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Polyelectrolytes Revisited: Reliable Determination of Intrinsic Viscosities
Author(s) -
Wolf Bernhard A.
Publication year - 2007
Publication title -
macromolecular rapid communications
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.348
H-Index - 154
eISSN - 1521-3927
pISSN - 1022-1336
DOI - 10.1002/marc.200600650
Subject(s) - intrinsic viscosity , polyelectrolyte , viscosity , extrapolation , polymer , thermodynamics , dilution , solvent , linearity , chemistry , phenomenological model , polymer science , materials science , organic chemistry , physics , mathematics , mathematical analysis , quantum mechanics
The linear extrapolation of ( η − η 0 )/( η 0 c ) towards c → 0 constitutes the basis of traditional methods to determine intrinsic viscosities [ η ], where η is the viscosity of polymer solutions of concentration c and η 0 is the viscosity of the pure solvent. With uncharged macromolecules this procedure works well; for polyelectrolytes it fails because of the pronounced non‐linearity of the above dependence at high dilution resulting from the increasing electrostatic interactions. This contribution presents a new method for the determination of [ η ]. It rests upon the application of the laws of phenomenological thermodynamics to the viscosity of polymer solutions and introduces a generalized intrinsic viscosity enabling a comparison of differently charged and uncharged polymers.