title: Extensive database of liquid phase diffusion coefficients of some frequently used test molecules in reversed-phase liquid chromatography and hydrophilic interaction liquid chromatography.
abstract: Diffusion plays an important role in all aspects of band broadening in chromatography. An accurate knowledge of molecular diffusion coefficients in different mobile phases is therefore crucial in fundamental column performance studies. Correlations available in literature, such as the Wilke-Chang equation, can provide good approximations of molecular diffusion under reversed-phase conditions. However, these correlations have been demonstrated to be less accurate for mobile phases containing a large percentage of acetonitrile, as is the case in hydrophilic interaction liquid chromatography. A database of experimentally measured molecular diffusion coefficients of some 45 polar and apolar compounds that are frequently used as test molecules under hydrophilic interaction liquid chromatography and reversed-phase conditions is therefore presented. Special attention is given to diffusion coefficients of polar compounds obtained in large percentages of acetonitrile (>90%). The effect of the buffer concentration (5-10mM ammonium acetate) on the obtained diffusion coefficients is investigated and is demonstrated to mainly influence the molecular diffusion of charged molecules. Diffusion coefficients are measured using the Taylor-Aris method and hence deduced from the peak broadening of a solute when flowing through a long open tube. The validity of the set-up employed for the measurement of the diffusion coefficients is demonstrated by ruling out the occurrence of longitudinal diffusion, secondary flow interactions and extra-column effects, while it is also shown that radial equilibration in the 15m long capillary is effective.
authors.affiliation: KU Leuven, Department for Pharmaceutical and Pharmacological Sciences, Pharmaceutical Analysis, Herestraat 49, Leuven, Belgium.
authors.forename: Huiying
authors.initials: H
authors.lastname: Song
authors.affiliation: Vrije Universiteit Brussel, Department of Chemical Engineering, Pleinlaan 2, 1050 Brussel, Belgium.
authors.forename: Yoachim
authors.initials: Y
authors.lastname: Vanderheyden
authors.affiliation: KU Leuven, Department for Pharmaceutical and Pharmacological Sciences, Pharmaceutical Analysis, Herestraat 49, Leuven, Belgium.
authors.forename: Erwin
authors.initials: E
authors.lastname: Adams
authors.affiliation: Vrije Universiteit Brussel, Department of Chemical Engineering, Pleinlaan 2, 1050 Brussel, Belgium.
authors.forename: Gert
authors.initials: G
authors.lastname: Desmet
authors.affiliation: KU Leuven, Department for Pharmaceutical and Pharmacological Sciences, Pharmaceutical Analysis, Herestraat 49, Leuven, Belgium. Electronic address: deirdre.cabooter@pharm.kuleuven.be.
authors.forename: Deirdre
authors.initials: D
authors.lastname: Cabooter
mesh_terms: D000097:Acetonitriles / Q000737:chemistry; D002851:Chromatography, High Pressure Liquid; D056148:Chromatography, Reverse-Phase; D062126:Databases, Chemical; D004058:Diffusion; D057927:Hydrophobic and Hydrophilic Interactions
chemical_list: D000097:Acetonitriles; C032159:acetonitrile
keywords: Curve fitting; HILIC; Molecular diffusion coefficients; RPLC; Taylor-Aris