Conductivity and dielectric relaxation in concentrated aqueous lithium chloride solutions

C. T. Moynihan, R. D. Bressel, C. A. Angell

Research output: Contribution to journalArticlepeer-review

62 Scopus citations

Abstract

This paper describes a study of the recently recognized phenomenon of conductivity relaxation in liquid electrolytes as it is observed in the system LiCl+water. Advantage has been taken of the supercooling ability of 6-20m solutions in this system to reduce solution temperatures to the vicinity of -100°C and thereby to increase the relaxation time characteristic of the conductance process sufficiently to permit its study with conventional ac conductance bridges operating in the frequency range 0.2-2 000 kHz. Extensive data are presented for four solutions in the concentration range 8.3-11.9m. When the frequency-dependent conduclance and capacitance data are analyzed in the dielectric modulus notation developed by Macedo, Bose, and IJtovitz, mean relaxation times for conductance are obtained which have a non-Arrhenius temperature dependence identical to that of the dc conductivity. Earlier studies of dielectric relaxation in these solutions, carried out at room temperature and gigahertz frequencies, are re-analyzed and shown to correspond to the high-temperature extension of the same phenomenon examined at low temperatures in the present study. The characteristic migration distance associated with the conductivity relaxation time, assessed using the Nernst-Einstein equation, is of ionic dimensions. The presence of subsidiary higher-frequency relaxations is noted and their origin considered in relation to Goldstein's ubiquitous "localized motions" in glasses.

Original languageEnglish (US)
Pages (from-to)4414-4424
Number of pages11
JournalThe Journal of chemical physics
Volume55
Issue number9
DOIs
StatePublished - Jan 1 1971
Externally publishedYes

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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