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Evidence for an Enhanced Hydronium Concentration at the Liquid Water Surface
Abstract
The recent demonstration of enhanced surface anion concentrations for aqueous electrolyte solutions strongly contrasts current textbook descriptions. Small cations are still expected to be repelled from the surface, but recent simulations predict that hydronium (H3O+) cations are instead preferentially adsorbed at the interface. Here we describe a comparative second harmonic generation (SHG) study of aqueous solutions of hydriodic acid (HI) and alkali iodides (NaI and KI), which establish lower limits of 55% and 34% larger surface iodide concentrations for HI solutions relative to NaI and KI solutions, respectively. This result implies that hydronium ions must exist in much higher densities near the liquid surface than do the alkali ions, in support of the theoretical predictions.
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Citations
Cited by
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Ball, P. (2008) · Chemical Reviews · doi:10.1021/cr068037a · Cited by 2,177
How Water’s Properties Are Encoded in Its Molecular Structure and Energies
Brini, E., Fennell, C. J., Fernandez-Serra, M., Hribar-Lee, B., Lukšič, M., & Dill, K. A. (2017) · Chemical Reviews · doi:10.1021/acs.chemrev.7b00259 · Cited by 518
Buch, V., Milet, A., Vácha, R., Jungwirth, P., & Devlin, J. P. (2007) · Proceedings of the National Academy of Sciences · doi:10.1073/pnas.0611285104 · Cited by 398
Autoionization at the surface of neat water: is the top layer pH neutral, basic, or acidic?
Vácha, R., Buch, V., Milet, A., Devlin, J. P., & Jungwirth, P. (2007) · Physical Chemistry Chemical Physics · doi:10.1039/b704491g · Cited by 178
Metadata
- Authors
- Petersen, P. B., & Saykally, R. J.
- Venue
- The Journal of Physical Chemistry B
- Publisher
- American Chemical Society (ACS)
- Published
- 2005-03-30
- Volume
- 109
- Issue
- 16
- Pages
- 7976-7980
- ISSN
- 1520-5207 (ISSN-L)
- 1520-6106
- OpenAlex
- W2087243552
- Cited by
- 243
- References
- 0
- FWCI
- 10.45
- Type
- journal article
- Language
- en
- Open access
- closed
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- Petersen, P. B., & Saykally, R. J. (2005). Evidence for an Enhanced Hydronium Concentration at the Liquid Water Surface. The Journal of Physical Chemistry B. https://doi.org/10.1021/jp044479j
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