Nuclear Chemistry

Nuclear chemistry has many applications in knowing facts from the past, present, and future. From
half-life of elements up to extraterrestrial bodies, nuclear chemistry plays an important role. In this
topic, the students will understand the equations and reactions involved in nuclear chemistry. Some
of the vital and diversified applications of nuclear chemistry are discussed further with factual
problems for student’s exercise.

The Spitzer Space Telescope, which is sensitive to infrared radiation,

is shown here against an infrared image of the sky. Because the
intensity of cosmic rays increases with altitude, electronic equipment
on satellites such as Spitzer is especially susceptible to damage from
ionizing radiation. Courtesy of NASA, JPL/Caltech

Outcomes
At the end of discussion, the student should be able to:

 Understand radioactivity
 Describe cosmic rays and how they influence Earth and atmosphere.
 Write, balance, and interpret equations for simple nuclear reactions.
 Define modes of nuclear decay which includes alpha decay, beta decay, positron
emission, and electron capture.

1
  Interpret the kinetics of radioactive decay using first-order rate equations.
 Use Einstein’s equation.
 Describe nuclear fission and fusion.
 Discuss the potential of both fission and fusion as energy sources.
 Explain penetrating power and ionizing power.
 Solve applications of radioisotopes.

Introduction

Nuclear Chemistry is the branch of chemistry that deals with the changes in the nuclei.
Conventional energy sources, such as coal, petroleum will be exhausted in the near future.
Scientists are searching non-conventional energy sources such as solar-energy, nuclear energy etc.
Utilization of nuclear energy came after the discovery of radioactivity.
For solar energy, we have cosmic rays. Cosmic Rays are subatomic particles traveling at high
speeds that constantly bombard Earth. Majority are atomic nuclei: 87% hydrogen nuclei, 12%
helium nuclei, and the rest are heavier nuclei. It can originate outside the solar system.
Cosmic rays originate from solar flares on the sun, which can accelerate highly charged cations
until they approach the speed of light. The distribution of atomic nuclei reflects composition of the
sun. Hydrogen and helium are the most prevalent. Carbon, nitrogen, oxygen, neon, magnesium,
silicon, and iron are also present.
The energies of cosmic rays are much higher than in other areas of chemistry. Chemical energies
usually measured in kJ/mol. Also, cosmic ray energies can be measured in electron volts (eV),
where 1 eV = 96.5853 kJ mol-1 (cosmic rays are in the MeV or GeV range). Upon entering the
atmosphere, cosmic rays start to collide with gas molecules and induce nuclear reactions; for an
instance, the formation of radioactive 14C.
When a free neutron is absorbed by a nitrogen nucleus, a proton is emitted and 14C is produced.
The terrestrial carbon is 98.9% 12C and 1.11% 13C. Both are stable, however, 14C is unstable and
undergoes spontaneous radioactive decay. Particles are ejected and a nitrogen atom is formed.

Radioactivity

Becquerel in 1896 observed that uranium or its compounds 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 and create new elements. Radioactivity is an irreversible process and emits more
heat than that of any of the chemical processes (109 cal mol-1). After discovery of Uranium’s
radioactivity, Ernest Rutherford demonstrated two distinct types of radiation. One type was

2
stopped by thin pieces of aluminum, alpha rays. The second type passed through the aluminum,
beta rays.

In magnetic field, alpha and beta rays are deflected which indicates carrying a charge. Alpha and
beta rays were deflected in opposite directions, indicating they held opposite charges. One type of
particle was deflected more than the other indicating their mass to charge ratios were different. A
third type of radiation, gamma rays, was revealed and which passed through the magnetic field
undeflected.

Figure 1: A thin sheet of aluminum blocks alpha rays but not beta rays. In a magnetic field, beta
and alpha particles are deflected in different directions, while gamma rays are undeflected.

Alpha particles, α, are the more massive and positively charged particles. Alpha particles are
helium nuclei, 42𝐻𝑒 . Beta particles, 𝛽 − 𝑜𝑟 −10𝛽 , are lighter and negatively charged. Beta particles
are electrons, −10𝑒 , emitted from the nucleus. Gamma rays, γ, are the particles unaffected by the
magnetic field. Gamma rays are high-energy photons of electromagnetic radiation emitted by the
nucleus, 00𝛾 .

