C
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, - - - - P.W. ATKINS---....... . ._
Physical Chemistry
Fourth Edition
P. W. ATKINS
Solutions Manual for
Physical Chemistry
FOURTH EDITION
P W. Atkins, 1990
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
577
PART 1: EQUILIBRIUM
1. The properties of gases
Exercises
1.1
V;
Pr= Vr X p; (3]
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=
24atm
nRT an 2
p= V-nb- V 2
For xenon, Table 1.4 gives a= 4. l 94 L2 atm mol - I and
nRT
V-nb
an 2
- 2
V
Therefore,
4.194atm
Vr
1.3 p;= V Xpr [3]
I
1.4
1 atm
Torr
760
3.38 atm
Vr
Tr= V X T; [5]
I
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]
Therefore,
!.14 V;
Tr = -V--- X 340 K = !. 14 x 340 K = 388 K
I
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) =
(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
.
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
1.12
nRT
(a) p=v[1J
1.0 mol
8.206 X
(i) p =
(ii) p =
1.0 mol
8.206 X
w-~
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
= 1.003 atm
an 2
and p = 1.003 atm - 1.09 x 10- 2 atm = 0.992 atm = 1.0 atm
an 2
5.49 x 10 atm
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=
RT
Vm=0.88 V~, = 0 .88 p
Therefore,
p
RT
(a) Z=RTx0.88 p =0.88
(b) V~= - =
1.1 L
pV"'
ZRT
20 atm
_
=1.059Lmo l- 1
2.0mol
(a) x(H 2) = . mol= 0.67
30
22
.4 L
b
u
1-
32.9 x
""' -
=5.46 X 10 - "9 m 1
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
= 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
p
Vr = ---'x V; [3] andp = pgh [Example 1.2]
Pr
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
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
RT
M=
Fig 1.1
0.540 x 105 m- s --
1.0
p/10 Po
10
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
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' =
11
1
1
_ x 50.2 Torr= 0.184 Torr
_ x p3 =
273 16
273 16
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
.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
a
RT
(b) From p = V m_ b- V~ [11 b], we obtain V m= --a-+ b [rearrange llb]
p+
v2
m
L'
I ,
6 .493 - atm mo 2.30 atm + (12.5 L mol 1)2
Von=
28.72Lmol - 1
- - - - - + 5.622 X 10 - 2 L mol - 1
2.34
= 12.3 L mol -
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
3
)
29
3
( 4.nx8.86x10- m
1/3
=0.28nm
1.11
Hence
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
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__
RT
V m( 1 -
~) - V ~'
13
14
a ] -1 +b-, + .. .)
=RT(
- 1+ [ b - vm
RT VITI V;;,
Compare this expansion with
B+C
p = -RT( 1+ , + . .. ) [lOb]
Vm
V"' V;;,
__
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
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~,
)2+ ... }
RT{
vm
a ) 1 ( 2 ab
a ) 1
}
l+ b- RT VITI+ b - RT+2R 2 T 2 v ~ + ...
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
That is,
-
which solve to
vc
v~
v~
Pc=-----:;+]
It follows that
1.15
pVm
pV"'
B
C
- = 1 + - + -, +(lOb]
RT
Vm
V~,
15
16
whence
B 1 p+C 1p 2
vm
v~,
=-+-+
8 RT+
1
BB 1 RT+ C 1 R 2 T 2
vm
+ =B+-+
von
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
~=
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]
=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
17
pMgdh .
.
dp
Mgdh
RT , 1mplymg that
=-Iff
w = -mgh[3]
w= -mgh (3]
=- 65 kg x 9.81 m s- 2 x 4.0 m =- 2.6 k~
2.3
w=
-pcx ~V
(5]
w-> m 3
as 1 Pa m3 = 1 J .
2.4
(a)
w = -p 0 ~V[5]
4.50 g
~
n = 16.04g mol-l= 0.280) mol
RT=2.577kJmol - 1, V;=l2.7L. Vr=16.0L
_
2.5
Vr
w= -nRTin V [7]
I
16.0L
. L = -167 J
12 7
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=-pcxl-.V[5]
2.7
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
2.8
750 x 10' g
n
22 .99 g mol - 1
q=nl-.H /f,, =
750x 101 g
22. 99 g mo 1
q
.
229 J
C=- [Sect1on 2 SJ = -- =89 8J K- 1
!-. T
2.55 K
.
29
.
89 .8JK - 1
3.0mol
= 30 J K- 1 mol - 1
19
20
Hence
Cv= C"- R = (30- 8.3) J K- 1mol - 1=22 J K- 1mol - 1
2.10
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
2.11
q=C!).T=nC,,!).T
= - Pcx/). V
21
2.14
11H'! = 811H f((C0 2 , g)~ 5!1Hf((H 20 , l)- !1Hf (eb, l) [eb = ethylbenzene]
H 2(g) +
~ 0 2 (g)
Giving
CfiH12(/) + H2(g)~CoH 14 (/)
2.16
/!,. U =
!1nM= - 4 mol
Therefore
!1U f = -442 kJ mol - 1+9.9 kJ mol - 1= -432 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
22
2.18
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 ~ =
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
~He=
-2.80 MJ mol - 1
Hence
~Uc = ~He;
therefore
~Uc =-
~n~ =
2.80 MJ mol - 1
~H=
+2.8 MJ mol - 1
~H =~H=
2.36 MJ mol - 1
-1.72 MJ mol - 1
!1H 6
=-
40 kJ mol - 1
=-
395.41 kJ mol - 1
The difference is
C(gr)---.,> C( d)
2.24
q = n!:l.H 'ji
1.5g
1
. g mol _ 1 x ( - 5645 kJ mol - ) = -25 kJ
342 3
6.25 X W J
,
65kg x 9.81ms-
2.25
9.8m
t;.H'j
Ml f'(8)
23
24
L vJSJ; hence
J
0=~H 2 -2C - H 2
v(~H 2 )
= + 1, v(C) = - 2, v(H 2) = -1
2.28
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) .
2.29
1:1H 9 /( k1 mol - 1)
2NO(g) + 0 2(g) ~ 2N0ig)
-114.1
t(- 110.2)
N2(g) +
0 2 (g)~
2NO(g)
180.5
+11.3
2.30 (a)
-436.75
H89.4)
-392.1
Hence , 1:1H f (KC10 3 , s) =- 392.1 k1 mol - 1
(b)
-425.61
02(g)~C02(g)
-393.51
tN 2 (g) + t0 2 (g)~NO(g)
- !(75.5)
2.31
-946.6
+90 .25
-127.5
+ 52.5
1
25
26
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
Problems
2. 1 (a) w = -p ,t..V [5]
0
nRT
VI=-- =
5.0g
44 .01 gmo l- 1
X - -- - - - - - - - - - - -
l.Oatm
w-' m'
=2.73L=2.73 x
-5.0g
44. 0 1 g mo l
= -
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
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,
vm- b=7 .5 -
4.3 X
w= -
ri p d v =
B)
n JrRT(
i vlll 1 + vm
d vm
28
5.25 cm 3
6.29 cm 3
1
3
Vm; = 0mmol = 75.0cm mol- , Vmr= 70mmol
7
89.9cm mol-
and so
s(
(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 ,
:J
:J
tl.(p V)
( -
as !!.. T = 0
Therefore,
tl.H = 83.51-13.81 = 69 .71
2.5
q 18.02 g mol - 1
tl.Hvar =-=
10
x22.2k1 = +40k1mol- 1
n
g
c~J mol-l)
!!..H = q + l.81 kJ
qRT
V=-p!!..Hvap
32.5 kJ
2C(s) +
3H 2 (g)~C2H6(g)
!!..Hf7(T2) = !!..Hf7(T1) +
!!..CP dT [17]
4.77 x 10- 3
8.54 x 105 K2
K
T - - -y""""2 - -
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
3~ 0 - 2~ 8) K
103 K
= - 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
M
Vm =- where pis the density; therefore:
( 1
1 )
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
~n 8 =
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
2130
5X
(-
393.51)
5X
(-
285.83)
mol- 1)
~H, = ~U,+2RT
+ 2C6H 6 (g),
-1267
~n 8 =
+2mol
31
32
2.13
!1H 9 =
11
+ H 2 0~4CH 3 CH(OH)COOH
Therefore,
reaction.
2.14
11H~
- 5645 kJ mol - 1
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
m~O)
OB
10
12
30
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
+3.6
+4.0
+4.2
m~O)
33
34
K+ (g)
20.8
K+(g) + F- (g)
+ CH 3COOH (/)
K +(g) + F HOOCCH 3(g)
734
KF CH3COOH(s)
3.1
KF (CH 3COOH)
35.2
w =-
2.16
w= -F
= -70 kJ mol - 1
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
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
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)
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
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 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+
~~) dT
tilb(n- TD - ilc( ~ - ~)
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
10- 3 J K- 2 mol- 1
373\5 K- 298\5
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)
39
ay
a2
3.1 Show that ax ay = ay ax [Box 3.1]
a2t
a2t
a2t
a2t
a2t
(c) - = - (2t+e')=e'
as at as
ay
atas
a
(tes+2s) = es
at
-=-
(:8p
1 +p(5)p
3.4
We use
din
~)
dp + (
a = ~(~~)
~)
dT
-~e~
v ap} r
v aT} p
dT =-JCdp+adT
(:~ r = (aavGnRT) r =Q
3.5
a = ~(:~
3.6
=0+0=Q
[4]
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 -
dp = ~ d (~) = _ V d'V = _ dV = 1C dp
p m
v
vv
41
42
bp
Therefore - = Kbp
p
bp
(~!f)
3.8
8 x 10- 4
7.35 X 10 7 atm
= -11-cp
[10]
q =-
(~!f)
q = Q[adiabatic process]
3.9
w = - pex
~ V=
- 600Torr X
1.013 X 105 Pa
760Torr
- 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
q = Q [adiabatic process]
~U= Cv~T =
200 K
= 24.6L
3.11
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
-0.46 kJ
3.12
~v=(:~b ~T=aV~T[4]
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
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
Cv 37 .11-8.31
.
c=R=
[Cp-Cv=R , Cp from Table 2.10]
8 31
=3.47
nRTi
V. = '
Pi
298 K
10 atm
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
------
-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=_.!!.
"
(Tr T;)
Pcx
Pex
Tr- T;= --(Vr- V;) = --nR ---Cv
Cv
Pr p;
63.09 g
45
46
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
atm
2.3 x 10- 6
1.013 X 105 Pa = 2.3 X 10-11 Pa-l
Consequently' since
~ V=
a=~(:~P
~v=(:~P ~T=aV~T
= 8.61
10- 5K -I
1.0 X 10- 3 m3 X (- 30 K)
~V= - 2.8cm 3
47
M
p
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 -
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
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
cp-
Cp-Cv
nT = -----;;v- - p
(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=
(:~
=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 =
The difference is
tiHm- tiUm = apV"' tiT= 3.8 m1 mol - 1
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
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
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
50
dp =
p dV
V dt
p dT
T dt
1 dp
p dt
1 dV
V dt
1 dT
T dt
d In V
dt
d In T
dt
e-rtTr
'
dInT
1
so - - = - dt
rT
which integrates to
1 1 1
p = p; e- rtTwith -=- - rT rv
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
=___!!!!____=!!_+ 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)
(:~)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)
~==
(: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,=
a,=
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
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
vm
= 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
and so
T1 =2000K x ( 1-
5.105 x 10.
