UNIT 11

NUCLEAR CHEMISTRY

OBJECTIVES
After studying this Unit, you will be able to:
l

know about radioactivity and nature

of different types of radiations.

learn about the radioactive decay

series.

define nuclear binding energy and

rate of radioactive decay.

know about artificial nuclear

reactions and synthetic elements.

learn about nuclear fission, principle

of nuclear and breeder reactors.

know about nuclear fusion reactions

lear n about applications of

radioisotopes including radiocarbon dating.

If the radiance of a thousand suns were to burst

into the sky, that would be like the splendour of
the Mighty One.
Bhagvad Gita

Chemistry is mostly concerned with extra

nuclear atomic structure rather than the
nucleus. Nevertheless, there are many aspects
of nuclear science that are important to
chemistry. Nuclear chemistry is concerned
with nuclear stability and the process of
nuclear changes. Examples of these processes
are radioactivity, artificial transmutations,
nuclear fission and nuclear fusion. The
energies involved in some of these processes
are million times greater than those in
ordinary chemical reactions. In this Unit, we
shall deal with some important aspects of
nuclear chemistry.
11.1

THE NUCLEUS

An atom of any element consists of a positively

charged nucleus surrounded by one or more
negatively charged electrons, the whole atom
as such being electrically neutral. Nearly all
the mass of an atom is concentrated in the
nucleus, which has a radius of about 1015 m,
i.e., about 105 times that of the atom. The
nucleus consists of positively charged protons
and electrically neutral neutrons, collectively
known as nucleons. The atomic number, Z of
an atom is the number of protons in the nucleus
that defines the identity of an atom. The
mass number, A, of an atom is the integer
nearest to the relative atomic mass and is equal
to the number of nucleons in the nucleus; it
follows that the number of neutrons in the same
nucleus is A-Z. A particular nuclear species with
a specific atomic number and a mass number
is referred to as, nuclide. Nuclides of the same
element of different mass numbers are called
isotopes of that element.

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CHEMISTRY

11.2 DISCOVERY OF RADIOACTIVITY AND

NATURE OF RADIATIONS
The phenomenon of radioactivity was accidentally
discovered by French scientist Henri Becquerel,
who in 1896 reported that uranium salts emitted
a radiation with properties similar to X-rays
(discovered earlier by Rntgen, 1895).
Investigations of Pierre and Marie Curie in later
years led to the discovery that the atoms of
certain other elements such as thorium, radium
and polonium undergo spontaneous decay and
emit similar radiations. These elements are said
to be radioactive and the phenomenon is known
as radioactivity. Three types of radiation from
recognised radioactive elements are, -particles
(helium nuclei), -particles (electrons of nuclear
origin having high kinetic energy) and -radiation
(high frequency radiation). It was realized that
radioactivity of an element is independent of its
physical state, its chemical environment or
temperature, suggesting that it is a property of
nucleus.
Rutherford studied the penetrating power of
these radiations and their behaviour in electric
and magnetic field. His conclusions are
summarized below:
) particles are fast moving helium nuclei
(a) Alpha (
(He2+ or 24He) with energy about(6 - 16)1013J.
They penetrate a few centimeters of air causing
ionization of some molecules but they are
stopped by a few sheets of paper or a very thin
metal foil.
) Particles are fast moving electrons.
(b) Beta (
Their energies are about (0.03 - 5.0) 1013 J,
but since they are much lighter than -particles,
they travel much faster and have a range of
Photographic plate

 -particles

 -particles

 -rays
Electromagnetic
field

Lead casing

Radium source

Fig. 11.1 Radiation from a radioactive element

radium and the effect of a magnetic field
on the same.

penetration of 1-2 m in air. Their total ionizing

effect is about the same as that of -particles
but it is effective over much longer distances.
(c) Gamma () radiation is a very short wavelength
(and therefore very high energy) radiation that often
accompanies or emission. It has great
penetrating power and is stopped only by a
thickness of about 15-20 cm of lead. On passage
through matter they are capable of ejecting highspeed electrons.
The effect of a magnetic field on the radiation
obtained from radium is shown in Fig. 11.1.
11.2.1 Group Displacement Law
The chemical consequences of radioactive decay
may be summarised as follows:
Emission of an -particle (a helium nucleus)
lowers the atomic number by two and mass
number by four; emission of a -particle (an
electron of nuclear origin) raises the atomic number
by one and leaves the mass number unchanged.
Thus, the new element may be displaced either to
the left (two places in case of -emission) or to the
right (one place in case of -emission) in the
periodic table. This displacement is known as
Group Displacement Law. The emission of radiation affects neither atomic number nor mass
number. The new element formed in this way is
usually known as the daughter element and the one
that has undergone decay, the parent element. For
example, the decay of

238
92

U nucleus by an -particle

emission produces a thorium nucleus

234
90

Th . This

nuclear reaction is represented by the equation:

238
92

234
90

Th + 24 He

It may be pointed out that there is a

conservation of both atomic number and mass
number in the equation of a nuclear reaction.
In case an -emission is followed by two
successive -emissions, a nuclide which is isotopic
with the original one may be produced, e.g.,
238
92

-
U

234
90

-
Th

234
91

-
Pa

234
92

The nuclides having same mass numbers but

different atomic numbers such as
234
90

Th ,

234
91

Pa , and

234
92

U are known as isobars.

In addition to , and emissions, two other

types of decay processes are also observed, viz.
+ emission and K-capture.

