Kinetics of oxidation ofcis-, andtrans-chlorobis(ethylenediamine)isothiocyanatocobalt(III)ion with peroxodisulphate in aqueous alcoholic mixtures

Holba, Vladislav; Grančičová, Ol'ga; Paulenová, Alena

doi:10.1007/bf01022336

Cited by 5 publications

(2 citation statements)

References 27 publications

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“…Recently, there has been a series of reports on solvent effects on peroxydisulphate oxidations of transition-metal complexes (37,38). In all of the systems studied, decreases in rates with increasing organic cosolvent were observed, in agreement with the present study.…”

Section: Solvent Effectssupporting

confidence: 81%

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Kinetics and mechanism of oxidation of nickel(II) tetraazamacrocycles by the peroxydisulphate anion in aqueous and binary aqueous mixtures

Haines¹,

Northcott²

1992

Can. J. Chem.

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The kinetics of oxidation of several nickel(I1) tetraazamacrocycles by the peroxydisulphate anion have been studied in water and in binary aqueous mixtures. The reactions proceed via an ion-pairing pre-equilibrium, followed by metal ion-assisted peroxy-bond fissure within the ion-pair solvent shell. The derived rate law isIon-pairing constants have been determined and have been found to be little influenced by steric factors, but do depend on solvent composition. Rate constants have been extracted using the rate expression and activation energies have been estimated from temperature dependences.ROBERT I. HAINES et SANDRA J. NORTHCOTT. Can. J. Chem. 70, 2785 (1992.Op6rant en milieux dans l'eau et dans des melanges binaires aqueux, on a CtudiC la cinetique de l'oxydation, par l'anion peroxydisulfate, de plusieurs complexes de t6traazamacrocycles avec le nickel(II). Les reactions se produisent par le biais d'un pre-Cquilibre de paires d'ions, suivis d'un bris de la liaison peroxy assist6 par l'ion mktallique, h I'intCrieur de la couche de solvant de la paire d'ions. La loi de vitesse qui en derive estOn a determine les constantes de formation des paires d'ions et on a trouvC qu'elles ne sont pratiquement pas influencees par des facteurs steriques; elles dependent toutefois de la composition du solvant. On a extrait les constantes de vitesse en utilisant une expression de vitesse et on a evaluC les energies d'activation a partir des dipendances sur la temperature.[Traduit par la redaction]

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Section: Solvent Effectssupporting

confidence: 81%

“…In all of the systems studied, decreases in rates with increasing organic cosolvent were observed, in agreement with the present study. Holba et al (36,37) did not detect ion-pairing, which is not unexpected since their cationic complexes were singly charged.…”

Section: Solvent Effectsmentioning

confidence: 99%