Evaluation of a structure-driven retention model for temperature-programmed gas chromatography

The solvation parameter model is suitable for describing the retention properties of compounds of varied structure in temperature-programmed gas chromatography. An empirical second-order model provides a good account of the change in system constants as a function of program rate. These relationships codify the reduction in retention time at higher program rates and changes in elution order (selectivity) with program rate. The prediction of retention times from structure, while quite good, is probably adversely affected by descriptor quality and the possibility of a mixed retention mechanism on polar stationary phases. Plots of experimental against predicted temperature-programmed retention times for varied compounds are linear but generally contain a small bias from an ideal model (slope of one and an intercept of zero). The average absolute deviation in temperature-programmed retention times on three columns (DB-210, DB-1701 and EC-Wax) varied from 0.15 to 0.89 min with the best results obtained at higher program rates on the columns of lower polarity.