Nuclear Chemistry

IITIAN'S HUB
THE
Radioactivity
Scientists have known since 1896 that many
nuclides are radioactive: that is, they
spontaneously emit radiation. Early studies
of radioactive nuclei, by the New Zealand
physicist Ernest Rutherford in 1897 showed
that there are three common types of radiation with markedly
different properties: alpha (), beta () and gamma () radiation
and named after the first three letters of the Greek alphabet.

IITIAN'S HUB
THE
Alpha()Radiation is Helium nucleus, 4
2 He
2
that contain
two protons and two neutrons. Alpha () emission reduces the
mass number by 4 and the atomic number by 2.
U238 Th234 + 4 + 
92 90 2

Electron Capture: Nucleus captures an inner-shell electron and

converts a proton into a neutron. The mass number is unchanged,
but the atomic number drops by 1.
IITIAN'S HUB
THE
Beta () Radiation is an electron. It carries a negative charge,
and negligible mass. Beta emission () occurs when a neutron
decays into a proton. The product has the same mass number,
but the atomic number increases by 1.
14 14 0 + 00
6C 7N + -1

IITIAN'S HUB
THE
Positron Emission: Conversion of a proton to a neutron
plus an ejected positron ( +). The mass number is unchanged,
but the atomic number decreases by 1.
C 11 B 11 +  0 + 0
6 5 +1 0

IITIAN'S HUB
THE
Gamma Radiation() is high-energy electromagnetic
radiation ( = 10–11 to
10–14 m). It has no
charge or mass.

IITIAN'S HUB
THE
Cause of Radioactivity
Why do some nuclei undergo radioactive decay
while others do not? Why, for instance, does a
C-14 nucleus, with six protons and eight neutrons,
spontaneously emit a particle, whereas a C-13
nucleus, with six protons and seven neutrons, is
stable indefinitely?

This is done by an atomic nucleus that, for some reason, is

unstable; it "wants" to give up some energy in order to shift to a
more stable configuration. During the first half of the twentieth
century, much of modern physics was devoted to exploring why
this happens, with the result that nuclear decay was fairly well
understood by 1960.
Till now we have many theories, which can explain phenomenon
of radioactivity.
IITIAN'S HUB
THE
Improper n/p Ratio
Inside the nucleus, protons are repelling each other but different
nucleons are attracting due to nuclear force. But if nucleus consist
improper n/p ratio, there imbalance in forces & it become unstable

The band of stability

Indicates n & p
Combinations giving
rise to observable
nuclei with measured
half-lives. The island of
stability corresponds
to predicted super
heavy nuclei first
observed in 1999.

IITIAN'S HUB
THE
Improper n/p Ratio
Too many neutrons in a nucleus lead it to emit a negative beta
particle, which changes one of the neutrons into a proton. Too
many protons in a nucleus lead it to emit a positron (positively
charged electron), changing a proton into a neutron. Too much
energy leads a nucleus to emit a gamma ray, which discards
great energy without changing any of the particles in the
nucleus. Too much mass leads a nucleus to emit an alpha
particle, discarding four heavy particles (two protons and two
neutrons).

IITIAN'S HUB
THE
• Nuclei with higher
neutron/proton ratios tend
to emit beta particles.

• Nuclei with lower

neutron/proton ratios tend
to favor positron emission,
electron capture, or alpha
emission.

IITIAN'S HUB
THE
Binding Energy
At the nuclear level, binding energy is also equivalent to the
energy liberated when a nucleus is created from other nucleons
or nuclei.
This nuclear binding energy (binding energy of nucleons into a
nuclide) is derived from the strong nuclear force and is the
energy required to disassemble a nucleus into the same number
of free unbound neutrons and protons it is composed of, so that
the nucleons are far/distant enough from each other so that the
strong nuclear force can no longer cause the particles to interact
The difference between the unbound system calculated mass and
experimentally measured mass of nucleus is called mass defect.
It is denoted by Δm. It can be calculated as follows:
Mass defect =
(unbound system calculated mass) - (measured mass of nucleus)

IITIAN'S HUB
THE
 IITIAN'S HUB
THE
Nuclear Shell Model
It is found that nuclei with even numbers of protons and neutrons
are more stable than those with odd numbers. In particular, there
are "magic numbers" of neutrons and protons which seem to be
particularly favored in terms of nuclear stability:
2,8,20,28,50,82,126
Out of the 264 nonradioactive
isotopes, 207 have an even number
of neutrons in their nuclei. Most
nonradioactive isotopes (156) have
even numbers of both protons and
neutrons, 51 have an even number
of neutrons but an odd number
of protons, and only 4 have an odd
number of both protons and
neutrons
IITIAN'S HUB
THE
Nuclei which have both neutron number and proton number
equal to one of the magic numbers can be called "doubly magic",
and are found to be particularly stable.

