CHAPTER 17

NUCLEAR CHEMISTRY

17.1

= , E = N A h , 1 Hz = 1 s 1

(a) =

3.00 108 m s 1
= 5.7 1013 m
20 1
5.3 10 s

E = 6.02 1023 mol1 6.63 1034 J s 5.3 1020 s 1

= 2.1 1011 J mol1

3.00 108 m s 1
= 6.4 1015 m
22 1
4.7 10 s

(b) =

E = 6.02 1023 mol1 6.63 1034 J s 4.7 1022 s 1

= 1.9 1013 J mol1

(c) =

3.00 108 m s 1
= 1.1 1013 m
21 1
2.8 10 s

E = 6.02 10 23 mol 1 6.63 1034 J s 2.8 1021 s 1

= 1.1 1012 J mol1

(d) =

3.00 108 m s 1
= 4..6 1012 m
6.5 1019 s 1

E = 6.02 1023 mol1 6.63 1034 J s 6.5 1019 s 1

= 2.6 1010 J mol1

17.3

We assume that all the change in energy goes into the energy of the ray
emitted. Then, in each case,

E
,
h

SM-471

 106 eV 1.602 1019 J

energy of 1 MeV =

1 eV
1 MeV

13
1
= 1.602 10 J MeV
1.602 1013 J
13
(a) E = (1.33 MeV)
= 2.13 10 J
1
MeV

=
=

2.13 1013 J
E
=
= 3.21 1020 s 1 = 3.21 1020 Hz
34
h
6.63 10 J s
c

3.00 108 m s 1
= 9.35 1013 m
3.21 1020 s 1

1.602 1013 J
13
(b) E = (1.64 MeV)
= 2.63 10 J
1 MeV

2.63 1013 J
E
=
= 3.97 1020 s 1 = 3.97 1020 Hz
34
h
6.63 10 J s

3.00 108 m s 1
= 7.59 1013 m
20 1
3.95 10 s

1.602 1013
(c) E = (1.10 MeV)
1 MeV

=
=

17.5

17.7

J
13
= 1.76 10 J

1.76 1013 J
E
=
= 2.65 1020 s 1 = 2.65 1020 Hz
34
h
6.63 10 J s
c

3.00 108 m s 1
= 1.13 1012 m
2.65 1020 s 1

(a) 31T

0
1

e + 23 He

Y 01 e +

(b)

83
39

(c)

87
36

(d)

225
91

(a)

8
5

Kr

0
1

83
38

e+

Sr

87
37

Pa 24 +

Rb

221
89

B 01 e + ZA E

Ac

A = 8 0 = 8, Z = 5 1 = 4, E = Be

so, 85 B 01 e + 48 Be

SM-472

(b)

63
28

Ni

Ni

e+

(c)

185
79

Au 42 + ZA E

so,

185
79

Au 42 +

(d)

7
4

0
1
0
1

63
29

A= 63 0 = 63, Z = 28 ( 1) = 29, E = Cu

63
28

Be +

0
1

e + ZA E

so,

so, 74 Be +

17.9

0
1

Cu

181
77

A= 185 4 = 181, Z = 79 2 = 77, E = Ir

Ir

e ZA E

A= 7 + 0 = 7, Z = 4 1 = 3, E = Li

e 73 Li

Na

24
12

128
50

Sn

128
51

Sb +

0
1

(c)

140
57

La

140
56

Ba +

0
1

(d)

228
90

(a)

24
11

(b)

Th

Mg +

224
88

0
1

e; a particle is emitted.
e; a particle is emitted.

e; a positron (+ ) is emitted.

Ra + 42 ; an particle is emitted.

B + 42 2 01 n +

17.11 (a)

11
5

13
7

(b)

35
17

Cl + 21 D 01 n +

(c)

96
42

Mo + 21 D 01 n +

(d)

45
21

Sc + 01 n 42 +

36
18

Ar

97
43

42
19

Tc

17.13 (a) A/Z = 68/29 = 2.34 > (A/Z ) based ; hence,

is neutron rich, and decay is most likely.

68
29

Cu

68
29

Cu

0
1

68
e + 30
Zn

(b) A/Z = 103/48 = 2.15 < (A/Z )based ; therefore,

103
48

Cd is proton rich, and + decay is most likely.

