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Fricke dosimeter

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20 views

Fricke dosimeter

Uploaded by

ksnaravind0002
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Fricke dosimeter

• Introduction

• Principle
• Composition
• Reaction mechanism
• Role of NaCl
• Analysis
• Calculation of absorbed dose
• Dose range
• Influence of various factors
Introduction
Fricke dosimeter is the best known and most broadly
applied chemical dosimeter. Fricke and Morse developed the
dosimeter in 1927.

Fricke dosimeter has been accurately standardized by


calorimetry and other physical methods and at present used
for absolute absorbed dose measurements with an accuracy of
1-2%. The Fricke dosimeter is widely accepted as a standard
in radiation chemistry and because of its accuracy and
reliability it is often used for calibrating other dosimeters.
Principle

When an air saturated dilute ferrous sulphate or ferrous


ammonium sulphate in 400 mol/m3 is exposed to ionizing
radiation ferrous ions are oxidized to ferric ions.

Fe+2 ^^^^^^^ Fe+3

Concentration of ferric ions gives the measure of absorbed dose.


The concentration is measured spectrophotometrically.
Composition

The standard dosimetric solution consists of air saturated


solution of
FeSO4 or Fe(NH4)2(SO4)2 - 1 mol/m3
NaCl - 1 mol/m3
H2SO4 - 400 mol/m3

Prepared in distilled water.


Reaction mechanism
H2O ^^^^^^^^ eaq, H+, OH, H2, H2O2
eaq + H3O+  H+ + H2O
H+ + O2  HO2
Fe2+ + HO2  Fe3+ + HO2-
HO2- + H+  H2O2
Fe2+ + H2O2  Fe3+ + OH + OH-
Fe2+ + OH  Fe3+ + OH-

Thus G(Fe+3) = 3G(H) + 2G(H2O2) + G(OH)

The generally agreed G(Fe+3) for Co-60 gamma rays is


1.61 mol/J or 15.5 (100 eV)-1 which is regarded as reference
standard of chemical dosimetry.
Role of NaCl
RH + OH  R + H2O ----(1)
R+ O2  RO2 ----(2)
Fe2+ + RO2 + H+  Fe3+ + ROOH ----(3)
Fe2+ + ROOH  Fe3+ + RO + OH- ----(4)
Fe2+ + RO + H+  Fe3+ + ROH ----(5)
Or
RH + RO  R + ROH ----(6)
Thus the chain may terminate at equation (5) or may regenerate
radical R that propagates the chain, by reaction (6).

Cl- + OH  Cl + OH-


Fe+2 + Cl  Fe3+ + Cl-
RH + Cl-  R + HCl
Thus in presence of sodium chloride G(Fe3+) remains unaffected.
Analysis
Absorption spectroscopy is generally more convenient than
titration, for it is rapid, accurate, and expedient for the analysis of low
ferric ion concentrations and small quantities of solution.
Ferric ion has two absorption peaks at 304 nm and 224 nm, the one
at 224 nm being more intense. At 304 nm the molar linear absorption
coefficient of ferrous ion is less than 0.05% of that of the ferric ion.
Measuring the optical density at the more intense 224 nm ferric ion
peak can double the sensitivity of this analytical method. However, at this
lower wavelength the absorption due to ferrous is not wholly negligible. In
addition, impurities from plastic container are reported to be more
troublesome at 224nm. Hence 304 nm is used for measurement of Fe3+ ion
concentration.
Absorbance of the irradiated dosimeters is measured against the
unirradiated solution from the standard flask. Optical density of the
unirradiated reference blanks in the dosimetric tubes is also measured
against solution in standard flask. Absorbance of the irradiated solution is
corrected for reference blank reading.
Calculation of absorbed dose
DF = A / { G  d}
To calculate the absorbed dose in water ( ASTM E 1026 ), use the equation,
DW = 1.004 DF
Hence, Dw = (1.004 (A)) / ( G  d)
ICRU 35 recommends the use of the product  G rather than individually
determined values of  and G. Both  and G have temperature coefficients as
0.7% and 0.15% per  C. Hence value of  G must be corrected for
temperature
t Gt’ = 352  10- 6 [ 1 + 0.007 (t - 25)]  [ 1 + 0.0015 ( t’ - 25) ]
1.004 (A)
Dw = --------------------------------------------------------------------------------------
352  10- 6 [ 1 + 0.007 (t - 25)]  [ 1 + 0.0015 ( t’ - 25 ) ] 1024  0.01
For Co-60 gamma rays (en/)w / (en/)d is 1.004.
Dose range
Dose range of Fricke dosimeter with adequate accuracy is 30

to 350 Gy with commonly employed 1 mol/m3 ferrous

sulphate solution.

The upper limit is set by oxygen depletion in the

solution ands lower limit by the sensitivity of analytical

method used for determining ferric ion concentration. With

special techniques it is possible to extend the useful range

beyond these limits.


Factors affecting the response of Fricke dosimeter

• Oxygen

• Ferrous ion concentration

• Sulphuric acid concentration

• Linear Energy Transfer (LET)

• Dose rate

• Temperature
Oxygen effect
Formation of ferric ions in Fricke dosimeter is directly
proportional to energy absorbed as long as some
oxygen remains in the solution.
When oxygen is completely exhausted, reaction
mechanism changes reducing G (Fe3+) to 0.85 mol/J
from 1.61mol/J.
Fe2+ + H + H+  Fe3+ + H2
Here one H atom oxidizes only one ferrous ion to
ferric instead of three.

Therefore, G (Fe3+) = G (H) +2G (H2O2)+ G (OH)


Ferrous ion concentration effect
The normal range of ferrous ion concentration is 0.1 mol/m3 to
10 mol/m3 . Both above and below this range of concentrations
ion air saturated solutions G(Fe3+) decreases.

Sulphuric acid concentration effect


The sulfuric acid concentration can be lowered to 50mol/m3
with only 2% drop in G(Fe3+) but below this concentration, the
G(Fe3+) falls and the system becomes unreliable. Therefore, a
concentration of 50 mol/m3 H2SO4 is the lowest that can be
used for reproducible dosimetry.
LET effect
The G(Fe3+) shows no significant dependence on
photon energy within the range from 0.60 MeV to 16 MeV.

At lower photon energy as the LET of radiation increases with


decreasing energy, G (Fe3+) shows decreasing values.

For heavier charged particles, which have higher LET the


decrease in G (Fe3+) is more pronounced.
Dose rate effect

The dosimeter response is independent of dose rate

between 1 mGy/sec to 40 Gy/sec for continuous irradiation.

With pulsed radiation G (Fe3+) remains constant up to

2 Gy/pulse of 1  sec. above this dose rate G (Fe3+) decreases.


Temperature effect
By increasing temperature during irradiation G (Fe3+)
increases slightly. The values reported for this temperature
dependence vary considerably, from insignificant to 0.16 % per
oC. The irradiation temperature is without much practical
significance from 10oC to 50oC.
The temperature at which the spectrophotometric
measurements are done is important as the molar linear
absorption coefficient increases by about 0.69% / oC for the
304 nm peak. For this reason it is important to know the
temperature at which the spectrophotometric measurements are
done.

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