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- W2061548277 abstract "Abstract The kinetics of the reduction of 12-tungstocobaltate(III) by the molecular and anionic forms of formic acid follow the rate laws -d[Co III M]/d t = 2 k 1 [Co III M] 2 [HCOOH] and -d[Co III M]/d t = 2 k 2 - [HCOO − ] [Co III M] 2 respectively at a constant alkali metal ion concentration. Although the low pH rate ( k 1 ) remains uninfluenced by the alkali cations, the magnitude of the apparent third-order rate constant ( k 2 ) for the oxidation of formate ion largely depends on both the nature and the concentration of the cation present. The cation catalytic order, K + > Na + >Li + , has been successfully explained with the help of the polarizability concept. A first-order dependence of k 2 on [K + ] but second-order dependence on [Na + ] and [Li + ] is observed. These cation assisted paths have been studied thoroughly and the rate constants for these cation accelerated paths along with that for the spontaneous process have been evaluated. Activation parameters corresponding to the rate constants of the spontaneous and sodium ion assisted paths have been determined. A cation bridged outersphere electron transfer mechanism with the generation of free radicals is suggested." @default.
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- W2061548277 date "1987-01-01" @default.
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- W2061548277 title "Kinetics and mechanism of the reduction of 12-tungstocobaltate(III) by formate. Catalysis by alkali metal ions through outersphere bridging" @default.
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- W2061548277 doi "https://doi.org/10.1016/s0020-1693(00)81235-9" @default.
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