Double layer (surface science)

A double layer (DL, also called an electrical double layer, EDL) 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 (either positive or negative), consists of ions 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'. A double layer (DL, also called an electrical double layer, EDL) 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 (either positive or negative), consists of ions 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'. Interfacial DLs are most apparent in systems with a large surface area to volume ratio, such as a colloid or porous bodies with particles or pores (respectively) on the scale of micrometres to nanometres. However, DLs are important to other phenomena, such as the electrochemical behaviour of electrodes. DLs play a fundamental role in many everyday substances. For instance, homogenized milk exists only because fat droplets are covered with a DL that prevents their coagulation into butter. DLs exist in practically all heterogeneous fluid-based systems, such as blood, paint, ink and ceramic and cement slurry. The DL is closely related to electrokinetic phenomena and electroacoustic phenomena. When an electronic conductor is brought in contact with a solid or liquid ionic conductor (electrolyte), a common boundary (interface) among the two phases appears. Hermann von Helmholtz was the first to realize that charged electrodes immersed in electrolyte solutions repel the co-ions of the charge while attracting counterions to their surfaces. Two layers of opposite polarity form at the interface between electrode and electrolyte.In 1853 he showed that an electrical double layer (DL) is essentially a molecular dielectric and stores charge electrostatically. Below the electrolyte's decomposition voltage, the stored charge is linearly dependent on the voltage applied. This early model predicted a constant differential capacitance independent from the charge density depending on the dielectric constant of the electrolyte solvent and the thickness of the double-layer. This model, with a good foundation for the description of the interface, does not consider important factors including diffusion/mixing of ions in solution, the possibility of adsorption onto the surface and the interaction between solvent dipole moments and the electrode. Louis Georges Gouy in 1910 and David Leonard Chapman in 1913 both observed that capacitance was not a constant and that it depended on the applied potential and the ionic concentration. The 'Gouy–Chapman model' made significant improvements by introducing a diffuse model of the DL. In this model the charge distribution of ions as a function of distance from the metal surface allows Maxwell–Boltzmann statistics to be applied. Thus the electric potential decreases exponentially away from the surface of the fluid bulk. The Gouy-Chapman model fails for highly charged DLs. In 1924 Otto Stern suggested combining the Helmholtz model with the Gouy-Chapman model: In Stern's model, some ions adhere to the electrode as suggested by Helmholtz, giving an internal Stern layer, while some form a Gouy-Chapman diffuse layer.