The Kinetics and Mechanism of Ruthenium(III)-Catalyzed Oxidation of Tris(2-amino ethyl)amine by Hexacyanoferrate(III) in Aqueous Alkaline Medium

Authors : Radhey Mohan NAIK, Abhishek SRIVASTAVA, Amit Kumar VERMA

Pages : 495-503

View : 16 | Download : 7

Publication Date : 0000-00-00

Article Type : Research Paper

Abstract :The kinetics of rutheniuminsert ignore into journalissuearticles values(III);-catalyzed oxidation of TREN, i.e. trisinsert ignore into journalissuearticles values(2-amino ethyl);amineinsert ignore into journalissuearticles values(3-hydrochloride); by an outer sphere electron transfer oxidant, potassium hexacyanoferrateinsert ignore into journalissuearticles values(III);, was investigated spectrophotometrically in aqueous alkaline medium. The extent of the reaction was followed by registering a decrease in absorbance at 420 nm insert ignore into journalissuearticles values(lmax of Feinsert ignore into journalissuearticles values(CN);63-); due to its consumption as a function of [OH-], ionic strength, [Feinsert ignore into journalissuearticles values(CN);63-], [TREN], and temperature by varying only one variable at a time and keeping all other variables constant. The rate data indicate that the reaction exhibited first order dependence in [oxidant] and at a lower concentrations of reductant. The overall reaction follows second order kinetics at constant [OH-] and proceeds via an associative Sn2 reaction path. The reaction was found to be first order at lower alkali concentrations, tending towards zero at higher concentrations. The rate of reaction increased linearly with increased ionic strength of the medium. A most probable mechanistic scheme explaining all the observed results has been proposed. Activation parameters were computed using the Arrhenius and Eyring equations, which provided additional support to the proposed associative Sn2 pathway.
Keywords : Ru III, catalyzed oxidation, oxidation of TREN, hexacyanoferrate III, oxidation of TREN