Nuclear Chemistry

The Interconversion of Mass and Energy

The total quantity of mass-energy in the universe is

constant.
Any reaction that releases or absorbs energy also loses or gains
mass.
E = mc2 or DE = Dmc2 so Dm = DE
c2
In a chemical reaction, the energy changes in breaking
or forming bonds is relatively small, so mass changes
are negligible.
In a nuclear reaction, the energy changes are enormous
and the mass changes are easily measurable.
 Nuclear binding energy (BE) is the energy required to break
up a nucleus into its component protons and neutrons.
BE + 199F 911p + 1010n
E = mc2
BE = 9 x (p mass) + 10 x (n mass) – 19F mass

BE (amu) = 9 x 1.007825 + 10 x 1.008665 – 18.9984

BE = 0.1587 amu 1 amu = 1.49 x 10-10 J

BE = 2.37 x 10-11J 1 amu = 931.5 MeV
binding energy
binding energy per nucleon =
number of nucleons
2.37 x 10-11 J
= = 1.25 x 10-12 J
19 nucleons
Nuclear binding energy per nucleon vs Mass number

nuclear binding energy

nuclear stability
nucleon
Enormous amounts of nickel and iron make up Earth’s core,
and nickel-58 is a very stable nuclide. Find the binding energy
per nucleon of 58Ni (mass of 58Ni atom = 57.935346 amu;
mass of 1H atom = 1.007825 amu; mass of neutron =
1.008665 amu).

Uranium-235 is an essential component of the fuel in nuclear

power plants. Calculate the binding energy per nucleon for
235U (mass of 235U atom = 235.043924 amu).
 The variation in binding energy per nucleon

The greater the binding energy per nucleon, the more stable the nuclide.
Example 19.2

The atomic mass of I is 126.9004 amu. Calculate the

nuclear binding energy of this nucleus and the corresponding
nuclear binding energy per nucleon.

29
Example 19.2 (1)
Strategy
To calculate the nuclear binding energy, we first determine the
difference between the mass of the nucleus and the mass of all
the protons and neutrons, which gives us the mass defect.
Next, we apply Equation (19.2) ∆ = ∆ .

Solution
There are 53 protons and 74 neutrons in the iodine nucleus.
The mass of 53 H atom is
53 × 1.007825 amu = 53.41473 amu
and the mass of 74 neutrons is
74 × 1.008665 amu = 74.64121 amu

30
Example 19.2 (2)

Therefore, the predicted mass for I is 53.41473 + 74.64121

= 128.05594 amu, and the mass defect is

∆ = 126.9004 amu − 128.05594 amu

= −1.1555 amu

The energy released is

∆ = ∆
= −1.1555 amu 3.00 × 10 m⁄s
= −1.04 × 10 amu . m ⁄s

31
Example 19.2 (3)
Let’s convert to a more familiar energy unit of joules. Recall that
1 J = 1 kg . m ⁄s . Therefore, we need to convert amu to kg:
amu . m 1.00 g 1 kg
∆ = −1.04 × 10 × ×
s 6.022 × 10 amu 1000 g

kg . m
= −1.73 × 10 = −1.73 × 10 J
s
Thus, the nuclear binding energy is . × . The nuclear
binding energy per nucleon is obtained as follows:

1.73 × 10 J
= = . × /
127 nucleons
32
The 238U Decay Series

A parent nuclide may undergo a

series of decay steps before a
stable daughter nuclide is formed.
 Detection and Measurement of
Radioactivity
An ionization counter detects radioactive emissions as
they ionize a gas.
Ionization produces free electrons and gaseous cations, which
are attracted to electrodes and produce an electric current.

A scintillation counter detects radioactive emissions by

their ability to excite atoms and cause them to emit light.
Radioactive particles strike a light-emitting substance, which emits
photons. The photons strike a cathode and produce an electric
current.
Detection of radioactivity by an ionization counter
Geiger-Müller Counter
A scintillation “cocktail” in tubes to be placed in
the counter
 Units of Radioactivity

The SI unit of radioactivity is the becquerel (Bq), defined

as one disintegration per second (d/s).