243
97

(c)
243
97

260
105

260
105

Cd 01 e +

103
47

Ag

Bk has Z > 83 and is proton rich; therefore, decay is most likely.

Bk 42 +

(d)

103
48

239
95

Am

Db has Z > 83; therefore, decay is most likely.

Db 42 +

256
103

Lr

SM-473

17.15

235
92

231
90

231
91

227
89

227
90

U 42 +

231
90

Th

e+

231
91

Pa

Pa 42 +

227
89

Ac

Ac

e+

227
90

Th

Th 42 +

223
88

Ra

223
88

Ra 42 +

219
86

Rn

219
86

Rn 42 +

215
84

Po

215
84

215
85

211
83

211
84

Th

Po

0
1

0
1

e+

215
85

At

At 42 +

211
83

Bi

Bi

211
84

0
1

0
1

e+

Po 24 +

Po

207
82

Pb

17.17 To determine the charge and mass of the unknown particle, it helps to

write 11 p and 01 n for the proton and neutron, respectively; and

for the particle and positron, respectively.

N + 42 178 O + 11 p

(a)

14
7

(b)

248
96

Cm + 01 n

249
97

Bk +

(c)

243
95

Am + 01 n

244
96

Cm +

(d)

13
6

C + 01 n 146 C +

17.19 (a)

20
10

Ne + 42 48 Be + 168 O

(b)

20
10

Ne +

(c)

44
20

Ca + 42 +

(d)

27
13

Al + 21 H 11 p +

20
10

Ne 168 O +

0
1

24
12

0
1

e+

Mg

48
22

Ti

28
13

Al

SM-474

0
1

e and 01 e

17.21 In each case, identify the unknown particle by performing a mass and

charge balance as you did in the solutions to Exercises 17.5 and 17.7.
Then write the complete nuclear equation.

N + 42 178 O + 11 p

(a)

14
7

(b)

239
94

Pu + 01 n

240
95

Am +

0
1

17.23 (a) untriquadium, Utq (b) unquadpentium, Uqp

(c) binilunium, Bnu

1 Ci
5
17.25 activity = (4.7 105 Bq)
= 1.3 10 Ci
10

3.7
10
Bq

17.27 1 Bq = 1 disintegration per second (dps)

106 Ci 3.7 1010 dps

4
(a) (2.5 Ci)

= 9.2 10 dps
1 Ci
1 Ci

= 9.2 104 Bq
(b) 142 Ci = (142) (3.7 1010 dps) = 5.3 1012 Bq
103 Ci 3.7 1010 dps
8
(c) (7.2 mCi)

= 2.7 10 dps
1 Ci
1 mCi

= 2.7 108 Bq

1 rad
17.29 dose in rads = 1.0 J kg 1 2
= 1.0 102 rad
1
10 J kg

dose equivalent in rems = Q dose in rads

1 rem
2
2
=
(1.0 10 rad) = 1.0 10 rem
1
rad

2
1.0 10 rem 100 rem/Sv = 1.0 Sv

1 rem
1
17.31 1.0 rad day 1 = (1.0 rad day 1 )
= 1 rem day
1 rad

SM-475

100 rem = 1 rem day 1 time

time = 100 day

17.33 k =

0.693
t1/ 2

(a) k =

0.693
= 5.63 102 a 1
12.3 a

(b) k =

0.693
= 0.83 s 1
0.84 s

(c) k =

0.693
= 0.0693 min 1
10.0 min

17.35 We know that initial activity N0 , and final activity N . Therefore,

final activity
N
=
= e kt
initial activity N 0
k=

0.693 0.693
=
= 0.132 a 1
5.26 a
t1/ 2

final activity = initial activity e kt

= 4.4 Ci e (0.132 a

50 a )

= 6.0 103 Ci

17.37 In each case, k =

0.693
N
= e kt , and the percentage
, N = N 0 e kt ,
t1/ 2
N0

remaining

= 100% ( N / N0 )
(a) k =

0.693
= 1.21 104 a 1
3
5.73 10 a

percentage remaining = 100% e (1.21 10

(b) k =

0.693
= 0.0563 a 1
12.3 a

SM-476

4 1

a 2000 a )

= 78.5%

percentage remaining = 100% e (0.0563 a

11.0 a )

