NUCLEAR CHEMISTRY

The Basics

Compiled by: E.S. Espiritu

Chapter
Map
 The Nucleus

• The nucleus is composed of nucleons

– protons
– neutrons
• A nucleus is characterized by two numbers
– atomic mass number(A; total # of nucleons)
– atomic number (Z; number of protons)
Z X
A
Nuclide Symbolism
 27
13 Al

• total number of nucleons is 27

• total number of protons is 13
• the number of neutrons is 14
 Isotopes
§ Example: Naturally occurring chromium
consists of four isotopes. It is 4.31% 2450Cr,
mass = 49.946 amu, 83.76% 2452Cr, mass =
51.941 amu, 9.55% 2453Cr, mass = 52.941
amu, and 2.38% 2454Cr, mass = 53.939 amu.
§ Relative or Average Atomic Mass (in the
Periodic table) is based on these isotopes.

6
 Subatomic Particles
one atomic mass unit (u) is defined as 1/12th the mass of
a carbon-12 atom
Particle mass in kg mass in u
-31 -4
electron 9.11 x 10 kg 5.485 x 10 u
-27
proton 1.673 x 10 kg 1.0073 u
-27
neutron 1.675 x 10 kg 1.0087 u
 Mass Defect

• Carbon-12 has a mass of 12.000 u

• Its nucleus contains 12 nucleons (6 p & 6n)
• Each nucleon has a mass >1 u
• The mass of a nucleus is slightly less than
the mass of the individual nucleons
• The missing mass is called the mass defect
• mass defect:m = mass nucleons - mass nucleus
 Einstein’s Equation

• Energy and mass can be interconverted

• E = mc2
• When protons & neutrons are packed
together to form a nucleus, some of the
mass is converted to energy and released
• This amount of mass is equal to the force of
attraction holding the nucleons together
Einstein’s Equation

• The total energy required to break

up a nucleus into its constituent
protons & neutrons
• binding energy = mc2
• The nuclear binding energy is
measured in MeV which is much
larger than the few eV required to
hold electrons to an atom
Binding Energy
A measure of the force holding a nucleus together.
Eb = ΔEnucleus formation
Equals the energy needed to separate the component
nucleons (p+ + n0) of an atom.
Component parts
of a nucleus

Einstein (special relativity): E = mc2

Eb = ΔE = (Δm)c2
with:
§ Δm = (mass of p+ + n0) – (mass nucleus)
c = speed of light = 3.00 x 108 ms-1
 Binding Energy
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 = sum of nucleons – mass of nucleus

= 12.09900 – 12.00000 g/mol
= 0.09900 g/mol
 Nuclear Binding Energy
Determine the binding energy and binding energy per nucleon for 12C.
Δm = 0.09900 g/mol = 9.900 x 10-5 kg/mol

ΔE = 9.900 x 10-5 kg/mol (3.00 x 108 m/s)2

ΔE = 8.91 x 1012 kg m2s-2 mol-1
Eb = 8.91 x 1012 J mol-1 (1J = 1kg m2 s-2)
§ = 8.91 x 109 kJ mol-1

Since 12C has 12 nucleons:

8.91 x 109 kJ mol-1
Eb/nucleon = = 7.43 x 109 kJ mol-1
12
Binding Energy Curve

• graph peaks at A=56

• the more BE released
per nucleon, the more
stable the nucleus
• mass number of 56 is
maximum possible
stability
 Nuclear Binding Energy
Eb/nucleon for stable isotopes:

Maximum stability: 56 Fe. Thus:

• heavier nuclei can split (nuclear fission) to increase stability.
• light nuclei can coalesce (nuclear fusion) to gain stability.
 How Many Neutrons?
§ The number of neutrons in a nucleus can vary
§ Range limited by the degree of instability
created by

having too many neutrons

too few neutrons
§ Stable nuclei do not decay spontaneously
§ Unstable nuclei have a certain probability to
decay
 Nuclear Stability Facts
§ The greater the number of protons, the more
neutrons are needed
§ “Magic numbers” of protons or neutrons
which are unusually stable

2, 8, 20, 28, 50, 82, 126
• Sn (Z=50) has 10 isotopes; In (Z=49)& Sb (Z=51)
have only 2
• Pb-208 has a double magic number (126n, 82p) & is
very stable
Band of Nuclear Stability
§ A plot of the known isotopes
on a neutron/proton grid
gives
§ Stable isotopes form a band
of stability from H to U
§ Z:N ratios to either side of
this band are too unstable &
are not known
Stability of Atomic Nuclei
 Stability of Atomic Nuclei
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.

