The development and determination of chemically distinct solute parametersfor use in linear solvation energy relationships

Linear solvation energy relationships (LSERs) have been used to correlate h undreds of chemical systems. However, several of the solute parameters used in the LSERs do not model any one specific type of interaction, but rather are blends of multiple interactions. Thus, LSERs generated with these para meters cannot be rigorously interpreted to provide a complete understanding of the forces underlying solute-solvent interactions. In this work, the de velopment of a new set of chemically distinct solute parameters based on Ko vats retention indices on a variety of GC stationary phases is presented. T he determination of the parameters does not utilize the same initial input estimates as to the values of the parameters which were used in previous st udies and which were based on descriptors that reflected a blend of molecul ar properties. Using this new method, a set of parameters describing the di polarity, polarizability, size, and hydrogen bond acidity of 53 compounds h as been determined. The parameters are shown to be superior to older parame ters in that they are chemically "purer" (i.e. are not blends of multiple i nteractions). The success of these new parameters in LSERs for the correlat ion of gas/water and water/octanol partitioning, and retention in gas chrom atography is also presented. (C) 2001 Elsevier Science B.V. All rights rese rved.