β Scribed by Sheila Srivastava; Ajaya Awasthi; Kulina Singh
No coin nor oath required. For personal study only.
Kinetic investigations on Ru(III)βcatalyzed oxidation of cyclopentanol and cyclohexanol by acidic solution of Nβbromoacetamide (NBA) in the presence of mercury(II) acetate as a scavenger have been carried out in the temperature range of 30β45Β°C. Similar kinetics was followed by both the cyclic alcohols. Firstβorder kinetics in the lower concentration range of NBA was observed to tend to zero order at its higher concentrations. The reaction exhibits a zeroβorder rate dependence with respect to each cyclic alcohol, while it is first order in Ru^III^. Increase in [H^+^] and [Cl^β^] showed positive effect, while successive addition of acetamide exhibited negative effect on the reaction rate. Insignificant effect of sodium perchlorate, D~2~O, 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. Β© 2005 Wiley Periodicals, Inc. Int J Chem Kinet 37: 275β281, 2005
π SIMILAR VOLUMES
The Ru[lll) Schiff base complex, 1 Ru[ L)CI,ICI; L = Gis[picolinaldehyde) o-phenylenediimine. catalyzes the oxidation of secondary alcohols by N-methylrnorpholine-N-oxide( NMO) or thal-Iium(lll) acetate as oxidant, Kinetic studies showed the formation of R u ( V ) species as the active intermediate
The oxidation of phosphinic, phenylphosphinic, and phosphorous acids by N-bromoacetamide (NBA) in acid solution, results in the formation of corresponding higher oxyacids of phosphorus. The reaction is first order with respect to NBA, second order in the oxyacid and inverse first in hydrogen ions. T