TY - JOUR
T1 - Diffusiophoretic and diffusioosmotic velocities for mixtures of valence-asymmetric electrolytes
AU - Gupta, Ankur
AU - Rallabandi, Bhargav
AU - Stone, Howard A.
N1 - Funding Information:
We are thankful for the financial support from the Andlinger Center for Energy and the Environment at Princeton University and the NSF via grant CBET-1702693. We thank Suin Shin and Jessica L. Wilson for useful discussions. We also acknowledge the two anonymous referees for their comments and suggestions as they were crucial to significantly improving our manuscript.
Publisher Copyright:
© 2019 American Physical Society..
PY - 2019/4
Y1 - 2019/4
N2 - Diffusiophoresis and diffusioosmosis are electrokinetic phenomena where relative motion is induced between a charged surface and a surrounding electrolyte due to a concentration gradient of ions. In the literature, a relative velocity between a surface and the electrolyte has been derived for a valence-symmetric (z:z) electrolyte. In this article, we reformulate the governing equations in a convenient form based on a systematic generalization of the nonlinear Poisson-Boltzmann equations in the limit of a thin double layer, which allows us to derive results for diffusiophoretic and diffusioosmotic velocities for a mixture of electrolytes with a general combination of cation and anion valences. We find that the relative motion depends significantly on ion valences. We also provide analytical approximations for the diffusiophoretic and diffusioosmotic velocities and discuss their accuracy and applicability. Further, we tabulate diffusiphoretic velocities for some common cases, which highlights the importance of asymmetry in cation and anion valences. Finally, we discuss the validity of our assumptions and the importance of effects such as finite ion size, dielectric decrement, and surface conduction for typical experimental conditions.
AB - Diffusiophoresis and diffusioosmosis are electrokinetic phenomena where relative motion is induced between a charged surface and a surrounding electrolyte due to a concentration gradient of ions. In the literature, a relative velocity between a surface and the electrolyte has been derived for a valence-symmetric (z:z) electrolyte. In this article, we reformulate the governing equations in a convenient form based on a systematic generalization of the nonlinear Poisson-Boltzmann equations in the limit of a thin double layer, which allows us to derive results for diffusiophoretic and diffusioosmotic velocities for a mixture of electrolytes with a general combination of cation and anion valences. We find that the relative motion depends significantly on ion valences. We also provide analytical approximations for the diffusiophoretic and diffusioosmotic velocities and discuss their accuracy and applicability. Further, we tabulate diffusiphoretic velocities for some common cases, which highlights the importance of asymmetry in cation and anion valences. Finally, we discuss the validity of our assumptions and the importance of effects such as finite ion size, dielectric decrement, and surface conduction for typical experimental conditions.
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U2 - 10.1103/PhysRevFluids.4.043702
DO - 10.1103/PhysRevFluids.4.043702
M3 - Article
AN - SCOPUS:85065039170
SN - 2469-990X
VL - 4
JO - Physical Review Fluids
JF - Physical Review Fluids
IS - 4
M1 - 043702
ER -