期刊
JOURNAL OF PHYSICAL CHEMISTRY B
卷 117, 期 20, 页码 6276-6281出版社
AMER CHEMICAL SOC
DOI: 10.1021/jp401285f
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资金
- Japan Science and Technology Agency (JST) PRESTO program
- Div Atmospheric & Geospace Sciences
- Directorate For Geosciences [1238977] Funding Source: National Science Foundation
Specific ion effects at aqueous interfaces play key roles in many important phenomena. We recently reported that ions interact specifically over unexpectedly long distances on the surface of sub-micromolar electrolyte solutions (Enami et al. J. Chem. Phys. 2012, 136, 154707). Whether the anionic and cationic headgroups of the organic amphiphiles present at most water/hydrophobe interfaces act similarly or display new behaviors, however, is not known. Here we report the results of experiments in which we apply online electrospray ionization mass spectrometry (ESI-MS) to investigate how carboxylate, RCOO- (R = CH3, C5H11, C7H15), and alkylammonium, R'(CH3)(3)N+ (R' = CH3, C14H29), ions affect the ratio chi = I-/Br- at the aerial interface of 1 mu M (NaI + NaBr) aqueous solutions. We found that chi is systematically but selectively depressed by these ionic amphiphiles and minimally affected by the neutral surfactant 1-octanol. The depressing effects induced by cationic headgroups are stronger than those caused by anionic surfactants and always increase with the length of the alkyl chains.
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