Cottrell Equation
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Cottrell Equation
In electrochemistry, the Cottrell equation describes the change in electric current with respect to time in a controlled potential experiment, such as chronoamperometry. Specifically it describes the current response when the potential is a step function in time. It was derived by Frederick Gardner Cottrell in 1903. For a simple redox event, such as the ferrocene/ferrocenium couple, the current measured depends on the rate at which the analyte diffuses to the electrode. That is, the current is said to be "diffusion controlled." The Cottrell equation describes the case for an electrode that is planar but can also be derived for spherical, cylindrical, and rectangular geometries by using the corresponding Laplace operator and boundary conditions in conjunction with Fick's second law of diffusion.Bard, A. J.; Faulkner, L. R. “Electrochemical Methods. Fundamentals and Applications” 2nd Ed. Wiley, New York. 2001. : i = \frac where, : i = current, in units of A : n = numbe ...
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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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Fick's Laws Of Diffusion
Fick's laws of diffusion describe diffusion and were derived by Adolf Fick in 1855. They can be used to solve for the diffusion coefficient, . Fick's first law can be used to derive his second law which in turn is identical to the diffusion equation. A diffusion process that obeys Fick's laws is called normal or Fickian diffusion; otherwise, it is called anomalous diffusion or non-Fickian diffusion. History In 1855, physiologist Adolf Fick first reported* * his now well-known laws governing the transport of mass through diffusive means. Fick's work was inspired by the earlier experiments of Thomas Graham, which fell short of proposing the fundamental laws for which Fick would become famous. Fick's law is analogous to the relationships discovered at the same epoch by other eminent scientists: Darcy's law (hydraulic flow), Ohm's law (charge transport), and Fourier's Law (heat transport). Fick's experiments (modeled on Graham's) dealt with measuring the concentrations and f ...
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Limiting Current
The faradaic current is the current generated by the reduction or oxidation of some chemical substance at an electrode. The net faradaic current is the algebraic sum of all the faradaic currents flowing through an indicator electrode or working electrode. Limiting current The limiting current in electrochemistry is the limiting value of a faradaic current that is approached as the rate of charge transfer to an electrode is increased. The limiting current can be approached, for example, by increasing the electric potential or decreasing the rate of mass transfer to the electrode. It is independent of the applied potential over a finite range, and is usually evaluated by subtracting the appropriate residual current from the measured total current. A limiting current can have the character of an adsorption, catalytic, diffusion, or kinetic current, and may include a migration current. Migration current The difference between the current that is actually obtained, at any particular val ...
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Electroanalytical Method
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. Theref ...
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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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Ligand
In coordination chemistry, a ligand is an ion or molecule (functional group) that binds to a central metal atom to form a coordination complex. The bonding with the metal generally involves formal donation of one or more of the ligand's electron pairs, often through Lewis bases. The nature of metal–ligand bonding can range from covalent to ionic. Furthermore, the metal–ligand bond order can range from one to three. Ligands are viewed as Lewis bases, although rare cases are known to involve Lewis acidic "ligands". Metals and metalloids are bound to ligands in almost all circumstances, although gaseous "naked" metal ions can be generated in a high vacuum. Ligands in a complex dictate the reactivity of the central atom, including ligand substitution rates, the reactivity of the ligands themselves, and redox. Ligand selection requires critical consideration in many practical areas, including bioinorganic and medicinal chemistry, homogeneous catalysis, and environmental chemi ...
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Fick's Law Of Diffusion
Fick's laws of diffusion describe diffusion and were derived by Adolf Fick in 1855. They can be used to solve for the diffusion coefficient, . Fick's first law can be used to derive his second law which in turn is identical to the diffusion equation. A diffusion process that obeys Fick's laws is called normal or Fickian diffusion; otherwise, it is called anomalous diffusion or non-Fickian diffusion. History In 1855, physiologist Adolf Fick first reported* * his now well-known laws governing the transport of mass through diffusive means. Fick's work was inspired by the earlier experiments of Thomas Graham, which fell short of proposing the fundamental laws for which Fick would become famous. Fick's law is analogous to the relationships discovered at the same epoch by other eminent scientists: Darcy's law (hydraulic flow), Ohm's law (charge transport), and Fourier's Law (heat transport). Fick's experiments (modeled on Graham's) dealt with measuring the concentrations and ...
