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The Effect of Sodium Thiocyanate on the Corrosion Dissolution Rate of Silver in Thiosemicarbazide Solutions L. F. Kozin and B. I. Danil’tsev Vernadsky Institute of General and Inorganic Chemistry, National Academy of Sciences of Ukraine,
pr. Akad. Palladina, 32/34, Kiev-142, 03680 Ukraine e-mail:
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Received February 18, 2003 Abstract — The effect of thiocyanate on the corrosion dissolution rate of silver in thiosemicarbazide (TSC) ammonium–chloride–bromide solutions was studied by using gravimetry and rotating disc electrode technique. The corrosion dissolution of silver was shown to be preceded by the formation of dithiosemicarbazide molecules due to the oxidation with iron (III) ions. The “second ligand” phenomenon is discussed, which consists in an increase in the corrosion dissolution rate of silver upon adding sodium thiocyanate (STC) to a TSC solution because of the decrease in the adsorption layer thickness. A synergism was discovered in the case of the corrosion dissolution of silver in a solution containing both thiosemicarbazide and sodium thiocyanate. The composition of the adsorption layer formed on a silver electrode and involving silver, sulfur (AgHS and Ag2S), as well as carbon, nitrogen, and oxygen forming the base of adsorption layers, was investigated by means of Auger spectrometry. The kinetic parameters (rate constants and reaction orders) were determined and a mechanism of the corrosion dissolution of silver in TSC, STC, and TSC + STC solutions is proposed.
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