Cavity ring-down spectroscopy and relative rate study of reactions of HCO radicals with O2, NO, NO2, and Cl2 at 295 K

Yuki Ninomiya, Masashi Goto, Satoshi Hashimoto, Yoshihisa Kagawa, Kazunari Yoshizawa, Masahiro Kawasaki, Timothy J. Wallington, Michael D. Hurley

Research output: Contribution to journalArticle

30 Citations (Scopus)

Abstract

Cavity ring-down absorption spectroscopy was used to measure k(HCO + O2) = (5.9 ± 0.5) × 10-12, k(HCO + NO) = (1.9 ± 0.2) × 10-11, and k(HCO + Cl2) = (7.6 ± 0.7) × 10-12 cm3 molecule-1 s-1 in 4-10 Torr of N2 diluent at 295 K. FTIR/smog-chamber techniques were used to measure the following rate constant ratios in 15-750 Torr of N2 diluent at 295K: k(HCO + O2)/k(HCO + Cl2) = 0.85 ± 0.02, k(HCO + NO)/k(HCO + Cl2) = 2.80 ± 0.10, and k(HCO + NO2)/k(HCO + Cl2) = 8.45 ± 0.38. Consistent results were obtained from the two different techniques. In 15-700 Torr of N2 diluent at 295 K the reaction of HCO with Cl2 proceeds via a single channel giving HC(O)Cl + Cl, reaction of HCO with NO gives CO in a yield indistinguishable from 100%, and reaction of HCO with NO2 gives a 70% yield of CO and a 30% yield of CO2. Ab initio calculations show that the reaction of HCO radicals with Cl2 proceeds via the formation of the HC(O)Cl2 complex, which decomposes, rapidly to HC(O)Cl and a Cl atom.

Original languageEnglish
Pages (from-to)7556-7564
Number of pages9
JournalJournal of Physical Chemistry A
Volume104
Issue number32
DOIs
Publication statusPublished - Aug 1 2000
Externally publishedYes

Fingerprint

Carbon Monoxide
diluents
Spectroscopy
cavities
rings
Absorption spectroscopy
spectroscopy
Rate constants
smog
Atoms
Molecules
absorption spectroscopy
chambers
atoms
molecules

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry

Cite this

Cavity ring-down spectroscopy and relative rate study of reactions of HCO radicals with O2, NO, NO2, and Cl2 at 295 K. / Ninomiya, Yuki; Goto, Masashi; Hashimoto, Satoshi; Kagawa, Yoshihisa; Yoshizawa, Kazunari; Kawasaki, Masahiro; Wallington, Timothy J.; Hurley, Michael D.

In: Journal of Physical Chemistry A, Vol. 104, No. 32, 01.08.2000, p. 7556-7564.

Research output: Contribution to journalArticle

Ninomiya, Y, Goto, M, Hashimoto, S, Kagawa, Y, Yoshizawa, K, Kawasaki, M, Wallington, TJ & Hurley, MD 2000, 'Cavity ring-down spectroscopy and relative rate study of reactions of HCO radicals with O2, NO, NO2, and Cl2 at 295 K', Journal of Physical Chemistry A, vol. 104, no. 32, pp. 7556-7564. https://doi.org/10.1021/jp001188b
Ninomiya, Yuki ; Goto, Masashi ; Hashimoto, Satoshi ; Kagawa, Yoshihisa ; Yoshizawa, Kazunari ; Kawasaki, Masahiro ; Wallington, Timothy J. ; Hurley, Michael D. / Cavity ring-down spectroscopy and relative rate study of reactions of HCO radicals with O2, NO, NO2, and Cl2 at 295 K. In: Journal of Physical Chemistry A. 2000 ; Vol. 104, No. 32. pp. 7556-7564.
@article{0533d2958e424c6b9e779eb143228015,
title = "Cavity ring-down spectroscopy and relative rate study of reactions of HCO radicals with O2, NO, NO2, and Cl2 at 295 K",
abstract = "Cavity ring-down absorption spectroscopy was used to measure k(HCO + O2) = (5.9 ± 0.5) × 10-12, k(HCO + NO) = (1.9 ± 0.2) × 10-11, and k(HCO + Cl2) = (7.6 ± 0.7) × 10-12 cm3 molecule-1 s-1 in 4-10 Torr of N2 diluent at 295 K. FTIR/smog-chamber techniques were used to measure the following rate constant ratios in 15-750 Torr of N2 diluent at 295K: k(HCO + O2)/k(HCO + Cl2) = 0.85 ± 0.02, k(HCO + NO)/k(HCO + Cl2) = 2.80 ± 0.10, and k(HCO + NO2)/k(HCO + Cl2) = 8.45 ± 0.38. Consistent results were obtained from the two different techniques. In 15-700 Torr of N2 diluent at 295 K the reaction of HCO with Cl2 proceeds via a single channel giving HC(O)Cl + Cl, reaction of HCO with NO gives CO in a yield indistinguishable from 100{\%}, and reaction of HCO with NO2 gives a 70{\%} yield of CO and a 30{\%} yield of CO2. Ab initio calculations show that the reaction of HCO radicals with Cl2 proceeds via the formation of the HC(O)Cl2 complex, which decomposes, rapidly to HC(O)Cl and a Cl atom.",
author = "Yuki Ninomiya and Masashi Goto and Satoshi Hashimoto and Yoshihisa Kagawa and Kazunari Yoshizawa and Masahiro Kawasaki and Wallington, {Timothy J.} and Hurley, {Michael D.}",
year = "2000",
month = "8",
day = "1",
doi = "10.1021/jp001188b",
language = "English",
volume = "104",
pages = "7556--7564",
journal = "Journal of Physical Chemistry A",
issn = "1089-5639",
publisher = "ACS Publications",
number = "32",

