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

Anthony J. Midey; Itzhak Dotan; A. A. Viggiano

doi:10.1016/j.ijms.2008.02.005

Reactions of PO_xCl_y^- ions with O₂(a ¹Δ_g), H₂O, and Cl₂ at 298 K

Anthony J. Midey, Itzhak Dotan, A. A. Viggiano

Research output: Contribution to journal › Article › peer-review

Abstract

The rate constants and product branching ratios for the reactions of phosphorus oxychloride anions, PO_xCl_y^- for x = 1-2 and y = 1-3, with O₂(a ¹Δ_g), Cl₂, and H₂O have been measured in a selected ion flow tube (SIFT) at 298 K. A mixture of O₂(a ¹Δ_g) 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 PO_xCl_y^- ions, searching for pathways to the terminal PO₂^- and PO₃^- ions observed in combustion chemistry with POCl₃ present. None of the PO_xCl_y^- ions react with H₂O or O₂(a ¹Δ_g). The O₂(a ¹Δ_g) 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 PO_xCl_y^- ions react with Cl₂, excluding PO₃^- and PO₂Cl₂^-. Depending on the reactant ion, Cl^-, Cl₂^- or PO₂Cl₂^- product ions form.

Original language	English
Pages (from-to)	7-10
Number of pages	4
Journal	International Journal of Mass Spectrometry
Volume	273
Issue number	1-2
DOIs	https://doi.org/10.1016/j.ijms.2008.02.005
State	Published - 1 Jun 2008
Externally published	Yes

Bibliographical note

Funding 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.

Keywords

Chlorine
Kinetics
Oxygen singlet delta
Phosphorus oxychloride
Water

Access to Document

10.1016/j.ijms.2008.02.005

Cite this

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

abstract = "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.",

keywords = "Chlorine, Kinetics, Oxygen singlet delta, Phosphorus oxychloride, Water",

author = "Midey, {Anthony J.} and Itzhak Dotan and Viggiano, {A. A.}",

note = "Funding 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. ",

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AU - Midey, Anthony J.

AU - Dotan, Itzhak

AU - Viggiano, A. A.

N1 - Funding 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.

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N2 - 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.

AB - 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.

KW - Chlorine

KW - Kinetics

KW - Oxygen singlet delta

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