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Electrokinetic flows about conducting drops

Published online by Cambridge University Press:  02 April 2013

Ory Schnitzer
Affiliation:
Department of Mathematics, Technion – Israel Institute of Technology, Haifa 32000, Israel
Itzchak Frankel
Affiliation:
Department of Aerospace Engineering, Technion – Israel Institute of Technology, Haifa 32000, Israel
Ehud Yariv*
Affiliation:
Department of Mathematics, Technion – Israel Institute of Technology, Haifa 32000, Israel
*
Email address for correspondence: udi@technion.ac.il

Abstract

We consider electrokinetic flows about a freely suspended liquid drop, deriving a macroscale description in the thin-double-layer limit where the ratio $\delta $ between Debye width and drop size is asymptotically small. In this description, the electrokinetic transport occurring within the diffuse part of the double layer (the ‘Debye layer’) is represented by effective boundary conditions governing the pertinent fields in the electro-neutral bulk, wherein the generally non-uniform distribution of $\zeta $, the dimensionless zeta potential, is a priori unknown. We focus upon highly conducting drops. Since the tangential electric field vanishes at the drop surface, the viscous stress associated with Debye-scale shear, driven by Coulomb body forces, cannot be balanced locally by Maxwell stresses. The requirement of microscale stress continuity therefore brings about a unique velocity scaling, where the standard electrokinetic scale is amplified by a ${\delta }^{- 1} $ factor. This reflects a transition from slip-driven electro-osmotic flows to shear-induced motion. The macroscale boundary conditions display distinct features reflecting this unique scaling. The effective shear-continuity condition introduces a Lippmann-type stress jump, appearing as a product of the local charge density and electric field. This term, representing the excess Debye-layer shear, follows here from a systematic coarse-graining procedure starting from the exact microscale description, rather than from thermodynamic considerations. The Neumann condition governing the bulk electric field is inhomogeneous, representing asymptotic matching with transverse ionic fluxes emanating from the Debye layer; these fluxes, in turn, are associated with non-uniform tangential ‘surface’ currents within this layer. Their appearance at leading order is a manifestation of dominant advection associated with the large velocity scale. For weak fields, the linearized macroscale equations admit an analytic solution, yielding a closed-form expression for the electrophoretic velocity. When scaled by Smoluchowski’s speed, it reads

$${\delta }^{- 1} \frac{\sinh ( \overline{\zeta } / 2)/ \overline{\zeta } }{1+ { \textstyle\frac{3}{2} }\mu + 2\alpha {\mathop{\sinh }\nolimits }^{2} ( \overline{\zeta } / 2)} ,$$
wherein $ \overline{\zeta } $, the ‘drop zeta potential’, is the uniform value of $\zeta $ in the absence of an applied field, $\mu $ the ratio of drop to electrolyte viscosities, and $\alpha $ the ionic drag coefficient. The difference from solid-particle electrophoresis is manifested in two key features: the ${\delta }^{- 1} $ scaling, and the effect of ionic advection, as represented by the appearance of $\alpha $. Remarkably, our result differs from the small-$\delta $ limit of the mobility expression predicted by the weak-field model of Ohshima, Healy & White (J. Chem. Soc. Faraday Trans. 2, vol. 80, 1984, pp. 1643–1667). This discrepancy is related to the dominance of advection on the bulk scale, even for weak fields, which feature cannot be captured by a linear theory. The order of the respective limits of thin double layers and weak applied fields is not interchangeable.

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Papers
Copyright
©2013 Cambridge University Press

