RADIOCHEMICAL METHODS

OF ANALYSIS

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 Early Pioneers in Radioactivity

Rutherfo Roentge
rd: n:
Discoverer Alpha Discoverer of X-
and Beta rays rays 1895
1897

The Becquer
Curies: el:
Discoverers of
Discoverer of
Radium and
Radioactivity
Polonium 1900-
1896
1908
All atoms nuclei, except hydrogen, is made up of a collection of
protons and neutrons.
The chemical properties of an atom are determined by its atomic
number, Z, the number of protons.
The sum of neutrons and protons is the mass number, A.
The nuclei of isotopes of an element contain the same number of
protons, but have different numbers of neutrons.
Radioactive isotopes (radionuclide's), undergo spontaneous
disintegration, which ultimately leads to stable isotopes.
Radioactive decay of isotopes occurs with the emission of
electromagnetic radiation in the form of x-rays or gamma ray.
Accompanying this emission is the formation of electrons, positrons
and the helium nucleus.

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Some of the most chemically important types of radiation from
radioactive decay are listed in the table. Four of these types - alpha
particles, beta particles, gamma-ray photons and X-ray photons can
be detected and counted.

Product Symbol Charge Mass Number

Alpha particle  +2 4

Beta particles

Negatron - -1 1/1840 (~0)

Positron + +1 1/1840 (~0)

Gamma ray  0

X-Ray  0 0

Neutron n 0 1

Neutrino v 0 0

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Alpha Decay:
 Alpha decay is a common radioactive process encountered with
heavier isotopes.
 The alpha particle is a helium nucleus having a mass of 4 and a
charge of +2.
• Alpha particles are charged particles so they are deflected by
electric and magnetic radiation.
• These are heavier particles so their mean velocity is less than
other nuclear emissions that have same kinetic energy
• Size of alpha particles prevents them from penetrating them into
substances and they are easily stopped by a few centimeters of
air, or by the skin.
• They have defined energy in narrow range.
• Alpha particles rapidly lose their kinetic energy as they penetrate
into the matter. Owing to the rapid loss, alpha particles are
highly effective in ionizing matter through which they pass. They
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interact with electron and converted into helium atom
α-
Decay…………………..

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 Applications: α-
Decay…………………..
 Researchers are currently trying to use the damaging nature of alpha
emitting radionuclides inside the body by directing small amounts
towards a tumor. The alphas damage the tumor and stop its growth
while their small penetration depth prevents radiation damage of the
surrounding healthy tissue. This type of cancer therapy is called
unsealed source radiotherapy

 Alpha decay can provide a safe power source for radioisotopes, e.g;
thermoelectric generators used for space probes and artificial heart
pacemakers. Alpha decay is much more easily shielded against than
other forms of radioactive decay. Plutonium-238, a source of alpha
particles, requires only 2.5 mm of lead shielding to protect against
unwanted radiation.

 Most smoke detectors contain a small amount of the alpha emitter

americium-241

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Beta Decay:

Beta decay is a radioactive process in which, the atomic number changes but the
mass number stays the same.
Three types of  decay are encountered: negatron formation, positron formation
and electron capture. Example of these three process are:
 negatron formation 14
6 C 14
7 N  
-
 v

 positron formation
65
30 Zn29
65
Cu   
 v

 electron capture 48
24 Cr  0
1 e48
23V  X  rays

Negatrons (-) are electrons that form when one of the neutrons in the nucleus is
converted to a proton.
A positron (+), with the mass of the electrons, forms when the proton in the nucleus is
converted to neutron.

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β-
Decay…………………..

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 β-
Decay…………………..
• Beta particles are deflected by electric and magnetic field.

• Beta particles have the medium penetrating power.

• Bata particles can penetrate about 500 times the distance penetrated
by alpha particles of same energy.

• They can be stopped by 3mm layer of lead.

• Kinetic energy is continuous and have broad spectrum of energy.

• They move with the speed of light.

