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Selective adsorption of ions to aqueous interfaces and its effects on evaporation rates

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RSC Faraday Lecture

By exploiting the strong charge-transfer-to-solvent (CTTS) resonances of selected anions in aqueous electrolytes, their interfacial adsorption properties are measured by UV-SHG spectroscopy. Temperature and concentration dependences are determined, with the goal of establishing a molecular description of selective ion adsorption. A study of thiocyanate reveals that its strong adsorption is driven by hydration forces and impeded by a novel entropy effect. A study of nitrite indicates adsorption as an ion pair with sodium. Evaporation rates are measured by combining liquid microjet technology and Raman thermometry. The relationship between surface propensities of ions and evaporation rates is investigated. A detailed molecular mechanism for both selective ion adsorption and aqueous evaporation is explored.

  • W. S. Drisdell, R. J. Saykally, R. C. Cohen “Effect of Surface Active Ions on the Rate of Water Evaporation”, J. Phys. Chem. C 114, 11880 (2010).
  • D.E. Otten, P. Shaffer, P. Geissler, R.J. Saykally “Elucidating the Mechanism of Selective Ion Adsorption to the Liguid Water Surface”, PNAS 109, 701 (2012).
  • D. E. Otten, R. Onorato, R. Michaels, J. Goodknight, R. J. Saykally “Strong Surface Adsorption of Aqueous Sodium Nitrite as an Ion Pair”, Chem. Phys. Lett. 519, 45 (2012).

This talk is part of the Theory - Chemistry Research Interest Group series.

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