A different view of structure-making and structure-breaking in alkali halide aqueous solutions through x-ray absorption spectroscopy

J Chem Phys. 2014 Jun 28;140(24):244506. doi: 10.1063/1.4881600.

Abstract

X-ray absorption spectroscopy measured in transmission mode was used to study the effect of alkali and halide ions on the hydrogen-bonding (H-bonding) network of water. Cl(-) and Br(-) are shown to have insignificant effect on the structure of water while I(-) locally weakens the H-bonding, as indicated by a sharp increase of the main-edge feature in the x-ray absorption spectra. All alkali cations act as structure-breakers in water, weakening the H-bonding network. The spectral changes are similar to spectra of high density ices where the 2nd shell has collapsed due to a break-down of the tetrahedral structures, although here, around the ions, the breakdown of the local tetrahedrality is rather due to non-directional H-bonding to the larger anions. In addition, results from temperature-dependent x-ray Raman scattering measurements of NaCl solution confirm the H-bond breaking effect of Na(+) and the effect on the liquid as similar to an increase in temperature.

Publication types

  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Alkalies / chemistry
  • Hydrogen Bonding
  • Ions
  • Sodium Chloride / chemistry*
  • Solutions / chemistry*
  • Spectrum Analysis, Raman
  • Water / chemistry*
  • X-Ray Absorption Spectroscopy

Substances

  • Alkalies
  • Ions
  • Solutions
  • Water
  • Sodium Chloride