
Zw = ( 2nmkT) 112
(p/atm) x 1.0133 x 105 Pa
(2n X 32.0 X 1.6605 X 10- 27 kg X 1.381 X 10- 23 J K -I X 300 K) 112
= 2.72 x 1027 m- 2 s- 1 x (p/atm)
= 2.72 x 10 23 em - 2 s- 1 X (p/atm)
Hence, (a) at l.Oatm, Zw=2.7x10 23 cm- 2 s- 1 , (b) at l.Ox10- 6 atm, Zw=

2.7 x 10 16 cm- 2 s- 1, and (c) at 1.0 X 10 10 atm, Zw = 2.7 x 10 13 em - 2 s- 1.
The nearest-neighbor distance in titanium is 291 pm, so the number of atoms
per cm 2 is approximately 1.2 X 10 15 (the precise value depends on the details of
the packing, which is hcp, and the identity of the surface) . The number of
collisions per exposed atom is therefore Zw/(1.2 x 10 15 em - 2):
(a) Whenp == l.Oatm, Zatom=2.3X108 s- I, (b) whenp = l.O,uatm, Zatom =
230 s- 1, and (c) when p = 10- 10 atm, z.,om=0.02 s- 1 .
24.11
dN
.
p
dt=k,[Bk]-Zw A With Zw= (2nmkT)It2
nRT
[Bk]=[Bk] 0 e-k,r andp=v
Therefore, the pressure of helium inside the container obeys
dp kTdN kk,T
pAkTIV
dt =Vdt =V[Bk]oe-k,r_ (2nmkT) 112
A ( kT
If we write a = kk,T[Bk ]0/ V, b = V nm
)lt2 , the rate equation becomes
446
dp
-= ae-k"-bp p = O at t=O
dt
'
The solution is therefore
Since [Bk] = t[Bk] 0 when t=4.4h, it follows from the radioactive decay law
([Bk] = (Bk] 0 e-k") that
In 2
k, = 4.4 X 3600 S = 4.4 X 10-5 S - 1
We also know that
[Bk] 0 =
a=
1.0 X 10- 3g
18
g mol_ 1x 6.022 x 1023 mol - 1= 2.5 X 10
244
1.381 X 10- 23 J K -l X 4.4 X 10- 5 s- 1X 298 K X 2.5 X 1Ql 8
1.0 x 10 6 m3
kk,T(Bk] 0
= 0.45Pas- 1
b=
:rr X (2.0 X 10- 6 m) 2 ( 1.381 X 10 - 23J

1.0 X 10- 6 m 3
K X 298 K) 1/2
-l
2:rr X 4.0 X 1.6605 X 10- 27 kg
= 3.9X 10- 3s - 1
Hence ,
= 120 PaX {e-4.4x 10 -5(r/s) - e - 3.9x 10 - '(r/s)}

(a) t = 1 h, p = 120 PaX {e- 0 16- e- 14} ='100 Pa
(b) t = 10 h, p = 120 Pax {e- 16 - e - 140} = 24 Pa
24.12 The time required is that for the H 20 molecules to effuse from the bulb
through the circular hole representing the cold tube. We established in
Problem 24.8 and Exercise 24.6 that
Po
t = rlnp-,r=
(2:rrm) 112 V
kT
Ao
447
Therefore,
~)
2 3
50
1 Torr
2n X 18.02 X 1.6605 X 10- 27 kg) 1/2 (
X ( - X 10- m)
t=
x
xln -----2
3
( 1.381 X 10- 23 J K -I X 300 K
:n X (3.0 X 10- m)
10 ,uTorr
= 0.12 sIn 1.0 X 10 5 = 1.4 s
24.13 The atomic current is the number of atoms emerging from the slit per
second, which is ZwA with A= 1 x 10- 7 m 2. We use
p
Zw = (2:nmkT)I t2
(p/kPa) x 103 Pa
1
(2:n X (M/g mol- ) X 1.6605 X 10- 27 kg X 1.381 X 10 23 J K 1X 380 K) 112
-1 35 1026 -z -1
p/kPa
- . x
m s x (Mig mol-1)1'2
(a) Cadmium:
= 1.7 x 10 14 s- 1
(b) Mercury:
152
ZwA = 1.35 X 1026 m -z s- 1X 1 X 10- 7 m 2 X ( 00. )It2

2
24.14
1.4 x 10zo s-1

112 (~2
ZAA=a ( 4kT)
_
ZAs- a
:nm
(8kT)
:n,u
112(!!f__)
k2T'
[10]
a(H 2) = 0.27 nm 2, a(I 2) = 1.2 nm 2

4 x 8.314 J K -I mol - 1x 400 K) 112
Z(Hz, Hz)= 0.27 X 10-IR m2 X ( :n X 2.02 X 10-3 kg mol - l
5
0.5 X 1.0133 X 10 Pa
)2
X ( 1.381x10- 23 JK- 1X400K
=3.3x 1034 m - 3s - 1
448
Similarly , with M (12) = 254 g mol- 1,

Z(1 2, 12) = 1.3 X 1034 m- 3s- 1
For the H 2, 12 collisions, we use
2.02 X 254 u
fi = 2.02+254 = 2 .00u
a(H 2, 12) =t{a(H2) + a(1 2) + 2(aa') 112 }
[Example 24.14]
= H0.27 + 1.2+ 2 x V(0.27 X 1.2)} nm 2 = 0.65 nm 2

Hence,
Z(H2, 12) = 0.65 nm2X (
8 x 8.314 J K - l mol- 1 x 400 K) 112

nx 2.00 X 10-3 kg mol - l
0.5 X 1.0133 X 105 Pa ) 2

( 1.381xl0 - 23 JK - 1x400K
24.15 The work required to go from a distance R from the center of a planet
of mass m' to infinity is
w=
"' Gmm'
Gmm'
--dR= - R2
R
J
R
This can be expressed in terms of the gravitational acceleration g by

considering the difference in work required to go from R and R + h:
Gmm ' Gmm' _ Gmm'{
1 }
1 - 1+h!R
~w = -R-- R+h - -R=
G~m' { 1 -
(1 - i + .. ) } =
Therefore, for small displacements,

~w=
Gmm'h
R2
We write this
~w = mgh
and hence identity g as Gm ' IR 2
G~7'h + ...
449
Next, the energy available after the initial boost is E = 1mu 2 ; and so the
minimum escape velocity is
2Gm')I'2
u= ( ~
=(2gR) 112
(a) u = (2 x 9.81 m s- 2 x 6.37 x 106 mY ' 2 = 11.2 km s- 1
m(Mars) R(Earth) 2
(b) g(Mars) = m(Earth) x R(Marsr x g(Earth)
= 0.108 x
6.37)2
2
2
( 3 _38 x 9.81 m s- = 3.73 m s-
Hence,
Since
8k~1 /2
c= nm}
nmc 2 nMc 2
T = Bk=BR
and we can draw up the following table:
He
Earth
Mars
11.9
2.4
23.6
4.8
189
39
[c= 11.2 km s- 1]
[c= 5.0 km s- 1]
24.16 The probability of a molecule possessing an energy E is proportional to

e-Ei kT
[Boltzmann, Section 19.1]. Consider a one dimensional system; then
E=tmu.;. The probability of the molecule having a velocity in the range ux to
ux + dv, is therefore
f( Ux) dux= K e -nw~/ 2 kT dux

The constant K is found in the same way as in the text (by normalization to
1), and we conclude that
j(u ) =
x
m )112 e-mv;l2k T
__
( 2nkT
450
which is eqn 5.
24.17 Write the mean velocity initially as a, then in the emerging beam
(vJ = K
J:
uJ(ux) du x
where K is a constant which ensures that the distribution in the emergent

beam is also normalized. That is,
K fb
==-m
e-'
dx = tKerf(b)
j[
where erf(z) is the error function
(Table 12.2]:
erf(z)=~Jz e-x dx
2
j[
.2
Therefore , K = erf( b)
The mean velocity of the emerging beam is
u >= K -m- )112Ja u e- mv;t2kT du
( 2nkT
o x
x
<x
= K
_m_ )1'2 ( __
kT)
( 2nkT
m
J" duxd
- (e- m v ~2k T)
du ,
kT )lt2(e-ma212kT - 1)
= - K __
( 2nm
Now use
a= (v,)initial =
c~:)
112
(Obtain this expression most quickly by setting a= oo in the expression for

(vx)fina1, and erf(b) = 1] . It follows that

e - ma2t2kT = e -
1hr
and erf(b) = erf (
.n~' 2 )
Therefore,
1
(vx)=CkT)1121 1 - e.nm
erf ( .n~
"']
12 )
From tables of the error function [expanded versions of Table 12.2],

erf(ll.n 112 ) = erf(0.56) = 0.57 and e - 1'" = 0.73. Therefore ,
(vx) = 0.47(vx)initia1
24.18
f(u)=4.n(2:Trzu 2e - '""2'2kT [6]
The proportion of molecules with a speed less than c is
p = fc f( U) du = 4.n (_!!!____) 3/2 fc U2 e -nw2f2kT du

2.nkT
0
0
We write a = m/2kT; then
11
a)3/2 -d f c e-avl du = -4.n (a)312
d 1 f ca 2e-x-d.x
,
( da
.n
da a 112
112
-_-4.n (a)3/
- 2 {--1 (1)3/
- 2 f ca e -xl d.x + (1)
- -d f calll e -xl d.x }
= - 4.n .n
1/2
.n
2 a
Then we use
(dca
12
' )
- f cattl e- -'-, dx= - xe-c 2a
da 0
da
da
11
451
452
and hence
P= erf(ca 112)
2ca 112
- - - e-cZa
1[, 1/2
_ (3kT) 112
_ (3kT) 112 (.!!!:_) 112 _ (~) 112
, and
Now, c- m
, so ca 112 m
kT
2
2
Therefore 61 per cent of the molecules have a speed less than the root mean
square speed and 39 per cent have a speed greater than the root mean square
speed .
For the proportions in terms of the mean speed c, replace c by c =
(8kT/xm) 112 = (8/3x) 112c, so ca 112 =2/x 112 . Then
2ca 112
P= erf(ca 112) - - e -tZa
1[, 1/2
= erf
(x~'2)- ~ e-
41
"
= 0.889-0.356 = 0.533
That is, 53 per cent of the molecules have a speed less than the mean, and
47 per cent have a speed greater than the mean .
24.19 Consider a range of speeds t:w around c* and nc *, then
f(nc *)
f(c *)
(nc *)2e - mn 2c 2f2kT

C *2 e -mc2t2kT
6]
f(3c *) _
_ _
_
Therefore, f(c *) -9 x e 8 -3.02 x 10 3
f(4c *)
--=16
xe- 15 =4....:..;..:;__....::..::..._
9 x 10- 6
f( c *)
24.20 The rate of growth of volume, du/dt, is equal to the product of the
collision frequency Zw, the surface area, A, and the volume added by each
arriving molecule, V m/ N A. Therefore ,
The kinetic th eory of gases
453
dv
dt=sZwA Vm/NA
where s is the sticking probability . For a spherical particle ,
v = j .n:r 3 and A= 4.n:r 2 , so

dv
dr
dr
- = 4.n:r 2 - =A dt
dt
dt
Consequently,
dr
sp Vm
dt = sZwvm/ N A = (2.n:mkT) 1/ 2N A
We know the number density, not the pressure, so we use
nRT nNAkT N
p = - = -- =-kT=.NkT
The molar volume is

M
vm =pTherefore ,
dr _ s.N (MRT_\ 112

dt pNA 2.n: }
Since .N~ 3 x 10 15 cm - 3 = 3 x 1021 m- \ M = 207 g mol- 1, p = 11.5 gem -\ T=
935 K, and s = 1, we obtain
3 x 102 1 m - 3
dr
- ~ -------;::,..----:-------::----::
dt
6.022 x 1023 mol - 1 x 11 .5 x 103 kg m- 3

X
c.07
10 - 3 kg mol-l
~~14
1K
- I
mol - l X 935 K) 112
=7 X 10- 6 m S- 1, or 7 X l0 - 4 cm S- 1
Therefore , in 0.5 ms the growth in radius of the particle cannot exceed about
7 ,urn s- 1 x 0.5 ms = 4 nm.
25. Molecules in motion

Exercises
25.1
= 5.35 x l0 - 2 MX 135.5Scm2 mol- 1

=7.25 S mol dm - 3 cm 2 mol - 1
K= cAm
[1]
=7 .25 X w- 3 em -l, or 7.25 mS em -l
25.2
K =
l
RA
[Section 25.1]
2.75 em
351 Q x (2 .2 cm) 2 = 1. 6 mS em - l
25.3
Am=A~ - 'Xc
1 12
[2]
Therefore, for two concentrations c and c'

A~- Am =
-'J[(c' "2 - Cl/2)
-(109.9-106.1)Scm 2 mol- 1
and 'J[=-c'"2- clt2 {(6.2 x 10 3)1'2-(1.5 x 10 2)1'2}Ml/2
A~ - Am
= 86.9 S cm 2 mol- 1M112

Therefore,
A~=
Am+ 'J[cl/2
= 109.9 S cm 2 mol- 1+ 86.9 S cm 2 mol - 1M- 112 x (6 .2 x 10- 3 M) 112

= 116.7 S cm 2mol - 1
25.4 A.= zuF [8]

= 1 x 6.85 x 10- 8 m 2s- 1V - l x 9.6485 x 104 C mol- 1
= 6.61 x 10- 3 Q- 1m 2 mol - 1 [1 V = 1 A Q , 1 A = 1 Cs - 1]
=6.61 mS m 2 mol - 1 = 66.1 S cm 2 mol- 1
25.5 s = uE
=
[7]
35 .0V
7. 92 X 10- 8 m 2 s- 1 V - I x - - ----::-8.00 X 10- 3 m
Molecules in motion
25.6
u+
(4 = - - -
u+
+u _
[11]
4.01
4.01 +8.09
[Table 25.2]
= 0.331
25.7
A~ = v+A.++v_A._
A~(KCl)
= A.(K+) +A.(cn = 149.9 s cm 2 mol- 1
A~(KN0 3 )
= A.(K+) +A.(NO:J ) = 145.0 S cm 2 mol- 1
A~,(AgN0 3 )
Hence
[3]
= A.(Ag+) +A.(NO:J) = 133.4 S cm 2 mol- 1
A~(AgCl)
= A~(AgN0 3 ) + A~(KCl) - A~(KNO,)

= 133.4 + 149.9-145.0 S cm 2 mol- 1
= 138.3 S cm 2 mol - 1
w-s) {(1 + 1.4 x 0.040_ )
1.91 x
Hence, A~ = ( 2 X 0.0 40
91
10
112
- 1 A~
= 0 . 022A~
= 0.022 X (349.6 + 40.9) S cm 2 mol-' = 8.59 S cm 2 mol- 1

K = cA~ = 0.040
mol dm - 3 x 8.59 S cm 2 mol- 1
= 3.4 X 10- 4 s cm- 1, or 0.34 mS cm- 1

C
0.206cm- 1
R -- -; -- 3.4 X 10- 4 S cm - 1 6.1
25.9
A.
u =-
zF
102 Q
[8]
38 .7 S cm 2 mol - 1
u(Li+) 4.01
- 9.6485 x 104 C mol- 1
10- 4 S c-l cm 2
= 4.01x10- 4 cm 2 s- 1 Y - 1 [1CQ = 1AsQ=1 Ys]
455
456
Molecules in motion
50.1Scm 2 mol- 1 _
x _4 2 _ 1 _ 1
u(Na )-9.6485 x 104 Cmol_ 1 - 5 19 10 em s V
+ _
kT
25.10 a = - 6n71D
6n X
[20 and Example 25 .7]
1.381 X 10- 23 1 K - I X 293 K

1.00 X 10- 3 kg m- 1 S- 1 X 7.1 X 10 - 11 m2 s- 1
= 3.02 X 10- 9 m
25.11
ukT uRT
[16]
ez
zF
D=-=-
7.40 X 10- 8 m2 s- 1 v
- IX
8. 314 J K - I mol - l X 298 K
9.6485 x 104 C mol
kT
25. 12 a = - 6n71D
[20 and Example 25.7]

1.381
10- 23 1 K -
5.4 X 10- 9, or 5.4 nm
IX
293 K
Molecules in motion
which implies th at
(x 2)
(5.0 X 10- 3 m) 2
3
t= 2D=2 x 3.17 x 10 9 m2 s 1= 3 9 x 10 s
25.14
kT
a=--
6n17D
[20 and Example 25.7]

1.381
= 4.2
X JO - IIl
r=2D
10- 23 1 K
- I
298 K
m , or 420 pm
(300 X 10- 12 m) 2
2 X 2.13 X 10 9 m 2 S 1
_.1. 2
25 . 15
[28]
=21 ps
25.16
(x 2) 112 =(2Dt) 112
(a) (x 2) 112 = (2
[26b]
2. 13 X 10 - 9 m 2 S-
(b) (x 2) 112 = (2 X 5.21
lX
1.0 s) 112 = 65 ,urn
10 - 10 m 2s- 1X 1.0 s) 112 = 32 ,um
[Data from Table 25 .4.]
(1.0 X 10- 3 m) 2
(a) Iodme : t = 2 X 2.13
Sucrose: t =
(b) Since
10-9 m2s- 1 240 s, about 4 min.
(1.0 X 10- 3 m) 2
m s = 960 s, about 16 min.
x . x
2 5 21 10 10 2 1
(CC
(x 2), for a 10 fold increase in distance,
Iodine: t = 2.4 x 104 s, about 7 h .

Sucrose: t = 9.6 x 104 s, abou t 27 h.
457
Molecules in motion
458
Problems
Preliminary calculation :
'K
=R and
'K
= cA. m> hence C = KR = cA. mR
Therefore, from the data

C = 0.0200 mol dm - 3x 138.3 S cm 2 mol - 1X 74.58 Q
= 206.3 cm 2dm - 3= 0.2063 cm - 1
25 1
K(CH3COOH)
R(KCI)
33 .21 Q
K(KCI)
R(CH 3COOH)
300.0 Q
Therefore,
33.21
1C(CH3COOH) = 300.0 X 1.1639 X 10 - 2sem -I = 1.288 X 10 - 3sem - I
But this value includes a contribution of 7.6 X 10- 4 sem - I from the water;
hence the conductivity of the acetic acid itself is (1.288 - 0.76) x 10- 3S em - 1=
5.3 X 10- 4 s cm - 1. Therefore ,
5.3 X 10- 4 S cm - 1
Am = 0.100moldm 3 5.3Scm2mol - l
Therefore, we draw up the following table:

elM
0.0005
0.001
0.005
0.010
0.020
0.050
(c/M)l/2
R/Q
Am/(S cm 2 mol - 1)
0.0224
3314
124.5
0.032
1668
123.7
0.071
342.1
120.6
0.100
174.1
11 8.5
0.141
89.08
115 .8
0.224
37.14
111 .1
The value of Am are plotted against c 112 in Fig. 25.1. The limiting value is
A~ = 126 cm 2 mol - 1. The slope is -76.5; hence ':1{ =76.5 S cm 2 mol - 1M- 112
(a) Am = (50.1 + 76.8) S cm 2 mol - 1-76.5 S cm 2 mol - 1X (0.010) 112
= 119.2 S cm 2 mol - 1
(b) 'K =cAm= 0.010 mol dm - 3X 119.2 S cm 2 mol - 1
= 1.192 S cm 2dm - 3 = 1.192 mS cm - 1
C
0.2063 cm - 1
(c) R = ;=1.192 x 10-3 Scm - 1 173.1 Q
Molecules in motion
126
1\.
124
"'E 122
Fig25.1
'
~
~
'
E12
118
11 6
1(
'
'\
003
006
009
.V(c/M)
1"'-
012
~.
075
1(
25.3 c = - = i\~
i\m
[c small, conductivity of water allowed for in the data.]
1.887 X 10- 6 S cm - 1
c= 138 .3 S cm 2 mol_ 1 [Exercise 25.7]
= 1.36 X 10-Kmol em - 3 = 1.36 X 10- 5 M

K ,P
= (1.36 X 10- 5) 2 = 1.86 X 10- 10
We can correct for activities using Y= w - AVc= 0.996; hence

1.86 X 10- 10 = 1.85 X 10- IO
K,P=y~ X
25.4
i\~(NaCH,C0 2 )
= A.(Na+) + A.(CH 3C02) = 91.0 S cm 2 mol - 1
i\~(HCl). =A.(H + )
A~(NaCI)
i\~(CH,COOH)
+A.(Cl-) =425.0 S cm 2 mol- 1
=A.(Na +) +A.(cn = 128.1 S cm 2 mol- 1

=A.(H+) +A.(CH 3C02)
= i\~(HCl) + i\~(NaCH 3 C0.1 )- i\~(NaCl)
= (425 .0 + 91.0 -128.1) S cm 2 mol - 1
= 387.9 S cm 2 mol - 1
Am
'K
1\~
c~
cRi\~
a=-=-=--
0.2063 cm - 1
-0.020 X 10- 3 mol cm- 3 X 888 Q X 387.9 S cm 2 mol - 1
=0.030
459
460
Molecules in motion
with A~ = A.(H + )+A.(CH 3 C02) = 390 . 5Scm 2 mol - 1 We draw up the following
table using Am=Kic = CicR and C = 0.2063cm - 1:
Am/ (S cm 2 mol- 1)
105cAm/(S cm- 1)
100/ (Am/S cm 2 mol- 1)
0.49
0.99
1.98
15.81
63 .23
252.9
68 .5
3.36
1.46
49.5
4.90
2.02
35.6
7.05
2.81
13.0
20.6
7.69
6.56
41.5
15.2
3.22
81.4
31.1
We now plot 100/ Am against 105 cAm (Fig. 25.2). A least-squares fit of the data
40
Fig 25.2
.::-1
'E
ll
$
(
a
30
/
/v
20
10
,.,
./fti'
100
gives an intercept at 0.352 and a slope of 0.01559. Since we are actually

plotting
100 S cm 2 mol- 1 _ 100 S cm2 mol - 1 102 S cm 2 mol - 1 (105cAm) S cm - 1
Am
Nm
+ K a (A om) 2
S em - l x 105
the slope of the plot is
102 S 2 em mol - l
Slope = 105 Ka(A~r
10- 3 S2 em mol-l
Ka (A~f
= 0.352
Molecules in motion
Hence,
10- 3S2 em mol - l
K. = 0.352 x (390.5 S cm 2 mol - 1?
= 1.86 X 10-s mol em - 3= 1.86 X 10 -s M

Therefore, pK. = -lg 1.86 x 10- 5 =4.73
25.6 s = uE
lOY
with E = - =10Vcm- 1
1. 00 em
[7]
10- 4 cm 2 S- 1 X 10 V cm- 1 = 4.0 X 10- 3em s- 1

s(Na+) = 5.19 X 10- 4 cm 2 S- 1 X 10 V cm - 1 = 5.2 X 10- 3em s- 1
s(Li+) = 4.01
s(K+) = 7.62 X 10- 4 cm 2 s- 1 X 10 V cm - 1 = 7.6 X 10- 3em s- 1

d
t=- with d=l.Ocm:
s
t(Li +) =
l.Ocm
4.0 x 10 3ems
-250s
---
t(Na+) = 190 s, t(K +) = 130 s likewise.

