Titrimetric method based on potentiometric titration to evaluate redox couples in wine and polyphenols

Abstract

Polyphenols are electroactive compounds, each molecule having reductive (Rd) and oxidative forms (Ox) due to the presence of several phenolic hydroxyls. Direct study of Rd/Ox forms was conducted using potentiometric titration in two steps: First, a complete reduction of the polyphenol Rd/Ox couples by titanium III chloride TiCl₃ (100 % Rd), and then, oxidative titration by dichlorophenolindophenol DCPIP (100 % Ox). The second curve represents the totality of polyphenol couples titration with, for each couple, a characteristic E₀ point representing the equilibrium between the concentration of Rd and Ox forms (Rd/Ox = 1). This value was typical for each polyphenol. We conducted several preliminary experiments with a model polyphenol (catechin) to establish the analysis conditions. The titration solution concentration was N/10 in HCl N and N/20 in water for TiCl₃ and DCPIP respectively. The concentration of this solution diminished very rapidly, i.e. within 24 h for TiCl₃ and DCPIP (under nitrogen and in darkness) and regularly needed a fresh preparation. To control the consistency and precision of the method we performed a few tests on pure products (e.g. hydroquinone/quihydrone, Fe III, Fe II, Cu II) permitting comparison between theoretical and experimental E₀ values. Our result indicated less than 5 % variation and curves with a high reproducibility.