3
 Table 1. Comparison among α, β, and γ rays

Radioactive Decay

Nuclear reactions are written in a format similar to chemical reactions. Reactants and products are
atoms or subatomic particles instead of molecules. Nuclide symbols (E) are written to represent
the composition of a nuclide.
𝑚𝑎𝑠𝑠 𝑛𝑢𝑚𝑏𝑒𝑟
𝑎𝑡𝑜𝑚𝑖𝑐 𝑛𝑢𝑚𝑏𝑒𝑟 𝐸

These symbols can be used to represent atoms, ions, and nuclei. Nuclide symbols for subatomic
particles are the following:
𝑁𝑒𝑢𝑡𝑟𝑜𝑛, 10𝑛
𝑃𝑟𝑜𝑡𝑜𝑛, 11𝑝
𝐸𝑙𝑒𝑐𝑡𝑟𝑜𝑛, −10𝑒

Atomic number is equivalent to the charge of the nucleus. Nuclear reactions are written using
nuclide symbols.
14
7𝑁 + 10𝑛 → 14
6𝑁 + 11𝑝

4
Nuclear reactions are balanced when the sums of the mass numbers and atomic numbers for both
sides of the equation are equal.
For the radioactive decay, it follows an exponential law. At any instant of time, the rate of
disintegration is proportional to the number of atoms (N) present, i.e.,
𝑑𝑁 𝑑𝑁 𝑑𝑁⁄𝑑𝑡
− ∝ 𝑁 𝑜𝑟 − = 𝜆𝑁 𝑜𝑟 𝜆 =
𝑁 𝑑𝑡 𝑁
Where λ = disintegrating constant, may be defined as the ratio of the amount of the substance
which disintegrates in a unit time to the amount of the substance present.
The negative sign indicates that with passage of time ‘t’ the number of atoms decreases.

𝑑𝑁
So, = −𝜆𝑑𝑡
𝑁

Integrating we have, 𝑙𝑜𝑔𝑒 𝑁 = −𝜆𝑡 + 𝐶 [C = integration constant]

Let ‘𝑁0 ’ be the number of atoms present initially, i.e., when t=0
Then 𝑙𝑜𝑔𝑒 𝑁0 = 𝐶
Therefore, 𝑙𝑜𝑔𝑒 𝑁 = −𝜆𝑡 + 𝑙𝑜𝑔𝑒 𝑁0
𝑁
Or 𝑙𝑜𝑔𝑒 𝑁 = −𝜆𝑡
0

Thus, 𝑁 = 𝑁0 𝑒 −𝜆𝑡
When M0 = original mass and M = mass at a time t, the equation becomes

𝑀 = 𝑀0 𝑒 −𝜆𝑡
Hence, the decay curve is exponential in nature.

Figure 2. Decay of Radioactive Substance

5
If t is the half-life of the radioactive element, then we can write,
𝑁 1
= = 𝑒 −𝜆𝑡
𝑁0 2
𝑙𝑜𝑔𝑒2 0.693
Thus, 𝑡= = .
𝜆 𝜆

The above equation is a relation between half-life of a radioactive element and its disintegration
constant.
Half-life is the time required for half- of the atom to decay away. Half-lives for radioactive
isotopes can be short as a fraction of a second or as long as millions of years, see Table 2.

Table 2. Half-lives of some Radioactive Isotopes

The unit of radioactivity is curie. The curie is defined as that quantity of any radioactive substance
which gives 3.7 x 1010 disintegrations per second (Bq). The curie is a very large unit. Hence for
all practical purposes millicurie [1 mCi = 10 -3] and the microcurie [1 µCi = 10 -6] are used.

Problem 1
The half-life of carbon-14 used in radiocarbon dating, is 5730 years. What is the decay constant
for carbon-14?

6
Problem 2
Assuming that it was to remain undisturbed since 1898 A.D., calculate how much of Madam
Curie’s 200 mg of radium would be left in the year 8378 A.D. (t 1/2 of radium is 1620 years).

