Thiolato sulfur as an electron-transfer bridge. Chromium(II)-catalyzed aquation of thiolatobis(ethylenediamine)chromium(III) complexes in aqueous perchloric acid media

1976 ◽  
Vol 15 (1) ◽  
pp. 139-145 ◽  
Author(s):  
Charles J. Weschler ◽  
Edward. Deutsch
Keyword(s):  
Electron Transfer ◽  
Perchloric Acid ◽  
Acid Media ◽  
Aqueous Perchloric Acid

Acid–base behaviour of the ferricyanide ion in perchloric acid media. Spectrophotometric and kinetic study

1990 ◽  
Vol 68 (2) ◽  
pp. 228-235 ◽  
Author(s):  
Pedro L. Domingo ◽  
Begoña García ◽  
José M. Leal
Keyword(s):  
Kinetic Study ◽  
Perchloric Acid ◽  
Decomposition Reaction ◽  
Acid Base ◽  
Acid Media ◽  
Protonation Equilibria ◽  
Aqueous Perchloric Acid ◽  
Protonated Species ◽  
Heterolytic Dissociation ◽  
Homolytic Dissociation

A wide study was carried out of the acid–base behaviour of ferricyanide ions in aqueous perchloric acid media in the range 0.1–11.5 M. This study shows that protonation and decomposition of the ferricyanide ions occur simultaneously. The three successive protonation equilibria were found in the acidity ranges 0.1–4.0, 3.5–8.5, and 7.0–11.5 M HClO4, respectively. A kinetic study was also made of the decomposition reaction at 60 °C. The kinetic data are explained by considering a reaction mechanism involving homolytic and heterolytic dissociation steps. The homolytic and heterolytic rate constants corresponding to each of the four protonated species were determined, along with the acid–base protonation constants, pK1 = −6.25 ± 0.10; pK2 = −3.23 ± 0.03; and pK3 = −0.60 ± 0.02. Keywords: acid–base behaviour, protonated species, decomposition, homolytic dissociation, heterolytic dissociation.

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