Muonium kinetics in sub- and supercritical water

Muonium is long-lived in pure water and has been studied over a very wide range of temperatures and pressures, from 5degreesC to over 400degreesC and from 1 to 400 bar. We have determined rate constants for representative reactions of muonium in aqueous solution; equivalent data on H atom kinetics is sparse and stops well short of the maximum temperature and pressure attained in our experiments. The results show remarkable deviations from the predictions of standard reaction theories. In particular, rate constants pass through a maximum with temperature well below the critical point. This seems to be a general phenomenon, since we have observed it for spin-exchange and chemical reactions that are diffusion limited at low temperatures, as well as for activated reactions. We believe that a key factor in the drop of rate constants at high temperature is the cage effect, in particular the number of collisions between a pair of reactants over the duration of their encounter. Whatever the reason, the implications are profound for both the efficiency of supercritical water oxidation reactors and for the modelling of radiation chemistry in pressurized water nuclear reactors. (C) 2002 Elsevier Science B.V. All rights reserved.