= 53.8%

17.39 (a) From Table 17.5, t1/ 2 = 4.5 109 a

k=

0.693
0.693
=
= 1.54 1010 a 1
9
t1/ 2
4.5 10 a

fraction remaining =

N
= e kt
N0

= e (1.54 10

10 1

4.5 109 a )

= e 1.4 = 0.50
After 1 half-life, 50% remains.
(b) fraction remaining =
t1/ 2 = 1.26 109 a, k =

N 3
= ;
N0 5

0.693
= 5.50 1010 a 1
9
1.26 10 a

3
= e kt
5
10 1
3
= e (5.50 10 a x )
5
x = 9.3 108 a

17.41 Let dis = disintegrations

activity from old sample =

1500 dis/0.250 g
= 600 dis g 1 h 1
10.0 h

activity from current sample = 921 dis g 1 h 1

0.693
0.693
k=
=
= 1.21 104 a 1
3
t1/ 2
5.73 10 a
old activity N , current activity N 0
N
old activity
N
N
=
= e kt , 0 = e kt , ln 0
current activity N 0
N
N
Solve for t ( = age) :

SM-477

= kt

N
921
ln 0
ln

N
600 = 3.54 103 a
t=
=
k
1.21 104 a 1

17.43 In each case, k =

activity in Ci =

0.693
, activity in Bq = k N
t1/ 2 (in s)

activity in Bq
3.7 1010 Bq Ci 1

Note: Bq (= disintegrating nuclei per second) has the units of nuclei s 1

0.693

1a
11 1
(a) k =

= 1.37 10 s
3
7
1.60 10 a 3.17 10 s
1 mol 6.02 1023 nuclei
18
N = (1.0 10 g)
= 2.7 10 nuclei

1 mol
226 g

1Ci
activity = 1.37 1011 s 1 2.7 1018 nuclei

10
3.7 10 Bq
= 1.0 103 Ci
0.693
1y
(b) k =

7
28.1 a 3.17 10

10 1
= 7.80 10 s
s

1 mol 6.02 1023 nuclei

16
N = (2.0 106 g)
= 1.3 10 nuclei

1 mol
90 g

1 Ci
activity = (7.80 1010 s 1 ) (1.3 1016 nuclei)

10
3.7 10 Bq
= 2.7 104 Ci
0.693
1y
(c) k =

7
2.6 a 3.17 10

9 1
= 8.4 10 s
s

1 mol 6.02 1023 nuclei

18
N = (0.43 103 g)
= 1.8 10 nuclei

147
g
1
mol

1 Ci
activity = (8.4 109 s 1 ) (1.8 1018 nuclei)
= 0.41 Ci
10
3.7 10 Bq

SM-478

17.45 k =

0.693 0.693
=
= 0.0861 d 1
t1/ 2
8.05 d

N = N 0 e kt and

N
= e kt
N0

Taking natural log of both sides gives

N
ln
= kt
N0
Because activity is proportional to N (Eq. 2), we can write
final activity
ln
= kt
initial activity

Solving for t gives

final activity
1
1
10
t = ln
ln
=
= 45 d
1
500
0.0861
d
k

initial activity

N
17.47 (a) activity N ; and, because ln
= kt
N0
final activity
ln
= kt
initial activity

32
ln = k 12.3 d
58

k = 0.048 d 1
t1/ 2 =

0.693
0.693
=
= 14 d
k
0.048 d 1

N
1
(b) ln
= 0.048 d 30 d = 1.4
N0

N
= fraction remaining = 0.25
N0

17.49 k =

0.693 0.693
=
= 0.131 a
t1/ 2
5.27 a

SM-479

-1
N
0.266 g
=e kt =e-(0.131 a )(2.50 a ) =
N0
N0

N 0 = 0.370 g
0.370 g
100 = 26.4%
1.40 g

17.51 Since radioactive decay follows first-order kinetics, the rate of loss of X is
d[X]
= k1 [X]
dt

(1) Y, which is an intermediate, is lost in the first reaction but formed in

the second one, so its rate equation can be expressed as
d[Y]
= k1 [X] k2 [Y]
dt

(2) Z is the final product of the two consecutive reactions so its rate law is
d[Z]
= k2 [Y]
dt

(3) As discussed in Chapter 13, the integrated form of equation (1) is

[X] = [X]0 e- k1t

(4) Substituting this expression into the rate law for Y and rearranging
gives
d[Y]
+ k2 [Y] = k1 [X]0 e- k1t
dt

(5) This linear first-order differential equation has the solution

[Y] =

k1
(e- k1t -e- k2t )[X]0
k2 k1

when [Y]0 = 0 .

