Nuclear

Chemistry

HISTORY

Radioactivity was discovered by Henry Bequerel in

1896 by observing uranium salts emit energy.
Madame Curie and her husband extended
Bequerels work on radioactivity
Curie was the first to use Radioactivity to describe
the spontaneous emission of alpha, beta, and
gamma particles from an unstable nucleus.
Both Curies suffered the effects of radiation
poisoning.
Rutherford took over and bombarded gold with
alpha particles

Identification of Radiation

Penetrating Effects

Nuclear Chemistry
Nuclear chemistry is the study of reactions that
involve changes in the nuclei of atoms.
Radioactive decay is the spontaneous
disintegration of alpha, beta, and gamma
particles.
Radioactive decay follows first-order kinetics.

NUCLEAR STABILITY

Kinetic stability describes the probability that a

nucleus will undergo decomposition to form a
different nucleus (radioactive decay)

Thermodynamic Stability - the potential energy

of a particular nucleus as compared with the sum
of the potential energies of its component protons
and neutrons. (Binding energy)

Stability radioactive decay

Light elements are stable if the neutrons

and protons are equal, i.e. 1:1 ration,
heavier nuclides require a ratio of 1:1.5
Magic numbers of protons and neutrons
seem to exist, much like 8 electrons to
make elements and ions Nobel.

Magic Numbers

Even number protons and neutrons are stable

compared to odd ones
Magic numbers (protons or neutrons)
2,8,20,28,50,82 and 126
For example tin has 10 stable isotopes, even number,
but on either side of elemental tin indium and
antimony have only two stable isotopes
Nuclei with magic numbers of both protons and
neutrons are said to be doubly magic and even more
stable i.e. Helium-4 two protons and two neutrons and
Pb-208 with 82 protons and 126 neutrons
Could be shells for nucleons, like electrons

Stability radioactive decay

Number of stable nuclides related to numbers of
protons and neurons

Nuclear Stability

Nuclear Stability

Stability radioactive decay

Nucleons are protons and neutrons

The strong nuclear force keeps the nucleus
together by overcoming the repulsive force of
the protons.
Neutrons are present to help dissipate the
repulsive forces between the protons
As the atomic number (number of protons)
increases, so does the number of neutrons to
shield the repulsion of the protons
All nuclides with 84 or more protons are
unstable and radioactive. This means the
strong force is only strong enough neutralize
the force of 84 protons.

Decay Series

The HalfLives of
Nuclides
in the
238
92U
Decay
Series

Carbon Radioactive Decay Products

Name
Carbon-10
Carbon-11
Carbon-12
Carbon-13
Carbon-14
Carbon-15
Carbon-16

Mass
(amu)

Mode(s) of
Natural
Half-Life
Decay
Abundance
Positron Emis. 19.45 s
Positron Emis. 20.3 min

12.00000
13.00335
Decay
Decay

(Stable)
(Stable)
5730 y
2.4 s

Decay

0.74 s

98.89 %
1.11 %

Types of Radioactive Decay

Decay processes

Neutron-rich nuclei, converts a neutron to a

proton, thus lowering the neutron/proton
ration
Neutron-poor nuclei, net effect of converting
a proton to a neutron thus causing an
increase neutron/proton ratio
Heavy nuclei, Z>200 just unstable
regardless of the neutron/proton ratio, just
too many positive protons

Decay Types
Alpha particle emitters (Mass number
changes)

Nuclei with atomic mass number>200

The daughter nuclei contains two fewer
protons and two fewer neutrons than the
parent
U-238, Th-230

Types of Radioactive Decay

Decay processes

Neutron-rich nuclei, converts a neutron to a

proton, thus lowering the neutron/proton
ration
Neutron-poor nuclei, net effect of converting
a proton to a neutron thus causing an
increase neutron/proton ratio
Heavy nuclei, Z>200 just unstable
regardless of the neutron/proton ratio, just
too many positive protons

Decay Types
Beta particle decay

Too many neutrons

Atomic number increases, thus more
protons
Neutron splits into a proton and electron
called transmutation.
10n 11 P + -1o
Examples Th-234, I-131

234
Th
90

234
91 Pa +

0
-1 e

Decay Types
Electron Capture

Neutron-poor nuclides
Electron in an inner shell reacts with a proton
1 P+
0 1 n
1
-1
0
A

X +

0
-1

Z-1

X + x-ray

No change in mass number

Example iron-55

Decay Types
Positron Emission
Neutron-poor nuclides
Same mass as an electron, but opposite charge,
the positron emission is opposite beta decay
P

