| Abstract: | Kinetic investigations on Ru(III)‐catalyzed oxidation of cyclopentanol and cyclohexanol by acidic solution of N‐bromoacetamide (NBA) in the presence of mercury(II) acetate as a scavenger have been carried out in the temperature range of 30–45°C. Similar kinetics was followed by both the cyclic alcohols. First‐order kinetics in the lower concentration range of NBA was observed to tend to zero order at its higher concentrations. The reaction exhibits a zero‐order rate dependence with respect to each cyclic alcohol, while it is first order in RuIII. Increase in [H+] and [Cl?] showed positive effect, while successive addition of acetamide exhibited negative effect on the reaction rate. Insignificant effect of sodium perchlorate, D2O, and mercury(II) acetate on the reaction velocity was observed. Cationic bromine has been proposed as the real oxidizing species. Various thermodynamic parameters have been computed. A suitable mechanism in agreement with the kinetic observations has been proposed. © 2005 Wiley Periodicals, Inc. Int J Chem Kinet 37: 275–281, 2005 |
