Abstract
AbstractThe adsorption of TBP on Hg electrode from aqueous NaClO4 media has been studied using differential capacity and chronocoulometric measurements. TBP adsorbs in two steps, the first corresponding to a flat and second to a perpendicular orientation. Both orientations were observed in the entire investigated potential range. The maximal measured surface concentration (Γmax) of TBP reaches a value of 1.55×10−10 mol cm−2, which corresponds to the theoretical value for densely packed molecules in perpendicular orientation. Γ value of the first isotherm step plateau is about 7 to 15% smaller than Γmax and decreases strongly at potentials more negative than −0.9 V due to the repelling of negative charges between the electrode and the phosphate group. The standard Gibbs energy of adsorption was found to reach the value of −34 kJ mol−1.
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