Abstract
Adsorption of thiourea on dropping mercury and gallium electrodes from aqueous 0.5 M Na 2SO 4 at 32°C was determined on the basis Of capacitive charge measurements carried out by a computerized chronocoulometric apparatus. Adsorption measurements on Ga were carried out both in a neutral solution and in an acidic solution of pH ≈ 4; in the latter medium, which avoids Ga surface oxidation produced by thiourea adsorption, the capacitive charge was corrected for the faradaic contribution due to hydrogen evolution by a special procedure. Adsorptivity of thiourea is higher on Ga than on Hg even at charge densities as negative as —12 μC cm −2, where both anionic specific adsorption and metal surface oxidation can be ruled out. The above difference in adsorptivity is explained tentatively by a certain coupling between the orientation of adsorbed water molecules and electron spillover, whose extent is expected to be greater on Ga than on Hg at the same negative charge density.
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