Modelling spur chemistry for alkaline and acidic water at high temperatures

Abstract

The effect of pH and associated ionic strength on the primary yields in the radiolysis of pressurised water has been assessed by diffusion-kinetic calculations for temperatures in the range 100-300°C. Account has been taken for ionic strength I up to 0.1 mol kg -1 , assuming that the counter ions of H ? in acid solutions and of OH -in base solutions have unit charge. In acid solutions, the H ? ions react with eaq . The decrease in G(eaq ) and the increase in G(H) with decreasing pH becomes substantial for [H ? ] C 1 9 10 -4 m, but the primary yields of oxidising species are almost constant. In alkaline solutions, the OH -anions affect the spur chemistry of radiation-generated protons and hydroxyl radicals for [OH -] C 1 9 10 -4 m. The scavenging of H atoms and hydrogen peroxide becomes significant for [OH -] C 1 9 10 -2 m. The total yields G(OH) ? G(O -) and G(H 2 O 2 ) ? G(HO 2 -) are independent of base concentration below 0.01 m. In more alkaline solutions, G(OH) ? G(O -) increases, whereas G(H 2 O 2 ) ? G(HO 2 -) decreases with increasing [OH -]. Calculations showed the substantial yield of the reaction O -? eaq in 0.1 m base solution. Spur chemistry in alkaline hydrogenated water is not affected by the presence of H 2 if less than 0.001 m of hydrogen is added.

A Numerical Simulation of Radiation Chemistry for Controlling the Oxidising Environment in Water-Cooled Nuclear Power Reactors

“…considered in this study, the production rates for alkaline and hydrogenated solutions can be assumed the same as for neutral water at 300 • C [24].…”