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Faraday Constant
In physical chemistry, the Faraday constant, denoted by the symbol and sometimes stylized as ℱ, is the electric charge per mole of elementary charges. It is named after the English scientist Michael Faraday. Since the 2019 redefinition of SI base units, which took effect on 20 May 2019, the Faraday constant has the exactly defined value given by the product of the elementary charge ''e'' and Avogadro constant ''N''A: : : :. Derivation The Faraday constant can be thought of as the conversion factor between the mole (used in chemistry) and the coulomb (used in physics and in practical electrical measurements), and is therefore of particular use in electrochemistry. Because 1 mole contains exactly entities, and 1 coulomb contains exactly elementary charges, the Faraday constant is given by the quotient of these two quantities: :. One common use of the Faraday constant is in electrolysis calculations. One can divide the amount of charge (the current integrated over time) ...
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Laplace's Equation
In mathematics and physics, Laplace's equation is a second-order partial differential equation named after Pierre-Simon Laplace, who first studied its properties. This is often written as \nabla^2\! f = 0 or \Delta f = 0, where \Delta = \nabla \cdot \nabla = \nabla^2 is the Laplace operator,The delta symbol, Δ, is also commonly used to represent a finite change in some quantity, for example, \Delta x = x_1 - x_2. Its use to represent the Laplacian should not be confused with this use. \nabla \cdot is the divergence operator (also symbolized "div"), \nabla is the gradient operator (also symbolized "grad"), and f (x, y, z) is a twice-differentiable real-valued function. The Laplace operator therefore maps a scalar function to another scalar function. If the right-hand side is specified as a given function, h(x, y, z), we have \Delta f = h. This is called Poisson's equation, a generalization of Laplace's equation. Laplace's equation and Poisson's equation are the simplest exa ...
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Electric Current
An electric current is a stream of charged particles, such as electrons or ions, moving through an electrical conductor or space. It is measured as the net rate of flow of electric charge through a surface or into a control volume. The moving particles are called charge carriers, which may be one of several types of particles, depending on the conductor. In electric circuits the charge carriers are often electrons moving through a wire. In semiconductors they can be electrons or holes. In an electrolyte the charge carriers are ions, while in plasma, an ionized gas, they are ions and electrons. The SI unit of electric current is the ampere, or ''amp'', which is the flow of electric charge across a surface at the rate of one coulomb per second. The ampere (symbol: A) is an SI base unit. Electric current is measured using a device called an ammeter. Electric currents create magnetic fields, which are used in motors, generators, inductors, and transformers. In ordinary con ...
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Diffusion-controlled Reaction
Diffusion-controlled (or diffusion-limited) reactions are reactions in which the reaction rate is equal to the rate of transport of the reactants through the reaction medium (usually a solution). The process of chemical reaction can be considered as involving the diffusion of reactants until they encounter each other in the right stoichiometry and form an activated complex which can form the product species. The observed rate of chemical reactions is, generally speaking, the rate of the slowest or "rate determining" step. In diffusion controlled reactions the formation of products from the activated complex is much faster than the diffusion of reactants and thus the rate is governed by collision frequency. Diffusion control is rare in the gas phase, where rates of diffusion of molecules are generally very high. Diffusion control is more likely in solution where diffusion of reactants is slower due to the greater number of collisions with solvent molecules. Reactions where the activ ...
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Analyte
An analyte, component (in clinical chemistry), or chemical species is a substance or chemical constituent that is of interest in an analytical procedure. The purest substances are referred to as analytes, such as 24 karat gold, NaCl, water, etc. In reality, no substance has been found to be 100% pure in its quality, so a substance that is found to be most pure (for some metals, 99% after electrolysis) is called an analyte. See also *Analytical chemistry *Immunoassay *Magnetic immunoassay Magnetic immunoassay (MIA) is a type of diagnostic immunoassay using magnetic beads as labels in lieu of conventional enzymes (ELISA), radioisotopes (RIA) or fluorescent moieties ( fluorescent immunoassays) to detect a specified analyte. MIA involv ... References Analytical chemistry {{Analytical-chemistry-stub ...
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