1
1

A
Z

n +

1
0

X +

A
Z-1

Example C-11

0
+1

0
+1

Decay Types
Electron Capture

Neutron-poor nuclides
Electron in an inner shell reacts with a proton
1 P+
0 1 n
1
-1
0
X +

A
Z

0
-1

X + x-ray

A
Z-1

No change in mass number

Example iron-55

Decay Types
Gamma Emission 00
Many nuclear decay daughters are in an elevated, or
excited, energy state
These meta stable isotopes emit gamma rays to
lower their potential energy
This emission can be instantaneous, or delayed for
sever hours
Te-99m has a half life of about 6 hours
98
43

Tc*

98

43

Tc +

Decay Types
Spontaneous Fission
Very massive nuclei Z > 103
Usually large amounts of energy are
released
Usually neutrons are released
Example:
25498Cf 11846Pd + 13252Te + 4 10n

Decay Types
Various Types of Radioactive Processes Showing the
Changes That Take Place in the Nuclides

Radioactive Decay

Radiochemical Dating
n = t/t1/2
t - time, t1/2 - time for a half-life, and n - the
number of half-lives

At/Ao = 0.5n
Ao - amount initially present, At - amount at
time t, and n - the number of half-lives

If we know what fraction of sample is

left (At/Ao) and its half-life (t1/2), we can
calculate how much time has elapsed.

Radiocarbon Dating of Artifacts

Calibration Curves

Kinetics of Radioactive Decay

Radioactive decay is a first order process, but
using atoms instead of concentration
Radioactive decay rates

Activity is defined as the number of nuclei that decay

per unit time
A = -N/t, the units are usually disintegrations per
second or minute (dps), dpm
The activity is directly proportional to the number of
atoms, thus A(Rate)=kN

The first order rate law is lnN/N0 = -kt

Also t1/2

ln1/2N0/N0 = -kt1/2 t1/2 = 0.693/k

Example problem
Fort Rock Cave in Oregon is the site where
archaeologists discovered several Indian
sandals, the oldest ever found in Oregon.
Analysis of the 14C/12C ratio of the sandals
gave an average decay rate of 5.1 dpm per
gram of carbon. Carbon found in living
organisms has a C-14/C-12 ratio of 1.3 X 10-12,
with a decay rate of 15 dpm/g C. How long ago
was the sage brush in the sandals cut? The
half life of carbon-14 is 5730 years. Note dpm
is disintegrations per minute

Sample Problem Solution

First calculate the rate constant k from the half-life:
k=0.693/5730 = 0.000121 yr-1
Substitute into the first order rate equation.
ln(N/N0) = kt
t = ln(N/N0)/k = ln(15/5.1)/0.000121
t = 8910 years old sandals

Practice
A mammoth tusk containing grooves made by a
sharp stone edge (indicating the presence of
humans or Neanderthals) was uncovered at an
ancient camp site in the Ural Mountains in 2001.
The 14C/12C ratio in the tusk was only 1.19% of
that in modern elephant tusks. How old is the
mammoth tusk?

Practice
Radioactive radon-222 decays with a loss of one
particle. The half-life is 3.82 days. What
percentage of the radon in a sealed vial would
remain after 7.0 days?

Nuclear Transformations

Rutherford (1919) was the first to carry out a

bombardment reaction, when he combined an alpha
particle with nitrogen-14, creating oxygen-17 and a
proton
The next successful bombardment reaction was
done 14 years later when Aluminum-27 to make
phosphorus-30 and a neutron
If the bombarding particle has a positive charge then
repulsion by the nucleus hinders the process, thus
particle accelerators are required.
Cyclotron and linear accelerator
Neutrons, do not suffer from the repulsive effect
Synthetic elements have been made, called
transuranium elements

Cyclotron
Nuclear reactions can be induced by accelerating a
particle and colliding it with the nuclide.

Cyclotron
An Aerial View of Fermilab, a High Energy Particle
Accelerator Cyclotron.

The
Accelerator
Tunnel at
Fermilab

Detection and Uses of Radioactivity

Geiger counter, high energy from radioactive

substances ionizes the Ar, thus allowing a
current to flow. The more ions the more
current, thus more radioactive
Scintillation counter, measures the amount of
light given off by a phosphor such as ZnS,
which is measured by a photometer
Badges

Geiger Counter
One can use a device like this Geiger counter to
measure the amount of activity present in a
radioactive sample.
The ionizing radiation creates ions, which conduct a
current that is detected by the instrument

Geiger Counter

Thermodynamic Stability
This is done by comparing the mass of the individual protons
and neutrons to the mass of the nucleus itself. The difference
in mass is called the mass defect (m), which when plugged
into E = mC2, or E = mC2 for change in energy

