Prediction of retention indices. V. Influence of electronic effects and column polarity on retention index.

ABSTRACT

The retention index increment for addition of a methylene group to an analyte molecule is shown for 1-halo-n-alkanes to be different from 100 i.u., a value that is customarily assigned according to the current convention in retention index prediction. In temperature-programmed gas chromatography using linearly interpolated retention index I, a linear regression equation, I=AZ+(GRF), with the number of atoms (Z) in the molecule as variable can describe the retention of 16 homologous series of organic compounds on non-polar and polar columns with characteristic A (linear regression coefficient) and (GRF) (group retention factor) values. A molecular model of retention on the basis of electron density and electron density distribution relative to that of n-alkane is proposed. This model brings out the inter- and intramolecular electronic effects in the analyte molecule and its dipole-dipole interaction with the stationary liquid phases, as variations in the A value. The (GRF) value varies with the connectivity ability of a functional group for extended conjugation, substitution, etc., but is most influenced by hydrogen bonding (H-bonding) with the stationary liquid phase. One can estimate the sequence of elution of a mixture of organic compounds from any two of the three parameters on the right-hand side of the above equation or retrieve the retention indexes of an entire homologous series from its A and (GRF) values. The fact that each analyte molecule has its own A value on different columns makes column difference (deltaI) compound-specific rather than column-specific, a departure from previous assumptions.