Nuclear Chemistry

P. Nagaraja
Assistant Professor in Chemistry
AP IIIT, RK Valley, RGUKT

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 Introduction
• Nuclear chemistry is the study of nuclear reactions, its uses and effects
on biological systems
• Reactions that involves the transformation of one nuclei into another
nuclei are called nuclear reactions
• Unlike chemical reactions, nuclear reactions involves a change in the
identity of the atom
• Nuclear chemistry depends on the phenomenon of radioactivity
• Radioactivity is used to diagnose and treat many diseases in medicine
• Nuclear fission is used to generate electricity and nuclear weapons

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 The structure of nucleus

Quarks are the smallest particles exists in nucleons

They are held together by strong force called gluon

Neutron converts to proton by the emission of β-particle

Proton converts to neutron by the emission of positron

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 Mass defect
• The mass of nucleus is equal to sum of masses of protons and neutrons
• It is found that the mass of a nucleus is always lesser than the mass of nucleons. The
difference between the expected mass and actual mass of nucleus is known as mass
defect (or)
• The mass difference between a nucleus and its constituent nucleons is called mass defect
• The mass defect is given by the formula
• ∆m = mexpected – mactual
• For example, consider helium nucleus having 2 protons and 2 neutrons

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 Binding energy
• This mass difference can be accounted by using the famous Einstein equation from his
theory of relativity, E= mC2
• Where E = energy, m = mass and C = light velocity
• This equation relates mass and energy
• According to this equation, this mass difference is released in the form of energy during
the formation of nucleus from nucleons. This energy is termed as binding energy
• Greater the mass defect, greater the binding energy of the nucleus
• The amount of energy released during the formation of a nucleus is called binding energy
(or)
• It may also defined as the amount of energy required to convert a nucleus into its
constituent protons and neutrons
• Binding energy is a direct measure of nuclear forces between proton and neutron
• Binding energy is directly proportional to nuclear stability

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 binding energy per nucleon
• Binding energy can be calculated from Einstein equation, E = mC2
• It may re-written as,
• ∆E = ∆mC2 Joules
• ∆E = Binding energy, ∆m = mass defect, C = light velocity

• Binding energy = ∆m x 931.5 MeV = 0.03038 x 931.5 = 28.3 MeV

• Mean binding energy per nucleon is given by, 28.3/4 = 7.075 MeV
• The binding energy per nucleon is a measure of the stability of the nucleus
• Greater the binding energy per nucleon, more the stability of nucleus

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 Nuclear stability
➢ Values of binding energy per nucleon can be
used to compare the stability of different nuclei
➢ In figure, binding energy per nucleon plotted
against mass number
➢ Binding energy per nucleon at first increases
upto the mass number 56 reaching about
1.4*10-12 J
➢ It then decreases slowly to about 1.2*10-12 J for
heavy nuclei
➢ This trend indicates that nuclei of intermediate
mass numbers are more tightly bound, and
therefore more stable than those with smaller
and larger mass numbers

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 Radioactivity

❖ The phenomenon of radioactivity was discovered by Henri Bacquerel

❖ After Uranium, two new radioactive elements were discovered by his student Madam Curie namely
Polonium (Po) and Radium (Ra)
❖ Element 96 is named as Curium (Cm) in honor of Madam Curie for her contributions to Nuclear Chemistry

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 Nuclear stability
• Some atomic nuclei are stable and some are unstable and undergo
radioactive decay to form stable nuclei
• Atoms of smaller atomic number (Z=20) are stable and contain equal
number of protons and neutrons
• As atomic number increases, the repulsion between protons increases and
requires more number of neutrons
• Thus the neutron-to-proton (n/p) ratios of stable nuclei increases with
increasing atomic number
• For atoms, upto Z=20, n/p = 1.0
• For atoms, 21- 83, n/p = 1.5
• If Z>83, it is even greater than 1.5 and mostly unstable and hence
radioactive

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Types of radioactive decay

1. Nuclei above belt of stability (high n-to-p ratio)

These neutron rich nuclei move towards the belt of
stability by emitting beta particles
Emission of beta particles decreases the neutron
number and increases the proton number
2. Nuclei below belt of stability (low n-to-p ratio)
These proton rich nuclei move towards the belt of
stability by emitting positrons
Emission of positrons decreases the proton number
and increases the neutron number
3. Nuclei with atomic number >84
These heavy nuclei tends to undergo alpha emission,
which decreases both the number of neutrons and
protons

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 Types of radioactivity
• If nuclei is unstable it emits small particles like alpha, beta rays etc., to
gain stability

Atomic number = Number pf protons in the nucleus

Mass number = Total number of protons and neutrons in the nucleus

➢ Atoms of the same element have same number of protons

➢ Atoms of the given element having different number of neutrons are called Isotopes
➢ Isotopes have different mass numbers
For example, Hydrogen, Deuterium and tritium are isotopes of H
Uranium contain U-234, U-235 and U-238
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 Alpha radiation
• Alpha radiation occurs when an unstable nucleus emits 2 protons and 2 neutrons
• Because He-atom contain 2 protons and 2 neutrons, the symbol for alpha particle
is identical to helium atom
• When an atom emits alpha particle, it becomes lighter atom
• It can be represented using the following nuclear equation