For the distance moved during a half-cycle , write
d=
lnv s dt = fl nv uE dt = u fl nv sin(2.n:vt) dt
0
uE
uxlOVcm -
.n:v
.n:X 10
. X 103S
_1 =3.18x10- 3 uVscm- 1
That is, diem= 3.18 X 10- 3 X (u/cm 2 v
- I
s- 1)
Hence,
d(Li +) = 3.18 X 10- 3 X 4.0 X 10- 4 em= 1.3 X 10- 6 em
d(Na+) = 1.7 X 10- 6 em , d(K +) = 2.4 X 10- 6 em
These correspond to about 43, 55, and 81 solvent molecule diameters
respectively.
25.7
t(H+) =
u(H +)
u(H +)+u(cn
3.623
3.623 + 0.791
[llb]
82
461
462
Molecules in motion
When NaCI is added ,

c(H +)u(H +)
t(H +) - ----,----,--,----,---,---:-:--:-:---::-::----:----:-=:-:-----:-::~
- c(H +)u(H+ + c(Na +)u(Na +) + c(CI )u(CI )
( 1OJ
1.0 X 10- 3 X 3.623

1.0 X 10
X 3.623 + 1.0 X 0.519 + 1.001 X 0.791
=0.0028
25.8 t =
zcVF
zcAFx
!!it (Section 25 .2] = J""M
1
21 mol m- 3 x n x (2.073 x 10- 3 m) 2 x 9.6485 x 104 C mol - 1 x

18.2 X 10- 3 A
XM
x/mm)
1.50 ( M/s
Then we draw up the following table:

M ls
200
400
600
800
1000
64
0.48
0.52
128
0.48
0.52
192
0.48
0.52
254
0.48
0.52
318
0.48
0.52
Hence, we conclude that
t+ =
0.48 and
t_
= 0.52.
For the mobility of K + we use

t+ =
. 1. +
N
(12]
to obtain
t + i\~
0.48 x 149.9 S cm 2 mol- 1

u+ = F = 9.6485 X 104 Cmol - 1
=7.5x 10- 4 cm 2 s- l y-l
..1.+ = t+ i\~
(12]
= 0.48 x 149.9Scm2 mol - 1
= 72 S cm 2 mol- 1
Molecules in motion
zcA F
t =-- x +
I
!:it
25.9
463
[Problem 25.8]
Since the density of the solution is about 0.682 g cm- 3 , the concentration c is
related to the molality m by
1
elM= _ x m/(mol kg- 1) = 14.7m/ (mol kg- 1)
0 682
(2.073 X 10- 3 m) 2= 1.350 X 10- 5 m2

czAF 1.350 X 10- 5 m 2 X 9.6485 X 104 C mol - 1
I !:it =
5.000 X 10- 3 A X 2500 s
Xc
A = nr 2 = n
=0.1042 m 2 mol - 1 x c
=0.1042/mm x elM =0.153/mm x m/(mol kg- 1)
and so
t+
= 0.153 x (x/mm) x m/(mol kg - 1)
(a)
t+
= 0.153 X 286.9 X 0.013 65 = 0.60
(b)
t+
= 0.153 X 92.03 X 0.042 55= 0.60
Therefore, t(H+) = 0.60 and the mobility is not as abnormal as in water where
t(H +) = 0.82.
C
25.10
0.2063 cm - 1
R=-=
o-s s em _ =3.75MQ
x 55
. x1
A~ =A.(H +) +A.(OH - ) =
349.8 + 197.6 S cm 2mol - 1 = 547.4 S cm 2 mol - 1
Am
x
5.5 x 10-x Scm- 1
and so a = - = - = - - - - - - =
- - - - --=---:A~ cA~ 55 .5 mol dm - 3 x 547.4 S cm 2 mol - 1
= 1.8 x 10- 9
We then write
Kw = a(H +)a(OH- ) = c(H+)c(OH - )/M 2
= a 2c(H20nM 2 = a 2 X (55 .5?

= (1.8 X 10- 9) 2 X (55.5) 2 = 1.0 X 10 - 14
pKw = -Jg Kw= 14.0
pH= -lg a(H +) = -lg K ~ 2 = - -!Ig Kw=7.0
464
Molecules in motion
'!J' = -
25 .11
RT
-
de
dx
X -
(15)
de (0.05 - O.lO)M
dx =
O.lOm
= -0.50Mm-l
RT= 2.48 X 103 J mol- 1 =2.48 X 103 N m mol - 1
- 2.48 kN m mol - 1
1
O.lOM
x (-0.50Mm - )
(a) '!F =
= 12 kN mol - 1, 2.1 X
(b) '!F =
w--20 N molecule- 1
- 2.48 kN m mol - 1
x (-0.50Mm - 1)
_ M
0 075
= 17 kN mol - l' 2.8 X 10- 20 N molecule- 1

(c) '!F =
- 2.48 kN m mol - 1
x (- 0.50Mm - 1)
_ M
0 05
= 25 kN mol-l ' 4.1

25.12
D
s = kT'!F
w-20 N molecule - 1
[Section 25.4]
1.381 X 10- 23 J K -l X 298.15 K

= 1.26 x 10" m s- 1('!1'/N)
['!F is the force per molecule.]
(a) s = l.26x10"ms - 1 x 2.1 x l0- 20 = 2.7nms- 1

(b)
S=
1.26 X 10" m S- 1 X 2.8 X 10- 20 = 3.5 nm s- 1
(c)
S=
1.26 X 10" m s- 1 X 4.1
10- 20 = 5.2 nm S- 1
We could monitor the concentration by refractive index, optical rotation ,

infrared spectroscopy . The initial flux through a region is the same at every
point because dc/clx is a constant except at the left boundary and at the right ,
open side (Fig. 25 .3a). The initial change is then as shown in Fig. 25.3b. This
initial distortion is then magnified as time goes on , and as dc/clx is no longer
the same everywhere, dcldt changes everywhere (Fig. 25.3c) . After a long
time, the concentration becomes virtually uniform and sinks toward 0.075 M
(Fig. 25.3d).
Molecules in motion
25 .13
uRT
D=-
[16]
zF
ze
and a=-6nryu
[Example 25.7]
8.3141 K - I mol- 1 X 298.15 K X u

D = - - - - - - . . . , . . .4 - - --...,....---9.6485 x 10 C mol - 1
=
so
2.569 X 10- 2 V
D/(cm 2 s- 1) =
X u
2.569 X 10- 2 X u/(cm 2 s- 1 v-I)
1.602 x w- 19 c
a= - - - - - - , 3- --,--..,......1
1
6n X 1.00 X 10- kg m- s-
8.50 X
- IH
c kg -
X u
ms
8.50 X 10-IRy
u
- l
m3 S- l
[1J = lCV, lJ =l kgm 2 s- 2]
and so
a/m = 8.50 X l0- 14/(u/cm 2 s- 1 V
and therefore
a/pm = 8.50 X l0 - 2/(u/cm 2 s- 1 V
- I)
- I)
We can now draw up the following table using data from Table 25 .2:
104 u/(cm 2 s- 1 V - 1)
10 5 D/cm 2
a/pm
4.01
1.03
212
Na+
K+
5.19
1.33
164
7.62
1. 96
112
7.92
2.04
107
465
Molecules in motion
466
The ionic radii themselves (i .e. , their crystallographic radii) are

Li +
Na+
K+
Rb +
59
102
138
149
and it would seem that K + and Rb + have effective hydrodynamic radii that
are smaller than their ionic radii . The effective hydrodynamic and ionic
volumes of Li + and Na + are
4n
--gna
and
4n
3 nr ~
respectively , and so the
volumes occupied by hydrating water molecules are
4n
(a) Li +: ~V=3 X (212 3 -59 3)
10- 36 m3 = 3.9 X 10- 29 m 3
The volume occupied by a single H 20 molecule is approximately (4n/3) X

(150 pm) 3 = 1.4 X 10- 29 m 3 . Therefore, Li + has about three firmly attached H 2 0
molecules whereas Na + has only one (according to this analysis).
25.14 If diffusion is an activated process , we expect
D rx e -E,I RT
Therefore , if the diffusion constant is D at T and D' at T' ,
R In (D'/D)
E = - _ __:__ ___:_
a
(;,-~)
8.314 J K - l mol - 1 x In 2.89)
_
( 2 05
--------~-.!..._ = 9 3 kJ mol - 1
1
1
.
----298 K 273 K
That is , the activation energy for diffusion is 9.3 kJ mol - 1

25.15
c = A(nDt) 112
and we know that n 0 =
[24]
342
10 g
g mol _ 1 x 6.022 x 1023 mol- 1 = 1.76 x 1022
Molecules in motion
A= .nR 2 = 19.6 em\ D = 5.21 x 10- 6 cm 2 s- 1 [Table 25.4]
A(nDt) 112 = 19.6 cm 2 x (n x 5.21 x 10- 6 cm 2 s- 1 x t) 112
=7.93 x 10- 2 cm 3 x (tl s) 112

x2
4Dt
25 cm 2
4x5.2lx10- 6 cm 2 s- 1 xt
1.20 X 106
(tis)
Therefore ,
e -1.20x 10/(1/s)}
= 2.22 x 1023 em - 3 x
{e
(tis) 112
- 1.20 x wot( t/s)}
-369M X
(tis) 112
(a) t=10s,
e - 1.2 x I(}'
c=369MX~=0
(b) t=1yr=3.16x10 7 s,
e -o.o3R
25.16
(x 2) = 2Dt
[26b]
'
kT
D= - 6nary
[Example 25.7]
kT
kTt
Hence, r y =
D-a = 3na (x-')
n
6
1.381 X 10- 23 1 K -I X 298.15 K X t

3n x 2.12 x 10
m x (x 2)
t
= 2.06 X
10- 15 1 m- 1 X (x 2)
467
Molecules in motion
468
and therefore
ti s
30
60
90
120
10s(x2)/cm2
1037]/(kg m- 1 s- 1)
88.2
0.701
113.5
128
1.45
144
1.09
1.72
Hence , the mean value is 1.2 X 10- 3 kgm - 1 s- 1

25.17 The current /i carried by an ion j is proportional to its concentration ci,
mobility ui , and charge number lzJ Therefore,
/i = Aciui lzil
where A is a constant. The total current passing through a solution is
The transport number of the ion j is therefore
t = ~ = Aciuilzd = ciuilzil
'
I
A
L ciui lzd L ciui lzil
If there are two cations in the mixture ,
t'
c'u 'z'
c'u '
-= - - = - i f z'= z"
t" c"u"z" c"u"
25.18 Consider the consequence of the passage of 1 mol of electrons through
the cell
Ag IAgCl lHCl( c1) IHCl( c2) IAgCII Ag
Molecules in motion
469
Right compartment: 1 mol Cl - are formed, butt_ mol migrate out across the
junction, giving a net change of (1- L) mol= t + mol.
Left compartment: 1 mol Cl- is lost (by formation of solid AgCI), but t_ mol
flows in across the junction , giving a net change of ( -1 + t+) mol= - t + mol.
The reaction Gibbs function is therefore
Therefore, since !'!..G= -FE,
For the same cell without transfer, the Nernst equation gives
-RT a 2
E=--lnF
a1
Therefore, E, = t+E
For electrodes reversible with respect to the cations, 1 mol M + is generated
butt+ mol migrates out , giving a net change of (1- t + ) mol= t_ mol. By the
same argument,
25.19
ac a 2c
at= D ax 2
no
e -x2t4DI
[21] with c= A(.nDt)"2 [24]
' then
When c =a- e- bx-tl
t"2
& = _ I (aft 312 ) e-bx 2il +a X_

~2
'
e-bx-11
at
t" 2
c bx 2
=--+-c
2
2t
t2
Molecules in motion
470
ac
-= -
ax
a112 (-2bx)
X
__
'
e - bx-tr
a c = - (2b)
ax2
t (atl / 2)
=_
=D
e -bx 2t r
+ ( tla/2) (2bx)
- t- 2 e -bx2t r
2
2bt c+ (2bx)
2c = _ (-1)c+ (bx \c
t
2Dt
Dt
2
}
ac
at as required .
Initially the material is concentrated at x = 0. Note that c = 0 for x > 0 when

t=O on account of the very strong exponential factor [e-bx 21 '~0 more strongly
than 1/t 1 ' 2 ~ oo ]. When x .= 0, e -x 2140' = 1. We confirm the correct behavior by
noting that (x) = 0 and (x 2) = 0 at t = 0 [26], and so all the material must be at
x=Oatt = O.
25.20
N!
P(x) = t(N+s)!t(N-s)! 2N [A2]
, s=xld
N!
P( 6d)= t(N+6)!t(N-6)!2N
(a) N=4 , P(6d)=Q
[m!=oo form < O]
6!
1 1
(b) N = 6, P(6d) = !0! 26= 2_6 = = 0.016
64
6
12!
12 X 11 X 10
(c) N=12, P(6d) = , ,212 = x x 212 = 0.054
93
3 2
[NB 0!=1]
25.21 Draw up the following table based on eqns A2 and A3:
N
10
20
P(6A.hxact
P( 6A.) Approx.
0
0.004
0.016
0.162
0.313
0.0297
0.0439
0.0417
0.0739
0.0725
Molecules in motion
30
40
60
100
P(6A.)Exact
P( 6,1,) Approx
0.0806
0.0799
0.0807
0.0804
0.0763
0.0763
0.0666
0.0666
471
The points are plotted in Fig. 25.4. The discrepancy is less than 0.1 per cent
010
Fig25.4
E act
p
If-.
~sy
when N > 60.
20
r!nPt
fie
40
- -
60 n 80
100
26. The rates of chemical reactions

Exercises
26.1
1 d[J]
dt
(1],
u=--
SO
d[J]
-dt =V1V
VJ
The reaction has the form

0=3C+D-A-2B
Rate of formation of C = 3v = 3.0 M s- 1
Rate of formation of D = v = 1.0 M s- 1
Rate of consumption of~= v = 1.0 M s- 1
Rate of consumption of B =2v=2.0 M s- 1
26.2
1 d[J]
v=-V1 dt
[1]
For the reaction 2A + B__,.. 2C +3D ,

1
v = tx 1.0 M s- =0.50 M s-
Vc
= + 2; hence
Rate of formation of D = 3v = 1.5 M s- 1

Rate of consumption of A= 2v = 1.0 M s- 1
Rate of consumption of B = v = 0.50 M s- 1
26.3 The rate is expressed in
1
M s- ;
therefore
MS- =(k) X M X M
requires the units of k to be
M-
s -I
(a) Rate of formation of A= v = k[AJ[BJ

(b) Rate of consumption of C = 3v = 3k[AJ[BJ
26.4
d~~J = k[AJ[BJ[CJ
1 d[JJ .
v = - - w1th v1 = vc = 2
V1 dt
The rates of chemical reactions

1 d[C]
Therefore v=2dt=!k[A1[B1[C]
The units of k must satisfy

M S-
= (k1X
M X M X M
= (k 1M 3
which requires k to have the units

26.5
2N 2 0 5 ~ 4N0 2 + 0 2 ,
M-
s- 1
v = k[N 20 51
Therefore, rate of consumption of N20 5 = 2v = 2k[N 20 51

d[Nz0 s1
dt
[Nz0 s1 = [NzOs1o e -Zkt

which implies that
1
[NzOs1o
t = 2k In [N 20 51
and therefore that
Since the partial pressure of N20 5 is proportional to its concentration ,

p(NzOs) = Po(NzOs) e- Zkt
(a) p(N 20
5)
= 500 Torr X e- 2.76 x 111 - 'x 102 = 499 Torr
(b) p(N 20 5) = 500 Torr X e -z. 76 x 111 - 'x 6000 = 424 Torr
26.6 (a) For a second-order reaction, denoting the units of k by [k1:
M
s- 1 = [k1 x
2
M ,
implying that [k1 =
M-
s- 1
For a third-order reaction ,

M
s- 1 = [k1 x
M\
implying that [k1 =
s- 1
(b) For a second-order reaction

atm s- 1 = [k1 x atm 2 , implying that [k1 = atm - 1 s- 1
For a third-order reaction
atm s- 1 = [k1 x atm 3 , implying that [k1 = atm- 2 s- 1
473
474
In 2
k= 28 .1 y =0.0247 y- l
Hence, with [Sr] replaced by its mass ,
m = 1.00 flg x e- 0.0247(tly)
(a) m = 1.00 flg x e- oo247xIB = 0.64 flg
(b) m = 1.00 flg X e-0 0247 x7o = 0.18 flg
26.9
1
[A ]0 ([B] 0 - x)
kt= [B]o- [A]o In ([A]o- x)[B]o [7b]
which rearranges to
[A]o[B ]o{ ek<IB Ju- JAJo)l - 1}
X= [ B]o e<IBJu - IAJo)kl - [ A]o
0.050 X 0.100 MX {e(O.I00-0.050) x0.11 xt/s - 1}
0.100 X e<O.I00- 0.050)x0. 11 X tis - 0.050
0.100 MX (e 5.5 xl0-.1tis_1)
2e5.5x 10-.1,/s _ 1
(a) x=
0.100 MX (e 0055 -1)

2eooss _1
5.1 x 10- J M
which implies that [NaOH] = 0.050 - 0.0051 M= 0.045 M and [CH3COOC2H 5] =

0.100 - 0.0051 M= 0.095 M
(b) x =
0.100 MX (e 33 -1)
e _
=0.049 M
2 33 1

Hence,
(NaOHJ = 0.050-0.049 M= 0.001 M
[CH 3COOC 2 H 5] = 0.100-0.049 M= 0.051 M
26.10
Rate of consumption of A= k[A][B]
= 3.67x10-3 M- I S- IX
0.255 mol 0.605 mol

1.70L X 1.70L
= 1.96Xl0 - 4 MS-I
and hence
Likewise,
d~~J = - 2k(A](B) = - 2 X (1.96 X 10= - 3.92 X 10- 4 M S-
MS- 1)
d(P]
dT = k[AJ[B] = 1.96 X 10- 4 Ms- 1

dn 8
d(B]
dt
dt
- = - - X V = -3.92 X 10- 4 M s- 1 X 1.70 L
= - 6.66 X 10- 4 mol S - I

u0 = k(A](B) = 1.96 X 10- 4 Ms- 1
Hence,
d(A] = - 2k(Af
dt
which solves to
475
476
2
1
1
Hence, 2kt 112 = [A]o - [A]o = [A]o
1
1
and tuz = 2k[A) 0 = 2 X 2.62 X 10- 3 M- 1 S- 1 X 1.70 M
= 112 s
26.12 The rate of consumption of A is
d[A) = -2k[Af
dt
[vA = -2)
which solves to
Therefore,
= 2 X 3.50 X 10- 4 M- 1 S- 1 X 0.011 M- 0.260 M
26.13 [B] 0 =t[A] 0 , hence [A] 0 =0.624M. For the reaction 2A~B, [A]=
[A] 0 - 2[B]. We can therefore draw up the following table
tis
600
1200
1800
2400
[B)/M
[A)/M
0
0.624
0.089
0.446
0.153
0.318
0.200
0.224
0.230
0.164
477
The data are plotted in Fig. 26.1a. We see that the half-life of A from its
initial concentration is approximately 1200 s, and that its half-life from the
~)
(b)
1-4
06
" "'
/
/
........
i'-..,
02
1200
tis
/
~
Fig 26. 1
2400
/
1200
tis
2400
concentration at 1200 s is also 1200 s. This indicates a first-order reaction. We

confirm this conclusion by plotting the data accordingly, using
[A] 0
d[A]
In [A] = kAt If d t = -kA[A]
First, draw up the table :

tis
[A]o
In [A]
600
1200
1800
2400
0.34
0.67
1.02
1.34
and plot the points (Fig. 26.1b ). The points lie as a straight line, which
confirms first-order kinetics . Since the slope of the line is 5.6 X 10- 4 , we
conclude that kA = 5.6 x 10- 4 s- 1 To express the rate law in the form
v = k [A]
we note that
1 d[A]
v = - Zd t = - tx ( -kA[A]) = tkA [A]
and hence k = tkA = 2.8 X 10- 4 S- 1
Ea
26.14 Ink = In A-RT [13a]
Ea
Ink'= lnA - RT'
478

