Add time:07/20/2019 Source:sciencedirect.com
Both monovalent cations and anions show a regular gradation, according to their sizes, in their effect on the rate and the activation parameters for the dissociation of tris(2,2′-bipyridine)-Fe(II) complex in acid. ΔS and ΔH of activation in M, 0.1 M and 0.01 M acid decrease in the order Cl− > Br− > I− for anions and Li+ > Na+ > Cs+ for cations. The effect of the bulky tetra-alkyl ammonium ions is anomalous and does not depend on their sizes. The effect of the anions can be rationalized in terms of their involvement with the vacant coordination site of the partially bonded intermediate. The effect of cations is probably due to their altering the water structure at high concentration. The anomalous of the tetra-alkyl ammonium ions supports this view.
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