Anions populate fluid interfaces specifically. Here, we report experiments showing that on hydrogenbonded 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

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... 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-μM 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/μM) −1/3 , distances. Our findings point to the extended hydrogenbond networks of water and methanol as likely conduits for such interactions. © 2013 AIP Publishing LLC. [http://dx.