Larry Brown

Tom Holme

Chapter 14
Nuclear Chemistry

Jacqueline Bennett • SUNY Oneonta

www.cengage.com/chemistry/brown
Learning Outcomes

• write, balance, and interpret equations for simple nuclear

reactions.
• interpret the kinetics of radioactive decay using first-order rate
equations.
• use the chart of the nuclides to understand and explain how
radioactive decay processes increase nuclear stability.
• discuss the potential of both fission and fusion as energy sources
and identify the pros and cons of the two technologies.
• explain how penetrating power and ionizing power combine to
determine the effect of radiation on materials, including living
tissues.

2
 The Nature of Radioactivity
Henri Becquerel (1896)
• U salts emitted rays that “fog” a photographic plate.
• U metal was a stronger emitter.

Marie and Pierre Curie

• Isolated Po and Ra that did the same.
• Marie Curie called the phenomenon radioactivity

Thomson and Rutherford

• Studied the radiation, and found two types: α and β.

Villard
• Discovered g radiation.

© 2008 Brooks/Cole 3
 The Nature of Radioactivity

Name Symbol Charge Mass (g) Pen. Power*

alpha 4 4He +2 6.65 x 10-24 0.03 mm
2 2
beta 0b 0e
-1
-1 9.11 x 10-28 2 mm
-1
gamma 0g g 0 0 100 mm
0
*Distance at which half the radiation has been stopped by water.

© 2008 Brooks/Cole 4
 Nuclear Reactions
Rutherford & Soddy (1902)
“Radioactivity is the result of a natural change of a
radioactive isotope of one element into an isotope of
a different element”.
226 222 4
88
Ra 86
Rn + 2
He
Radium-226 Radon-222 alpha particle

mass no. (A) 226 222 + 4

atomic no. (Z) 88 86 + 2

Note: A and Z must balance

© 2008 Brooks/Cole 5
 Alpha and Beta Particle Emission
Alpha – a nucleus ejects a helium nucleus:

238 234 4
92
U 90
Th + 2
He

Beta – a nucleus ejects an electron:

90 90 0
38
Sr 39
Y + -1
e
How does a nucleus eject an e-? A series of steps, but the
net result is:
1 1 0
0
n 1
p + -1
e
neutron proton electron
© 2008 Brooks/Cole 6
 Radioactive Series

A decay product
(daughter isotope) is
often unstable...

A radioactive series.

The neutron number = N

N=A-Z

© 2008 Brooks/Cole 7
 Other Types of Radioactive Decay
Positron emission
Positron = positive electron ( +10 e or b+). Antimatter.

43 43 0
21
Sc 20
Ca + +1
e

Antimatter is annihilated by collision with matter:

b+ + e - 2g

© 2008 Brooks/Cole 8
 Other Types of Radioactive Decay
Electron capture (EC)
An inner-shell e- (K shell) is captured by the nucleus.

7 0 7
Be + e 3
Li
4 -1

Sometimes called K-capture.

© 2008 Brooks/Cole 9
 Alpha and Beta Particle Emission
Radioactive iodine-131 is used to test thyroid function. It
undergoes beta decay to form a new element. Write a
balanced equation for the process.

A = 131 Look up Z for I (Z = 53)

131 0 131
53
I e + Xe
-1 54

Add b (product).
Calculate the Z and A for the new isotope

Look up the element with Z = 54

© 2008 Brooks/Cole 10
 Section 19.1
Nuclear Stability and Radioactive Decay

Types of Radioactive Decay

Return to TOC

Copyright © Cengage Learning. All rights reserved 11

Example Problem 14.1

• Complete the equations for each of the following nuclear

decay processes.

210
84 Po ¾¾
® 206
82 Pb + ?

230
90 ® ? + 24 He
Th ¾¾

12
Example Problem 14.2

• Complete the equations for each of the following beta decay

reactions using the beta nuclide symbol to represent the beta
particle.
234
90 Th ¾¾
® 234
91 Pa + ?

234
91 ®? +
Pa ¾¾ 0
-1 b +n

𝜈 𝑎𝑛𝑑 𝜈ҧ - A neutrino and its antineutrino have identical masses, estimated to be on the order of a million times less than
the mass of an electron. The neutrino and antineutrino are a matter–antimatter pair, like the positron and the electron. 13
Example Problem 14.3

• Complete the following equations with the correct particles

and identify the mode of decay.

15
8 O ¾¾
® 15
7 N + ?

