Mechanism of Electric Polarization of Water Contact Layer at Its Interface with the Ion Crystal Surface

S. V. Shevkunov S. V. Shevkunov
Российский электрохимический журнал
Abstract / Full Text

Molecular mechanisms of the electric polarization of supercooled water at its interface with the basal face of β-AgI crystal are studied by computer simulation. By the background of thermal fluctuations at 260 K, the gradual growth of the molecular film from vapor is reproduced from the submonomolecular stage to the bulk liquid and the mechanism of electric double layer formation is analyzed in detail. Polarization of the contact layer of water is caused by the local fields at its interface with the crystal surface. The potential difference in the electric double layer emerging on the basal face of the single crystal reaches 0.88 V but is different on different faces as regards both its magnitude and sign. The asymmetry in the spatial charge distribution in the H2O molecule is responsible for the different strength of water adhesion to the surface of crystal faces containing either positive or negative ions in their crystallographic surface layer. In an aqueous electrolyte containing ionic impurities, the electric double layer field induces compensating motion of mobile charge carriers to the crystal surface and their adsorption. As a result of contact-layer polarization, a micro-crystal immersed into an electrolyte droplet exerts the distilling effect on the latter, and the adsorption of mobile ions on the surface of a solid-crystalline particle can affect its activity as the center of heterogeneous nucleation of atmospheric moisture.

Author information
  • Peter-the-Great St. Petersburg Polytechnic University, St. Petersburg, 195251, Russia

