BASARA GNANA SARASWATHI CAMPUS KAKATIYA HILLS

Sec: Star SC Nuclear Chemistry Date: 20-10-2020

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FUNDAMENTAL PARTICLES
During the nuclear transformations various sub-atomic particles are
involved which are called fundamental particles because it is believed that
the atoms themselves are built up from such basic units.
1. Electrons: These are the most important particles and the first to be
recognized. They are also known as negatrons because of negative charge
and equal to 1.6  10 19 coulomb or 4.8  1010 e.s.u and their mass is equal to
9.11  10 31 kg . They are denoted by e , 1 e0 and as   p a r t ic le s when emitted

by radioactive nuclei.
2. Protons: The nucleus of ordinary hydrogen isotope (Protium) was named as
proton by E.Rutherford. They have one unit of positive electronic unit and
mass is equal to 1.67  10 27 kg . They are denoted by p, 11H.
3. Neutrons: It was first discovered by James Chadwick during bombardment of
beryllium nuclei with fast moving   p a r tic le s . These are chargeless particles
and of mass slightly more than that of proton. They are denoted by n or 01 n .
While the electron and the proton are stable particles capable of
independent existence, the neutron is unstable particle when present
outside the nuclei and disintegrate as
Neutron( 01 n)   Proton( 11 H)  Electron( 01 e)  Neutrino( 00 n )

However, neutrons are captured by atomic nuclei much faster than they
have a chance to decay and form its isotope.
4. Positrons: Positrons are the antiparticles of electron, They have one unit of
positive electronic charge and the same mass as electron. They are denoted
by 0
1 e or 1  . They are discovered by Carl D. Anderson in 1932 during
studies on cosmic rays.
When a particle and its antiparticle meet, both are annihilated (destroyed
completely) and their mass gets converted into an energy form such as  -
radiation. The energy equivalent produced is given by Einstein’s mass-
energy equation (E  mc2 ). Positrons, though they are stable non-
disintegrating particles but found to exist not more than a micro-second as
our surroundings are rich in electrons.
A number of other fundamental particles like antiproton, neutrino and
mesons have also been discovered. Photons are also sometimes treated as
fundamental particles as they can be assigned momentum while in motion.
NUCLEAR PROPERTIES OF ELEMENTS
Nuclear size: Rutherford scattering experiment indicated that atomic nuclei

were extremely small and were possibly small than 1012 cm in diameter.
But, neutron scattering experiment is more helpful in estimating nuclear
radii and general relationship has been found between for nuclear radii, R
and nuclear mass numbers, A.
1
R  R0 A 3

where R 0  1.33 10 13 cm and is a common constant for all nuclei.
Nuclear shape: A perfectly spherical nucleus will exert a uniform force of
attraction in all directions on the electrons surrounding it. A non-spherical
nuclear shape, and therefore a non-spherical distribution of protons in the
nucleus, gives rise to the property of nuclear quadrupole moments. Thus,

1 H, 8 O, 20 Ca, 28 Ni, 50 Sn and 82 Pb which have zero quadrupole moments but

majority of other nuclei are somewhat ellipsoidal in shape.

Nuclear composition: It is generally believed that atomic nuclei contains
protons and neutrons.   particles which consist of two protons and two
neutrons each are quite stable particles and thought that they may be
present in some atomic nuclei as such. The occurrence of some stable
isotopes of elements are as follows

Mass No. Neutron No. Atomic No. Nuclear species

Even Even Even 166
Odd Odd 8
Odd Even Odd 57
Odd Even 53
Based on this W.D.Harkins framed some rules are known as Harkin’s rules.
1. The elements up to atomic number 15 have nuclei with almost equal
number of protons and neutrons. In general, when the number of
protons and neutrons in a nucleus are not equal, the neutrons are in
excess. As we go to heavier nuclei, the excess of neutrons over the
protons tends to increase. The limit, the neutron-proton ratio in the
heavier stable nuclei reaches a value of 1.5.
2. The elements with even atomic numbers are more abundant in nature
and have large number of stable isotopes. The elements with odd
atomic numbers may have only one or two isotopes.
3. Elements with heavier atomic mass are generally less abundant.
4. Atomic nuclei have strong tendency to have an even number of
neutrons. Thus most of the elements with odd atomic numbers have
odd mass numbers also. Those with even atomic numbers have even
mass numbers.

