Kinetics and the Mechanism of Iron(II) Reduction of cis-α-halogeno(cetylamine) (triethylenetetramine)cobalt(III) Complex Ion in Aqueous Acid Medium |
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| Authors: | Kannappan Santhakumar Narayanasamy Kumaraguru Sankarlingam Arunachalam Mahadevimanglam Narayanasamy Arumugham |
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| Institution: | (1) Ecole Polytechnique Fédérale de Lausanne, EPFL-ENAC- LPAS, Station 6, CH-1015 Lausanne, Switzerland;(2) School of Chemistry, Bharathidasan University, Tiruchirappalli, 620 024, Tamil Nadu, India;(3) Department of Chemistry, Vellore Institute of Technology, Vellore, 632 014, Tamil Nadu, India |
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| Abstract: | The kinetics and mechanism of iron(II) reduction of cis- α-chloro/bromo(cetylamine)(triethylenetetramine) cobalt(III) surfactant complex ions were studied spectrophotometrically
in an aqueous acid medium by following the disappearance of CoIII using an excess of the reductant under pseudo-first-order conditions: FeII = 0.25 mol dm−3, H+ = 0.1 mol dm−3, μ = 1.0 mol dm−3 ionic strength in a nitrogen atmosphere at 303, 308 and 313 K. The reaction was found to be second order and showed acid
independence in the range H+ = 0.05−0.25 mol dm−3. The second order rate constant increased with CoIII concentration and the presence of aggregation of the complex itself altered the reaction rate. The effects of FeII], H+] and μ] on the rate were determined. Activation and thermodynamic parameters were computed. It is suggested that the reaction of
Fe2+(aq) with CoIII complex proceeds by an inner-sphere mechanism. |
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