Surface conductivity

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Surface conductivity is an additional conductivity of an electrolyte in the vicinity of the charged interfaces. [1] Surface and volume conductivity of liquids correspond to the electrically driven motion of ions in an electric field. A layer of counter ions of the opposite polarity to the surface charge exists close to the interface. It is formed due to attraction of counter-ions by the surface charges. This layer of higher ionic concentration is a part of the interfacial double layer. The concentration of the ions in this layer is higher as compared to the ionic strength of the liquid bulk. This leads to the higher electric conductivity of this layer.

Contents

Smoluchowski was the first to recognize the importance of surface conductivity at the beginning of the 20th century. [2]

There is a detailed description of surface conductivity by Lyklema in "Fundamentals of Interface and Colloid Science" [3]

The Double Layer (DL) has two regions, according to the well established Gouy-Chapman-Stern model. [1] The upper level, which is in contact with the bulk liquid is the diffuse layer. The inner layer that is in contact with interface is the Stern layer.

It is possible that the lateral motion of ions in both parts of the DL contributes to the surface conductivity.

The contribution of the Stern layer is less well described. It is often called "additional surface conductivity". [4]

The theory of the surface conductivity of the diffuse part of the DL was developed by Bikerman. [5] He derived a simple equation that links surface conductivity κσ with the behaviour of ions at the interface. For symmetrical electrolyte and assuming identical ions diffusion coefficients D+=D=D it is given in the reference: [1]

where

F is the Faraday constant
T is the absolute temperature
R is the gas constant
C is the ionic concentration in the bulk fluid
z is the ion valency
ζ is the electrokinetic potential

The parameter m characterizes the contribution of electro-osmosis to the motion of ions within the DL:

The Dukhin number is a dimensionless parameter that characterizes the contribution of the surface conductivity to a variety of electrokinetic phenomena, such as, electrophoresis and electroacoustic phenomena. [6] This parameter and, consequently, surface conductivity can be calculated from the electrophoretic mobility using appropriate theory. Electrophoretic instrument by Malvern and electroacoustic instruments by Dispersion Technology contain software for conducting such calculations.

See also

Surface Science

Surface conductivity may refer to the electrical conduction across a solid surface measured by surface probes. Experiments may be done to test this material property as in the n-type surface conductivity of p-type. [7] Additionally, surface conductivity is measured in coupled phenomena such as photoconductivity, for example, for the metal oxide semiconductor ZnO. [8] Surface conductivity differs from bulk conductivity for analogous reasons to the electrolyte solution case, where the charge carriers of holes (+1) and electrons (-1) play the role of ions in solution.

Related Research Articles

<span class="mw-page-title-main">Electro-osmosis</span>

Electroosmotic flow is the motion of liquid induced by an applied potential across a porous material, capillary tube, membrane, microchannel, or any other fluid conduit. Because electroosmotic velocities are independent of conduit size, as long as the electrical double layer is much smaller than the characteristic length scale of the channel, electroosmotic flow will have little effect. Electroosmotic flow is most significant when in small channels. Electroosmotic flow is an essential component in chemical separation techniques, notably capillary electrophoresis. Electroosmotic flow can occur in natural unfiltered water, as well as buffered solutions.

<span class="mw-page-title-main">Electrophoresis</span> Motion of charged particles in electric field

Electrophoresis is the motion of dispersed particles relative to a fluid under the influence of a spatially uniform electric field. Electrophoresis of positively charged particles (cations) is sometimes called cataphoresis, while electrophoresis of negatively charged particles (anions) is sometimes called anaphoresis.

In plasmas and electrolytes, the Debye length, is a measure of a charge carrier's net electrostatic effect in a solution and how far its electrostatic effect persists. With each Debye length the charges are increasingly electrically screened and the electric potential decreases in magnitude by 1/e. A Debye sphere is a volume whose radius is the Debye length. Debye length is an important parameter in plasma physics, electrolytes, and colloids. The corresponding Debye screening wave vector for particles of density , charge at a temperature is given by in Gaussian units. Expressions in MKS units will be given below. The analogous quantities at very low temperatures are known as the Thomas–Fermi length and the Thomas–Fermi wave vector. They are of interest in describing the behaviour of electrons in metals at room temperature.

<span class="mw-page-title-main">Zeta potential</span> Electrokinetic potential in colloidal dispersions

Zeta potential is the electrical potential at the slipping plane. This plane is the interface which separates mobile fluid from fluid that remains attached to the surface.

