Existence of oriented ion-hydroxide clusters in concentrated aqueous NaCl solution at pH 13

J Phys Chem B. 2008 Jan 31;112(4):1262-6. doi: 10.1021/jp075031w. Epub 2008 Jan 4.

Abstract

We probe the local electronic structure at solvated Na+ ions in 1 M aqueous NaCl solutions as a function of pH. A dramatic change in the Na+ white line intensity in X-ray absorption is observed for high pH values, reflecting a changing local electronic structure at the Na+ ions when OH- is present. Given the relative abundance of sodium and hydroxide ions, we conclude that one OH- affects at least 2.4+/-0.6 Na+ ions in an electronically noticeable way at pH 13. From the experimental data we infer that spatially extended clusters or networks incorporating Na+ and OH- can exist in the electrolyte solution. The experimental data are complemented by molecular dynamics simulations, which indicate the presence of structured clusters incorporating Na+, OH-, and solvent molecules.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Hydrogen-Ion Concentration
  • Hydroxides / chemistry*
  • Oxygen / chemistry
  • Sodium Chloride / chemistry*
  • Solutions
  • Surface Properties

Substances

  • Hydroxides
  • Solutions
  • Sodium Chloride
  • hydroxide ion
  • Oxygen