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Aquation of chloropentaamminecobalt(III) Perchlorate in chloride-ion containing water–nonaqueous solvent mixtures

✍ Scribed by Warren L. Reynolds; Elaine S. Barber

Publisher
John Wiley and Sons
Year
1975
Tongue
English
Weight
353 KB
Volume
7
Category
Article
ISSN
0538-8066

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✦ Synopsis

The equilibrium quotients for the formation of Co(NH3) SCl2+ from Co(NH3) 50Hz3+ and CI1were 3.74 f 0.25 M-' and 6.07 f 0.54 M-' at 45.OoC in 10: 1 mole ratio water: dimethyl sulfoxide and in 25 w/w yo aqueous ethanol, respectively, and those for the formation ofthe ion pair C O ( N H ~) ~O H ~~+ . C ~-were 1.21 f 0.20 M-' and 1.58 f 0.1 7 M-l, respectively, in the same solvents. The aquation and anation rate constants were determined at 45.OoC for these two solvents over the range of chloride-ion concentrations 0.0 5 [Cl-] 5 0.9 M . The aquation rate constant was essentially independent of chlorideion concentration in each solvent over this range. The inverse of the pseudo-first-order anation rate constant was linearly dependent on the inverse of the chloride-ion concentration in each solvent. The least squares relationships between (l/kan) and (I/[Cl-]) gave intercepts and ratios of intercept to slope which were analyzed in terms of I d and D mechanisms. It was concluded that the data were not satisfied by a D mechanism, but that they were consistent with an I d mechanism.

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