Scavenging the water cation in concentrated acidic solutions

Picosecond pulse radiolysis techniques were used to observe the kinetics of the SO4(•-), H2PO4(•), Cl2(•-), and Br2(•-) species formed in the fast oxidation of concentrated and highly acidic solutions of SO4(2-), PO4(3-), Cl(-), and Br(-). Experimental results were compared with model predictions to gain insight into the possible mechanisms occurring on the fast time scales. Simple kinetics involving the oxidizing OH(•) radical formed by radiolytic water decomposition could not account for the observed yields at the very short times (within the electron pulse ∼7 ps). Diffusion-kinetic simulations of the spur reactions induced by the incident electrons show that additional oxidation of the solutes must occur at very short times and involves their direct ionization along with scavenging of the highly oxidizing H2O(•+) radical formed in the initial ionization of the water medium. The fraction of H2O(•+) radicals scavenged varies as 0.26, 0.68, 0.92, and 0.97 for PO4(3-), SO4(2-), Cl(-), and Br(-) solutions, respectively. These studies represent the first semiquantitative estimation of the H2O(•+) radicals scavenging fractions for such a wide range of solutes.