| Summary: | 碩士 === 東海大學 === 化學系 === 91 === Kinetic studies of the oxidations of Fe(CN)5L3- and Ru(NH3)5L2+ (L= pyridine( py )、isonicotinamide( isn )、4-aminopyridine( 4-ampy ) complexes by peroxydisulfate ion (S2O82-) have been carried out at different ionic strengths. For Fe(CN)5L3- complexes, rate constants increase with increasing ionic strengths. On the contrary, rate constants decrease with increasing ionic strengths for Ru(NH3)5L2+. Linear relationship was observed for the plots, logk vs. , in agreement with Debye-Hückel theory. The rate constants of oxidation at μ＝0 can be obtained from the intercepts of the plot, and the values are 0.51(Fe(CN)54ampy3-)、1.27×10-2(Fe(CN)5Py3-)、1.30×10-2(Fe(CN)5isn3-)、3.67×105(Ru(NH3)54-ampy2+)、3.12×105(Ru(NH3)5py2+)、1.04×105M-1s-1(Ru(NH3)5isn2+) respectively. The analysis of the kinetic results according to Marcus theory with the correction of QIP and K, we found that k0Ru(corr)/k0Fe(corr) . This implies that Fe(CN)5L3-－S2O82- system has reached the non-adiabatic region.
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