Branching ratios for competing channels in the reaction of HOCO radicals with NO

Rouslan Olkhov, Qiang Li, Michael Osborne, Ian Smith

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29 Citations (Scopus)


The yields of CO2 from the reactions of HOCO radicals with O2 and with NO have been compared using the technique of time-resolved infrared absorption. In two separate series of experiments, HOCO radicals have been generated by (i) broadband ultraviolet photolysis of acrylic acid (CH2CHCOOH) and (ii) the reaction, Cl + HCOOH → HCl + HOCO, following pulsed laser photolysis of Cl2 at 351 nm. In the latter experiments, the observed CO2 yields were corrected for the loss of Cl atoms by the reactions Cl + NO + He → ClNO + He and Cl + ClNO → Cl2 + NO. Our measurements on the rate of Cl + NO + He yield a value of the third-order rate constant of (5.1 ± 0.7) × 10−32 cm6 molecule−2 s−1. The results of the main experiments show that the yield of CO2 from the reaction between NO + HOCO is appreciably less than that from O2 + HOCO and is dependent on the total pressure in the range 10 to 100 Torr. We interpret this as showing that the reactions HOCO + NO → HNO + CO2 and HOCO + NO(+M) → HOC(O)NO(+M) occur at similar rates, with the latter reaction being favoured at the higher total pressure.
Original languageEnglish
Pages (from-to)4522-4528
Number of pages7
JournalPhysical Chemistry Chemical Physics
Issue number20
Publication statusPublished - 24 Sept 2001


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