Problem 3
A radioactive source contains one microgram (µg) of 𝑃𝑢239 . This source is estimated to emit 2300
α-particles / sec. in all directions. Estimate half-life of 𝑃𝑢239 from this data.

Radiocarbon Dating
14
C is continually formed through the interaction of cosmic rays with the atmosphere. The 14C is
incorporated into living plants and animals and the 14C/12C ratio remains constant over time. When
a plant or animal dies, 14C is no longer incorporated and its activity decreases with time. An
artifact’s age is determined by measuring its 14C/12C ratio and then comparing it to the 14C/12C
ratio of living organisms.
First order kinetics equations are used to determine the age of the artifact. Dendrochronology,
which is based on counting growth rings in long-lived trees, has been used to calibrate carbon
dating. Ages are determined to within ±40 to 100 years. Objects less than 60,000 years old can be
carbon dated.

Problem 4
A piece of cloth is discovered in a burial pit in the Philippines. A tiny sample of the cloth is burned
from CO2, which is then analyzed. The 14C/12C ratio is 0.250 times the ratio in today’s atmosphere.
How old is the cloth?

Alpha Decay
During alpha decay, an alpha particle is emitted from the nucleus. The mass number decreases by
4. The atomic number decreases by 2.
238 234
92𝑈 → 90𝑇ℎ + 42𝐻𝑒
The reactant nucleus is the parent and the product nucleus is the daughter.

Problem 5
Complete the equations for each of the following nuclear decay processes.

7
 210 206
84𝑃𝑜 → 82𝑃𝑏+ ?
230
90𝑇ℎ → ? + 42𝐻𝑒
Beta Decay
During beta decay, a beta particle and an antineutrino, ṽ, are emitted from the nucleus. A neutron
decays into a proton, a beta particle, and an antineutrino. The proton remains in the nucleus.
A neutron decays into a proton, a beta particle, and an antineutrino. The proton remains in the
nucleus.
1
0𝑛 → 11𝑝 + 0
−1𝛽 +ṽ
The atomic number increases by 1.
14 14 0
6𝐶 → 7𝑁 + −1𝛽 +ṽ

Problem 6
Complete the equations for each of the following nuclear decay processes.
234 234
90𝑇ℎ → 91𝑃𝑎+ ?
234
91𝑃𝑎 → ? + −10𝛽 + ṽ

Binding Energy
Binding energy is the energy released when a nucleus is formed from a collection of free nucleons.
Binding energy is also the energy required to take apart a nucleus. The greater the binding energy,
the more stable the nucleus.
In 1905, Einstein established from theoretical standpoint that mass and energy are mutually
convertible. The famous equation in this regard is
𝐸 = 𝑚𝑐 2
Where E = energy; c = velocity of light

A Helium-4 atom is composed of 2 protons and 2 neutrons. Each proton has a mass of 1.00727647
atomic mass unit (amu). Each neutron has a mass of 1.0086649 amu. The sum of 2 protons and 2
neutrons is 4.03188278 amu. The difference between calculated mass and measured mass is the
mass defect, ∆𝑚. The atomic mass of helium is 4.002602 amu. Thus, the ∆𝑚 for helium is
0.02928078 amu. The missing mass is converted to binding energy, according to Einstein equation:

8
 1.661 × 10−27 𝑘𝑔 𝑚 2
𝐸 = (0.02928078 amu × ) (299792458 )
1 𝑎𝑚𝑢 𝑠

𝐸 = 4.37113 × 10−12 𝐽

The energy released for one 42𝐻𝑒 nucleus is 4.37113 × 10−12 𝐽. For one mole of 42𝐻𝑒 , the energy
released is
4.37113 × 10−12 𝐽 6.02214 × 1023 𝑎𝑡𝑜𝑚𝑠
𝐸=( )( )
1 𝑎𝑡𝑜𝑚 42𝐻𝑒 𝑚𝑜𝑙

𝐸 = 2.63236 × 1012 𝐽⁄𝑚𝑜𝑙

Problem 7
Calculate the energy released by a nucleus of uranium-235 if it splits into a barium-141 nucleus
and a krypton-92 nucleus according to the equation below.
235
92𝑈 + 10𝑛 → 236
92𝑈 → 141
56𝐵𝑎 + 92
36𝐾𝑟 + 3 10𝑛

Transmutation, Fission, and Fusion

There are three categories of nuclear reactions: transmutation, where one nucleus changes into
another, either by natural decay or in response to some outside intervention; fission, a heavy
nucleus splits into lighter nuclei; fusion, light nuclei merge into a heavier nucleus.

