Abstract
Silver electrodeposition from aqueous AgNO3 solutions never gives compact, smooth plates unless an organic additive such as tartaric acid (H2A) is used as growth inhibitor. However, depending on the bulk pH, H2A may exist either as a neutral molecule of H2A or as dissociated entities such as HA− or A2−. We have shown previously that the relevant parameter governing growth inhibition was the activity, αHA-, of tartaric monoanions when silver was plated from a solution of constant AgNO3 concentration. The aim of the present work is to show what happens when this concentration is no longer constant. In these conditions, the relevant parameter governing growth inhibition is proved here to be the bulk concentration of a neutral complex Ag(HA) formed in the solution between Ag+ and tartaric monoanions HA−. On this concentration depend most of the structural features of Ag deposits, e.g. their grain size, superficial roughness and even the amount of incorporated organic material.
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