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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)] ([(NH3)5CoOHCo(NH3)5]5+)
Authors:Franois P Rotzinger  Werner Marty
Institution:François P. Rotzinger,Werner Marty
Abstract:Recent work on the spontaneous (= acid-independent) cleavage of the mono-ol cation, i.e. equation image in Cl?/ClOurn:x-wiley:0018019X:media:HLCA19850680715:tex2gif-stack-1 and NOurn:x-wiley:0018019X:media:HLCA19850680715:tex2gif-stack-2/ClOurn:x-wiley:0018019X:media:HLCA19850680715:tex2gif-stack-3 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 NOurn:x-wiley:0018019X:media:HLCA19850680715:tex2gif-stack-4. 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?/ClOurn:x-wiley:0018019X:media:HLCA19850680715:tex2gif-stack-5 media have been re-interpreted in this work, and new data for NOurn:x-wiley:0018019X:media:HLCA19850680715:tex2gif-stack-6/ClOurn:x-wiley:0018019X:media:HLCA19850680715:tex2gif-stack-7 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.
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