CHEMISTRY FOR ENGINEERS

MODULE 1: NUCLEAR CHEMISTRY

The chemical energy that fuels life on Earth comes from sunlight. Plants convert the
radiant energy of the sun into chemical energy through photosynthesis, producing oxygen and
carbohydrates. Life on earth could not exist without energy from the sun, but where does the sun
get its energy? Stars, including our sun, use nuclear reactions that involve changes in atomic
nuclei to generate their energy. For example, the Sun produces energy by fusing hydrogen atoms
to form helium, releasing vast amounts of energy in the process. The fusion of hydrogen to form
helium is the dominant nuclear reaction for most of a star’s lifetime. Toward the end of its life,
the hydrogen in the star’s core is exhausted and the helium atoms fuse to form progressively
heavier elements. A select few stars end their lives in dramatic supernova explosions.

The nuclear reactions that occur when a star goes supernova are responsible for the
existence of all naturally occurring elements heavier than nickel. The chemical changes
(transformations of one form of matter into another) we have studied thus far have involved only
the electrons in atoms (composed of [electron-0.00055 amu], [proton-1.0073 amu] and [neutron-
1.0087 amu]). When we discussed these changes in atoms during reactions, we focused on
changes in the electronic structure of the atoms. However, there is a branch of chemistry called
nuclear chemistry that considers the changes and differences in atomic nuclei. This branch is the
borderline between physics and chemistry. It began with the discovery of radioactivity in 1896
by Antoine Becquerel, a French physicist, and has become increasingly important during the past
100 year.

Nuclear reactions are often accompanied by energy changes a million times greater than
in chemical reactions, energy changes so great that changes in mass are detectable. Moreover,
nuclear reaction yields and rates are not subject to the effects of pressure, temperature and
catalysis.

THE NUCLEUS

In 1911, Ernest Rutherford discovered that most of an atom is an empty space and
identifies the atomic nucleus.

 The nucleus is dense : 10 14 g/mL.

 It is composed of elementary particles called nucleons: proton and neutron. The
proton is the positively charged particle.
 The number of protons is called the atomic number, Z, of the element.
 The sum of the number of protons and neutrons is the mass number, A.
 Atoms with the same atomic number but different mass number are called isotopes.
 When talking about a single type of nucleus, the term nuclide is used.

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TYPES of RADIOACTIVE DECAY; BALANCING NUCLEAR EQUATIONS

Most nuclei in nature are stable and remain intact indefinitely. Radionuclides, however,
are unstable and spontaneously emit particles and electromagnetic radiation. Emission of
radiation is one of the ways in which an unstable nucleus is transformed into a more stable one
that has less energy. The emitted radiation is the carrier of the excess energy.
When a nuclide of an element decays, it emits radiation and under most
circumstances, changes into a nuclide of different element. The three natural types of
radioactive emission are:

1. Alpha (α) Decay

Involves the loss of an α particle from a nucleus. For each α particle emitted by
the parent , A decreases by 4 and Z decreases by 2 in the daughter.

-This is the most common means for a heavy, unstable nucleus to become stable.

2. Beta (β) Decay

This involves the ejection of β- particle from the nucleus. This change does not
involve expulsion of β- particle that was in the nucleus, rather, a neutron is converted
into a proton, which remains in the nucleus, and a β- particle, which is expelled
immediately.

3. Positron (β+) Emission

This involves the emission of a β+ particle from the nucleus, when a proton is
converted to a neutron. The daughter has the same mass number, but has a lower atomic
number.

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4. Electron (e-) capture

This occurs when the nucleus interacts with an electron in an orbital from a low
atomic energy level. This has the same net effect as positron emission.

5. Gamma(γ) emission
This involves the radiation of high energy γ photons from an excited nucleus. Many
other types of decay are accompanied by γ emission.

ACTIVITY

1. Write balanced equations for the following nuclear reactions:

a. Naturally occurring thorium-232 undergoes a decay.
b. Zirconium-86 undergoes electron capture.
c. A nuclide undergoes β- decay and produces cesium-133.
2. Write a nuclear reaction for each step in the formation of 84𝑃𝑜 218 from 92 𝑈 238 , which
proceeds by a series of decay reactions involving stepwise emission of α, β, β, α, α, α, α
particles, in that order.

NUCLEAR TRANSMUTATION

Thus far we have examined nuclear reactions in which a nucleus decays spontaneously.
A nucleus can also change identity if it is struck by a neutron or by another nucleus. Nuclear
reactions induced in this way are known as nuclear transmutations. In 1919, Ernest Rutherford
performed the first conversion of one nucleus into another, using alpha particles emitted by
radium to convert nitrogen-14 into oxygen-17:

Such reactions have allowed scientists to synthesize hundreds of radioisotopes in the

laboratory. Nuclear transmutations are sometimes represented by listing, in order, the target
nucleus, the bombarding particle, the ejected particle, and the product nucleus.

NUCLEAR STABILITY

There are several ways that an unstable nuclide might decay, but can we predict how it
will decay? Two key factors determine the stability of a nuclide.

1. Neutron to Proton Ratio

This primarily relates to nuclide that undergo three modes of beta decay.
Because like charges repel each other, it may seem surprising that a large number of
protons can reside within the small volume of the nucleus. At close distances,
however, a strong force of attraction, called the nuclear force, exists between nucleons.

