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Ionization properties of interfaces and linear polyelectrolytes: a discrete charge Ising model

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  • Borkovec, Michal
  • Daicic, John
  • Koper, Ger J.M.

Abstract

The proton binding characteristics of ionizable interfaces and linear polyelectrolytes are different. While ionizable interfaces protonate in a single broad protonation step, linear polyelectrolytes often show distinct two-step protonation behavior. We explain this phenomenon on the basis of a discrete charge Ising model. The interaction energies between two sites are derived by considering two point charges in a dielectric medium in contact with an electrolyte solution. A semi-infinite dielectric is used to model the planar interface, while a dielectric cylinder mimics the linear polyelectrolyte. For the plane, the inter-charge potential is stronger and much more long ranged than for the cylinder. This results in a mean-field like behavior for the planar system, while for the cylinder the interactions are short ranged and the system behaves in a non-mean-field like fashion. The model is in semi-quantitative agreement with experimental data for fatty-acid monolayers, water–oxide interfaces, and various linear polyelectrolytes.

Suggested Citation

  • Borkovec, Michal & Daicic, John & Koper, Ger J.M., 2001. "Ionization properties of interfaces and linear polyelectrolytes: a discrete charge Ising model," Physica A: Statistical Mechanics and its Applications, Elsevier, vol. 298(1), pages 1-23.
    • Handle: RePEc:eee:phsmap:v:298:y:2001:i:1:p:1-23
    DOI: 10.1016/S0378-4371(01)00207-2
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