Electrochemical behaviour of ferrocenes in tributylmethylphosphonium methyl sulfate mixtures with water and 1,2-dichloroethane

Abstract

Electron transfer (ET) reactions in ionic liquid (IL)|organic solvent (1,2-dichloroethane, DCE) and IL|water mixtures were investigated using a Pt disk ultramicroelectrode (UME) along with ferrocene (Fc) and ferrocenemethanol (FcCH2OH) redox probes as electroactive species dissolved in the respective mixtures. The IL utilized was tributylmethylphosphonium methyl sulfate (P4441CH3SO4). The diffusion coefficient of each redox species was determined at each incremental increase of DCE or water to the IL using a chronoamperometric technique that is concentration independent. The IL|DCE mixture exhibited little change in the Fc diffusion coefficient, DFc, up to a DCE mole fraction (χDCE) of 0.5; the observed value, 2.0 × 10−8 cm2 s−1, agrees well with that typically reported for ILs in the literature. After which, the DFc quickly rose to a value commonly found in conventional molecular solvents, 1.3 × 10−5 cm2 s−1 (at χDCE = 0.8). An analogous result was not observed for IL|water mixtures using FcCH2OH, such that [Formula: see text] varied from 0.2 to 1.2 × 10−9 cm2·s−1 at a [Formula: see text] of 0 to 0.8. It was proposed that a large increase in the DFc in the IL|DCE mixture versus [Formula: see text] in the IL|water series was owing to P4441CH3SO4’s more hydrophobic character. Its hydrophobicity was quantified by measuring the formal ion transfer potentials of the IL component ions at a water|DCE immiscible interface.