Oxidation of copper(II)-coordinated diethylenetriamine by hexacyanoferrate(III) ion. A kinetic investigation |
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| Affiliation: | 1. Sinop University, Faculty of Arts and Sciences, Physics department, Sinop, Turkey;2. Ondokuz Mayıs University, Blacksea Advanced Technology Research and Application Center, Samsun, Turkey;3. Giresun University, Faculty of Engineering, Department of Industrial Engineering, Giresun, Turkey;4. Food Engineering Department, Faculty of Engineering, Ondokuz Mayıs University, Samsun, Turkey;5. Ondokuz Mayıs University, Faculty of Arts and Sciences, Physics department, Samsun, Turkey;1. University of Tuebingen, Institute of Physical and Theoretical Chemistry, Auf der Morgenstelle 18, 72076 Tuebingen, Germany;2. Reutlingen University, Process Analysis & Technology, Alteburgstrasse 150, 72762 Reutlingen, Germany;3. Robert Bosch GmbH, Automotive Electronics, Postfach 1342, 72703 Reutlingen, Germany;4. Center for Light-Matter Interaction, Sensors & Analytics (LISA+), Auf der Morgenstelle 15, 72076 Tuebingen, Germany |
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| Abstract: | The stoichiometry and kinetics of the reaction between [Cu(dien)(OH)]+ and [Fe(CN)6]3− in aqueous alkaline medium are described. The rate equation − (d[Fe(III)]/dt = {k1[OH−]2[[Cu(dien)(OH)]+] + k2[OH−] × [[Cu(dien)(OH)]+]2}([Fe(III)]/[Fe(II)]) (Fe(III) = [Fe(CN)6]3−; Fe(II) = [Fe(CN)6]4−, the 4:4:1 OH−/Fe(III)/[Cu(dien)(OH)]+ stoichiometric ratio and the nature of the ultimate products identified in the reaction solution suggest the fast formation of a doubly deprotonated Cu(III)-diamido complex which slowly undergoes an internal redox process where the ligand is oxidised to the Schiff base H2NCH2CH2NCHCHNH.The [[Cu(dien)(OH)]+]2 term in the rate equation is explained with the formation of a transient μ-hydroxo mixed-valence Cu dimer. A two-electron internal reduction of the Cu(III) complex yielding a Cu(I) intermediate is suggested to account for the presence of monovalent copper in a precipitate which forms at relatively high reactant concentrations and in the absence of dioxygen. |
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