Abstract

Abstract The behavior of potential sweep voltammograms for the ion-transfer across the liquid/liquid interface with preceding chemical reactions is discussed. The theoretical results are expressed in the form of the working curves for the peak current, peak potential, and half-peak potential as a function of the kinetic-current parameter, which contains the rate and equilibrium constants of the preceding chemical reaction and the rate of the potential sweep. The working curves are applied to analyze the voltammograms for the transfer of Pb2+ ion to nitrobenzene facilitated by 1,4,7,10,13,16-hexathiacyclooctadecane present in nitrobenzene from aqueous medium containing citrate3− ion. The dissociation and association rate constants and the formation constant of Pb2+–citrate3− complex in W-phase are 4.5 × 104 s−1 and 8.0 × 1010 M−1 s−1and 106.3 M, respectively.

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