1.38 x w- )
8.314JK - Imoi - I x ln ( 2.80 x 10 3
2
Rln(k'!k)
Hence, E.=
(r- r)
1
1
303 K- 323 K
= 64 .9kJmol - 1
For A , we use
A =k x eE,tRT
= 2 .80 X 10 -3 MS- I X e64.9x I03/8.3 I4 x303
=4.32X 108MS-I
26.15 The first step is rate-determining; hence
u = k[Hz0 2][Br-J
The reaction is first-order in H 20 2 and in Br- , and second-order overall.
26.16 We assume a pre-equilibrium (as that step is fast) , and write
The rate-determining step then gives
26.17 We assume a pre-equilibrium (as the initial step is fast) , and write
K=
[Unstable helix]
[A][B]
, implying that [Unstable helix]=K[A][B]
The rate-determining step then gives
u=
d[Double helix]
dt
= k 1[Unstable helix]
The equilibrium constant is the outcome of the two processes

A+B:;:=
k,
[Unstable helix], K = k-,
kz
k,

Therefore, with u=k[A][B],
k=k 1 k 2 /k~.
26.18 The rate of change if [A] is
d(A] = -k[A]"
dt
Hence,
IAI d(A]
[A]"= -k
IAio
Therefore, kt=
(n~ 1) {[A~"_ 1 - [A;0_
2n - l
= (
Hence,
t 112 cx
f' dt= -kt

1}
-1) 1
~ X [A]o''-1
1/[A](j- 1
26.19 Maximum velocity= kb[E] 0 [following eqn 24]
d[P]
also
kb[S]
dt = k[E] 0 , k = KM + [S]
[24a]
Therefore, since
we know that
kb[E]o = {
=
KM+(S]}
[S]
u
0.035 + 0.110}
X115X10- 3 MS-I
.
0.110
= 1.52 X 10- 3 M S- 1
26.20 From Exercise 26.19, it follows that we require
[S] - I
KM+[S] - 2
479
480
which is satisfied when [S] = KM

1
26.21
k'
k= ka[A]+ k;
a b
[28]
Therefore, with [A] interpreted asp, for two different pressures

1 - -1 = 1 (1- - 1)
k
ka p
k'
p'
and hence
1
p'
ka=ll =
12 Pa - 1.30 X 103Pa
1
NHJ(aq) + H 20(/)~NHt(aq) + GH-(aq), pKb

k'
pKb = pKw-PKa= 14.00 - 9.25=4.75

Therefore,
and
k=k' Kb= 1.78 X 10- 5 X 4.0 X 1010 M- 1 s- 1 =7.1
1
-= k+ k'([NHt] + [OH-])
lOS s- 1
[Example 26.8]
= k + 2k' K~ 2 [NH3]1' 2
[[NHt) = [OH-] = (Kb[NH3]) 112]
=7. 1 X 105 s- 1 +2 X 4.0 X 10 10 M- 1 S- 1 X (1.78 X 10- 5) 112 X (0.15 M) 112

= 1.31 x 108 s- 1 , hence r = 7.63 ns
1
26.23 -= k + k'([B] + [C])

i
[Example 26.8]
481
k .
.
1 { [B] + [C]}
K = k', 1mplymg that ~ = k 1 + . K
and therefore that
(3.0x w- 6 st 1
2 X 2.0 X 10- 4 M
1
+ 2.0 X 10- 16 M
1/r
[B] + [C]
k=
1+
=
1.7 X 10- 7 S- 1
and therefore
k 1.7x10- 7 s- 1
k' =-=
8.5 X 108 M-I SK 2.0 x w- 16 M
Problems
26.1 Inspection of the data suggests that the production of water is increasing
as 1- e-k', which suggests that we should test for first-order kinetics. For a
first-order reaction of the form A~ B + C, with B the water,
d~~] = k[A] = k{[A]
0-
[B]}
which solves to
[B] = [A] 0(1- e-k~ = [B] ., (1 - e-k')

where [B] ., is the concentration or (what is equivalent in this case) the volume
when the reaction is complete. It follows that
[B].,
In [B]., _ [B] = kt
tis
V.,
v., - v
tn{
v:~ v}
30
60
90
120
150
2.0
3.3
5.0
6.7
10.0
0.69
1.20
1.61
1.90
2.30
482

/
Fig 26.2
2.0
/
/
/
/
/
/
/<
04
30
60
90
120
150
t/s
The points are plotted in Fig. 26.2. They fall on a straight line, confirming
first-order kinetics. The slope is 1.31 X 10- 2, so k = 1.31 X 10- 2 s- 1. The C4H6 is
probably reactive under the conditions of the experiment.
26.2 An Arrhenius plot tests the linearity of
E.
lnk=lnA--
RT
by plotting Ink against liT. We therefore draw up the following table:
T/K
773.5
786
797.5
810
810
824
834
103/(T/K)
-ln(k/s- 1)
1.29
6.42
1.27
5.83
1.25
5.48
1.23
4.81
1.23
4.80
1.21
4.21
1.20
3.81
The points are plotted in Fig. 26.3. The slope of the line is 2.9 x 104 , implying
that
E. =2.9 X 104 K X R=240 kJ mol - 1
The extrapolated intercept lies at -30, implying that
A =e3os- I = 1.1 x 1013 s- I
26.3 If the reaction is first-order, the partial pressure of cyclopropane should

obey
1/
483
Fig 26.3
..A
L
/
125
120
1-30
tOJ/fT/K}
Po
ln-=kt
p
and (1/t) lnp 01p should be a constant. We test this by drawing up the
following table:
p 01Torr
200
300
400
400
600
600
tis
piT orr
100
186
200
173
100
373
200
347
100
559
200
)20
7.3
7.3
7.0
7.1
7.1
7.2
104 (
_1_) In Po
tis
The values in the last row of the table are virtually constant, and so (in the
pressure range spanned by the data) the reaction has first-order kinetics with
k=7.2 x 10- 4 s- 1
26.4
1112
r'11 .,
ij~U-7 2 ~~Np_; 2 ~~Pu
with t 112 = 23 .5 min and t ;,2 = 2.35 day.

[U] =
[U)o
e - kr
In 2
- 1]
[ 19a, k=-=0.0314min
t\ 12
484
i~~~ = (k' ~ k) (e-k'- e-k 'r)

[Pu]
[U] 0 = 1 +
[ 19b, k' =
~ 1~ = 0.295 day-' J
ke-k''-k'e-k'
k' - k
These three functions are plotted in Fig. 26.4.

(a}
10
....v
.\
Np
Np
Pu
"" r-.... ._
Pu
If
60
40
80
100
t/min
1/
0
""
,........._
t/day
A+B~P, d~~]=k[A]"'[B]"
and for a short interval M,

~[P]=k[A]"'[B]"
Therefore, since
~[P]
= [P],- [P] 0 = [P],
Q1=k[A]m- 1[BY M
[A]
(a)
(b)
L--
"\
20
V\
26.5
\/
05
I,..-
Fig 26.4
(b)
10
[Chloropropane]
[P
J
independent of [Propene] implies that m = 1.
ropene
[Chloropropane] _ {p(HCl)
[HCl]
-
10
7.5
0.06 0.035
5.0
O.D15
--
10
485
These results suggest that the ratio is proportional to about p 2 , and therefore
that m = 3 when A is identified with HCI. The rate law is therefore
d[Chloropropane]
dt
k[Propane][HCij3
and the reaction is first-order in propene and third-order in HCI.

26.6
2HCI~(HCib
HCI +
CH 3 CH=CH 2 ~Complex ,
K 1 ; [(HCih] = K 1[HCI]2
K2
[Complex] = K2[HCI][CH 3CH=CH 2]

(HClh +Complex~ CH 3CHCICH3 + 2HCI , k
rate = k[(HCI) 2][Complex]
= kK2[ (HCih][HCI][ CH 3CH=CH 2]
= kK2K 1[HClj3[CH 3CH=CH 2]
Use infrared spectroscopy to search for (HCih.
26.7
E.
R ln(k~rrl kerr)
_!__2_)
( T T'
[Exercise 26.14 from eqn 13a]
Rln3
- - - -- =- 20 kJ mol- 1
1
1
343 K
292 K
But kerr = kK 1K 2 [Problem 26.6]

In kerr= Ink+ In K 1 +In K2
a In kerr)
E. = -R ( a(l!T) v = E~ + !1U1 + !1U2
since
a InK) -!1U
( a(l!T) v =~
[van 't Hoff equation, Chapter 9]
Therefore, setting /1 U = !1H

E~ =E.-
!1U1- !1U2
= -20+ 14+ 14 kJ mol- 1 = + 8 kJ mol - 1
486
26.8
Ea=
Rln(k'/k)
1
T
1
T'
[Exercise 26.14 from eqn 13a]

TIK
300.3
300.3
341.2
T'IK
10- 7 k/(M - 1 S - 1)
10- 7 k' /(M - l S - 1)
E.l(kJ mol- 1)
341.2
1.44
3.03
15 .5
392.2
1.44
6.9
16.7
392.2
3.03
6.9
18.0
300.3
341.2
392.2
1.44
6.69
1.16
3.03
5.89
1.10
6.9
5.12
1.16
The mean is 16.7 kJ mol- 1 For A , use

A =k
eE,tRT

TIK
w- 7 k/(M-
s- 1)
E.fRT
10- 10 A/(M- 1 s- 1)
The mean is 1.14 x 10 10 M- 1 s- 1
26.9 - In k/(M- 1 s- 1) = -ln(A/M- 1 s- 1)
E.
+ RT [13a]
Draw up the following table:
ore
10
15
25
34.5
T/K
103 KIT
- In k/(M - 1 s- 1)
273
3.66
10.65
283
3.53
9.60
288
3.47
9.19
298
3.36
8.24
308
3.25
7.44
These points are plotted in Fig. 26.5. The slope is 7900, implying that E. =
7.9 x 103 R = 66 kJ mol- 1 The intercept lies at -18 .3, implying that

11
Fig 26.5
10
1.1
lt'
,
7
l.'
30
A I(M- 1 s- 1)
34 -'
7U/ (T/ K}
38
= e 18 3 = 8.9 x 107
Therefore, A= 8.9 x 107 M - 1 s- 1.

26.10
NHzOH - ~ NHzO - + HzO
NH20-
+ Oz~P
d[NH 20H]
-
dt
d[(NH OH)]
d;
kobs[(NHzOH)][Oz]
k[NH 20 - ][0 2]
kobs[(NHzOH)][0 2] = k[NHz0 - ][0 2]

and [(NH 20H)] = [NH 20H] + [NH 20-]
Therefore, kobs[NH 20H] = (k- kobs)[NH 20-]
1
1
kobs k
-=-+
.
smce K.
[NH 20H] 1 [H +]
= -+-k[NH 20 - ] k kK.
[NH 20 - ][H+]
[NHzOH]
Therefore, plotting 11 kobs against [H +] should give a straight line with slope
llkK. and intercept llk .
In the data, we are given [OH - ], so use Kw = [H +][oH - ]:
487
488

1
Kw
kobs
kK.[OH-]
-=-+---We therefore draw up the following table:
1/((0H-)/M)
10- 3/(kobs/s- 1)
0.50
1.00
1.6
2.4
2.00
4.64
1.00
3.53
0.63
3.01
0.42
2.83
5 oar
v
00
~
Fig 26.6
1/
1/
2000
10
1/ ((0H7/ mol dm-3)
20
The points are plotted in Fig. 26.6. The intercept is at 2.35 X 103, which
implies that
k = (2.35 x 103) - 1 s- 1 = 4.3 x 10- 4 s- 1
The slope is 1.15 x 103, implying that

Kw
kK.
1.15 X 103
_
= 1.15 x 103 s
s 1
Therefore,
1.0 x 10- 14
14
Ka= 4.3 X 10- 4 s- 1 X 1.15 X 103 s = 2 .0 X 10and hence pK. = 13.7.
489
or, in terms of pressure of A:

1
k~
- = -+-
k k.p k.kb
and we expect a straight line when llk is plotted against lip. We draw up the
following table:
p!Torr
84.1
11.0
2.89
0.569
0.120
0.067
1/(p/Torr)
10- 4 /(k/s- 1)
0.012
0.336
0.091
0.448
0.346
0.649
1.76
1.17
8.33
2.55
14.9
3.30
These points are plotted in Fig. 26.7. There are marked deviations at low
pressures, indicating that the Lindemann theory is deficient in that region.
4
./
!..-" v
d[P]
26.12
dt =
kb[E] 0[S]
KM + [S]
12
16
1/(p/mmHg)
[24a]
Write v = d[P]!dt, then

KM
1
1
1
-=--+--x-
kb[E]o
kb[E] 0 [S]
Fig 26.7
490
103[Sj/M
50
17
10
1/([Sj/M)
v/(mm 3 min- 1)
ll(v/mm 3 min - 1)
20 .0
16.6
0.0602
58.8
12.4
0.0806
100
10.1
0.0990
200
6.6
0.152
500
3.3
0.303
Fig 26.8
03
:/
/
., v
/
~
I'
0
100
200
300
400
500
1/([S]/M}
The points are plotted in Fig. 26.8. The intercept lies at 0.050, which implies
that 11 kb[E] 0 = 0.050 mm - 3 min. The slope is 5.06 X 10- 4 , which implies that
KM
kb[E]o = 5.06 X 10
-4
mm
- 3
mm M
and therefore that

5.06 X 10 - 4 mm- 3 min M
M
0.010
KM=
0.050mm- 3 min
26 13
2A~ B
[A]o
[A]= 1 + kt[A] 0
d[A] = -k[A] 2
dt
6c]
[B] = [B]o+H[A]o- [A]) = H[A]o - [A])

In terms of the pressure,
Po
PA = 1 + ktpo, Ps =
1(
2
Po-P A
491
The total pressure is p = p A+ p 8 = t(p 0 + p A); therefore,
{2+ktp 0 }
1 }
p =+Po { 1 + 1 + ktp 0 =+Po 1 + ktp 0
and therefore
p
Po
1 +tx
wherex=p 01a
1 +x
-= - --,
This function is plotted in Fig. 26.9. The final pressure is
700
fp 0 ,
and half way to
Fig 26.9
1\
075
\\
..........
050
r- r6
70
this pressure corresponds top= tPo The time needed to attain this pressure is
the solution of
1+tx
1 +x
- - = 24 or x = 1
'
Therefore, t= llp 0 k.
We test whether the data fit the expression just derived by rearranging it to
1- (p lp 0)
P0"-L-t- (p lpo) -t
[=
F]
492
and draw up the following table based on p 0 = 400 Torr:

tis
100
200
300
400
p!Torr
plpo
400
1
0
322
0.805
0.639
288
0.720
1.273
268
0.670
1.941
256
0.640
2.571
These points are plotted in Fig. 26.10. They fall on a good straight line,
confirming that the reaction is second-order. The slope is 6.4 x 103 , and so
pr)c = 6.4 X 10- 3 s- 1. Since Po= 400 Torr, this implies that k = 1.6 X
w- 5 Torr- 1 s- 1
,..I
20
.....,
"'~
.8.....,
"
""'ciO
.s
I
......
00
26.14
100
200
t XJO
/s
A~B
d(A]=-k[A]+k'[B] d[B]=-k'[B]+k[A]
dt
' dt
[A]+ [B] = [A] 0 + [B] 0 at all times.

Therefore, [B] = [A] 0 + [B] 0 - [A] .
d~~] = -k[A] + k'{[A] 0 + [B]
0-
[A]}
= -(k + k')[A] + k'([A] 0 + [B]o)
t.OO
Fig 26.10
493
The solution is
k'(( A]o + (B]o) + (k(A] 0 - k'[B] 0 ) e -(k+k')t
[A]=
k+k'
The final composition is found by setting t =
[A]~= (k:k,) ((A]

(B]~ = (A]
Note that
26.15
+ (B] 0 -
co :
+ [B] 0)
(A]~ = (k: k') ((A]o+ [B]o)
(B] ~ / (A] ~ = k/k'.
d~~] = k(A](B]
Let the initial concentrations be A 0 , B0 , and (P] 0 =0. Then , when an amount x
of Pis formed, the amount of A changes to A 0 -2x and that of B changes to
B0 - 3x. Therefore,
d(P] dx
dt= dt =k(Ao - 2x)(B0 -3x ) with x=O at t = O.
kdt=Ix
dx
(Ao - 2x)(B0 -3x)
= fo (
2Bo~ 3Ao) { 3(Ao~ 2x)- 2(B 0~ 3x)} dx

-1
= 6(2B0 - 3A 0)
kt=
{Ix
0
dx
x-tAo-
I x dx }
x-tBo
0
6(2B~~3Ao) {In c~::oo) -ln(x~:~o)}
-1
{(2x- A 0 )Bo}
= 6(2Bo - 3Ao) In Ao(3x- Bo)
1
{ (2x- Ao)Bo}
= 6(3Ao - 2Bo) In Ao(3x- Bo)
26.16
d~~] = - 2k(Af(B], 2A+ B~P
494
(a) Let [P] = x at t, then [A] =A 0 - 2x and [B] = 8 0 -x.

Therefore,
d[A]
dx
dt
- = - 2 - = -2k(A 0 -2x)-(B 0 -x)
dt
Therefore,
2x(A 0 -x)
kt = A~(Ao - 2x)z
kt = Jx
0
dx
(A 0 - 2x) 2 (A 0 - x)
We proceed by the method of partial fractions (which is employed in the

general case too), and look for the coefficients a, (J, andy in
1
(Ao-2x?(Ao - x)
a
(Ao - 2x)
fJ
-:------:--:-;;2 + - -
Ao-2x
+- Ao-x
which requires that

a(Ao-x) + (J(Ao-2x)(Ao-x) + y(Ao - 2xr = 1
(Aoa + A5(J + A5y)- (a 0 + 3(JA 0 + 4yA 0 )x + (2(J + 4y)x 2 = 1
This must be true for all x; therefore

A 0a + A[/3 + A5y = 1
a+ 3A 0 (J + 4A 0 y = 0
2(J+4y = O
These solve to give

a= 2/A 0 , {3 = -2/Afi, andy = 1/Afi. Therefore,
_fx { (2/A
kt -
0)
(A o- 2x)2
(2/Afi) (1/A 0)}

A o- 2x + A o-X dx
2x
+1- I{Ao-2x}
n-- AJ(A 0 -2x) AJ
A 0 -x
2x(A 0 -x)
kt= Afi(Ao-2x) 2 [Problem 26.16a]
26.17
with [A]=A 0 -2x, [B]=Bo-x , Bo=tAo

(a) [A]= tAo when x = tA 0 ; then
tAoXtAo
kti,2= Afix(tAor
3
3
2A5' so ri12=zw
(b) [B] = tBo when x = tBo = tAo; so the half-life is the same as in (a), and
3
tl,2=zw
(c) The reaction is
0 = -2A-B+P; vA = -2, v8 = -1
Define ; so that ; = 0 initially and 1 finally, and write
[B] = B0 (1-;), then [P]=B0 ; , [A]=A 0 -2B0 ;
dA
dt = -2k[A] 2[B]
= -2k(A 0 - 2B0 ; ) 2B0(1- ;)
but B 0 =tAo, so A 0 ~ = kA~(l- ;) 3 , and therefore
J: ( ~;;)3 J:
1
kAfi dt
Hence,
1
kAfit= t {( 1 _;
)2 -1 }= ;(2-;)
( - ;)2
21
495
496
and therefore
26.18
kt=
! 112 = ~
(n~ 1) {[A~"_ 1 - [A~0 _ 1 }
At t=t 112 , x = tA 0 , so
At t=t3,4, x= t A 0 ; [A] =t[A]o
Hence,
!112
2"-1-1
~ (f)" 1 -1
[Exercise 26.18, n*1]
27. The kinetics of complex reactions

Exercises
27.1 Step 1: initiation; Step 2: termination; Step 3: propagation; Step 4:
propagation; Step 5: propagation; Step 6: propagation; Step 7: propagation;

Step 8: termination.
d[Cr(C0) 5]
27.2
dt
I - k2[Cr(C0) 5][CO] - k3[Cr(C0) 5][M]
+ k4 [Cr(C0) 5M] = 0 [steady state]

I+ k4 [Cr(C0) 5M]
Hence, [Cr(C0) 5] = k [CO] + k [M]
2
3
d[Cr(C0) 5M]
dt
k3[Cr(C0) 5][M]- k4[Cr(C0) 5M]

k3I[M] - k2k4[Cr(C0) 5M][CO]
k2[CO] + k 3[M]
-J[Cr(C0) 5M]
.
k 2k4[CO]
tf J= k2 [CO] + k 3[M]
and we have taken
1
- = -
k4
ki[M] ~ k 2 k 4 [Cr(C0) 5 M][CO].
Therefore,
k [M]
3
+ --,----~
k2k4[ col
and a graph of
llf against [M] should be a straight line .
Apply the steady-state approximation to both equations:
498
The kinetics of complex reactions
2k I [R2] - k2[R] [R2] + k3[R I] - 2k4[R ]2 = 0
k2[R][R2] - k 3 [R '] = 0
The second solves to
and then the first solves to

k
[R] = ( k~[R2]
)1/2
Therefore ,
27.4 At 700 K , the branching explosion does not occur. At 800 K, it occurs
between 0.16 kPa and 4.0 kPa . At 900 K, branching occurs for pressures in
excess of 0.11 kPa.
27.5 Number of photons absorbed = <1> - 1 x Number of molecules that
react [Section 27.3]. Therefore,
Number absorbed
1.4 X 10- 3 mol X 6.022 X 1023 einstein - 1

