Voltammetry
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Voltammetry
Voltammetry is a category of electroanalytical methods used in analytical chemistry and various industrial processes. In voltammetry, information about an analyte is obtained by measuring the current as the potential is varied. The analytical data for a voltammetric experiment comes in the form of a voltammogram which plots the current produced by the analyte versus the potential of the working electrode. Theory Voltammetry is the study of current as a function of applied potential. Voltammetric methods involve electrochemical cells, and investigate the reactions occurring at electrode/electrolyte interfaces. The reactivity of analytes in these half-cells is used to determine their concentration. It is considered a dynamic electrochemical method as the applied potential is varied over time and the corresponding changes in current are measured. Most experiments control the potential(volts) of an electrode in contact with the analyte while measuring the resulting current (amperes). ...
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Electroanalytical Methods
Electroanalytical methods are a class of techniques in analytical chemistry which study an analyte by measuring the potential (volts) and/or current (amperes) in an electrochemical cell containing the analyte. These methods can be broken down into several categories depending on which aspects of the cell are controlled and which are measured. The four main categories are potentiometry (the difference in electrode potentials is measured), amperometry (electric current is the analytical signal), coulometry (charge passed during a certain time is recorded), and voltammetry (the cell's current is measured while actively altering the cell's potential). Potentiometry Potentiometry passively measures the potential of a solution between two electrodes, affecting the solution very little in the process. One electrode is called the reference electrode and has a constant potential, while the other one is an indicator electrode whose potential changes with the sample's composition. The ...
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Auxiliary 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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Working Electrode
The working electrode is the electrode in an electrochemical system on which the reaction of interest is occurring. The working electrode is often used in conjunction with an auxiliary electrode, and a reference electrode in a three electrode system. Depending on whether the reaction on the electrode is a reduction or an oxidation, the working electrode is called cathodic or anodic, respectively. Common working electrodes can consist of materials ranging from inert metals such as gold, silver or platinum, to inert carbon such as glassy carbon, boron doped diamond or pyrolytic carbon, and mercury drop and film electrodes. Chemically modified electrodes are employed for the analysis of both organic and inorganic samples. Special types * Ultramicroelectrode (UME) * Rotating disk electrode (RDE) * Rotating ring-disk electrode (RRDE) * Hanging mercury drop electrode (HMDE) * Dropping mercury electrode (DME) See also * Auxiliary electrode * Electrochemical cell * Electroche ...
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Dropping Mercury Electrode
A liquid metal electrode is an electrode that uses a liquid metal, such as mercury, Galinstan, and NaK. They can be used in electrocapillarity, voltammetry, and impedance measurements. Dropping mercury electrode The dropping mercury electrode (DME) is a working electrode made of mercury and used in polarography. Experiments run with mercury electrodes are referred to as forms of polarography even if the experiments are identical or very similar to a corresponding voltammetry experiment which uses solid working electrodes. Like other working electrodes these electrodes are used in electrochemical studies using three electrode systems when investigating reaction mechanisms related to redox chemistry among other chemical phenomena. Structure A flow of mercury passes through an insulating capillary producing a droplet which grows from the end of the capillary in a reproducible way. Each droplet grows until it reaches a diameter of about a millimeter and releases. The release ...
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Hanging Mercury Drop Electrode
A liquid metal electrode is an electrode that uses a liquid metal, such as mercury, Galinstan, and NaK. They can be used in electrocapillarity, voltammetry, and impedance measurements. Dropping mercury electrode The dropping mercury electrode (DME) is a working electrode made of mercury and used in polarography. Experiments run with mercury electrodes are referred to as forms of polarography even if the experiments are identical or very similar to a corresponding voltammetry experiment which uses solid working electrodes. Like other working electrodes these electrodes are used in electrochemical studies using three electrode systems when investigating reaction mechanisms related to redox chemistry among other chemical phenomena. Structure A flow of mercury passes through an insulating capillary producing a droplet which grows from the end of the capillary in a reproducible way. Each droplet grows until it reaches a diameter of about a millimeter and releases. The release ...
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Rotating Ring-disk Electrode
A rotating ring-disk electrode (RRDE) is a double working electrode used in hydrodynamic voltammetry, very similar to a rotating disk electrode (RDE). The electrode rotates during experiments inducing a flux of analyte to the electrode. This system used in electrochemical studies when investigating reaction mechanisms related to redox chemistry and other chemical phenomena. Structure The difference between a rotating ring-disk electrode and a rotating disk electrode is the addition of a second working electrode in the form of a ring around the central disk of the first working electrode. To operate such an electrode, it is necessary to use a potentiostat, such as a bipotentiostat, capable of controlling a four-electrode system. The two electrodes are separated by a non-conductive barrier and connected to the potentiostat through different leads. This rotating hydrodynamic electrode motif can be extended to ''rotating double-ring electrodes'', ''rotating double-ring-disk elec ...
