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• W2083173313 abstract "The dependence of the rate of hydrogenolysis of C2H6, C3H8, andn-C4H10on 0.3% Pt/Al2O3(AKZO CK303, EUROPT-3) has been determined at several temperatures, using short reaction pulses to minimise deactivation by carbon deposition. Rate maxima, which with C2H6occur at very low H2pressures, become broader and move to higher H2pressures as the chain-length or temperature increases. Criteria for selecting an appropriate rate expression with which to model the results is discussed in detail: one is selected that is based on the competitive chemisorption of the reactants, that of the alkane requiring the loss of more than one H atom to activate it. For each data set, optimum values of the constants of the rate equation are obtained by computation. Changes in the form of the kinetic curves are described by (i) values of the rate constantk1and the equilibrium constant for alkane chemisorptionKAthat increase with alkane chain length and with temperature, (ii) values ofKH, the adsorption coefficient for H2, that decrease with alkane chain-length but are not very temperature-dependent, and (iii) a decreasing degree of the needful alkane dehydrogenation as the chain-length increases. For C3H8andn-C4H10, true activation energies are respectively 82 and 76 kJ mol−1, and enthalpy changes for alkane chemisorption are 88 and 79 kJ mol−1. Apparent activation energies increase with H2pressure in consequence of the Temkin equation and show compensation effects. Rate dependences on H2pressure were measured at a single temperature using 0.3% Re-0.3% Pt/Al2O3(AKZO CK433, EUROPT-4): rates were faster than for Pt/Al2O3, and values ofk1,KA, andKHwere larger. Measurements were also made with catalysts partially deactivated by carbon deposition; slower rates were associated with lower values ofk1andKA. Changes in product selectivities with operating variables are recorded, but are only significant for PtRe/Al2O3, and forn-C4H10on Pt/Al2O3, where at 547 K the extent of internal C–C bond fission decreases as H2pressure increases. The difficulty of devising a simple rate expression to embrace all the experimental observations is discussed." @default.
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• W2083173313 date "1997-03-01" @default.
• W2083173313 modified "2023-10-16" @default.
• W2083173313 title "Alkane Transformations on Supported Platinum Catalysts" @default.
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• W2083173313 doi "https://doi.org/10.1006/jcat.1997.1490" @default.
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