A MOLECULAR MODELLING STUDY OF DICARBOXYLATE ANIONS AND ZINC OXALATE COMPLEX EXTRACTION BY DIPHOSPHONIUM EXTRACTANTS

A molecular modelling method is used as an aid to predict and to account for the results of solvent extraction of dianions by an ion-exchange extractants such as diphosphonium compounds (polymethylenebis(trioctylphosphonium)s abbreviated as CnBP2+). The extraction ability of CnBP2+ extractants was surprisingly dependent on the dianionic species and on the length of bridging methylene chain connecting the two phosphonium cationic centers which offers an effective molecular recognition field. The dianions studied are phthalate, isophthalate, terephthalate, dibenzoyltartrate and zinc oxalate complex. All of them have their negative charges carried by oxygen atoms. The extracted species considered for a dianion A2− are 1:1 and 2:2 ion-pair species such as (CnBP2+, A2−), (2 CnBP2+, 2 A2−rpar; with n = 2, 4, 6, 8, 10, 12. These ion-pair species are modelled and minimized. The total energy values obtained are processed to calculate the association energies of ion-pair species which allow comparison of 1...