Transition Metal Chemistry

, Volume 32, Issue 5, pp 570–575 | Cite as

Kinetics and mechanism of ruthenium(III) catalyzed oxidation of tetrahydrofurfuryl alcohol by cerium(IV) in sulfuric acid media

  • Yongqing Zhai
  • Hongmei Liu
  • Baosheng Liu
  • Yukai Liu
  • Jia Xiao
  • Weisong Bai
Article
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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 − , \({{\rm Ce}({\rm SO}_{4})_{2}}\) has been found as the kinetically active species. Furthermore, the rate constants of the rate determining step together with the activation parameters were evaluated.

Keywords

Cerium Ferrous Ammonium Sulfate Ferroin THFA Sulfuric Acid Medium 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.
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Copyright information

© Springer 2007

Authors and Affiliations

  • Yongqing Zhai
    • 1
  • Hongmei Liu
    • 1
  • Baosheng Liu
    • 1
  • Yukai Liu
    • 1
  • Jia Xiao
    • 1
  • Weisong Bai
    • 1
  1. 1.College of Chemistry and Environmental ScienceHebei UniversityBaodingP.R. China

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