Existence of oriented ion-hydroxide clusters in concentrated aqueous NaCl solution at pH 13.
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.
Aziz
Emad F
EF
BESSY m.b.H., Albert-Einstein Str. 15,12489 Berlin, Germany.
Eisebitt
Stefan
S
Eberhardt
Wolfgang
W
Cwiklik
Lukasz
L
Jungwirth
Pavel
P
D006863:Hydrogen-Ion Concentration; D006878:Hydroxides / Q000737:chemistry*; D010100:Oxygen / Q000737:chemistry; D012965:Sodium Chloride / Q000737:chemistry*; D012996:Solutions; D013499:Surface Properties
D006878:Hydroxides; D012996:Solutions; D012965:Sodium Chloride; C031356:hydroxide ion; D010100:Oxygen