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Long-range specific ion-ion interactions in hydrogen-bonded liquid films

Enami, Shinichi and Colussi, Agustín J. (2013) Long-range specific ion-ion interactions in hydrogen-bonded liquid films. Journal of Chemical Physics, 138 (18). Art. No. 184706. ISSN 0021-9606. https://resolver.caltech.edu/CaltechAUTHORS:20130701-134821926

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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.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1063/1.4803652DOIArticle
http://link.aip.org/link/doi/10.1063/1.4803652PublisherArticle
ORCID:
AuthorORCID
Enami, Shinichi0000-0002-2790-7361
Colussi, Agustín J.0000-0002-3400-4101
Additional Information:© 2013 AIP Publishing LLC. Received 21 January 2013; accepted 18 April 2013; published online 9 May 2013. This work was financially supported by the Japan Science and Technology Agency (JST) PRESTO program, and by the U.S. National Science Foundation (NSF) Grant No. AGS-1238977. We thank H. Mishra and M. R. Hoffmann (Caltech) for helpful discussion. We are grateful to Professor Theofanous (UC Santa Barbara) for valuable advice.
Funders:
Funding AgencyGrant Number
Japan Science and Technology Agency (JST) PRESTO programUNSPECIFIED
NSFAGS-1238977
Subject Keywords:drops; electrolytes; hydrogen bonds; ionisation; liquid films; long-range order; mass spectroscopy; organic compounds; permittivity; surface tension; velocity, viscosity
Issue or Number:18
Classification Code:PACS: 68.15.+e; 77.22.Ch; 82.30.Rs; 82.45.Gj; 66.20.-d; 68.03.Cd
Record Number:CaltechAUTHORS:20130701-134821926
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20130701-134821926
Official Citation:Long-range specific ion-ion interactions in hydrogen-bonded liquid films Shinichi Enami and Agustin J. Colussi, J. Chem. Phys. 138, 184706 (2013), DOI:10.1063/1.4803652
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:39171
Collection:CaltechAUTHORS
Deposited By: Jason Perez
Deposited On:01 Jul 2013 21:19
Last Modified:03 Oct 2019 05:04

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