Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Kinetics and Mechanisms of Thermal Decomposition Reactions of Cobalt(III) Complexes. Hexammine-, Halogenoammine- and Oxalatoamminecobalt(III) Complexes
Nobuyuki TanakaKenzo NagaseSaburo Nagakura
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1968 Volume 41 Issue 5 Pages 1143-1146

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Abstract

Kinetics of the thermal decomposition reactions of hexammme-,halogenoammine- and oxalatoamminecobalt(III) complexes in solid state has been studied by following the change in the cobalt (III) contents with time. It was found that the decomposition of these complexes was initiated by the change of the valence state of cobalt(III) to cobalt(II), and that these electrontransfer reactions were kinetically of a first order. The first-order rate constants, the activation energies and the frequency factors of these electron-transfer reactions were obtained. The values of the activation energies were found to increase in parallel with the increase in the difference between t2g and eg orbitals of the cobalt(III) complexes investigated. (The notations, t2g and eg, are used in the expression of an Oh-symmetry approximation for halogenoammine- and oxalatoamminecobalt(III) complexes.)

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