2.1 x 102 mol einstein -I
=3.3
10 18
27.6 For a source of power P and wavelength A. , the amount of photons (nr)
generated in a time t is
Pt
PAt
n =-- = - r hvNA hcNA

100 W X 45 X 60S X 490 X 10- 9 m
- 6.626 X 10 - 34 J S X 2.998 X 10 8 m s - 1 X 6.022 X 10 23 mol - 1
= 1.11 mol

The amount of photons absorbed is 60 per cent of this incident flux, or
0.660 mol. Therefore,
0.344 mol
<> = 0.660 mol
0 521
Alternatively, expressing the amount of photons in einsteins [ 1 mol

photons = 1 einstein], 1> = 0.521 mol einstein-'
Therefore,
k 1[AH][B]
[A - ] = k2(BH +]+k 3[A]
and the rate of formation of product is
d[AH]
27.8 -d-t-= k3[HAH +][B]
[HAH+]
K= (HA](H +]
[rate-determining]
[pre-equilibrium]
and hence
The acidity constant of the conjugate acid of B is
Therefore,
499
500
27.9 Step 1: initiation [radicals formed]; Steps 2 and 3: propagation

radicals formed]; Step 4: termination (non-radical product formed].
d(AH]
~=
- k.[ AH] - kc[ AH](B]
(i)
d~] =k.(AH] -kb(A] +kc(AH](B] -kd(A](B] =0
(ii)
dt= kb(A]- kc(AH](B]- kd(A][B] =0
d(B]
(i + ii) (A](B] = (zk;d) (AH]
k +2k [B])
(i-ii) (A]= ( a Zkbc
(AH]
Then , solving for [A]:
(A]=k(AH], k= ( k~b ) { 1+ [ 1+ 4kbk
k.kdc
J112}
from which it follows that

k.(AH]
k.
(B]= 2kd(A] = 2kkd
and hence that
d( AH]
( k.kc)
-dt- = - k.[AH]- Zkkd [AH] = kerJ AH]
27.10
d~~] = k[ A f(P]
(A] =A 0 -x, [P] = P0 +x, d[P]/dt= dx/dt
dx
dt =k(A 0 -x) 2(P0 +x)
(new

X
dx
(Ao-x) (P0+x)
kt
Solve the integral by partial fractions:
(Ao-x)2(Po+x)
(A 0-x) 2
{3
A 0-x
P0+x
+--+--
a(P0+ x) + {3(A 0- x)(P0+ x) + y(A 0- x) 2

(A 0-x) 2(P0+x)
Poa + AoPof3 + A6y = 1
a+ (A 0 - P0){3- 2AoY = 0
-{3+y=O
This set of simultaneous equations solves to

1
a
a = - - {3=y=-A0+ P0'
A 0+ P0
Therefore,
kt=
-
(Ao~ Po) J: {(A 0 ~xY + (Ao~ P (A 0 ~x + Po~x)} dx

0)
1 ){Ao-x
1 Ao1 (Ao+Po
1 )[ (Ao-x (Po+Po x)]}
(Ao+Po
1 ){ Ao(Ao-x)+
x
( 1 ) (A (P +x))}
(Ao+Po
Ao+Po
(Ao-x)Po
--
In -A-) +In - -
----+ - -
In
Therefore, with y = x/ A 0 and p = P01A 0,

y
1
{ p+y }
A 0(A 0+ P0)kt=l=Y+l+P In p( 1 - y)
The maximum rate occurs at

dvp
dt=O,
Up=
k[A]Z[P]
and hence at the solution of

2k (d[A])[A][P] + k[A]Z d[P] = 0
dt
dt
501
502
-2k[A][P]vr+k[Afvr =O [as vA= - vr]

k[A]([A]- 2[P])vr= 0
That is , the rate is a maximum when [A]= 2[P]; which occurs at A 0 - x =
2P0 +2x , or
x = t(A 0 -2P0 ), y = t(1-2p)
Substituting this condition into the integrated rate law gives
Ao(Ao + Po)ktmax = (
1 p) { t(1- 2p) +In
2~}
or
27.11
d[P] = k[A][P] 2
dt
kt=Jx
0
dx
(A 0 -x)(P0 +x) 2
Integrate by partial fractions [as in Exercise 27 .10]:

2
kt=(-1)fx{(-1) +(- 1
A 0 + P0
P0 + x
)[-1 +-1
A 0 + P0
P0 + x
A0- x
]}dx
(Ao ~ P0){ ( ~0 - P0+ x) + (A ~Po) [In (Po~ X)+ In (~~x) ]}
(Ao ~ PJ{ P0 (~ +x) + (Ao ~Po) In [~~:x2~;]}
Therefore, with y = xi[A] 0 and p = P0 /A 0 ,

A 0 (A 0 + P0 )kt= p(py+ y) +
(~) ln{p~1 ~)}
As in Exercise 27.10, the rate is a maximum when

dvr = 2k[A][P] (d[P]) + k (d[A]) [P]z
dt
dt
dt
= 2k[A][P]vr - k[P] vr
= k[P](2[A]- [P])vr= 0
503
That is, at [A]= t [P]

On substitution of this condition into the integrated rate law , we find
2-p
( 1 ) 2
Ao(Ao + Po)ktmax = 2p( 1 + p) + 1 + p In
or
2- p
2
(A 0 + P0) 2ktmax = - - +In2p
p
Problems
21.1
uo~ + +hv~(uo~+ ) *
(UO~+) * + (COOH)z~ UO~ + + H20 + C02 +CO
2Mn04 + 5(COOH)z+6H + ~ 10C0 2+ 8H 20 +2Mn 2+

17.0 cm 3 of 0.212 M KMn0 4 is equivalent to
f X 17.0 cm3 X 0.212 M = 9.01 X 10- 3 mol (COOH)z

The initial sample contained 5.232 g (COOH) 2, corresponding to
5.232 g/ (90.04 g mol- 1) = 5.81 X 10- 2 mol (COOH)2 Therefore, 5.81 X
10- 2 mol - 9.01 X 10- 3 mol= 4. 91 X 10- 2 mol of the acid has been consumed . A
quantum efficiency of 0.53 implies that the amount of photons absorbed must
have been (4.91 X 10- 2 mol)/0 .53 = 9.3 X 10- 2 mol. Since the exposure was for
300 s, the rate of incidence of photons was (9.3 x 10- 2 mol)/300 s = 3.1 x
10- 4 mol s- 1 Since 1 mol photons= 1 einstein , the incident rate is 3.1 X
10- 4 einstein S- 1 or 1.9 X 1020 S - 1.
27.2
M+hv;~M *,
I.
M * +O~M + Q,
M * ~M+hvt.
kq
kr
d[M*]
d t = I.-kr[M *] - kq[Q][M*] = O [steady state]
I.
and hence [M *]= kr + kq[Q]
504
and so
1 1 kq[O]
-=-+-Ie
I.
kela
If the exciting light is extinguished, [M *], and hence fc, decays as e-krt in the
absence of a quencher. Therefore we can measure kql kef. from the slope of
life plotted against [Q], and then use keto determine kq. We draw up the
following table:
1//e
2.4
4.0
6.3
Fig 27.1
......... v
/f-""
~
2
0
.J
,... v
v
0005
0010
[Q]/ M
The points are plotted in Fig. 27 .1. The intercept lies at 2.0, and so I.=
112.0 = 0.50. The slope is 430, and so
k
_q =430M- 1
kef.
Then, since I. = 0.50 and ke= (In 2)/t112 ,

kq=0.5Q X 430 M-IX
27.3
ln2
X _6 S 5.1 X 108 M- IS-I
29 10
H+N0 2 ~0H+NO , k=2 . 9x10 10 M - 1 s- 1
OH + OH~ H 20 + 0 , k' = 1.55 x 109 M- 1 s- 1

0+0H~0 2 + H,
k"= 1.1 x 1010 M- 1 s- 1

[H]o = 4.5
w-IO
505
mol cm- 3, [NOz]o = 5.6 X w-IO mol cm - 3.
d[O] = k'[OH] 2 + k"[O][OH]

dt
d[O,]
dt
--=
k"[O][OH]
d[OH]
-dt-= k[H][N0 2] - 2k'[OH] 2 - k"[O][OH]
d[NO]
T,-=
-k[H][N0
2]
d~~] = k"[O][OH]- k[H][N0
2]
These equations serve to show how even a simple sequence of reactions leads
to a complicated set of non-linear differential equations. Since we are
interested in the time behavior of the composition we may not invoke the
steady-state assumption. The only thing left is to use a computer, and to
integrate the equations numerically. The outcome of this is the set of curves
shown in Fig. 27.2 (they have been sketched from the original reference). The
Fig 27.2
\
\
1-"
02
~
'OH
II
J.
"r-...
......
1--
t/ms
10
similarity to an A~ B~ C scheme should be noticed (and expected), and the

general features can be analyzed quite simply in terms of the underlying
reactions.
506
27.4
+ Cl 2_,. CIO + CI
p(CI 2) =constant
[CI 2 at high pressure]
Therefore, the reaction in probably pseudo-first order , and
[O]=[O]oe-k'r
That being so,
[0] 0
In [O] =k't=k[CI 2]t=k[CI2]
x;
where k' = [CI 2]k, u is the flow rate , and dis the distance along the tube. We
diem
[O]o
In [O]
10
12
14
16
18
0.27
0.31
0.34
0.38
0.45
0.46
0.50
0.55
0.56
0.60
The points are plotted in Fig. 27.3. The slope is 0.0189 , and so k[CI 2]/u =
0.0189 cm- 1
0.6
v
/'
0.5
0.3
0.2
Fig 2 7.3
,/
v
0
./
./V'
10
20
d/ cm
Therefore ,
0.0189 cm- 1 xu
k=
(Cl 2 ]
0.0189 cm- 1 x 6.66 X 102 em s- 1

2.54 X 10- 7 M
507
[There is a very fast 0 + CIO ~ Cl + 0 2 reaction, and so the answer given here
is actually twice the true value .]
27.5
CH 3 CH 3 ~2CH 3 ,
k.
CH3 + CH 3CH3~ CH4 + CH 3CH2, kb

CH3CH2~CH2= CH2 + H,
kc
H + CH 3 CH 3 ~H 2 + CH 3 CH 2 ,
H + CH 3 CH 2 ~CH 3 CH 3 ,
kd
ke
d[CH 3CH3]
dt
= - k.[CH3CH 3]- kb[CH3J[CH3CH 3]- kd[CH 3CH 3J[H]
+ kc[CH3CH2][H]
which implies that [CH 3] = 2k.l kb.

d[CH 3CH2J
dt
= kb[CH3][CH3CH3]- kc[CH3CH 2]
+ kd[CH3CH3J[H]- ke[CH3CH2J[H] = 0
These three equations give
[H] =
kc
[CH 3CH 3]
ke + kd[CH3CH2J
[CH3CH2f - (
~:) [CH3CH3][CH3CH2]- ( ~:~:) (CH3CH3f = 0

2
or [CH3CH2J = {
2~c + [ ( 2~) + G:~:)
which implies that
]"
2
}
[C~JCHJ]
508
If k. is small in the sense that only the lowest order need be retained ,
The rate of production of ethene is therefore

d[CH 2CH]
(k k L- )1'2
2
- -= k [CH CH] = _a_c"-_d [CH CH]
dt
c
3 2
ke
3 3
The rate of production of ethene is equal to the rate of consumption of ethane

[the intermediates all have low concentrations], so
d[CH3CH3] _ _
_ (kkckd) 112
dt
- k[CH3CH3], kkc
Different o!ders may arise if the reaction is sensitized so that k. is increased.

27.6
CH3CHO~CH3 +CHO,
k.
CH3 +CH3CHO~CH4+CH zCHO ,

CH 2 CHO~CO+CH 3 ,
kc
CH 3 ~ CH 3CH 3,
kd
CH3+
kb
d[CH 4]
- d-t - =kb[CH 3][CH3CHO]
d[CH 3CHO]
dt
-k. [CH3CHO]- kb[CH 3CHO][CH 3]
d[CH]
= k.[CH3CHO]- kb[CH3CHO][CH3] + kc[CH2CHO]- 2kd[CH3]2 = 0
d[CH 2CHO]
dt
kb[CH3][CH3CHO]
. - kc[CH2CHO] = 0
Adding the last two equations gives
509
Therefore,
d[CH]
4
--
dt
=k
( k
-
2kd
)vz[CH CH0] 312

3
3
d[CH CHO] = - k [CH CHO] - k
dt
(~)
2kd
112
[CH CH0] 312
3
Note that to lowest-order in k.,
-k
d(CH3CHOJ
dt
(~)t'2[CH 3CH0]3'2
2kd
and the reaction is three-halves order in CH 3CHO.

27.7
(i)
d[COC1 2]
dt
= kc[COCl](Clz]
d(COCl]
(ii)
dt
= kb[Cl][CO]- k!,[COCl]- kc[COCl][Cl2J = 0
d(Cl]
(iii)
i l i = 2k.[C12]- 2kaCIJZ- kb[Cl][COJ + k~[COCl]

+ kc[COCl][Cl2] = 0
..
kb[Cl][CO]
From (u): [COCI] = k!, + kc[Clz]
(iv)
Then (iii) becomes

k
k.(C1 2 ]-k~[CJ]2=0, so (Cl]=K 112 [Cl 2] 112 ; K = k:
a
Substitution in (iv), and that into (i), gives the rate law
1
d[ COCl2] kcK K 112 [CO][ ClzP12 .
dt
l+(kc/k~)[Clz]
With K =kb/kb
For the numerical solution, write a= [COC1 2 ], b = [C1 2], c =[CO], x = [COCl],
andy = [Cl], and replace the differential equations by
(i) a(t;+ 1) = a(t;) + kcx(t;)b(t;) D..t
(ii) x(t;+ 1) =x(t;) + {kbJ(t;)c(t;)- k~x(t;)- kcx(t;)b(t;)} M
(ii) y(t;+ I)= y(t;) + {2k.b(t;)- 2k~y(tY
- kby(t;)c(t;) + k~x(t;) + kcx(t;)b(t;)} M
510
and iterate the solutions.
27.8
d~~] = ki[M][I]
[initiation]
d[R]
dt = - 2k~(1 + a[M])[Rf
[termination]
d~~] = - k;(l + b[M])[R][M]
[propagation]
In the steady state
d~~] = ki[M][I]- 2k~(1 + a[M])[Rf= 0

which solves to
ki[M][I]
[R] = { 2k~(1 + a[M])

d[M]
dt = =
} 112
o
{
ki[M][I] } 112
kp( 1 + b [M])[M] 2k~(1 + a [M])
k ) 112{ 1 + b[M]
(1 + a[M])
-k; ( ~
27.9 (M)N = -1 -p
lt11[I]l'2[MP'2
[12]
d
d
d d
=M 2(1-p)- p p" = M 2(1-p) - p - (1 - p) - 1
dp dp "
dp dp
2:
M 2(1+p)
(1 - p)2

PI /2M
Hence, oM = - 1- p
=M 3 (1 - p)~ p- p-"" p"

dp dp dp L.J
II
=M\1-p)- p - p - (1-pt 1
dp dp dp
M\1+4p+p~
(1 - p) 3
(M
)N=
M 2 (1 + p)
( - p) 2
1
[Problem 27 .9]
(M 3)N M(1 + 4p+p 2)

Therefore, (M 2)N =
1_ p2
.. d[O]
(u)
dt = kc[Oz][H]- kct[Hz][O] = 0
d[OH]
(iii) ~= u. - kb[Hz][OH] + kc[Oz][H] + kct[Hz][O] = 0
..
(kc) [Oz][H]
From (u), [0] = kct [Hz]
From (i + iii), u. + 2kct[H 2][0] - kc[H] = 0
Hence u. +
2kc[Hz][02]
[Hz]
- kc[H] = 0
511
512
and so
[H] = k _ 2k [O ]
c
c
2
Thus , [H)-+ oo if 2kc[02]---+ kc.
27.12
A---+2R , I .
A+ R---+ R + B, kP
R + R---+ R 2, k,
The latter implies that [R] = (I.I k,) 112 , and so
d[ A] = _ I _ k
dt
d[B]
(!.:)
k
112
(I
k.)
112
dt=kp[A][R] = kr
[A]
Therefore, only the combination kpf k!' 2 may be de termined if the reaction
attains a steady state.
27.13
Cl 2+ hv---+ 2Cl, I .
Cl + CHC1 3---+ CC1 3+ HCl , k .
CC1 3+ Cl 2---+ CC1 4+ Cl, kb
2CCIJ + Clz---+ 2CCI4, k c
d[CC14]
(i) -d-t-= 2kc[CCI3p[Clz] + kb[CCI 3][CI2]
d[CCI 3]
(ii) - d-t - = k.[CI][CHClJ]- kb[CCI3][CI2] -2kc[CCI3]2[Cl2] = 0
d[Cl]
(iii) ~ = 2I. - k.[Cl][CHCI 3] + kb[CCI 3][CI 2] = 0
.
(1v)
d[CI 2]
~=
Therefore,
- I. -kb[CC1 3][Cl 2] -kc[CCIJ]2[Clz]

I , = kc[CC1Jf[C12]
513
[(ii +iii)]
which implies that

1 ) 112( I ) 112
[CCI)]= ( ~
[C~z]
Then, with (i),
d[ CCI4]
kbi !12 [Cl 2] 112
-d-t-=2I.. +
kl /2
c
When the pressure of chlorine is high, and the inhibition rate is slow (in the
sense that the lowest powers of I .. dominate) , the second term dominates the
first, giving
d[CCI] k I 112
___
4 =-b-"-[Cl]ltz =kii tz[Cl]l /2
dt
k~ /2
2
a
2
with k = kb/ k~ 12 It seems necessary to suppose that Cl + Cl recombination
(which needs a third body) is unimportant.
In the photostationary state I , - k[Bf = 0

Hence,
12
[B] = ( )' oc [A] 112 [because I oc [A]]

The illumination may increase the rate of the forward reaction without
affecting the reverse reaction. Hence the position of equilibrium may be
shifted toward products.
27.15
A+hv-A*, I.
A * +A-A 2 , k
A *-A+hvr, kr; Ir=kr[A *]
-d[A] 1
<1>=-- X dt
I,
514
d~~] = - 1. -
k[A *][A]+ kr[A *]
d[A*]
~ = 1. -k[A*][A]
-kr[A *] = 0
which solves to
I.
[A*]= kr+k[A]
Therefore ,
d[A]
dt= -
(kr- k[A])I.
la + kr+k[A]
-2kl.[A]
kr+k[A]
Consequently,
2k[A]
4> =-----:,.----:,
kr+k[A]
If k[A] ~ kr, 4> = 2(k/kr)[A], and the efficiency is determined by the
availability of A molecules in the vicinity of A *. If k[A] ;;> kr , 4> = 2, and the
rate is determined by the excitation step, because there is now plenty of A to
react to form A 2 .
27.16 Write the differential equations for [X] and [Y]:

(i)
d~] = k.(A][X] -
(ii)
dt = kb[X][Y] -
d[Y]
kb[X][Y]
kc[Y]
and express them as finite-difference equations:

(i) X(ti +I)= X(ti) + k. [A ]X(ti) !:J.t- kbX(ti)Y(ti) !:J.t
(ii) Y(ti +l)=Y(ti) - kcY(ti) !:J.t+kbX(ti) !:J.t
and iterate for different values of [A], X(O) , and Y(O).
For the steady state,
(i)
d~~] = k.[ A] [X] -
kb[X] [Y] = 0

(ii)
d[YJ
dt = kb[XJ[Y]- kc[YJ = 0
which solve to
Hence,
k
k [A]
[X] = _:, [Y]= - kb
kb
27.17
(i)
d~~J = k.(AJ + kb[Xj2[Y]- kc[BJ[X]- kd[XJ
(ii)
d~~J = - kb[Xj2[Y] + kc(BJ[X]
Express these equations as finite-difference equations:

(i) X(t;+I) = X(t;) + {k.[A] + kbX 2(t;)Y(t;) - kc[B]X(t;)- kd[X]} M
(ii) Y(t;+ I)= Y(t;) + {kc[B]X(t;)- kbX 2(l;)Y(t;)} !:J.t

and iterate. See Figs . 27.7 to 27.9 of the text.
27.18
(i)
d~~J = k.[AJ[Y]- kb(XJ[Y] + kc[BJ[X]- 2kd[X]
(ii)
dt= -
d(Y]
k.[AJ[Y]- kb(X](Y] + ke[Z]
Express these differential equations as finite-difference equations:
(i) X(t;+ I) = X(t;) + {k.(A]Y(t;) - kbX(l;)Y(t;) + kc[B]X(l;)- 2kdX 2 (t;)} M