24 6
2)2
= 2000K
2000 K
3.11
av T(a~
ap} T[definition of H]
(a(U+pV))
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
-1 [chain relation]
11#
1/Cp
Therefore,
#Cp =-
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
(aaT
~) P
# = c;
(aiiil'B)
273
373 K
273 K
lOOK
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}
T
2na
= V _ nb - RV 3 (V - nb) [Problem 3.8]
nRTI(V - nb)
TI(V - nb)- (2na / RV )(V - nb)
~~--~~~~~~~~=
nAR
3
(3V, - 1) 2
RTV~
4Ty;
Hence,
..
and
CP - Cv= 1.1R = 9.2 J K - I mol- 1
3.14
dH = Vdp, so 11H =
Vdp
57
58
dp
iplly=
) {
1 )
1 }
pl/y-1
IPi
Pr
yA ( Pr
Pi )
y )
= y-
yA (
= y-
11-t
nRy
y
1
1
cp
cp
y-1 = - -1 =~= cp - Cv =R
1 --
1-cp
yp)l/2
For argon, y =
so
!'!.S=
q;v [4b]
25 X 103 1
(b) !'!.S= 373.15 K 671 K - 1
T,
4.2
500
298
r r
Heat extracted=
=
CP dT=
(a+ bT) dT
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
4.4
1.75 X 103 g
. g mol_ 1x ( -3.00 J K- 1mol - 1) = -195 J K- 1
26 98
p;
4.5
+26JK- 1
Vr
ilS = nR In V [7]
I
p;V;
nR = T
=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
f..Svap =
61
Since the vaporization occurs reversibly , f..S 101 =0 so f..Ssurr= - 87.81 K- 1 mol- 1
4.8
/)
+92.61 K - 1 mol - 1
11 ,
s) -125 9 (0 2 , g)
(a)
t..G 9 = t..H 9
f..H 9 =
T t..s e
62
4.10
4.11
!:l.S 6
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
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 = -nR In 2+nCv In 2
=n(Cv- R) In 2
4.14
2.9]
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
4.17
Tc
295 K
(b) t:=Th-Tc[ 15] = 303K-295K
36 9
= 20kJ
qh Th
qc c
4.18 - = T, therefore
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
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
!: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
I:J.Hvap
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
=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
= 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
/ 2Rt
That is,
2
I Rt)
!::iS = nCP In ( 1 + nCpTi
Since n =
500 g
_ g mol
63 6
7.86 mol ,
(1
67
68
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
M e = .!lG 9
il(p V) = .!lG 9
Tr
Tr
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
283 K
363
278 2
X
273 283
+0.27 1 K- 1
= ~H(T) - T ~S(T)
=(
T{
~S(Tr)- ~CP In ~}
For
~A
we use
~A = ~G-~(pV)=~G-p ~V
=~G - pM ~(lip)
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
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
=7.8km
4.10
t.G 9 = t.H 9
Hence t.S 9 =
(55.000-26.120) kJ mol - 1
_ K
= +96.864 J K - I mol - 1
298 15
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)
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
TIK
14.14
16.33
(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
74
298 K
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
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
=
BTh) dTc
= 0.016 mol.
4.21
qh
VB
-=nRlnTh
VA
(b) 0 [adiabatic]
Vo
75
(d) 0 [adiabatic]
Therefore
Therefore
rJ.dqT = 0
dq qh qc
VaVo
- =- +- = nR In - T Th Tc
VAVC
Va
However , Pcx(V 8 - VA) < nRTh InVA
because less work is done in the irreversible expansion, so
v v/ v/ v VY
v v v v/ v/
10v/ v v Vv
/
v/
L7/
/ / /V
Fig4.4
Entropy
76
= (Th- Tc)nR In
V:v
[isothermal expansion]
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)
Therefore ,
.
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
Pr
5.1
-3.81
t1S =
5.2
(a
-36 .5 J K- 1
m
5.3
Therefore,
Vr
Pi
tlS = nR In -= nR In-
5.4
Vi
Pr
Hence,
- 330 K
X (-
25.0 J K- 1) = +8 .25 kJ
36
60
f)
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
- 0.55 k1 mol - 1
= -2.63 x 10- 8 Pa - 1
5.8
~G = V ~P
[10]
~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)
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]
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
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,
Alternatively
(!~)T
= (:;)
J!~)
I (:n
= +1
5 7
(:~) v = - (
=(
:n
!~)
=-
(!~ p(!~)
v [chain relation]= (
s=
I(!~) J~~
Tl (!~)
[?]
:~) v [inversion]
[Maxwell , chain relation]
[inversion]
aVT
=c
[(aH/aS)p= T,
[inversion]
by analogy with
(aU!aS)v= T]
_P_
5.8
T=
dV
Therefore dS = nR- = nR d In V
Hence, Srx.nR ln V
5.9
(~~),=T, (~~ s =V
Furthermore,
(~H)
ap
[dHexact]
ap
83
84
T(as)
+v
ap
T
=-T(mp +v
[Maxwell]
= -:RT + V=Q
nRT an 2
(b) For p = V _ nb- V2 [Table 1.5]
T=
( 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
-v
v=
Therefore,
a!!\
nb- 2na/ RT
( ap T = 1 - (2pa/ R 2 T 2)
O.llL
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)
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
5.12
[chain relation]
(!~)
v = -1
I(!~
p(
Therefore
~ 1 Cv= p-
aTher
:n
r [chain relation]
RTV
nap
Hence, nr=RTV
nr~ 0 asp~ 0,
s . I4
dG=
( a~
ap)
(ac)
ap r
dp= Vdp
din V =- xr
dp
or
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
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 =
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'
=r
~G+
(1-r)
=r
~G +
(1 -
~H -
r)(~H -
T'
~CP
In r- T ~CP(1-r)
T ~CP)- T'
~CP
In r
Ks= -~(a~ =
v ap) s
1jv(ap)
av s
1
Ks= - - -
v(-~)
YP
Hence , YPKs = -1
5.17
dS=
TdS =
dV [S=S(V, T) ]
dV
:~)
=(
:~) v [Maxwell]
qrev =nRT
5.18
r dV
J
i
(Vr-
nb)
V -nb =nRT!n ~
89
90
TdS=
T(!~)
Use (
!~)
(:;) T
=(
dT+
T(:;)
dp
:~) :~ = ~ x
P(
CP
= - (:B P [Maxwell]
5.19
-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
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
w- 7
Therefore,
tn y = -9.43 x
w- + 6.05 x w- = -9.42 x w4
y=0 .9991
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
4pBIR~1,
Fig5.2
y 12
01
10
....
001
10
0 01
08
01
v
7 0
4p ~H
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
I::!.Srus = 1::!. V mX
10- 6 m3 mol- 1
= +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
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
y = t hpgr (15]
w-2 N m- 1
e 2Y Vml rRT
(1 N = 1 kg m s- 2]
(13a]
=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
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
= 1.4 mol s- 1
dm
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=
= 1.4kg
--
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)
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
0.0208
X298 .15K
Problems
+ 5.42 kPa K - 1
(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
97
98
(a)
th~re
C.ooo ~ cm -3
0.917 cm-3)
= -1.63 cm 3mol - 1
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
250g
g mol - l
18 02
.
= -2.7 K
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
...
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
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
!"J.Hrus
T
p=p * + !"J.V In T * (6a)
fus
28
30
- !"J.Hvap
1 )
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*
100
Fig 6.4
a
80
SA
/_..;A
_.d Vb
.s 40
20
~ .-<
-10
.--: ~ F"""
-s
--
p~ *)
10
15
101
102
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
4.8 x l0 - 10 m
_ m = 5 X 10- 5 (1 in 20 000)
10 5
~A=
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
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
9 51
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
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
Therefore, if V11 = Va ,
~A
is independent of pressure.
dp
dT = T~V[S]
Therefore ,
Then, since
~ (~H)
dT
T2
dT
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
m!M
m 1M+PVIRT
xP
P(mRTIPVM)
(mRTI PVM) + 1
mPA
RT
= rnA+ 1' A= PVM
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
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
=
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
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,
Therefore, u = (
2y)I/2
bP
(a)
nAMA+ncMc=m
where m is the mass of the sample . We also know that
0.005
p/x
6 X 103
0.012
6.4
X 103
0.019
6.4 X 103 kPa
109
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
134 Pa
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
y =
A
XA P ~
p~ + (p ~ - p~)XA
0.920 X 400
= 0 968
150+ (400-150) X 0.920 - -
Kr = - --
!'l.Hrus
110
Hence p 8 = - - nA +ns
which solves to
mApB
mAMBpB
ms(P s- Ps)
ms(P~- Ps)
7.7
-11Hrus (1
lnx 8 = - Ry.- T*1) [17]
905
=272.70K (-0.45aC)
7.8
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
0.1333 x 30 K kg mol- 1
_ K
0.381kgmol- 1
10 5
381 g mol- 1
na1 V~map 6
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 =
440 Torr
390Torr
111
112
7.11
-0.35 k1
298K
+1.21 K - 1
2:
X1
In X 1
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
86.17 g mol - 1
0 8600
100.20 g mol - 1 =
m(Hex) M(Hex)
m(Hep)- M(Hep)
7.15
x=
""'
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
114
103 g
n(N 2) -18.02 g mol
p(Nz)
6.51 x 107 Torr
= 0.27 mmol.
7.17 Use the result established in Example 7.14 that the amount of C0 2 in
1 kg of water is given by
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)
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
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)
.
.
For 1 kg of b1smuth , n(B1) =
1000 g
_ g mol
208 98
= 4.785 mol
(!!.._)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 =
pgx 0 .29 x 10
_2
w-
m4 kg-l
k _
m4 g 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
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{)
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
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
"" '""'
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
1
with m=m/(mol kg- )
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 -
119
18.04 cm 3 mol - 1
VA =(::) =(::J MA
ns
Therefore,
MA
a 1
- wM - P
Aaw P
V =A
and hence
~ = VA+w~(~)
p
MA
dw
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
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
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
= 0 993 mol
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
(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{)
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
124
Therefore,
ft..G = Pi(N 2 ) Vi In
t - 0.562p V + p V In 2
Rrfx 8
7.10
nB
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]
= 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
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
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
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
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
[pslxsp;]
0
[psi Ks]
1.00 [p 8 1xsKs]
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
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
7.15 fA.A =
"B
(nG E))
A
"D
anGE) = GE + n (acE)
( anA
an A "B
liB
Therefore,
amA)
xA ( -a
XA
and so
p. T
127
+x 6 (ams)
=0 [divide through by dxA]
ax A p. T
128
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
7.17
nA dVA +n 8 dV 6 =0 (6)
Hence
Therefore,
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
7.18
-~Crus
lnxA =~
[Section 7.5]
(I 1)
~Hrus
lnx =--- --A
T*
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)
= ---:; 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
+ TI)
+ RT In aA
=,u~(p)+ J:+nVmdp+RTinaA
and hence that
J:+nVm dp
-RT!n aA
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
Salt,water;C=~
Po~-,
HPO~
HPO~- ~H + +PO~
H + +oH-~H2 0
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 -
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).
133
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
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\
1\
85
IV
83
(CF,)
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
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.
For bismuth
RT*2
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
0.1
0.2
0.3
0.4
!J. TIK
Tr!K
22.7
522
45.4
499
68.1
476
141
x(Bi)
0.1
0.2
0.3
0.4
!:lTIK
48 .3
546
96.6
497
145
449
Tr
(a)
600
'
~
~
a "'
an"
0
Bi
"""'
'
\
So id t i L
400
a'
Liq id
1\..
so
Fig8.12
\a'
r-..
jSOii , U:lL
lj
;".
x(Cd)
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
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.