}

TY - JOUR

T1 - Cavity ring-down spectroscopy and relative rate study of reactions of HCO radicals with O2, NO, NO2, and Cl2 at 295 K

AU - Ninomiya, Yuki

AU - Goto, Masashi

AU - Hashimoto, Satoshi

AU - Kagawa, Yoshihisa

AU - Yoshizawa, Kazunari

AU - Kawasaki, Masahiro

AU - Wallington, Timothy J.

AU - Hurley, Michael D.

PY - 2000/8/1

Y1 - 2000/8/1

N2 - Cavity ring-down absorption spectroscopy was used to measure k(HCO + O2) = (5.9 ± 0.5) × 10-12, k(HCO + NO) = (1.9 ± 0.2) × 10-11, and k(HCO + Cl2) = (7.6 ± 0.7) × 10-12 cm3 molecule-1 s-1 in 4-10 Torr of N2 diluent at 295 K. FTIR/smog-chamber techniques were used to measure the following rate constant ratios in 15-750 Torr of N2 diluent at 295K: k(HCO + O2)/k(HCO + Cl2) = 0.85 ± 0.02, k(HCO + NO)/k(HCO + Cl2) = 2.80 ± 0.10, and k(HCO + NO2)/k(HCO + Cl2) = 8.45 ± 0.38. Consistent results were obtained from the two different techniques. In 15-700 Torr of N2 diluent at 295 K the reaction of HCO with Cl2 proceeds via a single channel giving HC(O)Cl + Cl, reaction of HCO with NO gives CO in a yield indistinguishable from 100%, and reaction of HCO with NO2 gives a 70% yield of CO and a 30% yield of CO2. Ab initio calculations show that the reaction of HCO radicals with Cl2 proceeds via the formation of the HC(O)Cl2 complex, which decomposes, rapidly to HC(O)Cl and a Cl atom.

AB - Cavity ring-down absorption spectroscopy was used to measure k(HCO + O2) = (5.9 ± 0.5) × 10-12, k(HCO + NO) = (1.9 ± 0.2) × 10-11, and k(HCO + Cl2) = (7.6 ± 0.7) × 10-12 cm3 molecule-1 s-1 in 4-10 Torr of N2 diluent at 295 K. FTIR/smog-chamber techniques were used to measure the following rate constant ratios in 15-750 Torr of N2 diluent at 295K: k(HCO + O2)/k(HCO + Cl2) = 0.85 ± 0.02, k(HCO + NO)/k(HCO + Cl2) = 2.80 ± 0.10, and k(HCO + NO2)/k(HCO + Cl2) = 8.45 ± 0.38. Consistent results were obtained from the two different techniques. In 15-700 Torr of N2 diluent at 295 K the reaction of HCO with Cl2 proceeds via a single channel giving HC(O)Cl + Cl, reaction of HCO with NO gives CO in a yield indistinguishable from 100%, and reaction of HCO with NO2 gives a 70% yield of CO and a 30% yield of CO2. Ab initio calculations show that the reaction of HCO radicals with Cl2 proceeds via the formation of the HC(O)Cl2 complex, which decomposes, rapidly to HC(O)Cl and a Cl atom.

UR - http://www.scopus.com/inward/record.url?scp=0034245843&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0034245843&partnerID=8YFLogxK

U2 - 10.1021/jp001188b

DO - 10.1021/jp001188b

M3 - Article

AN - SCOPUS:0034245843

VL - 104

SP - 7556

EP - 7564

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

SN - 1089-5639

IS - 32

ER -