(ii) Y(l; +I)= Y(t;) + {ke[Z]- k.[A ]Y(t;)- kbX(t;)Y(t;)} !:J.t
Solve these equations by iteration. More sophisticated procedures are

available programmed in the Library of Physical Chemistry Software that is
available to accompany the text.
515
28. Molecular reaction dynamics

Exercises
21'2acp
28. 1 z=~
[eqn 9 of Chapter 24]
_ (8kT) 112
and c= [eqn 7b of Chapter 24]
nm
4ap
.
,
Therefore, z = (nmkT) 112 w1th a=nd 2 = 4nR Similarly,
Z AA
4kT)
=a ( nm
112('!\
2
V} [eqn lOb of Chapter 24]
[NIV=plkT]
We express these equations in the form

16nR 2 x 1.0133 x 105 Pa
{n X (Mig mol - 1) X 1.6605 X 10- 27 kg X 1.381 X 10 - 23 J K -
z=~~------~--------~~----------=---~------~
1.10 X 10311 m- 2 s- 1 X R 2
(Mig mol 1) 112
ZA A
1.10 X 106 X (Ripm) 2 s- 1

(Mig mol - 1) 112
, ( 4 x 1.381 x 10- 23 1 K -I x 298.15 K)

4nR ,
n x (Migmo l- 1)xl.6605 x 10-- 7 kg
112
)2
1.0133 X 10 Pa
( 1.381 X 10 - 23 J K -I X 298.15 K
1.35 X 1055 m -J s- 1 X R 2
(Mig mol - 1) 112
1.35 X 1031 (Ripm) 2

m- 3 s- 1
(Mi g mol - 1) 112
(a) NH1 ; R=190pm, M = l7gmol - 1

1.10 X 106 X 1902 S- 1
z=
,
=9 .6 x l0 9 s- 1
171 2
I X
298.15 K} 112
Molecular reaction dynamics

(b) CO; R=180pm, M=28gmol - 1
1.10 X 106 X 1802
Z =
S- I = 6 7 X 109 S- I
281/2
.:::..:. :.--'-'-o..:::_.::..._
For the percentage increase at constant volume, use

1 dz 1 de
1 1 dZ 1
~ dT = e dT= 2T' Z dT= 2T
Therefore,
oz oT
oz oT
- = - and-=z 2T
Z 2T
and since oTIT= 10 K/298 K = 0.034, both z and Z increase by about
1.7 per cent.
28.2 In each case use f = e- E,.tRT [Section 28.1]:
E.
10 x 103 J mol- 1
401
(a) RT=8.314JK - 1mol - 1x300K 4 01 'f=e - = 0 018
E.
10 x 10 3 J mol- 1
RT- 8.314 J K -I mol- 1x 1000 K
(b)
100 x 103 J mol- 1

RT = 8.314J K 1mol 1x 300 K
E.
100x103 Jmol- 1
RT= 8.314 J K 1mol 1x 1000 K
E.
1.20, f= e-uo = 0.30

40.1, f= e - 40.I = 3.9 X 10-IR
12.0, f= e- 120 = 6.0 X 10- 6
28.3 The percentage increase is
of
1 ( df)
100E.
100x - =100x- xoT=--oT
f
f dT
RT 2
(a) Ea=10kJmol- 1,oT=10K
100
of 100x10x103 Jmol- 1x10K

y= 8.314JK- 1moi- 1XT 2
1.20 x 106
- (T/K) 2
{13 per cent at 300 K

1.2 per cent at 1000 K
517
518
(b) Ea = 100 kJ mol- 1, oT= 10 K
of 1.20 X 107
100- = ----,--.,..,..! (TIK?
130 per cent at 300 K

12 per cent at 1000 K
8X8.314JK- 1 moi- 1 X298K
8RT
28.4
kd =
"""3-i
[7] =
3TJ
6.61 x 103J mol- 1

TJ
6.61 x 103 m3 mol - 1 s- 1
6.61 x 103 kg m 2 s- 2 mol- 1

(TJ ikgm
s 1) xkgm
(TJikgm- 1 s- 1)
6.61 X 106 M- 1 S- 1 6.61 X 109 M- 1 S- 1

1
(TJ f kg m
1
)
(YJ/cP)
(a) Water, TJ = 1.00 cP, kd = 6.61 x 109 M- 1 s- 1

(b) Pentane,rJ = 0.22cP,kd =
6.61 X 109
_
M- 1 s- 1 =3.0x10 10 M- 1 s- 1
0 22
(c) Decylbenzene ,rJ =3.36cP,kd=
6.61 X 109
_
M- 1 s- 1 = 2.0x109 M- 1 s- 1
3 36
28.5
k2 = ac:fJ-~JI NAe-EiRT
(1]
= (3.72 X 10 12 M-l min -I) X e -E.tRT

3.72x10 12
- - - - X 10-3m3 mol-l S-1
60
Xe-E.fRT
Therefore, we must evaluate

9
3. 72 X 10 3
1-1 -I
a=
60
m mo s
X ( TC!J- ) 1/2
8kT
1
NA
16 X 100
with fJ- =
a=
16
+ 100 u = 13.79 u
3.72x109 m3 mol- 1 s- 1 ( nx13.79xl.6605x10- 27 kg )112

x
60 X 6.022 X 1023 mol- 1
8 X 1.381 X 10- 23 J K -I X 298 K
= 1.52 X 10- 19 m 2 ,
Of
0.152 nm 2
519
a*
P =-
28.6
For the mean collision cross section, write a A= ndi, as= nd~, and a = nd 2 ,
with d = f(dA + do):
a = -!-n(dA + ds) 2 = tn(di + d~ + 2dAds)
=t(aA + as+ 2a~ 2 a~ 2 )
=-!-{0 .95 + 0.65 + 2 X (0 .95 X 0.65yt 2} nm2 = 1.03 nm 2
Therefore,
P
9.2 X 10- 22 m 2
= 1.03 X 10-IS m 2
28.7
dt = k2[A][B]
8.9 X 10- 4
d[P]
Therefore, the initial rate is
28.8
k
!::J.Ht = E.- RT [20b]

kT RT
x [19]
h
pe
= Be 6511 Re-tJ.HitRT B= -
520
Therefore,
A= e B e 65 11 R, implying that
Therefore, since
~H * =
~5 1 = R (In~- 1)
8681 K X R ,
E. = ~H * + RT= (8681 K + 303 K)R

= 8984 K X 8.314 J K - I mol - 1=74.7 kJ mol - 1
1.381 X 10- 23 J K -I X 303 K 8.3141 K -I mol - 1X 303 K
B=
x-----=
----6.626 X 10- 34J s
105 Pa
= 1.59 x 10 11 m3 mol- 1s- 1= 1.59 x 10 14M - 1s- 1
and hence
13
1
2.05 X 10 M - l s- )
}
~S * = R { In ( 1.59 x 1014 M Is I -1
= 8.314J K - I mol - 1x (-3 .05) = -25 J K - I mol - 1
28.9
~H * =
E. - RT [20b], ~H 1 =9134 K x R=75.9 kJ mol - 1
~S* =R (In ~-1)
[Exercise 28.9]
kT RT
with B = - X(19] = 1.59 X 10 14 M - 1s- 1 at 30 C
h pe
Therefore,
1
14
7.78 x 10 )
~S * =8.314JK - mol - X { In ( 1. x l0 14 -1
59
+4.9 J K - I mol - 1
Hence ,
~G 1
~H * -
~s + =
75 .9-303 X 4.9 X 10- 3 kJ mol - 1
=74.4 kJ mol - 1
28.10
~H * =E" -2RT
[20a]
= 56.8-2 x 8.314 x 10- 3 x 338 kJ mol - 1=51.2 kJ mol - 1

k 2 =A e - E,tiiT implies that
A = kz e E) RT
=7 .84 X 10- 3 kPa - 1S- 1X e56.Rx iO'IR.3 14 x33R
= 4. 705 x 10 6 kPa - Is - I= 4. 705 x 10 3 Pa - Is - I
In terms of molar concentrations

V = kzPAPB = k z(RTn A][B)
and instead of
dp A
dt = -k2PAPB
and hence use
A= 4.705 x 103 Pa- 1s - 1x 8.314 J K - I mol - 1x 338 K

= 1.322 x 10 7 m 3 mol - 1s - 1
Then
kT RT
Xh pe
B= -
1.381 X 10- 23 X 338 K

6.626 X 10- 34 J s
8.314 J K - I mol - 1X 338 K

10 5 Pa
--------~~- x -------~-------
and
and hence
~:t.G +
28.11
= ~:t.H + - T ~:t.S + = 51.2-338 X ( -96.6 X 10 - 3) kJ mol - 1

= +83.9 kJ mol - 1
k2 = N A a
8k!:\ 112
*
lrfl-}
e -f>Eui RT,
which implies that
521
522
For identical particles, Jl =

A
4a*hp 9
(:n:mk3T3)1 tz
- {:n; X
tm,
so
4 X 0.4 X 10- 18 m 2 X 6.626 X 10- 34 J S X 10 5 Pa

50 X 1.6605 X 10- 27 kg X (1.381 X 10- 23 J K -I X 300 K) 3} 112
=7.78 x 10- 4
and hence
ilS t = R {In (
~)- 2} = 8.314 J K
-I
mol- 1{ln 7.78 X 10- 4 - 2}
= -76 J K - I mol- 1
28.12
kT
RT
pB
B = -X-
1.381 x 10- 23 J K -I X 298.15 K
8.314 J K -I mol - 1 x 298.15 K
--~~~~~~---x --------~---------34
6.626 x 10
Js
10 5 Pa
= 1.540 x 10 11 m 3 mol- 1 s- 1
= 1.540 X 10 14 M- 1 S- 1
Therefore,
12
4.6 X 10 )
}
(a) !lS *= R { In ( l.S 0x10 14 -2 =-45. 8JK- 1 mol- 1
4
(b) ilH *=E. -2RT=10.0- 2x2.48kJmol- 1
= +5.0 kJ mol- 1
(c) ilG *= ilH*- T ilS*= 5.0-298.15 K x ( -45.8 x 10- 3) kJ mol - 1
= +18.7 kJ mol- 1
523
28.13 If cleavage of a C-D or C-H bond is involved in the rate-determining

step, use
2
k 2(D)
(hk/' ) { 1
1 } [16]
k2 (H) = e'' A= 2kT 1-lgl-1-lgA
2X 12
!"-(CD)= +
u=l.71 u
2 12
1 X 12
!"-(CH)=--u=0.92u
1+ 12
A
1.054xl0- 34 Jsx(450Nm- 1) 112 { 1

1 }
1
x - -112- - x - - -- 27
1.71
0.92 112
(1.6605 X 10- kg) 112
2 X 1.381 X 10- 23 J K -I X 298 K
= -1.85
k 2(D) = e-185 = 0.156
Hence, k (H)
2
That is, k 2(H) = 6.4 X k 2(0), in reasonable accord with the data.
28.14
2
.!
_ (hk/' ) {-1 _ _
1 }
k 2(T)
(a) k 2(H) = e A- 2kT 1"-g 1-lgA
12X 3
flcr=12+3 u=2.40U,flcH =0.92u
1.054 X 10- 34 J S X k/' 2
A= _2_x_1_.3_8_1_x_10__-=2-=-3J-K-_...,.1-x T
1
1
}
X { (flcrlu)lt2 - (!"-cH/u)l'2 x
1
--
. -
1 112
93.65 X (krfN m- )
{
1
1
}
(T/K)
X (/A-cr/u)lt2- (!"-CH/u)l/2
93.65 X 450
298
112
{
X
1
1 }
2.401/2 -0.921/2 =-2.65
k 2(T)
Therefore, k2(H) = e - 265 = 0.071, so kz(H) = 14k2(T)
524
Molecula r reaction dynamics
93.65
(b) A=
1750
298
X
112
{
X
1
1 }
7.20112- 6.861'2 = -0.12
12 X 16
_
since .uC 2C 160) = - - - u =6 86 u
12+ 16
.
12 X 18
_
=.u C2C 1x0)=--u=7 20u
12 + 18
.
kC 2CIRO)
Therefore , kC 2C 160)
e-
12
= 0.89
and k( 12C 160) = 1.1 X kC 2C 180)

Increasing the temperature reduces the magnitude of A, so the isotope effect is
likewise reduced.
28.15
1gk2 =1gk2' +2AzAzsf 112 (24)
Hence , lg k2= lg k 2 - 2Az Az 8 ! 112

= lg 12.2-2 X 0.509 X 1 X ( -1)
and k2=20.9M - 2min - 1
0.0525 112= 1.32
28.16 Fig. 28.1 shows that lg k, is proportional to the ionic strength for neutral
0. 19
Fig 28. 1
.;:::--
'c
.J
~0. 17
............
:>-... ............
o--..
"
~.!2>
I
..__
............
\..1....
0. 15
05
1.0
1.5
molecules. From the graph , the intercept at 1=0 is -0.18 , so k~=

0.66M - 1min- 1.
-

[H +J[A -]
28.17
Ka= (HA]YHA y ~ =
525
[H +J[A - Jy ~
(HAJ
[HA]Ka
Therefore , [H +j = [ _ 2
A 1Y
[HA]
and lg[H +j = lg Ka+ Ig [A _ - 2lg Y
= lg K.
+ lg [HAJ_ 2A/ 112
[A-]
Write u = k2[H +J[B] ,

then lg u = lg(k 2[B]) + lg[H +j
= lg(k2[B]) + lg
-1
- gu
[[~~i + 2Al
112
[BJ[HA]
+ 2Aflt2 , uo_k
- 2 [A _
That is, the logarithm of the rate should be proportional to the square root of
the ionic strength , lg u ex: / 112 .
Problems
28.1
A=NAa * C:f..l~
1 12
[Exercise 28 .1l ; f..l= t m(CH 3)J
K)
s x 1.381 x 10- 23 1 - l x 298 112

=a * X 6.022 X 1023 mo l-l X ( .n: X f X 15 .03 X 1. 6605 X 10 27 kg
= 5.52 x 1026 x a * mol - 1m s- 1
2.4 x 10 10 mol - 1dm 3s- 1 2.4 x 107 mol - 1m 3s- 1
(a) a *= 5.52 x 1026 mol - 1m s- 1 = 5.52 x 1026 mol - 1m s- 1
= 4.4 X 10-20 m2
(b) Take a=.n:d 2 = .n: X (154 X 2 X 10- 12 m) 2 =3 .0 X 10- 19 m 2
a * 4.4 X 10- 20
0.15
Hence P=-;;= . x
3 0 10 19
526
28.2 Draw up the following table as the basis of an Arrhenius plot:

TIK
600
700
800
1000
103 KI T
k/(cm 3 mol- 1s- 1)
ln(k/cm 3 mol- 1s- 1)
1.67
4.6 X 1()2
6.13
1.43
9.7 X 103
9.18
1.25
1.3x10S
11.8
1.00
3.1x106
15.0
The points are plotted in Fig. 28.2. The least-squares intercept is at 28.3,
30
Fig 28.2
i"
V)
.....
0
r-....
"'-.,
E: 20
E:
I"'-
"'~
.......
2!:."'
~
"'
10
10
' ' "'
10~(T/K}
20
which implies that

A/(cm 3 mol- 1s- 1) = e 28 3 = 2.0 x 10 12
As in Problem 28.1,
6
3
1
27
= Aexptl(:n;m) l/2 = 2.0x 10 m mol-l s- X ( :n;X46X 1.6605x 10- kg )1/2
1
23
23
4N A kT
4 x 6.022 x 10 mol
1.381 x 10 J K -lx 750 K
= 4.0 X 10- 21 m2, or 4.0 X 10- 3 nm 2

4.0 X 10- 3 nm 2
P =-= 0 60
a
. nm 2 =0.007
a*
527
28.3 For radical recombination, Ea = 0. The maximum rate of recombination

is obtained when P = 1 (or more), and then
k2=A
=a*NAC:~t~
112
=4a*NA(::)
112
[~t= tmJ
a* =nd 2 = 7C X (308 X 10- 12 m) 2= 3.0 X 10- 19 m2

Hence,
1.381 x w- 23 1 K -l x 298 K) 112
k2 = 4 X 3.0X 10-19m2X 6.022 X l023mol-l X ( :JCX 15.03 X 1.6605 X 10 27 kg
= 1.7 x 108 m 3mol- 1s- 1= 1.7 x lOu M- 1s- 1
This rate constant is for the rate law
v = k 2[CH3]2
d[CH 3]
----ctt=
- 2k 2[CH3]2
Therefore,
and its solution is

1
1
[CHJ]- [CHJ]o = 2k2t
For 90 per cent recombination, [CH 3] = 0.10 X [CH3]0 , which occurs when
2k2t = [CHJ]o' or t= 2k2[CHJ]o

The concentration of CH3 radicals in a mixture in which the mole fraction is
2 X 0.10/(1 +0.10) =0.18 and the total pressure is pis 0.20p, expressed as a
molar concentration. That is
Therefore,
9RT
t = - - -k2 X 0.40p
9x8.314JK- 1mol- 1x298K

1.7 X 108 m3 mol- 1s- 1X 0.36 X 1.013 X 105 Pa
=3.6 ns
28.4 Draw up t.h e following table for an Arrhenius plot:
528
ere
-24.82
-20 .73
-17.02
-13.00
-8.95
TIK
103/(T/K)
ln(k/s - 1)
248.33
4.027
-9.01
252.42
3.962
-8.37
256.13
3.904
-7.73
260.15
3.844
-7.07
264.20
3.785
-6.55
The points are plotted in Fig. 28.3. The intercept at liT= 0 is +34.8 and the
Fig 28.3
/
;:::-
'"'
g-
"
.s
I
I
J.
_;
37
38
39
t.O
1.1
703/(T/ K}
slope is -10.91 x 103 The former implies that ln(A/s - 1)=34.8 , and hence that
A = 1.3 x 10 15 s- 1 The slope implies that E) R = 10.91 x 103 K, and hence that
Ea = 90.7 kJ mol- 1
In solution
!lH ~ =
11H ~ =90.7
E .. - RT, so at -20 C,
kJ mol- 1 -8.3141 K - I x 253 K= +88.6 kJ mol - 1
For a first-order reaction we write
and hence identify

kT
kl = - etJ.SI ! R e h
llS ~
E) RT
by writing
e =A
e-E) RT
529
and hence obtaining
~S 1 =R{ln (:~) -1}

15 1
}
6.626 x l0 - 34 Jsxl.3xl0 s- )
=8.314JK - ImoJ - I x { In ( 1.381 x l0 2J JK lx 253K
-1
= +37.5 J K - I mol - 1
Therefore,
T ~5 1 = 88.6 kJ mol - 1-253 K x 37.5 J K -I mol - 1
= +79.1 kJ mol- 1
~G 1 = ~H 1 -
28.5
lg k = lg k o + 2AzAz 81 112 with A= 0.509
M-
112.
This expression suggests that we should plot lg k against 1 112 and determine z 8
from the slope, since we know that lzA I = 1. We draw up the following table:
ffM
0.0025
0.0037
0.0045
0.0065
0.0085
(I/M)' '2
lg(k/M - 1 s - 1)
0.050
0.021
0.061
0.049
0.0067
0.064
0.081
0.072
0.092
0. 100
These points are plotted in Fig. 28 .4. The slope of the limiting line is 2.4.
010
Fig 28.4
J
v
0'
.?
/__
0
ODS
006
OD7 OD8
1'12
009
010
Since this slope is equal to 2A zAz 8 x M 112 = 1.018zAz 8 , we have zAzn = 2.4. But
lzAI = 1, and so lzsl = 2. Furthermore , zA and z 8 have the sa me sign because
ZAZB > 0. (The data refer to I - and s2 o~- . )
530
28.6 The work w needed to bring two ions from infinity to a separation
a medium of relative permittivity E, is
w=
z'z"e 2
4.7tE0E,
R '~
R '~
in
[Coulomb potential x charge]
The electrical work is a contribution to the Gibbs function, so

~G '~ = ~G '~ +
z'z"N e 2
A
4.nt: 0 t:,R '~
Since kerr <X e -t.GitRr, the effect of ionic charge is to change kerr to kerr, where
2
(
-z'z"N e )
kerr=kcrrexp ( 4.nt:ot:,R '~~T =kerrexp
-z'z"e
4.nt:ot:,R '~ kT
If z' and z" have the same sign, kerr < kerr; if they have opposite signs, kerr > kerr
because the formation of the complex is favored. Note that the higher the
value of E" the smaller the effect of ionic charge. We shall write the
expression above as
e2
z'z"B
lnkerr =lnkerr - - - , B=
E,
4.7tE0
R '~kT
and plot In kerr (or Ig kerr) against 11 E" expecting to get a straight line with
slope proportional to z'z". We draw up the following tables:
(a) Bromophenol blue; z'z"=(-1)x(-2)=2
E,
60
65
70
75
79
103/E,
lg kerr
16.7
-0.987
15.4
0.201
14.3
0.751
13.3
1.172
12.7
1.401
(b) Azodicarbonate; z'z"=(-2)x(+1)=-2

E,
27
35
45
55
65
79
103/E,
lgkcrr
37.0
12.95
28.6
12.22
22.2
11.58
18.2
11.14
15.4
10.73
12.7
10.34