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
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
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
a'
b= b'
9.2
K=e-t-.c
I RT
[Sa]
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
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
dInK -!'! H e
d(l!T) =-R- [llb]
148
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 = - - - -
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
9.6
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 ,
1
1
Hence,x 6 =l+K=l+O.I06
X1
0.904
= 0.096
n6=
140g
21.50g
--;;_;r-, n1 = M , n = ----;;;r-
----;;;r-
M=0.904
21.50 g= 19.4 g
~G 6 < 0
at 298 K:
(a)
~G 6 /(kJ
(b)
~G 6/(kJ
(c)
~G 6/(kJ
(d)
~G 6 /(kJ
(e)
~G 6 /(kJ
149
150
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
!1G 6
- RTln K
_
(!1G e - !1G 6 ' ) _ 100 In Kl K'
g - lOOx
!1Ge
InK
-In (1 +
!'.~ = ~t.K
K)
Hence
100t.K
- -=-glnK
K
9.13
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
NH 4 CI(s)~NH 3 (g)
+ HCI(g)
(.!!.._)
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
151
152
(c) D.H 9 =
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'
2.303RlgK'IK
2.303R(pKw-pK~)
T'
T T'
2.303
293 K
303 K
= +56 .1 k1 mol - 1
9.16
D.G 9 = D.H 9
D. H e
T= D.S e
(a) CaC0 3(s)--7 CaO(s) + C0 2(g)
153
9.17
-124.10 3 1 mol - 1
8.314x103 1mol _ 1 = - 14 91
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
w-J
X 5.40-
[Example 9.7]
t X ( -1.82) = 3.61
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
Kb =
[CH3COOH][OH - ]
[CH 3C02]
Then, since [CH 3COOH] = [OH - ] and [CH 3C0i]=S, the nominal
concentration of the salt ,
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]
K..
[H3o +p
A
! lg A
Hence,
pH = t
[Exercise 9.19b]
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)
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
(a)
=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)
pK., = 2.12
pK.,=7 .2
8
6
~,_ __
r--
r--.-.
01.
o6
o.a
mfi4/mol kg 1
02
10
Problems
9.1
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)
K=plp e
x In
12.8 Torr
0Torr [p e = 750.3 Torr]
75
(!_- _!__)
T'
(12]
157
158
t...G e (T) =
= 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
1500 Torr
0Torr
75
= -1.72 kJ mol- 1
Therefore, for the reaction
CO(g) +
H 2 (g)~H 2 CO(g),
e -10.99 = 1.68 X
10 -5
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
PA/P 9
PA,P e
1- a 2
=0.392
Hence, K=
4 X 0.392 2 X (764.31750.1)
_ .
=0 .740
1 0 3922
p VM
a= --- -1
mRT
=0.764
Hence,
K
R In K'/K
[12)
T T'
R ln(5.71/0.740)
1
437 K
1
471 K
=+103kJmol- 1
160
= + 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
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
-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
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
p(P)
K" =p(A)'
implying that
163
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
dinK
t:J.H e = RT 2
-9
...
-10
Fig9.3
1\.
\..
~
11
'
-12
~.
290
"\.
300 VK
"
320
310
Therefore,
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
t:J.S ~P
Therefore , for
3A(l)~
+261JK- 1 mol - 1
41.5 kJ mol - 1
= __3_9_8_K__
A 3(l)
165
Therefore
( -a~
ap
=K
T
(aK,,)
y -ap
+K
T
"
(aK)
- ')
ap
=0
) = _ (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- )
(2- ) 2
(1- ,;)4
.;
2 -.;
2(2- .;)
1
166
Therefore
(2- s)s =a
(;e)
(1- s) 2
1
s-1( 1+ap/p
-
112
l--
,/"
/
I
0.5
Fig 9.4
1/
I
v
0
0.1
10
apl p ""
100
1000
p(N0 =
2)
We choose the root with the positive sign because p must be positive.
For equal absorptions,
[p= l/12]
167
Therefore
Since p=
395 mm
_
mm =5.27
75
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 =
f'>..G=f'>..H-Tf'>..S
t..S I = t..S +
T'
f'>..C
_P
dT
168
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 -
(1 1)
- i T'
/).c(;
2-
; ,, )
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)
+ ( -2738 K 2)
+ ( -8.288 X 10- 5 K -
I)
-225.31 kJ mol - 1
Note that the f3 andy terms are not significant (for this reaction and
temperature range).
169
K=[Hg 2 +J[C1 - f
32 9
.4
S = 1.25 x 10- 5 M
10.2
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 - )
r(Cl - )
r(F - ) [I]
=
181 pm
pm [Example 10.3] = 1.38
131
[Table 2.5]
Equilibrium electrochemistry
171
I=!
1
.)
2: m;z1
I= t(az~ + bz2_ )m
/(KCI) =
! (1 + l)m = m
10.5
10.6
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
Equilibrium electrochemistry
/(KCI) = m , I(CuS0 4 ) = 4m
Y =(y'~y'~ ) 11 s
s=p+q[4a]
with p = 1, q = 2, s = 3, Y+ = (y +y~.-)" 3
10.9
10- 3
-Aiz+z -1 1 112
10. 10
lgy =
1+81112
[7]
[m = m!m 9 ]
Y
8
w-'
0.930
-2.01
10.0 x
0.907
-2.01
w-'
20.0 x
0.879
-2 .02
w-)
Equilibrium electrochemistry
- ll
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:
L:
Mn 2+(aq)+2e - - Mn(s) 8 =?
8 = 1.36 Y- 8 (Mn, Mn 2 +)
(a) R:
L:
Overa ll (R -L):
(b)
+ 0.80 y
zn +(aq) + 2e - - Zn(s)
- 0.76 y
R : 2H +(aq) + 2e - - H 2(g)
L:
R -L:
(c)
R:
L:
R-L:
Cd 2 +(aq) + 2e - -Cd(s)
-0.40 y
+0.40 y
- 0.74
4
+0.36 y
(d)
+ 1.56 y
- 1.10 y
R:
+0.45 y
L:
Cl,(g) + 2e - - 2Cqaq)
+ 1.36Y
173
Equilibrium electrochemistry
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:
-0.62 y
(f) R:
+ 1.23 y
+0.34 y
+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
H +(aq) + e - ~!H2(g)
+1.10 y
+0.22 y
+0.22 y
+ 1.23 y
0
+ 1.23 y
-0.83 y
2Na+(aq)+2e - ~2Na(s)
-2.71 y
Equilibrium electrochemistry
175
or more simply
Na(s) IN aOH(aq) IH2(g) IPt
+0.54 v
(e) R:
L:
2H + (aq)+2e - ~H 2 (g)
R:
10.17
Hg +(aq)+2e - ~Hg(/)
L:
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
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)
176
Equilibrium electrochemistry
(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:
-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
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:
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
2.303
25.693 mY
(- 0.18+2x(-0.11))=-0.62Y
2
-0.40 y
+0.07 y
-0.47 y
10.21
!'!.H 9
=2
a!'!.G 9 )
-( aT
!'!.G
01
!'!.H
[!'!.G=!'!.H-T!'!. S ]
- 0 .259 kJ mol - 1 K
- I
x ( -0 .259 K - 1) kJ mol - 1
""' +22UskJmo l- 1
10.22
115
x ( 'I K 'I' )
Hence ,
S= .\
xn
1
]
C u 2 +(aq)+2e - ___.,.Cu(s)
L:
Overall: Cu 2 +(aq)
+0.34
()
RT
E=E e - - ln Q
vF
25.693 x IW ' V
= 0 .34V -
a(H +) 2
ln a(Cu +)
+ 0 .34
177
178
Equilibrium electrochemistry
25 .693 x
= 0.34 Y-
w- 3 Y
In
1
X _ x
16
w- x[m(Cu 2 +) = 35]
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:
+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
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
R: Cu 2 +(aq)+2e - -?Cu(s)
L:
+0.34 Y}
+0.14
+0.48 y
2 X 0.48 Y
_
InK= 25.693 mY= +37.4, K = l.7 x IOih
+0. 16Y}
L:
Cu +(aq)+e--?Cu(s)
+0.52Y
InK=
-0.36 y
_ my
25 693
-0.36 y
+0.36 y
Equilibrium electrochemistry
S(AgCI) = m(Ag +)
10.24
AgCI(s)~Ag+(aq)
+ Cqaq)
w-w
S(BaS0 4) = m(Ba 2 +)
BaS0 4 (s)~Ba2+ (aq)
+ so~ - (aq)
X K~, [K ~,
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
Equilibrium electrochemistry
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
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
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:
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
Equilibrium electrochemistry
Problems
10.1
R:
+0.62V
L:
-0 .36V
R- L:
Pb(s) +
Hg~SO.(s)~
+0 .9R V
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(/)
181
182
Equilibrium electrochemistry
v= 10
Therefore ,
9
10.3
-!l.G 9
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
II
3.5 X 10-x(p/atm?
183
Equilibrium electrochemistry
10.4
RT
E=E e -2FlnQ ,
Q=
H 2(g)+Cl2(g)->2HCl(aq)
v =2
= 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
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
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
+ constant x m 112
184
Equilibrium electrochemistry
(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
Fig 10. 1
0272
.Ql
.I
:0,.
027
Lil
/
L
02fJJ
0
(}02
004
006
008
0 10
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
Equilibrium electrochemistry
10.6
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
Equilibrium electrochemistry
=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
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:
AgX(s)+e - ~Ag(s)+X - (m 1 )
J-Ig
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
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.)
Equilibrium electrochemistry
187
and
m
Y )
E=0.05139V x ( ln0.09141 +ln0.5328
0.05328
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
H 2(g)IHCl(m)IAgCl(s)IAg(s)
RT
2RT
2RT
2RT
RT
= E 8 - F In m-2 x 2.303 F lg Y
[m ;; mfm 8 ]
188
Equilibrium electrochemistry
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
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
Equilibrium electrochemistry
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
10.10
!:iCe =
-vFEe
l::iS e =
[d(WC = dTIK]
190
Equilibrium electrochemistry
w-9 e 2WC) 3
+ 3 x 5.869 x
(a:ee)P
I (V / C) = -4.8564
0
+ 1.7607 x
w-x(ercr
Therefore, at 25.00 C,
(a!~
and
= -6.4566 x
)
oT "= -6.4566
(aEe
w-
v;oc
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
~ s e(H 2 )-
s e (AgCl)
Equilibrium electrochemistry
5 9 ( en= D,.S 9
191
S 9 (Ag) + t S 9 (H 2) + S 9 (AgCI)
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
/ 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
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
Equilibrium electrochemistry
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]
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)
Fig 10.5
Equilibrium electrochemistry
Therefore,
(a) E= 9
= 9 +
RT
RT
Flna(OH - t= 9 -Flna(OH - )
6
2.303RT
F
pOH
2.303RT
(pKw- pH)
!).=
(pOHr- pOH;)
11 .3 eV
eV
~H 2 + Uup(g)
3.22 eV
H(aq)+ Uup(g)
~H 2 + Uup (aq)
1.5 eV
H (aq) + Uup(s)
193
194
Equilibrium electrochemistry
!:!.H e =+ 1.07 eV
10.16
MX(s)~M + (aq)
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
[m = m i m e ]
Equilibrium electrochemistry
S 2 +SC-KJy;_=o
to give
Therefore, since
y;_ = e -4.h!l6AC '"
K , e +4.60MC"!
5= - ---
For t;,.T=
Therefore
dlnaA -MA
-MAd!;,.T
-d
T =-K anddlnaA=
K
/':,.
[.u =,u 6
+ RTin a]
195
Equilibrium electrochemistry
196
Therefore
Therefore,
XAJXB- d In a
=-
xA
x8
1
=m
= -1
111
m d In a 8 = -1
m
Jill d In ym
0
[A' = 2.303A]
and so
= 1+-(-!A')
Jill m
0
112
(A'm )
dm=l- f -
~m 3 12
= 1-jA'm 112
and hence
Equilibrium electrochemistry
Therefore,
11HrusXA 11 T
11Hrus 11 T
Rx 8 T * 2
vRM 8 T * 2M A
197
PART 2: STRUCTURE
!Yi=aT 4 (9b)
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
-
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
~p = O.OlOO
= Po X 1.00 X 10- 4
1.055 x
w-34 1 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 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
[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=;:
..: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.
