NUCLEAR CHEMISTRY

Since the chemistry of an atom is determined by the number and arrangement of its electrons, the properties of
the nucleus are not of primary importance to chemists. In the simplest view, the nucleus provides the positive
charge to bind the electrons in atoms and molecules.

Atomos, the Greek root of the word atom, means “indivisible.” It was originally believed that the atom was the
ultimate indivisible particle of which all matter was composed.

Subsequently, scientists learned that the nucleus of the atom can be described as containing neutrons and protons.
In fact, in the past three decades it has become widely accepted that even the protons and neutrons are composed
of smaller particles called quarks.

Nuclear Chemistry is the branch of chemistry that deals with changes in the nuclei. It is quite obvious that the
conventional energy sources, such as coal, petroleum will be exhausted in near future. The idea of exploiting
nuclear energy came after the discovery of radioactivity.

RADIOACTIVITY

Soon after radioactivity was discovered emanating from uranium, physicist Ernest Rutherford demonstrated that
two distinct types of radiation could be distinguished. One type was stopped by thin pieces of aluminum, whereas
the other penetrated the metal sheets.

Those that were stopped by the metal he called alpha rays and those that passed through were called beta rays.
In a magnetic or electric fi eld, the two types of radiation were deflected in different directions, indicating that
they had opposite charges. One of the particles was deflected more than the other, indicating that their charge to
mass ratios were different. This experiment also revealed a third type of radiation, which passed through the fi
eld undeflected. Rutherford called it a gamma ray.

Becquerel in 1896 observed that uranium or its compound emit a kind of rays spontaneously. These rays can
affect photographic plate. He named this phenomenon of emission of spontaneous radiation by uranium as
radioactivity. The atoms of some of the elements were found to exhibit radioactivity, such as radium, thorium,
polonium etc. As compounds of those elements exhibit radioactivity, so it can be said that radioactivity is a nuclear
phenomenon. Radioactive elements emit the radiation of new elements.

Radioactivity is an irreversible process and emits more heat than any of the chemical processes. The rays emitted
are alpha (α), beta (β), and gamma (γ).

Property α particles β particles γ-rays

Streams of positively charged

Streams of fast moving Similar to x-rays and
particles which are merely
Nature negatively charged neutral in nature. Very
nuclei of He, each consisting 2
particles small wavelenths
protons and 2 neutrons

Representation [ 42𝐻𝑒]+2or α 0
−1𝑒 or −𝟏𝟎β or β γ
1
of hydrogen atoms
Mass 4 amu (atomic mass unit) 1836 No mass
or 0.000548 amu

Posssess positive charge of 2 Possess negative charge

Charge units – 9.6x10-10 esu or 3.2x10- of 1 unit = 4.8x10-10 esu No charge
19
coulomb or 1.6x10-19 coulomb

Nearly 1/10th the speed of light 2.36x108 to 2.83x108 Nearly same as light
Velocity
or 20,000 to 30,000 km/sec m/sec 3x108 m/sec

Penetrating
Low Medium Maximum
power
NUCLEAR STABILITY

Nuclear stability can be considered from both a kinetic and a thermodynamic point of view. Thermodynamic
stability, as we use the term here, refers to the potential energy of a particular nucleus as compared with the sum
of the potential energies of its component protons and neutrons.

Nuclear symbol is where the composition of a nucleus is shown. The atomic number appears as a subscript and
mass number as a superscript both appearing at the left side, as shown below
𝑀𝑎𝑠𝑠 𝑛𝑢𝑚𝑏𝑒𝑟 → 𝐴
𝐴𝑡𝑜𝑚𝑖𝑐 𝑛𝑢𝑚𝑏𝑒𝑟 → 𝑍 𝑋 ← 𝑒𝑙𝑒𝑚𝑒𝑛𝑡 𝑠𝑦𝑚𝑏𝑜𝑙
Many nuclei are radioactive; that is, they decompose, forming another nucleus and producing one or more
particles. An example is carbon-14, which decays as follows:

Where −10𝑒 represents an electron, which is called a beta particle, or β particle, in nuclear terminology. This
equation is typical of those representing radioactive decay in that both A and Z must be conserved. That is, the Z
values must give the same sum on both sides of the equation (6=7-1), as must the A values (14=14-0).

It is instructive to examine how the numbers of neutrons and protons in a nucleus are related to its stability with
respect to radioactive decay. Figure shows a plot of the positions of the known nuclides as a function of the
number of protons (Z) and the number of neutrons (A -Z). The stable nuclides are said to reside in the zone of
stability.

