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Interactions in Water Across Interfaces: From Nano to Macro-Scale Perspective

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Transport and Reactivity of Solutions in Confined Hydrosystems

Abstract

In this work we first revisit the surface forces between two (model) mineral surfaces, mica, across an aqueous solution (KNO3) over a broad range of concentrations. The significantly improved resolution available from the extended surface force apparatus (eSFA) allows the distinction of hydrated-ion structures. Above concentrations of 0.3 mM, hydrated-ion correlations give rise to multiple collective transitions (4 ± 1 Å) in the electrical double layers upon interpenetration. These features are interpreted as the result of hydrated-ion ordering (layering), and are responsible for hydration forces, in contrast to the traditional interpretation invoking water layering. At concentrations as low as 20 mM, attractive surface forces are measured in deviation to the DLVO theory. The estimated hydration number of the ions in the confined electrolyte is significantly below that of the bulk. A confined 1–3 nm thick ionic layer condensates at concentrations >100 mM, i.e. below bulk saturation. This study leads to new insights into crystal growth in nano-confinement that differs from the classical theory of crystallization. Finally, the impact of the properties of confined water or solution and in-pore crystallization on the macro-scale description of soil water distribution is discussed.

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Acknowledgements

I would like to acknowledge M. Heuberger, N.D. Spencer, J.F. van der Veen, and S. Chodankar for scientific discussions. Technical support for the eSFA was provided by J. Vanicek, M. Elsener and G. Cossu. This work was supported by the Swiss National Science Foundation. Selected figures from [11] reproduced by permission of the PCCP Owner Societies.

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Authors and Affiliations

  1. Environmental Engineering and Science, Department of Civil & Environmental Engineering, University of Illinois at Urbana-Champaign, Illinois, USA

    Rosa M. Espinosa-Marzal

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  1. Rosa M. Espinosa-Marzal
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Correspondence to Rosa M. Espinosa-Marzal .

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Editors and Affiliations

  1. Institute of Earth Sciences, University of Orléans, Orléans, France

    Lionel Mercury

  2. Department of Transducers Science and Technology, MESA+ Institute for Nanotechnology, University of Twente, Enschede, The Netherlands

    Niels Tas

  3. The Hydrological Service; Research Division, Israeli Water Authority, Jerusalem, Israel

    Michael Zilberbrand

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Espinosa-Marzal, R.M. (2014). Interactions in Water Across Interfaces: From Nano to Macro-Scale Perspective. In: Mercury, L., Tas, N., Zilberbrand, M. (eds) Transport and Reactivity of Solutions in Confined Hydrosystems. NATO Science for Peace and Security Series C: Environmental Security. Springer, Dordrecht. https://doi.org/10.1007/978-94-007-7534-3_1

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