Brønsted Catalysis Equation
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Brønsted Catalysis Equation
The Brønsted catalysis equation or law of correlation, after Johannes Nicolaus Brønsted, gives the relationship between acid strength and catalytic activity in general acid catalysis. :\log k = \alpha*\log(K_a) + C A plot of the common logarithm of the reaction rate constant k versus the logarithm of the ionization constant Ka for a series of acids (for example a group of substituted phenols or carboxylic acids) gives a straight line with slope α and intercept C. The Brønsted equation is a free-energy relationship. The relationship implies that the Gibbs free energy for proton dissociation is proportional to the activation energy for the catalytic step. When the relationship is not linear, the chosen group of catalysts do not operate through the same reaction mechanism. Specific and general catalysis is also found in base catalysed reactions and base Brønsted equation also exists with constant β. The Brønsted equation gives information about a reaction mechanism. Reac ...
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Johannes Nicolaus Brønsted
Johannes Nicolaus Brønsted (; 22 February 1879 – 17 December 1947) was a Danish physical chemist who is best known for developing the Brønsted–Lowry acid–base theory; he developed the theory at the same time as (but independently of) Martin Lowry. Biography Brønsted was born in Varde, Denmark on 22 February 1879. His mother died shortly after his birth, and his father died when Brønsted was 14 years old; he then moved to Copenhagen with his older sister and his stepmother. In 1897, Brønsted began his studies as a chemical engineer at the Polytechnic Institute in Copenhagen. After his first degree, Brønsted changed fields and received his magister degree in chemistry in 1902 from the University of Copenhagen. In 1905, he became an assistant at the Chemical Institute and obtained his doctoral degree in 1908. In the same year, Brønsted became a professor of physical and inorganic chemistry at the University of Copenhagen. In 1929, Brønsted was a visiting profess ...
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Activation Energy
In the Arrhenius model of reaction rates, activation energy is the minimum amount of energy that must be available to reactants for a chemical reaction to occur. The activation energy (''E''a) of a reaction is measured in kilojoules per mole (kJ/mol) or kilocalories per mole (kcal/mol). Activation energy can be thought of as a magnitude of the potential barrier (sometimes called the energy barrier) separating minima of the potential energy surface pertaining to the initial and final thermodynamic state. For a chemical reaction to proceed at a reasonable rate, the temperature of the system should be high enough such that there exists an appreciable number of molecules with translational energy equal to or greater than the activation energy. The term "activation energy" was introduced in 1889 by the Swedish scientist Svante Arrhenius. Other uses Although less commonly used, activation energy also applies to nuclear reactions and various other physical phenomena. Temperature ...
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Bell–Evans–Polanyi Principle
In physical chemistry, the Evans–Polanyi principle (also referred to as the Bell–Evans–Polanyi principle, Brønsted–Evans–Polanyi principle, or Evans–Polanyi–Semenov principle) observes that the difference in activation energy between two reactions of the same family is proportional to the difference of their enthalpy of reaction. This relationship can be expressed as : E_\text = E_0 + \alpha \Delta H, where : E_0 is the activation energy of a reference reaction of the same class, : \Delta H is the enthalpy of reaction, : \alpha characterizes the position of the transition state along the reaction coordinate (such that 0 \leq \alpha \leq 1). The Evans–Polanyi model is a linear energy relationship that serves as an efficient way to calculate activation energy of many reactions within a distinct family. The activation energy may be used to characterize the kinetic rate parameter of a given reaction through application of the Arrhenius equation. The Evans–Pola ...
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Free-energy Relationship
In physical organic chemistry, a free-energy relationship or Gibbs energy relation relates the logarithm of a reaction rate constant or equilibrium constant for one series of chemical reactions with the logarithm of the rate or equilibrium constant for a related series of reactions. Free energy relationships establish the extent at which bond formation and breakage happen in the transition state of a reaction, and in combination with kinetic isotope experiments a reaction mechanism can be determined. Free energy relationships are often used to calculate equilibrium constants since they are experimentally difficult to determine. The most common form of free-energy relationships are linear free-energy relationships (LFER). The Brønsted catalysis equation describes the relationship between the ionization constant of a series of catalysts and the reaction rate constant for a reaction on which the catalyst operates. The Hammett equation predicts the equilibrium constant or react ...
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Phenylene
In organic chemistry, the phenylene group () is based on a di-substituted benzene ring ( arylene). For example, poly(''p''-phenylene) is a polymer built up from ''para''-phenylene repeating units.p. C-9, Section 11.6, Handbook of Chemistry and Physics, 62nd Edition, 1981-1982, CRC Press The phenylene group has three structural isomer In chemistry, a structural isomer (or constitutional isomer in the IUPAC nomenclature) of a compound is a compound that contains the same number and type of atoms, but with a different connectivity (i.e. arrangement of bonds) between them. The ...s, based on which hydrogens are substituted: ''para''-phenylene, ''meta''-phenylene, and ''ortho''-phenylene. References Arenediyl groups {{Aromatic-stub ...