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=-
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
0.10Js - 1 X3.16X10 8 s
em
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
(P!W) x (J../nm) s- 1
1. x _ 16
=5 .03xl0 15 (P/W)x(A/nm)s - 1
99 10
600
he
+mv 2 = hv- <t> = - -<I>
J..
(a) hc!J..=
SO
S- 1
no ejectio n occurs
19
~ mv 2
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
11.19
(a) !!.E=
6.626 x w- 341 s
w-1 5s
corresponding to N A
(b) !!. E =
7X
7 x 10- 19J
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
and
203
204
h
..,...-----,--=
112
(2mef'...)
1.226 nm
10.0 = 123 pm
(b) f'...=l.OkV , A. =
1.226 nm
1.
3 6
39pm
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
205
Problems
11.1
8nhc (
p = ---;:s- e'"m r -1
1.439 X 10- 2 m K
he
8nhc
2.205 X 104 K
Ak -
(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
10- 4 1 m - 3
xT
and if we plot Amax against liT we can obtain h from the slope. We draw up
the following table:
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
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]
2
J2cU 8nkT ( 1 1)
J pcU=8nkT y =- M-M
1
= 8; X 1.381 X
\o
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
(jE)2{ e
(T e
V 2T
11 1.,.
Cv = 3R-
}2
(14],classicalvalue=3R
-1
115
.
2
nx
1f' 2= -L sin 2-L
P(a,b)=fh
= (
=
dx
Z- L
sin
2~x) I ~'
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
[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:
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
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
J..m .. J =Sk= 2.88 mm K, in accord with observation.
Fig11 2
Energy : hv;
Mommtum: h/A.;
Energy: hut
Mommtum: h/A. f
e+ p cos e
209
210
p 2 cos 2 8'
hv
hvr
)2
(hvr
)2
h2
---:;-(vr + vf - 2v;vr cos 8)
c-
4
m cC
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 =
. 2mrx)
=iN-, ( x - -L s m
- - ~~-
2nJT
11
(c) N 2
J"' e- rt"r
2
dr
II
II
1
2
'
II
J'
sin'
ed(:l
II
'
II
4
I
=N 24'a 5 X - X n=32na 5N 2 = I if N=
,
3
(32na 5) 11 -
II
= -
'
cos'
II
</J
d</J by symmetry
j'' d</J = 2n
II
11.10
(a)
x" dx
II
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
1/J
dr = N '
II
,~ e
-i2u,
dr
II
II
2
COS </J
d</J
211
212
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
d2
(b) dx 2 cos kx =
d2
(c) -k=O
' yes ' eigenvalue=O .
dx 2
d2
(d) dx 2 kx=O ; yes; eigenvalue=O.
1fJ =
eikx
11.14
eikx
+ 0.32 e - ik.r
(T)=N
ItfJ*(:~)tjJdr
I (f)
tfJ *
tfJ*tfJ dr
11.15
'k
dtjJ
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
Therefore, (p x) = Q
2
d'f/J
'
oo
-oo
d'f/J
1/J * dx dx=-2a
J~
-oo
x e- "'' dx=O
[by symmetry]
Therefore, (px) = Q
( Gor)
1/2
32.Jrao
[Problem 11.10]
r)
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
1/2
[Problem 11.10]
- 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
(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
K
11 E
E
(D.9L)2 - [}
K!U
1
0. - 1 =0.23, or 23 per cent
81
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
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
he hw h (k)J t2
Therefore - = - = - ' }. 2n 2n m
.1.=2nc
27
(1.673 x
kg)
Nm-J
855
w-
[elementary physics)
(a) w =G)
f..= hw
10-' 4J Hz-\
w-'
5 Hz =3.3
X w -)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
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
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=
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
(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
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
300 K
we require
At this level,
= 1.8 X 10- 30 J
12.2
w=
G)
112
,
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
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)
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
12
(
1
1 )
m) 2 1.008 + 126.90
1=
1022 EIJ
v/GHz
0
0
2.62
396
7.86
1188
15.72
2376
12.5
h2
- 2m ax2+ ayl + az 2 1/J = E1jJ
h2
(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, ...
1/J -
L L L
I
Sin
Sin
Sin
(b) (x)=
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
K =
k , ={2m(h2
V')}"2
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
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 - ~
(:-~)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
1(
and so
Zone A:
lfJA
=A
eikx
+A
e-ikx
k = (2m/h2 ) 112
e -ik'x
e - ikx
k = (2mE!h 2) 112
A=
B=
H(
1 + :) B + ( 1- : )
(1 + ~)
~ (1 + ~)
B, =
k'
k'
B'}
C ei!k-k') L
C ei!k+k')L
1
.
A. 2 sin 2 k' L
P=IAI2=1+G' With G= 4(1-A.)
and
P~
1.
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
226
(7 )
2m~ll2
L = 49 .09(proton), 69.42(deuteron)
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.
'
2 2
./::
1. 5
1.0
ddx.-~ = - 2g e - g.r' + 4g x
--
2.0
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 ;;:;
, =
dy-
d2
H;:-2yH;,= -2uH,
Therefore ,
227
228
(T)=
N 2(- t hw)
=
= t( v+t)hw [
12. 12
[dx=ady]
(x") = a "(y")
= a"
(a) (x 3)oc
[Box 12.1]
[x = ay]
J
J
(b) (x4)=as
VJ 2y 3dy=Q by symmetry
l/JY4VJdy
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}+
JH~
12.13 f.J-=
[x=ay]
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
= a(~)"z
(b)
VI = V
12.14
- 1
V =- -
e2
1
-=axbwithb=-1
4ne 0 r
[x-?r]
2(T)= - (V)
12.15
229
230
i sin X e- icf> ) d
t = 2/
;= -
h2 d2
21
d 2
h2
h2
h2
(a) fei<P = - -(i 2 ei<f>) = -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
'
hN 2
hN 22n(a 2 + 2b 2 + 3c 2)
(aa+2+
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,
h2
- - V 2ljJ=EljJ
2m
[18, with V = O]
and hence
2/E
1\?'!jJ = -
----,;r-'!fJ [19]
-2(2+ 1)Y2 _ 1 =
2/E
- ----,;r- Y
2 __ 1,
3h 2
implying that E = I
21
h2 Y 3. 3 , implying that E =
6h 2
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 -
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
/-'Y.I
/- oo
233
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 - '
2.998 x lORm s- 1
----::-::----c--::-;;-58.4 x 10 9 m
2.25
X 10- IXJ ,
corresponding to 14.0 eY
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
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]
! ; so j = t,
l = jl+h,jl+h - 1, . . . Jjl -
hl
'2, requires I = 2
236
1=8, 7, 6, 5, 4, 3, 2
hd!AH
-T
h&A
h&A
L=2 , S=O, 1 = 2
13.13 The probability density varies as
1
1/1 2= - e -2rlao
.na6
dr
2
)
ao
max
4 2
= -eao
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
--
1.
2p~
(c)
3d~2p;
L'll= - 1, allowed
(d)
5d~2s;
L'll = -2 , forbidden
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
2 (for S = t ) , ~(for S = t )
and~(forS = 2)
239
(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,
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
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\.
Ama x ,
2n 1 + 1
n~(n 1 +1) 2
n 2 (n + 1) 2
'2lt =-~-~--
-1.
max
2nl
+1
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 .
(The answer, 3.40 eV, is the ionization energy of an H atom that is already in
an excited state, with n=2.)
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, ...
2) = 137175 cm -
1
,
185187 cm- 1,
~=K(1-2_)
n--7 oo
,
n-' '
A
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
for the
0--7 P transition
242
1
A.
P)I
K'
[tiE= hv=
n2
:c]
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
E(b22p, 2P) =-
610 36
10
_7 em
243
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
9 . 109 39 X 1W 11 kg
+ 9.109 39 X
1. 67262x
= 3 .3429
In
I11
=
IW
11
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
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
= ao
82
6a 0
I"'
0
( 4p3 -
e -P dp
245
dR
(angular momentum) 2
m er 3
(nh) 2
= - -3 [postulated]
mer
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
2:
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-
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.
Molecular structure
249
(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
1J1 dr = +
14.13
J(s+V2p) d7:
=!
(s 2 +2p 2 +2V2sp) dr
=!(1+2+0)=1
as
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
a2= - - -
cos <I>- 1
[19]
cos 92.2
0 0370
=cos 92.2 - 1 =
Molecular structure
251
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
aLeig
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
:rex
3:rc
Molecular structure
253
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.
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
-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
,...
IV
-100
....... ~
~~~ 2
't'+
~
'
~ ~~~
't'
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
14.6
w-
P = 8.6x
(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
tjJ 2 = 4.9 X
w-
pm- 3 , so P = 4.9 X
w-
Molecular structure
257
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.
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)
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
111 S- 1
,t = - = - -- - -- - - - - , - - - - - - - -
6.
4.6 X l0 - 7 m, or 460 nm
260
Molecular structure
1/J, =
(L2)
112
sin (n:rrx)
L with n = 4, 5 respectively and the two wavefunctions
3'2(2 v1 2 (2)
~
1)1
/2 (2)3/2
=41 ( 2:rr
~
(2-p)e -pt2
2
1/J2p, = R21Y10=
1( 1 )
4 2:rr
=- -
=-1
112(2)
3/2pe -P12 cose
a0
(2)3'
2 pe- P12 (- 3 ) 112sin8cos
-
Y6 a0
8:rr
=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
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
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
e2
h2
e2
e2 1
4nt:0 r6
4nt:0 R
4nt:0 rA
2m
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
'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
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
: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
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
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
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
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
That is, the orbitals span 2A 1 + 8 1 +E. One selection of atomic orbitals is
therefore
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
the following table:
268
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 ~;
therefore C2v
ah
D3
'----v---'
D 3h
(d) Cylinder: E , C. , C2 ,
therefore
ah ;
D ., h
ah;
D 2h
a ~;
ah,
(b) Anthracene: E , C2 ,
(c) Dichlorobenzenes:
C2,
Czv
i; C2h
ah ; D 2h
ah; D zh
(b)
I~
(c)
I~
Fig 15. 1
~
C;,
c,
(e)
(h)
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
Bz
Bl
BIB2
Cz
Ov
a'v
1
1
1
-1
-1
1
-1
1
-1
1
-1
-1
=A 2
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:
= ~ (V3xp,
I=
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
a~;
Czv
D 2h
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
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,
274
S,
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
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
A~.
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:
277
x= 1, indicating T 2. Therefore , in
Td , f-7 AI+ Tl + T 2.
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
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,._
279
[column 9)
[column 1)
[column 9]
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...
0
2
0'2p, 0'2p , 4
[column 1]
1/J(AI) = N2p,
(column 4]
[column 9]
1fJ(8 1)=N2p,
(column 2]
[column 3]
280
._
1/J(B 2)=02pz-0'2pz
1fJ(A2) =02p,-0'2p,
[column 7]
[columnS]
a1 =
b1 =
el =
.)
