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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. Theref ...
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Analytical Chemistry
Analytical chemistry studies and uses instruments and methods to separate, identify, and quantify matter. In practice, separation, identification or quantification may constitute the entire analysis or be combined with another method. Separation isolates analytes. Qualitative analysis identifies analytes, while quantitative analysis determines the numerical amount or concentration. Analytical chemistry consists of classical, wet chemical methods and modern, instrumental methods. Classical qualitative methods use separations such as precipitation, extraction, and distillation. Identification may be based on differences in color, odor, melting point, boiling point, solubility, radioactivity or reactivity. Classical quantitative analysis uses mass or volume changes to quantify amount. Instrumental methods may be used to separate samples using chromatography, electrophoresis or field flow fractionation. Then qualitative and quantitative analysis can be performed, often with t ...
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Fluoride Selective Electrode
A fluoride selective electrode is a type of ion selective electrode sensitive to the concentration of the fluoride ion. A common example is the lanthanum fluoride electrode. Lanthanum fluoride electrode In the lanthanum fluoride electrode, the sensing element is a crystal of lanthanum fluoride (LaF3), doped with europium(II) fluoride (EuF2) to create lattice vacancies. Such a crystal is an ionic conductor by virtue of the mobility of fluoride ions which jump between lattice vacancies. An electrochemical cell may be constructed using such a crystal as a membrane separating two fluoride solutions. This cell acts as a concentration cell with transference where the fluoride transport number is 1. As transference of charge through the crystal is almost exclusively due to fluoride, the electrode is highly specific to fluoride. The only ion which significantly interferes is hydroxide (OH−). Generally such "alkaline error" can be avoided by buffering the sample to a pH below 7. Cell ...
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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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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 * Electrochemistry ...
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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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Reduction Potential
Redox potential (also known as oxidation / reduction potential, ''ORP'', ''pe'', ''E_'', or E_) is a measure of the tendency of a chemical species to acquire electrons from or lose electrons to an electrode and thereby be reduced or oxidised respectively. Redox potential is expressed in volts (V). Each species has its own intrinsic redox potential; for example, the more positive the reduction potential (reduction potential is more often used due to general formalism in electrochemistry), the greater the species' affinity for electrons and tendency to be reduced. Measurement and interpretation In aqueous solutions, redox potential is a measure of the tendency of the solution to either gain or lose electrons when it is subjected to change by introduction of a new species. A solution with a higher (more positive) reduction potential than the new species will have a tendency to gain electrons from the new species (i.e. to be reduced by oxidizing the new species) and a solution with ...
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Bulk Electrolysis
Bulk electrolysis is also known as ''potentiostatic coulometry'' or ''controlled potential coulometry''. The experiment is a form of coulometry which generally employs a three electrode system controlled by a potentiostat. In the experiment the working electrode is held at a constant potential (volts) and current (amps) is monitored over time ( seconds). In a properly run experiment an analyte is quantitatively converted from its original oxidation state to a new oxidation state, either reduced or oxidized. As the substrate is consumed, the current also decreases, approaching zero when the conversion nears completion. The results of a ''bulk electrolysis'' are visually displayed as the total coulombs passed (total electric charge) plotted against time in seconds, even though the experiment measures electric current ( amps) over time. This is done to show that the experiment is approaching an expected total number of coulombs. Fundamental relationships and applications T ...
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Electron
The electron ( or ) is a subatomic particle with a negative one elementary electric charge. Electrons belong to the first generation of the lepton particle family, and are generally thought to be elementary particles because they have no known components or substructure. The electron's mass is approximately 1/1836 that of the proton. Quantum mechanical properties of the electron include an intrinsic angular momentum ( spin) of a half-integer value, expressed in units of the reduced Planck constant, . Being fermions, no two electrons can occupy the same quantum state, in accordance with the Pauli exclusion principle. Like all elementary particles, electrons exhibit properties of both particles and waves: They can collide with other particles and can be diffracted like light. The wave properties of electrons are easier to observe with experiments than those of other particles like neutrons and protons because electrons have a lower mass and hence a longer de Broglie wavele ...
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PH Meter
A pH meter is a scientific instrument that measures the hydrogen-ion activity in water-based solutions, indicating its acidity or alkalinity expressed as pH. The pH meter measures the difference in electrical potential between a pH electrode and a reference electrode, and so the pH meter is sometimes referred to as a "potentiometric pH meter". The difference in electrical potential relates to the acidity or pH of the solution. Testing of pH via pH meters (pH-metry) is used in many applications ranging from laboratory experimentation to quality control. Applications The rate and outcome of chemical reactions taking place in water often depends on the acidity of the water, and it is therefore useful to know the acidity of the water, typically measured by means of a pH meter. Knowledge of pH is useful or critical in many situations, including chemical laboratory analyses. pH meters are used for soil measurements in agriculture, water quality for municipal water supplies, sw ...
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Electron Transfer
Electron transfer (ET) occurs when an electron relocates from an atom or molecule to another such chemical entity. ET is a mechanistic description of certain kinds of redox reactions involving transfer of electrons. Electrochemical processes are ET reaction. ET reactions are relevant to photosynthesis and respiration. ET reactions commonly involve transition metal complexes, In organic chemistry ET is a step in some commercial polymerization reactions. It is foundational to photoredox catalysis. Classes of electron transfer Inner-sphere electron transfer In inner-sphere ET, the two redox centers are covalently linked during the ET. This bridge can be permanent, in which case the electron transfer event is termed intramolecular electron transfer. More commonly, however, the covalent linkage is transitory, forming just prior to the ET and then disconnecting following the ET event. In such cases, the electron transfer is termed intermolecular electron transfer. A famous exa ...
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Thermodynamic Activity
In chemical thermodynamics, activity (symbol ) is a measure of the "effective concentration" of a species in a mixture, in the sense that the species' chemical potential depends on the activity of a real solution in the same way that it would depend on concentration for an ideal solution. The term "activity" in this sense was coined by the American chemist Gilbert N. Lewis in 1907. By convention, activity is treated as a dimensionless quantity, although its value depends on customary choices of standard state for the species. The activity of pure substances in condensed phases (solid or liquids) is normally taken as unity (the number 1). Activity depends on temperature, pressure and composition of the mixture, among other things. For gases, the activity is the effective partial pressure, and is usually referred to as fugacity. The difference between activity and other measures of concentration arises because the interactions between different types of molecules in non-ideal gas ...
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