(6) Since [X]+[Y]+[Z]=[X]0 at all times, [Z]= [X]0 ([X]+[Y]), or

k e- k2t -k2 e- k1t

k1
[Z] = [X]0 [X]0 e- k1t +
(e- k1t -e- k2t )[X]0 = [X]0 1 + 1

k2 k1
k2 k1

(7) The values of the rate constants can be found from the half-lives:
k1 =

0.693
= 0.0253 d -1
27.4 d

k2 =

0.693
= 0.0371 d -1
18.7 d

SM-480

Using these constants and assuming [X]0=2.00 g, equations (4), (6) and (7)
are graphed below.

grams

1.5

X (g)
Y (g)
Z (g)

0.5

0
0

25

50

75

100

125

150

t (days)

17.53 If isotopically enriched water, such as H 218 O, is used in the reaction, the

label can be followed. Once the products are separated, a suitable

technique, such as vibrational spectroscopy or mass spectrometry, can be
used to determine whether the product has incorporated the

18

O. For

example, if the methanol ends up with the O atom from the water
molecules, then its molar mass would be 34 g mol1 , rather than

32 g mol1 found for methanol with elements present at their natural

isotopic abundance.
17.55 The vibrational frequency is proportional to the reduced mass of the two

atoms that form the bond according to the equation:

SM-481

1
2

where =

mA mB
mA + mB

Because we are not given , it is easiest to make a relative comparison by

taking the ratio of for the CD molecule versus for the CH
molecule:
1
2

C D
=
C H
1
2

k
CD
k

CH
=
CD

CH

mC mH
mC + mH
=
mC mD
mC + mD

(12.011) (1.0078)
12.011 + 1.0078
(12.011) (2.0140)
12.011 + 2.0140

12.105

13.019
=
= 0.73422
24.190

14.025

We would thus expect the vibrational frequency for the CD bond to be

approximately 0.73 times the value for the CH bond (lower in energy).
17.57 Remember to convert g to kg.

(a) E = mc 2 = (1.0 103 kg) (3.00 108 m s 1 ) 2

= 9.0 1013 kg m 2 s 2 = 9.0 1013 J

(b) E = mc 2 = (9.109 1031 kg) (3.00 108 m s 1 ) 2

= 8.20 1014 kg m 2 s 2 = 8.20 1014 J

(c) E = mc 2 = (1.0 1015 kg) (3.00 108 m s 1 )2 = 90 kg m2 s 2 = 90 J

(d) E = mc 2

E = (1.673 1027 kg) (3.00 108 m s 1 )2 = 1.51 1010 J

17.59 m =

3.9 1026 J s 1
E
=
= 4.3 109 kg s 1
1 2
2
8
c
(3.00 10 m s )

17.61 1 u = 1.6605 1027 kg

SM-482

In each case, calculate the difference in mass between the nucleus and the
free particles from which it may be considered to have been formed. Then
obtain the binding energy from the relation Ebind = mc 2 .
(a)

62
28

Ni: 28 1 H + 34 n

62
28

Ni

m = 61.928 u (28 1.0078 u + 34 1.0087 u) = 0.5862 u= 0.586 u (SF)

1.6605 1027 kg
28
m = (0.5862 u)
= 9.7339 10 kg
1u

28
Ebind = (9.7339 10 kg) (3.00 108 m s 1 ) 2
= 8.7605 1011 kg m 2 s 2 = 8.7605 1011 J
Ebind /nucleon =

(b)

239
94

8.7605 1011 J
= 1.41 1012 J nucleon 1
62 nucleons

Pu: 94 1 H + 145 n

239
94

Pu

m = 239.0522 u (94 1.0078 u + 145 1.0087 u) = 1.9425 u

1.6605 1027 kg
27
m = 1.9425 u
= 3.2255 10 kg
1
u

27
Ebind = 3.2255 10 kg (2.997 108 m s 1 ) 2 = 2.897 1010 J
2.897 1010 J
Ebind /nucleon =
= 1.212 1012 J nucleon 1
239 nucleons
(c)

