Kinetics and equilibrium constants of some pentacyanoferrate(II) complexes of nitrogen and sulfur containing heterocycles
✍ Scribed by Yakup Baran; Ahmet Ülgen
- Publisher
- John Wiley and Sons
- Year
- 1998
- Tongue
- English
- Weight
- 127 KB
- Volume
- 30
- Category
- Article
- ISSN
- 0538-8066
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✦ Synopsis
The kinetics of the substitution reactions of ion with a series of 3Ϫ Fe(CN) H O 5 2 nitrogen and sulfur containing heterocycles were studied in aqueous media. In the presence of excess ligand, varied over a large range of concentrations, second-order rate constants were calculated at Activation parameters for the formation reactions were ϭ 0.100 M NaClO . 4 found, ⌬H* and ⌬S*, and respectively. The results are inter-28 Ϯ 6 kJ/mol 135 Ϯ 20 J/mol, preted as being consistent with dissociative, SN 1 mechanism. The kinetics of formation and dissociation were studied by stopped-flow technique at several temperatures. An investigation of the kinetics of exchange of coordinated heterocycles for 1,3,5-triazine, yielded rate saturation that is typical of a limiting SN 1 mechanism. Activation parameters of the limiting firstorder specific rate of dissociations were found with ⌬H* and ⌬S* and 53 Ϯ 2 kJ/mol 105 Ϯ respectively. From the specific rates of formation and dissociation reactions the equi-5 J/mol, librium constants were calculated.