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 Nuclide and Nuclear equation
• Nuclide is a nucleus of an atom having specific protons and neutrons
• A nuclear reaction is an equation that represents the changes that occur
during radioactivity or nuclear processes
• For example, consider the alpha decay of U-238

The original atom is called parent

nuclide, and the products are
called daughter nuclide

In nuclear equation, the sum of

atomic and mass numbers on
both sides must be equal

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 Beta radiation
• Beta radiation occurs when an unstable nucleus emits an electron
• Beta decay involves the conversion of a neutron to proton with emission of an e-

• When an atom emits beta particle, it atomic number increases by 1

• For example, consider the nuclear equation for the beta decay of Radium-228

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 Gamma radiation
• Gamma radiation is a form electromagnetic radiation having high frequency
• Gamma rays emission does not change either mass number or atomic number
• Gamma rays are usually emitted in conjunction with other rays
• For example, the alpha emission of U-238 is also accompanied with gamma rays

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 Positron emission
• Positron emission occurs when an unstable nucleus emits a positron
• Positron emission involves the conversion of a proton to neutron

• When an atom emits positron, it atomic number decreases by 1

• For example, the nuclear equation for the positron emission of P-30 is

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Types of radioactivity-Summary

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 Kinetics of radioactive decay
• Radioactivity is a natural process that takes place in environment
• Radioactivity occurs due to instability of atomic nuclei beyond atomic number 83
• Different radioactive nuclides undergo decay at different rates
• Radioactive decay is a first order process
• Nuclear decays are usually expressed in half-lives
• The time required for half of the radioactive nuclides to decay is known as its half life
(t1/2)
• Half life is a characteristic kinetic parameter for each radioactive nuclei
• Nuclides that decay slowly will have long half-lives while nuclides that decay faster will
have short half-lives
• For example, the half life of Sr-90 is 28.8 yrs
• If we start with 10.0 gms of Sr-90 it will be 5.0 g in 28.8 yrs and 2.5 g in next 28.8 yrs

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 Half life calculation
• Radioactive decay is a first order process and hence its rate is directly proportional to the number
of radioactive nuclei, N in a sample
• Rate = kN where, k = decay constant
• The rate at which a sample decays is called its activity
• It is often expressed as number of disintegrations per second (dps)
• Units are Bacquerel (1Bq = no. of dps/atom) or Curie (1 Ci = 3.7*1010 dps)
• From first order kinetics, ∆𝑁
∆𝑡
= -kN
• The integrated rate equation may be written as
𝑁𝑡 • No = number of nuclei initially
ln 𝑁𝑜
= -kt
• Nt = number of nuclei after ‘t’ sec
• The ratio Nt/No gives the fraction of atoms remaining after ‘t’ sec

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 Half life calculation
• The relation between rate constant k and half life is given by

t1/2 = 0.693
𝑘
• From the above equations,
1. If the activity is measured in the laboratory over a period of ‘t’ sec, k can be calculated
2. If k is known, the fraction of a radioactive sample still present after sometime can be calculated
3. If k is known, the time required to decay to a fraction of the original activity can be found

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(C)

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 Uses of radioactivity - Radiocarbon dating
• In certain situations, age of a material can be determined based on rate of
radioactive decay of an isotope
• Naturally occurring carbon contains 99.9% C-12 and 0.01% C-13 and traces of
another isotope C-14
• Carbon-14 are present to the extent 1 atom per 1012 atoms in nature
• Carbon-14 is a beta emitter with a half life of 5730 years that is 1.00 gm of C-14
shows 14 disintegrations per minute
• Carbon-14 is formed in the atmosphere by the nuclear reactions of neutron in
cosmic radiation

• C-14 oxides to 14CO2 and enters into carbon cycle

• By measuring the amount of C-14 we can estimate the age of fossils and artifacts
with the help of radiocarbon dating

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➢ If an animal or plant dies the ratio of
C-14 to C-12 decreases
➢ By measuring this ratio and comparing it with
atmosphere, we can estimate the age of an object
➢ For example, if the ratio diminishes to half to that
of the atmosphere, the object is one half life,
or 5700 years old

Limitations:
The ratio of C-14 to C-12 is assumed to be constant
However it is not correct due to variations in
atmosphere. Hence it has to be compared with
another data

▪ Similarly, the age of rocks can be estimated by

measuring the ratios of Lead-206 to U-238
isotope
❖ U-238 has half life of 4.5*109 years
✓ It was found that the oldest rocks has an age of
3*109 years
✓ Scientist estimated that it is required that 1 to
1.5*109 years for earth to become solid
✓ The age earth is about4 to 4.5*109 years26
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