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NUCLEAR CHEMISTRY

+ emission A positively charged beta particle

( +) is known as positron. The emission of a
positron ( +) results into a decrease of atomic
number by one unit. It is now believed that
-emission involves the transformation within
the nucleus of a neutron to proton or proton to
neutron. Thus

n p+ + - ; p+ n + b +
An example of + emission is
Na Ne + e ( )
K-capture In some nuclides, the nucleus may
capture an electron from the K shell. The
vacancy created is filled by electrons from higher
levels giving rise to characteristic X-rays. This
process is known as K-electron capture or simply
K-capture. An example of K-capture is:
22
11

22
10

0
+1

Ba + e - 133
55 Cs + X - ray
The change in the nucleus is represented by
133
56

p+ + e - n ; the neutron produced remains in

the nucleus and the atomic number decreases
by one unit as a result of K-capture.


 ray





Annihilation

Positron emission

X-ray

Example 11.1
What may be the place of a daughter
element in the periodic table, which is
218
obtained after the nuclide 84 Po undergoes
an emission followed by two successive
emissions?
Solution
The loss of one particle will reduce the mass
number by four and atomic number by two.
Subsequent two emissions will increase the
atomic number by two without affecting the mass
number. Hence, the new element will be only an
isotope of the parent nuclide with mass number
four less, i.e., 214
84 Po and hence its position in the
periodic table remains unchanged.

218
84 Po

11.2.2

214
82 Pb

214
83 Bi

214
84 Po

Radioactive Decay Series

Radioactive heavy nuclei decay by a series of

- and/or -emissions, finally resulting in the
formation of a stable isotope of lead. All the
nuclei formed from initial to the final stable
element constitute a series. There are four decay
series distinguished by whether the mass
numbers are divided by 4 or whether when
divided by four, there are remainders of 1, 2, or 3.
232
The parent of (4n) is 90 Th and its end product
208
is 82 Pb . The corresponding parents of the
238
235
(4n + 2) and (4n + 3) series are 92 U and 92 U ,

respectively. An artificial series (4n + 1) starts

209
Bi . These
with Plutonium, 241
94Pu and ends in 83
Electron capture

Electronic transition
from valence orbital

Fig. 11.1(a) +- emission and K-capture of electron.

Table 11.1

series are summarized in Table 11.1.

As an illustration, the complete uranium
decay series is given on next page and
schematically presented further in Fig. 11.2.
The Decay Series

Series

Name of the
Series

Parent Element

End Stable
Element

4n
4n + 1
4n + 2
4n + 3

Thorium series
Neptunium
Uranium series
Actinium

Thorium232
Plutonium241
Uranium238
Uranium235

Lead208
Bismuth209
Lead206
Lead207

Value of n for
the Parent Element
58
60
59
58

Value of n for
the End Element
52
52
51
51

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CHEMISTRY
238
92

U -

230
90

218
84

Th -

Th

214
82

Po

234
91

226
88

Po

214
84
210
84

234
90

Po -

Ra

Pb

210
82

206
82

Pa -

Pb -

11.2.3 Nuclear Stability and Neutron/

Proton ratio

Rn

A plot of N (the neutron number) against Z (atomic

number or number of protons) is shown in
Fig. 11.3. From this, it is clear that for stable
nuclides up to Z =20, N = 20 (40Ca), the relationship
can be represented by a line with a slope of
45 degree, i.e., the maximum stability is attained
when N = Z. At higher values of Z, the graph
becomes curved with the slope of the curve
gradually increasing. To the right of curve where
the N/Z ratio is lower than that required for
stability, a radioactive nuclide can decay by
+ emission or K-electron capture, which
produces a daughter nucleus with a ratio of
(N + 1)/ (Z - 1). To the left of the curve, a radioactive
nuclide would be neutron rich and would decay
by emission to produce a daughter nucleus
with a lower N/Z ratio of (N 1)/ (Z + 1). In either
case, the daughter nuclide might be stable (i.e.,
have N/Z ratio within the stable range) or undergo
further decay until stability is attained. This
behaviour is explained by the strong n-p as well
as p-p attractive forces operative at the level of
nuclear distances. For heavier nuclides, p-p
repulsions start to offset the attractive forces and
an excess of neutrons over protons is required
for stability.

234
92
222
86

214
83

Bi

210
83

Bi

Pb

238

9
4.5 10 y

 decay

234

230

5
2.5 10 y

 decay

Mass Number

4
8 10 y

226

1600y

222

218

3.8 d

3 min

214
20 min

200 s

=second
s
min =minutes
=days
d
=years
y

210
138 d
206

130
81 82 83 84 85

86 87 88 89 90 91 92

120

Atomic Number

Example 11.2
238
92

206
82

In the decay series U to

Pb , how many
-particles and how many -particles are
emitted?
Solution
The change in mass is 238 206 = 32 units. It
means that 32 / 4 = 8 -particles are emitted.
With the emission of 8 -particles, the change
in atomic number will be 8 2 = 16, i.e.,
the new element would have atomic number
92 16 = 76. But the final product Pb, has
atomic number 82. It means there would have
been an emission of 82 76 = 6 particles.

100
Neutron mumber (N )

Fig. 11.2 The Uranium-238 series. The times are the

half-lives of the nuclides.

110

90

Neutron rich
nuclei

80
70
60
50
40
30

N-Z

Proton
rich
nuclei

20
10
0

10 20 30 40 50 60 70 80
Atomic number (Z )

Fig. 11.3 A plot of number of neutrons (N) against the

atomic number (Z) for a range of stable nuclei.

