Proton magnetic resonance chemical shifts and the hydrogen bond in concentrated aqueous electrolyte solutions

E. J. Sare, C. T. Moynihan, C. A. Angell

Research output: Contribution to journalArticle

29 Scopus citations

Abstract

Proton chemical shifts have been measured over the temperature range 0-100° for concentrated solutions in 28 salt-water systems. A wide variety of cation charge/radius ratios and anion basicities are included. For salts of a given cation, correlations of the magnitude of the downfield shift, and especially of the temperature dependence of the shift, are found with the anion basicity. This is attributed to the importance in these solutions of hydrogen bonds between cation-solvated water molecules and nearest neighbor anions. The interpretation is consistent with the further finding that, for constant anion and salt/water ratio (R), shifts may be correlated with the hydrolysis constant of the various cations. The magnitude of the downfield shift for R = 10 Al(NO3)3 is striking. Solutions of thiocyanate ions are anomalous. The relation of the temperature dependence of the shift to temperature-induced hydrogen bond rupturing, to solution configurational heat capacities, to solution glass transition temperatures, and to hydration number assessments, is considered.

Original languageEnglish (US)
Pages (from-to)1869-1876
Number of pages8
JournalJournal of physical chemistry
Volume77
Issue number15
DOIs
StatePublished - Jan 1 1973
Externally publishedYes

ASJC Scopus subject areas

  • Engineering(all)
  • Physical and Theoretical Chemistry

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