Chapter20 Nuclear Chemistry PDF

Chemistry: The Molecular Science
Moore, Stanitski and Jurs
Chapter 20: Nuclear Chemistry
© 2008 Brooks/Cole 1
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 γ radiation.
The Nature of Radioactivity
Name Symbol Charge Mass (g) Pen. Power*

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

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
Radioactive Series
A decay product
(daughter isotope) is
often unstable...
A radioactive series.
The neutron number = N

N=A-Z
Other Types of Radioactive Decay
Positron emission
Positron = positive electron ( +10 e or β+). Antimatter.
43 43 0
21
Sc 20
Ca + +1
e
Antimatter is annihilated by collision with matter:
β+ + e- 2γ
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.
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 β (product).
Calculate the Z and A for the new isotope
Look up the element with Z = 54
Stability of Atomic Nuclei
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”.
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: β emission (n0 → p+ + e-).
 Too light: β+ emission or e- capture (p+ → n0).
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
15 P
0
+1
e + 28
14
Si
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 28
12
Mg
0
-1
e + 28
13
Al
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
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 n0: 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
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
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

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
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)
Half Life
Isotope Decay Process Half-life
238 238 234 4
92 U 92U 90Th + 2He 4.15 x 109 y
3 3 3 0
1H 1H 2 He + -1 e 12.3 y
14 14 14 0
6C 6C 7N + -1 e 5730 y
131 131 131 0
53 I 53I 54 Xe + -1 e 8.04 d
123 123
53 I 53I + -10e 123
52
Te 13.2 h
57 57 57 0
24 Cr 24Cr 25 Mn +-1 e 21 s
28 28 28 0
15 P 15P 14 Si + +1e 0.270 s
99m 99m 99
43 Tc 43Tc 43Tc + γ 6.0 h
“m” = “metastable” – it decays to a more stable version of the same isotope
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.

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
Since:
ln Nt = −kt + ln N0
or ln N = -kt
N0
ln A = -kt
A0
ln 2 0.693
As usual t½ = k = k
Geiger counter: an Ar-filled tube under high voltage.
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
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
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.
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.
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
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.
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
Nuclear Fission
Chain reactions are possible:
Small amounts of 235U

do not capture all of the
n 0.
(stays under control).
Nuclear bombs exceed

the critical mass; the
chain reaction grows
explosively.
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.
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).
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.
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.
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 γ-radiation.

R = 9.33 µJ deposited/g of tissue
Nuclear Radiation: Effects & Units
α, β, and γ 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: α = 10 - 20, β = 1, γ = 1
Background Radiation
Key: Source % of total (millirems/yr)
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.
Applications of Radioactivity
Food Irradiation
• γ-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.
Medical Imaging
• γ-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 → 2γ
0
-1
• The γ-rays emit in opposite directions.

• Detectors show the origin of the γ-rays
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.

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Chemistry: The Molecular Science

Moore, Stanitski and Jurs

Chapter 20: Nuclear Chemistry

Marie and Pierre Curie

Thomson and Rutherford

Name Symbol Charge Mass (g) Pen. Power*

mass no. (A) 226 222 + 4

Note: A and Z must balance

Beta – a nucleus ejects an electron:

The neutron number = N

Antimatter is annihilated by collision with matter:

Sometimes called K-capture.

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

Look up the element with Z = 54

• Even-Z isotopes are more common than odd.

Unstable isotopes decay so that the daughter will

Elements with Z<83

Einstein (special relativity): E = mc2

Δm = mass of nucleus – sum of nucleons

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

Since 12C has 12 nucleons:

0 40 80 120 160 200 240 A

ln [X]t = −kt + ln [X]0

[X]0 = initial concentration of isotope X

Half life: t½ = ln 2 = 0.693

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

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

39% of the original sample remains.

Then: A = N = fraction of atoms remaining

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

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

Mammals eat the plants…

t½ (14C ) = 5.73 x 103 years.

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

Longer times are difficult to measure reliably.

Rutherford produced the first transmutation:

α particles are not ideal. Positive particles are hard

Elements with Z > 112 do not have permanent names.

Temporary names: 112 ununbium (Uub)

Small amounts of 235U

(stays under control).

Nuclear bombs exceed

Reactor fuel rods are

But… yield highly radioactive waste

104 nuclear plants in the U.S.

Laboratory fusion is an attractive power source:

Commercial fusion reactors are not very likely to

gray (Gy) SI unit.

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

rem roentgen equivalent in man.

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

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

Quality factors: α = 10 - 20, β = 1, γ = 1

Key: Source % of total (millirems/yr)

Po(s) remains in the lungs and decays:

A common household hazard.

PET (positron emission tomography)

• The γ-rays emit in opposite directions.

• Rapidly growing cells are more susceptible to

• Cancerous cells divide and grow more rapidly than

• Malignant cells are more likely to be killed than

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