The mass of an atom is always less than the mass of

the subatomic particles

Protium is the only exception, since there is no defect

The other isotopes of hydrogen deuterium and tritium have
defects
Mass of neutron = 1.008665 amu
Mass of proton = 1.007276 amu
Mass of electron = 0.0005446623 amu , note mass of
electron is not really necessary in calculations since it
subtracts out when finding the difference

Subatomic Particles
Particle

Mass(g)

Charge

Electron(e)

9.11 x 10-28

-1

Proton(p)

1.67 x 10-24

+1

Neutron(n)

1.67 x 10-24

Particle

6.64 x 10-24

+2

Positron

9.11 x 10-28

+1

Thermodynamic Stability

Just like a molecule is more stable that its

atoms, an nucleus in more stable than its
individual atoms.
Energy changes for nuclear process are
extremely large when compared to normal
chemical and physical changes, thus very
valuable energy source.
Normal units are expressed per nucleon, in
MeV (million electron volts)
MeV = 1.60 X 10-13 J OR amu = 931 MeV
All nuclei have different relative stabilities, see
figure 18.9

Sample problem:

Calculate the changes in mass (in amu) and energy (in J/mol
and eV/atom) that accompany the radioactive decay of 238U to
234Th and an alpha particle. The alpha particle absorbs two
electrons from the surrounding matter to form a helium atom.

Solution (Note: AMU = g/mole)

m = mass prod. mass react.
m = (mass 234Th + mass 42He) - mass238U
m = (234.43601 + 4.002603) - 238.050788 = -0.004584 amu or
-4.584X10-6kg
E = mC2 E =( -4.584X10-6kg)(2.998X108m/s)2
=-4.120X1011 j/mole
E = -0.004584 amu X 931 MeV/amu
Divide by the mass number to get energy per nucleon, called
binding energy

Practice
What is the binding energy of 60Ni? The mass of a
60Ni atom is 59.9308 amu. The mass of an electron
is 9.10939 x 10-31 kg and 1 amu is 1.66054 x 10-27
kg.

Thermodynamic Stability

Notice that Iron is the most stable nuclide

E is negative when a process goes from a
less stable to a more stable state
In nuclear reactions more stable nuclei can
be achieved by combining nuclei (fusion) or
splitting a nucleus (fission)
Lighter elements typically undergo fusion,
while elements heavier than iron undergo
fission.

Thermodynamic Stability

For lighter elements, fusion processes lead to

nuclei with greater binding energy, whereas heavy
elements are formed through other processes.

Artificial Elements
Scientists have been transmuting elements
since 1919 when oxygen-17 and hydrogen-1
were produced from nitrogen-14 and
particles.
14
7

N +

He

17

O +

Artificial transmutation requires bombardment

with high velocity particles.
Alpha particles are positively charged so how
do they strike the nucleus, since the nucleus
is positively charged?

Energy in Nuclear Reactions

In the types of chemical reactions we have
encountered previously, the amount of mass
converted to energy has been minimal.
However, these energies are many thousands of
times greater in nuclear reactions.

Energy in Nuclear Reactions

For example, the mass change for the decay of 1
mol of uranium-238 is 0.0046 g.
The change in energy, E, is then

E = (m) c2
E = (4.6 106 kg)(3.00 108 m/s)2
E = 4.1 1011 J

Linear Accelerator

Linear Accelerator

Cyclotron

Fission Process
Discovered in the 1930s when U-235 was
bombarded with neutrons
Neutrons, due to their neutral charge do not require
accelerators

11n +

235

92

141

56

Ba +

92

36

Kr + 3 11n

This process delivers 2.1X1013J/mole, compared to

8.0X105j of energy for the combustion of methane
About 26 million times more energy
Another splitting process produces the elements Te-137
and Zr-97, with two neutrons
There are 200 different isotopes of 35 different element
produced, thus the nucleus fragments in many different
ways

Fission Process
Since neutrons are produced, then it is possible
to have a self-sustaining reaction

If the average production of neutrons is less than

one, the reaction is called subcritical
If the neutron production is equal to one then it is
called critical
If the neutron production is greater than one then the
reaction is called super-critical
To achieve the a critical state, then a critical mass is
required
If the mass is too small then the neutrons escape
before splitting other nuclei

Nuclear Fission

How does one tap all that energy?

Nuclear fission is the type of reaction
carried out in nuclear reactors.

Nuclear Fission

Bombardment of the radioactive nuclide with a neutron

starts the process.
Neutrons released in the transmutation strike other
nuclei, causing their decay and the production of more
neutrons.

