title: Long-range specific ion-ion interactions in hydrogen-bonded liquid films.
abstract: 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-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.: <ri - rj>∕nm = 150 (c∕μM)(-1∕3), distances. Our findings point to the extended hydrogen-bond networks of water and methanol as likely conduits for such interactions.
authors.affiliation: The Hakubi Center for Advanced Research, Kyoto University, Kyoto 606-8302, Japan. enami.shinichi.3r@kyoto-u.ac.jp
authors.forename: Shinichi
authors.initials: S
authors.lastname: Enami
authors.forename: Agustín J
authors.initials: AJ
authors.lastname: Colussi
mesh_terms: D000838:Anions / Q000737:chemistry; D004573:Electrolytes / Q000737:chemistry; D006860:Hydrogen Bonding; D000432:Methanol / Q000737:chemistry*; D014867:Water / Q000737:chemistry*
chemical_list: D000838:Anions; D004573:Electrolytes; D014867:Water; D000432:Methanol