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NUCLEAR CHEMISTRY

When the value of Z becomes greater than 82

some nuclides attain greater stability (i.e. decay
by -emission) which reduces the initial N/Z
value to (N 2)/(Z 2), the more important
consequence being the reduction of Z leading to
the reduction of p-p repulsions.
From the above discussion, it appears that,
the neutron-proton ratio plays a vital role in
deciding the stability of nuclides as also the
kinds of decay they undergo.
Example 11.3
What may be the new neutron and
proton ratio after a nuclide, 238
92 U loses an
-particle?
Solution
If the original neutron-proton ratio was N/Z
(146/92), the new ratio will be (N-2)/ (Z-2), i.e.,
144/90.
11.2.4

Nuclear Binding Energy

The mass of hydrogen atom is equal to the sum

of the masses of a proton and an electron. For
other atoms, the atomic mass is less than the
sum of the masses of protons, neutrons and
electrons present. This difference in mass
termed as, mass defect, is a measure of the
binding energy of protons and neutrons in the
nucleus. The mass-energy relationship
postulated by Einstein is expressed as:
E = mc2
(11.1)
Where E is the energy liberated, m the loss
of mass and c is the speed of light.
Consider the helium nucleus which contains
2 protons and 2 neutrons; the mass of helium
nucleus on 12C =12 mu, scale is 4.0017 mu. The
masses of individual isolated proton and neutron
are 1.0073 and 1.0087 mu respectively. The total
mass of 2 protons and 2 neutrons is (2 1.0073)
+ (2 1.0087 = 4.0320 mu. The loss in mass or
mass defect for helium nucleus is
4.0320mu 4.0017mu = 0.0303 mu
Since 1mu = 1.66057 1027 kg and
c = 2.998 108 ms1
E = 0.0303 1.66057 1027 6.02 1023
(2.998 108)2 kg m2s2 mol1
= 2.727 1012 J mol1
Thus, the molar nuclear binding energy of
helium nucleus, 4He, is 2.73 1012 J mol1.

Binding energy of a nucleus is generally

quoted as energy in million electron volts (MeV)
per nucleon. One million electron volts are
equivalent to 9.6 10 10 J mol 1. Thus, the
formation of helium nucleus results in the
release of 2.7 1012/9.6 1010 MeV = 28 MeV
(approximately).
In comparing the binding energies of different
nuclei, it is more useful to consider the binding
energy per nucleon. For example, helium
nucleus contains 4 nucleons (2 protons and 2
neutrons), the binding energy per nucleon in
this case is 28/4 = 7 MeV.
Binding energies of the nuclei of other
atoms can be calculated in a similar manner.
Fig. 11.4 shows the binding energies of the
nuclei of atoms plotted against their
respective mass number. Three features of
interest may be noted in this figure. First,
nuclei with mass number around 60 have the
highest binding energy per nucleon. Second,
species of mass numbers 4, 12, and 16 have
high binding energy per nucleon implying that
the nuclei 4He, 12C, and 16O. are particularly
stable. Third, the binding energy per
nucleon decreases appreciably above mass
number 100.

Fig. 11.4 A plot of nuclear binding energy per

nucleon against the mass number for
naturally occurring nuclides.

The form of relationship between, binding

energy per nucleon and mass number indicates
that heavy nuclei would release mass (and
therefore energy) on division (or fission) into two

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CHEMISTRY

nuclei of medium mass and that the light nuclei

would release mass (and therefore energy) on
fusion to form heavier nuclei. These processes
called fission and fusion are described later in
this Unit.
11.2.5

Rate of Radioactive Decay

The decay of a radioactive element is a random

process and is independent of external factors
such as temperature and environmental
changes. The rate of decay of a nucleus follows
the natural exponential law (first order kinetics,
Unit 6) and if the number of parent nuclide
present at any time is No and the number of
nuclei after time (t ) in seconds is Nt, then
Nt = No e kt
(11.2)
Where k is the radioactive decay constant for
a particular nuclear species. The duration of time
during which half of the nuclei originally present
decay is called the half-life of the isotope. Thus,
Nt = No and its relationship to k is obtained as
follows:
e kt = Nt / No =
k t1/2 = ln2
t 1/2 = (ln 2) / k = 0.693 / k
(11.3)
where t1/2 is the half-life period. The half-life of
a particular radioactive isotope is a
characteristic constant of that isotope. Values
of t1/2 range from millions of years (e.g., 4.5 109 y
for

238
92

U ) to fractions of seconds (e.g. 104 s for

214
84

Po ). Kinetically, the radioactive decay process

is a first order reaction. The disintegration rate is
also referred to as activity. The SI unit of
radioactivity is the becquerel (Bq) named after
Antoine Becquerel which is equal to one
disintegration per second. The older unit, curie,
named after Marie Curie is still used; one curie
(Ci) is defined as the amount of radioactive
isotope that gives 3.7 1010 disintegrations per
second (the activity associated with 1 g of
radium-225 with half-life of 1600 years). Thus, 1
Ci = 3.7 1010 disintegrations s1 = 3.7 1010 Bq.

Example 11.4
The atomic mass of 19F is 18.9984 mu. If
the masses of proton and neutron are
1.0078 mu and 1.0087 mu, respectively,
calculate the binding energy per
nucleon (ignore the mass of electrons).
(1 mu = 931 MeV)

Solution
Mass defect
= [{ (9 1.0078)+ (10 1.0087)} 18.9984]mu
= 0.1588 mu
Binding energy per nucleon
= (0.1588 931) MeV/ 19
= 7.78 MeV
Example 11.5
Calculate t1/2 for 241 Am in years given that
it emits 1.2 1011 -particles per gram per
second.
Solution
1 gram of Am contains NA / 241 nuclei = No,
using the equation
Rate of decay = 1.2 1011 g1 s1
= k No = k NA / 241
= k 6.02 1023 /241
11
k = 1.2 10 241 / 6.02 1023
= 4.8 1011 s1
and t1/2 = ln2/k = 0.693/k
t1/2 = 0.693 / (4.8 1011 s1)
= 1.44 1010 s = 462.9 years.
11.3

ARTIFICIAL NUCLEAR REACTIONS

The first artificial transmutation was carried out

by Rutherford in 1919 who bombarded nitrogen
gas with alpha particles and obtained hydrogen
and oxygen,
14
7

He

18

( 9F)

17

Fig. 11.4 (a) Artificial transmutation.

