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Kinetics and mechanism of the reductions of azido- and isothiocyanatopentacyanocobaltate(III) by ruthenium(II) ammine species in aqueous solution

โœ Scribed by Adedayo B. Adegboro; J.Folorunso Ojo; Olusegun Olubuyide; Oluyemisi T. Sheyin

Publisher
Elsevier Science
Year
1987
Tongue
English
Weight
432 KB
Volume
131
Category
Article
ISSN
0020-1693

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โœฆ Synopsis

The reductions of azido-and isothiocyanato-pentacyanocobaltate(II1) by hexaammine-and aquapentaammineruthenium(I1) have been investigated in aqueous solution at I = 0.20 mol dmm3 (LiCl) and the values at 25 "C of the rate constants (dm3 mol-' s-l) are ky = 1.71 and kNCs = 0.8 1 for the Ru(NH~)~~+ reactions and kN = 2.06 and kNCs = 0.99 for the Ru(NH3)sH202+ riactions. The reductions are acid-independent in the acid concentration range [H*] = (0.01-0.10) mol dmp3 (HCl), but they are dependent on ionic strength. The low kN,/kNCS ratios obtained and conformity with the modified Marcus equation (based on linear freeenergy) of the data suggest an outer-sphere mechanism for the reductions. Activation parameters obtained for the reductions by hexaammine-ruthenium(I1) are eN,(kJ mol-') = (83.1 f 5.7), LLs*'N,(J mol-' K-l) = (38.6 + 1.9) AH*Ncs(kJ mol-') = (84.0 * 2.2),

A,S*,os(J mol-' K-') = (35.9 i: 7.9)

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