Transmutation
10
B reacts via neutron capture to produce 11B, an unstable intermediate nucleus called the
compound nucleus, which decays almost instantly like an activated complex in a chemical

9
reaction. The compound nucleus decays almost instantly, emitting particles and energy to produce
a stable nucleus.
10
5𝐵 + 10𝑛 → 11
5𝐵 → 73𝐿𝑖 + 42𝐻𝑒
Nuclear Fission
In 1939, German scientist Hahn and Strasman bombarded uranium atom with neutrons and
obtained two elements with atomic numbers 56 and 36.
235
92𝑈 + 10𝑛 → 236
92𝑈 → 141
56𝐵𝑎 + 92
36𝐾𝑟 + 3 10𝑛
This phenomenon of splitting a nucleus into two approximately equal fragments is called nuclear
fission or simply fission. The generated neutrons again can bombard another 235U atoms and
another fission can occur and this phenomenon will occur within 10 -8 sec. This process of repeated
fission is known as chain reaction and as a result it can generate a huge amount of energy, 1 g of
U-235 will generate 2 x 107 kcal, and this amount of energy will be generated within 10 -6 second.
The generation of huge amount of energy leads to an explosion wit a temperature of one crore
degree. This nuclear fission reaction is the principle of atomic bomb.

235
Figure 3. Chain reaction as a result of bombardment of 92𝑈 with one neutron and three
secondary neutrons are released.

10
Energy released in a Fission Reaction
It has been estimated that the mass generated after fission is not equal to the total weight of uranium
underwent fission and bombarding neutrons. A small fraction of mass is lost and is converted to
energy according to the equation: E = mc2
For the reaction,
235
92𝑈 + 10𝑛 → 236
92𝑈 → 141
56𝐵𝑎 + 92
36𝐾𝑟 + 3 10𝑛

The mass lost is 0.2153 amu which is equivalent to an energy of ≈ 200 𝑀𝑒𝑉
Highlight:
It can be shown that when 1 kg of uranium had completely underwent fission, the energy
released would be 8.2 x 1013 J, which is sufficient to supply energy at the rate of 2.2 megawatt
continuously for one year.

To utilize the energy released during the fission, we are to control the chain reaction to get heat
energy according to necessity. Now a days, in an atomic reactor, the motion of neutrons are
retarded by graphite or heavy water to control the chain reaction. Once retarded and controlled,
the heat generated is being absorbed by molten Na-K alloy and this heat is utilized in generating
steam for thermal power.

Atomic Fusion
At a very-high temperature, two nuclei combine to give comparatively heavy nucleus, i.e., two
nuclei combine to give a new atom. This phenomenon is known as atomic fusion. And during this
fusion reaction some mass is destroyed, that means such a fusion process would also lead to
liberation of huge amount of energy which causes explosion.
2
1𝐻 + 21𝐻 → 42𝐻 𝑒 + 𝐸𝑛𝑒𝑟𝑔𝑦
This fusion released about 26.6545 MeV. The difficulty is to attain the high temperature for such
fusion process. But it is believed that such condition is attained for preparing thermonuclear bomb
such as hydrogen bomb. The transformations for fusion reactions are:
3
i. 1𝐻 + 21𝐻 → 42𝐻 𝑒 + 10𝑛 + 17 𝑀𝑒𝑉
3
ii. 1𝐻 + 11𝐻 → 42𝐻 𝑒 + 20 𝑀𝑒𝑉

11
Nuclear Reactors
A nuclear reactor is an apparatus in which nuclear fission is produced in the form of a controlled
self-sustaining chain reaction. It is a device where nuclear fission of U-235, U-233, Pu-239 and
chain reaction takes place and produces heat, neutrons, and radio-isotopes. The uranium oxide fuel
is embedded into fuel rods and placed in a water-covered reactor core. The water carries heat
released to the steam turbine. Steam turns the turbine which generates electricity. The chain
reaction is initiated by a source of neutrons. The chain reaction is regulated via control rods. The
control rods are inserted between the fuel rods to slow or stop the chain reaction. Control rods are
composed of cadmium or boron and regulate the chain reaction by absorbing extra neutrons to
maintain a steady rate of fission.

