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The effects of additives, concentration of the co- and counter-ions and the temperature in polar-ionic mobile phase systems were studied. The influence of pH, MeOH content and alcohol additives were investigated in the reversed-phase mode. The difference in the change in standard enthalpy Δ(ΔH°), entropy Δ(ΔS°), and free energy Δ(ΔG°) was calculated from the linear van't Hoff plots derived from the ln α vs 1/T curves in the temperature range 5–40 °C. Unusual temperature behavior was observed on Chirobiotic TAG for most of the analytes: decreased retention times were accompanied with increased separation factors with increasing temperature, and separation was entropically-driven. For two of the studied analytes enthalpically-driven enantioseparations were observed. 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