Nuclear forces: When accelerated protons of increasing energy approach other

protons, it is found that the forces of repulsion increase according to
Coulomb’s law and happens upto a distance of the order of 10 12 cm. When
the approach is over still small distances, a strong forces of attraction
develops and the forces of repulsion and attraction balance at a distance of
1.3  10 13 cm. Further closer distances than 1.3  10 13 cm, protons attach to

one another and their separation needs much stronger force. Neutrons
behave similarly towards protons and other neutrons in the matter of
increase in the forces of attraction with decreasing distances. However, do
not show any initial repulsion.

Mass defect
For all nuclei it is observed that the observed atomic mass of all known
isotopes (except hydrogen) is always less from the sum of the masses of
protons and neutrons present in it. This difference between expected mass
(calculated by adding the masses of protons and neutrons) and the actual
mass of the isotope is called mass defect. It is denoted by  m and expressed
in atomic mass units.
Consider 24 He nuclei, it has 2 protons and 2 neutrons. Its expected mass is

Expected mass  (2  1 .0 0 7 5 8  2  1 .0 0 8 9 3 )

 4 .0 3 3 0 2 a .m .u

But, the actual mass of helium  4 .0 0 3 9 0 a .m .u

Mass defect,  m  4 .0 3 3 0 2  4 .0 0 3 9 0

 m  0 .0 2 9 1 2 a .m .u

Binding energy
The mass defect is converted into energy which is released in the formation
of the nucleus. The amount of energy which released during the formation
of a nucleus from its protons and neutrons is called binding energy. The
same of energy is required to separate the nucleons.
Binding energy is calculated according to Einstein mass-energy relation,
B.E  mc2

Where  m mass defect and ‘c’ is is velocity of light in vacuum.

When  m  1 a .m .u

B.E  1.66  10 27  (3  108 )2 ( 1a.m.u  1.66  10 27 kg)

B.E  14.94  10 11 J

14.94  10 11
B.E   931.5 MeV
1.604  10 19
 B .E   m  9 3 1 .5 M e V

As the mass defect increases binding energy of the nucleus increases. But,
the stability of a nucleus can be determined when binding energy is divided
by the number of nucleons, this is called binding energy per nucleon or
mean binding energy. The average binding energy for most of the stable
nuclei is around 8 MeV. Iron has the maximum average binding energy
(8.79 MeV) and its nucleus is thermodynamically most stable.
Packing fraction
The difference of actual isotopic mass and the mass number is defined in
terms of packing fraction.
Actual isotopic mass  Mass number
Packing fraction   104
Mass number
Packing fraction can be positive, negative or even zero. Carbon ( 12
6 C ) has zero

packing fraction. In general, an isotope with negative or zero packing

fraction has greater the binding energy per nucleon and they are more
stable.
Magic Number
Nuclei with 2, 8, 20, 28, 50, 82 or 126 protons or neutrons have been found
to be particularly stable with a large number of isotopes. These numbers
which are often referred as magic numbers.
Nuclei such as 24 He, 16
8 O,
40
20 Ca and 208
82 Pb which contain protons equal to 2, 8,
20 and 82 respectively (all magic numbers) and neutrons equal to 2, 8, 20
and 126 respectively (also magic numbers) are most stable.
Instability of atomic nuclei
From the study of the behaviour of atomic nuclei following general causes
for instability of atomic nuclei can be listed.
1. For a given atomic number the neutron-proton ratio is too high
2. Atomic number is above 82.
3. There are more than 126 neutrons in the nucleus.
4. There is a stable isobar of some other nuclide nearby.
All the nuclei occurring in nature are stable and all the man-made nuclei
are unstable. An unstable nuclei tends to change into some stable nuclei at
a characteristic rate.
Theory of Radioactivity and Neutron-Proton Ratio
The stability of a nucleus found to depend on the neutron-proton ratio in
the nucleus. When a graph is drawn between number of protons and
neutrons it reveals that
1. The shaded portion in the graph represents the region or zone or belt
of stability.
2. The lower elements (up to Z=20), the stable nuclei have equal number

of protons and neutrons i.e., n  1.

p

3. For higher elements to be stable, there must be more neutrons than

protons i.e., n  1.
p

4. A nucleus whose n ratio lies above or below the stability belt is

p

radioactive or unstable.
Some general rules for predicting how an unstable nucleus may
change to acquire stability can be stated as follows.
1. The unstable nuclei have an excess of neutrons which lies above the
stability belt, this excess may be reduced by
(i) Emission of neutrons
(ii) Emission of  - particles or electrons
Neutron  Proton   

2. The unstable nuclei have less number of neutrons which lies below
the stabiliyt belt, this imbalance may be reduced by
(i) Emission of  -particles or positrons
Proton  Neutron   

(ii) Capture of a K or sometimes L-shell electron by the nucleus.