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References

Anderson, J. L. 1989 Colloid transport by interfacial forces. Annu. Rev. Fluid Mech. 30, 139165.Google Scholar
Batchelor, G. K. 1967 An Introduction to Fluid Dynamics. Cambridge University Press.Google Scholar
Baygents, J. C. & Saville, D. A. 1989 The circulation produced in a drop by an electric field: a high field strength electrokinetic model. In Drops & Bubbles, Third International Colloquium, Monterey 1988 (ed. Wang, T.), AIP Conference Proceedings, vol. 7, pp. 717. Am. Inst. Physics.Google Scholar
Baygents, J. C. & Saville, D. A. 1991a Electrophoresis of drops and bubbles. J. Chem. Soc. Faraday Trans. 87 (12), 18831898.CrossRefGoogle Scholar
Baygents, J. C. & Saville, D. A. 1991b Electrophoresis of small particles and fluid globules in weak electrolytes. J. Colloid Interface Sci. 146 (1), 937.CrossRefGoogle Scholar
Booth, F. 1951 The cataphoresis of spherical fluid droplets in electrolytes. J. Chem. Phys. 19, 13311336.CrossRefGoogle Scholar
Derjaguin, B. V. & Dukhin, S. S. 1974 Nonequilibrium double layer and electrokinetic phenomena. In Electrokinetic Phenomena (ed. Matijevic, E.), Surface and Colloid Science, vol. 7, pp. 273336. John Wiley.Google Scholar
Dukhin, S. S. 1993 Non-equilibrium electric surface phenomena. Adv. Colloid Interface Sci. 44, 1134.CrossRefGoogle Scholar
Frumkin, A. 1946 New electrocapillary phenomena. J. Colloid Sci. 1 (3), 277291.Google Scholar
Happel, J. & Brenner, H. 1965 Low Reynolds Number Hydrodynamics. Prentice-Hall.Google Scholar
Keh, H. J. & Anderson, J. L. 1985 Boundary effects on electrophoretic motion of colloidal spheres. J. Fluid Mech. 153, 417439.CrossRefGoogle Scholar
Khair, A. S. & Squires, T. M. 2009a The influence of hydrodynamic slip on the electrophoretic mobility of a spherical colloidal particle. Phys. Fluids 21, 042001.Google Scholar
Khair, A. S. & Squires, T. M. 2009b Ion steric effects on electrophoresis of a colloidal particle. J. Fluid Mech. 640, 343356.CrossRefGoogle Scholar
Landau, L. D. & Lifshitz, E. M. 1960 Electrodynamics of Continuous Media. Course of Theoretical Physics, Permagon.Google Scholar
Leal, L. G. 2007 Fluid Mechanics and Convective Transport Processes. Advanced Transport Phenomena, Cambridge University Press.Google Scholar
Levich, V. G. 1962 Physicochemical Hydrodynamics. Prentice-Hall.Google Scholar
Levine, S. & O’Brien, R. N. 1973 A theory of electrophoresis of charged mercury drops in aqueous electrolyte solution. J. Colloid Interface Sci. 43 (3), 616629.CrossRefGoogle Scholar
Lyklema, J. 1995 Fundamentals of Interface and Colloid Science, vol. II. Academic.Google Scholar
Mugele, F. & Baret, J. C. 2005 Electrowetting: from basics to applications. J. Phys.: Condens. Matter 17, R705R774.Google Scholar
O’Brien, R. W. 1983 The solution of the electrokinetic equations for colloidal particles with thin double layers. J. Colloid Interface Sci. 92 (1), 204216.CrossRefGoogle Scholar
O’Brien, R. W. & Hunter, R. J. 1981 The electrophoretic mobility of large colloidal particles. Can. J. Chem. 59 (13), 18781887.Google Scholar
O’Brien, R. W. & White, L. R. 1978 Electrophoretic mobility of a spherical colloidal particle. J. Chem. Soc. Faraday Trans. 74, 16071626.Google Scholar
Ohshima, H., Healy, T. & White, L. 1984 Electrokinetic phenomena in a dilute suspension of charged mercury drops. J. Chem. Soc. Faraday Trans. 2 80 (12), 16431667.Google Scholar
Pascall, A. J. & Squires, T. M. 2011 Electrokinetics at liquid/liquid interfaces. J. Fluid Mech. 684, 163191.Google Scholar
Saville, D. A. 1977 Electrokinetic effects with small particles. Annu. Rev. Fluid Mech. 9, 321337.Google Scholar
Saville, D. A. 1997 Electrohydrodynamics: the Taylor–Melcher leaky dielectric model. Annu. Rev. Fluid Mech. 29 (1), 2764.Google Scholar
Schnitzer, O., Frankel, I. & Yariv, E. 2012 Streaming-potential phenomena in the thin-Debye-layer limit. Part 2. Moderate-Péclet-number theory. J. Fluid Mech. 704, 109136.Google Scholar
Schnitzer, O. & Yariv, E. 2012a Dielectric-solid polarization at strong fields: breakdown of Smoluchowski’s electrophoresis formula. Phys. Fluids 24 (8), 082005.Google Scholar
Schnitzer, O. & Yariv, E. 2012b Induced-charge electro-osmosis beyond weak fields. Phys. Rev. E 86 (6), 061506.Google Scholar
Schnitzer, O. & Yariv, E. 2012c Macroscale description of electrokinetic flows at large zeta potentials: nonlinear surface conduction. Phys. Rev. E 86, 021503.CrossRefGoogle ScholarPubMed
Schnitzer, O. & Yariv, E. 2012d Strong-field electrophoresis. J. Fluid Mech. 701, 333351.Google Scholar
Smoluchowski, M. 1903 Contribution to the theory of electro-osmosis and related phenomena. Bull. Intl Acad. Sci. Cracovie 184, 199.Google Scholar
Tseluiko, D., Blyth, M. G., Papageorgiou, D. T. & Vanden-Broeck, J. M. 2008 Electrified viscous thin film flow over topography. J. Fluid Mech. 597, 449475.Google Scholar
Yariv, E. 2005 Induced-charge electrophoresis of nonspherical particles. Phys. Fluids 17 (5), 051702.Google Scholar
Yariv, E. 2008 Nonlinear electrophoresis of ideally polarizable spherical particles. Europhys. Lett. 82, 54004.Google Scholar
Yariv, E. 2010a An asymptotic derivation of the thin-Debye-layer limit for electrokinetic phenomena. Chem. Engng Commun. 197, 317.Google Scholar
Yariv, E. 2010b Migration of ion-exchange particles driven by a uniform electric field. J. Fluid Mech. 655, 105121.Google Scholar
Yariv, E. & Davis, A. M. J. 2010 Electro-osmotic flows over highly polarizable dielectric surfaces. Phys. Fluids 22, 052006.Google Scholar
Yariv, E., Schnitzer, O. & Frankel, I. 2011 Streaming-potential phenomena in the thin-Debye-layer limit. Part 1. General theory. J. Fluid Mech. 685, 306334.CrossRefGoogle Scholar