Dielectric spectroscopy and conductivity of polyelectrolyte solutions

F. Bordi, C. Cametti, R. H. Colby

Research output: Contribution to journalReview articlepeer-review

224 Scopus citations


The dielectric and conductometric properties of aqueous polyelectrolyte solutions present a very complex phenomenology, not yet completely understood, differing from the properties of both neutral macromolecular solutions and of simple electrolytes. Three relaxations are evident in dielectric spectroscopy of aqueous polyelectrolyte solutions. Near 17 GHz, water molecules relax and hence this highest frequency relaxation gives information on the state of water in the solution. At lower frequencies in the MHz range, free counterions respond to the applied field and polarize on the scale of the correlation length. This intermediate frequency relaxation thus provides information about the effective charge on the polyelectrolyte chains, and the fraction of condensed counterions. However, the presence of polar side chains adds a further polarization mechanism that also contributes in this intermediate frequency range. At still lower frequencies, the condensed counterions polarize in a non-uniform way along the polyelectrolyte chain backbone and dielectric spectroscopy in the kHz range may determine the effective friction coefficient of condensed counterions. In this review, we analyse in detail the dielectric and conductometric behaviour of aqueous polyelectrolyte solutions in the light of recent scaling theories for polyelectrolyte conformation and summarize the state-of-the-art in this field.

Original languageEnglish (US)
Pages (from-to)R1423-R1463
JournalJournal of Physics Condensed Matter
Issue number49
StatePublished - Dec 15 2004

All Science Journal Classification (ASJC) codes

  • Materials Science(all)
  • Condensed Matter Physics


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