Calcium provides a good example of the

exceptional stability of "doubly magic" nuclei
since it has two of them. The existence of
several stable isotopes of calcium may have to
with the fact that Z=20, a magic number. The
two highlighted isotopes have neutron
numbers 20 and 28, also magic numbers.
Magic numbers for nuclei are analogous to noble-gas electron
configurations for atoms. A nucleus with 2, 8, 20, 28, 50, 82,
or 126 protons or neutrons is particularly stable, just as an atom
having a noble-gas electron configuration with 2, 10, 18, 36, 54,
or 86 electrons tends to be stable.
IITIAN'S HUB
THE
The existence of these magic numbers suggests closed shell
configurations, like the shells in atomic structure. They represent
one line of reasoning which led to the development of a shell model
of the nucleus.

IITIAN'S HUB
THE
Radioactivity Series
Natural isotopes, of which there are about forty, end up
transforming themselves into other isotopes until they become a
stable isotope of lead. All transmutations occur because of alpha
and beta emissions.
It must be noted that in natural
radioactive series, the changes in mass
numbers are produced by the emission of
 particles only because emission of 
particles do not bring about any change in
mass number.

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.
IITIAN'S HUB
THE
4n series (Thorium series)
The 4n chain of Th-232 is commonly
called the “Thorium series."
Beginning with naturally occurring
thorium-232, this series includes the
following elements: Actinium,
bismuth, lead, polonium, radium, and
radon.

IITIAN'S HUB
THE
4n+1 series (Neptunium series)
The 4n + 1 chain of Np-237 is
commonly called the "neptunium
series." In this series, only two of
the elements are found naturally,
bismuth and thallium.

IITIAN'S HUB
THE
4n+2 series (Uranium series)
The 4n+2 chain of U-238 is commonly
called the "radium series" (sometimes
"uranium series"). Beginning with
naturally occurring uranium-238, this
series includes the following elements:
astatine, bismuth, lead, polonium,
protactinium, radium, radon, thallium,
and thorium.

IITIAN'S HUB
THE
4n+3 series (Actinum series)
The 4n+3 chain of U-235 is commonly
called the "actinium series". Beginning
with the naturally-occurring isotope
U-235, this decay series includes the
following elements: Actinium,
astatine, bismuth, francium, lead,
polonium, protactinium, radium,
radon, thallium, and thorium.

IITIAN'S HUB
THE
Kinetics of Radioactivity
Nuclear decay is a first-order process. The kinetics of such a
process obey this equation: dN
  N
dt
Particular radionuclides decay at different rates, each having its
own decay constant (λ). The negative sign indicates that N
decreases with each decay event.
 t 1 N0 2.303 N0
N  N 0e t  ln t log
 N  N
In radioactive decay, this process time constant is also the mean
lifetimefor decaying atoms. Each atom "lives" for a finite amount
of time before it decays, and it may be shown that this mean
lifetime is the arithmetic mean of all the atoms' lifetimes, and that
it is τ, which again is related to the decay constant as follows:
1

 IITIAN'S HUB
THE
Half life ( t ) 1/2

A more commonly used parameter is the half-life. Given a sample

of a particular radionuclide, the half-life is the time taken for half
the radionuclide's atoms to decay. The half life is related to the
decay constant as follows:
2.303 2.303 0.693
t1 2  log 2   0.301 
  

IITIAN'S HUB
THE
Radiation Measurement
Radioactive emissions are invisible. We can’t see, hear,
smell, touch, or taste them, no matter how high the
dose. We can, however, detect radiation by measuring
its ionizing properties.

