Effect of salt additives on partition of nonionic solutes in aqueous PEG–sodium sulfate two-phase system

Partition of 12 nonionic organic compounds in aqueous PEG-8000–Na2SO4 two-phase system was examined. Effects of four salt additives (NaCl, NaSCN, NaClO4, and NaH2PO4) in the concentration range from 0.027 up to ca. 1.9 M on binodal curve of PEG-sulfate two-phase system and solute partitioning were explored. It was found that different salt additives at the relatively high concentrations display different effects on both phase separation and partition of various nonionic solutes. Analysis of the results indicates that the PEG–Na2SO4 ATPS with the up to 0.215 M NaCl concentration may be viewed as similar to the ATPS without NaCl in terms of the Collander equationʹs predictive ability of the partitioning behavior of nonionic compounds. All ATPS with each of the salt additive used at the concentration of 0.027 M may be viewed as similar to each other as the Collander equation holds for partition coefficients of nonionic solutes in these ATPS. Collander equation is valid also for the compounds examined in the ATPS with additives of NaSCN and NaClO4 at the concentrations up to 0.215 M. The observed similarity between these ATPS might be explained by the similar effects of these two salts on the water structure. At concentrations of the salt additives exceeding the aforementioned values, different effects of salt additives on partitioning of various nonionic solutes are displayed. In order to explain these effects of salt additives it is necessary to examine the intensities of different solute–solvent interactions in these ATPS within the framework of the so-called Linear Solvation Energy Relationship (LSER) model.