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Issue 10, 1985
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Kinetics and mechanism of the reactions of PH3 with O(3P) and N(4S) atoms

Abstract

The reactions of ground-state oxygen and nitrogen atoms with phosphine have been studied using a discharge-flow system with detection of both free-radical and molecular species by molecular-beam sampling mass spectrometry. By observing the decay of PH3 in an excess of O, the rate constant for the reaction O + PH3 [graphic omitted] products (1) was determined to be k1=(4.6 ± 0.8)× 10–11 cm3 molecule–1 s–1. The products are principally H2PO and H with <10% of the reaction proceeding to PH2 and OH. Observation of the molecular species H3PO is reported for the first time. HPO and PO were also detected and a new mechanism for the reaction of oxygen atoms with phosphine is suggested. The reaction N + PH3 [graphic omitted] products (2) was observed to be very slow with an upper limit for the rate constant of k2⩽ 4.0 × 10–14 cm3 molecule–1 s–1.

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Article type: Paper
DOI: 10.1039/F29858101531
Citation: J. Chem. Soc., Faraday Trans. 2, 1985,81, 1531-1541
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    Kinetics and mechanism of the reactions of PH3 with O(3P) and N(4S) atoms

    P. A. Hamilton and T. P. Murrells, J. Chem. Soc., Faraday Trans. 2, 1985, 81, 1531
    DOI: 10.1039/F29858101531

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