• When Z is odd, an even-N isotope is more stable.

 160 “even-even”
 110 “odd-even” or “even-odd”
 Only 4 “odd-odd” isotopes known
 Band of Stability & Type of Decay
Unstable isotopes decay so that the daughter enters the
“peninsula of stability”.
Elements with Z > 83
Most decay by alpha emission.

Elements with Z < 83

Use a periodic table to determine whether an isotope is too
heavy or too light and hence its mode of decay.
 Band of Stability & Type of Decay
Elements with Z < 83
Compare A with the element’s average atomic weight.
§ If A > (average mass) it is too heavy
 It has excess n0

  emission is likely

• n0 → p+ + e-

§ If A < (average mass) it is too light

 It is n0 deficient
 + emission (or e- capture) is likely
• p+ → n0 + e+ (or p+ + e- → n0)
 Band of Stability & Type of Decay
14 15 16
Example 14 15 16
Si
Si PP SS
Predict how 28P will decay. 28.09
28.09 30.97
30.97 32.07
32.07
Atomic weight of P = 30.97
28P is too light.
28
15 P
0
+1
e + 28
14
Si
28 0 28
β+ decay or e.c. 15 P + -1e 14 Si

Example
How will 28Mg decay? 28 Mg is too heavy. β decay.
11
11 12
12 13
13
Na
Na Mg
Mg Al
Al
28
Mg
0
-1
e + 28
13 Al
12
22.99
22.99 24.31
24.31 26.98
26.98
 Radioactivity

• The spontaneous decomposition of an

unstable nucleus into a more stable nucleus
by releasing fragments or energy.
• Sometimes it releases both.
 Electromagnetic Radiation
§ Electromagnetic radiation is a form of
energy that can pass through empty space
§ It is not just a particle, and it is not just a
wave. It may be both.
 Electromagnetic Radiation

§ The shorter the wavelength, the more energy it

possesses
§ gamma rays are very energetic
§ radio waves are not ver energetic
 The Nature of Radioactivity
Antoine 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  radiation.
 The Nature of Radioactivity
Name Symbol Charge Mass (g) Pen. Power*
4 4 4
alpha 2 He 2+
2 α 2 He +2 6.65 x 10-24 0.03 mm
0 0
beta -1 e -1 β -1 9.11 x 10-28 2 mm
0
gamma 0 γ γ 0 0 100 mm
*Penetrating Power: Water layer to absorb 50 % of the radiation.

mα ≈ 10,000 mβ
 Radiation Energetics
§ Alpha Particles

relatively heavy and doubly charged

lose energy quickly in matter
§ Beta Particles

much smaller and singly charged

interact more slowly with matter
§ Gamma Rays & X-rays

high energy

more lengthy interaction with matter
 Some Types of Radioactive
Decay

• Alpha Decay (increases N:Z ratio)

• Beta Decay (decreases N:Z ratio)
• Gamma Decay
 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

Note: A and Z must always balance:

Mass number (A) 226 = 222 + 4
Atomic number (Z) 88 = 86 + 2
 Nuclear Reactions
• Nuclear reactions involve changes
in the nucleus, whereas chemical
reactions involve the loss, gain,
and sharing of electrons.
• Different isotopes of the same
element may undergo very
different nuclear reactions, even
though an element’s isotopes all
share the same chemical
characteristics.
 Nuclear Reactions
(cont.)
• Unlike chemical reactions, the rates
of nuclear reactions are unaffected
by temperature, pressure, and the
presence of other atoms to which
the radioactive atom may be
bonded.
• Nuclear reactions, in general, give
off much more energy than
chemical reactions
Nuclear
Equations
General Nuclear Equations
 Alpha Emission

• ZAX A-4Y + 4
Z-2 2

• Identity of the atom changes

• 92235U 231Th + 4
90 2

• Quick way for a large atom to lose a lot of nucleons

Alpha Emission
 Beta Emission

• Ejection of a high speed electron from the nucleus

• ZAX Z+1 Y + -1 
A 0

• 1940K 20 Ca + -1 
40 0

• Identity of atom changes

Beta Emission
 Gamma Emission

• Emission of high energy electromagnetic radiation

• Usually occurs after emission of a decay particle
forms a metastable nucleus
• Does not change the isotope or element
Gamma Emission
Positron Emission
Electron Capture
 Hazards of Radiation Types
§ Alpha Emissions

easily shielded

considered hazardous if alpha emitting material is
ingested or inhaled
§ Beta Emissions

shielded by thin layers of material

considered hazardous is a beta emitter is ingested
or inhaled
§ Gamma Emissions

need dense material for shielding

considered hazardous when external to the body
 Radioactive Decay Rates
§ Relative stability of nuclei can be expressed
in terms of the time required for half of the
sample to decay
§ Examples: time for 1 g to decay to .5 g

Co-60 5 yr

Cu-64 13 h

U-238 4.51 x 109 yr

U-235 7.1 x 108 yr
 Half-Life
The time required for half of a sample to decay
 Half-Life
§ The level of radioactivity of an isotope is
inversely proportional to its half-life.

