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In electrochemistry, ITIES (interface between two immiscible electrolyte solutions) is an electrochemical interface that is either polarisable or polarised. An ITIES is polarisable if one can change the Galvani potential difference, or in other words the difference of inner potentials between the two adjacent phases, without noticeably changing the chemical composition of the respective phases (i.e. without noticeable electrochemical reactions taking place at the interface). An ITIES system is polarised if the distribution of the different charges and redox species between the two phases determines the Galvani potential difference. Usually, one electrolyte is an aqueous electrolyte composed of hydrophilic ions such as NaCl dissolved in water and the other electrolyte is a lipophilic salt such as tetrabutylammonium tetraphenylborate dissolved in an organic solvent immiscible with water such as nitrobenzene, or 1,2-dichloroethane. Charge transfer reactions of an ITIES Three major cla ...
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Electrochemistry
Electrochemistry is the branch of physical chemistry concerned with the relationship between Electric potential, electrical potential difference and identifiable chemical change. These reactions involve Electron, electrons moving via an electronically conducting phase (typically an external electrical circuit, but not necessarily, as in Electroless nickel-phosphorus plating, electroless plating) between electrodes separated by an ionically conducting and electronically insulating electrolyte (or ionic chemical species, species in a Solution (chemistry), solution). When a chemical reaction is driven by an electrical Voltage, 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 aforementioned electron ...
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Nitrobenzene
Nitrobenzene is an aromatic nitro compound and the simplest of the nitrobenzenes, with the chemical formula C6H5 NO2. It is a water-insoluble pale yellow oil with an almond-like odor. It freezes to give greenish-yellow crystals. It is produced on a large scale from benzene as a precursor to aniline. In the laboratory, it is occasionally used as a solvent, especially for electrophilic reagents. As confirmed by X-ray crystallography, nitrobenzene is a planar molecule. Production Nitrobenzene is prepared by nitration of benzene with a mixture of concentrated sulfuric acid, water, and nitric acid. This mixture is sometimes called "mixed acid." The production of nitrobenzene is one of the most dangerous processes conducted in the chemical industry because of the exothermicity of the reaction (Δ''H'' = −117 kJ/mol). World capacity for nitrobenzene in 1985 was about 1,700,000 tonnes. The nitration process involves formation of the nitronium ion (NO2+), followed by an e ...
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Ion Transport Number
In chemistry, ion transport number, also called the transference number, is the fraction of the total electric current carried in an electrolyte by a given ionic species : :t_i = \frac Differences in transport number arise from differences in electrical mobility. For example, in an aqueous solution of sodium chloride, less than half of the current is carried by the positively charged sodium ions (cations) and more than half is carried by the negatively charged chloride ions (anions) because the chloride ions are able to move faster, i.e., chloride ions have higher mobility than sodium ions. The sum of the transport numbers for all of the ions in solution always equals unity: :\sum_i t_i = 1 The concept and measurement of transport number were introduced by Johann Wilhelm Hittorf in the year 1853. Liquid junction potential can arise from ions in a solution having different ion transport numbers. At zero concentration, the limiting ion transport numbers may be expressed in term ...
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Distribution Law
Distribution law or the Nernst's distribution law gives a generalisation which governs the distribution of a solute between two immiscible solvents. This law was first given by Nernst who studied the distribution of several solutes between different appropriate pairs of solvents. C1/C2 = Kd Where Kd is called the distribution coefficient or the partition coefficient. Concentration of X in solvent A/concentration of X in solvent B=Kď If C1 denotes the concentration of solute X in solvent A & C2 denotes the concentration In chemistry, concentration is the abundance of a constituent divided by the total volume of a mixture. Several types of mathematical description can be distinguished: '' mass concentration'', '' molar concentration'', '' number concentration'', ... of solute X in solvent B; Nernst's distribution law can be expressed as C1/C2 = Kd. This law is only valid if the solute is in the same molecular form in both the solvents. Sometimes the solute dissociates or ass ...
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Ionic Partition Diagram
Similar to Pourbaix diagrams for the speciation of redox species as a function of the redox potential and the pH, ionic partition diagrams indicate in which phase an acid or a base is predominantly present in a biphasic system as a function of the Galvani potential difference between the two phases and the pH of the aqueous solution. One of the functions of these diagrams is to reveal drug transport across biological membranes. See also * ITIES *Lipophilicity *Partition coefficient In the physical sciences, a partition coefficient (''P'') or distribution coefficient (''D'') is the ratio of concentrations of a chemical compound, compound in a mixture of two immiscible solvents at partition equilibrium, equilibrium. This rati ... References Electrochemistry {{electrochem-stub ...
