Overpotential
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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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Tafel Equation
The Tafel equation is an equation in electrochemical kinetics relating the rate of an electrochemical reaction to the overpotential. The Tafel equation was first deduced experimentally and was later shown to have a theoretical justification. The equation is named after Swiss chemist Julius Tafel." It describes how the electrical current through an electrode depends on the voltage difference between the electrode and the bulk electrolyte for a simple, unimolecular redox reaction ". Ox + n e^- \leftrightarrows Red Where an electrochemical reaction occurs in two half reactions on separate electrodes, the Tafel equation is applied to each electrode separately. On a single electrode the Tafel equation can be stated as: where * the plus sign under the exponent refers to an anodic reaction, and a minus sign to a cathodic reaction, *\eta : overpotential, V * A : " Tafel slope", V * i : current density, A/m2 *i_0 : "exchange current density", A/m2. A verification plus further explanati ...
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Chlorine
Chlorine is a chemical element with the Symbol (chemistry), symbol Cl and atomic number 17. The second-lightest of the halogens, it appears between fluorine and bromine in the periodic table and its properties are mostly intermediate between them. Chlorine is a yellow-green gas at room temperature. It is an extremely reactive element and a strong oxidising agent: among the elements, it has the highest electron affinity and the third-highest electronegativity on the revised Electronegativity#Pauling electronegativity, Pauling scale, behind only oxygen and fluorine. Chlorine played an important role in the experiments conducted by medieval Alchemy, alchemists, which commonly involved the heating of chloride Salt (chemistry), salts like ammonium chloride (sal ammoniac) and sodium chloride (common salt), producing various chemical substances containing chlorine such as hydrogen chloride, mercury(II) chloride (corrosive sublimate), and hydrochloric acid (in the form of ). However ...
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Faraday Efficiency
Faraday efficiency (also called ''faradaic efficiency'', ''faradaic yield'', ''coulombic efficiency'' or ''current efficiency'') describes the efficiency with which charge (electrons) is transferred in a system facilitating an electrochemical reaction. The word "Faraday" in this term has two interrelated aspects. First, the historic unit for charge is the faraday, but has since been replaced by the coulomb. Secondly, the related Faraday's constant correlates charge with moles of matter and electrons (amount of substance). This phenomenon was originally understood through Michael Faraday's work and expressed in his laws of electrolysis. Sources of faradaic loss Faradaic losses are experienced by both electrolytic and galvanic cells when electrons or ions participate in unwanted side reactions. These losses appear as heat and/or chemical byproducts. An example can be found in the oxidation of water to oxygen at the positive electrode in electrolysis. Some electrons are diverte ...
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Electrochemical Reaction Mechanism
In chemistry, an electrochemical reaction mechanism is the step by step sequence of elementary steps, involving at least one outer sphere electron transfer, by which an overall chemical change occurs. Overview Elementary steps like proton coupled electron transfer and the movement of electrons between an electrode and substrate are special to electrochemical processes. Electrochemical mechanisms are important to all redox chemistry including corrosion, redox active photochemistry including photosynthesis, other biological systems often involving electron transport chains and other forms of homogeneous and heterogeneous electron transfer. Such reactions are most often studied with standard three electrode techniques such as cyclic voltammetry(CV), chronoamperometry, and bulk electrolysis as well as more complex experiments involving rotating disk electrodes and rotating ring-disk electrodes. In the case of photoinduced electron transfer the use of time-resolved spectroscopy ...
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Cyclic Voltammetry
Cyclic voltammetry (CV) is a type of potentiodynamic electrochemical measurement. In a cyclic voltammetry experiment, the working electrode potential is ramped linearly versus time. Unlike in linear sweep voltammetry, after the set potential is reached in a CV experiment, the working electrode's potential is ramped in the opposite direction to return to the initial potential. These cycles of ramps in potential may be repeated as many times as needed. The current at the working electrode is plotted versus the applied voltage (that is, the working electrode's potential) to give the cyclic voltammogram trace. Cyclic voltammetry is generally used to study the electrochemical properties of an analyte in solution or of a molecule that is adsorbed onto the electrode. Experimental method In cyclic voltammetry (CV), the electrode potential ramps linearly versus time in cyclical phases (Figure 2). The rate of voltage change over time during each of these phases is known as the experiment ...
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Galvanic Cell
A galvanic cell or voltaic cell, named after the scientists Luigi Galvani and Alessandro Volta, respectively, is an electrochemical cell in which an electric current is generated from spontaneous Oxidation-Reduction reactions. A common apparatus generally consists of two different metals, each immersed in separate beakers containing their respective metal ions in solution that are connected by a salt bridge or separated by a porous membrane. Volta was the inventor of the voltaic pile, the first Battery (electricity), electrical battery. In common usage, the word "battery" has come to include a single galvanic cell, but a battery properly consists of multiple cells. History In 1780, Luigi Galvani discovered that when two different metals (e.g., copper and zinc) are in contact and then both are touched at the same time to two different parts of a muscle of a frog leg, to close the circuit, the frog's leg contracts. He called this "bioelectricity, animal electricity". The frog ...