IITIAN'S HUB
THE
Biological Effects of Radiation
When ionizing radiation passes through tissue it removes an
electron from water to form H2O+ ions. The H2O+ ions react with
another water molecule to produce H3O+ and a highly reactive
•OH radical. Free radicals generally undergo chain reactions,
producing many radicals in the biomolecules.
-rays are particularly harmful because
they penetrate in the same way as X
rays.
-particles interact with the skin and
-particles interact up to 1 cm into
the tissue
-particles are particularly dangerous
when ingested or inhaled.

IITIAN'S HUB
THE
Medical use of radioactivity
The origins of nuclear medicine date to 1901, when the Henri
Danlos first used radium in the treatment of a tuberculous skin
lesion. Uses of radioactivity have become a crucial part of
modern medical care, both diagnostic and therapeutic.
Vivo Procedures : Therapeutic Procedures:
A person’s blood volume Cancerous tumors can be
can be found by injecting treated by irradiation with
a small amount of rays from this cobalt-60 source.
radioactive Chromium-51.

IITIAN'S HUB
THE
Imaging Procedures:
Imaging procedures give diagnostic
information about the health of body organs
by analyzing the distribution pattern of
radioisotopes introduced into the body.

Depending on the disease and the organ, a

diseased organ might concentrate more of
the radiopharmaceutical than a normal
organ and thus show up as a radioactive
“hot” spot against a “cold” background.

The radioisotope most widely used today is

technetium-99m, whose short half-life of
6.01 hours minimizes a patient’s exposure to
harmful effects.
IITIAN'S HUB
THE
Dating with Radioisotopes
Biblical scrolls are found in a cave near the
Dead Sea. Are they authentic? A mummy is
discovered in an Egyptian tomb. How old is it?
The burned bones of a man are dug up near
Lubbock, Texas. How long have humans lived
in the area? These and many other questions
can be answered by archaeologists using a
technique called radiocarbon dating.

(The Dead Sea Scrolls are 1900

years old and authentic, the
mummy is 3100 years old, and the
human remains found in Texas are
9900 years old.)

IITIAN'S HUB
THE
Carbon Dating
Carbon has two stable, nonradioactive isotopes: 12C and 13C. In
addition, there are trace amounts of the unstable isotope 14C on
Earth. The neutrons resulting from the cosmic ray interactions
participate in the following nuclear reaction on the atoms of N2
in the atmospheric air:
1
0 n  147 N 
 146 C  11 p
Plants take up atmospheric carbon dioxide by
photosynthesis, and are ingested by animals,
so every living thing is constantly exchanging
carbon-14 with its environment as long as it
lives. Once it dies, however, this exchange
stops, and the amount of carbon-14 gradually
decreases through radioactive beta decay.
14
 147 N  10  e
C  IITIAN'S HUB
THE
6
By measuring the present 14C /12C ratio in the traces of any once-
living organism, archaeologists can
determine how long ago the organism
died. Human or animal hair from well-
preserved remains, charcoal or wood
fragments from once-living trees, and
cotton from once living plants are all
sources for radiocarbon dating.

IITIAN'S HUB
THE
Rocks Dating
Just as radiocarbon measurements allow dating of once-living
organisms, similar measurements on other radioisotopes make
possible the dating of rocks.

IITIAN'S HUB
THE
Nuclear Reactor
Nuclear Reactors “control” the fission of 235U and use the energy
produced to heat water that drives steam turbines.

IITIAN'S HUB
THE
Nuclear Fission
It is the fragmentation of heavy nuclei to form lighter, more
stable ones.

Nearly 400 different fission pathways have been identified for

U-235, yielding nearly 800 different fission products. One of
the more frequently occurring pathways generates Ba-142 and
Kr-91, along with two additional neutrons plus the one
neutron that initiated the fission:
238 1 91 142 1
U  n 
 Kr  Ba  3 0n IITIAN'S HUB
THE
92 0 36 56
 Neutrons released in the fission of 235U can induce three more
fissions, then nine, and so on leading to a chain reaction.

• If there are not enough radioactive nuclides in the path of the

ejected neutrons, the chain reaction will die out.
• Therefore, there must be a certain minimum amount of
fissionable material present for the chain reaction to be
sustained: Critical Mass.

IITIAN'S HUB
THE
Sub & Supercritical mass

IITIAN'S HUB
THE