Thermal Rearrangements among the Pentenes

Hurd, Charles D.; Goodyear, George H.; Goldsby, A. R.

doi:10.1021/ja01293a013

Cited by 13 publications

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“…Frey and Hepp (15) found only olefins with double bonds at the point of scission of smaller products from the initial paraffin, and the butene obtained by thermal decomposition of n-pentane has been identified (15,31) as 1-butene. In view of the interconversion of 1-and 2-butene (21) and of 1-and 2-pentene (22) during partial decomposition, it appeared possible that other than 1-alkenes would result from pyrolysis of n-octane. Identification of the chemical individuals formed was therefore undertaken to prove or disprove the absence of isomerized decomposition products.…”

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confidence: 99%

Thermal Decomposition of n-Octane

Marschner¹

1938

Ind. Eng. Chem.

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Because of the lack of complete and accurate thermal decomposition data upon normal paraffins between hexane and hexadecane, the behavior of n-octane in the neighborhood of 570" C. and at atmospheric pressure was studied. The noctane was isolated from petroleum in quantities large enough to permit the determination of the amounts of essentially all its pyrolysis products. The effect of temperature, extent of decomposition, and nature of the apparatus in which pyrolysis was effected were studied. A slight revision of the free-radical theory improves somewhat its agreement with the experimental data. The effect of a carbonized surface upon the pyrolysis was studied, and the bearing of these results upon the theory of thermal decomposition is discussed. The liquid products obtained were thoroughly examined for evidences of rearrangement of olefins and of isomerization of the carbon skeleton. A semiquantitative analysis of all the chemical individuals found among the liquid hydrocarbons is presented. The probable manner in which they were produced, as indicated by the evidence available, is outlined. M ANY thorough researches upon the thermal decomposition of alkanes a t atmospheric pressure have been published recently, but nearly all of this work has been carried out upon the relatively simple gaseous members of the series. A certain amount of attention has been given to much larger alkanes. Hexadecane was extensively studied by Gault (1 7) and an approximately thirty-carbon paraffin by Waterman (50). However, because of the large number of gaseous and particularly of liquid products which result, complete and accurate analyses of all products have not been obtained as in the case of the small homologs. With the notable exception of the investigations of Frey and Hepp (15), little work has been done upon the pyrolysis of alkanes of intermediate carbon content. This is somewhat surprising, since efficient columns for the fractionation of gases (36) and liquids (IS), permitting analysis of the complex mixtures resulting from the decomposition of relatively small amounts of hydrocarbon, have been available for several years. To bridge this gap, the present work was undertaken; the compound chosen was n-octane.Several workers have reported preliminary studies upon n-octane pyrolysis; their results are condensed in Table I.The data are of little value because of the few accurate determinations of time and extent of decomposition. Such gas analyses as are reported show little concordance. Moldavskir (SO) observed that pressure exerted a marked influence on the pyrolysis and that iron exhibited a catalytic effect. Hugel and Szayna (19) obtained evidence of splitting at all carbon-to-carbon linkages of the molecule in nickel and iron apparatus. Decomposition in the presence of added catalysts has also been reported (IO, 28, 99, 35, 64). Much more thorough work by Dintzes and associates (6-8) coincided with the present study; similar experimental conditions were employed, with the single exception that decomposition was car...

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confidence: 99%

Thermal Decomposition of n-Octane

Marschner¹

1938

Ind. Eng. Chem.

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confidence: 99%

“…The conversion of pentene-1 into butadiene may proceed in two ways: A preliminary isomerization into pentene-2 suggests itself from the work of Hurd (70, 74). An alternative mechanism, available for high thermal input rates, consists of demethanation by (a) activation of the double bond, (6) loss of a hydrogen atom in the /3-position to the activated'double bond, (c) formation of pent-2en-l-yl (CH2CH=CHCH2CH3) from pentane-1,2,3-triyl (CH2CHCHCH2CH3), (d) full activation of the C-C bond holding the terminal methyl group, and (e) union of atomic hydrogen and the free methyl radical to form methane:…”

Section: Pentenesmentioning

confidence: 99%

Conversion of Hydrocarbons into Butadiene.

Egloff¹,

Hulla²

1944

Chem. Rev.

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“…Hurd, Goodyear and Goldsby (51) found that the thermal reaction of pentene-1 yielded at 580-600°C. small amounts of pentene-2, trimethylethylene, re-butane, isobutane, and larger amounts of isopropylethylene.…”

Section: Molecules With Five Carbon Atomsmentioning

confidence: 99%

Isomerization of Hydrocarbons.

Wilson¹

1937

Chem. Rev.

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Thermal Rearrangements among the Pentenes

Cited by 13 publications

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Thermal Decomposition of n-Octane

Thermal Decomposition of n-Octane

Conversion of Hydrocarbons into Butadiene.

Isomerization of Hydrocarbons.

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