The shorter the half-life, more unstable the
nucleus
§ The half-life of a radionuclide is constant
§ Rate of disintegration is independent of
temperature or the number of radioactive
nuclei present
 Half-life = the time it takes for
one-half of a sample to disappear.
 Half-Life of some Isotopes
Isotope decay Half-life
238 234 4
92 U → 90 Th + 2 He 4.46 x 109 y
14 14
6 C → 7 N + 0
-1
e 5730 y
3 3
1 H → 2 H + 0
-1
e 12.3 y
131
53
I → 131
54
Xe + 0
-1
e 8.04 d
123
53
I + -10e → 123
52
Te 13.2 h
57
24
Cr → 57
25
Mn + 0
-1
e 21 s
28 28
15 P → 14
Si + 0
+1
e 0.270 s
99m
43
Tc → 99
43
Tc +  6.0 h
“m” = “metastable” Decays to more stable version of the same isotope
 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
§Americium-243 has a half-life of 7370 y. For a sample containing
10.0 μg of this isotope, calculate the mass (μg) of the isotope that
remains after 22,110 years.
243
§ 95 Am → 239
93 Np + 4
2
He

Find the number of half lives in 22,110 y:

22,110 y = 3.00
7,730 y

So sample reduces by ½ three times:

10.0 μg x ½ x ½ x ½ = 10.0 μg x ⅛ = 1.25 μg
Alternative solution:
§ Given: half-life, solve for k using
t½ = ln 2 = 0.693
k k
§ Given: t= 22,110 years, solve for [X]t using

ln [X]t = −kt + ln [X]0

 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
 Rate of Radioactive Decay
This is 1st order. The number atoms, N, will follow: (same as the previous
formula but using other symbols such as A for activity or N for number of atoms)
ln Nt = −kt + ln N0

or ln N = -kt
or ln A = -kt N0
A0

ln 2 0.693
As usual t½ = =
k k
 Half-Life
Ir decays with a rate constant of 9.3 x 10-3 d-1
192

(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.

Carbon-14 Dating
High-energy cosmic rays eject n0 from atoms in the upper
atmosphere. 14C is produced by collision:
14 14 1
7
N + 10n C + H6 1

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 of carbon.
 Carbon-14 Dating
After death the uptake stops. Stored 14C decays.

t½ (14C ) = 5.73 x 103 y

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

A0 = 15.3 min-1 g-1 carbon
A50,000y = 0.030 min-1 g-1 carbon

≈ 2 h-1 g-1 carbon

Longer times are difficult to

measure reliably.

Prehistoric cave painting

 Carbon-14 Dating
Ancient charcoal was converted into 4.58 g of CaCO3 with
total A = 3.2 min-1. Find the age of the charcoal.
For carbon-14: t½ = 5730 y and A0 = 15.3 min-1 g-1 carbon

gcarbon= 4.58 g MC = 4.58 g 12.01 g = 0.550 g

MCaCO3 100.1 g

A= 3.2 min -1
= 5.82 min-1g-1 carbon
0.550 g

ln A = -kt = - ln 2t or t= ln A
A0 t½ -t½ A0
ln 2
t = -8267 ln 5.82= 8.0 x 103 y
15.3
 Decay Series
A series of elements produced
from the successive emission of alpha
& beta particles
 Trying To Reach Nuclear
Stability
§ Some nuclides (particularly those Z>83) cannot
attain a stable, nonradioactive nucleus by a single
emission.
§ The product of such an emission is itself
radioactive and will undergo a further decay
process.
§ Heavy nuclei may undergo a whole decay series of
nuclear disintegrations before reaching a
nonradioactive product.
Radioactive Decay Series
The Four Known Decay Series
Parent # of Decay Final Product
Radioisotope Steps of Series
Uranium-238 14 Lead-206
Thorium-232 10 Lead-208
Uranium-235 11 Lead-207
Plutonium-241 13 Bismuth-209
Artificial Transmutations
Nuclear reactions can occur if a particle collides with a
nucleus.

