Kinetic studies of the electron transfer reactions in iron(II) and iron(III) systems. XI. Electron transfer reaction between aquairon(II) and tris(1,10-phenanthroline)iron(III) in water mixed with methanol, ethanol, 1-propanol, and ethylene glycol.

The electron transfer reaction Fe2+aq+Fe(phen)33+→Fe3+aq+Fe(phen)32+ has been investigated in order to find out the influence of the dielectric nature of media on the reaction rates, by the method of stopped-flow spectrophotometry. As the reaction media, were used aqueous mixtures with various alcohols, such as methanol, ethanol, 1-propanol, and ethylene glycol at their various mole fractions x. The second-order rate constant k grows larger approximately linearly with the increase in x, in a sequence: methanol<ethylene glycol<ethanol<1-propanol. When In k is plotted against D−1 (the reciprocal dielectric constant), all points come together on a single straight line with a positive slope, indifferent to the kinds of the alcohols used. This fact suggests that the reaction proceeds through three successive elementary processes, Fe2+aq+Fe(phen)33+\overseti→[Fe(H2O)62+·Fe(phen)33+]\oversetii→[Fe(H2O)63+·Fe(phen)32+]\oversetiii→Fe3+aq+Fe(phen)32+, in which Process i is the formation of an outer-sphere ion-pair ...

[1]  S. Hayashida,et al.  Kinetic studies of the electron transfer reactions in Iron(II) and Iron(III) systems. IX. Electron transfer reactions between Iron(II) and Iron(III) in water mixed with ethanol, 1-propanol, ethylene glycol, glycerol, and pentaerythritol. , 1980 .

[2]  M. Kimura,et al.  Kinetics of the oxidation reactions of iodide and iron(II) ions by tris(1,10-phenanthroline)iron(III) ion in aqueous mixtures of methanol and ethanol , 1978 .

[3]  J. Beattie,et al.  Structure of hexaaquairon(III) nitrate trihydrate. Comparison of iron(II) and iron(III) bond lengths in high-spin octahedral environments , 1977 .

[4]  T. Meyer,et al.  Unusual activation parameters in the oxidation of hexaaquairon(2+) ion by polypyridine complexes of iron(III). Evidence for multiple paths for outer-sphere electron transfer , 1974 .

[5]  T. Meyer,et al.  Kinetics of the oxidation of hexaaquoiron(2+) by polypyridine complexes of ruthenium(III). Negative enthalpies of activation , 1973 .

[6]  N. Sutin,et al.  THE KINETICS OF THE OXIDATION OF IRON(II) AND ITS SUBSTITUTED tris-(1,10- PHENANTHROLINE) COMPLEXES BY CERIUM(IV) , 1963 .

[7]  N. Sutin,et al.  The Kinetics of the Formation of the Monoazide Complex of Iron(III) , 1963 .

[8]  Rudolph A. Marcus,et al.  On the theory of oxidation—Reduction reactions involving electron transfer. V. Comparison and properties of electrochemical and chemical rate constants , 1963 .

[9]  R. Connick,et al.  RATE OF ELIMINATION OF WATER MOLECULES FROM THE FIRST COÖRDINATION SPHERE OF PARAMAGNETIC CATIONS AS DETECTED BY NUCLEAR MAGNETIC RESONANCE MEASUREMENTS OF O17 1 , 1961 .

[10]  N. Sutin,et al.  The Kinetics of the Reactions of Substituted 1,10-Phenanthroline, 2,2'-Dipyridine and 2,2',2″-Tripyridine Complexes of Iron(III) with Iron(II) Ions1 , 1961 .

[11]  N. Sutin,et al.  The Kinetics of the Oxidation of the Iron(II) Ion by the Tris-(1,10-phenanthroline)-iron (III) Ion1 , 1961 .

[12]  J. Silverman,et al.  The Exchange Reaction between the Two Oxidation States of Iron in Acid Solution , 1952 .

[13]  Gösta. Åkerlöf,et al.  DIELECTRIC CONSTANTS OF SOME ORGANIC SOLVENT-WATER MIXTURES AT VARIOUS TEMPERATURES , 1932 .

[14]  G. Scatchard.  Statistical Mechanics and Reaction Rates in Liquid Solutions. , 1932 .