15
(b)
(oJ
10
13
1\
\
0-5
'
,."
Fig 28.5
~
~
11
1\
\
L
-1{}
11. -~? 16
IC.F'/c,
12
/'
12
-0
531
18
10
10
''
20 _,/ 30
1U/ c,
1.0
The points are plotted in Fig. 28.5 . The lines are reasonably straight and have
slopes with signs appropriate to the activated complex.
a*= {
e
28.7 a
4ns0d(I- Eca)
}2 [Example 28.2]
Taking a=nd 2 gives
Thus, a* is predicted to increase as I- Eca decreases. The data let us

construct the following table :
a */nm 2
Cl 2
Br2
Iz
Na
0.45
0.72
0.77
0.97
0.42
0.68
0.72
0.90
0.56
0.97
1.05
1.34
Rb
Cs
All values of a* in the table are smaller than the experimental ones, but they
do show the correct trends down the columns. The variation with Eea across
the table is not so good, possibly because the electron affinities used here are
poor estimates. Can you find better values to use?
532
28.8
[J] * =k J~ [J]e- k'dt+[J]e-k' [10]
a[J] *
__ = k[J]
e -kr
at
c~~l)
a[J]
+ - e-kr _ k[J]
at
e-kt
J' (aa[J])' e
2
a [J] * _
ax-' - k
e-kr
2
-kl
x-
dt +
(a [J]) -k,
ax-' e
Then, since
we find that
Da:~r =k J~ C!~l) e-k'dt+C!~])
e -kt
=kJ' (a[J]*) dt+ a[J]*

o
at
at
a[J]*
=k[J] * + -
at
which rearranges to eqn 9. When t=O , [J] * = [J], and so the same initial
conditions are satisfied. (The same boundary conditions are also satisfied.)
28.9 Use an integration routine or, failing that, Simpson's rule specified in
Example 22.6. Write z 2 =kx 2/4D, r=kt,j=(A/n 0 )(.nD!k) 11 2 [J] *, and evaluate
28.10
q e '!NA =2 .561 x 10- 2(T!K) 512 (M!g mol - 1) 312
For T = 300 K, M= 50 g mol R
1.027
1
,
q 9 T!NA
(T/K)
= 1.4 x 10
312
q (Non-lmear)=--x (ABC/cm - 3) 112

0
[Box 20.2)
[Box 20.2]

For T=300 K, A =B=C=2 cm- 1, a=2, qR(NL)=900
R .
0.6950
(TIK)
q (Lmear) = -- X (B/cm- 1)
0
[Box 20.2]
For T=300K, B=lcm- 1, a=l, qR(L)=200,

qv = 1 and qE = 1 [Box 20.2]
KkT
k2=h K
['15]
KkT RT N Aij~
= - X - X --e-6.Er/RT (14c) =A e-E,tRT
h
p
qfjq~
We then use
qfj/NA =q fjT/NA= 1.4 X 107 (above)

q~INA= q~Tf N 8 = 1.4 x 10 7
[above]
312
ij~l N A= q~TqR(L)I NA =2 X 1.4 X 107 X 200 = 7.9 X 109
[The factor of 2312 comes from me= mA + m =2m A and q T oc m 312]
8
RT 8.314 J K -
p9
~ekT
mol- 1x 300 K
105 Pa
kT
h =h=
=2.5x10- 2 m 3 mol- 1
1.381 x 10- 23 1 K - I x 300 K

6.626x10-34Js
=6.25 x1012s-l
Therefore,
6.25 X 10 12 s- 1X 2.5 X 10- 2 m3 mol-l X 7.9 X 109

(1.4 X IQ7) 2
=6.3 x 10 6 m 3mol- 1s- 1, or 6.3 x 109 M- 1s- 1
If all three species are non-linear,
qfj/NA = 1.4 X 107 X 900= 1.3 X 1Q 10 =q~/NA

ij~/ N A=2 312 X 1.4 X 107 X 900 = 3.6 X 10 10
6.25 X 10 12 S- 1X 2.5 X 10- 2 m3 mol-l X 3.6 X 10 10

A=
(1.3 X 10 10 ) 2
533
534
Therefore,
A(NL)
3.3 X 104
P= A(L) = 6.3 X 109 5.2 X 10-6

28.11 The structure of the activated complex is shown in Fig. 28.6a . The three
moments of inertia are:
/A = 2mo X (44 pm) 2 = 1.3 X 10- 47 kg m2

la=mH X (68 pm) 2 +2mo X (17 pm) 2 = 9.6 X 10- 48 kg m 2
ic = mH X (68 pm) 2 + 2m 0 X (48 pm) 2 = 2.3 X 10- 47 kg m2
Fig 28.6
The rotational constants are therefore
1.054 x 10- 34 1 s
A= --=-----..,.,....----,--10
1
4ncJA 4n x 2.998 x 10 cms- X/A
2.8 X 10- 46 em -I
(JA/kgml
= 22cm - l
2.8 x 10- 46 cm - 1
B = 9.6 x 10 48
29 cm - 1
C-
2.8X 10- 46 cm - 1
12cm - 1
2.3 X 10 47
Since I(D z) = 2mo X (37 pm) 2 = 21 X 10- 48 kg m2 ' we also have B(Dz) = 31 em Then from Box 20.2,
I.
535
4003/2
q*R = 1.027 X t X (22 X 29 X 12)1/2 = 47
400
qR(D 2) = 0.695 X t X 31= 4.5
The vibrational partition functions are
qv =
1 -e
-~<VIkT for each mode
1
1-e
V/280cm
1.03
[forv=1000cm- 1]
The complex has 2N - 6 = 3 modes, but one is the reaction coordinate and is
discarded. Hence, q*v = (1.03) 2= 1.06. For D 2 itself, qv = 1. The translational
partition functions are
H: q 6 TJ N A= 2.561 x 10- 2 x 400 5' 2 x 1.01 3'2= 8.3 x 104
D: q 6 T!NA=2.3X 105
Complex: q 6 T/NA = 4.3x 105
The electronic partition functions are
qE(H) = 2
[doublet ground state], qE(D 2) = 1
q*E(Complex) = 2
[odd number of electrons, presumably a doublet]
Therefore, bringing all these fragments together with

kT 1.381 X 10- 23 1 K -I X 400 K
8.34 x 10 12 s- 1
h
6.626 x 10- 34 1 s
RT
e=3.28 X 10- 2 m3 mol- 1
gives
8.34 X 10 12 s- 1X 3.28 X 10- 2 m3mol- 1X 4.3 X lOS X 47 X 1.06 X 2
A = --------------~----~------------------4
5
8.3 X 10 X 2.3 X 10 X 4.5 X 1.03 X 2
= 6.6X 10 10 M-IS-I
k=A e-E.IRT = 6.6 X 10 10 M- 1 S- 1 X e-IO.Si
= 1.8 X 106 M- 1 S- 1
536
(The experimental value is about 4 x 105 M- 1 s- 1. )

28.12 The structure of the activated complex is shown in Fig. 28 .6b . The
(one) moment of inertia is [Table 16.1]
mHmo)
(mo) {mH X (96 pm)-, + m
I= -----;;:;- (96 pm + 89 pm? + --;;;
(89 pm)-}
= 3.9 X 10 - 47 kg m2
B=
2.8 X 10- 46 cm - 1
3. 9 X 10- 47
400
qR=0 .6952 x u
[Problem 28 .11] =7.1 cm - 1
[a=1]=39
Since 3N- 5 = 4, there a.re four vibrational modes of the complex, and
counting one as a reaction coordinate gives qv = (1.03) 3 = 1.09. All other
contributions are as in Problem 28.11, which gave 6.6 x 10 10 M - 1 s- 1 . Therefore
39 1.09
A=6 6x 10 10 M- 1 s- 1 x - x --= 5 6x 10 10 M- 1 s- 1
.
47 1.06
.
and hence k should be modified by the same factor (0.85) , to give k=
1.5 X 106 M - 1 S- 1.
28.13 Consider (for example) the following models (in order of complexity).
(1) Collinear attack, varying R(HD) and R(DD) independently. (2) Broadside
attack, varying R(H-D 2) and R(DD) independently . (3) Attack at same
angle to the D-D axis, once again varying bond lengths independently. At
this level of simplicity , you have to modify only the rotational partition
functions in order to go between the various models.
28.14
q; = q;vq; v [y is the direction of diffusion]
q= q;q:q':
[for an atom at the bottom of a well]
For classical vibration, q v = kTI hv. The rate of diffusion is essentially the rate
of change of concentration at a particular region of the surface , -d[x]ldt. This
is also equal to [xpv , and asK; = [xPI[x] we arrive at
d[x]
- dt=v[x]K ;=k 1[x]

Therefore,

k1
537
=vKt=v(~8 (~t) e-pu
where qt and q are the (vibrational) partition functions at the top and foot of
the well respectively. Therefore,
2
kT{(kT/hvt)
kl=h (kT/hv)3
3
v
e-PH=~e-pu
(a) v t =v; k 1 =ve-PtJ.E

k 1 =lOll Hz e -60x IQ.1/R.3 14 x5oo = 5 .4 X 104 s-1
But D =J.. 2/2r=td 2k 1 [Chapter 25, eqn 28]
=+ x (316 pm) 2 x 5.4 x lif s- 1= 2.7 x 10- 15 m 2 s- 1
(b) vt =+v; k 1 =4ve-PtJ.E =2.2x 10 5 s- 1

D = 4 X 2.7 X w- 15 m 2 s- 1= 1.1 X w-14 m 2 s- 1
kT qt
k 1 =-x-e-PtJ.E [Problem 28.14]
h
q
28.15
1.027
(T/K) 312
qR=-- X(B/cm- 1) 312
0
[Box20.2, A = B=C]
=80
q=q':q:q-:=(:83
Therefore,
=4x 106 s- 1
Consequently,
D=80 X 2.7 X 10- 15 m 2 s- 1=2 X 10- 12 m 2s- 1 if vt=v
and 8 X 10- 12 m 2s- 1 if vt=tv.
28.16 The change in intensity of the beam, d/, is proportional to the number
of scatterers per unit volume, .N,, the intensity of the beam, I, and the path
538
length dl. The constant of proportionality is defined as the collision cross

section, a. Therefore,
di = - aN,! dl, or d In I = -aN, dl
If the incident intensity (at I= 0) is I 0 and the emergent intensity is I, we can
write
I
lnori=I
e -ox,t
l o=- aNI
s ,
-----"-o_ _
28.17 It follows that, since N, and I are the same for the two experiments ,
a(CH2F2)
a(Ar)
In 0.6
In o.g
[Problem 28.16]
=5
CH 2F2 is a polar molecule; Ar is not. CsCI is a polar ion pair and is scattered
more strongly by the polar CH 2F 2 .
29. Processes at solid surfaces

Exercises
29.1
3.51 X 1022 X (piTorr)

2 1
Zwl(cm - s- ) = {(T/K) X (Mig mol - ')}"2 [1]
2.03
10 21X (piTorr)
(T=298 K]
Hence, we can draw up the following table:

H2
C3Hs
Ml(g mol- 1)
2.02
44.09
Zwl(cm - s- 1)
(i) 100 Pa
(ii) 10- 7 Torr
1.1x102'
1.4Xl0 14
2.3 X 1020
3.1 X 10 13
29.2
[100 Pa = 0.750 Torr]
{Zwl(cm - 2 s- 1)} X {(TIK) X (Mig mol - 1)} 112

piTorr=
3.51 x 1022
{Zwl(cm - 2s - 1)} X (425 X 39.95) 112
3.51 X 10 22
=3.71 x 10 - 21x Zwl(cm- 2s - 1)
The collision rate required is

4.5x10 20 s- 1
_
Zw= nx (0.075 cm)z=2.55 x 1022 cm -2 s- '
Hence p = 3.71 x 10- 21x 2.55 x 1022 Torr=94 Torr
35 X 760 )
-3.51 X 1022 X ( 1.0133 X 105
29.3
Zw-
(80X4.00)"2
- 2
em
- I
[1, p converted to Torr]
Processes at solid surfaces
540
w-
w-
10 m) 2= 6.52 X
20
The area occupied by a Cu atom is t X (3.61 X
m 2 [in
an fcc unit cell , there is the equivalent of two Cu atoms per face]. Therefore ,
20
rate per Cu atom= 5.2 X 1024 m - 2 s- 1X 6.52 X
m2
=3.4 x 105 s- 1
w-
29.4 The entropy of adsorption is typical of chemisorption [Table 29.2]. The

residence lifetime is
fl /2
1:o e E,.f RT
[10]
= 1 X 10- 14 s X ei20x i0318.3 J4 x400
(E.= -L'l.Had)
= 50s
29.5
f 112 =
[10]
1: eE,I RT
0
8.314JK - 1mol - 1x ln -0.36)

( 3.49
R In(t; ,21t 112)
E.= (1
1) =-------1-----1--~~
T'
2548 K
2362 K
= 610 kJ mol - 1
u=t 112 e -E,t RT = 3.49 s X e -6JO xJ0318.3 J4x2362 =0 . 11 ps
R in(t; 121t 112 )
29.6
(~-!_)
E, =
T'
with
E, =
r;,2/t112 = 1.35
8.314 J K -I mol- 1x In 1.35
(
29.7
[Exercise 29 .5]
(} =
60~
1
1
K -1000 K)
:~p
=3 .7kJmol - 1
[2], which implies that
0.15
1
(a) P = 0.85 x 0.85 kPa - J 0.21 kPa
0.95
(b) p = 0.05
1
0. 85 kPa - 1 22 kPa
p C~ (}) ~
=
which solves to
K = (m 1p 2/m 2p 1) -1
Pz - (mJpzl mz)
mJ) (Pz)
p; -1
(~
mJ)
1- (mz
1
X Pz
0.44 3.0
-X--1
0.19 26.0
1
0.44
x3.0kPa =0.19kPa - l
1
-0.19
Therefore,
0.19 kPa X 26.0 kPa
1
e =1+0.19kPa 1X26.0kPa= 0 83
0.19 X 3.0
82 = 1 + 0.19 x 3.0 = 0 36
29.9
tJ /2
= ro eE)RT
[10] = 10- 13s X e)( 2AH kJ mo J- I)
[at 298 K]
(a) Ea= 15 kJ mol - 1, t 112 = 10- 13 s X e605 =4 x 10- 11 s

(b) Ea=150kJmol - 1, t 112 =10 - 13 sxe 605 =2 x10 13 s
The latter corresponds to abo ut 600 000 y. At 1000 K, t 112 = 10- 13 s x
e,18.314 kJ moJ- I
(a) t 112 =6x10 - 13 s, (b) t 112=7x10- 6 s
29.10
Kp
8=-1+Kp
e 1
[2], which implies that K= _ xp1 8
But InK'= t'l.H(2_-~)

K
T'
[van 't Hoff equat ion]
541
542
1
Since () at the new temperature is the same, K ex- and
In_= !lH(~-~)
R
p'
T'
- 10.2kJmol (
1
1 )
=8.314JK- 1 mol _ 1 x 298K-313K
=
-0.197
which implies that p' = 12 kPa x e 0 197 = 14 kPa

29.11 (a) On gold, () = 1, and v=k()=constant, a zeroth-order reaction. (b)
On platinum, () = Kp (as Kp ~ 1) , so v = kKp , and the reaction is first-order.
29.12 (a) For adsorption without dissociation ,
Kp
. .
.
1
1
() = 1 + Kp ' which Implies that = 1 - Kp
and a plot of () against 11p should give a straight line.

(b) For adsorption with partial dissociation ,
(Kp) lt2
() =
1 + (Kp) 112 [3], which implies that
e= 1 + (Kp) 112
and a plot of () against 1/p 112 should give a straight line.

(c) For adsorption with complete dissociation ,
(Kp)l t3
() =
[by the same argument that led to eqn 3]
1 + (Kp)l t3
which implies that
e= 1 + (Kp)l'3
and so a plot of 1/() against 1/p 113 should give a straight line. In each case we
could rearrange the expressions into
p"
1
-() =p" +K"
[n = 1, .l2,
.l]
3

p" p"
1
or v=vo+voK"
and plot p"/V against p" , to expect a straight line .
29.13 Rate of adsorption of A= kaAP AN(l- (}A- es)

Rate of desorption of A= kctAN(} A
At equilibrium , the rates are equal, and so
kaAPAN(l- (}A- (}B)= kctAN(}A
Similarly for B:
k .sPsN(l- (}A- (}B)= k ctsN(}s
Solve this pair of simultaneous equations, writing

k.A
k.s
KA=-k 'KB = -k
dA
dB
which gives
(}A=
KAPA
}+
KsPs
(}B=-----KAPA + KsPs'
1 + KAPA + KBP B
is required .
Kp
K'p'
(}= 1 + Kp and(}'= 1 + K'p '
29.14
but (} = (}', so
Kp
K'p'
l+Kp
1+K'p'
-=--
which requires Kp = K'p' . We also know that

11H~=RT
a InK)
( iJT 8
[4]
and can therefore write

9
!1H.d-RT
2 (ln
K' -InK)_ RT 1n(K'IK)

T'-T
T'-T
RT 2 1n(plp')
4.8)
8.314 J K - I mol - 1 x (220 K) 2 X In TI
(
T' - T
60K
= -13 kJ mol - 1
543
544
29.15 The desorption time for a given volume is proportional to the half-life
of the adsorbed species, and as
(112 = To eEiRT
(10]
we can write
R ln(tlt')
(!__~)
T T'
T T'
where t and t' are the two desorption times. We evaluate Ea from the data for
the two ranges of temperature:
8 .314 J K - I mol- 1
27
1
Ea =
X In 2= 650 kJ mol 1
1
( 1856 K- 1978 K)
8.314JK - 1 mol - 1
2
1
) X In _ =700 kJ mol 03
1
1
( 1978 K 2070 K
To one significant figure , these values correspond to 700 kJ mol- 1
We write
t =to e7oo x IQ3/8.314 x 1856 = to.X 5 _03 X 1019
Therefore, since t = 27 min, to = 5.4 X 10- 19 min. Consequently ,

(a) At 298 K,
t=
5.4 X 10- 19 min
e700 xiQ3/8.314 x298 =2 X 10104 min
which is just about for ever.

(b) At 3000 K,
t= 5.4x 10- 19 minx e 700 x 1Q3' 8-314x298 = 8 x 10 - 7 min,
which corresponds to 50 Jl-S.
29.16 The rate of the reaction appears to be independent of the pressure of

ammonia, so the reaction is zeroth order. Check this by writing
545
and verifying that !!.pit is a constant , where !:!..p = p 0 - p.

8 kPa
(i) !!.pit=-= 16 Pa s- 1
500 s
(ii) !!.pit=
15 kPa
1000
s = 15 Pa s- 1
The two values are essentially the same , and k = 16 Pa s- 1 A zeroth-order

reaction occurs when the gas pressure is so high that the same amount of
adsorbed species is always present whatever the pressure (that is, () is constant
even though p varies).
Problems
29.1 Refer to Fig . 29 .1. The (100) and (110) faces each expose two atoms,
Fig 29. 1
(111)
~oYI3/2!
and the (111) face exposes four. The areas of the faces of each cell are (a)
(352pm) 2 =1.24xl0 - 15 cm2, (b) V2 x (352pmf=1.75xl0 - 15 cm 2 , and (c)
V3 x (352 pm? = 2.15 x w - ls cm 2. The numbers of atoms exposed per square
centimeter are therefore
(a) 2/1.24X l0- 15 cm 2 = 1.61 X 10 15 Cm - 2
(b) 211.75 X lO -
IS
cm 2 = 1.14 X 10 15 cm - 2
(c) 4/2.15 X 10- 15 cm 2 = 1.86 X 10 15 cm - 2

For the collision frequencies calculated in Exercise 29.1, the frequency of
collision per atom is calculated by dividing the values given there by the
546
number densities just calculated . We can therefore draw up the following

table:
Propane
Hydrogen
Z/(atom- 1 s- 1)
100 Pa
10- 7 Torr
100Pa
10- 7 Torr
(100)
(110)
(111)
6.8 X 105
9.6 X 105
5.9 X 105
8.7 x 10- 2
1.2 x 10- 1
7.5 x 10- 2
1.4 X 105
2.0 X 105
1.2 X 105
1.9 x 10- 2
2.1 x 10- 2
1.1 x 10- 2
29.2 Refer to Fig. 29.2. The (100) face exposes one atom per unit cell, and
the (110) and (111) faces expose about two. The areas of the three types of
face are (a) (316 pm) 2 = 9.99 x 10- 16 em\ (b) V 2 x (316 pm) 2 = 1.41 x 10- 15 cm 2 ,
and (c) V3 x (316 pmf = 1.73 x 10- 15 cm 2 . The number densities of exposed
atoms are therefore
(a) 1/9.99 X 10- 16 cm 2 = 1.00 X 10 15 cm - 2
(b) 2/1.41 X 10- 15 cm 2 = 1.41
10 15 em - 2
(c) 2/1.73 X 10- 15 cm 2 = 1.16 X 10 15 cm - 2

and the average number exposed is t (1.00 + 1.41) x 10 15 cm - 2 =
1.20 x 10 15 cm - 2 By the same procedure as in Problem 29.1, we draw
547
Propane
Hydrogen
Z/(atom- 1 s- 1)
100 Pa
10- 7 Torr
100 Pa
10- 7 Torr
(100)
(110)
(111)
1.0 x lOh
7.8 X 105
9.5 X 105
1.4x10- 1
1.0 x 10- 1
1.2 x 10- 1
2.3 X 105
1.6 X 105
2.0 X 105
3.lx10- 2
2.2 x w-2
2.1 x 10- 2
29.3 We draw up the following table:
p/Torr
0.19
0.97
1.90
4.05
7.50
11.95
4.52
5.95
8.60
12.6
18.3
25.4
pi VA is plotted against pin Fig. 29.3. The low-pressure points fall on a

