Radiolysis of water

The major
j p products of water radiolysis
y areare::
Free radicals (H.,.OH, . HO2 )
1. Hydrated electrons
2. Positive ions (H2O+, H3O+, H+ and OH+)
3. Molecular products (H2 and H2O2).
 Some
S off these
th actt as precursors which
hi h gives
i other
th products
d t byb
secondary reactions.
reactions.
• The precise sequence of reactions may not be the same for all
types of radiations and values of LET
LET..
• The presence of dissolved oxygen or air in the water also
affects the final yields of the products
products..
• The presence of dissolved solutes also alter the yields.
yields.
1. Mean LET in water Radiolysis
It varies with the nature of radiation and its energy.
energy. LET in water is
low for γ photons and high energy electrons.
electrons.
It increases with the mass in the case of p
particle radiation.
radiation.
2. Ionic Products
• The formation of negative ions by electron attachment is
negligible.
negligible
li ibl .
• Electrons prefer to recombine with positive ions, or to get
solvated during the relaxation time of water dipoles.
dipoles.
• The ionic products are detected by a mass spectrometer in the
radiolysis of water vapour.
vapour.
• From the relative yield of radiolysis of water it is clear that the
H2O+ is the only important ionic product .

3. Free radical products

• The all ionic products have short lives, they are in excited states
and recombine to yield free radicals.
radicals.
• In the presence of dissolved air or oxygen perhydroxyl radical
.OH is formed
formed..
2

4. The hydrated electron

• Each ion is to get solvated when dissolved in polar solvent as
water, liquid ammonia etc
etc.. due to the strong ion
ion‐‐dipole interaction
interaction..
 Radiation dosimeter
A radiation dosimeter is a device that measures exposure to ionizing 
radiation. 
Chemical dosimetr
Chemical dosimetry
Chemical dosimetry involves determination of dose by the
measurement of chemical changes induced in materials by ionising
radiation.
radiation
1. The Fricke dosimeter
This consists in measuring the extent of oxidation of Fe2+ to Fe3+ under
specified conditions. The Fricke solution is obtained by dissolving 0.4g
of ferrous ammonium sulphate and 0.06g of NaCl in 22 ml of 95‐98%
H2SO4 and making up the solution in distilled water to 1L, dissolved air
being present. A sample of this solution in a thick container is exposed
to radiation at the desired spot for a definite period of time.
Immediately thereafter, the amount of Fe3+ produced is determined
spectrophotometrically at the wave length of 304nm (The resulting
concentration of Fe3+ may be determined from an experimental plot of
optical
ti l density
d it against
i t concentration).
t ti ) TheTh unknown
k d
dose i readily
is dil
calculated from the measured yield of Fe3+, knowing that the yield is
15.5 Fe3+ ions per 100eV dose absorbed.
Radiolysis of Fricke dosimeter solution
 The . HO2  needed in step (3) is obtained by the reaction

The yield of the final product Fe3+ is related to the radical and
molecular yyields byy the expression
expression.
p .

G(Fe3+)air = 2GH2O2 + 3GH + GOH

= (2 x 0.8) + 3 ( 3.7 ) + 2.9 = 15

15..6