This converts a proton into a neutron. These are accompanied by
emission of X-rays and sometimes  -rays.
3. The nucleus with mass numbers above 200 emit  -particles, if the
new nucleus is still unstable on account of its size, may also emit
another  -particle. However, in this process the neutron-proton
ratio increases and hence it emit   particles.
Ex: For conversion of 238
92 U to stable 206
82 Pb , 8  -particles and 6  -particles


are emitted.

4. Nucleus are left in an excited after emission of  and  -particles. The

de-excitation may occur in any one of the following ways.
(i) Emission of one or more   radiations.

(ii) Emission of internal conversion electrons. Internal conversion is

an electromagnetic interaction between a nucleus and an electron in
the K- or L-shell. This results in the emission of the electron with a
kinetic energy.
(iii) Emission of electron-positron pair when the excitation energy is
in excess of 1.02 MeV per nucleus.

5. Spontaneous fission: In this process an unstable nucleus breaks up

into two fragments, both of which are heavy and have about half the
mass.
235 1 139 94
92 U  0n   56 Ba  36 Kr  3 01 n  Energy

RADIOACITIVITY
Whenever an unstable nucleus becomes stable one, energy is always
released; mass particles may or may not be emitted at the same time. When
these particles are emitted they come off with high speed ranging from a few
thousand kilometers per second to about 95 % of the velocity of light.

Such emission of photons or mass particles from the nuclei of an element is

called radioactivity or radioactive decay.
When the nuclei of an element undergo a radioactive transformation
spontaneously, such radioactivity is known as natural radioactivity. It is
shown by elements with atomic numbers above 83.
Ex: Radon, radium, uranium and all the transuranic elements.

Transmutation of elements
In a radioactive process nuclei of atoms of one kind change into nuclei of
atoms of another element. The changed nuclei readjust the number of
revolving electrons to become electrically neutral. This change of elements
through alterations in atomic nuclei is called transmutation of elements.
Some of such particle-nucleus interactions are
By   particles
14 4 17 1
7N  2 He  8O  1p (, p p ro c es s )

By neutrons
113 1 114
48 Cd  0n  48 Cd   (n,  p ro cess )

By protons
7 1
3 Li  1p  84 Be   ( p,  p r o c e s s )

In transmutation of elements even heavier accelerated particles like 13

6C and
14
7N have been used.
238 12 246
92 U  6C   98 Cf  4 01 n

Artificial radioactivity
When the nuclei of some elements on bombardment of fast moving or
accelerated particles like neutrons, protons etc., form a new unstable
nuclei, which immediately undergo transformation to more stable nuclei by
emitting particles and photons or just photons is known as induced or
artificial radioactivity of the parent nuclei.
Ex: Bombardment of aluminium metal sheet by   particles yields
phosphorus-30 nuclei and neutrons. This phosphorus-30 is unstable and
spontaneously undergoes transformation to silicon-30 by emitting positron.
27 4 30 1
13 Al  2 He  15 P  0n

30
15 P  30
14 Si  
 TYPES OF RADIATIONS
The radioactive radiations are of three types. These were sorted out by
Rutherford (1902) by passing them between two oppositely charged plates.
The one bending towards the negative plate carried positive charge and were
named -(alpha) rays. Those bending towards the positive plate and
carrying negative charge were called -(beta) rays. The third type of
radiation, being uncharged, passed straight through the electric field and
were named -(gamma) rays. ,  and -rays could be easily detected as they
cause luminescence on the zinc sulphide screen placed in their path.

Comparison of Properties of , and -rays

Property -rays -rays -rays
Helium nuclei Fast electrons Electromagnetic
Nature 4
2 He 0
1 e radiation
One-tenth of
Velocity Velocity of light Velocity of light
velocity of light
Penetrating
Low Moderate High
Power
Paper or 0.01
Several cm thick
mm thick 1 cm of
Stopped by lead/concrete
aluminium aluminium
layer
sheet
Group Displacement Law
The two most common emissions from atomic nuclei are  and  -particles.
When an  -particle is ejected by the nucleus of element, the product or
daughter element has two protons and two neutrons less and when a  -
particle is ejected, the daughter element has same mass number but has
atomic number increases by one unit.

