Cyclic Voltammetry
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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 experimen ...
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Bordwell Thermodynamic Cycle
A Bordwell thermodynamic cycle use experimentally determined and reasonable estimates of Gibbs free energy (ΔG˚) values to determine unknown and experimentally inaccessible values. Overview Analogous to Hess's Law which deal with the summation of enthalpy (ΔH) values, Bordwell thermodynamic cycles deal with the summation of Gibbs free energy (ΔG) values. Free energies used in these systems are most often determined from equilibriums and redox potentials, both of which correlate with free energy. This is with the caveat that redox scales are not absolute and thus it is important that all electrons are evaluated in redox pairs. This removes the offset of a given reference potential, otherwise the values are reported as potentials (V) against that reference. It is also worth recognizing that the values of the pKa system are just moderately transformed Keq values. When working with equilibrium energy values such as ΔG˚ and E˚1/2 values it common to employ a naught (˚) ...
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Tetrabutylammonium Hexafluorophosphate
Tetrabutylammonium hexafluorophosphate is a salt with the formula NBu4PF6. It is a white powder that is used as an electrolyte in nonaqueous electrochemistry. It is highly soluble in polar organic solvents such as acetone and acetonitrile. The salt consists of a positively charged tetrabutylammonium, a quaternary ammonia cation and a weakly basic hexafluorophosphate Hexafluorophosphate is an anion with chemical formula of . It is an octahedral species that imparts no color to its salts. is isoelectronic with sulfur hexafluoride, , and the hexafluorosilicate dianion, , and hexafluoroantimonate . In this an ... anion. These species are chemically inert, which allows the salt to serve as an inert electrolyte over a wide potential range. Given the sensitivity of electrochemical experiments, this salt is usually further purified, e.g., by recrystallization from aqueous or absolute ethanol. References {{Hexafluorophosphates Tetrabutylammonium salts Hexafluorophosphates ...
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Graphite Electrodes
Graphite () is a crystalline form of the element carbon. It consists of stacked layers of graphene. Graphite occurs naturally and is the most stable form of carbon under standard conditions. Synthetic and natural graphite are consumed on large scale (300 kton/year, in 1989) for uses in pencils, lubricants, and electrodes. Under high pressures and temperatures it converts to diamond. It is a weak conductor of heat and electricity. Types and varieties Natural graphite The principal types of natural graphite, each occurring in different types of ore deposits, are * Crystalline small flakes of graphite (or flake graphite) occurs as isolated, flat, plate-like particles with hexagonal edges if unbroken. When broken the edges can be irregular or angular; * Amorphous graphite: very fine flake graphite is sometimes called amorphous; * Lump graphite (or vein graphite) occurs in fissure veins or fractures and appears as massive platy intergrowths of fibrous or acicular crystalli ...
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Ultramicroelectrode
An ultramicroelectrode (UME) is a working electrode used in a voltammetry. The small size of UME give them large diffusion layers and small overall currents. These features allow UME to achieve useful steady-state conditions and very high scan rates (V/s) with limited distortion. UME were developed independently by Wightman and Fleischmann around 1980. Small current at UME enables electrochemical measurements in low conductive media (organic solvents), where voltage drop associated with high solution resistance makes these experiments difficult for conventional electrodes. Furthermore, small voltage drop at UME leads to a very small voltage distortion at the electrode-solution interface which allows using two-electrode setup in voltammetric experiment instead of conventional three-electrode setup. Design Ultramicroelectrodes are often defined as electrodes which are smaller than the diffusion layer achieved in a readily accessed experiment. A working definition is an electr ...
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Gold
Gold is a chemical element with the symbol Au (from la, aurum) and atomic number 79. This makes it one of the higher atomic number elements that occur naturally. It is a bright, slightly orange-yellow, dense, soft, malleable, and ductile metal in a pure form. Chemically, gold is a transition metal and a group 11 element. It is one of the least reactive chemical elements and is solid under standard conditions. Gold often occurs in free elemental ( native state), as nuggets or grains, in rocks, veins, and alluvial deposits. It occurs in a solid solution series with the native element silver (as electrum), naturally alloyed with other metals like copper and palladium, and mineral inclusions such as within pyrite. Less commonly, it occurs in minerals as gold compounds, often with tellurium ( gold tellurides). Gold is resistant to most acids, though it does dissolve in aqua regia (a mixture of nitric acid and hydrochloric acid), forming a soluble tetrachloroaurate an ...
