Reaction of Oxygen Atoms With Butadiene

Cvetanović, R. J.; Doyle, L. C.

doi:10.1139/v60-296

Cited by 20 publications

(7 citation statements)

References 5 publications

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“…The pressure effect in the rate of formation of carbon monoxide strongly suggests that this compound is fornled from decomposition of an energy-rich adduct as has been observed in the same pressure range in the cases of propylene (2) and 1,3-butadiene (15). With increasing pressure the excess energy tends to be renloved by collisions fro111 the "l~ot" product before it decon~poses and carbon n~onoxide production tllerefore decreases.…”

Section: Discussioxmentioning

confidence: 69%

Reaction of Oxygen Atoms With Benzene

Boocock¹,

Cvetanović²

1961

Can. J. Chem.

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The reaction of benzene with oxygen atoms produced by mercury photosensitized decomposition of ~litrous oside has been studied in a circulating systern a t roorn temperature. The maill reaction product is a non-volatile material probably largely aldehydic in character. This is tentatively assumed to result from the rearrangetnentand polymerization of the initially for~ned aclduct. Smaller alllou~lts of phenol and carbon monoxide are also formed. The rate of forlllatioll of carbon monoxide decreases with increasing pressure, suggesting an energyrich precursor.Oxygen atoms react with benzene much more slowly than with olefines. At 120" cyclopentene reacts about 150 times more quickly than benzene. 'The activation energy of the reaction of oxygen atoms with benzene has been estimated a t -1.6 to -1.9 kcal/rnole, with a n uncertainty of about 0.7 kcal/mole. INTRODUCTIOSReactions of a nurnber of unsaturated hydrocarbons with oxygen atoms generated by the mercury photosensitized decolnpositio~l of nitro~ls oxide have been studied in some detail in this laboratory, but attention has previously been concelltrated on alkenes and cycloalltenes (1-3). The present investigation is a further stage in these studies and has been u~ldertaltell in an attempt to derive some information on the attack of ground state oxygen atoms on an aronlatic n~~cleus. Unfortunately, the major part of the reaction product, a poly~neric inaterial of low volatility, could not be characterized; only a fraginentary pict~lre of the process has therefore been obtained. This is in sharp contrast to the relativelj-well-understood nlajor feat~ii-cs of the reactions of oxygen atoms with alkenes.Early attempts to obtain approximate valucs oi the rates of reactions of a nulllber of compounds with oxygen atonls (4) led to the co~lclusioll that benzene reacted very rapidly with oxygen atoms. In the present work, however, this reaction is found to be much slower tllall the corresponding reactions of alkenes. I n view of the electrophilic character of oxygen atoms (3), this finding is not ~lnexpectecl.Several worlters (4-7) have iilvestigated the reaction of beilzelle with oxygen atoms generated i l l electrical discharges. Chu, -\i, and O t l~n~e r (8) useel a flow system and generated oxITgell atollls by electrical discharge in illolecular oxygen. They obtained phenol yields of LIP to 13% per pass, in substantial agreement with the previous filldings of Avramenlto and co-workers (7). I-Iolvever, with water vapor instead of oxygen discharge they founcl no detectable amouint of phenol although rlvramenlto et al. clainled yields of up to 27% ~11lder si~llilar conditions.The presence of other reactive species and the need to rnaintaiil relatively low over-all pressures seriousl>~ conlplicate the use of electrical discharges in molecular oxygeil or in water vapor for fundaineiltal studies of the reactions of oxygen ato~lls with organic compouncls. Some of the potential complexities liave beell discussed elsewhere (8) in co~lllectioil with a s t~l d y of th...

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Section: Discussioxmentioning

confidence: 69%

Reaction of Oxygen Atoms With Benzene

Boocock¹,

Cvetanović²

1961

Can. J. Chem.

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“…For isoprene, Killus and Whitten [21] hypothesized 40% epoxides, and 30% aldehydes and 30% decomposition products with concomitant free radical production. Cvetanovik and Doyle [23] studied the O(3P) reaction with butadiene and found about 30% butene oxide and 22% 3-butenal (which results from 1,2 hydrogen transfer), uncorrected for any reactions with other radicals that may have formed in their system. In sharp contrast, we find about 84% epoxides, 3-12% decomposition products, and 9-19% terminal aldehydes and rearranged products, of which 0-9% result from 1,2 hydrogen transfer.…”

Section: Ground State Atomic Oxygen-isoprene Reactionmentioning

confidence: 99%

Atmospheric photooxidation of isoprene part I: The hydroxyl radical and ground state atomic oxygen reactions

Paulson

Flagan

Seinfeld

1992

Int J of Chemical Kinetics

204

186

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The OH reaction with isoprene is studied. Methyl nitrite photolysis experiments were carried out in an outdoor smog chamber in a n attempt to identify as completely as possible OHisoprene product distribution. Emphasis was placed on identification and quantification of oxygenated products. A Tenax-based cryo-trap thermal desorber used to trap, concentrate, and dry chamber samples for identification on a GC/MS is described. Analysis of the products revealed that O(3P) can form in reaction systems designed to study OH reactions that include high concentrations of NO, and consequently NOz, hence, this reaction is also examined. The yields of methacrolein and methyl vinyl ketone are determined as 25 t 3 and 35.5 t 4%, respectively, with an additional 4 t 2% as 3-methyl furan, totaling 65 t 4%. These results, combined with those of previous studies allow 80% of isoprene's products to be explicitly identified, and the general structure of the remaining products to be ascertained. The O(3P) reaction produces 84 5 8% epoxides, and 8 t 3% species which result in production of HOa, and subsequently, OH. A heretofore unidentified product of the O(3P) reaction, 2-methyl2-butenal, is identified. The rate constant of the N02-isoprene reaction is measured.

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“…1. 14,46,98, 127], Jones and Cvetanovic [52], Kato and Cvetanovic [39,59], Cvetanovic and Doyle [121], and Ref. Data, Vol.…”

Section: S Alcohols Aldehydes and Miscellaneous Oxygen Containinmentioning

confidence: 99%

Rate Constants for the Reactions of Atomic Oxygen (O 3P) with Organic Compounds in the Gas Phase

Herron¹,

Huie²

1973

Journal of Physical and Chemical Reference Data

187

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Rate constants for the reactions of atomic oxygen (0 ap) with organic compounds in the gas phase are compiled and critically evaluated. Data are given here as originally. reported in the literature for a total of 107 organic reactants. FrGm a critical evaluation of the data: recommended values for rate constants are given over specified temperature intervals, and where possible at 298 K and 1000 K.

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Reaction of Oxygen Atoms With Butadiene

Cited by 20 publications

References 5 publications

Reaction of Oxygen Atoms With Benzene

Reaction of Oxygen Atoms With Benzene

Atmospheric photooxidation of isoprene part I: The hydroxyl radical and ground state atomic oxygen reactions

Rate Constants for the Reactions of Atomic Oxygen (O 3P) with Organic Compounds in the Gas Phase

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