Pulse Radiolysis at High Temperatures and High Pressures

A set-up enabling pulse radiolysis measurements at high temperatures (up to 320°C) and high pressures (up to 140 bar) has been constructed in collaboration between Risö National Laboratory and Studsvik Energiteknik. The cell has been used for experiments with aqueous solutions with the purpose to determine activation energies for reactions of importance in reactor chemistry. The activation energy of the reaction e−aq+e−aq has been determined to be 22 kJ·mol−1 (5.3 kcal·mol−1) in good agreement with literature values. Furthermore, the activation energies of the reactions Cu2++OH (13.3 kJ·mol−1, 3.2 kcal.mol−1) and OH+OH (tentatively 8 kJ·mol−1, 1.9 kcal·mol−1) have been determined. The absorption spectrum of the OH radical has been determined up to temperatures of 200°C. The absorption maximum is found at 230 nm at all temperatures. The reaction between Fe2+ and OH radicals has been studied up to a temperature of 220°C. An activation energy of 9 kJ·mol−1 (2.2 kcal·mol−1) has been determined and the spectrum of the transient formed in the reaction has been determined at different temperatures.