Staudinger’s student, W. Kern, published the first work on synthetic polyelectrolytes (in 1939). Ten years later, Fuoss and Sadek prepared the first complex between two synthetic, oppositely-charged polyelectrolytes. At the time, it seemed evident that “strong electrostatic interactions…would lead to mutual precipitation.” However, Michaels could not measure an enthalpy of complexation and concluded it was driven by entropy or the “escaping tendency of microions.” With more sensitive calorimetric measurements, complexation enthalpies were again ascribed to the coulombic forces assembling the component polyelectrolytes. In this talk I will show how polyelectrolyte coacervates, complexes and multilayers, which are ultrathin films of complexes, rely on the loss of counterions, an entropic driving force, to assemble. The source of the enthalpic component is identified as changes in water structure. Using the Donnan equilibrium (Frederick Donnan: PhD Leipzig, 1896, with Wilhelm Ostwald) and measured enthalpies of complexation, the ion content of polyelectrolyte complexes may be accurately predicted.<br/><br/>

Created by kT: polyelectrolyte complexes and multilayers

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.