Kinetics of the pyrolysis of propylene. Part I

Simon, Michel; Back, M. H.

doi:10.1139/v70-048

Cited by 13 publications

(12 citation statements)

References 6 publications

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“…In the pyrolysis of propylene, for example, the products of the ene reaction, hexene-1 and 4-methylpentene-1, are major products and may contribute to secondary initiation. There are other major primacy c 6 products, however, formed by radial processes [20] which could be equally important in supplying secondary initiation. In the propylene pyrolysis the processes of primary and secondary initiation have not been well-defined at all temperatures.…”

Section: Formation Of Cyclopentene and 1 -Methylcyclopentenementioning

confidence: 99%

Ene reactions of olefins, part II. The addition of ethylene to propylene and to isobutene and the addition of propylene to propylene

Richard¹,

Back

1978

Int J of Chemical Kinetics

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The pyrolysis of ethylene-propylene and ethylene-isobutene mixtures has been studied in a static system over the temperature range of 682"-754'K and for initial pressures of each olefin of 33-300 torr. The following molecular ene reactions were observed and the rate constants measured: 25f0.3--"8,000f100000/2.3R?Using thermodynamic data, rate constants for the corresponding retro-ene decomposition reactions were calculated and compared to kinetic data reported for similar compounds. Other products were formed by radical chain processes, the main higher molecular weight ones being cyclopentene and 1-methylcyclopentene. A mechanism involving addition of ally1 radicals is suggested for the formation of these products.

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Section: Formation Of Cyclopentene and 1 -Methylcyclopentenementioning

confidence: 99%

Ene reactions of olefins, part II. The addition of ethylene to propylene and to isobutene and the addition of propylene to propylene

Richard¹,

Back

1978

Int J of Chemical Kinetics

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“…In Table 2, the rates of formation of the main products from mixtures of propylene and acetaldehyde in the ratio 0.07 are compared with the rates of formation of each of these products from the pyrolysis of acetaldehyde (21) and propylene (13) separately. The rates of formation of products from the pyrolysis of 40 Torr of propylene were not measured directly, but were obtained by extrapolation of rates measured at higher pressures (100-600 Torr).…”

Section: Resultsmentioning

confidence: 99%

“…The bimolecular reaction of propylene to give radicals, either with itself or with the reactant, has not been considered in inhibition studies, but may under some conditions be faster than the unimolecular dissociation (13).…”

Section: Introductionmentioning

confidence: 99%

The Co-Pyrolysis of Acetaldehyde and Propylene

Simon¹,

Back²

1973

Can. J. Chem.

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Analysis of both major and minor products of the thermal reaction of mixtures of propylene and acetaldehyde over the temperature range 750-800 "K and a t pressures below atmospheric show that both reactants initiate radical chains and that both addition and abstraction reactions of radicals with propylene are important. The relation to general mechanisms of the inhibiting effect of propylene in pyrolysis reactions is discussed. Introduction Propylene has long been known to inhibit the decomposition of many organic compounds (1-4). The inhibition has been explained by both addition and abstraction reactions of radicals with propylene. Both reactions reduce the apparent rate of reaction, the former by the formation of higher molecular weight products which lowers the rate of pressure increase, and the latter by the substitution of the relatively non-reactive allyl radical for the more reactive chain-carrying radical. A general mechanism has been formulated for such systems by Niclause et al. (5), who developed equations describing the rate of decomposition of an organic compound as a function of the concentration of additive for various types of chain mechanisms. With propylene they assumed that the predominant effect is the substitution of the allyl radical for the normal propagating radical, and for simplicity neglected addition reactions, as had been done by other authors (6, 7), although it was acknowledged that they could have some importance. Addition reactions were considered by Quinn (8) and by Marta et al. (9) in their studies of the effect of propylene on the pyrolysis of butane and of propionaldehyde, respectively, but their importance could not be assessed with any certainty because of incomplete product analysis. The relative importance of addition and abstraction reactions is a basic question in the mechanism of inhibition by propylene and in the related effect of self-inhibition of the pyrolysis of paraffins by the prod-

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“…This covers the range of several studies, but this product was not detected [2,[16][17][18]. Most of the analyses in these studies were done at pressures of 100 or 200 torr, and since the equilibrium concentration and the rate depend on the square of the concentration of propylene, the yields of 1,2-dimethylcyclobutane would be barely detectable at the lower pressures.…”

Section: B Propylenementioning

confidence: 99%

“…Recent studies of the thermal reactions of ethylene [I] and propylene [2] have shown that in each case initiation occurs by the respective bimolecular reactions :…”

Section: Introductionmentioning

confidence: 99%

Mechanism of the bimolecular reactions of ethylene and propylene

Back

1970

Int J of Chemical Kinetics

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Rate constants for the bimolecular reactions of ethylene and propylene to form radicals and to form cyclobutane or its derivatives have been calculated using thermodynamic and kinetic data. Comparison of these rates with the kinetics of the thermal reactions of ethylene and propylene show that cyclobutane and its derivatives are probably not important intermediates in the processes forming radicals.

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Kinetics of the pyrolysis of propylene. Part I

Cited by 13 publications

References 6 publications

Ene reactions of olefins, part II. The addition of ethylene to propylene and to isobutene and the addition of propylene to propylene

Ene reactions of olefins, part II. The addition of ethylene to propylene and to isobutene and the addition of propylene to propylene

The Co-Pyrolysis of Acetaldehyde and Propylene

Mechanism of the bimolecular reactions of ethylene and propylene

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