2
1

H: 1 H + n 21 H

m = 2.0141 u (1.0078 u + 1.0087 u) = 0.0024 u

1.6605 1027 kg
30
m = 0.0024 u
= 4.0 10 kg
1u

30
8
Ebind = 4.0 10 kg (3.00 10 m s 1 ) 2 = 3.6 1013 J
Ebind /nucleon =
(d)

3
1

3.6 1013 J
= 1.8 1013 J nucleon 1
2 nucleons

H: 1 H + 2 n 31 H

m = 3.016 05 u (1.0078 u + 2 1.0087 u) = 0.009 15 u

1.6605 1027

m = 0.009 15 u
kg = 1.52 1029 kg
1u

SM-483

Ebind = 1.52 1029 kg (3.00 108 m s 1 ) 2 = 1.37 1012 J

E bind /nucleon =
(e)

62

1.37 1012 J
= 4.57 1013 J nucleon 1
3 nucleons

Ni is the most stable, because it has the largest binding energy per

nucleon.
17.63 In each case, we first determine the change in mass, m = (mass of

products) (mass of reactants). We then calculate the energy released from

E = (m)c 2 .
(a) D + D 3 He + n
2.0141 u + 2.0141 u 3.0160 u + 1.0087 u
4.0282 u 4.0247 u
1.661 1027 kg
30
m = (0.0035 u)
= 5.8 10 kg
1u

2
30
E = mc = (5.8 10 kg) (3.00 108 m s 1 ) 2 = 5.2 1013 J
5.2 1013 J

1u
1
10

= 7.8 10 J g
24
4.0282
u

1.661 10 g

(b)

He + D 4 He + 11 H

3.0160 u + 2.0141 u 4.0026 u + 1.0078 u

5.0301 u 5.0104 u
1.661 1027 kg
29
m = (0.0197 u )
= 3.27 10 kg
1u

2
29
E = mc = (3.27 10 kg) (3.00 108 m s 1 )2 = 2.94 1012 J
2.94 1012 J

1u
11
1

= 3.52 10 J g
24
5.0301
u

1.661 10 g

(c) 7 Li + 11 H 24 He

SM-484

7.0160 u + 1.0078 u 2(4.0026 u)

8.0238 u 8.0052 u
1.661 1027 kg
29
m = (0.0186 u)
= 3.09 10 kg
1u

2
29
E = mc = (3.09 10 kg) (3.00 108 m s 1 ) 2 = 2.78 1012 J
2.78 1012 J

1u
11
1

= 2.09 10 J g
24
8.0238 u 1.661 10 g

(d) D + T 4 He + n
2.0141 u + 3.0160 u 4.0026 u + 1.0087 u
5.0301 u 5.0113 u
1.661 1027 kg
29
m = (0.0188 u)
= 3.12 10 kg
1u

2
29
E = mc = (3.12 10 kg) (3.00 108 m s 1 ) 2 = 2.81 1012 J
2.81 1012 J

1u
11
1

= 3.36 10 J g
24
5.0301
u

1.661
10
g

17.65

24
11

Na

24
12

Mg +

0
1

mass ( 24
11 Na) = 23.990 96 u
mass ( 24
12 Mg) = 23.985 04 u
The mass of the electron does not need to be explicitly included in the
calculation because it is already included in the mass of Mg.
24
m = mass ( 24
12 Mg ) mass ( 11 Na) = 23.985 04 u 23.990 96 u

= 5.92 103 u

m (in kg) = 5.92 103 u 1.661 1027 kg u 1 = 9.83 1030 kg

(a) E = mc 2 = (9.83 1030 kg) (3.00 108 m s 1 )2 = 8.85 1013 J
(b) E (per nucleon) =

8.85 1013 J
= 3.69 1014 J nucleon 1
24 nucleons

This simple calculation works because the number of nucleons is the same
on both sides of the equation.

