Physics
Scientific paper
Jul 1981
adsabs.harvard.edu/cgi-bin/nph-data_query?bibcode=1981natur.292..439m&link_type=abstract
Nature, Volume 292, Issue 5822, pp. 439-441 (1981).
Physics
Scientific paper
Although the chemical kinetics of reactive species in water at temperatures above 100 °C has received very little attention, the radiation chemistry of aqueous coolant at the high pressures (150 bar) and temperatures (330 °C) of pressurized and boiling-water nuclear reactors is of obvious interest to reactor chemists, engineers and designers1. There is a wealth of data2 on rate constants for reactions of the radiolytically important radicals e-aq, H, OH, O-, HO2 and O-2 at room temperature, but only a few rates have been measured3 up to 90 °C and only one4 up to 200 °C. It has thus become common5-9 to calculate the rate constants required for modelling water radiolysis in reactor conditions by extrapolating room temperature data using the Arrhenius equation k = A exp (-E/RT) where E, the assumed activation energy, has a value in the range 12-20 kJ mol-1. We report here the failure of this method to predict the rate of reaction of hydroxyl radicals with bicarbonate at temperatures up to 200 °C.
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