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

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Branching ratios for competing channels in the reaction of HOCO radicals with NO. / Olkhov, Rouslan; Li, Qiang; Osborne, Michael; Smith, Ian.

In: Physical Chemistry Chemical Physics, Vol. 3, No. 20, 24.09.2001, p. 4522-4528.

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@article{e47d4a3a94f84638a37813d4bb37865a,
title = "Branching ratios for competing channels in the reaction of HOCO radicals with NO",
abstract = "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.",
author = "Rouslan Olkhov and Qiang Li and Michael Osborne and Ian Smith",
year = "2001",
month = sep,
day = "24",
doi = "10.1039/b106071f",
language = "English",
volume = "3",
pages = "4522--4528",
journal = "Physical Chemistry Chemical Physics",
issn = "1463-9076",
publisher = "Royal Society of Chemistry",
number = "20",

}

RIS

TY - JOUR

T1 - Branching ratios for competing channels in the reaction of HOCO radicals with NO

AU - Olkhov, Rouslan

AU - Li, Qiang

AU - Osborne, Michael

AU - Smith, Ian

PY - 2001/9/24

Y1 - 2001/9/24

N2 - 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.

AB - 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.

U2 - 10.1039/b106071f

DO - 10.1039/b106071f

M3 - Article

VL - 3

SP - 4522

EP - 4528

JO - Physical Chemistry Chemical Physics

JF - Physical Chemistry Chemical Physics

SN - 1463-9076

IS - 20

ER -