Conversion of programmed-temperature retention indices from one set of conditions to another

In order to make programmed-temperature retention index (PTRI) data be shared by other chromatographers and laboratories, conversion of PTRI from one set of experimental conditions to another is investigated in detail in this work. It was found that the differences between the PTRIs at different heating rates are structurally dependent, especially the number of ring in molecules. Thus, with the help of molecule constitutional descriptors, equations of PTRI conversion to certain initial temperature, heating rate, and stationary phase were obtained with high correlation coefficients and low standard deviations. Calculation errors of PTRI conversion between different heating rates and between different initial temperatures were from 1.1 to 2.9 retention index units (i.u.), which is in the same order with experiment errors. It is well known that reproducibility of PTRI on a polar column is not as good as that on an apolar column because of the apolarity of the n-alkane homologues. Thus, topological descriptors were used for PTRI conversion between two columns with different polar stationary phases, giving better results than those obtained by constitutional descriptors. This shows that topological descriptors could provide more molecular structural information than constitutional descriptors. However, as constitutional descriptor has the advantages of clear physical meaning and very simple calculation, it is our first selection when the PTRI calculation accuracy is satisfied. The method developed is simple in calculation, easy to be performed with high accuracy.