1v
e =
1~12
f
=~ f (.n~-.n2+
A I: Ha,a, =
B1: Hb,b,
Hence:
E2:
= 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,
H , 2(a) e2
H , ,(a)e,(b) =
2/3
He 2(a) e2(b) =
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
U=
27
1.6291 X 10- kg
,
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
R=(-h )112
4ncB
We use
m 1m 2
126.904 X 34.9688
27 .4 146 u
282
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=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
~Gu+ l l2 =v-2(u+l)xcv+
[25b]
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 =
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
+~)A
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~~:
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
16.16
ov=-- rlps
5.3 ps
~_
_
uv1em 1
5.3 ps
(a) r = --=53 ps
0.1 - 5.3 ps
(b) r = - - = 5 ps
1
(c) r =
= 2 ns
100 x 106 s- 1em
-
16.17
ov =
(a) r=1
5.31 cm - 1
r/ps
(b) r= 100 X (1
16.18
[12b]
ov=50cm-i
ov =0.5 cm - 1
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
=805.3 K
N( upper) = e-sosJ K/T
N(lower)
(a) N(upper)=e -sos3129R =0.067
N(lower)
--
16.19
(1:15)
(1:5)
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)
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
:c (~)
v = ~c = 2
112
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
where
~Gu+ 1 12 =
~Gu+ 1 12 =
v-2(v + 1)xcv
[25b]
Therefore , since
~Gu+ l l2 =
(1 - 2xc)v - 2vxcv
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
288
R= ( 4:n:cB)
112
[Exercise 16.19]
34.9688 U =17.4844 U
Therefore:
R=
(
= 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
112
Problems
16.1
cU = ~ (2kT In 2) 112
A
[lib]
2
= 2. 998 X 10 Km S 1.237 x
IX
w-'
(m/u) 112
OA
OA
ov ov
2(2kT In 2)
--:-=-=v
v
c
OA
112
[ll a]=A
w-
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
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]
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
v2
16.4 LlGu+ ll2 =v-2(v+ l)x 0 v and De=-_
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
22.99 X 126.90
_
. +
. u = 19.464 u
22 99 126 90
292
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
mean: 20.51 cm - 1
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-(H3sCl)
1. 6266
3.1624 = 0.5144
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
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
]=
112
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
We use
11(CuBr) =
63.55 X 79.91
. + . u = 35.40 u
63 55 79 91
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
IC 60
c'~s)
295
= 1.414 60 X 10 -~s kg m2
10- 26 X (R
R 1f
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
16.10
(24c]
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 -
Hence,
D 0 = 5.33-0.132 eY = 5.20 eY
16.11
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
{ 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
De
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
Fig 16.3
,\
1=
1\\
1\ .......
tqo 80
40
- v_,.:;::<,....
........
1= 0
-v
ll
./
200
400
600
R/pm
BOO
1000
297
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
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
[Boltzmann distribution]
298
which occurs at
hcB
(21+1) 2- = 2
kT
or when
kT
)1 12
]max= ( 2hcB
-2
112
-2= 30
hcBJ(J + I )Ik T
{ 8J+4
dJ
hcB(21 + 1)
kT
3
}
e -hcBJ(J + I )tkT =O
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
v- (B ,+ I+ B, )J + (B,+ I- 8 , )1 2
299
Note that
/!iSf- /!iSj = 2B.,+I + (3Bu +l- Bu)J + (Bu +1+ Bu)J
= 2Bu +l + 4B u+ IJ
Hence,
!!iSf- l!iSj
t'!iSf-1- l!iSj+l
B., +1= 2(21+1) ,B.,= 2(21+1)
We then draw up the following table:
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
and obtain
)1/2with,u=l.6266x10 -
27
kg
[Exercise 16.1]
3
2963.3
2821.6
141.7
10. 12
300
v=O
m
z' =m-l x z and z' = R - z
Then also
m+om
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]
1'-1=
301
1 1)
h (
h (B-8')
h!).8
1'- 1= 4nc
W-B =4nc ~ =4nc88'
and
z z=
h 1).8
4ncB8' !).M
(!).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)
--------~--...,....
1
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
30 713.24 MHz
- -- 22
1396.06 MHz
29 990.54 MHz
22
1363.21 MHz
1/2
pm = 16 pm
1/2
pm = 210 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]
= 8B(Jmax+ -t)
=
(__!!__)
B
2hcB
112 =
(32Bk!:\ 112
he }
h )
R = 4:np.cB
1/2
= :rrc
(k!:\
1/2
!15 -;;}
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
I'
lg/= -c[J]/
[1c]
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
Electronic transitions
305
We write
w--' mmol -
em - I s- 1
= 1.63 x l0 1x cm 2 mmol- 1 s- 1
and hence obtain
!=
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
17.10
I
I'
c;=- [:i]tlg/withl=0.20cm
306
Electronic transitions
0.0010
0.0050
0.0100
0.0500
0.814
447
0.356
449
0.127
448
3.0 X 10- 5
452
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
1.00 kg
_ gmol_ 1
18 02
L=55 .5M
.sf/. =
t:dv
f X Emax X 2~v 1 12
[area= f
height X base]
mean:
449
Electronic transitions
v------<~
17.1
I'
[J =d lg/ [Ic]
1"-M
(J]max=
d lg - ,-
(J]min =
2.cl lg /" +I M
M)
=--;,Ig
Mil") =--;/g
I (
2l'1!\
l -7')
(1l+M/1"
307
Electronic transitions
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
.st1 =
dv = Emax
J:.,
212
e -'' r dv
= 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
~ii 1 12 =
Electronic transitions
309
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
I,
10 em - I
f = 1.44 x
w - l<Jx 1.8 x 10 15 =2 .6 x
w-
C~o - 4 ~ 5 ) x 10
m - = 3.66 x 10 cm -
10 1s M - 1 cm - 1 S -
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
Electronic transitions
.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)
EI(M- 1 cm- 1)
370
380
390
400
410
420
430
440
25 .6
11
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
Electronic transitions
311
-I"' - I"'
d/. -
c dV-C
Ed).). 2
-CEmax
I"'
e - (.l -.lu)' l 2y
). 2
d).
II
y=
~). f"
n
81
J.. 0
cEmax (2ny)
112
J.. 0
_"'
Therefore ,
8 In 2
= 1.0645
CE
CE max
4 In 2
J..5
ma~
(__!!___) 112
~A1 12
J.. 5
~). 1I'
~A 112 =
40 nm
w-~
~A 1 12 = 65
nm
312
Electronic transitions
: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
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'-A
a = A"-A
.
[In - J[H +]
Smce K . = [InH]
present]
we know that
Electronic transitions
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"
1.00
3.5
4.5
0.90
0.91
0.76
0.50
0.24
0.09
0.01
0.001
-...;;;.
Fig 17.3
!'....
1\
\
\
05
1\
\
\
0
0
[\-..
6 pH 8
314
Electronic transitions
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
6.0
7.0
8.0
pKa
7.1
7.0
6.7
mean: 6.9
600
400
Fig 17.4
'
\.
1\
'
200
1\
\
\
12
16
20
Electronic transitions
315
OzCL:;;-)--?0+0 *
is 6800 em -
I,
0 2(X)-7 0
+0 *
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 *
316
Electronic transitions
[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
2)
112
sin
(nnx)
2e
= - r,
!
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 =
Electronic transitions
317
h2
8me 2.
(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
.sa
.sa
D.v
1.5 x 10 14 s- 1
<:=- =
= 1.4 x 105 M - 1 cm - 1
318
Electronic transitions
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
'1/JuX'I/J udx
[given)
1(R)2}
S= 1 +-R +- {
a0 3 a0
e - Rtao
Electronic transitions
319
Rla0
fifo
0.737
1.376
1.093
0.573
0.233
0.08
0.02
O.Ql
Fig 17.5
lr"\.
10
\
\
1/
1\
~
0
0
That is,
l(R)J =0
R*- - - 1+
a0 3 a 0
320
Electronic transitions
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.
= -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
10- 27 ]
15.00 T
w-26 ]
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,
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
[Section 18.2]
w- 6 x7.0T=53f1T
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
2.2 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 .
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
18.17
10 14 =2 X 10 11
hv
g=/1-B 8
h
!1-B
9.27402 X 10
24
JT
7.14478 X 10 - ll T Hz- I
109 Hz
=2.0022
18.18 a= B(Iine 1) - B(line 2)
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
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
oN
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
10
6X
60 X 106 Hz
2n X (5 .2- 4.0)
300Hz
0.44 ms
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=
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
330
Magnetic resonance
Fig 18.6
5.7mT
18.6 We write P(N2s) = SS. mT
2
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
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
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~
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
ex
1/J
r_ y-
"
11
3x 2) dx X 2.n
cx (x - x .1)1~ 1 =Q
332
Magnetic resonance
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
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-'
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
N_ = e-P' = 1 when
19.2
q=
=
f3 = 0,
CJt~kT) 1/2
{'hr
[10]
2.00 X 10- 6 m 3
= 4.94 X 10 23 (T/ K) 312
X
19.3
(a)
= 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
T)
112
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-
+ 3e -
19.6
U - U(O)
N
L
.
'
E; e -/Jr;
he~
he
= _ _ X (O + 3500 em 3.156
N; e -flr;
N=q
I,
e-
J.4JRRx3SIKJt i9<XJ
N_
(N )
kin
N:
335
336
Therefore,
1.4388cmK x 540cm- 1
354 K
T = ~=
ln(0.90/0.10)
=
Inhcii/k
N+
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]
-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--
1.0
1\
"
01
..........
......;;;
.......
4
0
5
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
(/=1]
dq
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
NE e-P<
_ e -P<
1
[Example 19.6]
Nhcve-"CI'P
- 1 _ e -hciip
Nhcv
_1
e"e~'P
[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
(b) Sm = R In BT 312
At constant volume
Sm = R In CT 511
[23b]
T,
and 1).5 = ~ R In T
I
T,
1).5= C,, In T
I
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
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
(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=
(1.0 X 10- 2 m)
341
Therefore,
5
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
(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
J mol- l
and at 5000 K
Um- Um(O) = 14.10 kJ mol - 1
It follows that
(i) Sm =
(ii) Sm=
=
342
_)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
U - U(O)=
q=
300K
500K
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
1
P 0=-=(a) 0.953, (b) 0.641
q
e - hcf3' 1
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
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
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
19.8
(a)
n
_!_
no
jE
()
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
2
0.69
2
0.69
1
0
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
19.9
dIn q
1
(a) U- U(O) = -N~ with q= _ efJ'
1
V- U(O)
E e- flr
aE= - - -
1-e-P< = eP' -1
1a
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
E,
20.1
[18)
[Experimental: 3.4RJ
[Experimental: 3.2R]
(c)
v~=3,
[Experimental: 8.8R)
0.6950
TIK
q=--x (
')
a
Blcm
0.6950 X (TIK)
10.59
[Table 20.2]
[a= 1] = 0.06563(T/K)
2X
[Table20.2]
[a=2)=43.1
350
(}R
=k
= 1.4388 em K x B
= 1.4388 K x 27 .878
= 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
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]
312
X
(T/K)
101
20.8
Cv!R = f,f=
fJv) (
(T 1 _ e
e -JoviT )
Ovi T
[17]
352
"\
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
u- U(O)
N
Nee- P<
=-"'
e e -P; =
-q L.J
l+e-fl
I
Cv=
353
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 =
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-
G- G(O) = -nRTin q
[Table 20.1]
q=4+2e-fl'
2R ( t:/3)2 e -fir
(2 + e flc )2
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
In 3
Cv=t(3+v~+2vt,)R
[18]
355
356
[19]. Therefore,
n:
s
S",IR
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
20.17
[Table20.2]
=f
298
0.6950 X 1.
9987
v_
1
q - 1 _e -235BI2o7.2
qe
1.00
-
(}R]
Hence
S~ =
Urn- Um(O)
{ q~
}
T
+R lnNA+1
(Table20.1]
N A= 2.561
q T(I2)/ N A= 2.561
qT(I)/ N A= 2.561
20.18
qT/
357
TIK
B/cm -
0.6950
a
qR(J, ) = - - X - -1
1000
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]
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
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
Therefore , if B=5.0T,
2 X 9.274 X 10- 24 J T- 1 X 5.0 T
6.72
TIK
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
Um- Um(O)
T
+ R In q
[Table 20.1]
1 (2nlkT) 112
=iR+Rln- - 2
_ J.