SM-485

17.67 (a)

244
95

Am

(b)

235
92

U + 01 n

(c)

235
92

U + 01 n 101
42 Mo +

134
53

I+
96
40

107
42

Mo + 3 01 n

Zr +

Te + 2 01 n

138
52

132
50

Sn + 3 01 n

17.69 (a) 1 Ci = 3.7 1010 decays per second (dps)

decays per minute (dpm) for

60 s
4 pCi = 4 1012 Ci 3.7 1010 dps

1 min
= 9 dpm
103 L
(b) volume(L) = (2.0 3.0 2.5) m3
= 1.5 104 L
3
1
m

4 pCi 9 decays min 1

number of decays = (1.5 104 L)
(5.0 min)

4 pCi
1 L

5
= 7 10 decays

17.71 N 0 = number of

222

Rn atoms = 2.0 105 mol 6.0 1023 atoms mol1

= 1.2 1019 atoms

k=

ln 2 0.693
=
= 0.181 d 1
t1/2
3.82 d

1d
0.181
(a) rate of decay = k N =

4
d 8.64 10

19
(1.2 10 atoms)
s
= 2.52 1013 atoms s 1 (dps or Bq)

1 pCi
1 Ci
initial activity = (2.52 1013 Bq)
12

10
3.7 10 Bq 10 Ci

1 m3
1

3
3
2000 m 10 L
= 3.4 108 pCi L1

(b) N = N 0 e kt = 1.2 1019 atoms e 0.181 d

SM-486

1d

= 1.0 1019 atoms

activity
(c) ln
= kt
initial acitivity

1
4
l activity
ln
t = ln
=
1
8
k initial activity
0.181 d 3.4 10
= 1 102 days

17.73 (a) At first thought, it might seem that a fusion bomb would be more

suitable for excavation work, because the fusion process itself does not
generate harmful radioactive waste products. However, in practice, fusion
cannot be initiated in a bomb in the absence of the high temperatures that
can only be generated by a fission bomb. So, there is no environmental
advantage to the use of a fusion bomb. The fission bomb has the
advantage that its destructive power can be more carefully controlled. It is
possible to make small fission bombs whose destructive effect can be
contained within a small area.
(b) The principal argument for the use of bombs in excavation is speed,
and therefore cost-effectiveness, of the process. The principal argument
against their use is environmental damage.

17.75 k =

0.693
= 1.5 1010 a 1
4.5 109 a

1 N
t (= age) = ln

k N0
mass of 238 U
N
=
=
N 0 initial mass of 238 U

1
mass of 206 Pb
1+
mass of 238 U

(a)

N
1
1
=
=
, therefore age = t1/ 2 = 4.5 109 a
N 0 1 + 1.00 2.00

(b)

N
=
N0

1
1
1+
1.25

= 0.556

SM-487

1
t (= age) =
ln (0.556) = 3.9 109 a
10
1

1.5
10
a

3.7 1010 Bq
17.77 (a) activity = (17.3 Ci)

1 Ci

11
11
= 6.4 10 Bq = 6.4 10 nuclei s 1

1 nucleus
1u
16
N = (2.0 106 g)

= 5.0 10 nuclei
24
24
u

1.661 10 g
11
1
activity 6.4 10 nuclei s
=
= 1.3 105 s 1 = 1.1 d 1
k=
16
N
5.0 10 nuclei
t1/ 2 =

0.693
0.693
=
= 5.3 104 s = 15 h = 0.63 d
5 1
k
1.3 10 s

(b) m = m0 e kt = 2.0 mg e 1.11 d

2.0 d

= 0.22 mg

17.79 (a) Radioactive substances which emit radiation are most effective for

diagnosis because they are the least destructive of the types of radiation
listed. Additionally, rays pass easily through body tissues and can be
counted, whereas and particles are stopped by the body tissues.
(b) particles tend to be best for this application because they cause the
most destruction. (c) and (d)
67

131

I, 8d (used to image the thyroid);

Ga, 78 h (used most often as the citrate complex);

99m

Tc, 6 h (used for

various body tissues by varying the ligands attached to the Tc atom).

