Nuclear Chemistry

Chapter Goals
1.
2.
3.
4.
5.
6.
7.
8.
9.

The Nucleus
Neutron-Proton Ratio and Nuclear Stability
Nuclear Stability and Binding Energy
Radioactive Decay
Equations for Nuclear Reactions
Neutron-Rich Nuclei (Above the Band of
Stability)
Neutron-Poor Nuclei (Below the Band of
Stability)
Nuclei with Atomic Number Greater than 83
Detection of Radiation
2

Chapter Goals
10.
11.
12.
13.
14.
15.
16.

Rates of Decay and Half-Life

Disintegration Series
Uses of Radionuclides
Artificial Transmutations of Elements
Nuclear Fission
Nuclear Fission Reactors
Nuclear Fusion
3

Comparison of Chemical and

Nuclear Reactions

Nuclear Reactions
Elements may be
converted from one
element to another.
Particles within the
nucleus, such as
protons and neutrons,
are involved in
reactions.

Chemical Reactions
No new elements can
be produced, only new
chemical compounds.
Usually only the outer
most electrons
participate in reactions.

Comparison of Chemical and

Nuclear Reactions

Nuclear Reactions
Release or absorb
immense amounts of
energy, typically
1000 times more.
Rates of reaction are
not influenced by
external factors.

Chemical Reactions
Release or absorb
much smaller amounts
of energy.
Rates of reaction
depend on factors such
as concentration,
pressure, temperature,
and catalysts.
5

Beginning of Nuclear Science

In 1896, Henri Becqurel accidentally

discovered radioactivity in U salts.
In 1898, Marie and Pierre Curie
discovered two new radioactive elements
in U mine residue.

Po and Ra

In 1898, Ernest Rutherford discovered

that radioactivity has two distinct forms.

and radiation

Fundamental Particles of Matter

The Nucleus

The nucleus consists of protons and neutrons in a

very small volume.
Protons and neutrons are made of other
fundamental particles called quarks.
Nuclei have a diameter of approximately 10-12 cm
Nuclei have a density of approximately 2 x 1014 g/
cm3.
The strong nuclear force binds the nucleus
together at extremely short distances of 10-13 cm
8

Neutron-Proton Ratio and Nuclear

Stability

1.
2.

Terminology used in nuclear chemistry.

Nuclides denotes different nuclei.
Isotopes are nuclei that have the same number of
protons but different neutron numbers.
Isotopes are the same element.
Experimentally, it can be shown that nuclei have
a preference for even numbers of protons and
neutrons

The next table is all of the nonradioactive nuclides

broken into various combinations of protons and
9
neutrons.

Neutron-Proton Ratio and

Nuclear Stability

10

Neutron-Proton Ratio and

Nuclear Stability

Special stability is associated with

certain proton and neutron numbers

due to shell effects in nuclei similar to the

s, p, d, and f shells in atoms

These proton and neutron numbers

are called Magic Numbers.
Magic numbers are:
2 8 20 28 50 82 126
11

Neutron-Proton Ratio and

Nuclear Stability

Example nuclides with magic numbers of

nucleons includes:

12

Neutron-Proton Ratio and

Nuclear Stability

Example nuclides with magic numbers of

nucleons includes:

13

Nuclear Stability and Binding

Energy

The mass deficiency or mass defect of a

nucleus is determined in this fashion.

m = (sum of masses of all p+ , n and e - ) (actual mass of atom)

The mass defect is the mass of the nuclear

particles that has been used to bind the
nucleus in the nuclear binding energy or
strong nuclear force.

14

Nuclear Stability and Binding

Energy

Due to the Einstein relationship, we can

calculate the nuclear binding energy for a
nucleus.

E = mc

E = ( m)c

or
Binding Energy = ( m)c

2
15

Nuclear Stability and Binding

Energy

Calculate the mass deficiency for 39K.

The actual mass of 39K is 39.32197
amu per atom.

16

Nuclear Stability and Binding

Energy

Calculate the mass deficiency for 39K. The

actual mass of 39K is 39.32197 amu per
atom.

