Mechanism of oxidation of cyclohexanehexol (inositol) by quinquevalent vanadium

✍ Scribed by Ashok Kumar; Raj Narain Mehrotra

• Publisher: John Wiley and Sons
• Year: 1974
• Tongue: English
• Weight: 902 KB
• Volume: 6
• Category: Article
• ISSN: 0538-8066
• DOI: 10.1002/kin.550060103

✦ Synopsis

Abstract

The oxidation of inositol by quinquevalent vandadium in acid medium is a first‐order reaction both in vanadium (V) and inositol. The stoichiometry of the reaction is consistent with the use of two equivalents of vanadium (V) per mole of inositol with the formation of one mole of inosose. The reaction is catalyzed both by sulfuric and perchloric acid, but the rate is faster in sulfuric acid than in perchloric acid. In 1__M__–6__M__ perchloric acid solutions the reaction has shown a variable order in H^+^, but in solutions of 2__M__–5__M__ sulfuric and perchloric acid of constant ionic strength, the rate has a linear dependence on [H^+^]^2^. There is also a linear correlation between the rate and bisulfate ions in sulfuric acid at constant hydrogen ion concentration. The energy of activation is found to be 19 kcal/mole and a negative entropy value of − 14 e.u. A suitable mechanism, consistent with the kinetics in 2__M__–5__M__ acid solutions, is suggested and the values of various rate constants are evaluated.