Kinetics and Mechanism of Oxidation of Co (II) Edta by Chromium (VI) : Effect of Micelle

The kinetics of oxidation of metal ion complex [Co (II) EDTA] by chromium (VI) in perchloric acid medium has been investigated spectrophotometrically at 535 nm. The reaction is first order with respect to complex and the oxidant, and markedly inhibited by H+ under the conditions [Cr(VI)] << [Co(II)EDTA]. The reaction obeys the following rate law with respect to EDTA is as follows. K [H ] kK [Co(II)EDTA] [Cr(VI)] [CoYH O ] dt d a 2 a t 2 + − + = where Y = EDTA in the tetra negative form. In the oxidation of Co (II) EDTA by Cr (VI) anionic micelle (sodium dodecyl sulphate) caused acceleration at sub micelle concentration; where as neutral micelle (triton X-100) caused deceleration in rate. A possible mechanism consistent with the observed results is proposed.

[1]  E. Paetzold,et al.  Reactions in micellar systems. , 2005, Angewandte Chemie.

[2]  Kabir-ud-din,et al.  Micellar Effects on the Oxidation of d‐Glucose by Chromic Acid in Perchloric Acidic Medium , 2003 .

[3]  A. Zaki,et al.  Kinetics and mechanism of the heterogeneous catalyzed oxidative degradation of indigo carmine , 2003 .

[4]  S. Traina,et al.  Oxidation kinetics of Co(II)-EDTA in aqueous and semi-aqueous goethite suspensions , 1996 .

[5]  R. Marusak,et al.  Direct determination of the self-exchange rate of a nickel(IV/III) Bis(oxime-imine)complex. Investigatioin of orientation effects in electron-transfer reactions , 1990 .

[6]  H. Taube,et al.  Stereoselective electron-transfer reactions of (ethylenediaminetetraacetato)cobaltate(III), (propylenediaminetetraacetato)cobaltate(III), and (1,2-cyclohexanediaminetetraacetato)cobaltate(III) with TRIS(ethylenediamine)cobalt(II) , 1987 .

[7]  C. A. Bunton,et al.  Organic Reactivity in Aqueous Micelles and Similar Assemblies , 1987 .

[8]  E. Corey,et al.  A New Cr(VI) Reagent for the Catalytic Oxidation of Secondary Alcohols to Ketones. , 1986 .

[9]  M. Hussein,et al.  Inner-sphere oxidation of diaqua(nitrilotriacetato)cobaltate(II) by periodate in acetate medium. Isokinetic relationship for the oxidation of (aminopolycarboxylato)cobalt(II) complexes by periodate , 1983 .

[10]  D. Balasubramanian,et al.  Studies on the triton X-100: Alcohol: Water reverse micelles in cyclohexane , 1979 .

[11]  L. Sepúlveda Absorbances of solutions of cationic micelles and organic anions , 1974 .

[12]  R. Ramette Equilibrium constants from spectrophotometric data: Principles, practice and programming , 1967 .

[13]  R. G. Wilkins,et al.  Kinetic evidence pertaining to the structure of the cobalt(II)-EDTA complex in aqueous solution , 1967 .

[14]  W. Higginson 530. The extent of chelate ring formation in EDTA complexes of bivalent cations in solution , 1962 .