腐蚀学腐蚀动力学.pptVIP

4. Corrosion Kinetics At the electrode/electrolyte interface, a charge separation between the metal surface and the electrolyte occurs. The spatial region corresponding to the charge separation is called the electrical double layer. It is usually separated into two parts, the Helmholtz layer or compact double layer and the Gouy-Chapman layer or diffuse layer. The charge at the interface establish an electric field. Within the compact layer, the electric field reaches the order of 108 to 109 V/m, and hence has an influence on the charge transfer reaction. Since corrosion is an electrochemical process involving the charge transfer reaction, its rate is significantly influenced by the electrode potential or the electric field across the double layer. . 4.1The Electrical analogue of double layerThe electrical double layer is characterized by two layers of opposite charge facing each other, as in a capacitor. The electrical current can, however, pass across the metal-solution interface, although there is some resistance to it. The electrode can then be represented by an electrical analogue composed of a capacitor parallel to resistance RF called Faradaic resistance. The RF is called also the polarization resistance or charge-transfer resistance. When iF : Faradaic current ich : current of charge accumulated in the capacitorUsually iF ich . The electrode potential is proportional to the charge Q of the double layer. Thus, the electrode potential changes under an electric current across the double layer ; E = Eeq + ?(i) ?(i)= the additional voltage due to the current flow. 4.2 Charge transfer overpotential or Activation potentialFor charge transfer reaction in metal/solution interface: M(in lattice) ? M+z (hydrated in sol.) + ze- The chemical free energy change due to the dissolution or deposition of the metal is balanced by an equivalent quantity of electrical work done by the ions in crossing the electric field imposed by the equilibrium e