Solute-Stationary Phase Interaction in Gas Liquid Chromatography.Thermodynamic Parameters for Substituted Halogenobenzene Derivatives

概要

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Thermodynamic parameters were determined by variable temperature experiments on the gas liquid chromatography(GLC)relative retention values, log γ, of 3- and 4-substituted halogenobenzene derivatives under non-polar condition. These ΔΔH^○_S(R, X)had a compensational relation with the ΔΔS^○_S(R, X)values. The free energy change ΔΔG^○_S(R, X)which is estimated from the ΔΔH^○_S(R, X)and the ΔΔS^○_S(R, X)at 298K is less than -23kJ・mol<-1>. The ΔΔS^○_S(R)values could be explained by translational entropy change for the adsorbed active complex between the solute and stationary phase. It is suggested that the interaction could be mainly expressed by the physical adsorption exclusive of hydrogen bonding. The ΔΔG^○_S(R, X)values for each halogen derivative have been the excellent linear lines taking the same slopes for the monosubstituted benzene derivatives, ΔΔG^○_S(R). The regression analyses of their intercepts were given using the descriptor evaluated as the molecular volume σ_a(X)rather than σ_M(X). The regression analysis for polyhalogenobenzene was also given successfully using σ_a(X_n).
公益社団法人日本薬学会の論文
2001-01-01