The curie (Ci) is a more commonly used unit:

1 Ci = 3.70x1010 d/s
Kinetics of Radioactive Decay
N daughter
DN
rate = - rate = lN
Dt
DN
- = lN
Dt
ln N = ln N0 - lt
N = the number of atoms at time t
N0 = the number of atoms at time t = 0

l is the decay constant

ln 2
l =
t½
 Kinetics of Radioactive Decay

N = N0e-lt ln N = ln N0 - lt

ln N
N
Arsenic-76 decays by β- emission. If 3.4 x 10-8 mol of 76As
emits 1.53 x 1011 β- particles per second, find the specific
activity in
(a) Ci/g;
(b) Bq/g.

Chlorine-36 disintegrates by β- decay. If 6.50 x 10-2 mol of 36Cl

emits 9.97 x 1012 β- particles per hour, find the decay constant.
Sodium-24 (t1/2 = 15 h) is used to study blood circulation. If a
patient is injected with an aqueous solution of 24NaCl whose
activity is 2.5 x 109 d/s, how much of the activity is present in
the patient’s body and excreted fluids after 4.0 days?

Iron-59 (t1/2 = 44.5 days) is a β- emitter used to monitor spleen

function during disease or after trauma. If an accident victim
receives a 5.6-µCi dose, what fraction of the 59Fe nuclei will
have decayed after 17 days?
 Radioisotopic Dating
• Radioisotopes can be used to determine the ages of
certain objects.
• Radiocarbon dating measures the relative amounts of
14C and 12C in materials of biological origin.

– t1/2 of 14C = 5730 years

– The ratio of 14C/12C remains the same for all living organisms.
– Once the organism dies, the amount of 14C starts to decrease as it
decays to form 14N.
– Since 14C decays at a predictable rate, measuring the amount
present indicates the time that has passed since the organism
died.
– Can only be used for objects up to 36,000 years old
• 40K/40Ar ratios can be used to determine the age of
certain rocks (t1/2 of 40K = 1.3 x 109 years).
Radiocarbon Dating
14N + 01n 14C + 11H
7 6

14C 14N +-10b

6 7 t½ = 5730 years

Uranium-238 Dating
238U 206Pb + 8 24a + 6-10b
92 82 t½ = 4.51 x 109 years
Ages of Several Objects Determined by
Radiocarbon Dating

t = 1 ln A0
λ A
A sample of wood from an Egyptian mummy case has a
specific activity of 9.41 d min-1 g-1. How old is the case (t1/2 of
14C = 5730 yr)? 12C/14C ratio for living organisms results in a

specific activity of 15.3 d/min·g

A fragment of a woolen tunic found in an ancient cemetery in

Africa has a specific activity of 12.87 d min-1 g-1. How old is the
tunic?
 Nuclear Transmutation

Nuclear transmutation is the induced conversion of the

nucleus of one element into the nucleus of another.

This is achieved by high-energy bombardment of nuclei in

a particle accelerator.
14 4 1 17
7N + 2α → 1 p + 8O

Nuclear transmutation reactions can be described

using a specific short-hand notation:
reactant nucleus (particle in, particle(s) out) product nucleus
The above reaction can be written as: 14N (α, p) 17O.
 Nuclear Transmutation
14N + 24a 17O + 11p
7 8

27Al + 24a 30P + 01n

13 15

14N + 11p 11C + 42a

7 6

Cyclotron Particle Accelerator

Nuclear Transmutation
Example 19.3

Write the balanced equation for the nuclear reaction

Fe d, α Mn where d represents the deuterium nucleus (that
is, H ).

54
Example 19.3 (1)

Strategy

To write the balanced nuclear equation, remember that the first

isotope Fe is the reactant and the second isotope Mn
is the product. The first symbol in parentheses (d) is the
bombarding particle and the second symbol in parentheses α
is the particle emitted as a result of nuclear transmutation.

