Low-linear energy transfer radiolysis of liquid water at elevated temperatures up to 350[degrees]C Monte-Carlo simulations
Date de publication2012
Sujet(s)Dosimètre de Fricke
A re-examination of our Monte-Carlo modeling of the high-temperature radiolysis of liquid water by low-linear energy transfer (LET~0.3 keV/[micro]m) radiation has been undertaken in an attempt to reconcile our computed g-values (primary yields) of the various radiolytic products (e[superscript -][subscript aq], ¨OH, H¨, H[subscript 2], and H[subscript 2]O[subscript 2]) with recently reevaluated experimental data over the range from 25 up to 350 [degrees]C. The temperature dependence of the rate constant for the self-reaction of the hydrated electron (e[superscript -][subscript aq]) measured under alkaline conditions, and in particular the abrupt drop observed above 150 [degrees]C, was assumed, in contrast to previous study, to be valid also in near-neutral pH water. To best reproduce the currently available temperature-dependent g-values, we found it necessary to introduce a discontinuity in the temperature dependence at 150 [degrees]C of certain parameters that intervene in the physicochemical stage of the radiolysis, including the thermalization distance (r[subscript]th) and the dissociative attachment (DEA) of subexcitation electrons, and the dissociative decay of electronically and vibrationally excited water molecules. With the exception of g(H[subscript 2]) above 200 [degrees]C, all calculated g-values were consistent with the general observation that when the temperature is increased, the yields of free radicals g(e[superscript]-[subscript]aq), g(¨OH), and g(H¨) increase while the molecular yield g(H[subscript 2]O[subscript 2]) decreases.Although H[subscript 2] is a molecular product, g(H[subscript 2]) was observed to continue to increase with temperature for a reason that has been a matter of controversy recently. Our simulations show that the reaction of H¨ atoms with water previously proposed by Swiatla-Wojcik and Buxton can indeed account for the anomalous increase in g(H[subscript 2]) at high temperature if we use for the rate constant of this reaction the value of 10[superscript 4] M[superscript 1] s[superscript -1] at 300 [degrees]C. Finally, as a direct application of the Fricke (ferrous sulfate) dosimeter, we have calculated the spur lifetime ([tau]s) and its temperature dependence. The results show that our calculated [tau]s value is decreasing from 4.2×10[superscript -7] to 5.7×10[superscript -8] s over the temperature range 25-350 [degrees]C.