1
H are stable and no
The isotope 17
8 O and 1
further disintegration takes place. Charged
particles such as -particles, deuterons (heavy

hydrogen isotope, 12 D ), protons, and electrons can

be accelerated to very high speeds by fluctuating
electric and magnetic fields in machines such as
cyclotron, synchrotron, etc. (Fig. 11.5). These highspeed particles are more efficient in causing
nucleus to disintegrate on impact. Some typical
transmutations involving various particles are
summarised below:

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NUCLEAR CHEMISTRY

(1) Alpha particle induced reactions

9
4

4
2

12
6

1
0

Be + He C + n
Since -particle is used and a neutron is
produced, the reaction may be termed as (, n)
reaction. In another -bombardment nuclear
reaction, the isotope produced is itself
radioactive. Thus,
27
13

The isotope
+
( ) emission:

Al + 24 He
30
15

30
15

Some of the isotopes produced as a result of

neutron bombardment find applications in
different areas (see later uses of radioisotopes).
The preparation of isotopes of elements beyond
uranium involves many neutron-induced
reactions.
Example 11.6
What do you understand by the following
notations in respect of the types of artificial
transmutations?
(i) (n, ) (ii) (p, ) (iii) (, n) and (iv) (D, p)

P + 10 n

P undergoes decay by positron

+
P 30
14Si +
This was the first example of radioactivity
produced by artificial means.
(2) Deuteron- induced reactions:
30
15

(i)

12
6

C + 12H

13
7

N + 10 n ,

(D, n) reaction

2
14
4
(ii) 16
8 O + 1 H 7 N + 2 He , (D,a ) reaction
(3) Proton-induced reactions:

(i)

14
7

N + 11H

7
3

1
1

15
8

O + g , (p, g ) reaction

(ii) Li + H He + 24 He (p,a) reaction

(4) Neutron-induced reactions:
(i)
(ii)
(iii)

23
11

Na + 10 n

131
52 Te
14
7

4
2

24
11

+ 10 n

N + 10 n

14
6

Na + g , (n, g ) reaction

132
53 I

0
1e,

C + 11H,

(n, ) reaction

(n,p) reaction

Solution
(i) The striking particle is n and the particle
in the product is .
(ii) The striking particle is p (proton), the
particle produced is .
(iii) The striking particle is -particle (42He) and
one neutron is on the product side.
(iv) Deuteron ( 21H) is the striking particle and
one proton is in the product.
11.4 SYNTHETIC ELEMENTS INCLUDING
TRANSURANICS
Nuclear reactions involving the bombardment
technique by different particles have been used
to synthesise artificial elements such as
technetium, astatine, and transuranium

Dees
Spiral path of ions

High-frequency
voltage

Emerging ion

Positive ion
source

Negative electrode
to deflect beam
to target

Target material
Fig. 11.5 A Cyclotron. Positive ions are introduced at the centre of the cyclotron. Attraction of the ions will be
crossing the gap between the dees when the electric polarities are just right to accelerate them.
Magnet poles above and below the dees produce a magnetic field that keepthe ions moving in a
spiral path and at the end of their path, the ions encounter a negative electrode that deflects them
to a target material.

226
CHEMISTRY

elements (i.e., elements beyond Z > 92) which

follow uranium in the periodic table. The nuclear
reactions which are employed to synthesise some
of these elements are given below.
(1) Technetium:

Solution
Neutron with its neutral character has stronger
striking ability in nuclear reactions. Proton with
positive charge is not so effective to attack the
positively charged nucleus.

96
42

1
Mo + 12H 97
43 Tc + 0 n
(2) Neptunium and plutonium:
238
92
239
92

U + 10 n
-

-b
U

239
93

239
92

Example 11.8
Complete the following nuclear equations:

U + g

Pu is an -emitter with half-life of

2.4 104 years.
(3) Americium and curium
239
94

239
94

Pu + 10 n

240
94

240
94

Pu + 10 n

241
94

241
94

Pu

241
95

Pu + 24 He

242
96

Cm + 24 He

Cm + 10 n

245
98

Cf + 10 n

(5) Later elements

Bombardment with heavier nuclides produces
later elements. For example:
12
6

Cm +

254
102

No + 410 n

nobelium
250
98

Cf +

11
5

(ii)

239
94

Pu + ..........

257
103

Lr + 410 n

12
6

is

254
100

Fm with half-life of 3.3 hours. Thus, (to

241
mention the most stable isotopes) 95 Am
244
and 96 Cm are available in grams,
251

249
97

Bk , 249
98 Cf

253

and 98 Cf in milligrams, 99 Es (einsteinium) in

micrograms and the elements beyond
einsteinium only in few atoms. It may be pointed
out that so far elements, upto atomic numbers
109 have been identified.
Example 11.7
In artificial transmutation which has
stronger striking ability and why, proton
or neutron moving with the same speed?

