On the Solute-Stationary Phase Interaction in Gas Liquid Chromatography.Relative Retention Values for Mono-substituted Benzene Derivatives and Their Energy Partition by Means of Regression Analysis

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Thermodynamic parameters were determined by variable temperature experiments on the gas-liquid chromatography (GLC) relative retention values, log γ, of mono-substituted benzene derivatives. The free energy change ΔΔG^°_s which is estimated from the enthalpy ΔΔH^°_s and the entropy ΔΔS^°_s at 298 K is less than -15kJ・mol^<-1>, corresponding to an interaction between the sample and the liquid stationary phase. With regards to the co-linearlity with the standard entropy S°(B・・C) of the complex, between the sample and the liquid stationary phase, an excellent linear relationship of ΔΔS^°_s with the electron-donating and -withdrawing groups was obtained. The log γ can also be expressed by the linear combination of the descriptors σ_<s°>, μ^2/α, and σ_R which are the dispersion and repulsion, the induction and orientation, and the charge transfer interaction energies respectively, and from the evaluation of the standard coefficient by the z-score of log γ, (E_<dis>+E_<rep>)>E_<CT>>(E_<ind>+E_<ori>). Under non-polar conditions, (E_<dis>+E_<rep>) was dominant while under polar conditions, the ratio of [(E_<ind>+E_<ori>)+E_<CT>] increased to the level of (E_<dis>+E_<rep>).
公益社団法人日本薬学会の論文
1993-05-15