Premium
A Unified Interpretation of Kinetic Data on the Acid‐Induced Cleavage and of Product‐Analysis Data on Spontaneous Cleavage of the Mono‐ol Cation μ‐Hydroxo‐bis[pentaamminecobalt(III)] ([(NH 3 ) 5 CoOHCo(NH 3 ) 5 ] 5+ )
Author(s) -
Rotzinger François P.,
Marty Werner
Publication year - 1985
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.19850680715
Subject(s) - chemistry , cleavage (geology) , electrolyte , ion , inorganic chemistry , medicinal chemistry , stereochemistry , organic chemistry , geotechnical engineering , electrode , fracture (geology) , engineering
Recent work on the spontaneous (= acid‐independent) cleavage of the mono‐ol cation, i.e.\documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{*{20}c} {[({\rm NH}_{\rm 3})_5 {\rm CoOHCo(NH}_{\rm 3})_5]^{5 +} + {\rm H}_{\rm 2} {\rm O} \to {\rm [(NH}_{\rm 3})_5 {\rm CoOH}_{\rm 2}]^{3 +} + [({\rm NH}_{\rm 3})_5 {\rm CoOH]}^{{\rm 2} +}} \\ {[({\rm NH}_{\rm 3})_5 {\rm CoOH]}^{{\rm 2} +} + {\rm H}^ + \to [({\rm NH}_{\rm 3})_5 {\rm CoOH}_{\rm 2}]^{3 +} {\rm (fast),}} \\ \end{array}$$\end{document} in Cl − /ClO 4 −and NO 3 − /ClO 4 −mixed‐electrolyte media has established (by analysis of anion‐competition experiments) the existence of reactive ion pairs of the mono‐ol cation with Cl − and NO 3 − . Their existence must be allowed for in the analysis of the rate data for the acid‐induced cleavage (pH 0–1) of the mono‐ol cation in these mixed‐electrolyte media. Thus, previous data for acidic Cl − /ClO 4 −media have been re‐interpreted in this work, and new data for NO 3 − /ClO 4 −media have been analyzed in the same sense. This analysis removes an apparent discrepancy in the orders of magnitude of ion aggregate stability constants between the mono‐ol and similar binuclear cations.