17

Nuclear Stability and Binding

Energy

Calculate the nuclear binding energy

of 39K in J/mol of K atoms. 1 J = 1 kg
m2/s2.

m = (0.00110

amu

23 atoms
6.022

10
atom )(
mol)

= (6.624 10 20 amu mol)(1.661 10 24 g amu )

18

Nuclear Stability and Binding

Energy

Calculate the nuclear binding energy

of 39K in J/mol of K atoms. 1 J = 1 kg
m2/s2.

m = (0.00110

amu

atom

)(6.022 10

23 atoms

)
)

mol

= (6.624 10 20 amu mol)(1.661 10 24 g amu

= 0.00110

6 kg
=
1.10

10
mol
mol

19

Nuclear Stability and Binding

Energy

Calculate the nuclear binding energy

of 39K in J/mol of K atoms. 1 J = 1 kg
m2/s2.
E = mc = (1.10 10

)(3.00 10 )
)(9.00 10 )

= (1.10 10

6 kg

mol

10 kg m 2

= 9.90 10

6 kg

8m

mol

16 m 2

s2

10 J
=
9.90
10
mol
mol
20

Radioactive Decay

Nuclei whose neutron-to-proton ratio lies

outside the belt of stability experience
spontaneous radioactive decay.

Decay type depends on where the nuclei is
positioned relative to the band of stability.

Radioactive particles are emitted with
different kinetic energies.

Energy change is related to the change in

binding energy from reactant to products.
21

Radioactive Decay

22

Equations for Nuclear Reactions

Two conservation principles hold for

nuclear reaction equations.

The following principles hold for all nuclear
reactions.

1.

2.

The sum of the mass numbers of the reactants

equals the sum of the mass numbers of the
products.

The sum of the atomic numbers of the reactants
equals the sum of the atomic numbers of the
products.

23

Equations for Nuclear Reactions

1.

For the general reaction:

The two conservation principles demand

M1


=

M2 + M3

and

3.

Z1

Z2 + Z3

Where the M's are mass numbers,

And the Z's are atomic numbers.

24

Neutron Rich Nuclei (Above the

Band of Stability)

These nuclei have too high a ratio of

neutrons to protons.

Decays must lower this ratio and include:

beta emission

neutron emission

Beta emission is associated with the

conversion of a neutron to a proton;

1
0

1
1

0
1

n p +
25

Neutron Rich Nuclei (Above the

Band of Stability)

Beta emission simultaneously decreases the

number of neutrons (by one) and increases the
number of protons (by one).

Efficiently changes the neutron to proton ratio.

Examples of beta emission:

14
6

14
7

0
-1

C N +

226
88

Ra

226
89

0
-1

Ac +
26

Neutron Rich Nuclei (Above the

Band of Stability)

Neutron emission does not change the atomic

number, but it decreases the number of neutrons.

The product isotope is less massive by the mass of 1

neutron.

Examples of neutron emission

17
7

16
7

1
0

N N + n

137
53

136
53

1
0

I+ n
27

Neutron Poor Nuclei (Below the

Band of Stability)

These nuclides have too low a ratio of

neutrons to protons.

Nuclear radioactive decays must raise this
ratio

The possible decays include:

1.
2.

electron capture

positron emission

28

Neutron Poor Nuclei (Below the

Band of Stability)

29

Neutron Poor Nuclei (Below the

Band of Stability)

Electron capture involves the capture of an

electron in the lowest energy level in the atom by
the nucleus.

conversion of a proton to a neutron

30

Neutron Poor Nuclei (Below the

Band of Stability)

A positron has the mass of an electron but has a

positive charge.

The symbol is 0+1e.

Positron emission is associated with the

conversion of a proton into a neutron.

1
1

0
+1

1
0

p e + n

39
19
15
8

0
+1

39
18

0
+1

15
7

K e + Ar

O e + N
31

Nuclei with Atomic Number

Greater than 83

Alpha emission occurs for some nuclides,

especially heavier ones.

Alpha () particles are helium nuclei,
4 He, containing two protons and two
2
neutrons.

Alpha emission increases the neutron-toproton ratio.

32

Nuclei with Atomic Number

Greater than 83

All nuclides having atomic numbers

greater than 83 are beyond the belt of
stability and are radioactive.

Many of these isotopes decay by emitting

alpha particles.

