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Mechanism of oxidation of cyclohexanehexol (inositol) by quinquevalent vanadium
Author(s) -
Kumar Ashok,
Mehrotra Raj Narain
Publication year - 1974
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550060103
Subject(s) - perchloric acid , chemistry , sulfuric acid , vanadium , inorganic chemistry , reaction rate constant , activation energy , stoichiometry , order of reaction , ionic strength , entropy of activation , reaction mechanism , catalysis , kinetics , organic chemistry , aqueous solution , physics , quantum mechanics
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.