The following are some important observations concerning radioactive decay:

 All nuclides with Z>83 are unstable with respect to radioactive decay.
 Light nuclides are stable when Z equals A-Z, that is, when the neutron/proton ratio is 1.
 Heavier elements, the neutron/proton ratio required for stability is greater than 1 and increases with Z.
 Nuclides with even numbers of protons and neutrons are more often stable than those with odd numbers.
There are certain specific numbers of protons or neutrons that produce especially stable nuclides. These so-called
magic numbers are 2, 8, 20, 28, 50, 82, and 126. This behavior is reminiscent of that for atoms, where certain
numbers of electrons (2, 10, 18, 36, 54, and 86) produce special chemical stability (the noble gases).

THE NATURE OF NUCLEAR REACTIONS

Radioactive nuclei can undergo decomposition in various ways. These decay processes fall into two categories:
those that involve a change in the mass number of the decaying nucleus and those that do not. We will consider
the former type of process first.

 Alpha Decay
When a nucleus undergoes alpha decay, it ejects an alpha particle so that its mass number decreases by 4
and its atomic number decreases by 2. Uranium-238 is one example of a nuclide that decays by alpha
emission.

An α-particle production is very common mode of decay for heavy radioactive nuclides.
238 234 4
92U → 90Th + 2He

To be sure that we have accounted for every particle, compare the mass numbers on the left and right sides
of the equation (238=234 + 4). Repeat the process for the atomic numbers (92 = 90 + 2).

 Beta Decay
The β particle is assigned the mass number 0, since its mass is tiny compared with that of a proton or
neutron. Because the value of Z is -1 for the β particle, the atomic number for the new nuclide is greater
by 1 than for the original nuclide.
234 234 0
90Th → 91Th + −1e

131 131
53Xe → 54Xe + β
 Gamma Decay
Gamma decay is the emission of a high-energy photon and tends to accompany other types of decay. In
the nucleus, protons and neutrons occupy energy levels, analogous to the energy levels occupied by
electrons in an atom.
When alpha and beta particles leave the nucleus, some energy levels in the nucleus are no longer occupied.
Gamma radiation, which changes neither the mass number nor the atomic number of a nuclide,
accompanies the beta decay of most nuclei, including carbon-14. We can rewrite the decay of carbon-14
as follows, explicitly showing the emission of gamma radiation.
14 14 0 0
6C → 7N + −1e + 0γ

Note that the balance of the equation is unchanged by the emission of gamma radiation: gamma
rays are electromagnetic radiation, and so they have neither mass nor charge.

 Electron Capture
The nucleus captures an electron from the first (n=1) shell in the atom.
201 0 201
80Hg + −1e → 79Au + + 00γ

Difference between an electron capture ad beta decay is, for a beta decay, electron is emitted while for
electron capture an electron is absorbed by the nucleus.

 Positron Emission
The positron is a particle with the same mass as the electron but opposite charge.
22 22 0
11Na → 10Th + 1e

The positron shows an even more fundamental difference from the electron: It is the antiparticle of the
electron.

 Radioactive Decay
The radioactive decay follows an exponential law. At any instant of time, the rate of disintegration is
proportional to the number of atoms (N) present.

𝑑𝑁
= −𝑘𝑁
𝑑𝑡
𝑑𝑁
Where is the rate of disintegration, -k is the constant and N is the number of atoms. Further
𝑑𝑡
simplification of the equation we get;

𝑙𝑛𝑁 − 𝑙𝑛𝑁0 = −𝑘𝑡

𝑁
𝑙𝑛 = −𝑘𝑡
𝑁0
𝑵
Equation 1: = 𝒆−𝒌𝒕
𝑵𝟎

Where N is the final number of atoms, N0 is the initial number of atoms, k is the constant and Δt is the
change in time expanded as time final – time initial

Half life
Half-life of a radioactive element is the time required for half of the atoms to decay away. Half-lives for
radioactive isotopes can be as short as a fraction of a second or as long as millions of years.
The half-life (t1/2) of a radioactive sample is defined as the time required for the number of nuclides to
reach half of the original value

ln(2) 0.693
Equation 2: 𝑡1/2 = =
𝑘 𝑘
Where 𝑡1/2 is the half life of a sample, and k is the rate constant.

Combining equation 1 and equation 2, we get a unified formula for decay.

