Acta Phys. -Chim. Sin. ›› 2005, Vol. 21 ›› Issue (08): 929-933.doi: 10.3866/PKU.WHXB20050821

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Catalyzed Oxidation of Tetrahydrofurfuryl Alcohol by Cerium(Ⅳ) in Aqueous Sulphuric Acid Medium

SONG Wen-yu; ZHAO Rong-hui; JIANG Qing-mei   

  1. College of Chemistry and Environmental Science, Hebei University, Baoding 071002
  • Received:2004-12-13 Revised:2005-03-07 Published:2005-08-15
  • Contact: SONG Wen-yu E-mail:songwenyu@126.com

Abstract: The kinetics of trace Ir(III) catalyzed oxidation of tetrahydrofurfuryl alcohol(THFA) by Ce(IV) in aqueous sulphuric acid medium was studied by titrimetric technique of redox in the temperature range of 298~313 K. The order was found to be unity with respect to both Ce(IV) and Ir(III), and for tetrahydrofurfuryl alcohol the apparent reaction order was a positive fraction. It was found that the pseudo first order ([THFA]>>[Ce(IV)]) rate constant, kobs, increased with the increase of [H+] but decreased with the increase of [HSO4-]. Under the protection of nitrogen, however, the reaction system could induce polymerization of acrylonitrile, indicating the generation of free radicals. A reasonable mechanism involving a preequilibrium was proposed. From the relation between kobs and [HSO4-], Ce(SO4)2 was found to be the kinetically active species. The equilibrium constants and rate constants of the rate-determining step along with the activation parameters were evaluated.

Key words: Iridium(III) ion, Cerium(IV) ion, Tetrahydrofurfuryl alcohol, Catalyst, Kinetics, Mechanism