The DLVO theory explains the aggregation and kinetic stability of aqueous dispersions quantitatively and describes the force between charged surfaces interacting through a liquid medium. It combines the effects of the van der Waals attraction and the electrostatic repulsion due to the so-called double layer of counterions. The electrostatic part of the DLVO interaction is computed in the mean field approximation in the limit of low surface potentials - that is when the potential energy of an elementary charge on the surface is much smaller than the thermal energy scale, . For two spheres of radius each having a charge separated by a center-to-center distance in a fluid of dielectric constant containing a concentration of monovalent ions, the electrostatic potential takes the form of a screened-Coulomb or Yukawa potential,

Electrohydrodynamics (EHD), also known as electro-fluid-dynamics (EFD) or electrokinetics, is the study of the dynamics of electrically charged fluids. It is the study of the motions of ionized particles or molecules and their interactions with electric fields and the surrounding fluid. The term may be considered to be synonymous with the rather elaborate electrostrictive hydrodynamics. ESHD covers the following types of particle and fluid transport mechanisms: electrophoresis, electrokinesis, dielectrophoresis, electro-osmosis, and electrorotation. In general, the phenomena relate to the direct conversion of electrical energy into kinetic energy, and vice versa.

A surface charge is an electric charge present on a two-dimensional surface. These electric charges are constrained on this 2-D surface, and surface charge density, measured in coulombs per square meter (C•m−2), is used to describe the charge distribution on the surface. The electric potential is continuous across a surface charge and the electric field is discontinuous, but not infinite; this is unless the surface charge consists of a dipole layer. In comparison, the potential and electric field both diverge at any point charge or linear charge.

The ionic strength of a solution is a measure of the concentration of ions in that solution. Ionic compounds, when dissolved in water, dissociate into ions. The total electrolyte concentration in solution will affect important properties such as the dissociation constant or the solubility of different salts. One of the main characteristics of a solution with dissolved ions is the ionic strength. Ionic strength can be molar or molal and to avoid confusion the units should be stated explicitly. The concept of ionic strength was first introduced by Lewis and Randall in 1921 while describing the activity coefficients of strong electrolytes.

The Gibbs adsorption isotherm for multicomponent systems is an equation used to relate the changes in concentration of a component in contact with a surface with changes in the surface tension, which results in a corresponding change in surface energy. For a binary system, the Gibbs adsorption equation in terms of surface excess is:

<span class="mw-page-title-main">Nanofluidics</span>

Nanofluidics is the study of the behavior, manipulation, and control of fluids that are confined to structures of nanometer characteristic dimensions. Fluids confined in these structures exhibit physical behaviors not observed in larger structures, such as those of micrometer dimensions and above, because the characteristic physical scaling lengths of the fluid, very closely coincide with the dimensions of the nanostructure itself.

A streaming current and streaming potential are two interrelated electrokinetic phenomena studied in the areas of surface chemistry and electrochemistry. They are an electric current or potential which originates when an electrolyte is driven by a pressure gradient through a channel or porous plug with charged walls.

Electroacoustic phenomena arise when ultrasound propagates through a fluid containing ions. The associated particle motion generates electric signals because ions have electric charge. This coupling between ultrasound and electric field is called electroacoustic phenomena. The fluid might be a simple Newtonian liquid, or complex heterogeneous dispersion, emulsion or even a porous body. There are several different electroacoustic effects depending on the nature of the fluid.

The Dukhin number is a dimensionless quantity that characterizes the contribution of the surface conductivity to various electrokinetic and electroacoustic effects, as well as to electrical conductivity and permittivity of fluid heterogeneous systems. The number was named after Stanislav and Andrei Dukhin.

<span class="mw-page-title-main">Double layer (surface science)</span> Molecular interface between a surface and a fluid

In surface science, a double layer is a structure that appears on the surface of an object when it is exposed to a fluid. The object might be a solid particle, a gas bubble, a liquid droplet, or a porous body. The DL refers to two parallel layers of charge surrounding the object. The first layer, the surface charge, consists of ions which are adsorbed onto the object due to chemical interactions. The second layer is composed of ions attracted to the surface charge via the Coulomb force, electrically screening the first layer. This second layer is loosely associated with the object. It is made of free ions that move in the fluid under the influence of electric attraction and thermal motion rather than being firmly anchored. It is thus called the "diffuse layer".

Electrokinetic phenomena are a family of several different effects that occur in heterogeneous fluids, or in porous bodies filled with fluid, or in a fast flow over a flat surface. The term heterogeneous here means a fluid containing particles. Particles can be solid, liquid or gas bubbles with sizes on the scale of a micrometer or nanometer. There is a common source of all these effects—the so-called interfacial 'double layer' of charges. Influence of an external force on the diffuse layer generates tangential motion of a fluid with respect to an adjacent charged surface. This force might be electric, pressure gradient, concentration gradient, or gravity. In addition, the moving phase might be either continuous fluid or dispersed phase.