    S. V. Shevkunov

  1. Yan, J.Y. and Patey, G.N., Heterogeneous ice nucleation induced by electric fields, J. Phys. Chem. Lett., 2011, vol. 2, no. 20, p. 2555.
  2. Zielke, S.A., Bertram, A.K., and Patey, G.N., A molecular mechanism of ice nucleation on model AgI surfaces, J. Phys. Chem. B, 2015, vol. 119, no. 29, p. 9049.
  3. Tunega, D., Gerzabek, M.H., and Lischka, H., Ab initio molecular dynamics study of a monomolecular water layer on octahedral and tetrahedral kaolinite surfaces, J. Phys. Chem. B, 2004, vol. 108, no. 19, p. 5930.
  4. Zielke, S.A., Bertram, A.K., and Patey, G.N., Simulations of ice nucleation by kaolinite (001) with rigid and flexible surfaces, J. Phys. Chem. B, 2016, vol. 120, no. 8, p. 1726.
  5. Lupi, L., Hudait, A., and Molinero, V., Heterogeneous nucleation of ice on carbon surfaces, J. Am. Chem. Soc., 2014, vol. 136, no. 8, p. 3156.
  6. Singh, J. and Muller-Plathe, F., On the characterization of crystallization and ice adhesion on smooth and rough surfaces using molecular dynamics, Appl. Phys. Lett., 2014, vol. 104, p. 021603.
  7. Zhang, X.X., Lu, Y.J., and Chen, M., Crystallisation of ice in charged Pt nanochannel, Mol. Phys. 2013, vol. 111, no. 24, p. 3808.
  8. Lupi, L. and Molinero, V., Does hydrophilicity of carbon particles improve their ice nucleation ability?, J. Phys. Chem. A, 2014, vol. 118, no. 35, p. 7330.
  9. Moore, E.B., de la Llave, E., Welke, K., Scherlis, D.A., and Molinero V., Freezing, melting and structure of ice in a hydrophilic nanopore, Phys.Chem. Chem. Phys., 2010, vol. 12, no. 16, p. 4124.
  10. Bi, Y., Cabriolu, R., and Li, T., Heterogeneous ice nucleation controlled by the coupling of surface crystal-linity and surface hydrophilicity, J. Phys. Chem. C, 2016, vol. 120, no. 3, p. 1507.
  11. Zielke, S.A., Bertram, A.K., and Patey, G.N., Simulations of ice nucleation by model AgI disks and plates, J. Phys. Chem. B, 2016, vol. 120, no. 9, p. 2291.
  12. Argyris, D., Tummala, N.R., Striolo, A., and Cole, D.R., Molecular structure and dynamics in thin water films at the silica and graphite surfaces, J. Phys. Chem. C, 2008, vol. 112, no. 35, p. 13587.
  13. Wang, J., Kalinichev, A.G., and Kirkpatrick, R.J., Effects of substrate structure and composition on the structure, dynamics, and energetics of water at mineral surfaces: A molecular dynamics modeling study, Geo-chim. Cosmochim. Acta, 2006, vol. 70, no. 3, p. 562.
  14. Zeitler, T.R., Greathouse, J.A., and Cygan, R.T., Effects of thermodynamic ensembles and mineral surfaces on interfacial water structure, Phys. Chem. Chem. Phys., 2012, vol. 14, no. 5, p. 1728.
  15. Terranovaand, U. and de Leeuw, N.H., Structure and dynamics of water at the mackinawite (001) surface, J. Chem. Phys. 2016, vol. 144, p. 094706.
  16. Kratkii spravochnik fiziko-khimicheskikh velichin (A Brief Guide to Physicochemical Quantities), Mishchenko, K.P. and Ravdel, AA, Eds., Seventh Edition, Leningrad: Khimiya, 1974
  17. Damaskin, B.B. Drawing cations into the dense part of the double layer on the HG/H2O interface in 1 M solutions of KCl and KNO3, Russ. J. Electrochem., 2011, vol. 47, no. 3, p. 241.
  18. Alishahi, M., Kamali, R., and Abouali, O., Molecular dynamics study of electric double layer in nanochannel, Russ. J. Electrochem., 2015, vol. 51, no. 1, p. 49.
  19. Emets, V.V., Mel’nikov, A.A., and Damaskin, B.B., Electrical double layer in surface-inactive electrolyte solution and adsorption of halide ions from 0.1 M solutions on liquid Cd-Ga and In-Ga alloys in gamma-butyrolactone, Russ. J. Electrochem., 2016, vol. 52, no. 1, p. 7.
  20. Emets, V.V., Mel’nikov, A.A., and Damaskin, B.B., Electric double layer on renewable liquid (Cd-Ga) electrode in dimethylformamide solutions, Russ. J. Electrochem., 2017, vol. 53, no. 2, C. 117.
  21. Kompan, M.E., Malyshkin, V.G., Kuznetsov, V.P., Krivchenko, V.A., and Chernik, G.G., On energy accumulation in double layer on the surface of materials with low electron state density, Russ. J. Electrochem., 2017, vol. 53, no. 6, p. 561.
  22. Spravochnik khimika (Chemist’s Handbook), Nikolsky, B.P., Ed., Moscow: Khimiya, 1966. vol. 1.
  23. Hill, T.L., Statistical Mechanics: Principles and Selected Applications, New-York, McGraw-Hill, 1956.
  24. Aragones, J.L., MacDowell, L.G., and Vega, C., Dielectric constant of ices and water: A lesson about water interactions, J. Phys. Chem. A, 2011, vol. 115, no. 23, p. 5745.
  25. Schoenherr, M., Slater, B., Hutter, J., and VandeVondele, J., Dielectric properties of water ice, the ice Ih/XI phase transition, and an assessment of density functional theory, J. Phys. Chem. B, 2014, vol. 118, no. 2, p. 590.
