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
Sº(R, X) had a compensational relation with the ΔΔS
Sº(R, X) values. The free energy change ΔΔG
Sº(R, X) which is estimated from the ΔΔH
Sº(R, X) and the ΔΔS
Sº(R, X) at 298 K is less than −23 kJ·mol
-1. The ΔΔS
Sº(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
Sº(R, X) values for each halogen derivative have been the excellent linear lines taking the same slopes for the monosubstituted benzene derivatives, ΔΔG
Sº(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).
抄録全体を表示