Molecular origins of the zeta potential

Predota, Milan; Machesky, Michael L.; Wesolowski, David J.

doi:10.1021/acs.langmuir.6b02493

Molecular origins of the zeta potential

Journal Article · Mon Sep 19 00:00:00 EDT 2016 · Langmuir

DOI:https://doi.org/10.1021/acs.langmuir.6b02493· OSTI ID:1333097

Predota, Milan ^[1]; Machesky, Michael L. ^[2]; Wesolowski, David J. ^[3]

Univ. of South Bohemia, Ceske Budejovice (Czech Republic)
Univ. of Illinois, Champaign, IL (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

The zeta potential (ZP) is an oft-reported measure of the macroscopic charge state of solid surfaces and colloidal particles in contact with solvents. However, the origin of this readily measurable parameter has remained divorced from the molecular-level processes governing the underlying electrokinetic phenomena, which limits its usefulness. Here, we connect the macroscopic measure to the microscopic realm through nonequilibrium molecular dynamics simulations of electroosmotic flow between parallel slabs of the hydroxylated (110) rutile (TiO₂) surface. These simulations provided streaming mobilities, which were converted to ZP via the commonly used Helmholtz-Smoluchowski equation. A range of rutile surface charge densities (0.1 to –0.4 C/m²), corresponding to pH values between about 2.8 and 9.4, in RbCl, NaCl, and SrCl₂ aqueous solutions, were modeled and compared to experimental ZPs for TiO₂ particle suspensions. Simulated ZPs qualitatively agree with experiment and show that “anomalous” ZP values and inequalities between the point of zero charge derived from electrokinetic versus pH titration measurements both arise from differing co- and counterion sorption affinities. We show that at the molecular level the ZP arises from the delicate interplay of spatially varying dynamics, structure, and electrostatics in a narrow interfacial region within about 15 Å of the surface, even in dilute salt solutions. This contrasts fundamentally with continuum descriptions of such interfaces, which predict the ZP response region to be inversely related to ionic strength. In reality the properties of this interfacial region are dominated by relatively immobile and structured water. Furthermore, viscosity values are substantially greater than in the bulk, and electrostatic potential profiles are oscillatory in nature.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1333097

Journal Information:: Langmuir, Journal Name: Langmuir Journal Issue: 40 Vol. 32; ISSN 0743-7463

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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