Reactions of free radicals associated with low temperature oxidation of paraffins

Bell, E. R.; Raley, John H.; Rust, Frederick F.; Seubold, Frank H.; Vaughan, Worth E.

doi:10.1039/df9511000242

Cited by 155 publications

(48 citation statements)

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“…However, it can be concluded that the nature of the reaction products identified in this work indicates that there must be a complete analogy between the mechanisms of the thermal decomposition of the cyano-alkyl peroxides and that of the corresponding alkyl peroxides. In other words, a reaction scheme similar to that proposed by Vaughan et al (7), for the liquid phase deconlposition of t-butylhydroperoxide, can be used to account for the decomposition of cyanisopropyl hydroperoxide, if it is assumed that dismutation of cyanisopropoxy radicals, (NC)(CHJ*C-Q., produced by cleavage of the 0-0 bond, gives .CN free radicals. A similar mechanism mould be applicable t o the inore unstable di-(cyanisopropyl) peroxide.…”

Section: Discussionmentioning

confidence: 99%

The Reaction of 2-Cyano-2-Propyl Free Radicals With Oxygen: 2-Cyano-2-Propyl Hydroperoxide

Talât-Erben¹,

Önol²

1960

Can. J. Chem.

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The reaction with oxygen of cyanisopropyl free radicals generated by the polymerization catalyst 2,2′-azobisisobutyronitrile has been investigated. In xylene, or benzene, as solvent at 55° the products identified are: (1) a new compound, 2-cyano-2-propyl hydroperoxide; (2) acetone cyanohydrin; (3) hydrogen cyanide; (4) cyanogen; (5) acetone; (6) p-methyl benzaldehyde (in xylene only); and (7) tetramethylsuccinodinitrile. The hydroperoxide is surprisingly stable; its physical constants are: b.p. 37 °C at 1 mm Hg; m.p. −9 to −8°; [Formula: see text] 1.4138; d20 1.013 g/ml. In benzene under the same experimental conditions, only a very small amount of the hydroperoxide is obtained, the principal product being acetone cyanohydrin. A free-radical mechanism is proposed. The induced decomposition of the hydroperoxide, which is important in benzene, is almost completely inhibited in the presence of xylene. The new hydroperoxide can be used as a polymerization catalyst at moderately elevated temperatures.

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Section: Discussionmentioning

confidence: 99%

The Reaction of 2-Cyano-2-Propyl Free Radicals With Oxygen: 2-Cyano-2-Propyl Hydroperoxide

Talât-Erben¹,

Önol²

1960

Can. J. Chem.

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“…At very low conversions, -1/2% in this work, the concentration of performic acid is too low to affect the course of the reaction and a short chain reaction occurs (at 162" C aN, + aNZO extrapolates to 2.5 a t zero conversion). As conversion increases performic acid is coilsumed in [14], [15], and [16], leading to new products-the oxides of carbon-so that its concentration is held a t a low, stationary level which was not detected analytically. This particular scheme has the advantage that the production of carbon dioxide with an induction period is also accounted for explicitly.…”

Section: Depelzdence Of Products O N Co~zversionmentioning

confidence: 99%

“…The product of [5] is almost certainly a methyl peroxy radical, and some scheme must be devised to transform the peroxy methyl radical to a methoxy. Using an earlier suggestion of Bell et al (14) reaction [lo] has been postulated for this conversion (I).…”

Section: N20 ( P M O L E )mentioning

confidence: 99%

The Photooxidation of Azomethane. Iii

Wenger¹,

Kutschke²

1959

Can. J. Chem.

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I t is confirmed t h a t the yields of all products in the photooxidation of azomethane a t relatively high oxygen pressure depend on conversion in a manner which would be explained if a reactive hydrogen donor were produced in the early stages of the reaction. Evidence is presented which indicates t h a t formaldehyde cannot be active as a n inhibitor in the system a t 162' C. I t is suggested that methyl radicals react with oxygen in two ways. The third order formation of methyl peroxy radicals leads to methoxy radicals and, eventually, to methanol, while the bimolecular reaction between methyl radicals and oxygen leads to a vibrationally excited state of formaldehyde. Thc latter is thought to undergo oxidization to performic acid, which acts as the inhibitor in the system. Yields of formaldehyde, of nitrogen in excess of that formed in the primary process, and of nitrous oxide are linearly related regardless of the conversion up to about 4%. Methanol is a major product of the oxidation and, if account is taken of its yield, a carbon balance of the order of 90% is obtained.

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“…The basic mechanism of liquid phase oxidation, viz. formation of alkyl hydroperoxides by the reaction of alkylperoxy radicals with hydrogen atom donors, which can be the hydrocarbon itself, has been well established [8],…”

Section: Resultsmentioning

confidence: 99%

Emission FTIR analyses of thin microscopic patches of jet fuel residues deposited on heated metal surfaces

Lauer

Vogel

1984

Applied Surface Science

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Reactions of free radicals associated with low temperature oxidation of paraffins

Cited by 155 publications

References 0 publications

The Reaction of 2-Cyano-2-Propyl Free Radicals With Oxygen: 2-Cyano-2-Propyl Hydroperoxide

The Reaction of 2-Cyano-2-Propyl Free Radicals With Oxygen: 2-Cyano-2-Propyl Hydroperoxide

The Photooxidation of Azomethane. Iii

Emission FTIR analyses of thin microscopic patches of jet fuel residues deposited on heated metal surfaces

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