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Kinetics and mechanism of the acid-catalysed hydrolysis of the carbonatotetraimidazolecobalt(III) ion

✍ Scribed by Eleonora Danilczuk; Janusz Chatłas

Publisher
Springer
Year
1996
Tongue
English
Weight
431 KB
Volume
21
Category
Article
ISSN
0340-4285

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✦ Synopsis

The kinetics of the acid-catalysed hydrolysis of the [(imidazole)4Co(CO3) ] + ion was found to follow the rate law -dln[complex]/dt = k~K[H+]/(1 + K[H+]) in the 25-45 ~ range, [H +] 0.05-1.0 M range and I = 1.0 M. The reaction sequence consists of a rapid protonation equilibrium followed by the one-end dissociation of the coordinated carbonato ligand (rate-determining step) and subsequent fast release of the monodentate carbonato ligand. The rate parameter values, kl and K, at 25 ~ are 6.48 x 10-3 s -1 and 0.31 n -1, respectively, and activation parameters for k I are AH~ =86.1+l.2kJmo1-1 and ASI~=2.1_+6.3Jmol-IK -~. The hydrolysis rate increases with increase in ionic strength. The different ways of dealing with the data fit are presented and discussed. The kinetic results are compared with those for the similar cobalt(III) complexes.

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