Theoretical model of ion transfer-electron transfer coupled reactions at the thick-film modified electrodes

The dehydrogenation of 1,4-dihydronaphthalene by tetrachloro-p-benzoquinone in phenetole solution has been investigated. The present work does not fully confirm earlier studies which report that the reaction follows second-order kinetics and that the hydride ion transfer is rate determining. In the investigations described in this paper second-order kinetics are only observed in the later stages of the reaction and a 1:1 stoichiometry of the reactants in the process is not obtained. Substitution of tritium in the 1,4-positions of the hydrocarbon appears to not significantly affect the reaction rate. The present results indicate that charge-transfer complexes are formed in the reaction and it is suggested that electron transfer within these complexes could be the rate-determining step in the dehydrogenation.

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An in situ microscopic spectroelectrochemical study of a three-phase electrode where an ion transfer at the water|nitrobenzene interface is coupled to an electron transfer at the interface ITO|nitrobenzene

Journal of Electroanalytical Chemistry ◽

10.1016/j.jelechem.2003.11.048 ◽

2004 ◽

Vol 566 (2) ◽

pp. 371-377 ◽

Cited By ~ 27

Author(s):

Šebojka Komorsky-Lovrić ◽

Valentin Mirčeski ◽

Christian Kabbe ◽

Fritz Scholz

Keyword(s):

Electron Transfer ◽

Ion Transfer ◽

Three Phase

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Electron transport in clay-modified electrodes: study of electron transfer between electrochemically oxidized tris (2,2′-bipyridyl) iron cations and clay structural iron(II) sites

Canadian Journal of Chemistry ◽

10.1139/v92-227 ◽

1992 ◽

Vol 70 (6) ◽

pp. 1833-1837 ◽

Cited By ~ 16

Author(s):

Yan Xiang ◽

Gilles Villemure

Keyword(s):

Electron Transfer ◽

Modified Electrodes ◽

Quantitative Relation ◽

Cyclic Voltammograms ◽

Slow Electron ◽

Cathodic Current ◽

Peak Current ◽

Scan Speed ◽

Anodic Peak Current ◽

Structural Iron

The cyclic voltammograms of tris (2,2′-bipyridyl) iron(II) ([Fe(bpy)3]2+) adsorbed in clay-modified electrodes made from a range of different smectites were recorded. In all cases, at low scan speed (1 mV/s), the initial anodic peak current was much larger than the initial cathodic peak current. Partial reduction of the clay structural iron further increased the initial anodic to cathodic current ratio, suggesting that the discrepancy between the charge transferred in the anodic and cathodic scans was due to a slow electron transfer between the clay structural Fe(II) and the oxidized bipyridyl cations. However, no clear quantitative relation was found between the measured FeO contents of the different clays and the observed excess anodic currents. In fact, of all the clays tested only one, montmorillonite SWy-1, contained enough Fe(II) for it to account for all of the excess anodic charge transferred in the initial scan.

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Electron transfer between ferrocene and hexacyanoferrate(III) across the water/1,2-dichloroethane interface

Collection of Czechoslovak Chemical Communications ◽

10.1135/cccc19880903 ◽

1988 ◽

Vol 53 (5) ◽

pp. 903-911 ◽

Cited By ~ 13

Author(s):

Josef Hanzlík ◽

Jan Hovorka ◽

Zdeněk Samec ◽

Štefan Toma

Keyword(s):

Electron Transfer ◽

Aqueous Phase ◽

Rate Constant ◽

Potential Range ◽

Ion Transfer ◽

Potential Sweep ◽

Experimental Conditions ◽

Chemical Decomposition ◽

Kinetics Of

Kinetics of electron transfer between ferrocene or its derivative (1,1'-diethyl- or 1,1'-distearoylferrocene) in dichloroethane and hexacyanoferrate(III) in water was studied by means of convolution potential sweep voltammetry. Within the accessible range of experimental conditions no effect of either the potential or concentrations of reactants on the rate constant of electron transfer from the organic to the aqueous phase (ko→w = 1 . 10-7 m4 mol-1 s-1) was observed. Electron transfer was shown to occur far from the potential range, in which the ferricenium ion transfer can take place. However, the reaction was complicated by the chemical decomposition of ferricenium in dichloroethane (k = 0·346 s-1).

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