Kinetics and mechanism of the reaction of allyl chloride with trichlorosilane catalyzed by carbon‐supported platinum |
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Authors: | Bogdan Marciniec Hieronim Maciejewski Wojciech Duczmal Ryszard Fiedorow Dariusz Kityski |
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Institution: | Bogdan Marciniec,Hieronim Maciejewski,Wojciech Duczmal,Ryszard Fiedorow,Dariusz Kityński |
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Abstract: | The kinetics of substrate conversions in the commercially important hydrosilylation of allyl chloride with trichlorosilane, catalyzed by active carbon‐supported platinum, as well as the yields of the main product (3‐chloropropyltrichlorosilane) and by‐products (tetrachlorosilane, propyltrichlorosilane) have been studied. On the basis of the measurements performed, the pseudo first‐order rate constants (kobs, k1 and k2 from the model of competitive reactions) and activation energy (Ea = 11 kcal mol?1 (46.2 kJ mol?1)) were determined. The data obtained point to a non‐linear dependence of kobs on the catalyst amount. From the kinetic relationships, the kinetic equation was deduced. All the results of kinetic, IR spectroscopic and thermogravimetric measurements, as well as the derived kinetic equation, have confirmed the general model of consecutive–competitive reaction involving the formation of a surface complex C1 which can decompose in two directions according to the Chalk–Harrod mechanism. Copyright © 2003 John Wiley & Sons, Ltd. |
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Keywords: | hydrosilylation allyl chloride trichlorosilane kinetic equation Chalk– Harrod mechanism platinum catalyst |
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