Simulation of gas chromatographic separations and estimation of distribution-centric retention parameters using linear solvation energy relationships

• Published in: Journal of Chromatography A 2024-02, Vol.1717, p.464665, Article 464665
• Main Authors: Brehmer, Tillman, Duong, Benny, Boeker, Peter, Wüst, Matthias, Leppert, Jan
• Format: Article
• Language: English
• Subjects: Distribution-centric 3-parameter model; Linear Solvation Energy Relationship (LSER); Method optimization in gas chromatography; Retention models; Simulation of GC separations
• ISSN: 0021-9673
• DOI: 10.1016/j.chroma.2024.464665

•Rapid estimation of K-centric retention parameters calculated by LSER data.•Simulations of GC separations based on K-centric parameters with 95–99 % agreement.•Simulations of GC separation based on LSER data with 90–95 % agreement.•Temperature model for LSER system constants in a range between 40 °C to 200 °C.•Interpretation of the LSER system constants as enthalpy and entropy. For method development in gas chromatography, suitable computer simulations can be very helpful during the optimization process. For such computer simulations retention parameters are needed, that describe the interaction of the analytes with the stationary phase during the separation process. There are different approaches to describe such an interaction, e.g. thermodynamic models like Blumberg's distribution-centric 3-parameter model (K-centric model) or models using chemical properties like the Linear Solvation Energy Relationships (LSER). In this work LSER models for a Rxi-17Sil MS and a Rxi-5Sil MS GC column are developed for different temperatures. The influences of the temperature to the LSER system coefficients are shown in a range between 40 and 200 °C and can be described with Clark and Glew's ABC model as fit function. A thermodynamic interpretation of the system constants is given and its contribution to enthalpy and entropy is calculated. An estimation method for the retention parameters of the K-centric model via LSER models were presented. The predicted retention parameters for a selection of 172 various compounds, such as FAMEs, PCBs and PAHs are compared to isothermal determined values. 40 measurements of temperature programmed GC separations are compared to computer simulations using the differently determined or estimated K-centric retention parameters. The mean difference (RSME) between the measured and predicted retention time is less than 8 s for both stationary phases using the isothermal retention parameters. With the LSER predicted parameters the difference is 20 s for the Rxi-5Sil MS and 38 s for the Rxi-17Sil MS. Therefore, the presented estimation method can be recommended for first method development in gas chromatography.