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Charge Transfer Coefficient
Charge transfer coefficient, and symmetry factor (symbols ''α'' and ''β'', respectively) are two related parameters used in description of the kinetics of electrochemical reactions. They appear in the Butler–Volmer equation and related expressions. The symmetry factor and the charge transfer coefficient are dimensionless. According to an IUPAC definition, for a reaction with a single rate-determining step, the charge transfer coefficient for a cathodic reaction (the cathodic transfer coefficient, ''αc'') is defined as: :\frac = - \frac \left( \frac \right)_ The anodic transfer coefficient (''αa'') is defined by analogy: :\frac = \frac \left( \frac \right)_ where: *\nu: stoichiometric number, i.e., the number of activated complexes formed and destroyed in the overall reaction (with ''n'' electrons) * R: universal gas constant * T: absolute temperature * n: number of electrons involved in the electrode reaction * F: Faraday constant * E: electrode potential * I ...
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Chemical Kinetics
Chemical kinetics, also known as reaction kinetics, is the branch of physical chemistry that is concerned with understanding the rates of chemical reactions. It is to be contrasted with chemical thermodynamics, which deals with the direction in which a reaction occurs but in itself tells nothing about its rate. Chemical kinetics includes investigations of how experimental conditions influence the speed of a chemical reaction and yield information about the reaction's mechanism and transition states, as well as the construction of mathematical models that also can describe the characteristics of a chemical reaction. History In 1864, Peter Waage and Cato Guldberg pioneered the development of chemical kinetics by formulating the law of mass action, which states that the speed of a chemical reaction is proportional to the quantity of the reacting substances.C.M. Guldberg and P. Waage,"Studies Concerning Affinity" ''Forhandlinger i Videnskabs-Selskabet i Christiania'' (1864), 35P. W ...
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Electrode
An electrode is an electrical conductor used to make contact with a nonmetallic part of a circuit (e.g. a semiconductor, an electrolyte, a vacuum or air). Electrodes are essential parts of batteries that can consist of a variety of materials depending on the type of battery. The electrophore, invented by Johan Wilcke, was an early version of an electrode used to study static electricity. Anode and cathode in electrochemical cells Electrodes are an essential part of any battery. The first electrochemical battery made was devised by Alessandro Volta and was aptly named the Voltaic cell. This battery consisted of a stack of copper and zinc electrodes separated by brine-soaked paper disks. Due to fluctuation in the voltage provided by the voltaic cell it wasn't very practical. The first practical battery was invented in 1839 and named the Daniell cell after John Frederic Daniell. Still making use of the zinc–copper electrode combination. Since then many more batteries have be ...
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Electrochemical Kinetics
Electrochemical kinetics is the field of electrochemistry that studies the rate of electrochemical processes. This includes the study of how process conditions, such as concentration and electric potential, influence the rate of oxidation and reduction (redox) reactions that occur at the surface of an electrode, as well as an investigation into electrochemical reaction mechanisms. Two accompanying processes are involved in the electrochemical reaction and influence the overall reaction rate: * electron transfer at the interface between the electrode and the electrolyte * transport of the redox species from the interior of the solution to the surface of the electrode; the transport can occur by diffusion, convection and migration. Contributors to this field include Alexander Frumkin, John Alfred Valentine Butler, Max Volmer, and Julius Tafel. Butler-Volmer equation An elementary charge transfer step can be described by the Butler–Volmer model proposed by John Alfred Valenti ...
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Current Density
In electromagnetism, current density is the amount of charge per unit time that flows through a unit area of a chosen cross section. The current density vector is defined as a vector whose magnitude is the electric current per cross-sectional area at a given point in space, its direction being that of the motion of the positive charges at this point. In SI base units, the electric current density is measured in amperes per square metre. Definition Assume that ''A'' (SI unit: m2) is a small surface centred at a given point ''M'' and orthogonal to the motion of the charges at ''M''. If ''I'' (SI unit: A) is the electric current flowing through ''A'', then electric current density ''j'' at ''M'' is given by the limit: :j = \lim_ \frac = \left.\frac \_, with surface ''A'' remaining centered at ''M'' and orthogonal to the motion of the charges during the limit process. The current density vector j is the vector whose magnitude is the electric current density, and whose dire ...
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Overpotential
In electrochemistry, overpotential is the potential difference (voltage) between a half-reaction's thermodynamically determined reduction potential and the potential at which the redox event is experimentally observed. The term is directly related to a cell's ''voltage efficiency''. In an electrolytic cell the existence of overpotential implies that the cell requires more energy than thermodynamically expected to drive a reaction. In a galvanic cell the existence of overpotential means less energy is recovered than thermodynamics predicts. In each case the extra/missing energy is lost as heat. The quantity of overpotential is specific to each cell design and varies across cells and operational conditions, even for the same reaction. Overpotential is experimentally determined by measuring the potential at which a given current density (typically small) is achieved. Thermodynamics The four possible polarities of overpotentials are listed below. * An electrolytic cell's anode ...
