Journal
JOURNAL OF CHEMICAL PHYSICS
Volume 138, Issue 18, Pages -Publisher
AMER INST PHYSICS
DOI: 10.1063/1.4803652
Keywords
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Funding
- Japan Science and Technology Agency (JST) PRESTO program
- U.S. National Science Foundation (NSF) [AGS-1238977]
- Directorate For Geosciences
- Div Atmospheric & Geospace Sciences [1238977] Funding Source: National Science Foundation
- Div Atmospheric & Geospace Sciences
- Directorate For Geosciences [0964853] Funding Source: National Science Foundation
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Anions populate fluid interfaces specifically. Here, we report experiments showing that on hydrogen-bonded interfaces anions interact specifically over unexpectedly long distances. The composition of binary electrolyte (Na+, X-/Y-) films was investigated as a function of solvent, film thickness, and third ion additions in free-standing films produced by blowing up drops with a high-speed gas. These films soon fragment into charged sub-micrometer droplets carrying excess anions detectable in situ by online electrospray ionization mass spectrometry. We found that (1) the larger anions are enriched in the thinner (nanoscopic air-liquid-air) films produced at higher gas velocities in all (water, methanol, 2-propanol, and acetonitrile) tested solvents, (2) third ions (beginning at sub-mu M levels) specifically perturb X-/Y- ratios in water and methanol but have no effect in acetonitrile or 2-propanol. Thus, among these polar organic liquids (of similar viscosities but much smaller surface tensions and dielectric permittivities than water) only on methanol do anions interact specifically over long, viz.: < r(i) - r(j)>/nm = 150 (c/mu M)(-1/3), distances. Our findings point to the extended hydrogen-bond networks of water and methanol as likely conduits for such interactions. (C) 2013 AIP Publishing LLC.
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