55
Example 19.3 (2)

Solution
The abbreviation tells us that when iron-56 is bombarded with a
deuterium nucleus, it produces the manganese-54 nucleus plus
an particle. Thus, the equation for this reaction is

Fe + H → α + Mn

Check
Make sure that the sum of mass numbers and the sum of
atomic numbers are the same on both sides of the equation.

56
 Nuclear Fission

235U + 01n 90Sr + 143 Xe + 31n + Energy

92 38 54 0

Energy = [mass 235U + mass n – (mass 90Sr + mass 143Xe + 3 x mass n )] x c2

Energy = 3.3 x 10-11J per 235U

= 2.0 x 1013 J per mole 235U
Combustion of 1 ton of coal = 5 x 107 J
 Nuclear Fission
Representative fission reaction
235U + 01n 90Sr + 143 Xe + 31n + Energy
92 38 54 0
 Nuclear Fission
Nuclear chain reaction is a self-sustaining sequence of
nuclear fission reactions.
The minimum mass of fissionable material required to
generate a self-sustaining nuclear chain reaction is the
critical mass.

Non-critical

Critical
Nuclear Fission
Schematic Diagram of a Nuclear Reactor

refueling

U O
 Nuclear Fission

35,000 tons SO2 Annual Waste Production

4.5 x 106 tons CO2

70 ft3
3.5 x 106 vitrified
ft3 ash waste

1,000 MW coal-fired 1,000 MW nuclear

power plant power plant
 Nuclear Fission

Hazards of the
radioactivities in spent
fuel compared to
uranium ore

From “Science, Society and America’s Nuclear Waste,” DOE/RW-0361 TG

 Chemistry In Action: Nature’s Own Fission Reactor

Natural Uranium
0.7202 % U-235 99.2798% U-238

Measured at Oklo
0.7171 % U-235
 Nuclear Fission
•A nuclear power plant uses the large amount of
energy released in fission.

•This energy is used to boil water and create steam,

which turns a turbine and generates electricity.

•The dangers of generating nuclear power are

possible radiation leaks and the disposal of
nuclear waste.

•Radiation leaks can be minimized by containment

facilities within the power plant itself.

•Nuclear waste is currently buried, but it is unclear

whether this is the best method.
 Nuclear Fusion

Fusion Reaction Energy Released

2 2 3 1
1 H + 1H 1 H + 1H 6.3 x 10-13 J
2H
1 + 13H 4He
2 + 10n 2.8 x 10-12 J
6Li + 12H 2 4He 3.6 x 10-12 J
3 2

Tokamak magnetic
plasma
confinement
Element Synthesis in the Life Cycle of Star
 Radioisotopes in Medicine
• 1 out of every 3 hospital patients will undergo a nuclear
medicine procedure

Brain images
with 123I-labeled
compound
Focus on Health and Medicine
Radioisotopes Used in Treatment
 Radioisotopes in Medicine
Research production of 99Mo
98Mo + 10n 99Mo
42 42

Commercial production of 99Mo

235U + 10n 99Mo + other fission products
92 42 Bone Scan with
99mTc

99Mo 99mTc + -10b

42 43 t½ = 66 hours

99mTc 99Tc + -ray t½ = 6 hours

43 43
 Radioactive Tracers
• The isotopes of an element exhibit very similar chemical
and physical behavior.
– A small amount of radioactive isotope mixed with the stable
isotope will undergo the same chemical reactions, and can act
as a tracer.
• Radioactive tracers are used
– to study reaction pathways,
– to track physiological functions,
– to trace material flow,
– to identify the components of a substance from a very small
sample, and
– to diagnose a wide variety of medical conditions.
 The use of radioisotopes to image the thyroid gland

This 131I scan shows an A 99Tc scan of a healthy

asymmetric image that is thyroid.
indicative of disease.
 Some Radioisotopes Used as Medical Tracers

