title: Theoretical study of the accuracy of the pulse method, frontal analysis, and frontal analysis by characteristic points for the determination of single component adsorption isotherms.
abstract: The adsorption isotherms of selected compounds are our main source of information on the mechanisms of adsorption processes. Thus, the selection of the methods used to determine adsorption isotherm data and to evaluate the errors made is critical. Three chromatographic methods were evaluated, frontal analysis (FA), frontal analysis by characteristic point (FACP), and the pulse or perturbation method (PM), and their accuracies were compared. Using the equilibrium-dispersive (ED) model of chromatography, breakthrough curves of single components were generated corresponding to three different adsorption isotherm models: the Langmuir, the bi-Langmuir, and the Moreau isotherms. For each breakthrough curve, the best conventional procedures of each method (FA, FACP, PM) were used to calculate the corresponding data point, using typical values of the parameters of each isotherm model, for four different values of the column efficiency (N=500, 1000, 2000, and 10,000). Then, the data points were fitted to each isotherm model and the corresponding isotherm parameters were compared to those of the initial isotherm model. When isotherm data are derived with a chromatographic method, they may suffer from two types of errors: (1) the errors made in deriving the experimental data points from the chromatographic records; (2) the errors made in selecting an incorrect isotherm model and fitting to it the experimental data. Both errors decrease significantly with increasing column efficiency with FA and FACP, but not with PM.
authors.affiliation: Department of Chemistry, University of Tennessee, Knoxville, TN 37996-1600, USA.
authors.forename: Anna
authors.initials: A
authors.lastname: Andrzejewska
authors.forename: Krzysztof
authors.initials: K
authors.lastname: Kaczmarski
authors.forename: Georges
authors.initials: G
authors.lastname: Guiochon
mesh_terms: D000327:Adsorption; D000465:Algorithms; D002853:Chromatography, Liquid / Q000706:statistics & numerical data*; D003198:Computer Simulation; D020342:Finite Element Analysis; D008956:Models, Chemical; D008962:Models, Theoretical; D013499:Surface Properties; D013816:Thermodynamics