- 2R+Rln3
q = 1 + 5e-/lc
5t: e -/Jc
1 +5e-/J<
hcB
180(hcB{3)2e- 6hcB{J
( 1 + 5e -611cB/i)2
359
360
Cvl R =
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
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
cl~T) c~~~Trr
=~{8n/~~ i (:~rr
=
700
[Table 20.2]
ra=12]
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
M+ R In 9950
Therefore, Sm =
10.7R , or 89 J K - I mol- 1.
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
e ( hz(3 )
:rrm e
LlS~ = R In y e
V6 =
a6
1.0 mol
112
[Problem 20.13]
RT
=
pe
8.21
[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~ =
R In------:-:::------
q=
L (21 + 1)
e -f3h cE(J )
1=0
19.06 X 37.46}3/2
0 964
= { 20.07 X 36.46
=
363
qR(CHD,)qR(DCI)
a(CD 4)
+ 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
q9
(HDO)q 9 (HCI)
K = q e (H20)q e (DCI)
e -f3t>.Eu
{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
1
where q(x) = _ e - 1.4388 xxt(T/K)
1
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
<l>o=
Gm(T)- Hm(O)
qTqi
= -R In NA
Gm(T)- Gm(O)
= -
---
[Table 20.1]
(!:)e
1 0.6950 X 1000
qR=zX
60.864
qv =
5 711
1
_
e4-lfKUY/695.3
= 1.002
1
!]
1 0.6950 X 1000
qR=zX
1.9987
= 173.9
1
q v = 1 _ e- 2358.o7t695.3 = 1. 035
(!:)
(c) NH 3
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)-
365
366
Hence
~G ;;;(T)
198 +
= + 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
t X 0.6950 X
qE(Na) = 2.00
1163
= 2612
_
0 1547
[Problem 20.11)
[eqn9ofSection9.3]
8 7 ) 1/2
=0.83
( 8.7 + 4.0
[p=p 9 ]
Therefore,
2nm)
2nma
qT = ( f3hz XY= f3h2 , a=XY
Um-Um(O)=Sm=
Um- Um(O)
T
~(:;)=RT
+R(lnqm-lnNA+l)
(Table20.1]
[Sackur-Tetrode equation J
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
'\
\
\
I.
100
~~
'
.....
0
01
j....A
r--. -....
X
.......
~v
......
!.,.;'
1-0
I
a'
r-....
~
I
001
'\
001
.........
~
V)2
1\
...... r
"""'
....... ...._
L In qQ = R L ln(1- e-xo)
Q
20.15
N
NkT
(a) U-U(O)=--""e -e- f!c! = - q
qL.Ji
= nR{%-
2(
q2}
(!Y}
I.
369
370
q=
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
M;
M;
= 4+ -i(g!lsf3Br
2: M] [2: M1=o ]
M1
M1
Statisticalthermodynamics:the machinery
Ko =
)2
10
20
1 + 9(,usf3B)2 "'"1 + 9,u~/32B 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
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)
c,
371
(a}
(41}
(b)
(4 1)
(41)
(41}
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)
- +,
- 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
A= 2d sin 8
[2a]
A
8=arcsin d
2
A1
[2a, arcsin=sin - 1]
A,
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
NM
21.10 p = - VNA
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]
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
a
d220 = (22 + 22)1/2
it follows that
a
[1] = 81/2
143 pm
Diffraction methods
375
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
).
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
77
378
= 11.75
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]
i f{1
However , e bri = 1; h, k , and l are all integers. Hence all terms are unity, and
F,kt= [_
21.19 Refer to Fig. 21.3. The hatched area is 3 112R x 2R = 2V3R 2 . The net
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
Diffraction methods
377
NM
p= VNA' implying that
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
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.
21.23
p2
h1
(a) =2m =2m..1. 2 [p=h/..1.]
2X
(b) Write E = ! kT
[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
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
=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
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
f3 = 122 49';
hence
NM
2M
Since p = VNA = 1.662b3N~
we know that
2M
b = ( 1.662pNA
)lt3
1
= ( 1.662 X
)1'3
=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
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
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
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
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
Xma x
and
Xmin
300
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
d
hd
d
kd
sin a= (a/h)=--;;, cos a = (blk) =t;
and therefore
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,
az
ab
ba
ca
az
b2
ac
bc
ab cosy
ab cosy
b2
cb
c-'
ac cos {3
be cos a
ac cos {3
be cos a
cz
Hence,
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
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
Diffraction methods
389
22.1
f1.
3t:oPm
a+ 3kT= NA
22.2
p.
Therefore, k
1 1)
TT'
[6a]
3t:0
= NA (P-P')
and hence
p.2 = - - - - - -
T'
351~0 K
- 423\ K)
= 3.064 X 10- 59 C 2 m2
and hence
f1.
3t:oPm
Then
p.
a
corresponding to a'=--=
9.1 x 10- -' 4 em 3
4nEu
E,-1
22.3 - E,+2
pPm
M
[6b]- ---'----:-::---,-::--...,--;--1
--
=0.556
Hence,
E,
1 +2 X 0.556
_ 0.
1
556
4.8
74.12gmol- 1
_
1
3
Vm= 0.7l gcm _3 =103.6cm mol 5
n,-
Vm-Rm
103 .6-21.72
-1. 34
22.6
3EoRm
M{n~-1}
a = - - with R"'=- - , NA
p n~+2
Therefore,
a = 3c0M {n: -1}
pNA n~+2
[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].
[Section 22.1]
[3]
[IJ=lCV]
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
Hence,
E,
1 + 2x .
pN A (
fl )
_ x with x = EoM a + kT
1
3
3
8.854 X 10- 12 ]
- I
C 2 m 2 X 1.23 X J0 - 29 m 3
E,
1 + 2 X 0.848
_ _
= 18
1 0 848
111.0 g mol- 1
_ =51.6cm 3 mol - 1
2 .1 5 gem 3
n,-
58.4 g mol - 1
=27 .0cm 3 mol - 1,
. gem 3
216
393
394
{(0)12
-;. - (a)6
-;. }
12 6a 6} 24t:{ (a)l3
12a
F = - dV
dr with V = 4t:
Therefore, F= 4t: { ~ -7
=---;;-
2 -;.
- (a)7}
-;.
22.14
xM
xm=xVm [24]= p
-7.2 X 10- 7X 78.11 g mol- 1
0.879 gem 3
22.16
_
Xm- 6.3001
_1
S(S+1)
[Example 22.7]
TIK em 3 mol
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
-drp =
-2f1.
4m::or 3
dr
-1.11
10 - 19 Vm - 1 - 1.11
(r/m)
lOXV m -
(r/nm)
(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 -
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
the~' r
~.n N
a'). We
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
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
:o~)
112
= 4.275
10- 29 C X
= 4.275
= 4.275
= 4.275
(E,-1)
M
Pm = p E,+ 2
4n
NAJ.l
and Pm=)NAa '+ 9EokT
397
398
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)
-c
I
Fig 22.2
"'
~~
40
o...E
v
/
30
/
0
3
4
10~(T/K)
5
mpt.
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,
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
=0.35 D
1.38 x 10 - 23 cm 3
[from Problem 22.3]
400
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
- - = 1-x+x 2 -x -'+x~-
l+x
22.8
n~ - 1
n;+2
4na 'NAp
3M
M
For a gas,
Mp
p=y-= RT
Ill
[9 ]
402
~----------(----------~
Therefore,
n =
r
{11- 4.na,
+8.na'pNA/3M} ltz =
pNA/3M
{11- 4.na
+8.na'p/3kT}ltz
'p/3kT
112
2na'p
= 1 + - - [(1+ x) 112 = 1+ t x]
kT
Hence , n, = 1 + const.
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
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
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'
404
-1
,s
dVdr {-Aa
6a- } =0
-=4c - e-rta +
7
r
a7 A
r7 6
- = - e:-rla
2:rcN A
fa,r
dr + 2:rcN A
2:rc
2:rc
[22c]
3
=3- N AaI3+-N
3 A {1- ecikT}(a 2 -
a 3I )
dr
E~
405
kT, then
2:rc
2:rc
B = 3NAa~-3NAE(a~- ai}lkT
a
B=b-RT
Hence,
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]
U=--+Nu
-- = - i-Nu=-+N 2
However , N
"
Vdr
406
(b)
(a)
180"
Fig 22 7
!'-...
.........
t-....
90
D-2
0"4
.......
:--......
06
"r-..
08
b/{R +R J
1 2
e( v) =
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
160
120
Fig 22.8
'~
'\.
.......
r- ...!2...
"'r-...
........
r- r-
10
approach is E = t mv 2 , and so
(b)
8()=.n-2arcsin{l+Ze~<t">' " }
=3a6
[I
~ x"
e-ax
dx= - n! ]
a" +l
Therefore ,
(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
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
RT{ 1+B-+
c
}
232TI/c==.
M
M
[1b]
(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
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=
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
Macromolecules
2 .0
411
Fig 23.2
}
~
,~
5
8
Cp / mg cm-3
and hence
M=
=
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
the following table:
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
and hence
8.314J K - I mol - 1 X 298 K
M = ---~--,....----~-~--c:-----:-----:4
3
1
3
155 kg mol - 1
412
Macromolecules
1.0
...v
)_,..
I/
Fig23.3
2
0
02
06
DB
10
Cp / (g/ 100cm 3)
04
1.80-5 x 104 cm 7 g- 2
m7 kg- 2
R,ms = N 112l
23.6
Rg=
N1 12l
R
N = 3 ____2
( l
23.7
V3
)2= 3 ( 7 3 nm )2 = 6. 7
X
[r;]=lim (
c~ o
0.154 nm
r;/r; * -1)
c
[16].
103
Macromolecules
413
c/(g L - 1)
1.32
2.89
5.73
9.17
0.0731
0.0755
0.0771
0.0825
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
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"
J'
min -
60
t / min
1) 2
w-'3 s, or 5.0 Sv
12
kT
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
draw up the following table:
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
It fo llows that
M=
= 65.6 kg mol - 1
SRT
23.10
M = bD
3.2 X
[13]
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
-[P]L
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,
lnc=const.+
Mbw 2r 2
RT
[b=l-pu ,]
2
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
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 =
3 X 1.381 X 10
23
JK
298 K
2.4 X 10-R S
(::) 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]
}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-
v(P](Na +]L
(Na +]L- (Na +]R = (Na +]L + (Na+]R
(6a]
= -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
SRT
23.4
M = bD
(13]
kT
6n1]D
a = --=-----~--,---...,---------,-,----::,-------,
=3.4nm
SRT
23.5
M = bD
(13]
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
4n
3
=-N
3 Aa
Hence,
a= (
1
mol - ) 113
4n x 6.022 x 1023 mol - 1
=2.7nm
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
23.6
S= rw 2
1 dIn r
[9a] = w 2 dt [Exercise 23.8]
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)
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
Macromolecules
421
Then,
a= ( 3Vm
4nNA
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]
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
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
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
4nNA
113
Macromolecules
423
That is,
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
-[A] ~Y
ay )
a[A]
= RT ~[A]
424
Macromolecules
[A]/M
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
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
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
23.12
(ay)
f = - RT ac
[31]
ac
(ay)
~Y
=~
Macromolecules
425
Hence,
= -(c/M)(~y/mN
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
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
_(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
=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
II- n o
and ----rr-=28 m3 moJ -I
9.35
II- n o
and ----rr- = 0. 15 mol m- 3 x 0.33 m3 mol - 1 = 5.0 x 10 - 2
B= t NAur [4]
- 16.n
3 - 16.n
3 3
- 3 NAa crr - 3NAy R g [acr1 = yRg]
Macromolecules
427
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
112
)
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
-SdT+tdl
Since d U = T dS + t dl
[given],
(aa~ r = T(~~) r +t
= - T(!!__) + t
aT
[Box3.1J
=a
( !!__)
aT
'
1
(au)
at
=t-aT [above]
=0
-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;)}
=2.{"'
N LJ h I
-2_""
NLJ
hI .
h}
I
ij
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~
ij
a
=4:rr ( :rrii2
)3x83(:rr)II2
3
~
=2a2=Nl2
429
430
Macromolecules
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
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-
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
1/N ~ l.