No = original mass
N = expected mass
𝑁0 𝑡
Equation 3: 𝑙𝑛 = 0.693
𝑁 𝑡1/2
 Example 1:
The half-life period of radium is 1620 years. In how many years will one gram of pure element;
a. k disintegration constant of radium.
b. Lose 0.01 gram
c. Be reduced to 0.01 gram?
-
Given:
𝑡1/2 = 1620 yrs

Required:
N loses 0.01 gram
N is 0.01 gram

Solution:

ln(2) 0.693
Using equation 2, 𝑡1/2 = =
𝑘 𝑘
ln(2) 0.693 0.693 𝟒.𝟐𝟖𝒙𝟏𝟎−𝟒
a. 𝑘 = = = =
𝑡1/2 𝑡1/2 1620 𝒚𝒆𝒂𝒓

𝑁0 𝑡
Using equation 3, 𝑙𝑛 = 0.693 𝑡 , we manipulate the third equation in finding t, so we’ll have a
𝑁 1/2
formula of
𝑁
(𝑙𝑛 𝑁0 )
Equation 4: 𝑡 = 𝑡
0.693 1/2
Equation 4, will be used in solving for b and c
N = 1gram – 0.01gram = 0.99gram
𝑁 1
(𝑙𝑛 𝑁0 ) ln(0.99)
b. 𝑡 = 𝑡1/2 = ∗ 1620𝑦𝑟𝑠 = 𝟐𝟑. 𝟒𝟗 𝒚𝒓𝒔
0.693 0.693

Using the equation 4,

N = 0.01 gram

𝑁 1
(𝑙𝑛 𝑁0 ) ln(0.01)
c. 𝑡 = 𝑡1/2 = ∗ 1620𝑦𝑟𝑠 = 𝟏𝟎, 𝟕𝟔𝟓 𝒚𝒓𝒔
0.693 0.693

Example 2:

The half-life of molybdenum-99 is 67.0 h. How much of a 1.000-mg sample Mo-99 remains after 335 h?

Given:
t1/2 = 67 hrs
t = 335 hrs
N0 = 1 mg

Required:
N after 335 hrs

Solution:
𝑁 𝑡
Using equation 3, 𝑙𝑛 𝑁0 = 0.693 𝑡 , we manipulate the third equation in finding N, so we’ll have a
1/2
formula of

𝑁0
Equation 5: 𝑁 = 𝑡
𝑡1/2
𝑒 0.693
𝑁0 1𝑚𝑔
𝑁= 𝑡 = 335 = 0.031 𝑚𝑔
0.693
𝑡1/2
𝑒 0.693 67
𝑒

*Note: Learn to manipulate the Equation 3, to achieve the desired answer.

NUCLEAR TRANSMUTATION

In transmutation, one nucleus changes to another, either by natural decay or in response to some outside
intervention, such as neutron bombardment.
One of the goals of the medieval alchemists was to use chemical means to change a base metal, such as lead, into
gold, a precious metal. The alchemists failed, of course. As we now know, such a transmutation of one element
into another can occur only by a nuclear reaction.
In 1919 Lord Rutherford observed the first nuclear transformation, the conversion of one element into another.
He found that by bombarding 147N with α particles, the 178O nuclide could be produced:
14 4 17 1
7N + 2He → 8O + 1H
Fourteen years later Irene Curie and her husband Frederick Joliot observed a similar transformation from
aluminum to phosphorus, where 10n represents a neutron
27 4 30 1
13Al + 2He → 15P + 0n

10 11 ∗
5B + 10n → 5B → 73Li + 10n

The unstable intermediate nucleus ( 115B ∗ in the equation above) is called a compound nucleus. Like the activated
complex in a chemical reaction, it decays almost instantly, emitting particles and energy to produce a stable
nucleus. In this case, the compound nucleus decays by alpha particle emission.
The nuclear reaction, however, produces a compound nucleus with the same mass number as a stable isotope, but
which nonetheless decays because it is formed in a highly excited state. Transmutation reactions are used to
produce a number of medically useful radioisotopes.

NUCLEAR FISSION

Nuclear fission was discovered in the late 1930s when nuclides

bombarded with neutrons were observed to split into lighter elements.
In fission, this splitting of a nucleus is exactly what happens.
Not all nuclei can undergo fission, however, and those that do
are said to be fissionable or fissile. Some fission reactions are
spontaneous, meaning that a large nucleus simply breaks into
smaller pieces. Other fission reactions must be induced by
neutron bombardment.
(Neutron bombardment can also be used to increase the rate of
decay for what might already be a spontaneously fissile
nucleus.)
235 1 141 92
92U + 0n → 56Ba + 36Kr + 3 10n
235 1 137 97
92U + 0n → 52Te + 40Zn + 2 10n

Here we have 235 92U bombarded by a neutron, separating into

smaller parts. This makes it possible to produce a self-sustaining fission process—a chain reaction.

