Extrathermodynamic relationships in reversed-phase liquid chromatography

Kanji Miyabet, Georges Guiochon
Analytical Chemistry 2002 November 15, 74 (22): 5754-65
Enthalpy-entropy compensation (EEC) and linear free energy relationships (LFER) are extrathermodynamic correlations frequently used to discuss the mechanistic similarities of chemical equilibria and reaction kinetics. Although empirical, they are widely applied, proving the substantial effectiveness of fundamental studies based on them. Many attempts have been made to interpret theoretically the necessary conditions (or preconditions) of EEC and LFER. LFER is known to rest on the existence of EEC. However, the intimate correlations between EEC on one hand and LFER and the temperature dependence of LFER on the other hand were insufficiently discussed from the viewpoint of molecular structure contributions. We present a simple LFER model relating the slope and intercept of LFER to the compensation temperatures, themselves derived from EEC analyses, and to several parameters characterizing the molecular contributions to the changes in enthalpy and entropy associated with the passage from one phase of the chromatographic system to the other. A theoretical explanation is supplied for the intimate correlation between the two types of extrathermodynamic relationships, EEC and LFER. We demonstrate also that the characteristics of EEC and LFER depend on the structural parameters. This new model allows a proper interpretation of the temperature dependence of LFER. It should permit further progress of fundamental studies of chemical reaction mechanisms based on extrathermodynamic relationships.

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