Studies on the Specific Retention Ratio in Gas-Liquid Chromatography of Acyclic Saturated Hydrocarbons by Means of Lennard-Jones (12, 6) Potential Force Constants

Abstract

Many unknown Lennard-Jones (12, 6) potential force constants ε/k [K] of acyclic saturated hydrocarbons could be estimated from the linear relationship between known ε/k [K] (determined from the combined viscosity and 2nd virial coefficient data) and S^o₂₉₈ (g). The dispersion interaction term E_dis. in gas-liquid chromatography (GLC) can be determined by using the mixture rule as the difference of -2 [ε_iiε_jj]^1/2 for the solute-stationary phase and solute-mobile phase pairs. Parameter ε_ii^1/2×10^-8 erg^1/2 is linearly related to logγ measured by GLC of acyclic saturated hydrocarbons under apolar conditions. The correlation between logγ and S^o₂₉₈ (g), as well as that of logγ against E_dis., supports the dependencies of E_dis. and ΔH^o₅ (enthalpy of dissolution) on S^o₂₉₈ (g).