Kolthoff-Lingane equation

Likewise, if the Kolthoff-Lingane equation = (/ T/A(F) In(/d— /)-F const does not fit an experimental curve, it does not necessarily mean the depolarization due to the solubility of the final product (0) in electrolyte or electrode material, because the equation for (V-electron process without depolarization has the more complex form (2.42) or (2.44). 

Assuming that cathodic deposition of vanadium is diffusion-controlled, the polarization curves were linearized according to the Kolthoff-Lingane equation [30] ... 

Table 4,5,5 Results of linearization of polarization curves corresponding to cathodic deposition of vanadium from NaCI-accordance with the Kolthoff-Lingane equation...

Much attention, particularly among the Russian workers, has been given to the applicability of the Heyrovsky-Ilkovic versus the Kolthoff-Lingane equation for electrode reactions involving metal deposition. In practice, one plots the electrode potential versus log[(/i — /)//] or log(/ — i) and examines the linearity of the plot and also the value of the slope (theoretically 2.3RTjnF). It is expected that the Heyrovsky-Ilkovic equation should be applicable when alloy formation with the electrode material takes place and the metal formed diffuses away from the surface so that its surface activity is a function of the current density. Alloying and diffusion in the electrode will be functions of the metal deposited, electrode material, temperature, and the rate of deposition (current density) therefore, comparison is difficult or meaningless if several of these variables are varied simultaneously. 

Panchenko used a dropping bismuth electrode to study the reduction of Ag+ he found that the limiting current was proportional to concentration of Ag+ in the melt and that the Kolthoff-Lingane equation was valid. Naryshkin et obtained a linear plot of E versus log[(/ — i)ji] for the reduction of Zn + at a dropping lead electrode. 

Scrosati determined the solubility of PdO in the melt by chrono-potentiometry. The results, which are in good agreement with those obtained by potentiometry, indicated that PdO is completely dissociated in the melt. The diffusion coefficient for Pd - was reported. Schmidt et studied the reduction of Bi +, Pd +, Pt +, and Sb - voltammetrically with an inter-mittenly polarized platinum electrode. The shape of the current-voltage curves for Pd + and Pt was described by the Kolthoff-Lingane equation, whereas for Bi + and Sb + the Heyrovsky-Ilkovic equation was valid. The diffusion coefficients for the species were reported. 

Lingane JJ, Kolthoff IM (1939) Fundamental studies with the dropping mercury electrode. I. The Ilkovic equation of polarographic diffusion currents. J Am Chem Soc 61 825-834. doi 10.1021/ja01873a016... 

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