Atmospheric chemistry of methylcyclopentadienyl manganese tricarbonyl: Photolysis, reaction with hydroxyl radicals and ozone

T. J. Wallington; O. Sokolov; M. D. Hurley; G. S. Tyndall; J. J. Orlando; I. Barnes; K. H. Becker; R. Vogt

doi:10.1021/es990350p

Atmospheric chemistry of methylcyclopentadienyl manganese tricarbonyl: Photolysis, reaction with hydroxyl radicals and ozone

T. J. Wallington, O. Sokolov, M. D. Hurley, G. S. Tyndall, J. J. Orlando, I. Barnes, K. H. Becker, R. Vogt

Experimental Science Section

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Abstract

The atmospheric fate of MMT has been studied using laboratory smog chamber systems. MMT absorbs strongly in the UV-visible region from 210 to 400 nm with σ (333 nm) = (1.9 ± 0.2) x 10^-18 cm² molecule^-1 and undergoes photolysis at a rate estimated to be (1.3 ± 0.1) x 10^-2 s^-1 for a typical summer day at a latitude of 40°N. Photolysis gives CO in a molar yield that is indistinguishable from 100% and an unidentified species believed to be methylcyclopentadienyl manganese dicarbonyl (MMD), which also undergoes rapid photolysis liberating additional CO. Reaction of MMT with OH and O₃ proceeds rapidly with rate constants of k(OH) = (1.1 ± 0.3) x 10^- ¹⁰ and k(O3) = (7.7 ± 1.9) x 10^-18 cm³ molecule^-1 s^-1. During the day, the atmospheric loss of MMT proceeds essentially entirely via photolysis. At night reaction with O₃ can be significant.

Original language	English
Pages (from-to)	4232-4238
Number of pages	7
Journal	Environmental Science and Technology
Volume	33
Issue number	23
DOIs	https://doi.org/10.1021/es990350p
State	Published - Dec 1 1999

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title = "Atmospheric chemistry of methylcyclopentadienyl manganese tricarbonyl: Photolysis, reaction with hydroxyl radicals and ozone",

abstract = "The atmospheric fate of MMT has been studied using laboratory smog chamber systems. MMT absorbs strongly in the UV-visible region from 210 to 400 nm with σ (333 nm) = (1.9 ± 0.2) x 10-18 cm2 molecule-1 and undergoes photolysis at a rate estimated to be (1.3 ± 0.1) x 10-2 s-1 for a typical summer day at a latitude of 40°N. Photolysis gives CO in a molar yield that is indistinguishable from 100\% and an unidentified species believed to be methylcyclopentadienyl manganese dicarbonyl (MMD), which also undergoes rapid photolysis liberating additional CO. Reaction of MMT with OH and O3 proceeds rapidly with rate constants of k(OH) = (1.1 ± 0.3) x 10- 10 and k(O3) = (7.7 ± 1.9) x 10-18 cm3 molecule-1 s-1. During the day, the atmospheric loss of MMT proceeds essentially entirely via photolysis. At night reaction with O3 can be significant.",

author = "Wallington, \{T. J.\} and O. Sokolov and Hurley, \{M. D.\} and Tyndall, \{G. S.\} and Orlando, \{J. J.\} and I. Barnes and Becker, \{K. H.\} and R. Vogt",

year = "1999",

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doi = "10.1021/es990350p",

language = "English",

volume = "33",

pages = "4232--4238",

journal = "Environmental Science and Technology",

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TY - JOUR

T1 - Atmospheric chemistry of methylcyclopentadienyl manganese tricarbonyl

T2 - Photolysis, reaction with hydroxyl radicals and ozone

AU - Wallington, T. J.

AU - Sokolov, O.

AU - Hurley, M. D.

AU - Tyndall, G. S.

AU - Orlando, J. J.

AU - Barnes, I.

AU - Becker, K. H.

AU - Vogt, R.

PY - 1999/12/1

Y1 - 1999/12/1

N2 - The atmospheric fate of MMT has been studied using laboratory smog chamber systems. MMT absorbs strongly in the UV-visible region from 210 to 400 nm with σ (333 nm) = (1.9 ± 0.2) x 10-18 cm2 molecule-1 and undergoes photolysis at a rate estimated to be (1.3 ± 0.1) x 10-2 s-1 for a typical summer day at a latitude of 40°N. Photolysis gives CO in a molar yield that is indistinguishable from 100% and an unidentified species believed to be methylcyclopentadienyl manganese dicarbonyl (MMD), which also undergoes rapid photolysis liberating additional CO. Reaction of MMT with OH and O3 proceeds rapidly with rate constants of k(OH) = (1.1 ± 0.3) x 10- 10 and k(O3) = (7.7 ± 1.9) x 10-18 cm3 molecule-1 s-1. During the day, the atmospheric loss of MMT proceeds essentially entirely via photolysis. At night reaction with O3 can be significant.

AB - The atmospheric fate of MMT has been studied using laboratory smog chamber systems. MMT absorbs strongly in the UV-visible region from 210 to 400 nm with σ (333 nm) = (1.9 ± 0.2) x 10-18 cm2 molecule-1 and undergoes photolysis at a rate estimated to be (1.3 ± 0.1) x 10-2 s-1 for a typical summer day at a latitude of 40°N. Photolysis gives CO in a molar yield that is indistinguishable from 100% and an unidentified species believed to be methylcyclopentadienyl manganese dicarbonyl (MMD), which also undergoes rapid photolysis liberating additional CO. Reaction of MMT with OH and O3 proceeds rapidly with rate constants of k(OH) = (1.1 ± 0.3) x 10- 10 and k(O3) = (7.7 ± 1.9) x 10-18 cm3 molecule-1 s-1. During the day, the atmospheric loss of MMT proceeds essentially entirely via photolysis. At night reaction with O3 can be significant.

UR - https://www.scopus.com/pages/publications/0033237835

U2 - 10.1021/es990350p

DO - 10.1021/es990350p

M3 - Article

AN - SCOPUS:0033237835

SN - 0013-936X

VL - 33

SP - 4232

EP - 4238

JO - Environmental Science and Technology

JF - Environmental Science and Technology

IS - 23

ER -

Atmospheric chemistry of methylcyclopentadienyl manganese tricarbonyl: Photolysis, reaction with hydroxyl radicals and ozone

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