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 O2(a 1Δg), Cl2, and H2O have been measured in a selected ion flow tube (SIFT) at 298 K. A mixture of O2(a 1Δg) in O2 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 O2(a 1Δg). The O2(a 1Δg) rate constants have a limit of <1 × 10−11 cm3 s−1, except for PO2Cl− where a limit of <5 × 10−11 cm3 s−1 has been determined. The H2O rate constants have limits of <1 × 10−11 cm3 s−1. All of the POxCly− ions react with Cl2, excluding PO3− and PO2Cl2−. Depending on the reactant ion, Cl−, Cl2− or PO2Cl2− product ions form.