254
102

No + ..........
242
96

246
96

Cm +

12
6

254
102

(ii)

239
94

Pu + 24 He

242
96

Cm + 10 n

No + 410 n

Cm + 10 n

NUCLEAR FISSION

Two consequences of nuclear reactions,

phenomena of nuclear fission and nuclear fusion,
are important from the point of view of
harnessing nuclear energy for peaceful or
destructive purposes.
In a nuclear fission reaction, a heavy nucleus
splits up into two main fragments of lighter
nuclei and several neutrons. Of the three natural
isotopes of uranium ( 238
92 U ,
the

235
92

235
92

U , and

234
92

U,

U nucleus undergoes nuclear fission when

bombarded with slow neutrons. The 236

92 Ueformed
breaks up in several different ways, for example:

lawrencium

Many of the heavier isotopes are short lived.

The longest lived isotope of fermium, for example,

(i)

11.5

Am + b -

curium

246
96

Cm +

Pu + g

(4) Berkelium and californium:

241
4
243
1
95 Am + 2 He 97 Bk + 20 n
242
96

246
96

Solution

Pu + g

americium
239
94

(i)

-b
Np
239
94 Pu

235
92

U +10 n 236
92 U

140
56
144
54
144
55

Ba +
Xe +
Cs +

93
36
90
38
90
37

Kr + 3 10 n
Sr + 2 10 n
Rb + 2 10 n (11.4)

A loss in mass occurs releasing a vast quantity

of energy (2 1010 kJ/mol of 235 U): this is about
two million times that than obtained by burning
an equal weight of coal. With a small lump of
235
U, most of the neutrons released during fission
escape but if the mass of 235U exceeds a few
235
kilograms (critical mass of 92 U is 1 to 100 kg),
neutrons emitted during fission (on an average
2.5 neutrons per 235U nucleus) are absorbed by
nuclei causing further fission and so producing
more neutrons. The energy released can be
estimated by using the Einsteins equation:
E = mc2
(11.5)

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NUCLEAR CHEMISTRY
235
In the fission of 92 U by
slow neutrons, the mass of
reacting particles is equal to
the sum of the isotopic mass
235
of 92 U , i.e., 235.118 mu, and
the mass of one neutron, i.e.,
1.009 mu making up a total
of 236.127 mu. We have seen
that uranium nucleus splits
in different ways; in one of
such fission products, the
sum of the isotopic masses
with two neutrons is 94.936
95

139

(for 42 Mo ) + 138.95 (for 57 La )

First stage:
1 fission
+ 2 1.009 (for two neutrons)
= 235.904m u. Hence, the
Fig. 11.6 Schematic
mass converted into energy
is
= (236.127 235.904) mu
= 0.223 mu
Since 1 mu = 931.48 MeV, for one 235U fission,
(c)
the energy released = 0.223 931.48~ 208 MeV,
which corresponds to about 8.4 107 kJ of
235
energy per gram of 92 U .
The key to the liberation of energy in the
nuclear fission reaction is the production of two
or more neutrons per reaction initiated by one
neutron. Since each of these neutrons can
initiate a further nuclear reaction, a branching
chain reaction is possible and if this takes place

Second stage:
2 fissions

Third stage:
4 fissions

view of the start of a fission chain reaction.

to slow down the neutrons so that they are

captured and become effective to bring about
fission reaction, and
control rods made of boron steel or cadmium,
which are capable of absorbing neutrons and
are used to ensure that the neutron flux is
under control. The control rods are inserted
into the reactor and can be raised or lowered
to control the chain reaction.
The large amount of energy released from the
fission is used for steam generation through heat
exchangers to produce electricity. Twelve such
nuclear power plants have been set up in our

235

in a quantity of 92 U larger than a certain critical

amount (so that only a few neutrons escape), a
violent explosion with enormous liberation of
energy ensues. This is the principle underlying
the fission type of nuclear or atom bomb.
Schematic view of fission chain reaction is
presented in Fig.11.6.
11.5.1 Nuclear Reactors
If the nuclear fission reaction is made to occur
at a controlled rate, the energy released can be
harnessed for peaceful rather than destructive
purposes. The equipment employed to carry out
controlled fission reactions is called a nuclear
reactor (Fig. 11.7). A nuclear reactor consists of
three components:
235
(a) a fissile material (uranium enriched in 92 U ,
say, 2-3%),
(b) a moderator (graphite or heavy water, D2O)

Fig. 11.7

A Schematic diagram of one type of

nuclear reactor. This one is pressurized
water reactor, in which coolant is water
under pressure.

228
CHEMISTRY

country at different places and more such plants

are likely to come up the in near future.
11.5.2 Breeder Reactors
Natural uranium contains very little (0.72%) of
its fissionable isotope 235U and needs to be
enriched in the latter to be useful as a fuel in
nuclear reactor. A breeder reactor is one that
produces more fissionable nuclei than it
consumes. For example, when naturally more
238
abundant isotope of uranium, 92 U is
bombarded with fast neutrons, the following
nuclear transmutation occurs:
238
92

-b
-b
U + 10 n 239
239
239
92 U
93 Np
94 Pu

Here, the breeder reactor produces fissile

239
94

Pu from non-fissile uranium. Similarly,

naturally more abundant isotope of thorium,
232
90

Th , can be used to produce a fissible or

fissionable isotope of uranium,

232
90

1
0

Th + n

233
90

Th

233
91

233
92

U . Thus,
- -

Pa

233
92

In all reactors, heat from the core is extracted

by heat exchangers and is used to convert water
into steam, this is then used to drive turboalternators for producing electricity. In breeder
reactors, an alloy of sodium and potassium is
used as coolant. The liquid metal gives its heat
to water in a heat-exchanger.
11.6

NUCLEAR FUSION

Just as the fission of heavy nuclei is

accompanied by mass losses resulting into the
liberation of large amounts of energy, the fusion
of light nuclei is also accompanied by mass
losses and the evolution of large quantities of
energy. For example, the formation of helium
from hydrogen, deuterium ( 21H), or tritium (31H)
is, in principle, also capable of generating
immense amount of energy. Some such reactions
and energy release in each process are shown
below,
Fusion reaction
Mass loss
Energy
released
(kJ mol 1)
2
1