431
PART 3: CHANGE
24. The kinetic theory of gases
Exercises
24.1
c=
(::n
112
[7b]
(::n
112
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
kT
24.3 p = 2112aA
[Exercise 24.2]
, with A= a 112
Hence,
P=
1.4xl07 Pa
[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
112
X
10 23 J
298
K)
10-IRm2 Xp
zp
ZAA
(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
433
434
24.7
z=
(.n~~T)
112
ap
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
[Example 1.6]
= 21.3 kPa
p(N 2)=0.781atm
[Example l.6]
=79.1kPa
19
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)
- 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
kT
A.=-21/2
ap
[12b)
6.7 X 10-H m
(p/Pa)
p!atm
:Tr
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
436
p
Zw= (2nmkT) 112
24.13
(13b]
90Pa
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
pV
nR
T =-- = ~~~~~--~~~~~~
1
3
1
4.50 x 10
mol x 8.314 J K
mol
=267K
a 12 = n
n(:)
112
+~(~)
a=nd
2.02 X 28.0 U
2.02x 28 .0
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
X --------------~------~~------------~
3
3 2
)
(5.00 X 10- m
X 500 K) 112
24.15
kT
J..= 21120P (12b]
).. = --:-;;:--
[Example 24 .7]
pA 0 m L\t
( m )112
(2nmkT) 112 = pAo L\t 2nkT
M )112
= pAo L\t (
2nRT
) 112
260 X 10- 3kg mol- 1
1
1
(
x 2nx8.314JK- mol- X400K
=
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
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]
1J = tmA.cNA(A]
__ m (4RT) 112
a nM
3
Hence a=
(21]
[Exercise 24.18]
m (4RT)It2
nM
317
p~ = p~ + ( 16117Po) dV
nr4
- p-2 +
-
dt
= 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( =
439
440
7{=
29 mJ K - t m- t s-t
= 1.50 K m x
1<:
'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)
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
:rem
3p X 0.36 X 10 -
i Bm
1.07m2s- 1
l.06x10 - 5 m2s- 1
(p!Pa)
(p/atm)
441
Problems
24.1 The time for a slot to coincide with the location of a neighboring slot is
C~o)
l.Ocm
C~o)
/v
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) =
Therefore , as J oc f , / rx
(T1)
112
(5]
e-mu;mT
Since
TIK
we can write
442
fr:x
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
24.2
(N)
N
(X) = ~
;; Xi [A1, Pi=NJNJ
(a) (u,) =
1
{40x50+62x55+ +2x70+38x(-50)
328
328
{40x50+62x55+ +2x70+38x50
1
{40x502 +62x55 2 + +2x70 2} (mph) 2
328
= 3184(mph) 2
V(u;) = 56mph
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
K'
I(; <X
(T')I/2 x -C~
T 112 C v, so-=
-T
K
Cv
Therefore,
K'
K
dT
dt = KA dz
[Table 24.4]
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
=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
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
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
= -
K)
1/2
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)
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
446
dp
-= ae-k"-bp p = O at t=O
dt
'
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=
K X 298 K) 1/2
-l
= 3.9X 10- 3s - 1
Hence ,
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
24.14
ZAs- a
:nm
(8kT)
:n,u
112(!!f__)
k2T'
[10]
0.5 X 1.0133 X 10 Pa
)2
X ( 1.381x10- 23 JK- 1X400K
=3.3x 1034 m - 3s - 1
448
fi = 2.02+254 = 2 .00u
[Example 24.14]
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
G~m' { 1 -
(1 - i + .. ) } =
Gmm'h
R2
We write this
~w = mgh
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]
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
K fb
==-m
e-'
dx = tKerf(b)
j[
(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
1hr
.n~' 2 )
Therefore,
1
(vx)=CkT)1121 1 - e.nm
erf ( .n~
"']
12 )
24.18
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 *)
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 ,
453
dv
dt=sZwA Vm/NA
where s is the sticking probability . For a spherical particle ,
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
vm =pTherefore ,
dr
- ~ -------;::,..----:-------::----::
dt
c.07
10 - 3 kg mol-l
~~14
1K
- I
=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.
K= cAm
[1]
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]
-(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
Am+ 'J[cl/2
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~(KN0 3 )
A~,(AgN0 3 )
Hence
[3]
A~(AgCl)
1.91 x
Hence, A~ = ( 2 X 0.0 40
91
10
112
- 1 A~
= 0 . 022A~
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
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
= 3.02 X 10- 9 m
25.11
ukT uRT
[16]
ez
zF
D=-=-
7.40 X 10- 8 m2 s- 1 v
- IX
kT
25. 12 a = - 6n71D
10- 23 1 K -
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
= 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
(a) (x 2) 112 = (2
[26b]
2. 13 X 10 - 9 m 2 S-
lX
(1.0 X 10- 3 m) 2
Sucrose: t =
(b) Since
(1.0 X 10- 3 m) 2
m s = 960 s, about 16 min.
x . x
2 5 21 10 10 2 1
(CC
457
Molecules in motion
458
Problems
Preliminary calculation :
'K
=R and
'K
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
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
1.887 X 10- 6 S cm - 1
c= 138 .3 S cm 2 mol_ 1 [Exercise 25.7]
K,P=y~ X
25.4
i\~(NaCH,C0 2 )
i\~(HCl). =A.(H + )
A~(NaCI)
i\~(CH,COOH)
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
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?
lOY
with E = - =10Vcm- 1
1. 00 em
[7]
t(Li +) =
l.Ocm
4.0 x 10 3ems
-250s
---
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
- 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
( 1OJ
=0.0028
25.8 t =
zcVF
zcAFx
!!it (Section 25 .2] = J""M
1
x/mm)
1.50 ( M/s
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
t+ =
0.48 and
t_
= 0.52.
. 1. +
N
(12]
to obtain
t + i\~
(12]
= 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
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+
(a)
t+
(b)
t+
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 - ) =
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
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
- 2.48 kN m mol - 1
x (- 0.50Mm - 1)
_ M
0 05
D
s = kT'!F
w-20 N molecule - 1
[Section 25.4]
S=
(c)
S=
10- 20 = 5.2 nm S- 1
Molecules in motion
25 .13
uRT
D=-
[16]
zF
ze
and a=-6nryu
[Example 25.7]
so
2.569 X 10- 2 V
D/(cm 2 s- 1) =
X u
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
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
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 ~
4n
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
c = A(nDt) 112
[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]
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
-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
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
t = ~ = Aciuilzd = ciuilzil
'
I
A
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
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
' then
When c =a- e- bx-tl
t"2
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 .
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
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
20
r!nPt
fie
40
- -
60 n 80
100
1 d[J]
dt
(1],
u=--
SO
d[J]
-dt =V1V
VJ
1 d[J]
v=-V1 dt
[1]
v = tx 1.0 M s- =0.50 M s-
Vc
= + 2; hence
1
M s- ;
therefore
MS- =(k) X M X M
M-
s -I
d~~J = k[AJ[BJ[CJ
1 d[JJ .
v = - - w1th v1 = vc = 2
V1 dt
= (k1X
M X M X M
= (k 1M 3
2N 2 0 5 ~ 4N0 2 + 0 2 ,
M-
s- 1
v = k[N 20 51
5)
(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 ,
M-
s- 1
s- 1 = [k1 x
M\
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=
5.1 x 10- J M
0.100 MX (e 33 -1)
e _
=0.049 M
2 33 1
26.10
= 3.67x10-3 M- I S- IX
= 1.96Xl0 - 4 MS-I
and hence
Likewise,
MS- 1)
d(P]
d(B]
dt
dt
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,
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
[A] 0
d[A]
[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
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
u = k[Hz0 2][Br-J
The reaction is first-order in H 20 2 and in Br- , and second-order overall.
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]
u=
d[Double helix]
dt
= k 1[Unstable helix]
k,
[Unstable helix], K = k-,
kz
k,
k=k 1 k 2 /k~.
d(A] = -k[A]"
dt
Hence,
IAI d(A]
[A]"= -k
IAio
Therefore, kt=
2n - l
= (
Hence,
t 112 cx
-1) 1
~ X [A]o''-1
1/[A](j- 1
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
[S] - I
KM+[S] - 2
479
480
26.21
k'
k= ka[A]+ k;
a b
[28]
ka p
k'
p'
and hence
1
p'
ka=ll =
12 Pa - 1.30 X 103Pa
1
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
[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,
0-
[B]}
which solves to
[B].,
In [B]., _ [B] = kt
We therefore draw up the following table:
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
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 .,
[U)o
e - kr
In 2
- 1]
[ 19a, k=-=0.0314min
t\ 12
484
[U] 0 = 1 +
[ 19b, k' =
~ 1~ = 0.295 day-' J
ke-k''-k'e-k'
k' - k
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]"
Therefore, since
~[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
2HCI~(HCib
HCI +
CH 3 CH=CH 2 ~Complex ,
K 1 ; [(HCih] = K 1[HCI]2
K2
26.7
E.
R ln(k~rrl kerr)
_!__2_)
( T T'
Rln3
- - - -- =- 20 kJ mol- 1
1
1
343 K
292 K
a In kerr)
E. = -R ( a(l!T) v = E~ + !1U1 + !1U2
since
a InK) -!1U
( a(l!T) v =~
!1U1- !1U2
486
26.8
Ea=
Rln(k'/k)
1
T
1
T'
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
eE,tRT
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]
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
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
NH20-
+ Oz~P
d[NH 20H]
-
dt
d[(NH OH)]
d;
kobs[(NHzOH)][Oz]
k[NH 20 - ][0 2]
-=-+
.
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
Kw
kobs
kK.[OH-]
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
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
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
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]
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
26 13
2A~ B
[A]o
[A]= 1 + kt[A] 0
d[A] = -k[A] 2
dt
6c]
Po
PA = 1 + ktpo, Ps =
1(
2
Po-P A
491
{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
-= - --,
700
fp 0 ,
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
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
0-
[A]}
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'
+ (B] 0 -
co :
+ [B] 0)
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 (
= 6(2B0 - 3A 0)
kt=
{Ix
0
dx
x-tAo-
I x dx }
x-tBo
0
-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
494
d[A]
dx
dt
dt
Therefore,
2x(A 0 -x)
kt = A~(Ao - 2x)z
kt = Jx
0
dx
(A 0 - 2x) 2 (A 0 - x)
1
(Ao-2x?(Ao - x)
a
(Ao - 2x)
fJ
-:------:--:-;;2 + - -
Ao-2x
+- Ao-x
_fx { (2/A
kt -
0)
(A o- 2x)2
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
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 = ~
At t=t 112 , x = tA 0 , so
Hence,
!112
2"-1-1
~ (f)" 1 -1
27.2
dt
-J[Cr(C0) 5M]
.
k 2k4[CO]
tf J= k2 [CO] + k 3[M]
and we have taken
1
- = -
k4
Therefore,
k [M]
3
+ --,----~
k2k4[ col
and a graph of
498
k2[R][R2] - k 3 [R '] = 0
The second solves to
[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
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
0 521
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
Therefore,
499
500
d(AH]
~=
(i)
(ii)
d(B]
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}
d( AH]
( k.kc)
-dt- = - k.[AH]- Zkkd [AH] = kerJ AH]
27.10
d~~] = k[ A f(P]
dx
dt =k(A 0 -x) 2(P0 +x)
(new
dx
(Ao-x) (P0+x)
kt
(Ao-x)2(Po+x)
(A 0-x) 2
{3
A 0-x
P0+x
+--+--
-{3+y=O
Therefore,
kt=
-
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
dt=O,
Up=
k[A]Z[P]
501
502
2~}
or
27.11
d[P] = k[A][P] 2
dt
kt=Jx
0
dx
(A 0 -x)(P0 +x) 2
kt=(-1)fx{(-1) +(- 1
A 0 + P0
P0 + x
)[-1 +-1
A 0 + P0
P0 + x
A0- x
]}dx
dt
dt
= 2k[A][P]vr - k[P] vr
= k[P](2[A]- [P])vr= 0
503
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~+ ) *
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.
ln2
X _6 S 5.1 X 108 M- IS-I
29 10
w-IO
505
--=
k"[O][OH]
d[OH]
-dt-= k[H][N0 2] - 2k'[OH] 2 - k"[O][OH]
d[NO]
T,-=
-k[H][N0
2]
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
506
27.4
+ Cl 2_,. CIO + CI
p(CI 2) =constant
[O]=[O]oe-k'r
That being so,
[0] 0
x;
where k' = [CI 2]k, u is the flow rate , and dis the distance along the tube. We
draw up the following table:
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 ]
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.
