Thermodynamics-based retention maps to guide column choices for comprehensive multi-dimensional gas chromatography

Highlights: • Novel application of distribution-centric 3-parameter thermodynamic model of GC. • Rapidly evaluate column combinations for GC × GC before buying columns. • Extends easily to GC × GC × GC separations. -- Abstract: Comprehensive two-dimensional gas chromatography (GC × GC) provides enhanced separation power over its one-dimensional counterpart – gas chromatography (GC). This enhancement is achieved by the inclusion of a secondary column, the choice of which is a major determinant on the quality of the ultimate separation. When developing and optimizing a new GC × GC method, the choices of stationary phase chemistries, geometries and configurations (which phase serves in which dimension) are of fundamental importance, and must often be addressed even before the manipulation of instrumental conditions. These choices are often made using educated guesses, literature searches, or trial and error. Thermodynamic models of GC separations; however, provide a fast and easy means of acquiring information for guiding these choices. By using characteristic thermodynamic parameters (characteristic temperatures, T_char, and characteristic thermal constants, θ_char), we demonstrate the generation of maps that can inform the choices of column chemistries, phase ratios and configurations for GC × GC separations.