Neutron and blg radiolysis of water up to supercritical conditions. I. blg yields for H2, H· atom, and hydrated electron

Yields for H2, H• atom, and hydrated electron production in β/γ radiolysis of water have been measured from room temperature up to 400 °C on a 250 bar isobar, and also as a function of pressure (density) at 380 and 400 °C. Radiolysis was carried out using a beam of 2−3 MeV electrons from a van de Graaff accelerator, and detection was by mass spectrometer analysis of gases sparged from the irradiated water. N2O was used as a specific scavenger for hydrated electrons giving N2 as product. Ethanol-d6 was used to scavenge H• atoms, giving HD as a stable product. It is found that the hydrated electron yield decreases and the H• atom yield increases dramatically at lower densities in supercritical water, and the overall escape yield increases. The yield of molecular H2 increases with temperature and does not tend toward zero at low density, indicating that it is formed promptly rather than in spur recombination. A minimum in both the radical and H2 yields is observed around 0.4 kg/dm3 density in supercritical water.