40
19 ®? +
K ¾¾ 0
-1 b + n

40
19 K + ? ¾¾
® 40
18 Ar + n

𝜈 𝑎𝑛𝑑 𝜈ҧ - A neutrino and its antineutrino have identical masses, estimated to be on the order of a million times less than
the mass of an electron. The neutrino and antineutrino are a matter–antimatter pair, like the positron and the electron. 14
 Stability
of Atomic
Nuclei

© 2008 Brooks/Cole 15
 The Band of Stability
Stable nuclei have N ≥ Z.
• Nuclei with Z < 20: N / Z ≈ 1.
• Nuclei with Z > 20: N / Z gradually increases.
• 209Bi (Z = 83) is the heaviest stable nucleus.

• Even-Z isotopes are more common than odd.

• Even-N isotopes are more common than odd.
• 200 “even-even”; 120 “odd-even”; 4 “odd-odd”

Unstable isotopes decay so that the daughter will

enter the “peninsula of stability”.
© 2008 Brooks/Cole 16
 Predicting Nuclear Decay
Elements with Z > 83
Most decay by alpha emission.

Elements with Z<83

Use a periodic table
▪ Compare A with the element’s average atomic wt.
▪ Too heavy = too many n0: b emission (n0 → p+ + e-).
▪ Too light: b+ emission or e- capture (p+ → n0).

© 2008 Brooks/Cole 17
 Predicting Nuclear Decay
Example
14 15 16
Predict how 28P will decay.
Si P S
Atomic weight of P = 30.97 28.09 30.97 32.07
28P is too light.

β+ decay. 28 0
e + 28 Si
15 P +1 14

Example
How will 28Mg decay? Atomic weight of Mg = 24.31
11 12 13 28Mg is too heavy.

Na Mg Al β decay.
22.99 24.31 26.98 0 28
28
12
Mg -1
e + 13
Al
© 2008 Brooks/Cole 18
 Binding Energy
A measure of the force holding a nucleus together.
Eb = −ΔEnucleus formation
E released when component p+ + n0 combine.

Einstein (special relativity): E = mc2

Eb = -ΔE = -(Δm) c2
with:
Δm = (mass nucleus) − (mass of p+ + n0)
c = speed of light = 2.99792458 x 108 ms-1
= 3.00 x 108 ms-1

© 2008 Brooks/Cole 19
 20

Nuclear Binding Energy for Helium

This small amount of

mass—the mass defect—
is equivalent to a huge
amount of energy.

The nucleus weighs less

than its nucleons. Some
mass was converted to
energy that holds the
nucleus together.

Prentice Hall © 2005 General Chemistry 4th edition, Hill, Petrucci, McCreary, Perry
Chapter Nineteen
 Nuclear Binding Energy
Example
Determine the binding energy and binding energy per
nucleon for 12C. The mass of 12C =12.00000 g/mol,
mn=1.00867 g/mol, and mp=1.00783 g/mol.
6 n 0: 6 x 1.00867 = 6.05202
6 p+: 6 x 1.00783 = 6.04698
Total mass nucleons = 12.09900 g/mol

Δm = mass of nucleus – sum of nucleons

= 12.00000 – 12.09900 g/mol
= -0.09900 g/mol

© 2008 Brooks/Cole 21
 Nuclear Binding Energy
Determine the binding energy and binding energy per nucleon for 12C. The mass of
12C =12.00000 g/mol, m =1.00867 g/mol, and m =1.00783 g/mol.
n p

Δm = −0.09900 g/mol = −9.900 x 10-5 kg/mol

ΔE = −9.900 x 10-5 kg/mol (2.998 x 108 m/s)2

ΔE = –8.898 x 1012 kg m2s-2 mol-1
Eb = −ΔE = +8.9 x 1012 J mol-1 (1J = 1kg m2 s-2)

Since 12C has 12 nucleons:

Eb/nucleon = (8.9 x 1012 / 12) = 7.4 x 1011 J mol-1

© 2008 Brooks/Cole 22
 Nuclear Binding Energy
Eb/nucleon for stable isotopes:
32S 56Fe
84Kr
16O 119Sn

4He 205Tl
238U
Relative binding Energy
per nucleon

6Li
56Fe is the most stable.
Iron is the most abundant heavy
3H
nucleus in the universe!
3He

2H

0 40 80 120 160 200 240 A

© 2008 Brooks/Cole 23
 Rates of Disintegration Reactions
Radioactive decay is 1st –order:

ln [X]t = −kt + ln [X]0

[X]0 = initial concentration of isotope X

[X]t = concentration of X after time t
k = rate constant.

Half life: t½ = ln 2 = 0.693

k k

© 2008 Brooks/Cole 24
 Half Life
t1/2(239Pu) = 24,400 years:

1.000
Mass of 239Pu remaining (g)

0.500

0.250
0.125

00 24,400 48,800 73,200 97,600

t (years)

© 2008 Brooks/Cole 25
 27
Half-Life Is Characteristic of the
Radioisotope

Prentice Hall © 2005 General Chemistry 4th edition, Hill, Petrucci, McCreary, Perry
Chapter Nineteen
 Half-Life
192Idecays with a rate constant of 9.3 x 10-3 d-1
(a) What is t1/2 for 192Ir ? (b) What fraction of a 192Ir
sample would remain after 100 days?

