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• W1540820061 abstract "The radiation chemical yield for the reduction of dichromate, Cr(VI) → Cr3+, in an acidic aqueous perchloric acid solution of potassium dichromate, may be increased from 0.04 to >0.2 μ mol J-1 by adding acetic acid. The increased yield, G[-(Cr2O7)2-] is about the same in N2- and O2-saturated solutions. The molar linear absorption coefficient at 350 nm also is the same in both solutions (ϵm = 2800 M-1cm-1) at pH 0.4. The proposed mechanism to explain the enhanced response in N2-saturated solutions involves the efficient reaction of acetic acid with hydroxyl radicals by the abstraction of H from the methyl group; the resulting acid radicals react with relatively high yield to reduce Cr(VI). In O2-saturated solution, the acetic acid radical apparently goes through an acetic acid peroxyl radical by a bimolecular reaction to the tetroxide intermediate of acetic acid, which releases H2O2 with relatively high yield by a Bennett-type reaction. This additional H2O2, as a reducing agent, reacts slowly with dichromate and boosts the value of G[-(Cr2O7)2-]. The negative slope of the response (ΔA vs dose) continues to increase during the period immediately after irradiation of oxygenated solution, due to slow reaction of radiolytically-produced H2O2 with dichromate. There is also in both O2- and N2-saturated solution a long-term slow reaction involving oxidation of the organic substrate (in this case, acetic acid). Because of these instabilities, the solutions cannot readily be used for dosimetry without the presence of silver ions, which in the oxidized state, Ag2+, act to stabilize the solution after irradiation. The addition of silver dichromate at a concentration of 0.1 mM decreases the yield to G[-(Cr2O7)2-] = 0.17 μmolJ-1, but greatly improves the stability of the solution after irradiation. The absorbed dose range for the modified dichromate dosimeter when analyzed spectrophotometrically at 350 nm wavelength is approx. 2 × 102-2 × 103 Gy." @default.
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• W1540820061 date "1988-01-01" @default.
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• W1540820061 title "Dichromate dosimetry" @default.
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