RESUMO
Picosecond pulse radiolysis measurements were performed in neat D2O and H2O in order to study the isotopic effect on the time-resolved yield of the hydrated electron and hydroxyl radical. First, the absorption band of the hydrated electron in D2O, eD2O-, is measured between 250 and 1500 nm. The molar absorption coefficient of the solvated electron spectrum in D2O was determined using the isosbestic point method by scavenging the solvated electron using methyl viologen. The amplitude and shape of the absorption spectrum of the hydrated electron in D2O are different from those previously reported in the literature. The maximum of the hydrated electron in the D2O absorption band is ca. 704 nm with a molar absorption coefficient of (22 900 ± 500) L mol-1 cm-1. Based on this extinction coefficient, the radiolytic yield of eD2O- just after the 7 ps electron pulse was determined to be (4.4 ± 0.2) × 10-7 mol J-1, which coincides with the one for eH2O- in H2O. The time-dependent radiolytic yield of eD2O- was determined from a few ps to 8 ns. To determine the ODË radical yield, the contribution of the solvated electron and of the transient species produced by the electron pulse in the windows of the fused silica optical cell was taken into account for the analysis of the transient absorption measurements at 260 nm. Therefore, an appropriate experimental methodology is used for measuring low absorbance at two different wavelengths in ps pulse radiolysis. The yield of the ODË radical just after the 7 ps electron pulse was found to be (5.0 ± 0.2) × 10-7 mol J-1. In the spurs of ionization, the decay rate of eD2O- is slower than eH2O-, whereas the decay rate of ODË is similar to the one of OHË. Here, the established time-dependent yield of the solvated electron and the hydroxyl radical provide the foundation for improving the models used for spur reaction simulations in heavy water mainly for the chemistry of CANDU reactors.
RESUMO
The development of ultra-intense electron pulse for applications needs to be accompanied by the implementation of a practical dosimetry system. In this study four different systems were investigated as dosimeters for low doses with a very high-dose-rate source. First, the effects of ultra-short pulses were investigated for the yields of the Fricke dosimeter based on acidic solutions of ferrous sulfate; it was established that the yields were not significantly affected by the high dose rates, so the Fricke dosimeter system was used as a reference. Then, aqueous solutions of three compounds as fluorescence chemical dosimeters were utilized, each operated at a different solution pH: terephthalic acid - basic, trimesic acid - acidic, and coumarin-3-carboxylic acid (C3CA) - neutral. Fluorescence chemical dosimeters offer an attractive alternative to chemical dosimeters based on optical absorption for measuring biologically relevant low doses because of their higher sensitivity. The effects of very intense dose rate (TGy/ s) from pulses of fast electrons generated by a picosecond linear accelerator on the chemical yields of fluorescence chemical dosimeters were investigated at low peak doses (<20 Gy) and compared with yields determined under low-dose-rate irradiation from a 60 Co gamma-ray source (mGy/s). For the terephthalate and the trimesic acid dosimeters changes in the yields were not detected within the estimated (â¼10%) precision of the experiments, but, due to the complexity of the mechanism of the hydroxyl radical initiated reactions in solutions of the relevant aromatic compounds, significant reductions of the chemical yield (-60%) were observed when the C3CA dosimeter was irradiated with the ultra-short pulses.
Assuntos
Dosímetros de RadiaçãoRESUMO
Recently we measured the amount of the single product, Br(3)(-), of steady-state radiolysis of highly concentrated Br(-) aqueous solutions, and we showed the effect of the direct ionization of Br(-) on the yield of Br(3)(-). Here, we report the first picosecond pulse-probe radiolysis measurements of ionization of highly concentrated Br(-) and Cl(-) aqueous solutions to describe the oxidation mechanism of the halide anions. The transient absorption spectra are reported from 350 to 750 nm on the picosecond range for halide solutions at different concentrations. In the highly concentrated halide solutions, we observed that, due to the presence of Na(+), the absorption band of the solvated electron is shifted to shorter wavelengths, but its decay, taking place during the spur reactions, is not affected within the first 4 ns. The kinetic measurements in the UV reveal the direct ionization of halide ions. The analysis of pulse-probe measurements show that after the electron pulse, the main reactions in solutions containing 1 M of Cl(-) and 2 M of Br(-) are the formation of ClOH(-â¢) and BrOH(-â¢), respectively. In contrast, in highly concentrated halide solutions, containing 5 M of Cl(-) and 6 M of Br(-), mainly Cl(2)(-â¢) and Br(2)(-â¢) are formed within the electron pulse without formation of ClOH(-â¢) and BrOH(-â¢). The results suggest that, not only Br(-) and Cl(-) are directly ionized into Br(â¢) and Cl(â¢) by the electron pulse, the halide atoms can also be rapidly generated through the reactions initiated by excitation and ionization of water, such as the prompt oxidation by the hole, H(2)O(+â¢), generated in the coordination sphere of the anion.
Assuntos
Halogênios/química , Soluções/química , Ânions , Elétrons , Radical Hidroxila/química , Cinética , Oxirredução , Processos Fotoquímicos/efeitos da radiação , Radiólise de Impulso , Análise Espectral , Termodinâmica , Raios Ultravioleta , ÁguaRESUMO
Picosecond pulse radiolysis measurements using a pulse-probe method are performed to measure directly the time-dependent radiolytic yield of the OH(â¢) radical in pure water. The time-dependent absorbance of OH(â¢) radical at 263 nm is deduced from the observed signal by subtracting the contribution of the hydrated electron and that of the irradiated empty fused silica cell which presents also a transient absoption. The time-dependent radiolytic yield of OH(â¢) is obtained by assuming the yield of the hydrated electron at 20 ps equal to 4.2 × 10(-7) mol J(-1) and by assuming the values of the extinction coefficients of e(aq)(-) and OH(â¢) at 782 nm (ε(λ=782 nm) = 17025 M(-1) cm(-1)) and at 263 nm (ε(λ=263 nm) = 460 M(-1) cm(-1)), respectively. The value of the yield of OH(â¢) radical at 10 ps is found to be (4.80 ± 0.12) × 10(-7) mol J(-1).