  26. Hobbs, M.E., Jhon, M.Sh., and Eyring, H., The dielectric constant of liquid water and various forms of ice according to significant structure theory, Proc. Natl. Acad. Sci. U. S. A., 1966, vol. 56, no. 1, p. 31.
  27. Dengel, O., Eckener, U., Plitz, H., and Riehl, N., Ferroelectric behaviour of ice, Phys. Lett., 1964, vol. 9, no. 4, p. 291.
  28. Jackson, S.M. and Whitworth, R.W. Evidence for ferroelectric ordering of ice Ih, J. Chem. Phys. 1995, vol. 103, no. 17, p. 7647.
  29. Rusiniak, L., Electric properties of ice near solidification and melting temperature, Acta Geophys. Pol., 2004, vol. 52, no. 3, p. 363.
  30. Wyckoff, R.W.G., Crystal Structures, New York: Inter-science, 1965, vol. 1.
  31. Binder, K. and Heermann, D., Monte Carlo Simulation in Statistical Physics, Berlin: Springer, 1997.
  32. Shevkunov, S.V., The hydrate shell of a Cl ion in a planar nanopore. Thermodynamic stability, Russ. J. Electrochem., 2014, vol. 50, no. 12, p. 1118.
  33. Shevkunov, S.V., Structural transition in the OH− (H2O)n cluster in water vapors, Colloid J., 2008, vol. 70, no. 6, p. 784.
  34. Shevkunov, S.V., Charge separation in water molecule clusters under thermal fluctuations: 2. Ionization-recombination equilibrium, Colloid J., 2008, vol. 70, No. 5, p. 646.
  35. Shevkunov, S.V., Hydration of Cl- ion in a planar nanopore with hydrophilic walls.1. Molecular structure, Colloid J., 2016, vol. 78, no. 1, p. 121.
  36. Shevkunov, S.V., Numerical simulation of water vapor nucleation on electrically neutral nanoparticles, J. Exp. Theor. Physics, 2009, vol. 108, no. 3, p. 447.
  37. Shevkunov, S.V., Computer simulation of the initial stage of the nucleation of water vapors on the silver iodide crystal surface: 1. Microstructure, 2005, Colloid J., vol. 67, no. 4, p. 497.
  38. Shevkunov, S.V., Formation of the transition layer at the vapor-crystal interface, Dokl. Phys., 2005, vol. 50, no. 5, p. 234.
  39. Hale, B.N. and Kiefer, J., Studies of H2O on β-AgI surfaces: An effective pair potential model, J. Chem. Phys. 1980, vol. 73, no. 2, p. 923.
  40. Shevkunov, S.V., Computer simulation of dissociative equilibrium in aqueous NaCl electrolyte with account for polarization and ion recharging. Model of interactions, Russ. J. Electrochem., 2013, vol. 49, no. 3, p. 228.
  41. Shevkunov, S.V., Computer simulation of dissociative equilibrium in aqueous NaCl electrolyte with account for polarization and ion recharging. Ionization mechanism, Russ. J. Electrochem., 2013, vol. 49, no. 3, p. 238.
  42. Zamalin, V.M., Norman, and G.E., and Filinov, V.S., Metod Monte-Karlo v statistichskoi termodinamike (Monte-Carlo Method in Statistical Thermodynamics), Moscow: Nauka, 1977.
  43. Shevkunov, S.V., Interaction of water molecules with the electric field of an ionic-crystal surface, Russ. J. Electrochem., 2006, vol. 42, no. 1, p. 8.
  44. Shevkunov, S.V., Stimulation of vapor nucleation on perfect and imperfect hexagonal lattice surfaces, J. Exp. Theor. Phys., 2008, vol. 107, no. 6, p. 965.
  45. Wang, Ch., Lu, H., Wang, Zh., Xiu, P., Zhou, B., Zuo, G., Wan, R., Hu, J., and Fang, H., Stable liquid water droplet on a water monolayer formed at room temperature on ionic model substrates, Phys. Rev. Lett., 2009, vol. 103 p. 137801.
  46. Shevkunov, S.V., Layer-by-layer adsorption of water molecules on the surface of a silver iodide crystal, Russ. J. Phys. Chem., 2006, vol. 80, no. 5, p. 769.]
  47. Parshutkina, I.P., Churilova, I.L., Plaude, N.O., and Grishina, NP, Investigation of the effect of certain industrial gases on the efficiency of the regular ice-forming pyrodynamic compound with silver iodide, in Fizika oblakov i aktivnykh vozdeistvii. Trudy Tsentral’noi Aerologicheskoi Observatorii (Physics of Clouds and Active Impacts, Trans. Central Aerological Observatory), Plaude, N.O., Ed., St. Petersburg: Gidrometeoizdat, 1996, vol. 181, p. 69.
  48. Shevkunov, S.V., Structure and electric properties of the hydration shell of a singly charged chloride ion in a nanopore with hydrophilic walls, Russ. J. Electrochem., 2016, vol. 52, no. 5, p. 397.
  49. Shevkunov, S.V., Structure and electric properties of sodium ion hydrate shell in nanopore with hydrophilic walls, Russ. J. Electrochem., 2016, vol. 92, no. 9, p. 910.
  50. Shevkunov, S.V., Ion pairs in aqueous electrolyte microdrops under conditions of a flat nanopore, Russ. J. Electrochem., 2016, vol. 52, no. 11, p. 1064.
  51. Shevkunov, S.V., High temperature stability of hydrated ion pairs Na + Cl−(H2O)n under conditions of a flat nanopore, Russ. J. Electrochem., 2018, v. 54, no. 2, p. 153.