Fourier transform infrared study of the kinetics and mechanisms for the chlorine-atom- and hydroxyl-radical-initiated oxidation of glycolaldehyde

Niki, H.; Maker, P. D.; Savage, C. M.; Hurley, M. D.

doi:10.1021/j100292a038

Cited by 62 publications

(116 citation statements)

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“…1985 have been taken from the 1986 review of Atkinson 9 . Data published during the last decade (1986)(1987)(1988)(1989)(1990)(1991)(1992)(1993)(1994)(1995)(1996) are from the original references [10][11][12][13][14][15][16][17][18] , which are listed in Table 1 for each alcohol studied. The kinetic data listed in Table 1 include OH reaction rate constants for thirty three alcohols, of which nineteen are C1-C8 monofunctional alcohols (primary, secondary and tertiary) and fourteen are difunctional alcohols including diols, hydroxy ethers, and hydroxycarbonyls.…”

Section: Reaction Rate Constantsmentioning

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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Section: Reaction Rate Constantsmentioning

confidence: 99%

“…OH addition at the C=C bond for allyl alcohol 5,6 and mostly (ca. 78%) H-atom abstraction from the carbonyl carbon for hydroxyacetaldehyde 15 .…”

Section: Reaction Rate Constantsmentioning

confidence: 99%

Atmospheric chemistry of alcohols

Grosjean¹

1997

J. Braz. Chem. Soc.

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“…An early study by Niki et al (1987) gave a branching ratio of channels (37a) and (37b) to be 0.80 : 0.20. A more recent study by Magneron et al (2005) gave 0.22±0.06 for channel (37b), and a turbulent flow study with CIMS by Butkovskaya et al (2006a) obtained yields for the reactions (37a) and (37b) as 0.84 and 0.16, respectively.…”

Section: Oh + Toluenementioning

confidence: 99%

Fundamental Heterogeneous Reaction Chemistry Related to Secondary Organic Aerosols (SOA) in the Atmosphere

Akimoto¹

2016

Monogr. Environ. Earth Planets

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Citation: Akimoto, H. (2016), Fundamental heterogeneous reaction chemistry related to secondary organic aerosols (SOA) in the atmosphere, Monogr. Environ. Earth Planets, 4, 1-45, doi:10.5047/meep.2016.00401.0001. Abstract Typical reaction pathways of formation of dicarboxylic acids, larger multifunctional compounds, oligomers, and organosulfur and organonitrogen compounds in secondary organic aerosols (SOA), revealed by laboratory experimental studies are reviewed with a short introduction to field observations. In most of the reactions forming these compounds, glyoxal, methyl glyoxal and related difunctional carbonyl compounds play an important role as precursors, and so their formation pathways in the gas phase are discussed first. A substantial discussion is then presented for the OH-initiated aqueous phase radical oxidation reactions of glyoxal and other carbonyls which form dicarboxylic acids, larger multifunctional compounds and oligomers, and aqueous-phase non-radical reactions which form oligomers, organosulfates and organonitrogen compounds. Finally, the heterogeneous oxidation reaction of gaseous O 3 , OH and NO 3 with liquid and solid organic aerosols at the air-particle interface is discussed relating to the aging of SOA in the atmosphere.

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“…OH + HOCH 2 CHO. The available data are from relative rate studies at 298 K(Bacher et al [61], Niki et al [995], and Mellouki et al [900]). The recommendation is based on all these studies, which are in good agreement.…”

Section: -41mentioning

confidence: 99%