Reactions of POxCly- ions with O2(a 1Δg), H2O, and Cl2 at 298 K

The rate constants and product branching ratios for the reactions of phosphorus oxychloride anions, POxCly- for x = 1-2 and y = 1-3, with O-2(a (1) Delta(g)), Cl-2, and H2O have been measured in a selected ion flow tube (SIFT) at 298 K. A mixture of O-2(a (1) Delta g) in O-2 has been produced using a recently designed chemical singlet oxygen generator (sparger) with an emission detection scheme adopted previously in our laboratory. The experiments continue a series of investigations into the oxidation reactions of POxCly- ions, searching for pathways to the terminal PO2- and PO3- ions observed in combustion chemistry with POCl3 present. None of the POxCly- ions react with H2O or O-2(a (1) Delta g). The O-2(a (1) Delta g) rate constants have a limit of < 1 x 10(-11) cm(3) s(-1), except for PO2Cl- where a limit of <5 x 10(-11) cm(3) s(-1) has been determined. The H2O rate constants have limits of < 1 x 10(-11) cm(3) s(-1). All of the POxCly- ions react with Cl-2, excluding PO3- and PO2Cl2-. Depending on the reactant ion, Cl-, Cl-2(-) or PO2Cl2- product ions form. (C) 2008 Elsevier B.V. All rights reserved.