Table of Contents
ISRN Chromatography
Volume 2013, Article ID 460787, 9 pages
Research Article

Thermodynamic and Extrathermodynamic Studies of Enantioseparation of Imidazolinone Herbicides on Chiralcel OJ Column

Department of Environmental Sciences, University of California, Riverside, CA 92521, USA

Received 26 March 2013; Accepted 22 April 2013

Academic Editors: S. De Marino, Z. Liu, M. P. Marszall, and M. L. Trehy

Copyright © 2013 Wenjian Lao. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.


A homologous series of chiral imidazolinone herbicide was previously resolved on Chiralcel OJ column in high performance liquid chromatography. However, the mechanism of the chiral separation remains unclear. In this study, chromatographic behaviors of five chiral imidazolinone herbicides were characterized by thermodynamic and extrathermodynamic methods in order to enhance the understanding of the chiral separation. Thermodynamic parameters of this study were derived from equilibrium constant ( ) that was estimated from the moment analysis of the chromatographic peak. Van't Hoff plots of ( versus ) were linear at a range of 15–50°C, only nonlinear at a range of 5–15 °C with n-hexane (0.1%, trifluoroacetic acid)-2-propanol 60/40 (v/v) mobile phase. The enantiomer retention on the chiral column was entropy-driven at a lower temperature (5°C) and enthalpy-driven at a higher temperature (10 to 50°C). Enantioseparations of four of the five imidazolinone herbicides were enthalpy-driven, only entropy-driven for imazaquin. Enantioseparation mechanisms were different in between 5–10°C and 15–50°C probably due to the conformational change of the OJ phase. Enthalpy-entropy compensation showed similar mechanisms in retention and chiral separation for the five or enantiomers. Several extrathermodynamic relationships were able to be extracted to address additivity of group contribution.