Structure of polyethylene glycol/water mixtures as a separation medium of aqueous two-phase extraction systems studied by equilibrium analysis of thiocyanato complexation of Cobalt(II)

Aqueous two-phase systems (ATPS) utilizing polyethylene glycol (PEG) have been successfully used for the separation of various organic and inorganic compounds as an environmentally benign extraction method. However, a fundamental understanding of the role of the hydration structures around PEG chains in solute partitioning in ATPS remains elusive although it has been considered that PEG molecules are involved in separation. In the present work, the equilibria of Co(II) thiocyanate complexation reaction in aqueous PEG solutions were studied by spectrophotometry with varying ethylene oxide chain length and concentration of PEG. From the formation constants of the tetrahedral and octahedral Co(II) thiocyanate complexes obtained, a microheterogeneous structure consisting of pseudo phases formed by hydration of ethylene oxide (EO) chain and terminal hydroxyl (OH) groups in the PEG molecule in addition to the bulk water phase was estimated. It was revealed that the formation of tetrahedral Co(NCS)(4)(2-) complex proceeds in the EO pseudo phase by the involvement of hydrophobic ethylene groups, while the OH phase and the bulk phase inhibit the progress of the reaction. This indicates that Co(NCS)(4)(2-) is stable in hydrophobic hydration structure of water around the EO moiety. The EO phase imparts hydrophobicity to aqueous PEG solutions and plays a predominant role in partition of solute molecules in PEG-based ATPS.