Kinetics and mechanism of ruthenium(III) catalyzed oxidation of tetrahydrofurfuryl alcohol by cerium(IV) in sulfuric acid media |
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Authors: | Yongqing Zhai Hongmei Liu Baosheng Liu Yukai Liu Jia Xiao Weisong Bai |
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Affiliation: | (1) College of Chemistry and Environmental Science, Hebei University, Baoding, 071002, P.R. China |
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Abstract: | The kinetics and mechanism of ruthenium(III) catalyzed oxidation of tetrahydrofurfuryl alcohol (THFA) by cerium(IV) in sulfuric
acid media have been investigated spectrophotometrically in the temperature range 298–313 K. It is found that the reaction
is first-order with respect to CeIV, and exhibits a positive fractional order with respect to THFA and RuIII. The pseudo first-order (THFA]≫CeIV]≫RuIII]) rate constant k
obs decreases with the increase of HSO
4
−
]. Under the protection of nitrogen, the reaction system can initiate polymerization of acrylonitrile, indicating the generation
of free radicals. On the basis of the experimental results, a reasonable mechanism has been proposed and the rate equations
derived from the mechanism can explain all the experimental results. From the dependence of k
obs on the concentration of HSO
4
−
,
has been found as the kinetically active species. Furthermore, the rate constants of the rate determining step together with
the activation parameters were evaluated. |
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Keywords: | |
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