Prediction of rate constants of important reactions in water radiation chemistry in sub- and supercritical water: equilibrium reactions

Various studies have shown that rate constants of many reactions in water go through a plateau before reaching the critical point. In 2002, Ghandi et al. proposed a model that accounts for this behaviour called the cage effect model. In this work, we review the most important equilibrium reactions in the radiolysis of water and estimate their rate constants using this model. Equilibrium reactions are very important for water radiolysis, because some of the reactions are extremely fast. For example, the reaction H⁺+ e _aq⁻ ⇌ H^. could be the cause of a significant increase in the H atom yield in supercritical water (as compared with water vapor). (author)