H + 12H 24 He

2
1

H + 13 H 24 He + 10 n 0.018

4 11H 24 He + 2 +

0.026

0.029

2.3 109

1.79 109
2.6 109

Compared with fission reactions, fusion

reactions have the advantage that large amounts
of highly radioactive nuclides are not obtained
as by-products which may pose problem of safe
storage. However, the activation energies for
fusion reactions are very high, i.e., they require
very high temperature (> 106 K) to overcome
electrostatic repulsion between the nuclei. For
this reason, fusion reactions are referred to as
thermonuclear reactions. Till date, it has been
possible to produce a fusion reaction only if a
fission bomb is used to generate the high
temperature. This is the principle underlying the
hydrogen or thermonuclear bomb. A fusion
explosion is triggered by an atomic bomb which
generates the high temperature needed for the
fusion reaction.
Fusion reactions are believed to take place in
the sun and stars at temperatures above 107 K,
and the following processes have been suggested
as the chief source of suns energy:
1
1

H + 11H 12H + b + + neutrino

1
1

H + 12H 32 He + g

3
2

He + 32 He 24 He + 211 H
or in sum,
4 11H 24 He + 2 + + 2 neutrino
Intensive research is now under way to
produce controlled fusion reactions by lasers in
a plasma (an ionized gas at high temperature)
but so far no success has been reported in this
regard.

Example 11.9
Calculate the energy released per atom of
helium in the following:
2
1

H + 13 H 24 He + 10 n
(Given the masses : 2H = 2.014; 3H = 3.016;
He = 4.003 ; n = 1.009 mu)
Solution
Mass on the reactant side
= 2.014 + 3.016 = 5.030 mu
Mass on the product side
= 4.003 + 1.009 = 5.012 mu
Mass loss = 5.030 5.012 = 0.018 mu
Energy released per atom of helium
= (0.018 931) MeV = 16.76 MeV

229
NUCLEAR CHEMISTRY

Nuclear Waste Disposal A Big Problem

The used up uranium fuel rods from nuclear
power plants, are among the deadliest
substances known to man. Nuclear power
plants use the nuclear energy produced in
nuclear fission to heat water which turns
turbines that generate electricity. Each rod is
14-18 feet metal tube filled with uranium
pellets.
While a rod powers the plants for 18 months,
it is dangerous for 10,000 years. It can eat flesh
and cause cancer and birth defects. Nuclear
power plants have been storing old fuel rods
in big swimming pools like concrete tanks.
However this practice cannot continue, say the
people who run the power plants. In years to
come, the power plants may be running out of
space to store it. And as it piles up, there is a
greater chance the hot water could leak
through the ground and to the water under the
earths surface.On a smaller scale, nuclear
waste is disposed off by dumping it in thick
lead (Pb) containers which are buried in the
earth by drilling holes. However, the disposal
of nuclear waste is a big problem before the
countries which depend on nuclear power
plants for their electricity resources in a big
way. There are over four hundred power plants
globally which generate about 17 percent of
worlds electricity. In USA alone there are 131
power plants which generate 20 percent of the
countrys electricity; there by producing 2000
tonne of nuclear waste each year. Its disposal
is indeed a big problem.
11.7 APPLICATIONS OF RADIOACTIVITY
AND RADIOISOTOPES
Radioisotopes find numerous uses in different
areas such as medicine, chemistry, biology,
archeology, agriculture, industry, and
engineering. In this section, we shall present
some important applications of radioisotopes.
11.7.1

Tracers

By incorporating a small amount of a

radioisotope in a reaction system, one can trace
the course of the reaction. Such a sample of
radioisotope is called tracer. Since all the isotopes
of an element are chemically equivalent, the
monitored path of the isotope will indicate the
path of the reaction. For example, consider the

problem of determining the course of an

esterification such as:
O
C6 H5 C

* H C H C
+ CH3 O
6 5

OH

O
*
OCH
3

+ H2 O

Does the starred oxygen come from alcohol or

from the acid? By labelling the oxygen atom of
methanol with 18O and then using it in the
esterification, it can be proved that the starred
oxygen comes from the alcohol and not from the
acid as the ester is found enriched with 18O
isotope. Many other mechanistic applications
have been reported. The use of 14 C as a
radioactive tracer using labelled compounds is
well known. The dynamic nature of chemical
equilibria has been established by the use of
labelled compounds.
11.7.2

Activation Analysis

The absorption of neutron by any nucleus

produces an activated or energy rich species
that decays by a process characteristic of the
nucleus involved. The various isotopes of
elements differ considerably in their ability to
absorb neutron. By irradiating a mixture of
nuclei with neutrons to saturation limit, it is
possible to selectively activate certain elements,
detect their presence and measure their
concentration by measuring the intensity of the
induced radioactivity. The sensitivity of the
neutron activation analysis depends on the
neutron flux available for irradiation, the
availability of nucleus to absorb a neutron and
the energy of the decay process. This method is
very useful for determination of elements present
in trace quantities. For example, it is possible
to detect as little as 1040g of copper or tungsten
by activation analysis.
11.7.3

Age of Minerals and Rocks

The determination of age of minerals and rocks

is an important part of geological studies. This
may involve determination of either a species
formed during a radioactive decay or of the
residual activity of an isotope which is
undergoing decay.
The former may be illustrated by helium
dating. Helium present in uranium mineral has
almost certainly been formed from -particles. A
gram of uranium in equilibrium with its decay