If, on average, less than one neutron causes another fission

event, the process dies out; the reaction is said to be
subcritical. If exactly one neutron from each fission event
causes another fission event, the process sustains itself at the
same level and is said to be critical. If more than one
neutron from each fission event causes another fission event,
the process rapidly escalates, and the heat buildup causes a
violent explosion. This situation is described as
supercritical.

The critical state requires a certain mass of fissionable

material, called the critical mass.

During World War II an intense research effort (the Manhattan Project) was carried out by the United States to
build a bomb based on the principles of nuclear fission. This program produced the fission bombs that were used
with devastating effects on the cities of Hiroshima and Nagasaki in 1945. Basically, a fission bomb operates by
suddenly combining two subcritical masses of fissionable material to form a supercritical mass, thereby producing
an explosion of incredible intensity.

 Nuclear Reactors
 Pellets of enriched uranium oxide are embedded in fuel rods and covered with water in the reactor core.
To initiate fission, a source of neutrons must be incorporated into the reactor design. Once this neutron
source initiates fission, the chain reaction is self-sustaining. Control rods composed of cadmium or boron
absorb extra neutrons, regulating the number of neutrons that impact U-235 nuclei and maintaining a
steady rate of fission. Control rods can be inserted between the fuel rods to slow or stop the reaction.

Because of the tremendous energies involved, it seemed desirable after World War II to develop the fission
process as an energy source for producing electricity. Therefore, reactors were designed in which
controlled fission can occur. The resulting energy is used to heat water to produce steam to run turbine
generators, in much the same way that a coal-burning power plant generates energy.

NUCLEAR FUSION

Large quantities of energy are also produced by the fusion of two light nuclei. In fact, stars produce their energy
through nuclear fusion. Our sun, which presently consists of 73% hydrogen, 26% helium, and 1% other elements,
gives off vast quantities of energy from the fusion of protons to form helium:

1 1 2 0
1H + 1H → 1H + 1e
1 2
1H + 1H → 32H
3 3 4 1
2He + 2He → 2He + 2 1H
3 1 4 0
2He + 1H → 2He + 1e

Intense research is under way to develop a feasible fusion process because of the ready availability of many light
nuclides (deuterium, H-2, in seawater, for example) that can serve as fuel in fusion reactors.

Currently, scientists are studying two types of systems to produce the extremely high temperatures required: high-
powered lasers and heating by electric currents. At present, many technical problems remain to be solved, and it
is not clear which method will prove more useful or when fusion might become a practical energy source.
However, there is still hope that fusion will be a major energy source in the twenty-first century.

BIOLOGICAL EFFECTS OF RADIATION

Energy transferred to cells can break chemical bonds and cause malfunctioning of the cell systems. This fact is
behind the concern about the ozone layer in the earth’s upper atmosphere, which screens out high-energy
ultraviolet radiation from the sun. Radioactive elements, which are sources of high-energy particles, are also
potentially hazardous, although the effects are usually quite subtle. The reason for the subtlety of radiation damage
is that even though high-energy particles are involved, the quantity of energy actually deposited in tissues per
event is quite small. However, the resulting damage is no less real, although the effects may not be apparent for
years.

Radiation damage to organisms can be classified as somatic or genetic damage. Somatic damage is damage to the
organism itself, resulting in sickness or death. The effects may appear almost immediately if a massive dose of
radiation is received; for smaller doses, damage may appear years later, usually in the form of cancer. Genetic
damage is damage to the genetic machinery, which produces malfunctions in the offspring of the organism.

The biological effects of a particular source of radiation depend on several factors:

 The energy of the radiation. The higher the energy content pf the radiation, the more damage it can case
by the formation of free radicals and ions.
 The penetrating ability of radiation. The particles and rays produced in radioactive processes vary in their
abilities to penetrate human tissue: γ rays are highly penetrating; β particles can penetrate about 1 cm; and
α particles are stopped by the skin.
 The chemical properties of the radiation source. When a radioactive nuclide is ingested into the body, its
effectiveness in causing damage depends on its residence time.

Because of the differences in the behavior of the particles and rays produced by radioactive decay, both the energy
dose of the radiation and its effectiveness in causing biological damage must be taken into account. The rem
(which is short for roentgen equivalent for man) is defined as follows:
𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑟𝑒𝑚𝑠 = (𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑟𝑎𝑑𝑠)𝑥 𝑅𝐵𝐸
where RBE represents the relative effectiveness of the radiation in causing biological damage.