Polyelectrolytic Aspects of Conformational Transitions and Interchain Interactions in Ionic Polysaccharide Solutions: Comparison of Theory and Microcalorimetric Data

  • S. Paoletti
  • A. Cesàro
  • F. Delben
  • V. Crescenzi
  • R. Rizzo
Chapter
Part of the Polymer Science and Technology book series (NISS, volume 30)

Abstract

Analytical expressions are obtained to evaluate the electrostatic enthalpy of mixing the univalent-salt form of a polyelectrolyte with a neutral salt of the same valency in aqueous solution, following the theory developed by G. S. Manning, avoiding restrictive assumptions regarding the ionic parameters. An endothermic effect is always predicted for the enthalpy of mixing (corrected for the heat of dilution of the polyelectrolyte), which is function of the linear charge density parameter, ξ, of the ratio of neutral salt to the monomoles of polymer, and of the amount of salt initially present in the system. In this way a quantitative method is suggested to test the conformational parameters of polyelectrolytes and their dependence on ion-induced changes, provided that the main non-conformational effect of added salt on the polymer is mostly electrostatic. Specific effects (as site-binding), if present, should be additionally accounted for. However, in the case of the pH-induced conformational transition of polygalacturonate the electrostatic approach is able to give a self-consistent reference for the excess heat effects therein involved. The ionic polysaccharides which have been chosen for confronting the theoretical predictions with the experimental microcalorimetric data are polygalacturonate, polyguluronate, polymannuronate and alginate.

Keywords

Conformational Transition Polyelectrolyte Solution Condensation Theory Pectic Acid Simple Salt 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.
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Copyright information

© Plenum Press, New York 1985

Authors and Affiliations

  • S. Paoletti
    • 1
  • A. Cesàro
    • 1
  • F. Delben
    • 1
  • V. Crescenzi
    • 2
  • R. Rizzo
    • 2
  1. 1.Istituto di ChimicaUniversità di TriesteTriesteItaly
  2. 2.Istituto di Chimica FisicaUniversità di RomaRomeItaly

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