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Amperometry
Amperometry in chemistry is detection of ions in a solution based on electric current or changes in electric current. Amperometry is used in electrophysiology to study vesicle release events using a carbon fiber electrode. Unlike patch clamp techniques, the electrode used for amperometry is not inserted into or attached to the cell, but brought in close proximity of the cell. The measurements from the electrode originate from an oxidizing reaction of a vesicle cargo released into the medium. Another technique used to measure vesicle release is capacitive measurements. History Electrochemical or amperometric detection as it was first used in ion chromatography was single-potential or DC amperometry, useful for certain electrochemically active ions such as cyanide, sulfite, and iodide. The development of pulsed amperometric detection (PAD) for analytes that fouled electrode surfaces when detected eventually helped create a new category of ion chromatography for the determination ...
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IUPAC
The International Union of Pure and Applied Chemistry (IUPAC ) is an international federation of National Adhering Organizations working for the advancement of the chemical sciences, especially by developing nomenclature and terminology. It is a member of the International Science Council (ISC). IUPAC is registered in Zürich, Switzerland, and the administrative office, known as the "IUPAC Secretariat", is in Research Triangle Park, North Carolina, United States. This administrative office is headed by IUPAC's executive director, currently Lynn Soby. IUPAC was established in 1919 as the successor of the International Congress of Applied Chemistry for the advancement of chemistry. Its members, the National Adhering Organizations, can be national chemistry societies, national academies of sciences, or other bodies representing chemists. There are fifty-four National Adhering Organizations and three Associate National Adhering Organizations. IUPAC's Inter-divisional Committe ...
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Ferrocene
Ferrocene is an organometallic compound with the formula . The molecule is a complex consisting of two cyclopentadienyl rings bound to a central iron atom. It is an orange solid with a camphor-like odor, that sublimes above room temperature, and is soluble in most organic solvents. It is remarkable for its stability: it is unaffected by air, water, strong bases, and can be heated to 400 °C without decomposition. In oxidizing conditions it can reversibly react with strong acids to form the ferrocenium cation . The rapid growth of organometallic chemistry is often attributed to the excitement arising from the discovery of ferrocene and its many analogues, such as metallocenes. History Discovery Ferrocene was discovered by accident thrice. The first known synthesis may have been made in the late 1940s by unknown researchers at Union Carbide, who tried to pass hot cyclopentadiene vapor through an iron pipe. The vapor reacted with the pipe wall, creating a "yellow slu ...
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Linear Potential Sweep
Linearity is the property of a mathematical relationship ('' function'') that can be graphically represented as a straight line. Linearity is closely related to '' proportionality''. Examples in physics include rectilinear motion, the linear relationship of voltage and current in an electrical conductor (Ohm's law), and the relationship of mass and weight. By contrast, more complicated relationships are ''nonlinear''. Generalized for functions in more than one dimension, linearity means the property of a function of being compatible with addition and scaling, also known as the superposition principle. The word linear comes from Latin ''linearis'', "pertaining to or resembling a line". In mathematics In mathematics, a linear map or linear function ''f''(''x'') is a function that satisfies the two properties: * Additivity: . * Homogeneity of degree 1: for all α. These properties are known as the superposition principle. In this definition, ''x'' is not necessarily a rea ...
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Ferrocenium
Ferrocenium tetrafluoroborate is an organometallic compound with the formula e(C5H5)2F4. This salt is composed of the cation e(C5H5)2sup>+ and the tetrafluoroborate anion (). The related hexafluorophosphate is also a popular reagent with similar properties. The cation is often abbreviated Fc+ or Cp2Fe+. The salt is deep blue in color and paramagnetic. Ferrocenium salts are sometimes used as one-electron oxidizing agents, and the reduced product, ferrocene, is inert and readily separated from ionic products. The ferrocene–ferrocenium couple is often used as a reference in electrochemistry. The standard potential of ferrocene-ferrocenium is 0.400 V vs. the normal hydrogen electrode (NHE) and is often assumed to be invariant between different solvents. Preparation Commercially available, this compound may be prepared by oxidizing ferrocene typically with ferric salts followed by addition of fluoroboric acid. A variety of other oxidants work well also, such as nitrosyl tet ...
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Supporting Electrolyte
A supporting electrolyte, in electrochemistry, according to an IUPAC definition, is an electrolyte containing chemical species that are not electroactive (within the range of potentials used) and which has an ionic strength The ionic strength of a solution is a measure of the concentration of ions in that solution. Ionic compounds, when dissolved in water, dissociate into ions. The total electrolyte concentration in solution will affect important properties such a ... and conductivity much larger than those due to the electroactive species added to the electrolyte. Supporting electrolyte is also sometimes referred to as ''inert electrolyte'' or ''inactive electrolyte''. Supporting electrolytes are widely used in electrochemical measurements when control of electrode potentials is required. This is done to increase the conductivity of the solution (to practically eliminate the so-called IR drop), to eliminate the transport of electroactive species by ion migration in the electr ...
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