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.
Bibliographical noteFunding Information:
We would like to thank John Williamson and Paul Mundis for their technical support. This work has been supported by the Air Force Office of Scientific Research (AFOSR) under project number EP2303A. AJM is supported under Boston College Contract No. FA8718-04-C-0006. ID was supported under a National Research Council Research Associateship Award at AFRL.
- Oxygen singlet delta
- Phosphorus oxychloride