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Activity Coefficient
In thermodynamics, an activity coefficient is a factor used to account for deviation of a mixture of chemical substances from ideal behaviour. In an ideal mixture, the microscopic interactions between each pair of chemical species are the same (or macroscopically equivalent, the enthalpy change of solution and volume variation in mixing is zero) and, as a result, properties of the mixtures can be expressed directly in terms of simple concentrations or partial pressures of the substances present e.g. Raoult's law. Deviations from ideality are accommodated by modifying the concentration by an ''activity coefficient''. Analogously, expressions involving gases can be adjusted for non-ideality by scaling partial pressures by a fugacity coefficient. The concept of activity coefficient is closely linked to that of activity in chemistry. Thermodynamic definition The chemical potential, \mu_\mathrm, of a substance B in an ideal mixture of liquids or an ideal solution is given ...
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Nernst Equation
In electrochemistry, the Nernst equation is a chemical thermodynamical relationship that permits the calculation of the reduction potential of a reaction ( half-cell or full cell reaction) from the standard electrode potential, absolute temperature, the number of electrons involved in the redox reaction, and activities (often approximated by concentrations) of the chemical species undergoing reduction and oxidation respectively. It was named after Walther Nernst, a German physical chemist who formulated the equation. Expression General form with chemical activities When an oxidized species () accepts a number ''z'' of electrons () to be converted in its reduced form (), the half-reaction is expressed as: : Ox + ze- -> Red The reaction quotient ('), also often called the ion activity product (''IAP''), is the ratio between the chemical activities (''a'') of the reduced form (the reductant, ) and the oxidized form (the oxidant, ). The chemical activity of a dissolved spe ...
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1,2-dichloroethane
The chemical compound 1,2-dichloroethane, commonly known as ethylene dichloride (EDC), is a chlorinated hydrocarbon. It is a colourless liquid with a chloroform-like odour. The most common use of 1,2-dichloroethane is in the production of vinyl chloride, which is used to make polyvinyl chloride (PVC) pipes, furniture and automobile upholstery, wall coverings, housewares, and automobile parts. 1,2-Dichloroethane is also used generally as an intermediate for other organic chemical compounds, and as a solvent. It forms azeotropes with many other solvents, including water (at a boiling point of ) and other chlorocarbons. History In 1794, physician Jan Rudolph Deiman, merchant Adriaan Paets van Troostwijk, chemist Anthoni Lauwerenburg, and botanist Nicolaas Bondt, under the name of Society of Dutch Chemists (), were the first to produce 1,2-dichloroethane from olefiant gas (oil-making gas, ethylene) and chlorine gas. Although the ''Gezelschap'' in practice did not do much in ...
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Immiscible
Miscibility () is the property of two chemical substance, substances to mix in all mixing ratio, proportions (that is, to fully dissolution (chemistry), dissolve in each other at any concentration), forming a homogeneity and heterogeneity, homogeneous mixture (a Solution (chemistry), solution). Such substances are said to be wikt:miscible, miscible (etymologically equivalent to the common term "wikt:mixable, mixable"). The term is most often applied to liquids but also applies to solids and gases. An example in liquids is the miscibility of water and ethanol as they mix in all proportions. By contrast, substances are said to be wikt:immiscible, immiscible if the mixture does not form a solution for certain proportions. For one example, oil is not soluble in water, so these two solvents are immiscible. As another example, butanone (methyl ethyl ketone) is immiscible in water: it is soluble in water up to about 275 grams per liter, but will separate into two Phase (matter), phases b ...
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Galvani Potential
In electrochemistry, the Galvani potential (also called Galvani potential difference, or inner potential difference, Δφ, delta phi) is the electric potential difference between two points in the bulk of two phases. These phases can be two different solids (e.g., two metals joined), or a solid and a liquid (e.g., a metal electrode submerged in an electrolyte). The Galvani potential is named after Luigi Galvani. Galvani potential between two metals First, consider the Galvani potential between two metals. When two metals are electrically isolated from each other, an arbitrary voltage difference may exist between them. However, when two different metals are brought into electronic contact, electrons will flow from the metal with a lower voltage to the metal with the higher voltage until the Fermi level of the electrons in the bulk of both phases are equal. The actual numbers of electrons that passes between the two phases is small (it depends on the capacitance between the objects ...
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