Size-exclusion chromatography of polyelectrolytes: comparison with theory

A theoretical model for the free energy of partitioning of charged spheres into cylindrical pores of like charge, based on the linearized Poisson-Boltzmann equation, has been evaluated vis-a-vis the elution behavior of anionic polyelectrolytes on size-exclusion chromatography columns packed with por...

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Bibliographic Details
Published in:Journal of physical chemistry (1952) 1990-09, Vol.94 (18), p.7243-7250
Main Authors: Dubin, Paul L, Larter, Raima M, Wu, Christine J, Kaplan, Jerome I
Format: Article
Language:English
Subjects:
400100 - Analytical & Separations Chemistry
CALCULATION METHODS
Chemistry
CHROMATOGRAPHY
Colloidal gels. Colloidal sols
Colloidal state and disperse state
DATA
DIFFERENTIAL EQUATIONS
ELECTROLYTES
ENERGY
EQUATIONS
Exact sciences and technology
EXPERIMENTAL DATA
FREE ENERGY
General and physical chemistry
INFORMATION
INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY
MATERIALS
NUMERICAL DATA
PARTIAL DIFFERENTIAL EQUATIONS
PERMEABILITY
PHYSICAL PROPERTIES
POISSON EQUATION
POROUS MATERIALS
SEPARATION PROCESSES
THERMODYNAMIC PROPERTIES
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Summary:A theoretical model for the free energy of partitioning of charged spheres into cylindrical pores of like charge, based on the linearized Poisson-Boltzmann equation, has been evaluated vis-a-vis the elution behavior of anionic polyelectrolytes on size-exclusion chromatography columns packed with porous glass beads. Theoretical predictions of the dependence of the chromatographic partition coefficient on the relative dimensions of solute and pore were compared to experimental results obtained over a wide range of polyion molecular weights, pore sizes, and mobile-phase ionic strengths. Good agreement was found when the polyelectrolyte was modeled as a porous charged sphere, with the dimensions of its equivalent hydrodynamic sphere and a volume charge density dictated by an adjustable effective degree of dissociation.
ISSN:0022-3654
1541-5740
DOI:10.1021/j100381a053