Abstract
In the first part of the work, anodic oxidation of some selected low-permittivity liquids (1,4-dioxane, diethyl ether, diisopropyl ether, dichloromethane, trichloromethane, tetrahydrofuran, carbon disulfide, triethylamine, trihexylamine, ethyl acetate, 1-pentyl acetate) was investigated on platinum electrode in acetonitrile which provided a higher-permittivity medium to enable the electrode processes. The pure solvents containing supporting electrolyte were also studied, and in several solvents, very low currents flowed when their cyclic voltammograms were recorded between 0 and 4 V. Contrarily, dissolving them in acetonitrile, high currents could be recorded and their anodic peaks appeared. The most remarkable difference between the pure liquid and acetonitrile solution was produced by the amines. Trihexylamine was immiscible with acetonitrile, so its solubility was determined by using the cosolvent calibration method (mixture of acetonitrile and 1-propanol) for the voltammetric determination, and the saturated concentration of the amine was 44.253 ± 0.564 mM.
Highlights
Dielectric constant of solvents basically determines their usefulness for electrochemical investigations
Due to the low concentration of ions and the significant ohmic potential drop, a problem is encountered in low-permittivity solvents when thermodynamic properties of compounds or solvents themselves are in focus
It is clearly seen that carbon disulfide, triethylamine, and trihexylamine did not show any detectable current signal in the whole anodic potential range due to their very low permittivity and the very low concentration of ions presenting in the liquid phase
Summary
Dielectric constant of solvents basically determines their usefulness for electrochemical investigations. Low-permittivity solvents were studied by anodic oxidation in media with higher permittivity making possible charge transfer processes at significantly lower potentials. The experiment was carried out for making visible the differences between the liquids and their solutions prepared with acetonitrile according to the appearance of their peaks.
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