Isotope Body Part or Process

11C, 18F, 13N, 15O PET studies of brain, heart
60Co, 192Ir Cancer therapy
64Cu Metabolism of copper
59Fe Blood flow, spleen
67Ga Tumor imaging
123I, 131I Thyroid
111In Brain, colon
42K Blood flow
81mKr Lung
99mTc Heart, thyroid, liver, lung, bone
201Tl Heart muscle
90Y Cancer, arthritis
 PET and Brain Activity

These PET scans show brain activity in a normal person (left) and in
a patient with Alzheimer’s disease (right). Red and yellow indicate
relatively high activity within a region.
 Effects of Nuclear Radiation on Matter

Radioactive emissions collide with surrounding matter,

dislodging electrons and causing ionization. Each such
event produces a cation and a free electron.

The number of cation-electron pairs is directly related to

the energy of the incoming ionizing radiation.

Ionizing radiation has a destructive effect on living tissue.

The danger of a particular radionuclide depends on
- the type of radiation,
- its half-life, and
- its biological behavior.
 Molecular Interactions with Radiation

The interaction of ionizing radiation with molecules

causes the loss of an electron from a bond or a lone pair.
This results in the formation of free radicals, molecular
or atomic species with one or more unpaired electrons.
Free radicals are unstable and extremely reactive.
H2O +  H2O+ + e–
and e – + H2 O H + OH–

Double bonds in membrane lipids are very susceptible to

attack by free-radicals:
H + RCH CHR' RCH2 CHR'
 Units of Radiation

The gray is the SI unit for energy absorption.

1 Gy = 1 J absorbed per kg of body tissue.

The rad is more widely used: 1 rad = 0.01 J/kg or 0.01 Gy.

The rem is the unit of radiation dosage equivalent to a

given amount of tissue damage in a human.
no. of rems = no. of rads x RBE
The RBE is the relative biological effectiveness factor. The rem
allows us to assess actual tissue damage by taking into account
the strength of the radiation, the exposure time, and the type of
tissue.
1 rem of any type of radiation produces the
same amount of tissue damage.
 Sources of Ionizing Radiation

• There are several natural sources of background

radiation.
• Cosmic radiation increases with altitude.
• Radon is a radioactive product of uranium and thorium
decay.
– Rn contributes to 15% of annual lung cancer deaths.
• Radioactive 40K is present in water and various food
sources.
• Radioactive 14C occurs in atmospheric CO2.
Biological Effects of Radiation
Radiation absorbed dose (rad)
1 rad = 1 x 10-5 J/g of material
Roentgen equivalent for man (rem)
1 rem = 1 rad x Q Quality Factor
-ray = 1
b=1
a = 20
Penetrating power of radioactive emissions

The effect of radiation on living tissue

depends on both the penetrating power and
the ionizing ability of the radiation.

Penetrating power is inversely related to

the mass, charge, and energy of the
emission.
Detecting and Measuring Radioactivity
Measuring Human Exposure to Radioactivity
•The average radiation dose per year for a person
is about 0.27 rem.

•Generally, no detectable biological effects are

noticed for a radiation dose less than 25 rem.
•A single dose of 50–200 rem causes a temporary
decrease in white blood cell count.
•A dose of more than 100 rem causes radiation
sickness—nausea, vomiting, fatigue, etc.
•The LD50—the lethal dose that kills 50% of a
population—is 500 rem in humans, while 600
rem is fatal for an entire population.
 Chemistry In Action: Food Irradiation

Dosage Effect

Inhibits sprouting of potatoes, onions, garlics.

Up to 100 kilorad Inactivates trichinae in pork. Kills or prevents insects
from reproducing in grains, fruits, and vegetables.
Delays spoilage of meat poultry and fish. Reduces
100 – 1000 kilorads
salmonella. Extends shelf life of some fruit.
Sterilizes meat, poultry and fish. Kills insects and
1000 to 10,000 kilorads
microorganisms in spices and seasoning.
The Increased Shelf Life of Irradiated Food