Abstract
The oxidation of [CoII(nta)(ox)(H2O)2]3− and [CoII(nta)(ph)(H2O)2]3− (nta = nitrilotriacetate, ox = oxalic acid and ph = phthalic acid) by periodate have been studied kinetically in aqueous solution over 20–40 °C and a variety of pH ranges. The rate of oxidation of [CoII(nta)(ox)(H2O)2]3− by periodate, obeys the following equation: d[CoIII]/dt = [CoII(nta)(ox)(H2O)23−][H5IO6] {k4K5 + (k5K6K2/[H+]} while the reaction of [CoII(nta)(ph)(H2O)2]3− with periodate in aqueous acidic medium obeys the following rate law: d[CoIII]/dt = k6K8[CoII]T [IVII]T/{1 + [H+]/K7 + K8[IVII]T}. Initial cobalt(III) products were formed and slowly converted to final products, fitting an inner-sphere mechanism. Thermodynamic activation parameters have been calculated. A common mechanism for the oxidation of ternary nitrilotriacetatocobalt(II) complexes by periodate is proposed and supported by an excellent isokinetic relationship between ΔH* and ΔS* values for these reactions.
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