(a) t1/2 = (ln 2)/ k = (0.693)/(9.3 x 10-3 d-1) = 74.5 d

N
(b) ln = -kt = -(9.3 x 10-3 d-1)(100 d) = -0.930
N0
N
= e-0.930 = 0.394
N0

39% of the original sample remains.

© 2008 Brooks/Cole 28
 Rate of Radioactive Decay
The activity (A) of a sample of N atoms
• A = (disintegrations/time) observed.
• A = (constant) N
▪ constant = k if all decays are detected…
At t = 0 the activity A0 = (constant) N0
At a later time, t A = (constant) N

Then: A = N = fraction of atoms remaining

A0 N0

© 2008 Brooks/Cole 29
 Rate of Radioactive Decay
Since:
ln Nt = −kt + ln N0

or ln N = -kt
N0

ln A = -kt
A0

ln 2 0.693
As usual t½ = k = k

© 2008 Brooks/Cole 30
 Rate of Radioactive Decay
Geiger counter: an Ar-filled tube under high voltage.

© 2008 Brooks/Cole 31
 Rate of Radioactive Decay
A geiger counter measures disintegrations/sec (s-1).

Activity Units
becquerel (Bq) The SI unit (1 Bq = 1 s-1)

curie (Ci) 1 Ci = 3.7 x 1010 s-1

= decay rate of 1g of Ra

© 2008 Brooks/Cole 32
 Carbon-14 Dating
High-energy cosmic rays eject n0 from atoms in the
upper atmosphere. 14C is produced by collision:
14 1 14 1
7 N + 0n 6C + 1H

World-wide production of 14C ≈7.5 kg/year. It is:

• Evenly distributed
• Converted into 14CO2, then sugars
(photosynthesis).

Mammals eat the plants…

Activity (living organisms) = 15.3 min-1 g-1

© 2008 Brooks/Cole 33
 Carbon-14 Dating
After death the uptake stops. Stored 14C decays.

t½ (14C ) = 5.73 x 103 years.

Used to measure up to ≈ 9 half-lives ( ≈ 50,000 years)

A0 = 15.3 min-1 g-1
A50,000y = 0.030 min-1 g-1 (≈ 2 h-1 g-1)

Longer times are difficult to measure reliably.

© 2008 Brooks/Cole 34
Example Problem 14.4

• The half-life of carbon-14, used in radiocarbon dating, is 5730

years. What is the decay constant for carbon-14?

35
 Artificial Transmutations
Nuclear reactions can occur if a particle collides with
a nucleus.

Rutherford produced the first transmutation:

4 14 17 1
2 He + 7N
8
O +
1
H

α particles are not ideal. Positive particles are hard

to insert into a positive nucleus.

© 2008 Brooks/Cole 36
 37

The Cyclotron
Accelerated ion has
enough energy to
approach a nucleus.

Oscillator varies magnetic field

to accelerate the particle (like a
Prentice Hall © 2005 child on a playground swing).
th
General Chemistry 4 edition, Hill, Petrucci, McCreary, Perry
Chapter Nineteen
 38

Tony Stark Creating New Element Scene - Iron-Man 2 (2010)

Video from Youtube

Prentice Hall © 2005 General Chemistry 4th edition, Hill, Petrucci, McCreary, Perry
Chapter Nineteen
 Artificial Transmutations
Neutrons are better:
• No repulsion.
• Many elements are synthesized in this way.

239 1 240
94 Pu + 0n 94
Pu

240 1 241
94 Pu + 0
n 94
Pu

241 241
94 Pu 95
Am + 0e
-1

© 2008 Brooks/Cole 39
 Artificial Transmutations
The heaviest elements are produced by colliding
nuclei:
64 209 272 1n
28
Ni + 83 Bi 111 Rg +
0

Elements with Z > 112 do not have permanent names.

Temporary names: 112 ununbium (Uub)

113 ununtrium (Uut)
114 ununquadium (Uuq) etc.

© 2008 Brooks/Cole 40
 Nuclear Fission
Hahn and Strassman (1938) fired n0 at 135U. Ba was
produced!
• Nuclear fission had occurred.
235 1 236 141 92 1
92 U + 0
n 92 U 56 Ba + 36 Kr + 3 0 n

3 n0
produced

Very
exothermic

© 2008 Brooks/Cole 41
 Nuclear Fission
Chain reactions are possible:

Small amounts of 235U

do not capture all of the
n0.

(stays under control).

