The rates of exchange of bound water in (NH3)5MOH23+ with solvent water are characterized by the activation parameters AV* = -5.8 ± 0.2 cm3 mol-1, AH* = 23.2 ± 0.5 kcal mol-1, and AS* = 0.0 ± 1.6 cal deg-1 mol-1 when M = Cr; the corresponding data for M = Rh are -4.1 ± 0.4cm3mol-1,24.6 ± 0.3 kcal mol-1, and +0.8 ± 1.1 cal deg-1 mol-1. These figures suggest an associative mechanism for both reactions. Some theoretical implications of this conclusion are discussed.
In order to investigate optical properties of liquid systems under high pressure two cells were constructed and tested. Special attention was given to the possibility of investigating equilibria or rates of reactions of corroding liquids.
Electron exchange between ferrocene and the ferricinium cation proceeds with halftimes of a few milliseconds between -65" and -75°C. The second-order rate constants are best reproduced by calculations based on the Marcus tunnelling theory. Electron exchange between a series of aqua-ammines of CoII and Con' proceeds through bridged transition states. The energy of activation remains constant in this series but the entropy of activation becomes less negative as ammine ligands are replaced by hydroxo-ligands. Bridging mechanisms may operatc in other systems in which substantial reorganization of the primary co-ordination sphere is involved.
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