Soddy and Fajjan stated that “a daughter element obtained by an  -

emission lies two places to the left of the parent element in the periodic
table and has a mass number less by 4 units and when obtained by  -
emission lies one place to the right of the parent element and has the same
mass number as the parent element”. This is known as Group Displacement
Law.

On emitting a  -particle, the daughter element lies one position to the left
and there is no change in mass number. After ejection of a neutron position
of element in the table remains the same but the mass number decreases by
one.
Z2 Z 1 Z Z 1
A
Z 1 D3

 

A 4    A
Z  2 D2 Z 1 D1
A
ZP

n

A 1
Z D4

RADIOACTIVE SERIES
The whole series of elements starting with the parent radioactive element to
the stable end-product is called a Radioactive Disintegration Series.

Sometime, it is referred to as a Radioactive Decay Series or simply

Radioactive Series. All the
natural radioactive elements belong to one of the three series,
1) The Thorium Series or 4n Series 2) The Uranium Series or 4n+2
Series
3) The Actinium Series or 4n+3 Series
The Thorium Series
It begins with the parent element thorium-232 and ends with lead-208
which is stable. This series gets its name from the prominent member
thorium-232.

The Uranium Series

It commences with the parent element uranium-238 and terminates with
the stable element lead-206. It derives its name from uranium-238 which is
the prominent member of the series and has the longest half-life.

The Actinium Series

It starts with the radioactive element uranium-235. The end-product is the
stable element lead-207. This series derives its name from the prominent
member actinium-227.

The Neptunium Series

This series consists of elements which do not occur naturally. It commences
with neptunium-237 and terminates at bismuth-200. It derives its name
from the prominent member neptunium-237.
RATE OF RADIOACTIVE DECAY

Radioactive distintegations involve only single reacting units or atoms and

are, kinetically, changes of unimolecular and first order type. They are,
however, unique in this respect that their rates are independent of the
prevailing temperature or pressure and even of the chemical combinations
in which these elements exist.
Therefore the rate of decay is characteristic of an isotope and depends only
on the number of atoms present. If N be the number of undecayed atoms of
an isotope present in a sample of the isotope, at time t,
dN
 N
dt
dN
or   N
dt
where  dN means the rate of decrease in the number of radioactive atoms
dt

in the sample; and  is the proportionality factor. This is known as the

decay constant or disintegration constant.
When N=1 in the equation we have
dN
 
dt

Thus decay constant may be defined as the proportion of atoms of an

isotope decaying per second.
HALF-LIFE
The half-life or half-life period of a radioactive isotope is the time required
for one-half of the isotope to decay or, it may be defined as the time for the
radioactivity of an isotope to be reduced to half of its original value. Half-life
period is characteristic of a radioactive element. For example, the half-life of
radium is 1620 years. This means that 1g of radium will be reduced to 0.5 g
in 1620 years and to 0.25 g in further 1620 years; and so on. Some other
radioactive elements may have half-life of a fraction of a second and for
others it may be millions of years. The unit of half-life period is tim e  1 .

CALCULATION OF HALE-LIFE
dN
we can write    dt
N

On integration,
dN
    dt or –ln N = t + K(constant)
N

If N0 is the number of atoms at time t = 0, K = – ln N0

Substituting the value of K

 ln N  t  lnN0 or N 
ln  0    t
 N 

Using ordinary logs, N 

2.303 log  0    t
 N 

  N0
At half-life time  t1  , N 
 2  2
  
N 
 2.303 log  0   2.303 log 2  t 1
 N0  2
 2 
0693
t1  .
2 

THE ACTIVITY OF A RADIOACTIVE SUBSTANCE

It is defined as the rate of decay or the number of disintegrations per unit
time. The activity of a sample is denoted by A. It is given by the expression,
dN
A  N
dt

The activity of a radioactive sample is usually determined experimentally

with the help of a Geiger-Muller counter.

