Marcus received the Nobel Prize in Chemistry in for this theory. Astrophysics and Space Science Library.
Grahame modified Stern in This could occur if ions lose their solvation shell as they approach the electrode. He called ions in direct contact with the electrode "specifically adsorbed ions".
This model proposed the existence of three regions. The inner Helmholtz plane IHP passes through the centres of the specifically adsorbed ions. The outer Helmholtz plane OHP passes through the centres of solvated ions at the distance of their closest approach to the electrode.
Devanathan and Klaus Müller  proposed the BDM model of the double-layer that included the action of the solvent in the interface. They suggested that the attached molecules of the solvent, such as water, would have a fixed alignment to the electrode surface. This first layer of solvent molecules displays a strong orientation to the electric field depending on the charge. This orientation has great influence on the permittivity of the solvent that varies with field strength.
The IHP passes through the centers of these molecules. Specifically adsorbed, partially solvated ions appear in this layer. The solvated ions of the electrolyte are outside the IHP. Through the centers of these ions pass the OHP.
The diffuse layer is the region beyond the OHP. Further research with double layers on ruthenium dioxide films in by Sergio Trasatti and Giovanni Buzzanca demonstrated that the electrochemical behavior of these electrodes at low voltages with specific adsorbed ions was like that of capacitors. The specific adsorption of the ions in this region of potential could also involve a partial charge transfer between the ion and the electrode. It was the first step towards understanding pseudocapacitance.
Between and Brian Evans Conway conducted extensive fundamental and development work on ruthenium oxide electrochemical capacitors. In he described the difference between 'Supercapacitor' and 'Battery' behavior in electrochemical energy storage. In he coined the term supercapacitor to explain the increased capacitance by surface redox reactions with faradaic charge transfer between electrodes and ions. His "supercapacitor" stored electrical charge partially in the Helmholtz double-layer and partially as the result of faradaic reactions with "pseudocapacitance" charge transfer of electrons and protons between electrode and electrolyte.
The working mechanisms of pseudocapacitors are redox reactions, intercalation and electrosorption. The physical and mathematical basics of electron charge transfer absent chemical bonds leading to pseudocapacitance was developed by Rudolph A. Marcus Theory explains the rates of electron transfer reactions—the rate at which an electron can move from one chemical species to another. It was originally formulated to address outer sphere electron transfer reactions, in which two chemical species change only in their charge, with an electron jumping.
For redox reactions without making or breaking bonds, Marcus theory takes the place of Henry Eyring 's transition state theory which was derived for reactions with structural changes. Marcus received the Nobel Prize in Chemistry in for this theory. There are detailed descriptions of the interfacial DL in many books on colloid and interface science    and microscale fluid transport.
As stated by Lyklema, " This surface charge creates an electrostatic field that then affects the ions in the bulk of the liquid. This electrostatic field, in combination with the thermal motion of the ions, creates a counter charge, and thus screens the electric surface charge. The net electric charge in this screening diffuse layer is equal in magnitude to the net surface charge, but has the opposite polarity. As a result, the complete structure is electrically neutral.
The diffuse layer, or at least part of it, can move under the influence of tangential stress. There is a conventionally introduced slipping plane that separates mobile fluid from fluid that remains attached to the surface. The electric potential on the external boundary of the Stern layer versus the bulk electrolyte is referred to as Stern potential.
Electric potential difference between the fluid bulk and the surface is called the electric surface potential. It assumes that ions behave as point charges, which they cannot, and it assumes that there is no physical limits for the ions in their approach to the surface, which is not true. Stern, therefore, modified the Gouy-Chapman diffuse double layer. His theory states that ions do have finite size, so cannot approach the surface closer than a few nm.
The first ions of the Gouy-Chapman Diffuse Double Layer are not at the surface, but at some distance d away from the surface. This distance will usually be taken as the radius of the ion. As a result, the potential and concentration of the diffuse part of the layer is low enough to justify treating the ions as point charges.
Stern also assumed that it is possible that some of the ions are specifically adsorbed by the surface in the plane d , and this layer has become known as the Stern Layer. Therefore, the potential will drop by Y o - Y d over the "molecular condenser" i. Y d has become known as the zeta z potential. This diagram serves as a visual comparison of the amount of counterions in each the Stern Layer and the Diffuse Layer.
Thus, the double layer is formed in order to neutralize the charged surface and, in turn, causes an electrokinetic potential between the surface and any point in the mass of the suspending liquid. This voltage difference is on the order of millivolts and is referred to as the surface potential. The magnitude of the surface potential is related to the surface charge and the thickness of the double layer.
As we leave the surface, the potential drops off roughly linearly in the Stern layer and then exponentially through the diffuse layer, approaching zero at the imaginary boundary of the double layer. The potential curve is useful because it indicates the strength of the electrical force between particles and the distance at which this force comes into play. A charged particle will move with a fixed velocity in a voltage field. This phenomenon is called electrophoresis.
This boundary is called the slip plane and is usually defined as the point where the Stern layer and the diffuse layer meet. The relationship between zeta potential and surface potential depends on the level of ions in the solution. The figure above represents the change in charge density through the diffuse layer.
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XtremPro DVD +R DL 8X GB Min Recordable & White Inkjet Printable Printable Double Layer DVD 25 Pack Blank Discs in Spindle - Add To Cart There is a problem adding to cart. Double layer technology Optical Quantum OQDPRDL08WIP-H 8 X GB DVD+R DL White Inkjet Printable Double Layer Recordable Blank Media, Disc Spindle by Optical Quantum. A double layer or Helmholtz double layer (HDL) is an electrical double layer of positive and negative charges with a thickness equal to one molecule. This occurs at a surface where two different materials are in contact or at the surface of a metal or other substance capable of existing in a solution as ions and immersed in a dissociating solvent.