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Platinum
Platinum is a chemical element with the symbol Pt and atomic number 78. It is a dense, malleable, ductile, highly unreactive, precious, silverish-white transition metal. Its name originates from Spanish , a diminutive of "silver". Platinum is a member of the platinum group of elements and group 10 of the periodic table of elements. It has six naturally occurring isotopes. It is one of the rarer elements in Earth's crust, with an average abundance of approximately 5 μg/kg. It occurs in some nickel and copper ores along with some native deposits, mostly in South Africa, which accounts for ~80% of the world production. Because of its scarcity in Earth's crust, only a few hundred tonnes are produced annually, and given its important uses, it is highly valuable and is a major precious metal commodity. Platinum is one of the least reactive metals. It has remarkable resistance to corrosion, even at high temperatures, and is therefore considered a noble metal. Conse ...
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Glassy Carbon
Glass-like carbon, often called glassy carbon or vitreous carbon, is a non-graphitizing, or nongraphitizable, carbon which combines glassy and ceramic properties with those of graphite. The most important properties are high temperature resistance, hardness (7  Mohs), low density, low electrical resistance, low friction, low thermal resistance, extreme resistance to chemical attack, and impermeability to gases and liquids. Glassy carbon is widely used as an electrode material in electrochemistry, for high-temperature crucibles, and as a component of some prosthetic devices. It can be fabricated in different shapes, sizes and sections. The names ''glassy carbon'' and ''vitreous carbon'' have been registered as trademarks, and IUPAC does not recommend their use as technical terms. A historical review of glassy carbon was published in 2021. History Glassy carbon was first observed in the laboratories of The Carborundum Company, Manchester, UK, in the mid-1950s by Bernard ...
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Precipitate
In an aqueous solution, precipitation is the process of transforming a dissolved substance into an insoluble solid from a super-saturated solution. The solid formed is called the precipitate. In case of an inorganic chemical reaction leading to precipitation, the chemical reagent causing the solid to form is called the ''precipitant''. The clear liquid remaining above the precipitated or the centrifuged solid phase is also called the 'supernate' or 'supernatant'. The notion of precipitation can also be extended to other domains of chemistry (organic chemistry and biochemistry) and even be applied to the solid phases (''e.g.'', metallurgy and alloys) when solid impurities segregate from a solid phase. Supersaturation The precipitation of a compound may occur when its concentration exceeds its solubility. This can be due to temperature changes, solvent evaporation, or by mixing solvents. Precipitation occurs more rapidly from a strongly supersaturated solution. The formati ...
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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 ...
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Counter Electrode
The auxiliary electrode, often also called the counter electrode, is an electrode used in a three electrode electrochemical cell for voltammetric analysis or other reactions in which an electric current is expected to flow. The auxiliary electrode is distinct from the reference electrode, which establishes the electrical potential against which other potentials may be measured, and the working electrode, at which the cell reaction takes place. In a two-electrode system, either a known current or potential is applied between the working and auxiliary electrodes and the other variable may be measured. The auxiliary electrode functions as a cathode whenever the working electrode is operating as an anode and vice versa. The auxiliary electrode often has a surface area much larger than that of the working electrode to ensure that the half-reaction occurring at the auxiliary electrode can occur fast enough so as not to limit the process at the working electrode. When a three electrode ...
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Reference Electrode
A reference electrode is an electrode which has a stable and well-known electrode potential. The high stability of the electrode potential is usually reached by employing a redox system with constant (buffered or saturated) concentrations of each participant of the redox reaction. There are many ways reference electrodes are used. The simplest is when the reference electrode is used as a half-cell to build an electrochemical cell. This allows the potential of the other half cell to be determined. An accurate and practical method to measure an electrode's potential in isolation ( absolute electrode potential) has yet to be developed. Aqueous reference electrodes Common reference electrodes and potential with respect to the standard hydrogen electrode (SHE): * Standard hydrogen electrode (SHE) (E = 0.000 V) activity of H+ = 1 Molar * Normal hydrogen electrode (NHE) (E ≈ 0.000 V) concentration H+ = 1 Molar * Reversible hydrogen electrode (RHE) (E = 0.000 V - 0.0591 × pH) * ...
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