The Production of Free Radicals from Ethylene Oxide and the Catalysis of Other Reactions by Them

Fletcher, C. J. M.; Rollefson, G. K.

doi:10.1021/ja01302a014

Cited by 24 publications

(8 citation statements)

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“…Table II Major Products of the Decomposition of Acrolein in Benzene" at 500°M ole ratio acrolein/benzene = 2.00; contact time, 9.8 3 As was the case in toluene, small amounts of other substances were obtained, but these were not investigated.…”

Section: Resultsmentioning

confidence: 99%

Thermal Decomposition of Acrolein. The Attack of Methyl and t-Butoxy Free Radicals on Acrolein

Castro¹,

Rust²

1961

J. Am. Chem. Soc.

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The thermolysis of gaseous solutions of acrolein in the 500-600" region yields principally carbon monoxide, ethylene. propylene, hydrogen, methane, ethane, 1,3-butadiene and 1-butene in decreasing order of importance. The results are rationalized in part by a short chain decomposition of the aldehyde through vinyl radicals for which the unstable acrylyl fragment is a precuisor. Studies of the methyl radical induced decomposition of acrolein at 250" in the gas phase and the f-butyl hypochlorite photochlorination of the aldehyde a t 22" in solution allow rough approximations of kaddltlan/kabbtraction for methyl and t-butoxy free radicals to be made. These estimates are 4 and (max.), respectively.OXAR 51:. STEWAKI) . I XD OGDEN R. PIERCE Vol. 83 glycol column resolved carbon tetrachloride, t-butyl alcohol and t-butyl acrylate from a mixture of acrolein and acetone. The acrolein-acetone pair was resolved on P,B'-oxydipropionitrile. The blip corresponding to t-butyl acrylate was trapped ten times from the triethylene glycol column. Its infrared spectrum was identical with the spectrum of authen-A&nowledgment.-The authors are indebted to >/lr, F. L. ~~d~~~~ for patient assistance with the experimentation.128) This substance was prepared in poor yield from acrylyl chloride and l-butyl alcohol in t h e presence of P\TazCOj; b.p. 56' (80 m m . ) ,The first-order rate constaiits for the acid-catalyzed hydrolysis of sixteen fluoroalkyl-, w-cyanoalkyl-and n-alkylsiliconThe first-The correlations are discussed in terms of polar effects, hydrides have been determined using aqueous ethanolic hydrochloric acid (1.43 N , 95 v o l . -~, ethanol) a t 34.8". order rate constants are correlated using the Taft equation. steric effects and dative r-bonding.

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Section: Resultsmentioning

confidence: 99%

Thermal Decomposition of Acrolein. The Attack of Methyl and t-Butoxy Free Radicals on Acrolein

Castro¹,

Rust²

1961

J. Am. Chem. Soc.

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“…Fletcher and Rollefson (79,81) reinvestigated the reaction with special emphasis on the role of free radicals Their work led them to postulate a mechanism of the type suggested by Sickman, but of a more detailed nature: This mechanism is in good agreement with their rate measurements, analyses for formaldehyde and acetaldehyde, etc. By assuming that all the hydrogen found in the products comes from the decomposition of formaldehyde formed by reaction 1, and that all the ethane comes from reaction 5, they calculate that 14 per cent of the ethylene oxide decomposes by reaction 1.…”

Section: The Exact Relation Is and 2qukakbmentioning

confidence: 72%

“…Many investigations have been made using ethylene oxide as a sensitizer (58,79,80,81,121,287). The production of carbon monoxide has usually been used as an indication of the amount of decomposition of ethylene oxide, and hence of the number of methyl radicals generated in the system.…”

Section: The Exact Relation Is and 2qukakbmentioning

confidence: 99%

Experimental Methods of Determining the Activation Energies of Elementary Reactions.

Steacie¹,

LeRoy²

1942

Chem. Rev.

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“…less stable than its isomer CH3CH0 and it decomposes thermally at temperatures about 100' C. lower than the latter; in fact EO can be used to sensitize the thermal decomposition of CH,CHO (22). This compound is some 28 kcal.…”

Section: A C T 1 V I T Y T R a N S F E Rmentioning

confidence: 99%

Predictability of Chain Reactions

Benson¹

1964

Ind. Eng. Chem.

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The characteristic of a chain reaction is that the sum of the chain (or propagation) steps yields the overall reaction stoichiometry-the chain carriers canceling out in the addition. The closed reaction sequence involving the intermediates in a pyrolytic reaction is shown above (see Equation E). Reactant is consumed and products produced, but the concentration of intermediates which propagate the reaction is controlled only by distinct initiation and termination steps. The number of over-all reactions between the initiation and termination steps is called the chain length.In this article, pyrolytic and metathetical chain reactions are discussed in terms of our recently acquired knowledge of prototypes of their component steps-initiation, transfer, propagation, and termination.Predictability of products and product ratios is shown to be fairly good using Rice-Hertzfeld mechanisms and known data for radical reactions. Some semiquantitative generalizations concerning radical step reactions lead to about order-of-magnitude ability to predict overall chain rates.

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The Production of Free Radicals from Ethylene Oxide and the Catalysis of Other Reactions by Them

Abstract: pressure was 8.8 * 1.0 mm. after 8% pressure increase, and 3.8 * 1.0 mm. after 25% pressure increase.

Cited by 24 publications

References 0 publications

Thermal Decomposition of Acrolein. The Attack of Methyl and t-Butoxy Free Radicals on Acrolein

Thermal Decomposition of Acrolein. The Attack of Methyl and t-Butoxy Free Radicals on Acrolein

Experimental Methods of Determining the Activation Energies of Elementary Reactions.

Predictability of Chain Reactions

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