Figure 4. The general design used in all U.S. Nuclear Power Plants

Nuclear Waste

Several of the fission products in a nuclear reactor are radioactive. The radioactive products are
concentrated in the used or “spent” fuel rods. The fuel rods are referred to as high-level nuclear
waste. The half-lives of several of the products are very long, requiring special storage or disposal.
Spent fuel rods can be reprocessed into new fuel rods. Reprocessing is not carried out in the United
States due to regulatory concerns and nuclear nonproliferation treaties. All high-level waste is
currently stored on-site at the reactor. On-site storage is not a long-term solution.

Yucca Mountain, in southwest Nevada, was proposed as the site for an extensive feasibility study
for long term storage of high-level waste because it fulfills several general engineering
considerations. Yucca Mountain is extremely remote, the climate is dry, and the water level is
about 1000 feet below the potential burial vault. The storage facility must remain intact for
thousands of years. The construction materials will need to withstand the effects of high levels of
radiation.

12
 Figure 5. Waste Site
Nuclear reactors are of various types depending on their neutron spectrum, construction,
composition and purpose for which they are used. The reactors are differentiated by the following
features.

 Neutron energies:
(a) High energy as in fast reactors
(b) Intermediate energy
(c) Low energy as in thermal reactors

13
14
15
16
17
18
19
20
21
22
23
24
25
Interaction of Radiation and Matter

There are three factors governing the effects of radiation on matter:

The amount of radiation to which matter is exposed,

Penetrating power of the radiation, and

26
 Ionizing power of the radiation.

If radiation energy is greater than typical ionization energies for atoms and molecules, the radiation
could induce ionization in material encountered.

Radiation is classified as either ionizing or nonionizing. The distinction is based on the energy
carried by a photon or particle. Nonionizing radiation includes visible light, radio waves and
microwaves where photon energies are less than typical ionization energies. Ionizing radiation
includes alpha and beta particles, X-rays, and gamma rays where photon energies are greater than
typical ionization energies.

Ionization radiation can cause significant damage to any material encountered, including living
tissue, by free radical formation. It rejects electrons from atoms and molecules it encounters.
Meanwhile, free radicals scavenge electrons from other molecules, causing damage to tissue.
Through free radical formation, ionizing radiation can lead directly to cell death. On the other
hand, penetrating power must be taken into account when examining the impact of radiation on
matter. In definition, penetrating power is how far a particle penetrates into a material before its
energy is absorbed or dissipated.

Alpha particles have greater ionizing power. The relatively large size and charge of alpha particles
prevent alpha particles from penetrating deeply into matter. The dissipated energy can cause
surface burns on the skin, but do no serious harm because alpha particles cannot reach internal
organs. Alpha particles produced inside the body cause much greater damage because energy is
deposited in the internal organs. This is how radon gas causes serious tissue damage.

Beta particles have lower energy than alpha particles. Due to their smaller size/charge, most beta
particles can pass several centimeters into the body. Due to its penetrating power, beta radiation is
often more dangerous than that from alpha particles. While gamma particles can pass entirely
though the body, depositing energy in the vital organs, causing damage.

27
Figure 6: The possible health hazards from exposure to ionizing radiation depend on the
penetrating power of the radiation.

Ionizing and penetrating power must be considered when designing space-bound electronic
devices. Computer chips and other solid-state devices rely on carefully controlled distributions of
electrons and holes in semiconductor materials. Production of ions by ionizing radiation can cause
catastrophic failure of electronic devices. The single event effect results when a single ionizing
particle can produce large numbers of ions. For an instance, electronics in satellites are packaged
in “hardened” materials to protect against cosmic rays.

