Picosecond Pulse Radiolysis of Direct and Indirect Radiolytic Effects in Highly Concentrated Halide Aqueous Solutions

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2011-08, Vol.115 (33), p.9151-9159
• Main Authors: Balcerzyk, Anna, Schmidhammer, Uli, El Omar, Abdel Karim, Jeunesse, Pierre, Larbre, Jean-Philippe, Mostafavi, Mehran
• Format: Article
• Language: English
• Subjects: A: Kinetics, Spectroscopy; Absorption spectra; Anions; Aqueous solutions; Electron pulses; Electrons; Formations; Halides; Halogens - chemistry; Hydroxyl Radical - chemistry; Ionization; Kinetics; Oxidation-Reduction; Photochemical Processes - radiation effects; Pulse Radiolysis; Radiolysis; Solutions - chemistry; Spectrum Analysis; Thermodynamics; Ultraviolet Rays; Water
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/jp203609e

Recently we measured the amount of the single product, Br3 –, of steady-state radiolysis of highly concentrated Br– aqueous solutions, and we showed the effect of the direct ionization of Br– on the yield of Br3 –. Here, we report the first picosecond pulse-probe radiolysis measurements of ionization of highly concentrated Br– and Cl– aqueous solutions to describe the oxidation mechanism of the halide anions. The transient absorption spectra are reported from 350 to 750 nm on the picosecond range for halide solutions at different concentrations. In the highly concentrated halide solutions, we observed that, due to the presence of Na+, the absorption band of the solvated electron is shifted to shorter wavelengths, but its decay, taking place during the spur reactions, is not affected within the first 4 ns. The kinetic measurements in the UV reveal the direct ionization of halide ions. The analysis of pulse-probe measurements show that after the electron pulse, the main reactions in solutions containing 1 M of Cl– and 2 M of Br– are the formation of ClOH–• and BrOH–•, respectively. In contrast, in highly concentrated halide solutions, containing 5 M of Cl– and 6 M of Br–, mainly Cl2 –• and Br2 –• are formed within the electron pulse without formation of ClOH–• and BrOH–•. The results suggest that, not only Br– and Cl– are directly ionized into Br• and Cl• by the electron pulse, the halide atoms can also be rapidly generated through the reactions initiated by excitation and ionization of water, such as the prompt oxidation by the hole, H2O+•, generated in the coordination sphere of the anion.