Extraction of Some Univalent Salts into 1,2-Dichloroethane and Nitrobenzene: Analysis of Overall Extraction Equilibrium Based on Elucidating Ion-pair Formation and Evaluation of Standard Potentials for Ion Transfers at the Interfaces between Their Diluents and Water

Abstract

Sodium permanganate, sodium picrate (NaPic), Bu(4)NPic, Me(4)NPic, and Et(4)NPic were extracted at an ionic strength of 2 × 10(-5) to 0.08 mol dm(-3) and 25°C from water (w)-phases into the organic (o)-ones, 1,2-dichloroethane (DCE) and nitrobenzene (NB). Thereby, apparent distribution constants (K(D,±)) of the anions (A(-)) or the cations (M(+)) and ion-pair formation ones (K(MA)(org)) of the univalent salts (MA) in the o-phases were determined at 25 °C, where K(D,±) = ([A(-)](o)[M(+)](o)/[A(-)][M(+)])(1/2) = (K(D,A)K(D,M))(1/2) and K(MA)(org) = [MA](o)/[M(+)](o)[A(-)](o). Also, the K(ex) and K(D,MA) values with A(-) = Pic(-), MnO(4)(-) were estimated from the relations K(ex) (= [MA](o)/[M(+)][A(-)]) = K(MA)(org)(K(D,±))(2) and = K(MA)K(D,MA), respectively. Standard potentials (Δψ(tr)(0)) for ion transfers at the w/DCE and w/NB interfaces were evaluated from the log K(D,A) or log K(D,M) values by assuming the relations K(D,Pic) = K(D,Et4N) and = K(D,Me4N), respectively. The thus-obtained Δψ(tr)(0) values, especially for the w/DCE system, were in good agreement with the values based on the extra-thermodynamic assumption for Ph(4)As(+) and BPh(4)(-) transfers at the interfaces. In the present extraction systems, the ion-pair formation of MA in the w- and o-phases was less effective in the determination of their distribution constants into the two o-phases.