Discovery of radioactivity

Radiochemistry
Silberberg:

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Why important for life sciences:

Effect of radiation on cells
mutagenesis
radiotherapy

1896: Bequerel discovered that uranium

minerals emitted penetrating radiation that
produced bright images on photographic paper
1898: Marie Sklodowska Curie (1867-1934)
searched for other minerals that emitted
radiation, found intensity of the radiation is
directly proportional to CONCENTRATION of the
element in the samples, not to the nature of the
compound in which the element occurs
M & P Curie isolated 2 highly radioactive fractions;
named them polonium and radium.

An investigative technique (e.g. for mechanisms)

Took Marie Curie 4 years to isolate
0.1 g of RaCl 2 melted and
electrolysed it into Ra metal

Notation

mass number
charge in
nucleus

A
ZX

Common radioactive emissions

to be learnt

a alpha particles
positively charged helium nuclei

symbol of particle

b beta particles
electrons (negatively charged)
positrons
same mass as electrons but with positive
charge

N = number of neutrons = A Z

4
He
2
0
b
-1

0b
+1

g-rays
very high energy photons (electromagnetic
radiation)

Nuclear reactions

Radiochemistry

Nucleus: essentially all of atoms mass but only

volume

Protons and neutrons (elementary particles in nucleus): called

NUCLEONS
NUCLIDE: atom with a particular nuclear composition
specific numbers of nucleons

1012

of its

Most elements: mixture of ISOTOPES nuclides with

characteristic number of protons of the element but different
number of neutrons

e.g.,

Protons, neutrons and other particles are involved

High-energy electrons from outside atom can take part and
electrons and high-energy photons can be generated
Reactions accompanied by large changes in energy and
measurable changes in mass

12C, 13C, 14C

Some types of radioactive decay

Abundance of Elements in the Universe

H
1012

109

Relative Abundance

He
Fe

106

Bi

103

1
0

10

20

30

40

50

60

70

80

90

100

Atomic Number, Z
7

Explaining natural abundance

Nuclear stability and radioactive decay

Dust collapsing to star burns H to form He

He in star then burns to C, O, Ne, Mg (more stable)
Further burning forms elements up to Ni, Fe
These follow thermodynamic stability
Heavier elements less stable: they are formed in supernova
explosions
governed by (nuclear) kinetics, not thermodynamics
Abundance up to Fe and Ni largely controlled by nuclear
stability (lowest energy) and some kinetics
After that the heavier elements are governed by kinetics of
nuclear reactions in supernovae

Key factor in nuclear stability: RATIO of neutrons to protons

(N/Z)
N/Z 1 stable for lighter atoms
Heavier atoms: as number of protons increases their repulsive
forces become intense and number of neutrons increases even
more to stabilize them.
Strong selection for EVEN numbers of N and Z
an unpaired nucleon is less stable, just like unpaired
electron in a molecule.
Filled nucleon shells at 2, 8, 20, 28, 50, 82 (and 126, for N)
...analogous to filled electron shells at 2, 10, 18, 36, 54, 84...
If N/Z too high or not high enough, nuclide is unstable and
decays

10

Kinetics of nuclear decay

14 C

Decay rate = rate of change in number of nuclei at time t, Nt

Decay rate proportional to the number present
dNt /dt = kNt
Radioactive decay: consider NUMBER of nuclei rather than
their concentration otherwise identical to 1 st order chemical
reaction (t1/2 )
Units

g+

14 C + -1 b

Happens in upper atmosphere, like ozone generation

Some of the CO 2 taken in by plants in 14CO 2

So food contains 14CO 2
Every living thing maintains about the same 14C:12C ratio during its
lifetime since it keeps ingesting this fresh carbon
After death, 14C decays fi how long something has been dead

Curie (Ci) : 1 Ci = number of nuclei disintegrating each second in 1 g of 226 Ra

14 N

= 3.70 x 10 10 disintegrations per second (dps).

ln (N0/Nt) = ln(A 0/A t) = kt

Becquerel (Bq) = 1 disintegration per second (dps)

Often express radioactivity of a sample in terms of specific activity

decay rate per gram

11

A0 = activity in a living organism

Half-life of 14C = 5730 years.
Thus starting with 1.0 g of 14C, 0.50 g left after 5730 years, 0.25 g
after another 5730 years, etc.
12

Example

Example
The activity (per g) of an archaeological artifact is 5.02 dps. In living
organisms the 14 C activity is 15.3 dps. t1/2 of 14C = 5730 years.
How old are the bones?

The activity (per g) of an archaeological artifact is 5.02 dps. In living

organisms the 14 C activity is 15.3 dps.
t1/2 of 14C = 5730 years.
How old are the bones?

Working:
t1/2 = 5730 years
k = ln(2) / t1/2 = 1.21 x 10 4 yr1

learn

For unimolecular decay: A/A0 = e kt

5.02/15.3 = exp(1.21 x 10 4 t )
Take ln of both sides and re-arrange:
t = (1 / 1.21 x 10 4 yr1) ln (15.3/5.02) = 9210 years

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Example: radioisotope tracing in medicine

Effect of radiation on living matter

18
9F

used as tracer for brain. t1/2 = 110 min.

Sample has activity of 10 mCi L 1 when freshly made. 5 hours
later, patient given 1.0 mL.
Calculate dose (Ci) received by patient.

Non-ionising radiation: relatively harmless - electrons excited

Ionising radiation destructive effect on living tissue
UNITS
CURIE/BECQUEREL
number of decay events in a given time
no account of energy or its effect
RAD (Radiation Absorbed Dose): amount of radiation that
results in 0.01 J of energy being absorbed per kg of tissue

Learn how to do this

Answer
3
Decay constant k = (ln 2)/t1/2 = 6.310 min1
Hence fraction remaining after 5 h (= 5 60 min) is
exp(kt) = exp( 6.3103 min 1 5 60 min) = e 1.89 = 0.15
Hence dose in 1 L = 0.15 10 mCi
and dose in 1.0 mL = 0.15 10 10 3 mCi
= 0.15 10 10 3 10 +3 Ci

To account for differences in strength, exposure time and type of

tissue: multiply number of RADS by
relative biological effectiveness (RBE) FACTOR
The product is the REM (Roentgen Equivalent for Man) the
unit of radiation dosage for man

= 1.5 Ci
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Free Radicals

Doses
Penetrating power and ionising ability of the radiation
a easily stopped by skin however if ingested (e.g.,
plutonium-239) causes damage through extensive ionisation.

Species with one or more unpaired electrons

Highly reactive

Radicals captured, damage repaired by cellular mechanisms

b particles are more penetrating and cause ionisation.

g-rays MOST dangerous: penetrates deepest, energy is
absorbed and ionises the surrounding matter.
Ionising radiation causes electrons to be taken from molecular
bonds forming FREE RADICALS
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