UNITS OF RADIOACTIVITY
Radioactivity of radium is taken as a standard for measuring radioactivity
equivalent weights or equivalent quantities of different radioactive
substances. These weights are measured in curie units, C. One curie of
radium is taken as one gram of it. In one gram radium, on an average
3.7 1010 atoms disintegrate per second. So one curie of any radioactive
substances is such a quantity of it which gives 3.7 1010 atomic
disintegrations per second.
Rutherford is a more recent unit.
1 Rutherford = 106 dps
The S.I. unit is Becquerel
1 Bq = 1 dps
Since exposure to radioactive emanations is harmful, physiologists use a
unit for measuring the exposure dose. This is called a roentgen, r, and is
defined as the quantity of X or  radiations which produces 1.611012 ion
pairs in 1 gram of air. This is equivalent to absorption of 84 ergs of energy
per gram of air.
Another radiation unit used is a rad. The rad is the dosage of any nuclear
emanation (particles or photons) equivalent to the absorption of 100 ergs of
energy per gram of any material.
AVERAGE LIFE
In a radioactive substance, some atoms decay earlier and others survive
longer. The statistical average of the lives of all atoms present at any time is
called the Average life. It is denoted by the symbol  and has been shown to
be reciprocal of decay constant .
1



The average life of a radioactive element is related to its half-life by the

expression,
Average life = 1.44 × Half-life period
  1.44  t 1
2

The average life is often used to express the rate of disintegration of a

radioactive element. The average life of radium is 2400 years.
RADIOACTIVE EQUILIBRIUM
Let a radioactive substance A decay to give another radioactive substance B
which decays to form substance C. If A and B are the decay constants for
the two changes, we can write
 
A 
A
 B 
B
C

The rate of disintegration of A is also the rate of formation of B. When the

rate of disintegration of A (or formation of B) is equal to the rate of
disintegration of B, the amount of B does not change with lapse of time.
Then the radioactive equilibrium is said to be established between the
substance A and the substance B. At this stage
dN A dN B

dt dt

where NA and NB are atoms of A and B present at the equilibrium.

NA 
Since  A N A   BNB ,  B
NB A
But   t1
2

t 1 of B
NA
  2
NB t 1 of A
2

Thus the atoms of A and B are present in the ratio of their half-lives.
 The radioactive equilibrium differs from a chemical equilibrium in that it is
irreversible.

RADIOACTIVE DATING
The age of an old piece of wood can be determined by radioactive dating
technique. The atmosphere contains radioactive carbon dioxide, 14
CO2 , and

ordinary carbon dioxide, 12

CO2 , in a fixed ratio. A plant while alive takes up

both types of carbon dioxide and converts them to carbon-14 and carbon-12
photosynthesis. Thus a living plant contains radioactive carbon-14 and
stable carbon-12 in a fixed ratio. When the plant dies, the uptake of carbon
from the atmosphere stops. Hence, carbon-12 remains unchanged but
carbon-14 decays by  -emission.
14
6 C  14
7 N  01   Half  life  5730 years 
radioactive
12
6 C  No change
stable
14
C
As a result, 12
decreases with lapse of time.
C

Therefore the concentration of carbon-14 declines with time. The

concentration of carbon-14 can be measured by counting the radioactivity.
Knowing the concentration of carbon-14 in a given sample of old wood and
that in a living plant, the age of the sample can be calculated.
Differences between Nuclear Fission and Nuclear Fusion

Nuclear Fission Nuclear Fusion

1. A bigger (heavier nucleus splits Lighter nuclei fuse together to form

into smaller (lighter) nuclei. the heavier nucleus.
2. It does not require high Extremely high temperature is
temperature. required for fusion to take place.
3. A chain reaction sets in. It is not a chain reaction.

4. It can be controlled and energy It cannot be controlled and energy

released can be used for peaceful released cannot be used properly.
purposes.
5. The products of the reaction are The products of a fusion reaction
 radioactive in nature. are nonradioactive in nature.

6. At the end of the reaction nuclear No nuclear waste is left at the end
waste is left behind. of fusion reaction.

Differences between Nuclear Reactions and Chemical Reactions

Nuclear Reactions Chemical Reactions
1. Proceed by redistribution of nuclear Proceed by the rearrangement of
particles. extranuclear electrons.
2. One element may be converted into No new element can be
another. produced.
3. Often accompanied by release or Accompanied by release or
absorption of enormous amount of energy. absorption of relatively small
amount of energy.
4. Rate of reaction is unaffected by external Rate of reaction is influenced by
factors such as concentration, external factors.
temperature, pressure and catalyst.