Nuclear bombs exceed

the critical mass; the
chain reaction grows
explosively.
© 2008 Brooks/Cole 42
 Energy from Fission
Efission(235U) = 2 x 1013 J/mol.
1 kg of 235U ≈ 33 kilotons of TNT.

Natural U is 99.3%
238U (not fissile).

Reactor fuel rods are

enriched to 3% 235U.

Weapons-grade is
> 90% 235U.

© 2008 Brooks/Cole 43
 Energy from Fission
Nuclear power-plants produce “clean” energy.
• No atmospheric pollution. No CO2 emission.

But… yield highly radioactive waste

• Tens of thousands of tons in storage
• Long half-lives (239Pu, t1/2 = 24,400 yr)
• Can be vitrified (encased in “glass”)
• Vwaste = 2 m3/reactor/yr.
• Yucca Mountain, NV (salt dome).

104 nuclear plants in the U.S.

None built since 1979 (Three Mile Island).
© 2008 Brooks/Cole 44
Example Problem 14.6

• Calculate the energy released by a nucleus of uranium-235 if

it splits into a barium-141 nucleus and a krypton-92 nucleus
according to the equation shown below.

235
92 U+ n ®
1
0
236
92 U ®
* 141
56 Ba + 92
36
1
Kr + 3 n
0

45
 Nuclear Fusion
Light atoms can be joined:
1 4 0
4 1H 2 He + 2 +1e

Nuclear fusion.
Very exothermic (ΔE = -2.5 x 109 kJ/mol ).
The energy source for stars.

Laboratory fusion is an attractive power source:

• Hydrogen (the fuel) can be extracted from oceans.
• Waste products are short-lived, low-mass isotopes.

© 2008 Brooks/Cole 46
 Nuclear Fusion
Unfortunately, fusion is hard to produce on earth:
• H-atoms must be converted into a plasma – a
soup of bare nuclei and e-.
• T > 108 K required.
• The plasma is hard to contain
–magnetic “bottles” are used.

Commercial fusion reactors are not very likely to

occur in the near future.

© 2008 Brooks/Cole 47
 Nuclear Radiation: Effects & Units
rad radiation absorbed dose
1 rad = 0.010 J absorbed/kg of material

gray (Gy) SI unit.

1 Gy = 1 J absorbed/kg of material
1 Gy = 100 rad

Roentgen (R) dosage of X-ray and g-radiation.

R = 9.33 µJ deposited/g of tissue
© 2008 Brooks/Cole 48
 Nuclear Radiation: Effects & Units
, b, and g have different biological effects, so…

rem roentgen equivalent in man.

dose in rem = (quality factor) x (dose in rads)

seivert (Sv) SI version. 1 Sv = 100 rem

Quality factors:  = 10 - 20, b = 1, g = 1

© 2008 Brooks/Cole 49
 Section 19.7
Effects of Radiation

Effects of Short-Term Exposures to Radiation

Return to TOC

Copyright © Cengage Learning. All rights reserved 50

 51

How Far Will Radiation Penetrate?

Stopping distance depends on the density of the medium.

Prentice Hall © 2005 General Chemistry 4th edition, Hill, Petrucci, McCreary, Perry
Chapter Nineteen
 Background Radiation

Key: Source % of total (millirems/yr)

© 2008 Brooks/Cole 52
 Radon
Produced by naturally occurring U-deposits in the soil.
An inhalation hazard:
222 218 4
86
Rn 84Po + 2
He

Po(s) remains in the lungs and decays:

218 214 4
84
Po 82
Pb + 2
He

A common household hazard.

© 2008 Brooks/Cole 53
 Applications of Radioactivity
Food Irradiation
• g-rays kill bacteria, molds, spores…
• Food spoils much less rapidly.
• It does not make food radioactive.

Tracers
• Chemicals made with radioactive atoms.
• Introduced into plants, animals…
• Concentrate where used (rapid growth regions).
• Uptake can be monitored with a Geiger counter.

© 2008 Brooks/Cole 54
 Applications of Radioactivity
Medical Imaging
• g-emitters are often used (e.g. 99mTc)
▪ Gamma rays can exit the body
▪ Less damaging than α or β.
• Tracers are used by organs, bones…

PET (positron emission tomography)

• A β+ emitter is injected
e + +10e → 2g
0
-1

• The g-rays emit in opposite directions.

• Detectors show the origin of the g-rays
© 2008 Brooks/Cole 55
 Applications of Radioactivity
Chemotherapy = use of radiation to treat cancer.

• Rapidly growing cells are more susceptible to

radiation than mature cells.

• Cancerous cells divide and grow more rapidly than

normal cells

• Malignant cells are more likely to be killed than

normal cells.

© 2008 Brooks/Cole 56