Rutherford produced the first transmutation:

14
4
2
He + 7 N → 178 O + 1
1
H

An alpha particle …into another

converts one element element (O)
(N)…

α particles are not ideal. Positive particles are hard to

insert into a positive nucleus.
Artificial Transmutations
Neutrons work better:
• No repulsion
• Many elements are synthesized in this way.

239 1 240
94
Pu +0 n 94
Pu

240 1 241
94 Pu 0+ n 94 Pu
241
Pu 241
Am + e0
94 95 -1
 Artificial Transmutations
• Technicium (Tc) and Promethium (Pm) are the only
elements with Z ≤ 92 which do not occur in nature.
• All transuranium elements (Z > 92) are synthetic.
• Z ≤ 101 (Mendelevium; Md) elements are made by small
1
particle bombardment (α, n) of light
0 nuclei.
• Z > 101 are made by heavy-particle collision:

64
28
Ni +209
83
Bi 272
111
Rg + 10 n

Nickel nuclei fired at a Roentgenium

bismuth-209 target
 Nuclear Fission
Hahn and Strassman (1938) fired 10n at 235U. Ba was
produced!
Nuclear fission had occurred.
235 236 141 Ba + 92 Kr + 31 n
92
U +1 n 92
U 56 36 0
0

3 neutrons
produced

Very
exothermic

ΔH = -2 x 10-10 kJ/mol
 Nuclear Fission
Chain reactions are possible:
Small amounts of 235U can’t
capture all the neutrons.
(stays under control).
Nuclear bombs exceed the
critical mass; the chain reaction
grows explosively.

Efission(235U) = -2 x 1013 J/mol.

1 kg of 235U ≈ 33 kilotons of TNT.
 Nuclear Reactors
Thermal energy from fission is used to generate power in
a nuclear reactors.
• Control rods ( n10 absorbers: Cd, B…) keep it under control.
• UO2 pellets are the “fuel”
• The chain reaction is started by a neutron source.
238 234 4
94 Pu 92 U +
2
He
4 9 12 1
2
He + 4 Be 6C + n
0

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

• Reactor fuel rods are enriched to 3% 235U.
• Weapons-grade is > 90% 235U.
UO2 pellets
Nuclear Reactors
Nuclear Reactor
 Nuclear Reactor Pros & Cons
Nuclear power-plants produce “clean” energy.
• No atmospheric pollution. No CO2.

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.
• No long-term storage site available in the U.S.
104 nuclear plants in the U.S. None built since 1979
(Three Mile Island).
 Nuclear Reactors

The fraction of electricity generated by nuclear power in selected

countries.
(http://www.world-nuclear.org/info/Facts-and-Figures/Nuclear-generation-by-country)
 Nuclear Fusion
Light nuclei can be combined:
4 11H → 42He + 2 +1
e0
Nuclear fusion
• Very exothermic (ΔE = -2.5 x 109 kJ/mol ).
• The energy source for stars.

An attractive power source:

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

1 R = 9.33 µJ deposited/g of tissue
 Nuclear Radiation: Effects & Units
, , and  have different biological effects, so…

rem
Roentgen equivalent in man.
dose in rem = (quality factor) x (dose in rads)

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

Quality factors:
Film badge
 = 10 - 20,  = 1,  = 1 (monitors radiation dose)
 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 84 Po + He
2
t½ = 3.82 days

Po(s) remains in the lungs and decays:

218 214 4
Po Pb + He t½ = 3.10 min
84 82 2

A common household hazard.

• The “safe” level for Rn is controversial.
• ~6% of U.S. homes contain > 4 pCi/L of air
(U.S. EPA action level)
 Applications of Radioactivity
Food Irradiation
• -rays kill bacteria, molds, spores…
• Food spoils much less rapidly.
• It does not make food radioactive.
The radura
International symbol
for irradiated food
Tracers
• Chemicals made with radioactive atoms
• Introduced into plants, animals…
• Concentrate where used (rapid growth regions)
• Uptake can be monitored with a Geiger counter.
 Applications of Radioactivity
Medical Imaging
 -emitters are often used (e.g. 99m Tc)
 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
0
-1 e + +10e → 2
• The -rays emit in opposite directions.
• Detectors show the origin of the -rays.
 Applications of Radioactivity
Chemotherapy = use of radiation to treat cancer.
• Rapidly dividing cells are more susceptible to radiation
than mature cells.
• Cancerous cells divide and grow more rapidly than
normal cells.
 hair follicles, bone marrow… also affected.

• Malignant cells are more likely to be killed than

normal cells.