Mechanistic Comparison of Heterogeneous and Homogeneous Hydrogenation*

Augustine, Robert L.; Peppen, Jan Van

doi:10.1111/j.1749-6632.1969.tb56202.x

Cited by 14 publications

(6 citation statements)

References 35 publications

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“…One of the most famous mechanisms for aromatic hydrogenation over Pt catalyst is the Horiuti−Polanyi (H−P) mechanism, − which assumes an atomic hydrogen addition to aromatics on the catalyst surface. Applying the H−P mechanism in reverse to MCH dehydrogenation will result in a rate equation very similar to the one previously derived for the LHHW kinetic model.…”

Section: Resultsmentioning

confidence: 99%

Kinetic Model of the Dehydrogenation of Methylcyclohexane over Monometallic and Bimetallic Pt Catalysts

AlHumaidan

Cresswell

Garforth

2010

Ind. Eng. Chem. Res.

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Various kinetic models were developed for methylcyclohexane (MCH) dehydrogenation over supported Pt catalysts. The best fitting mechanistic model is of the non-Langmuirian/noncompetitive Horiuti-Polanyi type. In this model, the Horiuti-Polanyi aromatic hydrogenation mechanism, which assumes an atomic hydrogen addition to aromatics on the catalyst surface, is applied in reverse to MCH dehydrogenation. The model also assumes that hydrogen and MCH molecules adsorb noncompetitively on two different types of sites to accommodate the observed near zero-order dependence of reaction rate on MCH and the negative order dependence upon hydrogen. To account for the increase in the hydrogen inhibition effect with pressure, a non-Langmuirian adsorption isotherm is adopted, which assumes a nonlinear dependency between the adsorption equilibrium constant for hydrogen and the system pressure. The reversible and irreversible deactivation kinetics are satisfactorily included in the kinetic model.

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Section: Resultsmentioning

confidence: 99%

Kinetic Model of the Dehydrogenation of Methylcyclohexane over Monometallic and Bimetallic Pt Catalysts

AlHumaidan

Cresswell

Garforth

2010

Ind. Eng. Chem. Res.

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“…An example of this effect on product composition is the hydrogenation of 4-t-butylmethylenecyclohexane, (4), with both the cis, 5, and trans, 6, products formed in varying proportions depending on the catalyst and hydrogen pressure used [30, 311 (Table 3). In this instance the greater amount of 5 which is formed at lower pressures is ascribed to the greater stability of that half-hydrogenated species which has the carbon-metal absorption bond equatorial to the cyclohexane ring as in 8.…”

Section: H+c-c=====cc-c (3)mentioning

confidence: 99%

Organic Functional Group Hydrogenation

Augustine

1976

Catalysis Reviews

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“…(Pd). The topic of relating homogeneous and heterogeneous catalytic systems has been discussed extensively in recent years59 8,9,24,28,46,47 (to mention just a few references related to the subject). It is tempting to speculate that homogeneous hydrogen activation by strong "ordinary" bases, e.g.…”

Section: Summary and Concluding Remarksmentioning

confidence: 99%