Determination of Distribution Equilibrium-Potential Differences Based on Extraction with Several Crown Ethers by Nitrobenzene, 1,2-Dichloroethane and Dichloromethane

Extraction constants (Kex± & Kex) were determined at 298 K for the extraction of sodium picrate (NaPic) by nitrobenzene (NB), 1,2-dichloroethane (DCE) and dichloromethane using 3m-crown-m ethers and their benzo-derivatives (m = 5, 6; abbreviated as L) together with the determination of conditional distribution constants (KD,Pic) of picrate ion, Pic-, into these diluents. The K1,org (= [NaLPic]org/[NaL+]org[Pic-]org) values at the organic (org) phases, such as NB & DCE, were calculated from the relation Kex/Kex± = K1,org. Distribution equilibrium-potential differences (Dfeq) at extraction equilibria were evaluated from the equation Dfeq = -0.05916´(log KD,Pic - constant) at 298 K. Correlations of the above equilibrium constants, particularly Kex±, with Dfeq were examined. Furthermore, the standard formal potentials for Na+ transfers across the interfaces were briefly evaluated from calculated Dfeq, [Na+] and [Pic-]org. The above extraction systems were characterized by K1,org and the complex formation constants of Na+ with L in the org phases.