• Positron when react with matter they are slowed down and eventually
annihilated by reacting with electrons to form two equivalent gamma rays.
This is called back to back emission. Entire mass of gamma rays
is converted into gamma rays. Gamma emission at 0.511 Mev is indicative
of positron emission.
e- + e+ → 2 γ ( gamma rays) 10
Applications of positrons:

 It is used in biological sciences to see the spectacular effects on brain

scanning, this technique is known as positron emission tomography.

Applications of negatron:

 P32 is powerful tool in research of molecular biology and genetics.

 Tritium and C14 is used in labeling of organic compounds.

 S35 is used to label methionene to study proton synthesis.

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Gamma-Ray Emission:

Gamma rays are produced by nuclear relaxations.

Gamma-ray emission is the result of a nucleus in an
excited state returning to the ground state in one or
more quantized steps with the release of monoenergetic
gamma rays.
Generally, the lifetime of the excited states is very small,
of the order of 10-16 to 10 -13 seconds. The γ radiation is
emitted immediately after a preceding α or β decay.
The gamma-ray emission spectrum is characteristic for
each nucleus and is thus useful for identifying
radioisotopes.
Gamma radiation is highly penetrating
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ϒ-
Decay…………………..

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 ϒ-
Decay…………………..
Properties:
• They have no charge so they remain unaffected by electric and
magnetic field.

• Gamma rays usually are emitted along with other particles.

• Gamma rays are the most energetic form of electromagnetic
radiation, with a very short wavelength of less than one-tenth
of a nanometer.

• Gamma particles move with the speed of light.

• They have more penetration power than alpha and beta radiations.

• Gamma radiations from Co60 penetrate into 15cm steel.

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Gamma rays are also used for diagnostic purposes in nuclear
medicine in imaging techniquesIn industry principle use
include casting and weld.

103Ru 103Rh +
44 → 45
β - +γ
131I
53 →
131Xe
54 + β-
+ γ

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 Electron Capture Decay

• An electron from the closest energy level falls into the nucleus,
which causes a proton to become a neutron.

• A neutrino is emitted from the nucleus.

• Another electron falls into the empty energy level and so on

causing a cascade of electrons falling. One free electron, moving
about in space, falls into the outermost empty level, this cascade of
electrons falling creates a characteristic cascade of lines, mostly in
the X-ray portion of the spectrum. This is the fingerprint of electron
capture.

•4) The atomic number goes DOWN by one and mass number remains
unchanged
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Electron Capture Decay…………..

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Electromagnetic spectrum

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The Nuclear Stability Belt
Kinds of Radioactivity

The three main decays are

Alpha, Beta and Gamma
The blue grid below represents a quantity of C14. Each time you click,
one half-life goes by and turns red. Half % C14 %N14 Ratio of
C – blue
14 14
N - red lives
14
C to N 14

0 100% 0% no ratio

As we begin notice that no

time has gone by and that
100% of the material is C14
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The grid below represents a quantity of C14. Each time you click,
one half-life goes by and you see red. Half % C14 %N14 Ratio of
C – blue
14 14
N - red lives
C to N 14 14

0 100% 0% no ratio

1 50% 50% 1:1

After 1 half-life (5730 years), 50% of

the C14 has decayed into N14. The ratio
of C14 to N14 is 1:1. There are equal
amounts of the 2 elements.
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The blue grid below represents a quantity of C14. Each time you click,
one half-life goes by and you see red . Half % C14 %N14 Ratio of
C – blue
14 14
N - red lives
C to N 14 14

0 100% 0% no ratio

1 50% 50% 1:1

2 25% 75% 1:3

Now 2 half-lives have gone by for a total

of 11,460 years. Half of the C14 that was
present at the end of half-life #1 has now
decayed to N14. Notice the C:N ratio. It
will be useful later.
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The blue grid below represents a quantity of C14. Each time you click,
one half-life goes by and you see red. Half % C14 %N14 Ratio of
C – blue
14 14
N - red lives
C to N 14 14

0 100% 0% no ratio

1 50% 50% 1:1

2 25% 75% 1:3

3 12.5% 87.5% 1:7

After 3 half-lives (17,190 years) only

12.5% of the original C14 remains. For
each half-life period half of the material
present decays. And again, notice the
ratio, 1:7
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25
What is the half life
represented in this
graph?

