期刊
CHEMICAL PHYSICS LETTERS
卷 684, 期 -, 页码 433-442出版社
ELSEVIER SCIENCE BV
DOI: 10.1016/j.cplett.2017.06.018
关键词
Jones-Ray effect; Water; Ions; Interfaces; Surface tension; Second harmonic generation
资金
- Julia Jacobi Foundation
- Swiss National Science Foundation
- European Research Council [616305]
- Swiss National Science Foundation [200021163210]
The surface tension of electrolyte solutions exhibits a minimum at millimolar electrolyte concentrations and then rises with increasing concentration. This minimum, known as the Jones-Ray effect, has been hotly debated over the past 80 years. If not considered as an artifact, it is typically ascribed to a phenomenological rare binding site for ions or ion pairs. Here, we propose an alternative underlying mechanism, namely that the hydrogen bond network of water responds to the collective electrostatic field of ions by increasing its orientational order, supported by recent surface tension measurements of NaCl solutions in H2O and D2O, and second harmonic scattering experiments in combination with ion resonant second harmonic reflection experiments. Recent thermodynamic and purely electrostatic treatments of the surface tension provide support for this interpretation. In addition, concerns related to possible artifacts influencing the measurements are quantified experimentally. (C) 2017 The Author(s). Published by Elsevier B.V.
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