Universal Dielectric Enhancement from Externally Induced Double Layer Without ζζ-Potential

preprint2016arXivOpen access

Abstract

Motivated by recent experiments showing over 10410^4-fold increase in induced polarization from electrochemically inert, conducting materials in dilute saline solutions, we theoretically demonstrate a new mechanism for dielectric enhancement, in the absence of ζ−ζ-potentials at interfaces between non-insulating particles and an electrolyte solution. We further show that the magnitude of such enhancement obeys universal scaling laws, independent of the particle's electrical properties and valid across particle shapes: for a dilute suspension of identical, but arbitrarily shaped particles of a linear dimension aa and volume fraction ff, as ω→0ω\to0 the effective real dielectric constant of the mixture is enhanced from that of water by a factor 1+f (Pr+(a/λ)Pi)1+f~(P_r+(a/λ)P_i), and the frequency-dependent phase shift of its impedance has a scale-invariant maximum f Θf\,\mathsfΘ if particles are much more conductive than the solution. Here λλ is the solution's Debye length and PrP_r, PiP_i, Θ\mathsfΘ are dimensionless numbers determined solely by the particles' shape. Even for a very dilute electrolyte solution (e.g. 10−310^{-3} molar), sub-mm sized particles, at volume fraction f=0.1f=0.1, can give a 10410^4-fold dielectric enhancement, producing an easily observable phase shift maximum in a simple impedance measurement.We also derive frequency cutoffs as conditions for observing these enhancements, showing that insulating particles produce no enhancement without ζζ-potential.To prove these results for particles of arbitrary shapes, we develop a physical picture where an externally induced double layer (EIDL), in contrast to the Guoy-Chapman double layer on interfaces with significant ζζ-potentials, dominates the low-frequency dynamics and produces dielectric enhancement.

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