33

Nuclei with Atomic Number

Greater than 83

The transuranium elements (Z>92) also

decay by nuclear fission in which the
heavy nuclide splits into nuclides of
intermediate mass and neutrons.

34

Detection of Radiation

1.

Present radiation detection schemes

depend on the fact that particles and
radiations emitted by radioactive decay
are energetic and some carry charges.

Photographic Detection

Radioactivity affects photographic plates or

film as does ordinary light.

Medical and dental x-ray photographs are
made using this technique.

35

Detection of Radiation

2.

Fluorescence Detection

Fluorescent substances absorb energy from

high energy rays and then emit visible light.

A scintillation counter is an instrument
using this principle.

36

Detection of Radiation

3.

Cloud Chambers contain air saturated

with a vapor.

Radioactive decay particles emitted ionize

the air molecules in the chamber.

The vapor condenses on these ions.

Then the ion tracks are photographed.

37

Detection of Radiation

Diagram of a Simple Cloud Chamber

38

Detection of Radiation

A Cloud Chamber Photo from a Large Detector.

39

Detection of Radiation

4.

Gas Ionization Counters

The ions produced by ionizing radiation are

passed between high voltage electrodes
causing a current to flow between the
electrodes and the current is amplified.

This is the basis of operation of gas
ionization counters such as the GeigerMueller counter.

40

Detection of Radiation

Schematic of Geiger Counter

41

Detection of Radiation

Picture of a Geiger Counter

42

Rates of Decay and Half-Life

The rates of all radioactive decays are

independent of temperature and obey first
order kinetics.

The same relationships developed in
Chapter 16 apply here as well.

Rate of decay = k [ A] or
A0
ln = a k t
A
43

Rates of Decay and Half-Life

For counting radioactive decay the

relationship changes just slightly:

44

Rates of Decay and Half-Life

The half-life, t1/2, is related to the rate

constant by the simple relationship:

ln 2 0.693
t 12 =
=
ak
ak
45

Rates of Decay and Half-Life

How much 60Co remains 15.0 years after it is

initially made? 60Co has a half-life of 5.27
years.

46

Disintegration Series

Some nuclides are so far away from the

belt of stability, that it takes many nuclear
disintegrations (a series of them) to attain
nuclear stability.

Table 26-4 in the textbook outlines in
detail three of these disintegration series:

The 238U, 235U and 232Th series:

47

Disintegration Series

48

Uses of Radionuclides

Radioactive Dating

Radiocarbon dating can be used to
estimate the ages of items of organic
origin.

14C is produced continuously in the upper
atmosphere by the bombardment of 14N by
cosmic-ray neutrons:

49

Uses of Radionuclides

14C

atoms react with O2 to form CO2

The CO2 then is incorporated into plant life

by photosynthesis.

After the organism dies the 14C content

decreases via radioactive decay

The 14C half-life is 5730 years.

50

Uses of Radionuclides

The potassium-argon and uranium-lead

methods are used for dating older objects.

Potassium-argon method relies on the
electron capture decay of 40K to 40Ar

51

Uses of Radionuclides

The uranium-lead method relies on the

alpha decay of 238U to 234Th.

52

Uses of Radionuclides

1.

Estimate the age of an object whose 14C

activity is only 55% that of living wood.

Determine the rate constant for 14C.

53

Uses of Radionuclides

2.

Determine the age of the object.

54

Artificial Transmutations of
Elements

Bombardment of a nuclide with a nuclear

particle can make an unstable compound
nucleus that decays to a new nuclide by
emission of a different particle.

The rules for balancing equations for
nuclear reactions which were presented in
the section on radioactivity still hold.

55

Artificial Transmutations 

of Elements

Bombardment with Positive Ions

If the bombarding particle is positively charged,
it must be accelerated with sufficient energy to
overcome the coulomb repulsion of the positive
nucleus

bombarding particles penetrate the nucleus

Particle accelerators such as cyclotrons or linear

accelerators are used for this.

56

Artificial Transmutations 

of Elements

Example

reactions are:

57

Artificial Transmutations 

of Elements

58

Artificial Transmutations 

of Elements

59

Artificial Transmutations 

of Elements

60

Artificial Transmutations 

of Elements

Neutron Bombardment

Because neutrons have no charge, there is
no coulomb repulsion to their nuclear
penetration, so they do not have to be
accelerated.

