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Long-range specific ion-ion interactions in hydrogen-bonded liquid films
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10.1063/1.4803652
/content/aip/journal/jcp/138/18/10.1063/1.4803652
http://aip.metastore.ingenta.com/content/aip/journal/jcp/138/18/10.1063/1.4803652

Figures

Image of FIG. 1.
FIG. 1.

Schematic illustration of a droplet breakup and charge separation mechanism. is the thickness of the film. In our experiments, we sample the anions contained in the sub-micrometer-droplets generated from the center of the film, which are detected by online electrospray ionization mass spectrometry. Anions having the largest propensities for the air-liquid interface, such as I and ClO , produce the most intense mass signals. See text for details.

Image of FIG. 2.
FIG. 2.

The fractional iodide population: = [I]/([I] + [Br]) = = 0.49 + 0.43 ν/(129 + ν) in films of (5 M NaI + 5 M NaBr) solutions in HO as functions of gas velocity ν. Dashed lines correspond to 95% confidence limits. (Inset) ESI mass spectral I (m/z = 127) and Br (m/z = 79 + 81) signal intensities.

Image of FIG. 3.
FIG. 3.

The fractional iodide population: = [I]/([I] + [Br]) in films of (5 M NaI + 5 M NaBr) solutions in HO, methanol (MeOH), acetonitrile (AN), and 2-propanol (IPA) as functions of gas velocity ν. Solid lines are regressions to = A + B ν/(C + ν) functionals. Dashed lines correspond to 95% confidence limits.

Image of FIG. 4.
FIG. 4.

A depiction of interfacial concentration profiles and derived anion ratios: () = [I]/[Br] (inset), as functions of depth . Film thickness: = 1 − , is assumed to be an inverse function of gas velocity ν. = 0 corresponds to the position of the Gibbs dividing surface.

Image of FIG. 5.
FIG. 5.

The fractional iodide population: = [I]/([I] + [ClO ]) = = 0.49 − 0.40 ν/(86 + ν) in films of (5 M NaI + 5 M NaClO) solutions in HO as functions of gas velocity ν. Dashed lines correspond to 95% confidence limits. (Inset) ESI mass spectral I (m/z = 127) and ClO (m/z = 99 + 101) signal intensities.

Image of FIG. 6.
FIG. 6.

The fractional bromide population: = [Br]/([Br] + [NO ]) in films of (5 M NaBr + 5 M NaNO) solutions in HO as functions of gas velocity ν. Solid lines are regressions to = A + B ν/(C + ν) functionals. Dashed lines correspond to 95% confidence limits. (Inset) ESI mass spectral Br (m/z = 79 + 81) and NO (m/z = 62) signal intensities.

Image of FIG. 7.
FIG. 7.

Semi-logarithmic plots of the ratio of ESI mass spectral signal intensities = I/Br in films of (5 M NaI + 5 M NaBr) solutions in HO as a function of added NaClO or NaNO at ν = 66 m/s (upper panel) or 274 m/s (lower panel) gas velocities. Dashed lines correspond to the values of (0) = 1.45 and 3.50, respectively.

Image of FIG. 8.
FIG. 8.

Semi-logarithmic plots of the ratio of ESI mass spectral signal intensities = I/Br in films of (1 M NaI + 1 M NaBr) solutions in HO, methanol (MeOH), acetonitrile (AN), or 2-propanol (IPA) as a function of added NaClO or NaNO at ν = 160 m/s. Dashed lines correspond to values of (0).

Tables

Generic image for table
Table I.

Solvent properties at 298 K.

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/content/aip/journal/jcp/138/18/10.1063/1.4803652
2013-05-09
2014-04-21
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Long-range specific ion-ion interactions in hydrogen-bonded liquid films
http://aip.metastore.ingenta.com/content/aip/journal/jcp/138/18/10.1063/1.4803652
10.1063/1.4803652
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