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]
[H] =
kc
[CH 3CH 3]
ke + kd[CH3CH2J
[CH3CH2f - (
or [CH3CH2J = {
]"
2
}
[C~JCHJ]
508
If k. is small in the sense that only the lowest order need be retained ,
CH3CHO~CH3 +CHO,
k.
kc
CH 3 ~ CH 3CH 3,
kd
CH3+
kb
d[CH 4]
- d-t - =kb[CH 3][CH3CHO]
d[CH 3CHO]
dt
d[CH]
= k.[CH3CHO]- kb[CH3CHO][CH3] + kc[CH2CHO]- 2kd[CH3]2 = 0
d[CH 2CHO]
dt
kb[CH3][CH3CHO]
. - kc[CH2CHO] = 0
509
Therefore,
d[CH]
4
--
dt
=k
( k
-
2kd
3
d[CH CHO] = - k [CH CHO] - k
dt
(~)
2kd
112
[CH CH0] 312
3
-k
d(CH3CHOJ
dt
(~)t'2[CH 3CH0]3'2
2kd
(i)
d[COC1 2]
dt
= kc[COCl](Clz]
d(COCl]
(ii)
dt
d(Cl]
(iii)
..
kb[Cl][CO]
From (u): [COCI] = k!, + kc[Clz]
(iv)
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
510
27.8
d~~] = ki[M][I]
[initiation]
d[R]
dt = - 2k~(1 + a[M])[Rf
[termination]
[propagation]
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
Hence, oM = - 1- p
=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]
.. 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
27.12
A---+2R , I .
A+ R---+ R + B, kP
R + R---+ R 2, k,
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,
513
[(ii +iii)]
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.
12
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. -
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 .
d~] = k.(A][X] -
(ii)
dt = kb[X][Y] -
d[Y]
kb[X][Y]
kc[Y]
kb[X] [Y] = 0
d[YJ
dt = kb[XJ[Y]- kc[YJ = 0
which solve to
Hence,
k
k [A]
[X] = _:, [Y]= - kb
kb
27.17
(i)
(ii)
(i)
(ii)
dt= -
d(Y]
515
28. 1 z=~
_ (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]
z=~~------~--------~~----------=---~------~
1.10 X 10311 m- 2 s- 1 X R 2
(Mig mol 1) 112
ZA A
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
I X
298.15 K} 112
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)
100x103 Jmol- 1
RT= 8.314 J K 1mol 1x 1000 K
E.
of
1 ( df)
100E.
100x - =100x- xoT=--oT
f
f dT
RT 2
(a) Ea=10kJmol- 1,oT=10K
100
517
518
of 1.20 X 107
100- = ----,--.,..,..! (TIK?
8RT
28.4
kd =
"""3-i
[7] =
3TJ
s 1) xkgm
(TJikgm- 1 s- 1)
(TJ f kg m
1
)
(YJ/cP)
6.61 X 109
_
M- 1 s- 1 =3.0x10 10 M- 1 s- 1
0 22
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]
Xe-E.fRT
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
= 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]
28.8
k
= 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 ,
and hence
13
1
2.05 X 10 M - l s- )
}
~S * = R { In ( 1.59 x 1014 M Is I -1
28.9
~H * =
[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 + =
=74.4 kJ mol - 1
28.10
~H * =E" -2RT
[20a]
dp A
dt = -k2PAPB
kT RT
Xh pe
B= -
--------~~- x -------~-------
and
and hence
~:t.G +
28.11
8k!:\ 112
*
lrfl-}
e -f>Eui RT,
521
522
4a*hp 9
(:n:mk3T3)1 tz
- {:n; X
tm,
so
=7.78 x 10- 4
and hence
ilS t = R {In (
~)- 2} = 8.314 J K
-I
= -76 J K - I mol- 1
28.12
kT
RT
pB
B = -X-
--~~~~~~---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
= -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
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
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
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.
[A-]
-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
K)
a * 4.4 X 10- 20
0.15
Hence P=-;;= . x
3 0 10 19
526
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
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
527
k2=A
=a*NAC:~t~
112
=4a*NA(::)
112
[~t= tmJ
v = k 2[CH3]2
d[CH 3]
----ctt=
- 2k 2[CH3]2
Therefore,
For 90 per cent recombination, [CH 3] = 0.10 X [CH3]0 , which occurs when
Therefore,
9RT
t = - - -k2 X 0.40p
=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,
llS ~
E) RT
by writing
e =A
e-E) RT
529
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
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
z'z"N e 2
A
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
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
(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]
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
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
e -kt
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
1.027
1
,
q 9 T!NA
(T/K)
= 1.4 x 10
312
[Box 20.2)
[Box 20.2]
[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
[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
Therefore,
533
534
Therefore,
A(NL)
3.3 X 104
Fig 28.6
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
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
q*E(Complex) = 2
RT
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
= 6.6X 10 10 M-IS-I
= 1.8 X 106 M- 1 S- 1
536
mHmo)
(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
[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;q:q':
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]
537
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
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
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 .
2.03
10 21X (piTorr)
(T=298 K]
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
29.3
Zw-
(80X4.00)"2
- 2
em
- I
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-
1:o e E,.f RT
[10]
(E.= -L'l.Had)
= 50s
29.5
f 112 =
[10]
1: eE,I RT
0
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
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
[at 298 K]
29.10
Kp
8=-1+Kp
e 1
[2], which implies that K= _ xp1 8
T'
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
Kp
. .
.
1
1
() = 1 + Kp ' which Implies that = 1 - Kp
(Kp) lt2
() =
e= 1 + (Kp) 112
(Kp)l t3
() =
1 + (Kp)l t3
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
Similarly for B:
k .sPsN(l- (}A- (}B)= k ctsN(}s
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'
-=--
a InK)
( iJT 8
[4]
!1H.d-RT
2 (ln
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
545
(i) !!.pit=-= 16 Pa s- 1
500 s
(ii) !!.pit=
15 kPa
1000
s = 15 Pa s- 1
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
546
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
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
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
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=
1
(c-1)z
p
)V= - v + - - [6], z=-;
1-z
c mon
cVmon
p
z
29.4
0.52 Torr- 1
548
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
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
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
v. = c p c'
11
[9], In
v. =In c +-In p.
1
c2
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
up the following table:
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
N=
k~
4 8 x 10 lM
551
a=
6.2 x 10 17 nm~
4.8 x lQIH = 0.13 nm2
'
= ()V0 =~
''
1+Kp
-----,----,-~---,--------- =
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
w-) cm - 3 .
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
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]
We draw up the following table:
[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
[NH3-
t Nz + -}H z]
-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
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
555
(Po)t In(!!_)
, G =p-t Po
Po
1 + Kpo)
KG- - - F=k
( Po
and hence
(l+Kpo)
k
G=-+
-- F
Kpo
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-
Fig29.9
0.04
556
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]
PA =p -x, Ps= p -x
and write
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
(x-p)}
-p
(x-p)}
(p -
x8
x
x) }
28K { --+In
-p(p-x)
p-x
p
+K
r<:=;> +2pln(p~x)}
(p(px_ x)) {8
+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
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
u = 1 + K 112PV2
When (KpF) 1 12 ~ 1, u =
k)l/2
(K p~
29.14 Refer to Fig. 2.12. Let the number density of atoms in the solid be N.
-2n.N"rdzC6
dU={( R+z)-, + r-'}1
560
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
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
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.
-s dT + v dp +y da+JA. dn
+ n(a) dfl.
But since
dG(a) = y da+ fl. dn(a)
we conclude that
ady+ n(a) dJA. = = 0
dfl., = ----e dy
-if(~)=v.
561
562
29.16
(Ra~ dV.
~- - c2RT( dV. )
a
d lnp
dlnp
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~
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
30.1
1
an overpotential
[14a,f=FIRT]
ln(j'/j)
17'=17+(1 -a)f
125
138 mY
mY+(1-0.39) x (25.69mV) 1
zFDc
(19)
6
30.3 j L= --
eRn
zFo
(Example 30.4]
V S cm 2mol- 1m- 1
=el!J-e-YJ
=2sinh(1f17)
[a=0.5]
[ si nhx= e' - e -']
2
564
Dynamic electrochemistry
+x 25 _69rJ mY = 0.01946(ry/mY)
50
Fig 30.1
j/jo
' -1'--
r.....
1/
v
'\
1\
so
0
-100
7J/mV
r.JO
[Exercise 30.4]
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:
Dynamic electrochemistry
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+ )
We can therefore draw up the following table:
III/rnA
0.1
0.3
0.6
1.0
3.0
6.0
10.0
684
395
278
215
124
88
68.0
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-
566
Dynamic electrochemistry
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]
25.69 x
w-' Q
(UA cm - Z:,
[1 V= 1 A Q]
w-
3
Q
25.69 x
r=----,-4
7.9 x 10 -
33Q
25.69 x w- 3 Q
_ x _
0 79 10 12
Dynamic electrochemistry
567
w-ll A cm - 2 X e 76U/S I. 4
568
Dynamic electrochemistry
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
9 =-0.81 V
30.20
(a)
-t!.G 9 /vF
H 2 + !0 2 ~Hz0;
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)
Dynamic electrochemistry
569
+l.06 Y
v)
0.059
E(M, M+) = 9 (M, M+) + - -+( 2
lg 10-fi
0.35 v
= 9 (M, M+) - - z+
> 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:~
> 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
Dynamic electrochemistry
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
=
e -O.OI5!1' "'v)
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]
Dynamic electrochemistry
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
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
Dynamic electrochemistry
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
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)
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
Dynamic electrochemistry
R =
'
Scm
=4Q
1M x 267 S cm 2 mol- 1 x 5 cm 2
.
+
]L = ]L
2 X
= 5.5 X
It follows that
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
4 X 10 (// A?}
0.0257(// A) In { _ _ (1/ A)
1 36
573
574
Dynamic electrochemistry
30.5
4
E = Ec- ( ::) In {
(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,
/)
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)
We then draw up the following table:
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
x3.8Q=58mW.
Dynamic electrochemistry
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].
_ r_
+ afYJ - ta 2YJ 2f + }
= Jo{YJf + f (YJf)"(l- 2a) + }
-1
WJbr fw
cos wt dt = 0
Therefore ,
(j) = t(l- 2a)f%YJ6
=t
(1- 0. 76) X
=7 .2JA-A
vr
575
576
Dynamic electrochemistry
[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.
LX;, (y)
(xy) = (11 N)
(11 N)
L y;
L x;y;
[(xy) - (x)(y)f
(y)2]
P. W. ATKINS
Solutions Manual for
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