Nuclear reactors are often used as neutron
sources.

61

Artificial Transmutations 

of Elements

Neutrons with large kinetic energy are

called fast neutrons.

Slow neutrons ("thermal neutrons") have
had their excess energy decreased by
collisions with moderators

Common moderators are hydrogen,

deuterium, or the hydrogen atoms in paraffin.

Slow neutrons are more likely to be captured
by target nuclei.

62

Artificial Transmutations 

of Elements

63

Artificial Transmutations 

of Elements

64

Nuclear Fission

Some nuclides with atomic numbers greater than 80 are

able to undergo fission.

These nuclei split into nuclei of intermediate masses and emit one
or more neutrons.

Some fissions are spontaneous while others require

activation by neutron bombardment.

Enormous amounts of energy are released in these
fissions.

Some of the numerous possible fission paths for 235U (after

bombardment by a neutron) are:

65

Nuclear Fission

Some nuclides with atomic numbers greater than 80 are

able to undergo fission.

These nuclei split into nuclei of intermediate masses and emit one
or more neutrons.

Some fissions are spontaneous while others require

activation by neutron bombardment.

Enormous amounts of energy are released in these
fissions.

Some of the numerous possible fission paths for 235U (after

bombardment by a neutron) are:

66

Nuclear Fission

67

Nuclear Fission

Fission is energetically favorable for

elements with Z greater than 80

The product nuclides are more stable (near

the high part of the nuclear binding energy
curve).

68

Nuclear Fission Reactors

Electricity can be generated from

steam heated by nuclear fission
reactions.
Greatest danger of nuclear reactors is
core meltdown.
There have been two very serious
nuclear reactor accidents:
1.
2.

Three Mile Island in PA.

Chernobyl in the Ukraine.

69

Nuclear Fission Reactors

Description of Nuclear Reactors

Light Water Reactors use normal water as the
coolant and moderator.

Typical Reactor Fuels are:

235UO

239Pu

Moderator is the material that slows neutrons

from fast to thermal.

Commonly used moderators are graphite, water, heavy

water.

70

Nuclear Fission Reactors

Control Rods are usually made of boron which

is an efficient neutron absorber.

Control rods remove neutrons and slow the chain

reaction.

Cooling Systems

The reactor core must be cooled to remove the heat

from the nuclear reactions.

Some possible coolants are:

water - both normal and heavy

helium

liquid sodium

71

Nuclear Fission Reactors

Shielding provides workers and public

with protection from radiation.

Lead and concrete are commonly used in

commercial reactors.

72

Nuclear Fusion

Fusion, the merging of light nuclei to make

heavier nuclei, is favorable for very light
atoms.
Extremely high energies or temperatures
are necessary to initiate fusion reactions.
The energy source for stars is fusion.
The fusion reaction in main sequence
stars is:

73

Nuclear Fusion

Fusion is the most energetic process

in nature.

Fusion has produced all of the chemical

elements beyond H and He up to Fe.
Fusion is a potential energy source for
humans.

Thermonuclear or hydrogen bombs

have been in existence since the
1950s.
74

Nuclear Fusion

Controlled nuclear fusion is a very real

possibility.

Fusion reactors must contain this temperature

and not melt!
Some fusion reactors exist around the world

Nuclear fusion must occur at temperatures of 10

million oC.

However at present none can generate a

sustainable fusion reaction.

Potential energy source for the 21st Century.

75

Synthesis Question

How are thermonuclear or fusion

reactors designed so that the hot
plasma, temperature of approximately
10 x 106 degrees, does not touch the
sides of the reactor? The reactor
would melt if the plasma were to touch
the sides.
76

Synthesis Question

Most fusion reactors use intense

magnetic fields to confine the hot
plasma in the center of the reactor
away from the walls.

77

Group Question

Stars are enormous thermonuclear

fusion reactors generating enormous
amounts of heat and energy. What
keeps stars from blowing themselves
apart? How do they remain stable for
millions and billions of years?

78

End of Chapter 26

Nuclear science has been one of the

driving forces of science in the 20th
Century.

79