230
CHEMISTRY

products produces approximately 107g of helium

per year. So if the helium and uranium contents
of a mineral are known, the age of the mineral
can be estimated. The latter can be typified by
238

considering a rock containing 92 U which has a

half-life of 4.5 109 years. We have seen that in
238
92

U after a series of
206
decay gives the stable isotope 82 Pb as the end
the uranium decay series,

product. Assuming that initially the rock did not

contain any lead, we can determine the age of
the rock by measuring the ratio of

238
92

U and

206
82

Pb and using the equation,

Nt = No ekt
where No and Nt are the amounts of uranium
present initially (t = 0) and after the lapse of
time t, respectively and k is the decay constant.
Suppose, the molar ratio of uranium and lead
is 1:1, it means half of the uranium originally
present has undergone decay, finally giving the
lead isotope. The age of the rock in that case will
be equal to the half-life period of 92 U (i.e., 4.5
109 years). Most of the rocks contain lead/
uranium ratio much less than unity indicating
that the age of rocks may be less than the half-

proportion of 14C as it occurs in the atmosphere.

Once the plant or animal dies, the uptake of
carbon dioxide by it ceases and the level of 14C
in the dead begins to fall due to the decay which
14
C undergoes.
C 14
7 N +
The half-life (t1/2) period of 14C is 5770 years.
A comparison of the - activity of the dead
matter with that of the carbon still in circulation
enables measurement of the period of isolation
of the material from the living cycle. The method,
however, ceases to be accurate over periods
longer than two or three half-life periods of
14
C. The proportion of 14C to 12C in living matter
is 1:1012.
14
6

Example 11.10
The beta activity of 1g of carbon made from
green wood is 15.3 counts per minute. If
the activity of 1g of carbon derived from
the wood of an Egyptian mummy case is
9.4 counts per minute under the same
conditions, how old is the wood of the
mummy case? (t1/2 for 14C = 5770 years).

238

life period of
11.7.4

238
92

U.

Radiocarbon Dating
14

Radiocarbon ( 6 C ) dating of historical woodenderived objects is based on the knowledge that

the cosmic ray intensity (responsible for 14C
production) has been practically constant for
thousands of years. 14C is formed in the upper
atmosphere by the action of cosmic radiation on
14
N,
14
7
14

1
N + 10 n 14
6 C + 1H

The C so produced is eventually converted

into carbon dioxide, which in tur n is
incorporated into plants and trees by the process
of photosynthesis and then finds way into
animals which eat plants. Because of the natural
plant-animal cycle, an equilibrium is set up and
all living matter contains the same small

Solution
k = 0.693 / t 1/2 = 0.693 / 5770
= 1.20 104 year1
log No/ Nt = kt / 2.303
1.20 104 t / 2.303 = log N0 / Nt
= log 15.3/9.4
Hence t = 2.303 / 1.20 104 log 15.3 / 9.4
= 3920 years
11.7.5

Uses in Medicines and other Areas

A number of radioisotopes are used in medicine

either for diagnosis or treatment. For example,
32
15

P is used for relief in leukemia,

131
53

I is used in
60

the treatment of goiter and cancer and 27 Co is

used in the treatment of tumours and cancers.
The use of radium in the treatment of cancer is
well known. Among the industrial applications
of radioisotopes are the measurement of bulk
flow, mixing efficiency and leak measurements.

231
NUCLEAR CHEMISTRY

SUMMARY
Some naturally occurring elements are found to emit radiation. These elements are said
to be radioactive and the phenomenon is known as radioactivity. Three types of radiations
are emitted from radioactive elements. These are called alpha, beta, and gamma rays. The
alpha () rays are helium nuclei, beta ( ) rays are electrons of nuclear origin and gamma
() rays are electromagnetic radiation. An alpha emission reduces the atomic number by 2
and the mass number by 4, and a emission advances the atomic number by one unit
without changing the mass number. The emission of -rays affects neither the mass nor
the atomic number.
There are three natural decay series in which heavy nuclei decay by a series of -and/
or - emissions finally resulting in the formation of stable isotopes of lead. The three
series start with 232 Th, 238U, and 235U and end in 208Pb, 206Pb, and 207Pb, respectively.
The fourth is artificial series starting with 237Np and ending in 209Bi. The four decay series
are distinguished by whether the mass numbers are exactly divisible by 4 or whether,
when divided by four, there are remainders of 1, 2, or 3. For a particular radioactive decay
process, the number of nuclei decaying in a short period of time is proportional to the
number present and is independent of physical and chemical conditions surrounding the
atom. These decay processes follow the first order kinetics. The time taken to reduce the
number of nuclei to one-half of the original is referred to the half-life period of a nuclide.
The half-life of an unstable isotope is one of its fixed characteristic properties.
Nuclear changes can also be brought about by bombardment of nuclei with accelerated
particles like neutrons, deuterons, and protons. There is no essential difference between
natural radioactivity and the nuclear changes resulting from such bombardment. All
these changes involve the conservation of atomic number and mass number. A particularly
important process for the production of artificial radioactive isotope is the (n, ) reaction
which is applied to synthesise new elements. Many of the heavy nuclei can be induced to
break up into two fragments of intermediate size and a few neutrons; the process is called
nuclear fission. In a fission reaction, a loss in mass occurs releasing a vast amount of
energy. For the controlled production of energy by nuclear fission, different types of reactors
are employed and thus the energy can be put to peaceful uses.
Just as the fission of heavy nuclei is accompanied by large energy release, the fusion of
light nuclei is accompanied by mass losses and hence the evolution of large quantities of
energy. However, extremely high temperatures are required to initiate fusion reactions.
That is why the fusion reactions are also known as thermonuclear reactions.
Radioisotopes find a number of applications in different areas. Some of the important
ones include their uses as tracers, analytical applications, dating applications and
applications in the field of medicines.