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Radioactivity and Half-Life
Half-life is the time taken for half of a radioisotope to decay. This value is constant for that
particular radioisotope.
Usually questions about radioactivity involve
Half-life

The time over which the radioactivity has been measured

The quantity or intensity of the radiation.

Worked example 1.
A radioisotope has a half-life of 4 days. The radioisotope had an initial count rate of 800 counts per
minute. What will be the count rate after 16 days?

At start count rate = 800 counts min-1.

After 4 days = 400 counts min-1.

After 8 days = 200 counts min-1.

After 12 days = 100 counts min-1.

After 16 days = 50 counts min-1.

Worked example 2.
Thallium-208 has a half life of 3.1 minutes and decays by beta emission to form a stable isotope.
(a) What mass of a 2.08 g sample of Tl-208 will remain unchanged after
9.3 minutes?
(b) How many atoms will have decayed.
(c) Identify the stable isotope formed by the decay of Tl-208 by beta emission.

(a) At start mass = 2.08g

After 3.1 days = 1.04g

After 6.2 days = 0.52g

After 9.3 days = 0.26g

(b) At start no. of atoms = 2.08/ x 6.02 x 1023 = 6.02 x 1021

208

After 3.1 days no. of atoms of Tl-208 left undecayed= 3.01 x 1021

After 6.2 days no. of atoms of Tl-208 left undecayed= 1.505 x 1021

After 9.3 days no. of atoms of Tl-208 left undecayed= 0.7525 x 1021

No. of atoms of Tl-208 which have decayed= 6.02 x 1021 -0.7525 x 1021.
5.2675 x 1021
(c) Pb-208 has been formed.
Calculations for you to try.
1. Th-234 has a half-life of 24.1 days. What mass of a 20.4g sample will remain after 96.4 days?

At start mass = 20.4 g

After 24.1 days mass left = 10.2 g
After 48.2 days mass left = 5.1 g
After 72.3 days mass left = 2.55 g
After 96.4 days mass left = 1.275 g

2. A sample of Pu-242 has a mass of 1.21 g.

(a) How many atoms of Pu-242 are there in the sample?
(b) How many atoms of Pu-242 will remain after 3 half lives.
(c) Use the half life in the data book for Pu-242 to calculate the time it would
take to reduce the number of Pu-242 atoms in the sample to 1/8 of its original
value.
(a) No of atoms = 1.21/242 x 6.02 x 1023. = 3.01 x 1021
(b) No of atoms at start = 3.01 x 1021

After 3 half lives no. of atoms = 1/8 x 3.01 x 1021

= 3.76 x 1020
(c) 1/
8 of original value means that 3 half lives have passed.

3 x 3.79 x 105 years = 1.137 x 106 years

Calculations for you to try.
3. The count rate due to carbon-14 in ancient wooden timber was found to be
100 counts per minute. A sample of modern wood had a count rate of 1600 counts per minute.
Given that carbon-14 has a half life of 5570 years, calculate the age of the ancient timber.

At start count rate = 1600 counts min-1.

After 1 half-life = 800 counts min-1.

After 2 half-life = 400 counts min-1.
After 3 half-life = 200 counts min-1.

After 4 half-life = 100 counts min-1.

Age of timber = 4 x 5570 = 22 280 years.

4. A radioisotope used in a laboratory has a half life of 6.75 hours.

It had a count rate of 2000 counts per minute at 8.00 a.m. on Monday.
What would be the count rate at 11 a.m. the following day?
Between 8.00 a.m. and 11.00 am the next day 27 hours have passed.

Number of half-lives in 27 hours = 27/ = 4

6,75

Count rate 2000  1000  500  250  125 counts min-1.