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Neutrons are intimately involved in this attractive force. All nuclei other than contain
neutrons. As the number of protons in a nucleus increases, there is an ever greater
need for neutrons to counteract the proton–proton repulsions. Stable nuclei with
atomic numbers up to about 20 have approximately equal numbers of neutrons and
protons. For nuclei with atomic number above 20, the number of neutrons exceeds the
number of protons. Indeed, the number of neutrons necessary to create a stable
nucleus increases more rapidly than the number of protons. Thus, the neutron-
toproton ratios of stable nuclei increase with increasing atomic number, as illustrated
by the most common isotopes of carbon, 𝐶 ( 𝑛 𝑝 6 = 1) 12 , manganese, 𝑀𝑛 ( 𝑛 𝑝 25 =
1.20) 55 , and gold, 𝐴𝑢 ( 𝑛 𝑝 79 = 1.49) 197 . The dark blue dots in the figure represent
stable (nonradioactive) isotopes. The region of the graph covered by these dark blue
dots is known as the belt of stability. The belt of stability ends at element 83 (bismuth),
which means that all nuclei with 84 or more protons are radioactive. For example, all
isotopes of uranium, Z=92, are radioactive.

Predicting the mode of decay:

a. Neutron-rich nuclides. Nuclides with too many neutrons for stability( a high N/Z)
lie above the band of stability. They undergo β- decay , which converts a neutron
into a proton, thus reducing the value of N/Z.
b. Proton-rich nuclides. Nuclides with too many protons for stability(a low N/Z) lie
below the band. They undergo β+ emission and/or e- capture , both of which
convert a proton into a neutron thus increasing the value of N/Z.
c. Heavy nuclides. Nuclides with Z>83 are too heavy to be stable and undergo alpha
decay, which reduces their Z and N values by two units per emission.

2. Total mass of the nuclide

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THE KINETICS OF RADIOACTIVE DECAY

The Rate of Radioactive Decay

Radioactive nuclei decay at a characteristic rate regardless of the chemical substance in which
they occur. The decay rate, or activity (A) of a radioactive substance is the change in number of
nuclei (N) divided by the change in time.
∆N
Decay rate (A) = −
∆𝑡

The SI unit for radioactivity is Becquerel(Bq), which is defined as 1 disintegration per second
(1ds/s) . Another unit is the curie(Ci), where 1 Ci = 3.7 x 10 10 ds/s.

Half-life of Radioactive Decay

Decay rates are commonly expressed in terms of the fraction of nuclei that decay over a
given time interval. The half-life (t ½) of a nuclide is the time it takes for half the nuclei present
in a sample to decay. The number of nuclei remaining is halved after each half-life.

The half-life of a nuclear reaction is determined from its rate constant:

𝑁
ln 𝑁𝑡 = -kt
𝑜

where: No is the number of nuclei at t=0, Nt is the remaining nuclei after given
time t and k is the rate constant. To determine the rate constant:
𝑙𝑛2
k = 𝑡1/2

QUESTIONS
1.Iodine-131 has a half-life of 8 days. If there are 200 grams of this sample, how much of
I-131 will remain after 32 days?
2. Sodium-24 has a half-life of 15 hours. If there are 800 g of Na-24 initially, how long
will it take for 750 of Na-24 to decay?

3. The half-life of Oxygen-15 is 2 minutes, what fraction of a sample of O-15 will remain
after 5 half-lives?

4. It takes 35 days for a 512 gram sample of element X to decay to a final amount of 4
grams. What is the half-life of element X.

5.Plutonium-239 produced in breeder reactors has a half-life of 24100 years. How long
will it take for a sample of plutonium-239 to decay to 0.100% of its original value?

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THE INTERCONVERSION OF MASS AND ENERGY

The energies associated with nuclear reactions can be considered with the aid of Einstein’s
celebrated equation relating mass and energy:

𝐸 = 𝑚𝑐 2

where E stands for energy, m for mass, and c for the speed of light, 2.9979 x 108 m/s. This
equation states that the mass and energy of an object are proportional. If a system loses mass, it
loses energy (exothermic); if it gains mass, it gains energy (endothermic)

QUESTIONS:

1. How much energy is lost or gained when 1 mol of cobalt-60 undergoes beta decay? The
mass of a 60 60
27𝐶𝑜 atom is 59.933819 amu, and that of a 28𝑁𝑖 atom is 59.930788 amu.
2. Iron-56 is an extremely stable nuclide. Compute the binding energy per nucleon for Fe-
56 . (mass of Fe-56 atom = 55.934939 amu, mass of H-1 atom = 1.007825 amu, mass of
neutron= 1.008665 amu)

NUCLEAR FISSION and NUCLEAR FUSION

In nuclear fission, a heavy nucleus splits into two much lighter nuclei, emitting
several small particles at the same time . In nuclear fusion, the opposite process occurs:
two lighter nuclei, combine to form a heavier one. Both fission and fusion release
enormous quantities of energy.

The history of nuclear fission dates back to the mid-1930s when scientists
bombarded uranium-92 with neutrons in an attempt to synthesize transuranium
elements. Many of the unstable nuclide produced were tentatively identifies as having Z
> 92, but four years later, one of these was shown to be an isotope of Ba(Z=56). Lise
Meitner and Otto Frisch proposed that barium resulted from the splitting of uranium
nucleus into smaller nuclei, a process they called fission.

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In nuclear fission , neutron bombardment causes a nucleus to split into two smaller
nuclei and release neutrons that split other nuclei, giving rish to a chain reaction. In
nuclear power plants, they control the rate of chain reaction to produce heat that creates
steam , which is used to generate the electricity.

Potential hazards such as radiation leaks, thermal pollution, and disposal of

nuclear waste remain current concerns,

Nuclear fusion is the ultimate source of nearly all the energy on Earth because
almost all other sources depend, directly or indirectly on the energy produced by nuclear
fusion in the sun. But the sun and other stars generate more than energy; in fact, all the
elements larger than hydrogen were formed in fusion and decay processes within stars.

Nuclear fusion holds great promise as source of clean ,abundant energy, but it
required extremely high temperature and is not yet practical.

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