Gas‐phase chlorine‐initiated photooxidation of methanol and isopropanol

Ohta, Tomohiro; Bandow, Hiroshi; Akimoto, Hajime

doi:10.1002/kin.550140207

Cited by 27 publications

(28 citation statements)

References 16 publications

(9 reference statements)

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“…The product measurements from reactions of alcohols with OH radicals and CI atoms are consistent with the major pathways involving a-hydrogen abstraction which forms CH2OH, CH3CHOH, and (CH3)2COH radicals (Carter et al, 1979;Washida, 1981;Ohta et al, 1982;Meier et al, 1985). The CH2OH radical reacts with 02 to form as products 93% CH20 and 7% HCOOH (Ohta et al, 1982). Branching ratios for the formation of CH3CHOH radicals from the reactions of CH3CH2OH reactions with OH radicals or CI atoms are reported as 80 + 15% (Carter et al, 1979) and 75 + 15% (Meier et al, 1985).…”

Section: Oxygenated Organic Compoundssupporting

confidence: 52%

Section: Oxygenated Organic Compoundssupporting

confidence: 51%

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The production of carbon monoxide by the homogeneous NO x -induced photooxidation of volatile organic compounds in the troposphere

Altshuller

1991

J Atmos Chem

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The reaction mechanisms of products, along with their rates of reaction with hydroxyl radicals and their rates of photolysis, have been used to obtain carbon monoxide, CO, yields from the products of the homogenous atmospheric photooxidation from emissions of hydrocarbons and other volatile organic compounds, VOCs. Seasonally averaged CO yields are estimated for a number of types of VOCs. The annual production of CO is estimated for the contiguous United States from combustion sources of CO and from the atmospheric photooxidation of anthropogenic and biogenic emissions of volatile organic compounds. Limitations on estimates of CO yields and of CO production from various heterogeneous processes are discussed.

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Section: Oxygenated Organic Compoundssupporting

confidence: 52%

Section: Oxygenated Organic Compoundssupporting

confidence: 51%

The production of carbon monoxide by the homogeneous NO x -induced photooxidation of volatile organic compounds in the troposphere

Altshuller

1991

J Atmos Chem

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“…Perhaps surprisingly considering the current importance of alcohols in urban atmospheric chemistry, only a few studies have been carried out to characterize the products of the OH-alcohol reaction 14, [22][23][24][25][26] . Several of these laboratory studies have included the alcohol-chlorine atom reaction instead of, or in addition to, the alcohol-OH reaction (the two reactions involve similar mechanisms and lead to the same products, see reactions 1a and 1c).…”

Section: Product Studies and Reaction Mechanismsmentioning

confidence: 99%

“…The reaction of methanol with chlorine atoms has been studied by Ohta et al 22 and by Whitbeck 23 . The only product identified was formaldehyde.…”

Section: Methanolmentioning

confidence: 99%

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Atmospheric chemistry of alcohols

Grosjean¹

1997

J. Braz. Chem. Soc.

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A química atmosférica dos álcoois, os quais são largamente empregados como combustíveis de veículos leves (como o etanol no Brasil) e solventes industriais, foi revista com o foco centralizado em seus aspectos de cinética e mecanismos de reação. A oxidação dos álcoois na atmosfera envolve sua reação com radicais hidroxil (OH). São apresentadas constantes de velocidade para a reação álcool-OH de 33 álcoois saturados, incluindo compostos mono e difuncionais. As meias-vidas atmosféricas são, respectivamente, de uma semana para metanol e t-butil álcool, 2,5 dias para etanol, e de 8-15 h para outros álcoois. São descritos estudos de laboratório para os produtos de reações álcool-OH, e mecanismos são assinalados. Os produtos que predominam são o formaldeído para o metanol, acetaldeído para etanol, acetona para 2-propanol, 2-butanona e acetaldeído para o 2-butanol e acetona e formaldeído para o t-butil álcool.A reação de OH com os álcoois envolve a abstração de um átomo de hidrogênio da ligação C-H, ao passo que na ligação O-H esta abstração é negligível. Os radicais alquil (R) e α-hidroxialquil assim formados reagem então com oxigênio. Essa reação envolve adição para os radicais alquil (R + O2 → RO2) e abstração de H dos radicais α-hidroxialquil (ex. etanol + OH → CH3CHOH, CH3CHOH + O2 → HO2 + CH3CHO). A sequência de reações etanol → acetaldeído → nitrato de peroxiacetila (PAN, CH3C(O)OONO2) é descrita, sendo de grande relevância para a poluição atmosférica urbana no Brasil.Finalmente, recomenda-se que se façam estudos adicionais dos produtos, de maneira a desenvolver uma melhor compreensão da química atmosférica dos álcoois, e de seu papel na qualidade do ar urbano e regional.The atmospheric chemistry of alcohols, which are widely used as motor vehicle fuels (e.g. ethanol in Brazil) and as industrial solvents, has been reviewed with focus on kinetic data and on reaction mechanisms. Oxidation of alcohols in the atmosphere involves their reaction with the hydroxyl radical (OH). Alcohol-OH reaction rate constants are presented for 33 saturated alcohols including monofunctional and difunctional compounds. The corresponding atmospheric half-lives are one week for methanol and t-butyl alcohol, 2.5 days for ethanol, and 8-15 h for other alcohols. Laboratory studies of alcohol-OH reaction products are described and reaction mechanisms are outlined. Major products are formaldehyde from methanol, acetaldehyde from ethanol, acetone from 2-propanol, 2-butanone and acetaldehyde from 2-butanol and acetone and formaldehyde from t-butyl alcohol.The reaction of OH with alcohols involves H-atom abstraction from C-H bonds; H-atom abstraction from the O-H bond is negligible. The alkyl radicals (R) and α-hydroxyalkyl radicals thus formed react with oxygen. This reaction involves addition for alkyl radicals (R + O2 → RO2) and H-atom abstraction for α-hydroxyalkyl radicals (e.g. ethanol + OH → CH3CHOH, CH3CHOH + O2 → HO2 + CH3CHO). The reaction sequence ethanol → acetaldehyde → peroxyacetyl nitrate (PAN, CH3C(O)OONO2) is described and is r...

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A kinetic and product study of the gas-phase reaction of ozone with vinylcyclohexane and methylene cyclohexane

Grosjean¹,

Grosjean²

1997

Int. J. Chem. Kinet.

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Gas‐phase chlorine‐initiated photooxidation of methanol and isopropanol

Cited by 27 publications

References 16 publications

The production of carbon monoxide by the homogeneous NO x -induced photooxidation of volatile organic compounds in the troposphere

The production of carbon monoxide by the homogeneous NO x -induced photooxidation of volatile organic compounds in the troposphere

Atmospheric chemistry of alcohols

A kinetic and product study of the gas-phase reaction of ozone with vinylcyclohexane and methylene cyclohexane

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