Study of Some Cyano-Metal Complexes by Nuclear Magnetic Resonance. II. Kinetics of Electron Transfer between Ferri- and Ferrocyanide Ions

M. Shporer; G. Ron; A. Loewenstein; G. Navon

doi:10.1021/ic50025a022

Study of Some Cyano-Metal Complexes by Nuclear Magnetic Resonance. II. Kinetics of Electron Transfer between Ferri- and Ferrocyanide Ions

M. Shporer, G. Ron, A. Loewenstein, G. Navon

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Abstract

The kinetics of the electron-transfer reaction between Fe(CN)₆^-3 and Fe(CN)₆^-4 ions in aqueous solutions was studied by measuring the N¹⁴ n.m.r. line width. The reaction obeys a rate equation: rate = k[Fe(CN)₆^-3] [Fe(CN)₆^-4] with k = 9.2 ± 1.3 × 104 sec.^-1 M^-1 at 32° and an Arrhenius activation energy of 4.2 kcal./mole in the temperature range 25-40°. The effect of replacing the potassium by other alkali and alkaline earth cations is reported. The rate increases from H⁺ to Cs⁺ and from Mg⁺² to Sr⁺². Possible mechanisms, in view of the catalytic effect of the cations, are discussed. The effect of the presence of various cations on the N¹⁴ line width is reported and discussed.

Original language	English
Pages (from-to)	361-364
Number of pages	4
Journal	Inorganic Chemistry
Volume	4
Issue number	3
DOIs	https://doi.org/10.1021/ic50025a022
State	Published - 1 Mar 1965
Externally published	Yes

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title = "Study of Some Cyano-Metal Complexes by Nuclear Magnetic Resonance. II. Kinetics of Electron Transfer between Ferri- and Ferrocyanide Ions",

abstract = "The kinetics of the electron-transfer reaction between Fe(CN)6-3 and Fe(CN)6-4 ions in aqueous solutions was studied by measuring the N14 n.m.r. line width. The reaction obeys a rate equation: rate = k[Fe(CN)6-3] [Fe(CN)6-4] with k = 9.2 ± 1.3 × 104 sec.-1 M-1 at 32° and an Arrhenius activation energy of 4.2 kcal./mole in the temperature range 25-40°. The effect of replacing the potassium by other alkali and alkaline earth cations is reported. The rate increases from H+ to Cs+ and from Mg+2 to Sr+2. Possible mechanisms, in view of the catalytic effect of the cations, are discussed. The effect of the presence of various cations on the N14 line width is reported and discussed.",

author = "M. Shporer and G. Ron and A. Loewenstein and G. Navon",

year = "1965",

month = mar,

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doi = "10.1021/ic50025a022",

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journal = "Inorganic Chemistry",

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T1 - Study of Some Cyano-Metal Complexes by Nuclear Magnetic Resonance. II. Kinetics of Electron Transfer between Ferri- and Ferrocyanide Ions

AU - Shporer, M.

AU - Ron, G.

AU - Loewenstein, A.

AU - Navon, G.

PY - 1965/3/1

Y1 - 1965/3/1

N2 - The kinetics of the electron-transfer reaction between Fe(CN)6-3 and Fe(CN)6-4 ions in aqueous solutions was studied by measuring the N14 n.m.r. line width. The reaction obeys a rate equation: rate = k[Fe(CN)6-3] [Fe(CN)6-4] with k = 9.2 ± 1.3 × 104 sec.-1 M-1 at 32° and an Arrhenius activation energy of 4.2 kcal./mole in the temperature range 25-40°. The effect of replacing the potassium by other alkali and alkaline earth cations is reported. The rate increases from H+ to Cs+ and from Mg+2 to Sr+2. Possible mechanisms, in view of the catalytic effect of the cations, are discussed. The effect of the presence of various cations on the N14 line width is reported and discussed.

AB - The kinetics of the electron-transfer reaction between Fe(CN)6-3 and Fe(CN)6-4 ions in aqueous solutions was studied by measuring the N14 n.m.r. line width. The reaction obeys a rate equation: rate = k[Fe(CN)6-3] [Fe(CN)6-4] with k = 9.2 ± 1.3 × 104 sec.-1 M-1 at 32° and an Arrhenius activation energy of 4.2 kcal./mole in the temperature range 25-40°. The effect of replacing the potassium by other alkali and alkaline earth cations is reported. The rate increases from H+ to Cs+ and from Mg+2 to Sr+2. Possible mechanisms, in view of the catalytic effect of the cations, are discussed. The effect of the presence of various cations on the N14 line width is reported and discussed.

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JO - Inorganic Chemistry

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Study of Some Cyano-Metal Complexes by Nuclear Magnetic Resonance. II. Kinetics of Electron Transfer between Ferri- and Ferrocyanide Ions

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