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Electrochemistry
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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Hydrogen
Hydrogen is the chemical element with the symbol H and atomic number 1. Hydrogen is the lightest element. At standard conditions hydrogen is a gas of diatomic molecules having the formula . It is colorless, odorless, tasteless, non-toxic, and highly combustible. Hydrogen is the most abundant chemical substance in the universe, constituting roughly 75% of all normal matter.However, most of the universe's mass is not in the form of baryons or chemical elements. See dark matter and dark energy. Stars such as the Sun are mainly composed of hydrogen in the plasma state. Most of the hydrogen on Earth exists in molecular forms such as water and organic compounds. For the most common isotope of hydrogen (symbol 1H) each atom has one proton, one electron, and no neutrons. In the early universe, the formation of protons, the nuclei of hydrogen, occurred during the first second after the Big Bang. The emergence of neutral hydrogen atoms throughout the universe occurred about 370,000 ...
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Oxygen
Oxygen is the chemical element with the symbol O and atomic number 8. It is a member of the chalcogen group in the periodic table, a highly reactive nonmetal, and an oxidizing agent that readily forms oxides with most elements as well as with other compounds. Oxygen is Earth's most abundant element, and after hydrogen and helium, it is the third-most abundant element in the universe. At standard temperature and pressure, two atoms of the element bind to form dioxygen, a colorless and odorless diatomic gas with the formula . Diatomic oxygen gas currently constitutes 20.95% of the Earth's atmosphere, though this has changed considerably over long periods of time. Oxygen makes up almost half of the Earth's crust in the form of oxides.Atkins, P.; Jones, L.; Laverman, L. (2016).''Chemical Principles'', 7th edition. Freeman. Many major classes of organic molecules in living organisms contain oxygen atoms, such as proteins, nucleic acids, carbohydrates, and fats, as ...
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Silver
Silver is a chemical element with the Symbol (chemistry), symbol Ag (from the Latin ', derived from the Proto-Indo-European wikt:Reconstruction:Proto-Indo-European/h₂erǵ-, ''h₂erǵ'': "shiny" or "white") and atomic number 47. A soft, white, lustrous transition metal, it exhibits the highest electrical conductivity, thermal conductivity, and reflectivity of any metal. The metal is found in the Earth's crust in the pure, free elemental form ("native silver"), as an alloy with gold and other metals, and in minerals such as argentite and chlorargyrite. Most silver is produced as a byproduct of copper, gold, lead, and zinc Refining (metallurgy), refining. Silver has long been valued as a precious metal. Silver metal is used in many bullion coins, sometimes bimetallism, alongside gold: while it is more abundant than gold, it is much less abundant as a native metal. Its purity is typically measured on a per-mille basis; a 94%-pure alloy is described as "0.940 fine". As one of th ...
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Second
The second (symbol: s) is the unit of time in the International System of Units (SI), historically defined as of a day – this factor derived from the division of the day first into 24 hours, then to 60 minutes and finally to 60 seconds each (24 × 60 × 60 = 86400). The current and formal definition in the International System of Units ( SI) is more precise:The second ..is defined by taking the fixed numerical value of the caesium frequency, Δ''ν''Cs, the unperturbed ground-state hyperfine transition frequency of the caesium 133 atom, to be when expressed in the unit Hz, which is equal to s−1. This current definition was adopted in 1967 when it became feasible to define the second based on fundamental properties of nature with caesium clocks. Because the speed of Earth's rotation varies and is slowing ever so slightly, a leap second is added at irregular intervals to civil time to keep clocks in sync with Earth's rotation. Uses Analog clocks and watches often ...
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Aluminium
Aluminium (aluminum in American and Canadian English) is a chemical element with the symbol Al and atomic number 13. Aluminium has a density lower than those of other common metals, at approximately one third that of steel. It has a great affinity towards oxygen, and forms a protective layer of oxide on the surface when exposed to air. Aluminium visually resembles silver, both in its color and in its great ability to reflect light. It is soft, non-magnetic and ductile. It has one stable isotope, 27Al; this isotope is very common, making aluminium the twelfth most common element in the Universe. The radioactivity of 26Al is used in radiodating. Chemically, aluminium is a post-transition metal in the boron group; as is common for the group, aluminium forms compounds primarily in the +3 oxidation state. The aluminium cation Al3+ is small and highly charged; as such, it is polarizing, and bonds aluminium forms tend towards covalency. The strong affinity tow ...
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