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Fuel Cell
A fuel cell is an electrochemical cell that converts the chemical energy of a fuel (often hydrogen) and an oxidizing agent (often oxygen) into electricity through a pair of redox reactions. Fuel cells are different from most batteries in requiring a continuous source of fuel and oxygen (usually from air) to sustain the chemical reaction, whereas in a battery the chemical energy usually comes from substances that are already present in the battery. Fuel cells can produce electricity continuously for as long as fuel and oxygen are supplied. The first fuel cells were invented by Sir William Grove in 1838. The first commercial use of fuel cells came more than a century later following the invention of the hydrogen–oxygen fuel cell by Francis Thomas Bacon in 1932. The alkaline fuel cell, also known as the Bacon fuel cell after its inventor, has been used in NASA space programs since the mid-1960s to generate power for satellites and space capsules. Since then, fuel cells have b ...
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Battery (electricity)
An electric battery is a source of electric power consisting of one or more electrochemical cells with external connections for powering electrical devices. When a battery is supplying power, its positive terminal is the cathode and its negative terminal is the anode. The terminal marked negative is the source of electrons that will flow through an external electric circuit to the positive terminal. When a battery is connected to an external electric load, a redox reaction converts high-energy reactants to lower-energy products, and the free-energy difference is delivered to the external circuit as electrical energy. Historically the term "battery" specifically referred to a device composed of multiple cells; however, the usage has evolved to include devices composed of a single cell. Primary (single-use or "disposable") batteries are used once and discarded, as the electrode materials are irreversibly changed during discharge; a common example is the alkaline battery used ...
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Energy Barrier
In chemistry and physics, activation energy is the minimum amount of energy that must be provided for compounds to result in a chemical reaction. The activation energy (''E''a) of a reaction is measured in joules per mole (J/mol), kilojoules per mole (kJ/mol) or kilocalories per mole (kcal/mol). Activation energy can be thought of as the magnitude of the potential barrier (sometimes called the energy barrier) separating minima of the potential energy surface pertaining to the initial and final thermodynamic state. For a chemical reaction to proceed at a reasonable rate, the temperature of the system should be high enough such that there exists an appreciable number of molecules with translational energy equal to or greater than the activation energy. The term "activation energy" was introduced in 1889 by the Swedish scientist Svante Arrhenius. Other uses Although less commonly used, activation energy also applies to nuclear reactions and various other physical phenomena. ...
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Electrolyte
An electrolyte is a medium containing ions that is electrically conducting through the movement of those ions, but not conducting electrons. This includes most soluble salts, acids, and bases dissolved in a polar solvent, such as water. Upon dissolving, the substance separates into cations and anions, which disperse uniformly throughout the solvent. Solid-state electrolytes also exist. In medicine and sometimes in chemistry, the term electrolyte refers to the substance that is dissolved. Electrically, such a solution is neutral. If an electric potential is applied to such a solution, the cations of the solution are drawn to the electrode that has an abundance of electrons, while the anions are drawn to the electrode that has a deficit of electrons. The movement of anions and cations in opposite directions within the solution amounts to a current. Some gases, such as hydrogen chloride (HCl), under conditions of high temperature or low pressure can also function as electrolytes. El ...
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Partial Current
In electrochemistry, partial current is defined as the electric current associated with (anodic or cathodic) half of the electrode reaction. Depending on the electrode half-reaction, one can distinguish two types of partial current: * cathodic partial current ''Ic'' (called also cathodic current): is the flow of electrons from the electrode surface to a species in solution; * anodic partial current ''Ia'' (called also anodic current): is the flow of electrons into the electrode from a species in solution. The cathodic and anodic partial currents are defined by IUPAC. The partial current densities (''ic'' and ''ia'') are the ratios of partial currents respect to the electrode areas (''Ac'' and ''Aa''): :''ic = Ic/Ac'' :''ia = Ia/Aa'' The sum of the cathodic partial current density ''ic'' (positive) and the anodic partial current density ''ia'' (negative) gives the net current density ''i'':
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Electrochemical Reaction
Electrochemistry is the branch of physical chemistry concerned with the relationship between electrical potential difference, as a measurable and quantitative phenomenon, and identifiable chemical change, with the potential difference as an outcome of a particular chemical change, or vice versa. These reactions involve electrons moving via an electronically-conducting phase (typically an external electrical circuit, but not necessarily, as in electroless plating) between electrodes separated by an ionically conducting and electronically insulating electrolyte (or ionic species in a solution). When a chemical reaction is driven by an electrical potential difference, as in electrolysis, or if a potential difference results from a chemical reaction as in an electric battery or fuel cell, it is called an ''electrochemical'' reaction. Unlike in other chemical reactions, in electrochemical reactions electrons are not transferred directly between atoms, ions, or molecules, but via the af ...
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Electrode Potential
In electrochemistry, electrode potential is the electromotive force of a galvanic cell built from a standard reference electrode and another electrode to be characterized. By convention, the reference electrode is the standard hydrogen electrode (SHE). It is defined to have a potential of zero volts. It may also be defined as the potential difference between the charged metallic rods and salt solution. The electrode potential has its origin in the potential difference developed at the interface between the electrode and the electrolyte. It is common, for instance, to speak of the electrode potential of the M+/M redox couple. Origin and interpretation Electrode potential appears at the interface between an electrode and electrolyte due to the transfer of charged species across the interface, specific adsorption of ions at the interface, and specific adsorption/orientation of polar molecules, including those of the solvent. In an electrochemical cell, the cathode and the anode ha ...
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