<span class="mw-page-title-main">Interface and colloid science</span> Branch of chemistry and physics

Interface and colloid science is an interdisciplinary intersection of branches of chemistry, physics, nanoscience and other fields dealing with colloids, heterogeneous systems consisting of a mechanical mixture of particles between 1 nm and 1000 nm dispersed in a continuous medium. A colloidal solution is a heterogeneous mixture in which the particle size of the substance is intermediate between a true solution and a suspension, i.e. between 1–1000 nm. Smoke from a fire is an example of a colloidal system in which tiny particles of solid float in air. Just like true solutions, colloidal particles are small and cannot be seen by the naked eye. They easily pass through filter paper. But colloidal particles are big enough to be blocked by parchment paper or animal membrane.

Sedimentation potential occurs when dispersed particles move under the influence of either gravity or centrifugation in a medium. This motion disrupts the equilibrium symmetry of the particle's double layer. While the particle moves, the ions in the electric double layer lag behind due to the liquid flow. This causes a slight displacement between the surface charge and the electric charge of the diffuse layer. As a result, the moving particle creates a dipole moment. The sum of all of the dipoles generates an electric field which is called sedimentation potential. It can be measured with an open electrical circuit, which is also called sedimentation current.

<span class="mw-page-title-main">Diffusiophoresis and diffusioosmosis</span>

Diffusiophoresis is the spontaneous motion of colloidal particles or molecules in a fluid, induced by a concentration gradient of a different substance. In other words, it is motion of one species, A, in response to a concentration gradient in another species, B. Typically, A is colloidal particles which are in aqueous solution in which B is a dissolved salt such as sodium chloride, and so the particles of A are much larger than the ions of B. But both A and B could be polymer molecules, and B could be a small molecule. For example, concentration gradients in ethanol solutions in water move 1 μm diameter colloidal particles with diffusiophoretic velocities of order 0.1 to 1 μm/s, the movement is towards regions of the solution with lower ethanol concentration. Both species A and B will typically be diffusing but diffusiophoresis is distinct from simple diffusion: in simple diffusion a species A moves down a gradient in its own concentration.

Electrocapillarity or electrocapillary phenomena are the phenomena related to changes in the surface energy of the dropping mercury electrode (DME), or in principle, any electrode, as the electrode potential changes or the electrolytic solution composition and concentration change. The term "electro-capillary" is used to describe the change in mercury (Hg) electrode potential as a function of the change in the surface or interfacial tension of the Hg determined by the capillary rise method. The phenomena are the historic main contributions for understanding and validating the models of the structure of the electrical double layer. The phenomena are related to the electrokinetic phenomena and consequently to the colloid chemistry.

Dispersion Technology Inc is a scientific instrument manufacturer located in Bedford Hills, New York. It was founded in 1996 by Philip Goetz and Dr. Andrei Dukhin. The company develops and sells analytical instruments intended for characterizing concentrated dispersions and emulsions, complying with the International Standards for acoustic particle sizing ISO 20998 and Electroacoustic zeta potential measurement ISO 13099.

References

  1. 1 2 3 ISO International Standard 13099, Parts 1,2 and 3, “Colloidal systems – Methods for Zeta potential determination", (2012)
  2. M. von Smoluchowski, Physik, Z., 6, 529 (1905)
  3. Lyklema, J. "Fundamentals of Interface and Colloid Science", vol. 2, Academic Press, 1995
  4. Dukhin, S.S. and Derjaguin, B.V. "Electrokinetic Phenomena", John Wiley and Sons, New York (1974)
  5. Bikerman, J.J. Z.Physik.Chem. A163, 378, 1933
  6. Dukhin, A. S. and Goetz, P. J. Characterization of liquids, nano- and micro- particulates and porous bodies using Ultrasound, Elsevier, 2017 ISBN   978-0-444-63908-0
  7. Brown, W. L. (1 July 1953). "n-Type Surface Conductivity onp-Type Germanium". Physical Review. American Physical Society (APS). 91 (3): 518–527. Bibcode:1953PhRv...91..518B. doi:10.1103/physrev.91.518. ISSN   0031-899X.
  8. Shapira, Y.; Cox, S.M.; Lichtman, David (1976). "Chemisorption, photodesorption and conductivity measurements on ZnO surfaces". Surface Science. Elsevier BV. 54 (1): 43–59. Bibcode:1976SurSc..54...43S. doi:10.1016/0039-6028(76)90086-8. ISSN   0039-6028.