25
/
20
'7
E 15
t::
~ 10
-:,.0
"
,....
#-""
Fig 29.3
-- --
~~
8
p/ Torr
10
12
straight line with intercept 4.0 and slope 2.1. It follows that 1IV~=
2.1 Torrcm - 3/Torr=2.1 cm - 3 , or V~ =0.48cm' and 1/KV~=4.0Torrcm - ' .
Therefore ,
K=
4.0 Torr em ' x 0.48 cm 3
1
(c-1)z
p
)V= - v + - - [6], z=-;
1-z
c mon
cVmon
p
z
29.4
0.52 Torr- 1
548
Processes at soiid surfaces
We therefore draw up the following tables:

(a) 0 ac, p* = 3222 Torr
p/Torr
105
282
492
594
620
755
798
103z
32.6
87.5
152.7
184.4
192.4
234.3
247.7
103z
(1- z)(V/cm 3)
3.04
7.10
12.1
14.1
15.4
17.7
20.0
(b) 18 C, p* = 6148 Torr

piTorr
39 .5
62.7
108
219
466
555
601
765
103z
6.4
10.2
17.6
35 .6
75.8
90.3
97.8
124.4
10 3z
(1- z)(V/cm 3)
0.70
1.05
1.74
3.27
6.36
7.58
8.09
10.08
The points are plotted in Fig. 29.4, but we analyze the data by a least-squares
(a)
(b)
20
Fig 29.4
10
[.."
/
17
v .
jo/
..v
l7
IY
l,.Af'
01
02
v
v
0
0
ODS
procedure. The intercepts are at (a) 0.466 and (b) 0.303 . Hence,
1
- V = (a) 0.466 X 10- 3 cm - 3 , (b) 0.303 X 10- 3 cm - 3

C
mon
010
549
The slopes of the lines are (a) 76.10 and (b) 79.54. Hence,
c-1
-v =(a) 76 .10x 10- 3 cm 3 , (b) 79.54x 10- 3 cm - 3
C
mon
Solving the equations gives

c-1 =(a) 163.3, (b) 262.5
and hence
c= (a) 164.3, (b) 263.5

vmon=(a) 13.1cm3 , (b) 12.5cm3
29.5 For
v. = c p c'
11
[9], In
v. =In c +-In p.
1
To test the Freundlich
c2
isotherm , we plot In v. against In p, and to test the Langmuir isotherm, we

plot p!V. against p. Draw up the following table:
p!Torr
100
200
300
400
ln(p/Torr)
ln(V.fcm 3)
(p/V.)/(Torrcm- 3)
4.61
4.58
1.03
5.30
4.97
1.39
5.70
5.20
1.65
5.99
5.37
1.87
The points are plotted in Fig. 29.5 . The Freundlich isotherm (a) gives a
(b)
(a}
55
Fig 29.5
20
I/
~
5
ln{p!Torr}
)v
II
/
45
4
10
100
200
300
4 00
piTorr
significantly better straight line, and so gives the better representation of the
data.
550
29.6 We repeat the analysis specified in Problem 29.5, and begin by drawing
p!Torr
100
200
300
400
500
600
ln(p/Torr)
ln(V)cm 3)
(p!Va)I(Torr cm - 3)
4.61
-2.04
769
5.30
-1.90
1330
5.70
-1.80
1850
5.99
-1. 82
2410
6.21
-1.74
2860
6.40
-1.71
3330
The points are plotted in Fig. 29 .6. The Langmuir isotherm (b) gives a better
(b)
(a}
.,.,
-1-7
./
Fig 29.6
/.
./
.//
fl"
-21
1.5
./
/""
-20
55
0
65
100
In (p/Tarr)
200
300
1.00
500
p /Tarr
straight line and so is a better representation of the data. From that plot we
find an intercept at 297 and a slope of 5.1. It follows that 1/V~= 5.1 cm- 3 and
hence that V~=0.20cm 3 Since 1/KV~ =297Torrcm- 3 ,
1
K = 297Torr em -J x 0 .1 96 em3
0.0172Torr- l
Since V~= 0.20 cm 3 (at STP), the number of molecules adsorbed is

p V~
N=
k~
1.0133 X 105 PaX 0.20 X 10- 6 m3

= 1.381 x w- 23 1 K -I x 298 K
4 8 x 10 lM
The total area of the sample is 6.2 x 10 3 cm 2 = 6.2 x 10 17 nm 2 , so the area

occupied by each molecule is
551
a=
6.2 x 10 17 nm~
4.8 x lQIH = 0.13 nm2
When the pressure is 1 atm, corresponding to 760 Torr,

Kyo
'
= ()V0 =~
''
1+Kp
0.017:2 Torr- 1 x 760 Torr x 0.20 cm 3
-----,----,-~---,--------- =
1 + 0.0172 Torr - 1 x 760 Torr
0.19 cm1
29.7 For the Langmuir and BET isotherm tests we draw up the following
table (using p * =200 kPa = 1500Torr):
p/Torr
100
200
300
400
500
600
(p/Y;,)/(Torr cm - 3)
103z
103z
5.59
67
6.06
133
6.38
200
6.58
267
6.64
333
6.57
400
4.01
4.66
5.32
5.98
6.64
7.30
(1- z)(V/cm 3)
p!V. is plotted against pin Fig. 29.7a, and 103z/(1-z)V is plotted against z in
Fig 29.7
(b)
(3)
70
80
..........
II
.,
!-"
./
40
/
5{)
100
200
300
400
500
600
01
03 z 0 4
p/ Torr
Fig. 29.7b. We see that the BET isotherm is a much better representation
of the data than the Langmuir isotherm. The intercept in Fig. 29.7b is at
552
3.33 X w- 3 , and so 1/cVmon= 3.33 X

and so
w-) cm - 3 .
The slope of the graph is 9.93,
c-1
--=9.93 X 10- 3 cm- 3
cVmon
Therefore, c -1 = 2.98, and hence c = 3.98, Vmon= 75.4 cm 3 .
8=c 1p 11cz [9].
29.8
We adapt this isotherm to a liquid by noting that w. ex:(} and replacing p by

[A], the concentration of the acid. Then w.=c 1[A] 1'cz (with c~> c2 modified
constants) , and hence
1
lg w. =lg c 1 +-X lg(A]
Cz

(A]/M
0.05
0.10
0.50
1.0
1.5
lg((A]/M)
lg(w.fg)
-1.30
-1.40
-1.00
-1.22
-0.30
-0.92
-0.00
-0.80
0.18
-0.72
These points are plotted in Fig. 29.8a. They fall on a reasonably straight line
(a)
(b)
1"!.
06
05
1/
l.'
20
~"'15
~
./
10
J
5
0
Fig29.8
25
-05
-1{)
lg ([A]/M)
-1-5
II
0
10
20
1/([A]/M)
with slope 0.42 and intercept -0.80. Therefore, c2 = 110.42 = 2.4 and c 1 = 0.16.
(The units of c 1 are bizarre: c 1 = 0.16 g mol- 0 42 dmL 36 .)
553
The test of the Langmuir isotherm begins by adapting the gas-ph ase
adsorption isotherm to
K [A]
w=
" 1+K[A]
and arranging it into the form
-=1+-w,
K[A]
[A jiM
0.05
0.10
0.50
1.0
1.5
1/([Aj/M)
ll(w)g)
20
25
10
2.0
8.3
1.0
6.3
0.67
17
5.3
The points are plotted in Fig. 29.8b. The points do not fall on such a good
straight line, so we conclude that the Freundlich isotherm is a better
representation of the data than the Langmuir isotherm.
Kp
1
29.9 8 = - - and 1- 8 = - 1+ Kp
1+Kp
For a strongly adsorbed species, Kp 'P 1 and 1- 8 = 11 Kp. Since the reaction
rate is proportional to the pressure of ammonia and the fraction of sites left
uncovered by the strongly adsorbed hydrogen product, we can write
dp(NH3) = -k (NH )( _ ) = _ kcp(NH3)
1 8
dt
cP
3
Kp(H z)
To so lve the rate law , we write
p(Hz) = H po(NH3)- p(NH3)}
[NH3-
t Nz + -}H z]
from which it follows that, with p = p(NH 3),
-dp
kp
2kc
- - - - k=dt
p 0 -p
3K
This equation integrates as follows:
P (
I'll
Po)
p
1-- dp=k
J'
ll
dt
554
or
P - Po= k +Po
t
In!!_
Po
We write
and obtain
G =k+F
Hence, a plot of G against F shou ld give a straight line with intercept k at

F = 0. Alternatively, the difference G- F should be a constant, k . We draw up
tis
30
60
100
160
200
250
p/Torr
G/(Torr s- 1)
FI(Torr s- 1)
(G-F)/(Torr s- 1)
100
88
-0. 40
- 0.43
0.03
84
- 0.27
-0.29
0.02
80
-0.20
-0.22
0.02
77
-0.14
- 0.16
0.02
74
- 0.13
-0.15
0.02
72
-0.11
-0.13
0.02
Thus, the data fit the rate law , and we find k = 0.02 Torr s- 1
-dp
kp
29.10 dt=kcp(1 -8)= +Kp'
1
[Problem29.9]
where p = p(NH 3) and p' = p(H 2). For the reaction A-? B + C , p denotes p(A)
andp' denotesp(B) , butp ' =p 0 -p [from the stoich iometry]. Therefore ,
dp
kp
dt
1 + Kp 0 - Kp
and
P {
(1 Kp
+ -) } dp=
K- -
p
The integration leads to
Po
(p - Po)K - (1
and we write
+ Kp 0 )
I'
kdt=kt
In(!!_)
= kt
Po

F=
555
(Po)t In(!!_)
, G =p-t Po
Po
and hence obtain
1 + Kpo)
KG- - - F=k
( Po
and hence
(l+Kpo)
k
G=-+
-- F
Kpo
Therefore, by plotting G against F, we should get a straight line with intercept

k/ Kat F= 0 and slope 1 + 11 Kp 0 We draw up the following table:
tis
315
750
1400
2250
3450
3150
piTorr
F/(Torr s- 1)
G/(Torr s- 1)
95
85
-0.034
-0.032
75
-0.030
-0.027
65
-0.026
-0.021
55
-0.023
-0.018
45
-0 .021
-0.014
35
-O.Q18
-0.012
These points are plotted in Fig. 29.9. The extrapolated intercept lies at 0.013,
0.03
0.02
.Av
-I 0.01
"'t:
~
"
(::5
/
!"-
/
/
-0.01
-0.02
/
0
0.01
0.02
0.03
-F/Torr s-
and so k/ K = 0.013 Torr s- 1 The slope is 1.32, and so

l+Kp 11
--=1.32
Kpo
Fig29.9
0.04
556
Therefore , Kp 0 =3 .13 . Asp 0 =95Torr, K=0.033Torr- 1. Combining this

result with the value of k/ K obtained from the intercept gives k = 4.3 x
w-4s-l.
29.11 Refer in Fig. 29.10. Evaluate the sum of llr; , where r; is the distance
Fig29.10
+
+
-4
....
-4>-
:'<"
'
'------ c ___
__JL
J '-----
E ------'
from the ion i to the ion of interest , taking + 1/ r for ions of l ik~ charge and
-1/r for ions of opposite charge . The array has been divided into five zones.
Zones Band D can be summed analytically to give -In 2 = -0.69. The
summation over the other zones , each of which gives the same result , is
tedious because of the very slow convergence of the sum . Unless you make a
very clever choice of the sequence of ions (grouping them so that their
contributions almost cancel) , you will find the following values for arrays of
different sizes:
I0 X I 0
20 X 20
50 X 50
100 X 100
200 X 200
0.259
0.273
0.283
0.286
0.289
The final figure is in good agreement with the analytical value, 0.2892597 . ..
557
(a) For a cation above a flat surface, the energy (relative to the energy at
infinity, and in units of e 2/ 4:rre) is
Zone C + D + E = 0.29-0 .69 + 0.29 = -0.11
which implies an attractive state .
(b) For a cation at the foot of a high cliff, the energy is
Zone A+ B +C+ D + E=3 x 0.29+2 x (-0.69) = -0.51
which is significantly more attractive. Hence , the latter is the more likely
settling point (if potential energy considerations such as these are dominant).
29.12
kK p K p
A
(1 + KAPA + KaPs)
(14]
and we interpret vas -dpA!dt. We make the substitutions

[pA(O) =ps(O)= p, A+ B~PJ
PA =p -x, Ps= p -x
and write
A = kKAK 8 , B = 1 + Kp , K = KA+ K 8 , then the equation to solve is

dx
A(p-xf
dt
(B- kx) 2
and hence
' A dt--Ix(B-Kx)
( -x ) dx
P
I
2
We use
I
I
dx
1
(p-x)2= p-x + C
xdx .
p
(p-x) 2 p-x +ln(p- x)+C
x(x-2p)
---+2pln(p-x)+C
x-p
558
Hence
1
At = 8 2 {---~} -28K{__-l +In

p- x p
p-x
(x-p)}
-p
(x-p)}
+K-'{x(x-2p) +2p In - x-p

-p
(p -
x8
x
x) }
28K { --+In
-p(p-x)
p-x
p
+K
r<:=;> +2pln(p~x)}
(p(px_ x)) {8
28Kp + K p(2p- x)}
+2(pK 2 - 8K) In ( p - x)
Now substitute 8 = 1 + Kp and obtain
At = p~(-x-)
+ K x+2K In(_____)
p-x
p-x
2
For p = 1, KA=K8 =1, A =k we find

X
kt=--+4x-41n(1- x)
1- x
which is plotted in Fig. 29 .11 .
1-0
0-5
vv
I-- 1--
Fig 29.11
!---
'/
J
v
0
I
0
I
8
12
16
18 kt
20
559
and the reaction rate is
We write k = k'c 1K 112 , and the reaction rate is then

kpV2P~2
u = 1 + K 112PV2
When (KpF) 1 12 ~ 1, u =
k)l/2
(K p~
and the rate is independent of PF
29.14 Refer to Fig. 2.12. Let the number density of atoms in the solid be N.
Then the numbe r in the annulus between rand r+ dr and thickness dz at a

depth z below the surface is 2n.N" r dr dz. The interaction energy of these atoms
and the single adsorbate atom at a height R above the surface is
-2n.N"rdzC6
dU={( R+z)-, + r-'}1
560
if the individual atoms interact as -C6/d 6 , with d 2 = (R + z) 2 + r 2 The total

interaction energy of the atom with the semi-infinite slab of uniform density is
therefore
U =-2n.NC6
oo
dr
J0
J oo
0
r
dz{(R+z?+r 2P
We then use
oo
f oo
rdr
dr
o (a2+r 2)3
f o (a2+r 2)J= t
f oo
dx
_ 1
o (a 2+x)3- 4a4
and obtain
oo dz
-n.NC6
U = - t n.NC6 o (R+z)4= 6R 3
This result confirms that U oc 11 R 3 . [A shorter procedure is to use a

dimensional argument, but we need the explicit expression in the following .]
When
v = 4 { (~)
12_ (~) 6} = C12 _ C6
R
R
R 12 R 6
we also need the contribution from C 12 :
oo f oo
r
U'=2n.NCI2 f o dr o dz {(R+z)2+r2}6
1
= 2Jr.NCI2 X 10
f oo
dz
o (R + z)IO
2Jr.NC12
90R9
and therefore the total interaction energy is
2n.NC 12 n.NC6
U = 90R 9 - 6R 3
We can express this result in terms oft and a by noting that
cl2 = 4ta 12 and c6= 4ta 6 ' for then
For the position of equilibrium, we look for the value of R for which
dU/dR=O:
a9
a3
Therefore, 10R 10 = R 4
4
which implies that R = (~- ) 1 1 6 a= 0.858a. For a= 342 pm, R=294 pm.
29.15 A general change in the Gibbs function of a one-component system

with a surface is
dG=
-s dT + v dp +y da+JA. dn
Let G = G(g) + G(a) and n = n(g) + n(a); then

dG(g) = -S(g) dT + V(g) dp + JA.(g) dn(g)
dG(a) = -S(a) dT + y da+ JA.(a) dn(a)
At equilibrium, JA.(a) = JA.(g) =fl. At constant temperature, dG(a) = y da +

fl. dn(a) . Since dG in an exact differential, this expression integrates to
G(a) = ya+ JA.n(a)
Therefore,
dG(a) =a dy + y da+ fl. dn(a)
+ n(a) dfl.
But since
dG(a) = y da+ fl. dn(a)
we conclude that
ady+ n(a) dJA. = = 0
Since dfl. = RT dIn p, this relation is equivalent to

n(a)=- ady =-_!!__(~)
dfl.
RT dlnp
Now express n(o) as an adso rbed volume using

p e v.
n(a)= RTe
and express dy as a kind of chemical potential through

RT 9
dfl., = ----e dy
evaluated at a standard temperature and pressure (T 9 and p 9 ), then
-if(~)=v.
561
562

d,ul = -c2
29.16
(Ra~ dV.
which implies that
~- - c2RT( dV. )
a
d lnp
dlnp
However, we established in Problem 29.15 that

d,u l
-RTV.
--=- -
d Jnp
Therefore,
RT) ( dV. ) -RTV"
- c2 ( --;- d Jnp = -a- ' or c2 dIn V,, = d Jnp
Hence
dIn V~2 = dIn p , and therefore V,, = c 1p 11cz
29.17
1 + Kp '
f)
p=
K(1- 8)
dp
dV" =
v..v~
f) = __!_ f) =
v.
K(V.~ -
V.)
v.
RT)
( a
v. d In p = --RT
- va dp
pa
v~
K(V~ - V..) + K(V.~- V.f K( V~ - V,,) 2
d,u I = = _
(RT)
a
{K(V~ - V,,)}
Va
{
V~
}
V" K(V ao-V)2
dV.
a
(RT) V~dV,,
a (V. - V,,)
Therefore, we can adopt any of several forms,
= _
I=_ {RT/a)V.~}
~-~
0
=- {(
d~
= _
{(RT/a)}
1 -f)
0
d~
RTV !a) }
RTV
'
dfJ = - -' d ln(l- 8)
1- f)
a
30. Dynamic electrochemistry

Exercises
lnj=lnj0 +(1- a)f17
30.1
In~= (1 -a )f( 17' -
1
an overpotential
[14a,f=FIRT]
17), which implies that for a current density j' we require
ln(j'/j)
17'=17+(1 -a)f
125
138 mY
mY+(1-0.39) x (25.69mV) 1
30.2 j 11 =je - (l -allf [I4a]
= 55.0 rnA cm -2 X e-ll.nlX 12) mVm.n<l mV

=2.8 mAcm - 2
zFDc
(19)
6
30.3 j L= --
eRn
zFo
(Example 30.4]
2.5 X 10-1 M X 25 .69 X J0 - 3 V X 61.9 S cm 2 mol - 1

0.40 X 10 - 3 m
=9.9
V S cm 2mol- 1m- 1
=9.9 mol m- 3 X 10 3 XV Q - 1X 10 - 4 m2 mol - 1m- 1
30.4 L=e(l- a)f-l_e-"1'1 (II]

]o
=el!J-e-YJ
=2sinh(1f17)
[a=0.5]
[ si nhx= e' - e -']
2
564
Dynamic electrochemistry
and we use tfrJ =
+x 25 _69rJ mY = 0.01946(ry/mY)
The resulting graph is shown in Fig. 30.1.
50
Fig 30.1
j/jo
' -1'--
r.....
1/
v
'\
1\
so
0
-100
30.5 j=2j0 sinh(tfry)
7J/mV
r.JO
[Exercise 30.4]
2
= 1.58 rnA cm - x sinh(0.01946ry/mY)

(a) ry=lOmY
j = 1.58 rnA cm - 2 x sinh 0.1946 = 0.31 rnA cm- 2
(b) rJ = 100 mY
j = 1.58 rnA cm- 2 x sinh 1.946=5.41 rnA cm- 2
(c) rJ = -0.5 Y
j= 1.58 rnA cm- 2 x sinh( -9.73)=8300 rnA cm - 2
30.6
I= jS = 2joS sinh(0.01946ry/mY)
[Exercise 30.4]
,
. {0.01946(- 8 )}
=2X2.5mAcm--xl.Ocm 2 Xsmh
mY
= 5.0 rnA X sinh{0 .01946(- 8 )/mY}
[The zero-current cell potential is 8 when the ions are at unit activity.] We
can then draw up the following table:
565
/mY
500
600
700
771
800
900
1000
II I/rnA
487
69 .5
9.32
2.97
30.6
215
30.7
RT a(Fe 3 +)
E = 6 +FIn a (Fez+ )
[Nernst equation]
a(Fe 3 +)
/mY = 771 + 25.7ln a(Fez+ )
aFe 3 +)
1JimV = 1000- /mY = 229 - 25.7ln - (
2 +)
a Fe
and hence
I- 2joS sinh(0.019461]/mV)
3
a(Fe +)}
= 5.0 rnA x sinh{4.46- 0.50 In a(Fez+ )
III/rnA
0.1
0.3
0.6
1.0
3.0
6.0
10.0
684
395
278
215
124
88
68.0
The current falls to zero when

a(Fe 3 +)
4.46 = 0.50 In a(Fe 2 +)
which occurs when a(Fe 3 +) = 7480 x a(Fe 2 +).
30.8
I= 2JoS sinh(0.019461Jim V)
1J = 51 .39 mY x sinh-
= 51.39 mV x sinh- 1
[Exercise 30.4]
( 2~ 5)
20mA
)
,
( 2 x 2.5 rnA cm- 2 x 1.0 em-
= 51.39 mV x sinh- 1 4.0 = 108 mV .
566
30.9 The current-density of electrons is ju/e because each one carries a charge
of magnitude e. Therefore,
(a) PtjH 2jH +;j0 =0.79mAcm - 2 [Table 30.1]
0.79 mAcm - 2
1= 1.602 X 10- 19 C=4.9 X 10" cm -2 S- 1
(b) Pt IFel+ , Fe 2 +; j 0 = 2.5 rnA em - 2
2.5 rnA cm - 2
1 = 1.602 x 10 19 C = 1.6 x 1016 cm -2 s-1
(c) PbjH 2jH +;j0 =5.0 x 10- 12 Acm- 2
5.0 X 10- 12 A cm - 2
1= 1.602 x 10-19C =3 .1 x 107cm - 2s - l
There are approximately 1.0 cm 2/(280 pm) 2 = 1.3 x 10 15 atoms in each square
centimeter of surface. The numbers of electrons per atom are therefore
3.8 s- 1, 12 s- 1, and 2.4 x w-x s- 1 respectively. The last corresponds to less
than one event per year.
RTj
30.10
YJ =-F.
]o
[13]
which implies that

