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ELECTROCHEMICAL THEORY

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The electrochemical cells are of extreme importance in physical chemistry and in everyday life, and several examples of the two main types of electrochemical cells are in widespread use in all areas of manufacture and energy storage. The electrochemical cell, or galvanic cell, is a device that converts chemical energy into electrical energy or vice versa when a chemical reaction is occurring. | E ELECTROCHEMICAL THEORY Contents Thermod namics Double La er Kinetics Electrokinetics Electrocr stali ation H drogen E olution Oxygen Evolution Corrosion Non Farada Electrochemical Modi cation of Catal sts Acti it Thermodynamics S Panero Sapienza University of Rome Rome Italy 2009 Elsevier B.V. All rights reserved. The Electrical Double Layer and the Formation of Electric Potential at Interfaces The electrochemical cells are of extreme importance in physical chemistry and in everyday life and several examples of the two main types of electrochemical cells are in widespread use in all areas of manufacture and energy storage. The electrochemical cell or galvanic cell is a device that converts chemical energy into electrical energy or vice versa when a chemical reaction is occurring. Typically it consists of two electronically conducting phases solid or liquid metals and semiconductors connected by an ionically conducting phase e.g. aqueous or nonaqueous solution molten salt and ionically conducting solid . Whenever two phases that have significant electrical conductivities come into contact there is generally some redistribution of charge for instance by charge transfer across the metal-solution interface by orientation of dipoles near the interface and by adsorption of charged particles at the interface. The region containing this distribution of charge is known as the electrical double layer since the total charge excess on the one side of the interface must for reasons of overall electroneutrality be exactly equal and opposite to that on the other side. When a metal is immersed in a solution of an electrolyte the charge on the metal side of the interface corresponds to a surplus or deficit of electrons in the surface atomic layer. In most models the metal is taken to have a perfect planar surface. In practice there are always grain boundaries and point defects present. Even in the case of a perfect single crystal facet low coordination reconstruction surfaces may

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