We have constructed a group contribution method for estimating Kov
aacute.gif">ts retention indices by using observeddata from a set of diverse organic compounds. Our database contains observed retention indices for over35 000 different molecules. These were measured on capillary or packed columns with polar and nonpolar(or slightly polar) stationary phases under isothermal or nonisothermal conditions. We neglected anydependence of index values on these factors by averaging observations. Using 84 groups, we determinedtwo sets of increment values, one for nonpolar and the other for polar column data. For nonpolar columndata, the median absolute prediction error was 46 (3.2%). For data on polar columns, the median absoluteerror was 65 (3.9%). While accuracy is insufficient for identification based solely on retention, it is suitablefor the rejection of certain classes of false identifications made by gas chromatography/mass spectrometry.