Abstract
The decay kinetics of hydrated electron (eaq −) formed upon photolysis of aqueous solutions of sodium pyrene-1,3,6,8-tetrasulfonate at λ = 337 nm in the presence of phosphate anions (up to 2 mol L−1) was studied by nanosecond laser-pulse photolysis in a wide range of pH (3.5–10) and ionic strength (I, up to 2 mol L−1) values. At high pH values, where the HPO4 2− ions dominate, the eaq − decay kinetics depends only slightly on phosphate concentration (rate constant for the reaction is at most 2·105 L mol−1 s−1). The H2PO4 − ions react with eaq − at a rate constant of 2.8·106 L mol−1 s−1 (I = 0), which increases linearly with the parameter \(\exp ({{\sqrt I } \mathord{\left/ {\vphantom {{\sqrt I } {1 + \sqrt I }}} \right. \kern-\nulldelimiterspace} {1 + \sqrt I }})\) in accordance with the Debye-Hückel theory. The rate constant for quenching of eaq − by H3PO4 at pH ≤ 4 decreases linearly with the parameter \(\exp ({{\sqrt I } \mathord{\left/ {\vphantom {{\sqrt I } {1 + \sqrt I }}} \right. \kern-\nulldelimiterspace} {1 + \sqrt I }})\) due to the secondary salt effect and equals 1.6·109 L mol−1 s−1 at I = 0. The logarithm of the rate constant for quenching of eaq − by phosphates is linearly related to the number of the O-H bonds in the phosphate molecule.
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Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1277–1280, July, 2007.
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Levin, P.P., Brzhevskaya, O.N. & Nedelina, O.S. Kinetics of hydrated electron reactions with phosphate anions: a laser photolysis study. Russ Chem Bull 56, 1325–1328 (2007). https://doi.org/10.1007/s11172-007-0202-1
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DOI: https://doi.org/10.1007/s11172-007-0202-1