SM-488

14

Fraction of C remaining

17.81 (a)
1
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
0

10000

20000

30000

40000

time (y)

14

ln(Fraction of C remaining)

(b)
0
-0.5
-1
-1.5
-2
-2.5
-3
-3.5
-4
-4.5
-5

ln(N/No) = (-1.2110-4)time

10000

20000

30000

40000

time (y)

(c) The information can be obtained from the graphs or from the equation

ln

N
= kt
N0

If we want to have less than 1% of the original amount of

14

then we will want the value for which N / N0 is 0.01 or less.

ln 0.01 = (1.21 104 a 1 ) (t )
t = 3.8 104 a

SM-489

C present,

17.83 Radon-222 decays to polonium-218 by alpha emission with a half-life of

3.824 days.
222
86

Rn

218
84

Po + 42

t1/2 = 3.824 d

An alpha particle is the nucleus of 4 He . Assuming that (1) the alpha

particles are captured inside the container, (2) they behave as an ideal gas
and (3) the temperature is constant at 298 K, we can find the volume of the
container by calculating the number of moles of 42 formed in 15 days and
then applying the ideal gas law.

nHe = nPo = ninitial Rn n final Rn

k=

n final Rn N15 days

0.693
0.693
=
= 0.181 d -1
t1/2
3.824 d

N15 days = N 0 e kt = (2.5 g)e (0.181 d

-1

)(15 d)

=0.165 g

1 mol 222 Rn
Rn)

222
222.0175 g Rn
= 7.43 104 mol 222 Rn

n final Rn = (0.165 g

222

1 mol 222 Rn
Rn)

222
222.0175 g Rn
= 1.13 102 mol 222 Rn

ninitial Rn = (2.5 g

222

nHe = ninitial Rn n final Rn = 1.13 102 mol 7.43 104 mol

=1.06 10-2 mol

PV = nRT
nRT (1.06 10-2 mol)(0.08206 L atm K -1 mol-1 )(298 K)
=
P
1.00 atm
= 0.26 L

V =

17.85 (a) The rate will decrease because the heavier D atom makes the zero-

point energy of the X-D bond lower than that of the X-H bond. The X-D
bond energy is deeper in the potential energy well and requires slightly
more energy for dissociation.
(b) The activation energy would correspond to the bond dissociation
energy. As long as the force constant for the transition state is low, the

SM-490

bond dissociation energies for C-H and C-D will be the same except for
the small difference in their zero-point energies.

Ea (C D ) = Ea (C H ) + 1 2 h( C-H C-D )
Recall from problem 17.55:

1
2

where =

mA mB
mA + mB

CD
CH
=
= 0.73422
CH
CD
The ratio of rates will be the same as the ratio of the rate constants.

Ea( C H )

kC H Ae RT
=
=e
Ea (
)
kC D
CD
Ae RT
Ea(C D) Ea(C H) =
=

Ea (C D )
RT

RT

h( C-H C-D ) =

Ea (C D ) Ea( C H )

Ea( C H )

=e
1

RT

h( C-H 0.73422 C-H )

h(0.26578 C-H )

Noting that a typical C-H stretching frequency is about

3000 cm 1 or 9 1013 Hz (see, for example, Exercise 2.101)

kC H
=e
kC D

2 (6.62610

34

J s)(0.26578)(91013 s-1 )(6.021023 mol-1 )

(8.314J K -1 mol-1 )(298K)

= e1.925 = 6.86 7

(c) If the carbon atom is infinitely heavy, then it acts like a stationary wall
and does not vibrate. In that case, the H or D atomic mass can be used
instead of the reduced mass since only that atom is moving.

D
mH
=
= 0.70739
mD
H
Ea (D) Ea(H) =
kC H
=e
kC D

2 (6.62610

h( H D ) =

34

h( H 0.70739 H ) =

h(0.29261 H )

J s)(0.29261)(91013 s-1 )(6.021023 mol-1 )

(8.314J K -1 mol-1 )(298K)

= e2.119 = 8.32 8

This result suggests that the kinetic isotope effect can become even more
pronounced for heavier molecules.
SM-491

17.87 mtot = me + me+

= 2me = 2(9.109 39 10-31 kg)

=1.821 88 10-30 kg
E =mc 2
=(1.821 88 10-30 kg)(2.997 92 108 m s-1 ) 2
= 1.637 42 10-13 J
17.89 (a) 28 He 83 Li +
8
4

0
1

e followed by 83 Li 48 Be +

Be 2 42 He

(b)

14
8

O+

0
1

14
7

SM-492

0
1

e followed by