Industrial & Engineering Chemistry Research · 2008 · 23 citations · 21 references
EngineeringChemistryDimethyl ItaconateSolution (Chemistry)Chemical EngineeringBiphasic SystemHomogeneous CatalysisMolecular KineticsRhodium ComplexCatalysisHydrogenCatalytic SynthesisReaction EngineeringFree DmiHeterogeneous CatalysisCatalytic HydrogenationMolecular CatalysisReaction ProcessChemical Kinetics
The kinetics of the catalytic hydrogenation of dimethyl itaconate (DMI) was studied in a biphasic cyclohexane−water system and in a [Triton X-100/1-pentanol]/cyclohexane/water microemulsion, in both cases using the water-soluble catalyst complex Rh−TPPTS. The reaction was carried out at a pressure of 1.1 bar and in the temperature range 298−308 K. A typical profile of a zero-order reaction was observed in the case of the biphasic system. Against that the reaction order for DMI changed to 1 in a microemulsion. A rate law based on an Osborn−Wilkinson-like kinetics was used to describe the experimental results which were governed by the irreversible attack of free DMI at the rhodium complex. The activation energy of the rate-determining step is 53 kJ mol−1 and is similar in both systems.
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John A. Osborn, F. H. Jardine, J.F. Young et al. · Journal of the Chemical Society A Inorganic Physical Theoretical · 1966 · 1.4K citations
William S. Knowles · Accounts of Chemical Research · 1983 · 730 citations