PERIODIC PROCESSES ON A COPPER ELECTRODE IN CHLORIDE ELECTROLYTES
DOI:
https://doi.org/10.15421/jchemtech.v34i1.340769Keywords:
copper, dissolution, chloride electrolytes, passivation, periodic phenomena, amplitude and frequency of oscillationsAbstract
The aim of the work was to determine the region of periodic phenomena during currentless and anodic passivation of copper in CuCl2 solutions and to identify the influence of various factors on the process. Copper dissolution (grade M-99) was studied using the rotating disk electrode method. It is shown that periodic phenomena occur during chemical and anodic dissolution of copper in chloride electrolytes as a result of the formation of CuCl passive film with a certain thickness under conditions of the removal of diffusion limitations through an induction period lasting up to 2 min. An increase in the concentration of Cl−-ions causes a shortening of the induction period of oscillations; in highly concentrated NaCl solutions the induction period increases. The oscillations have a sawtooth shape with no homogeneity; the overall process is a superposition of oscillations with different amplitudes. With an increase in the current density to 3000 A/m2, sub-oscillations disappear. Over time, the oscillation amplitudes equalize and the potential value stabilizes at the level of the upper amplitude value. An increase in the concentration of chloride ions to a certain value reduces the frequency of oscillations and the value of the stationary potential of the copper electrode at which they occur, prolongs the oscillations in time and reduces their amplitude; an increase in the concentration of Cu(II) ions has the opposite effect on the amplitude value. A rise in temperature increases the frequency and chaotic state of oscillations, reduces their induction period and amplitude, and reduces the concentration limit of Cl−-ions above which oscillations do not occur. With an increase in the density of the anode current, the frequency of oscillations increases to a certain value and then stabilizes A mechanism of oscillations is associated with alternation of the processes of formation and dissolution of the passive layer.
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