ELECTROREDUCTION OF COBALT (II) AQUA COMPLEXES IN THE PRESENCE OF ACRYLIC ACID
DOI:
https://doi.org/10.15421/jchemtech.v32i4.316572Keywords:
complex compounds, electroreduction of cobalt(II), acrylate electrolytes.Abstract
Тhe material presented in this article is a logical continuation of the study of the peculiarities of the electroreduction process of complex compounds of 3d-metals. One of the 3d-metals that has recently been widely used in engineering is cobalt. Cobalt coatings have unique physical, mechanical and physico-chemical properties. They are produced from electrolytes of various compositions. Buffer mixtures are widely used to improve the quality of cobalt coatings. This is due to the fact that hydrogen is released duri ng the electroreduction reaction of cobalt cations. In this work, the kinetics of the electroreduction of Co2+ aqua complexes from perchlorate solutions was investigated. The results of chronovoltaic measurements were analysed in conjunction with quantum chemical modelling of the possible mechanisms of the cathodic process. It is shown that at potentials below -1.0 V relative to the chloride-silver reference electrode, the reaction [Co(H2O)6]2+ + 2ē = Co +6H2O is not only accompanied by the reaction 2H2O + 2ē = 2OH- + H2. There is also a more electropositive process of hydrogen release due to the electroreduction of intraspherical water molecules polarised by the central atom: [Co(H2O)6]2+ + ē = [Co(OH)(H2O)5]+ + ½H2. Acrylic acid has been successfully used to suppress this type of reaction during nickel electroplating. It was of interest to investigate the effect of acrylic acid on the cathodic water reduction processes in cobalt electrolytes. To this end, appropriate kinetic measurements were carried out. Quantum chemical calculations have shown that all possible stages of the electroreduction process of cobalt acrylate complexes are accompanied by a decrease in energy and are therefore energetically most favourable. Based on the results obtained, it is proposed to use monosubstituted acrylate complexes instead of homogeneous cobalt aqua complexes to inhibit even a slight hydroxide formation. Shiny homogeneous metallic cobalt films were obtained from acrylate electrolytes in the range of operating current densities from 2 to 8 mA/cm2.
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