Tracer studies of acid-catalyzed reactions

Hightower, Joe W.; Gerberich, H. R.; Hall, W. Keith

doi:10.1016/0021-9517(67)90007-3

Cited by 19 publications

(4 citation statements)

References 22 publications

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“…Experiments justifying this assumption are reported elsewhere. 6 The equations were used as follows. Suppose the starting mixture were 1-butene with a trace of radioactive m-2-butene.…”

Section: Methodsmentioning

confidence: 99%

Tracer studies of acid-catalyzed reactions. V. Carbon-14 kinetic studies of n-butene isomerization over alumina and silica-alumina catalysts

Hightower¹,

Hall²

1967

J. Phys. Chem.

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101

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“…Experiments justifying this assumption are reported elsewhere. 6 The equations were used as follows. Suppose the starting mixture were 1-butene with a trace of radioactive m-2-butene.…”

Section: Methodsmentioning

confidence: 99%

Tracer studies of acid-catalyzed reactions. V. Carbon-14 kinetic studies of n-butene isomerization over alumina and silica-alumina catalysts

Hightower¹,

Hall²

1967

J. Phys. Chem.

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101

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“…The isomerization of olefins was studied in a number of publications during the past (18)(19)(20)(21)(22)(23)(24)(25)(26)(27)(28)(29)(30)(31)(32)(33)(34)(35). Double-bond and cis-trans isomerization, as well as the skeletal rearrangement of these substances, were in the focus of interest (e.g., (18,19,33)).…”

Section: Introductionmentioning

confidence: 99%

Dehydrogenation of Light Alkanes over Zeolites

Narbeshuber

Brait

Seshan

et al. 1997

Journal of Catalysis

112

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The conversion of light paraffins to olefins and the secondary reactions of the unsaturated compounds were investigated on H-ZSM5 and H-Y zeolites between 733 and 823 K. Steady stateand transient response-isotope tracing studies revealed that two mechanisms of dehydrogenation are operative. The main pathway is represented by monomolecular, protolytic dehydrogenation. This reaction contributes most to steady state olefin production. Additionally, at the initial stages of the reaction, extra framework aluminum moieties are speculated to participate in high dehydrogenation activity. This pathway is blocked at later stages of the reaction by product (hydrogen) inhibition. The intrinsic rates of protolytic dehydrogenation and olefin desorption range in the same order of magnitude. At high protolytic dehydrogenation rates, olefin desorption represents the rate determining step. Depending on the process conditions, olefins undergo secondary cracking, oligomerization, or isomerization. The latter proceeds via intramolecular rearrangement, possibly via a cyclopropylcarbenium ion at high temperatures and low conversions. At reaction conditions where bimolecular cracking prevails, isomerization is concluded to occur via secondary cracking of di-or oligomers.

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“…If the simplified schematic indicated by Equations 3 and 4 is correct, we may expect in general that different activation energies would characterize the two reactionsfor example, Hightower et al (1967) on the isomerization kinetics of 1-butene over fluorided alumina. If this occurs, the extent of secondary isomerization would be different at the two temperatures, for a given conversion.…”

Section: )mentioning

confidence: 99%

“…Since the initial report, a number of catalysts, both heterogeneous (Heckelsberg et al., 1968, 1969) and homogeneous (Cal-To whom correspondence should be addressed. deron et al., 1967;Zuech, 1968), that are active for disproportionating olefins have been disclosed. The abundance of data, including results of mechanistic studies (Bradshaw et al, 1967;Clark, 1968;Crain, 1969;Mol et al, 1968), indicates that the reaction proceeds by two unsaturated pairs of carbon atoms combining in a four-center transition state which dissociates by breaking either set of opposite bonds.…”

Section: Synthesis Of Isoamylene Via Olefin Disproportionationmentioning

confidence: 99%