EXERCISES
11.1 Clearly state, what do you understand by the terms: mass number, nucleons and
nuclides.
11.2 Describe the properties of radiations which are emitted by radioactive nuclei.
11.3 Give one example each of (i) -emission (ii) - emission and (iii) K-capture. Write
the equation for these nuclear changes.
11.4 What is the Group Displacement Law? An element belonging to Group 1decays
by - emission. To which group of the Periodic table the daughter element will
belong?
11.5 How many - and - particles will be emitted when 232
90 Th changes into

208
82 Pb ?

232
CHEMISTRY

11.6 Write the nuclear reactions for the following radioactive decay:

11.7
11.8
11.9

11.10

11.11

(a)

238
92

U undergoes -decay

(b)

234
91

Pa undergoes - decay

22
(c) 11
Na undergoes + - decay.
How are the radioactive decay series distinguished? Which one of the decay series
is not natural but artificial?
What kinds of elementary particles are employed for the artificial transmutation
of elements? Comment on their effectiveness.
What is meant by nuclear binding energy? Calculate the binding energy per
nucleon of Li isotope, which has the isotopic mass of 7.016 mu. The individual
masses of neutron and proton are 1.008665 mu and 1.007277mu, respectively
and the mass of electron = 0.000548 mu.
The atomic mass of 16O is 15.995 mu while the individual masses of proton and
neutron are 1.0073 and 1.0087mu. The mass of electron = 0.000548 mu. Calculate
the binding energy of the oxygen nucleus in Joules.
The isotopic composition of rubidium is 85Rb - 72 percent and 87Rb - 28 percent.
87Rb is weakly radioactive and decay by - emission with a decay constant of
1.1 10-11 per year. A sample of the mineral pollucite was found to contain 450
mg Rb and 0.72 mg of 87Sr. Estimate the age of mineral pollucite, stating any
assumption made.

11.12 The isotopic masses of

2
1

H and 24 He are 2.0141 and 4.0026 mu respectively and

the velocity of light in vacuum is 2.998 108 ms1. Calculate the quantity of energy
(in J) liberated when two moles of 12 H undergo fusion to form one mole of
11.13 The radioactive isotope

60
27

4
2

He .

Co which has now replaced radium in the treatment of

cancer can be made by a (n, p) or (n, ) reaction. For each reaction, indicate the
appropriate target nucleus. If the half-life of

60
27

Co is 7 years, evaluate the decay

constant in s-1.
11.14 A piece of wood from an archeological source shows a 14 C activity which is 60%
of the activity found in fresh wood today. Calculate the age of the archeological
sample. (t1/2 14C = 5770 years)
11.15 What is a nuclear fission reaction? Explain the principle of atomic bomb and
working of a nuclear reactor to produce electricity.
11.16 What is meant by fissionable or a fissile isotope? How are such isotopes produced
artificially? Give an example.
11.17 In the neutron-induced fission reaction of

235
92

U , one of the products is

95
37

Rb , in

this mode, another nuclide and three neutrons are also produced. Identify the
other nuclide.
11.18 Explain the principle of:
(a) Activation analysis
(b) Breeder reactor.
11.19 Describe the chief applications of radioisotopes in:
(a) The study of reaction mechanism
(b) Medicines.
11.20 Complete the following nuclear reactions:
(a)
(c)

96
42

Mo (....., n)

55
25

97
43

Tc

Mn (n, )

(b) .. (, 2n)
(d)

246
96

Cm +

12
6

211
85

At

C .......... + 4 10 n

) ..
(f) 238
Al (,n) .
92 U (,
11.21 Complete the equations for the following nuclear processes:

(e)

27
13

(a)

35
17 Cl

+ 10 n .......... + 24 He

233
NUCLEAR CHEMISTRY

(b)

235
92 U

(c)

27
13

+ 10 n .......... +

1
2 0n

Al + 24 He .......... + 10 n

(d) .......... (n, p)

(e)

137
54 Xe

239
94

35
16

Pu (a, - ) ..........

11.22 Calculate the mass of 140La in a sample whose activity is 3.7 1010 Bq (1 Becquerel,
Bq = 1 disintegration per second) given that its t 1/2 is 40 hours.
[Hint: Mass = 3.7 1010 40 60 60 140/(NA + ln2)].
11.23 Calculate the binding energy per nucleon for 12C, 14N, 16O, and comment on their
relative magnitudes. Masses of proton and neutron are 1.0078 and 1.0087mu
respectively. (1mu = 931 MeV)
11.24 The activity of a sample of CO2 prepared from a contemporary wood gave a
count rate of 25.5 counts per minute (c.p.m). The same mass of CO2 from an
ancient wooden statue gave a count rate of 20.5 c.p.m in the same counter
condition. Calculate its age to the nearest 50 years taking t1/2 for 14C as 5770
years. What would be the expected count rate of an identical mass of CO2 from a
sample which is 4000 years old?
11.25 How is 14C produced in nature and what happens to it subsequently? Give
equations for these processes.
11.26 What do you understand by tracers? Give an example of a tracer that can be used
in determining the mechanism of a chemical reaction.
11.27 What are synthetic elements? Mention two synthetic elements and write the
nuclear equations leading to their synthesis.
11.28 What is meant by thermonuclear reactions and why are they so called? Why are
these reactions not useful for peaceful purposes?
11.29 Describe the principle of an atom bomb. What is meant by a critical mass? What
is the critical mass of

235
92

U?