Nuclear Fission

If there are not enough radioactive nuclides in the path of

the ejected neutrons, the chain reaction will die out.

Nuclear Fission

Therefore, there must be a certain minimum amount of

fissionable material present for the chain reaction to be
sustained: critical mass.

Nuclear Reactors

In nuclear reactors the heat generated by

the reaction is used to produce steam that turns
a turbine connected to a generator

Nuclear Reactors
The reaction is kept in check
by the use of control rods.
These block the paths of
some neutrons, keeping the
system from reaching a
dangerous supercritical
mass.

Fusion Process
Combining of nuclei, such as the reaction the occurs on
the sun
Problem is that the nuclei are positive in charge, thus

high temperatures (4X 107K) necessary to give the

nuclei the correct amount of kinetic energy to overcome
the repulsion
Electric current heat
Laser heat
Because to the high temperature then what about

containment?

Nuclear Fusion

Fusion would be a superior

method of generating
power.
The good news is that the
products of the reaction are
not radioactive.
The bad news is that in
order to achieve fusion, the
material must be in the
plasma state at several
million kelvins

Hydrogen Fusion
Heavier elements formed through the process
of fusion.

H +

1
1

H H

1
1

2
1

e (positron)

0
1

H + H He

1
1

2
1

3
2

2 He He + 2 H
3
2

4
2

1
1

Effects of Radiation

What happens when one is exposed to

radiation?
Somatic damage is damage to the organism
itself
Genetic damage is damage to the genetic
machinery, RNA DNA for example
Damage depends on the following factors

Quantities of Radiation
Unit

Parameter

Description

Curie (Ci)

Level of
Radioactivity
Level of
Radioactivity
Ionizing Energy
Absorbed
Amount of Tissue
Damage

3.7x1010 nuclear
disintegrations/s

Becquerel (B)*
Gray (Gy)
Sievert (Sv)

*SI unit of radioactivity

1 disintegration/s
1 Gy = 1 J/kg of tissue
mass
1Sv = 1Gy x RBE**

**Relative Biological Effectiveness

Damage Factors
The energy of the radiation, measured in rads
( radiation absorbed dose), where one rad = 10-2
J of energy deposited per kg of tissue

Since different radioactive particles do different kinds of

damage the rad is not the best way to consider the
effects

Penetrating ability of the radiation

Gamma highly penetrating, since electromagnetic

energy consisting of photons
Beta particles penetrate up to one cm
Alpha particles are stopped by the skin

Damage Factors
Ionizing ability of the radiation
Gamma radiation only occasionally ionize
Alpha particles, highly ionizing and leave a
trail of damage, since it is an ion itself, it will
strip electrons from other substances
Chemical properties of the radiation source.

Inert nuclides such as the noble gases pass

through the body
A radioactive substance such as iodine, can
be concentrated in a specific location of the
body. For iodine it is the thyroid.
rem = rads X RBE

About REM

rem is the radiation equivalent in man

rbe is the relative effectiveness of the radiation
in causing biologic damage, which is one for
betta and gamma, and 20 for alpha
Alpha particles have a higher rbe than beta
and gamma, since the helium nuclei is much
larger.

Acute Effects of Single Whole-Body Doses of

Ionizing Radiation
Dose(REM)

Toxic Effect

0.05-0.25

No acute effect, possible carcinogenic

or mutagenic damage to DNA
Temporary reduction in white blood cell
count
Radiation sickness: fatigue, vomiting,
diarrhea, impaired immune system
Severe radiation sickness: intestinal
bleeding, bone marrow destruction
Death, usually through infection, within
weeks
Death within hours

0.25-1.0
1.0-2.0
2.0-4.0
4.0-10.0
>10.0

Typical Radiation Exposures

for a Person Living in the
United States (1 millirem =
10-3 rem)

Sources of Radiation

Biological Effect of Radiation

Radon Gas Release from Rocks

Radiation Therapy
Nuclide

Half-Life

Treatment

14.3 d

Leukemia Therapy

Co

5.3 yr

External Cancer Therapy

13.3 yr

Thyroid Therapy

Cs

9.7 days

Ir

74 d

32
60

Radiation

123
131

192

Prostate cancer therapy

Coronary disease

Medical Imaging Radionuclides

Radiation
Nuclide
Emitted

Use

Tc

6.0

Bones, Circulatory system, Various

Organs

Ga

78

Tumors in the Brain and Other

Organs

Tl

73

Coronary Arteries, Heart Muscle

13.3

Thyroxin Production in Thyroid

Gland

99m

67

Half-Life
(hr)

201

123