Kinetics and mechanism of oxidation of tetrahydrofurfuryl alcohol by dihydroxydiperiodatonickelate (IV) complex in aqueous alkaline medium

✍ Scribed by Zhi-Ting Li; Feng-Li Wang; An-Zhou Wang

• Publisher: John Wiley and Sons
• Year: 1992
• Tongue: English
• Weight: 423 KB
• Volume: 24
• Category: Article
• ISSN: 0538-8066
• DOI: 10.1002/kin.550241103

✦ Synopsis

The kinetics of oxidation of tetrahydrofurfuryl alcohol by dihydroxydiperiodatonickelate (IV) complex in the temperature range of 20-35°C has been studied by spectrophotometry in aqueous alkaline medium. The reaction order in [Ni(IV)] was found to be unity and that in [alcohol] to be 1.64-1.69. The rate of oxidation increases with increase in [OH-] and decreases with increase in [IO,-], indicating that dihydroxymonoperiodatonickelate (IV) complex is the reactive species of oxidant. Salt effect studies indicated that the reaction is of ion-dipole type. Under the protection of nitrogen the reaction system does not induce polymerization of acrylonitrile or acrylamide, which indicates that a one-step two-electron transfer mechanism without free radical intermediate may be in operation. A mechanism involving a preequilibrium of an adduct formation between N i W ) and alcohol has been proposed. All the experimental phenomena can be explained by the equation derived from the mechanism. The activation parameters of the rate-determining step have been calculated.