Methods of Detecting Radiation

To assess radiation doses, the type and amount of radiation must be measured. The first
measurements used a zinc sulfide phosphor, which produced tiny flashes of light when struck by
radiation and the light flashes were counted manually. Also, a scintillation counter is used with a
fluorescent screen to detect radiation, but the resulting photon strikes a phosphor that releases an
electron instead of light flashes. A photomultiplier tube amplifies the electronic signal, producing
a current pulse registered electronically.

Another example is the Geiger counter. It is a portable detector used to measure radioactivity. A
glass tube containing a gas at low pressure (0.1 atm) is coated on the inside with a metal that acts
as a cathode. An anode wire runs down the center of the tube, and then a high voltage is applied
across the electrodes. Alpha and beta particles enter through a window and ionize the gas atoms.
The electrons released by the gas atoms are attracted to the anode, and ionize more gas as they
travel to the anode, releasing more electrons. When the avalanche of electrons reaches the anode,
a current pulse is recorded.

28
Figure 7: In a Geiger-Mueller tube, radiation passes through a thin window into a gas-filled tube,
producing ions in the gas. The resulting ions are attracted to oppositely charged electrodes,
producing a pulse of electric current.

A film-badge dosimeter monitors the radiation exposure for people who work with radioactive
isotopes. Radiation darkens photographic plates. The darkened badge and a record of exposure
provides a warning mechanism if safety levels are exceeded.

All measurement methods must take background radiation into account when making
measurements. Cosmic rays and natural radioactive isotopes in soil, air, and water are sources of
background radiation. Background radiation must be subtracted from measurements of radioactive
sources.

Measuring Radiation Dose

The interplay between ionizing power and penetrating power result in a number of different ways
to express radiation dose. The quality factor, Q, is used to calculate the equivalent dose and is also
known as the relative biological effectiveness (RBE). The value of Q varies from a value of one
for high-energy photons to about 20 for alpha particles.

29
 Table 2: Definitions and Units used to Quantify Exposure to Radiation

Modern Medical Imaging Methods

Modern imaging methods include the use of radioisotopes to obtain images of specific organs and
elaborate techniques such as positron emission tomography (PET). During an X-ray, X-ray
radiation passes through the body and a photographic image is produced based on the amount of
radiation absorbed. Bone absorbs X-rays more strongly than organs or other tissues, and is an
excellent orthopedic diagnostic tool. X-rays can also be used to examine the structure of some
organs, such as a chest X-ray to examine the lungs or heart.

The function of organs can be examined by selectively introducing small amounts of an

appropriate radioisotope into the target organ. Radiation from the isotope is monitored to produce
a detailed image of the organ. Structure, as well as function, can be revealed. The radioactive
isotopes are introduced into target organs by taking advantage of biochemistry. Certain atoms and
compounds are taken up specifically by particular organs. The thyroid gland uses iodine to produce
thyroid hormone. Radioactive 131I is introduced and carried to the thyroid via natural biochemical
pathways.

In the thyroid, the 131I undergoes beta decay. Detection of the gamma particles produces an image
of the thyroid gland. The procedure is extremely safe because the radiation dose is fairly small and
the half-life of the isotopes is not too long. PET images are based on isotopes that emit positrons.
Neutron-deficient isotopes tend to emit positrons. Available positron emitters are 11C, 18F, 13N,
and 15O. These elements are found in common organic molecules, allowing for easy incorporation
into appropriate biological molecules.

30
Each decay of the radioisotope releases a positron. Positrons have extremely short lifetimes in the
body. It travels no more than a couple of millimeters before encountering an electron. The positron
and electron undergo matter-antimatter annihilation. The positron-electron annihilation produces
two gamma rays 180 degrees apart. Detectors register the gamma rays, and computers map out the
path taken by the tagged compounds. The result is a map of a slice through the body.

Figure 8. Positron emission tomography (PET) produces high-quality images of the brain and
other organs.

31
 References

Brown L, Holme T. (2011). Chemistry for Engineering Students. Mary Finch.

https://ionlights.keybase.pub/books/Chemistry%20for%20Engineering%20Students%2C%202e.pdf

Jain J. (2015). Engineering Chemistry. Dhanpat Rai. https://pdfcoffee.com/engineering-chemistry-by-jain-

amp-jain-pdf-free.html

32