Abstract
The film-growth process occurring on platinum anodes when molten potassium thiocyanate is electrolysed at 190°C has been investigated. The kinetics of the process has been studied by the application of different relaxation techniques. The film growth controls the rate of the process, and its mechanism comprises a surface diffusion process occurring after SCN −-ion oxidation. The film-thickening stage approaches a parabolic growth law. The faradaic rectification of the film is discussed in terms of its physicochemical properties and the actual site where anodic and cathodic reactions take place.
Highlights
THE ELECTROCHEMISTRYof molten alkali thiocyanates has been the subject of several investigations
A first paper was published on a reference electrode for use in melts, including potassium thi0cyanate.l Electrode reactions of different ionic species dissolved in molten potassium thiocyanate have been reported.[2,3,4]
A polarographic E/i curve from KSCN melt exhibits two definite waves in the cathodic direction, which were attributed to thiocyanate-ion reduction and potassium-ion discharge, respectively, and one anodic wave related to thiocyanate-ion oxidation
Summary
Abstract-The film-growth process occurring on platinum anodes when molten potassium thiocyanate is electrolysed at 190°C has been investigated. The faradaic rectification of the film is discussed in termsof its physicochemicaplropertiesand theactualsite whereanodicand cathodic reactions take place. R&sum&On a Ctudie le pro&s de croissance du fiIm sur des anodes de platine pendant l’electrolyse du thiocyanate de potassium a 190°C. Le croissance du film controle la velocite du pro&s et son mecanisme comprend un pro&s de diffusion superficiel qui a lieu apr& l’oxydation de l’ion SCN-. Zusammenfassung-Es wurde der Wachstumsprozess eines Filmes untersucht , der an Platinelektroden auftritt, wenn geschmolzenes Kaliumthiocyanat bei 190°C elektrolysiert wird. Der geschwindigkeitsbestimmende Schritt ist der Wachstums prozess des Filmes. Sein Mechanismus schliesst eine Oberfliichendiffusion ein, die nach der Oxydation der SCN--Ionen auftritt. Die faradaische Gleichrichtung des Filmes wird diskutiert an Hand seiner physikalisch-chemischen Eigenschaften und des reellen Ortes, an dem die anodischen und kathodischen Reaktionen ablaufen
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