Sj0F)
l=Sj= ( RT YJ
An ohmic conductor of resistance r obeys YJ = lr , and so we can identify the

resistance as
RT 25.69 x 10- 3 V
r= Sj0 F= l.Ocm 2 Xjo
25.69 x
w-' Q
(UA cm - Z:,
[1 V= 1 A Q]
(a) PtjH 2 jH +;j0 =7.9 x 10- 4 Acm - 2
w-
3
Q
25.69 x
r=----,-4
7.9 x 10 -
33Q
(b) HgjH2IH +; jo= 0.79 x 10 - 12 A cm - 2

r=
25.69 x w- 3 Q
_ x _
0 79 10 12
3.3xl0 111 Q,or33GQ
567
30.11 For deposition of cations, a significant net current towards the

electrodes is necessary. For copper and zinc, we have 6 = 0.45 V and
-0.76 V respectively. Therefore, deposition of copper occurs when the
potential falls below 0.34 V and continues until the copper ions are exhausted
to the point that the limiting current density is reached. Then a further
reduction in potential to below -0.76 V brings about the deposition of zinc.
30.12 Take y = 1. The deposition of copper and zinc will occur when E is
less than 0.34 V and -0.76 V respectively. When the concentrations are
0.010 M, the electrode potentials that must be overcome are reduced by
(RT/2F) In 0.010 = -0.06 V, and the deposition potentials for copper and
zinc are respectively 28.0 V and -0.82 V.
30.13 Hydrogen evolution occurs significantly (in the sense of having a
current density of 1 rnA em - 2, which is 6.2 x 10 15 electrons em - 2 s- 1, or 1.0 x
2
w -K mol em - s - I, corresponding to about 1 cm.1 of gas per hour) when the
overpotential is -1 Y. Since E= 6 + (RTf F) In a(H +) =-59 mY x pH , this
rate of evolution occurs when the potential at the electrode is about
-1.06 V = -1 V (when pH = 1) . But both Ag + ( 9 = 0.80 V) and Cd2+
( 9 = -0.44 Y) have more positive deposition potentials and so deposit first.
30.14 Zinc will deposit from a solution of unit activity when the potential is
below -0.76 V . The hydrogen ion current toward the zinc electrode is then
j(H+) = 5 X
w-ll A cm - 2 X e 76U/S I. 4
= 1.3 X 10- 4 A cm - 2, or 0.14 rnA cm - 2
This corresponds to a negligible rate of evolution of hydrogen [Exercise

31.13], and so zinc may be deposited from the solution.
30.15 Use the same argument as in Exercise 30.14. The hydrogen-ion current
toward the platinum electrode when zinc starts to deposit is
j(H+) =0.79 rnA cm - 2 x e 7';otol. 4
=2.1 x 10.1 A cm- 2

and so there will be a considerable evolution of hydrogen before the zinc
deposition potential is attained.
30.16 Since 9 (Mg, Mg 2+) = -2.37 V, magnesium deposition will occur when
the potential is reduced to below this value. The hydrogen ion current density
is then
j(H+) = 5 X 10- 11 A cm - 2 X e 237015 1. 4 = 5.3 X 10'1 A cm - 2
568
which is a lot of hydrogen (106 Lcm- 2 s- 1), and so magnesium will not be
plated out.
30.17
FDc
k=-~-
FDc
[19], and so 0=-.]L
Therefore,
9.65 X 104 Cmol- 1 X 1.14X 10- 9 m2 s-l X0.66 mol m - 3
c5 =
28.9 X 10- 2 A m- 2
= 2.5 X 10- 4 m, Or 0.25 mm
30.18 The values of 9 (M, M+) are all far apart , and so simultaneous
deposition of the simple ions is unexpected. However, if the activities of the

ions are modified by complexation with CN- ions, the deposition potentials
may be brought into coincidence. The CN- has a different stability constant
for complex formation with each ion , and so modifies the deposition potentials
to different extents .
30.19 The cell half-reactions are
Cd(OH)z+2e-~Cd+20H-,
9 =-0.81 V
NiO(OH) + e- ~ Ni(OH) 2 + OH -, 9 = +0.49 V

Therefore, the standard cell potential is -1.30 V. If the cell is working
reversibly yet producing 100 rnA, the power it produces is
P=IE= 100 x 10- 3 Ax 1.3 V=0.13 W
30.20
(a)
-t!.G 9 /vF
H 2 + !0 2 ~Hz0;
!!1G 9 = -237 kJ mol- 1
Since v=2,
-(-237 kJ mol- 1)
&= 2 x 96.48 kC mol- 1 = + 1. 23 V
(b) CH 4+ 20 2 ~ C0 2 + 2H 20
t!.G 9 = 2!!1Gr'(H 20) + t!.Gr'(COz)- t!.G r'(CH4)
=2 x ( -237 .1) + ( -394.4)- ( -50.7) kJ mol - 1

= -817.9 kJ mol- 1
569
As written , the reaction corresponds to the transfer of eight electrons. It

follows that, for the species in their standard states ,
-( -817.9 kJ mol - 1)
E e = 8x96.48kCmol - 1
30.21
+l.06 Y
(a) E(H 2 , H +)=-0.059YpH=-7X0 .059Y=-0.41 V

(b) (0 2 , H+) = 1.23 V- 0.059 V pH= +0 .82 V
v)
0.059
E(M, M+) = 9 (M, M+) + - -+( 2
lg 10-fi
0.35 v
= 9 (M, M+) - - z+
Corrosion wi ll occur if E(a) or E(b) > E(M , M+).

(i) 9 (Fe, Fe 2+) = -0.44 V, z + = 2
(Fe, Fe 2 +) = -0.44-0.18 V = -0 .62 V < E(a and b)
> E(a)
(ii) (Cu , Cu +)=0.52-0.35Y=0.17V { < E(b)
,
{ > E(a)
E(Cu, Cu- +)=0.40-0.18Y=0.16Y < E(b)
(iii) E(Pb, Pb 2 +) = -0 .13-0.18 V = -0.31 Y { :
~i:~
(iv) (AI , A IH )= -1.66-0.12 Y= -1.78 Y < E(a and b)
> E(a)
(v) E(Ag , Ag+)=0.80-0.35 Y=0.45 Y { < E(b)
(vi) E(Cr , Cr 3 +) = -0.74-0 .12 Y= -0.86 Y < E(a and b)
(vii) (Co, Co 2 +)= -0.28-0.15 V = -0.43 V < E(a and b)
Therefore , the metals with a thermodynamic tendency to corrode in moist
conditions at pH= 7 are Fe, AI, Co , Cr if oxygen is absent, but if oxygen is
present, all seven elements have a tendency to corrode.
Problems
30.1
lnj=lnj0 +( 1 - a)fry
(14a]
570
Draw up the following table :
YJimV
50
100
150
200
250
ln(j/mA cm - 2)
0.98
2.19
3.40
4.61
5.81
The points are plotted in Fig. 30.2. The intercept is at -0.25, and so
8
Fig 30.2
v
2
._./
100
50
v
./
150
200
250
'7/mV
ju/(mA cm- 2) = e- 025 = 0.78. The slope is 0.0243 , and so (1- a)F/ RT=
0.0243 m V-I. It follows that 1- a= 0.62, and so a= 0.38. If YJ were large but
negative,
ljl = jo e- afl = 0.78 rnA em -2 X e -o..Jx,,l25.7 mv
=
0.78 rnA cm- 2X
e -O.OI5!1' "'v)
and we can draw up the following table:
YJimV
-50
-100
-150
-200
-250
j!(mA em -~)
1.65
3.50
7.40
15.7
33 .2
eRn
30.2 fL = zFO
[Example 30.4]
Draw up the following table using k =I IS with S = 40 cm 2 :
c/M
0.250
0.125
0.063
0.031
kf(mA cm - 2)
5.38
2.68
1.23
0.58
571
The points are plotted in Fig. 30.3. They fall on a good straight line with slope
22 .3. It follows that
60
Fig 30.3
.I
/
v
/
2{)
1/
/
0 1
elM
02
03
RT A.
zF X b= 22.3 rnA cm - 2/ M = 0.223 Am mol - 1
and therefore, since
RTA
-F =+x 0.0257 V x 40 S cm 2 mol- 1
z
=0.514 V S cm 2 mol - 1 = 0.514 X 10 - 4 A m 2 mol - 1
o=
0.514 X
10 -~
A m2 mol - 1
0.223 Am mol
0.23mm
Deposition may occur when the potential falls to below E and so simultaneous
deposition will occur if
572
RT
RT
9 (Sn , Sn2+) + F In a(Sn 2+) = 9 (Pb , Pb 2+) + F In a(Pb 2+)
2
2
or
2
a(Sn +)
In a(Pb2+)
(2F)
RT {Ee (Pb , Pb2+)- E e (Sn , Sn2+ )}
2 X ( - 0.126 +0.136) V
0.0257
0 78
That is, we require a(Sn 2+) = 2.2a(Pb 2+)
30.4
2RT
E=Ec - IR, + zF lng
[23a]
(If Ajo)2z
g
( __
I
1 A.}L
)112( __!_)lt2
1 A"'
h
RTA
with jL = zcF!J
[Example 30.4]
l
l
R s =KA
-. Am= A++A
- cAA m With
Therefore,
E = Ee
Il
2RT
cAAm- zF lng
(/
wth g = { 1 -
1A
kfb)
(A:A.) }"'{ (Aa~AJ

1-
RTA +c
RTA~c'
with a = ~ and a' = z'F
For the cell ZniZnS0 4(aq)IICuS0 4(aq)ICu, l = 5 em, A= 5 em\ c(M +) =
c(M' +) =1M, z = z' =2, A+= 107 S cm 2 mol- 1, A ~ = 106 S cm 2 mol - 1 [so we can
use A~ = A+]. Am= 107 + 160 S cm 2 mol- 1 =267 S cm 2 mol- 1 for both electrolyte
solutions. 6 = 0.25 mm (Problem 30.2], j 11 = 1 rnA em -z = j(,. We can also take
E 9 (a = 1) = 9 (Cu, Cu 2 +)- 9 (Zn , Zn 2 +)
= 0.34 - ( - 0.76)
v = 1.10 v
R =
'
Scm
=4Q
1M x 267 S cm 2 mol- 1 x 5 cm 2
.
+
]L = ]L
2 X
= 5.5 X
0.0257 V x 107 S cm 2 mol - 1 x 1M

0.25 X 10 - 3 m
w- 2 s v cm- 2 = 5.5 X 10- 2 A cm- 2
It follows that
(//5 10- Ar}

{ 1 _ 3 _6(1/ A)
3
E/V = 1.10- 3.8(// A)- 0.02571n
4 X 10V! A) }
= 1.10- 3.8(// A)- 0.02571n { _ _ (1/ A)
1 36
This function is plotted in Fig. 30.4. The power is
P=IE
1000 ~
100
Fig 30.4
"""" ""\
\
/
500
('\
\
'
17'
t...,...-
50
p
~0
2.()
].()
lg(I/ mA)
and so
4
P/W = 1.10(// A)- 3.8(// A)
4 X 10 (// A?}
0.0257(// A) In { _ _ (1/ A)
1 36
This function is also plotted in Fig. 30.4. Maximum power is delivered at

about 120 rnA and 0.6 V, and is about 60 mW.
573
574
30.5
4
E = Ec- ( ::) In {
A(jo~b) 112 } - IR,
(21]
P=IE=IEc-alln(f) -1 2R,
where a=4RT!zF and 10 =A(j0j 0)112 For maximum power,
dP =E -aln(!_)-a-2/R =0
d/
fo
which requires
In
(f)= (~a
-1) -
2:R,
This expression may be written
/)
Ec
2R, zFR,
In ( fo =c 1 -c2/ ; c 1 =-;-1, c2=-;;= RT
2
For the present calculation , use the data in Problem 30.4. Then
10 =A (j0 }!1) 112 = 5 cm 2 X (1 rnA em - 2) = 5 rnA
2 X 1.10 V
Cl
= 4 X 0.0257 V
1 = 20 .4
2 X 3.8 Q
2 X 0. 0257 V
148 Q V
Cz =
- I
= 148 A -
That is,
In(0.20//mA) = 20.4- 0.148(//mA)
limA
115
116
117
118
119
In(0.20//mA)
20.4- 0.148(//mA)
3.14
3.38
3.14
3.23
3.15
3.08
3.16
2.94
3.18
2.64
The two sets of points are plotted in Fig. 30.5. The lines intersect at I=
116.5 rnA, which therefore corresponds to the current at which maximum
power is delivered. The power at this current is
P = 116.5 rnA
1.10 V- 0.0154 V X 116.5 rnA X In ( -116.5)

- - (116.5 rnA?
5
x3.8Q=58mW.
3 4
Fig 30.5
3 3
RH'f>
\
1\
\
~
1..--4
LH
r\
1\
\
0
i\
~
2 9
116
115
30.6
/corr
= AJo efE14
118
117
119
I/mA
120
[26]
[as in Exercise 30.21].
withE= -0.62- ( -0.94) V =0.32 V

I curr =025x10-6AxetU214
xoom=6uA
_ r_
= io{1 + (1- a)YJf + 1(1- a)"17 2f +
+ afYJ - ta 2YJ 2f + }
= Jo{YJf + f (YJf)"(l- 2a) + }
-1
(j) =Jo{(YJ)f+H1-2a)f(YJ 2)+ }
WJbr fw
(17) = 0 because 2.n:

(17 2) =
cos wt dt = 0
[2.n:lw is the period]
t116 because -2WJbrlwcos2 wt dt = t

.n:
Therefore ,
(j) = t(l- 2a)f%YJ6
and (j) = 0 when a= t . For the mean current,

(I)= t(l- 2a)FJoSYJ~
=t
(1- 0. 76) X
=7 .2JA-A
7.90 X 10- 4 A cm- 2 X 1.0 cm 2

2
(0.0
X (10m V)
257
vr
575
576
30.8 Let rJ oscillate between rJ + and rJ _ around a mean value ry 0 . Then if rJ _ is

large and positive (and rJ + > rJ _),
j = j 0 e(l-a)qf = j 0 e 112qf [a= 0.5]
and rJ varies as depicted in Fig. 30.6a. Therefore, j is a chain of increasing and

Fig 30.6
decreasing exponential functions,

j= j 0 e(q _ +ytlf' 2 rx e'lr, during the increasing phase of rJ, where r:= 2RT!yF, y a
constant, and
j = j 0 e(q + -rtlf' 2 rx e -tt r, during the decreasing phase.
This is depicted in Fig. 30.6b.
cFD) {l-eN}
30.9 j= ( T
= h(l -
[19b; z=l]
eFq</RT)
The form of this expression is illustrated in Fig. 30.7. For an anion current,
cations
Fig 30.7
;:!
r-....
"\.
'
........
:an1ons
the sign ofT/cis changed, and the current of anions approaches its limiting
value as T/c becomes more positive (Fig. 30.7).
APPENDIX:
Linear regression
We seek the constants a and bin the expression y = a + bx that give closest
agreement with the experimental points. The technique is called linear
regression by the method of least squares. The recipe is as follow-s-. (1) Let (x;, y;) be the pairs of data points, i running from 1 to N.
(2) Form (x) = (11 N)
LX;, (y)
(xy) = (11 N)
(11 N)
L y;
L x;y;
(3) Then a = (y) - b(x)

b = {(xy)- (x)(y)}
(xz)- (x)2
(4) The quality of the fit is assessed by the coefficient of determination, r 2 ,

where
,
[(xy) - (x)(y)f
(y)2]
= [ (x2)- (x)2][ (y2) -
The closer r 2 is to 1, the better the fit .
P. W. ATKINS
Physical Chemistry
FOURTH EDITION
1997
H1l
fi
if
8 ,FJ 1 B
f]
P W. Atkins, 1990
~~
.:Y.
f,js\%H :~n?: 11::. + li'iJ A
J'IU)Clill Jt H: IR ;r:; 3 T 13 36 :ffl: 7 -"}

'l!fB-603-3946- 5311 FAX03- 3946- 5316
ISBN 4- 8079- 0466- 3

Printed in Japan

Solution Manual For Physical Chemistry 4th Edition

Загружено:

Сведения о документе

Оригинальное название

Авторское право

Доступные форматы

Поделиться этим документом

Поделиться или встроить документ

Параметры публикации

Этот документ был вам полезен?

Это неприемлемый материал?

Авторское право:

Доступные форматы

Solution Manual For Physical Chemistry 4th Edition

Загружено:

Авторское право:

Доступные форматы

PI:il~~AL

Solutions Manual for

All rights reserved. No part of this publication may be

Preface to the fourth edition

APPENDI X: Linea r regressio n

V; = 1.0 L= 1000 cm 3 , Vr= 100 cm 3 ,p;= 1.00 atm

1.00 mol x 0.0821 L atm K -I mol - I x 298.15 K

That is, the sample hasp= 24 atm, not 20 atm.

b = 5.105 x 10- 2 L mol- 1 Since n = 1.00 mol and V= 1.0 L,

l.OOmol x 0.0821LatmK - 1 mol - 1 x 298.15K

p = 25 .8 atm- 4.194 atm = 22 atm

The properties of gases

Vr = 4.65 L, V; = 4.65 L + 2.20 L = 6.85 L

V; = l.O L, V 1 = 100 em\ T; = 298 K

Internal pressure= quoted pressure+ atmospheric pressure

Vr= 1. 14 V; (a 14 per cent increase) , T; = 340 K

The properties of gases

V; = 2.0 m' , p; = 755 Torr , p 1 =(a) 100 Torr, (b) 10 Torr

Therefore, since there is on ly o ne vo lume,

The properties of gases

n = (1.995 + 4.380 + l.llS)

10- 2 mol= 7.490 X 10- 2 mol

0.1340 g L - l x 62.36 L Torr K - l mol - 1 x 298 K

n = 1.0 mol , T= 273.15 K (i) or 100 K (ii)

w- 2 L atm K -l mol - l X 273.15 K

L atm K - l mol - l X 1000 K

The properties of gases

(22.414 -1.0 X 6.380 X 10- 2) L

5.489 U atm mol- 2x (1.0 mol) 2

nRT 1.0 mol X 8.206 X 10- 2 L atm K - I mol- l X 1000 K

and p = 2.2'7 x 103 atm - 5.49 x 102 atm = 1.7 x 10 3 atm

Vc= 3b(12a) = 3 X 0.0226 L mol - 1 =6.78 x 10- 2 L mol - 1

~; (9]; for a perfect gas V~ = RTIp . Since the molar volume is 12

per cent smaller than that of a perfect gas,

ZRT 0.88 X 8.206 X 10- 2 L atm K - I mol - l X 300 K

The properties of gases

Since V"' <

v::, attractive forces dominate

Z = RT [9], implying that Vm=

Since Z = 0.86 , T= 300 K, p = 20 atm,

(a) V = n V"' = 8.2 X 10- 3 mol X 1.059 L mol - 1

n = n(H 2) + n(N 2) = 2.0 mol+ 1.0 mol= 3.0 mol

RT 8.206 x 10- 2 LatmK- 1 moi - 1 X 273.15K

= 1.00 atm mol - 1

p(H 2) = 2.0 mol x 1.00 atm mol - 1 = 2.0 atm

(c) p = p(H 2) + p(Nz) [7]

b= ! Vc [12a , Vc=98.7cm 3 mol - 1]

a= 27b 2pc= 3 V ~ pc [12b, Pc= 45.6 atm]

The properties of gases

As b is approximate ly the volume occupied per mole of particles

w - ~> m -' mol -

NA- 6.022x 1W' mol - l

Then, with Vrnol = }:rrr -',

9.3X J0 - "9 m-'

[Tc= 33 .23 K, Tabl e 1.3]

Hence , the gases named will be in corresponding states at T= 8 .968 x Tc and

T= 8.968 X 405.5 K = 3.64 X 10-' K

(b) For xe non, Tc= 289.75 K and Pc= 58.0 atm, so

T= 8.968 X 289.75 K = 2.60 X JO-' K

The properties of gases

p = 0.0781 x 58.0 atm = 4.5 atm

p = 0.0781 x 2.26 atm = 0.18 atm

Total pressure: p; = 1.0 atm