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Indene
Indene is an aromatic, polycyclic hydrocarbon with chemical formula . It is composed of a benzene ring fused with a cyclopentene ring. This flammable liquid is colorless although samples often are pale yellow. The principal industrial use of indene is in the production of indene/ coumarone thermoplastic resins. Substituted indenes and their closely related indane derivatives are important structural motifs found in many natural products and biologically active molecules, such as sulindac. Isolation Indene occurs naturally in coal-tar fractions boiling around 175–185 °C. It can be obtained by heating this fraction with sodium to precipitate solid "sodio-indene". This step exploits indene's weak acidity evidenced by its deprotonation by sodium to give the indenyl derivative. The sodio-indene is converted back to indene by steam distillation. Reactivity Indene readily polymerises. Oxidation of indene with acid dichromate yields homophthalic acid (''o''-carboxylpheny ...
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Phenalene
1''H''-Phenalene, often called simply phenalene is a polycyclic aromatic hydrocarbon (PAH). Like many PAHs, it is an atmospheric pollutant formed during the combustion of fossil fuels. It is the parent compound for the phosphorus-containing phosphaphenalenes. The name was proposed by German chemists in 1922 as a contraction of ''peri''phenonaphthalene. Reactions Phenalene is deprotonated by potassium methoxide to give the phenalenyl anion. See also * Zethrene * Cyclopentadiene Cyclopentadiene is an organic compound with the chemical formula, formula C5H6. It is often abbreviated CpH because the cyclopentadienyl anion is abbreviated Cp−. This colorless liquid has a strong and unpleasant odor. At room temperature, ... References Polycyclic aromatic hydrocarbons Tricyclic compounds {{hydrocarbon-stub ...
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Transition State
In chemistry, the transition state of a chemical reaction is a particular configuration along the reaction coordinate. It is defined as the state corresponding to the highest potential energy along this reaction coordinate. It is often marked with the double dagger (‡) symbol. As an example, the transition state shown below occurs during the SN2 reaction of bromoethane with a hydroxide anion: The activated complex of a reaction can refer to either the transition state or to other states along the reaction coordinate between reactants and products, especially those close to the transition state. Peter Atkins and Julio de Paula, ''Physical Chemistry'' (8th ed., W.H. Freeman 2006), p.809 According to the transition state theory, once the reactants have passed through the transition state configuration, they always continue to form products. History of concept The concept of a transition state has been important in many theories of the rates at which chemical re ...
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Reaction Mechanism
In chemistry, a reaction mechanism is the step by step sequence of elementary reactions by which overall chemical reaction occurs. A chemical mechanism is a theoretical conjecture that tries to describe in detail what takes place at each stage of an overall chemical reaction. The detailed steps of a reaction are not observable in most cases. The conjectured mechanism is chosen because it is thermodynamically feasible and has experimental support in isolated intermediates (see next section) or other quantitative and qualitative characteristics of the reaction. It also describes each reactive intermediate, activated complex, and transition state, which bonds are broken (and in what order), and which bonds are formed (and in what order). A complete mechanism must also explain the reason for the reactants and catalyst used, the stereochemistry observed in reactants and products, all products formed and the amount of each. The electron or arrow pushing method is often used in ...
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Gibbs Free Energy
In thermodynamics, the Gibbs free energy (or Gibbs energy as the recommended name; symbol is a thermodynamic potential that can be used to calculate the maximum amount of Work (thermodynamics), work, other than Work (thermodynamics)#Pressure–volume work, pressure–volume work, that may be performed by a closed system, thermodynamically closed system at constant temperature and pressure. It also provides a necessary condition for processes such as chemical reactions that may occur under these conditions. The Gibbs free energy is expressed as G(p,T) = U + pV - TS = H - TS where: * U is the internal energy of the system * H is the enthalpy of the system * S is the entropy of the system * T is the temperature of the system * V is the volume of the system * p is the pressure of the system (which must be equal to that of the surroundings for mechanical equilibrium). The Gibbs free energy change (, measured in joules in International System of Units, SI) is the ''maximum'' amount of ...
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Acid Strength
Acid strength is the tendency of an acid, symbolised by the chemical formula , to dissociate into a hydron (chemistry), proton, , and an anion, . The Dissociation (chemistry), dissociation or ionization of a strong acid in solution is effectively complete, except in its most concentrated solutions. : Examples of strong acids are hydrochloric acid (), perchloric acid (), nitric acid () and sulfuric acid (). A weak acid is only partially dissociated, or is partly ionized in water with both the undissociated acid and its dissociation products being present, in solution, in Equilibrium chemistry, equilibrium with each other. : Acetic acid () is an example of a weak acid. The strength of a weak acid is quantified by its acid dissociation constant, K_a value. The strength of a weak organic chemistry, organic acid may depend on substituent effects. The strength of an inorganic chemistry, inorganic acid is dependent on the oxidation state for the atom to which the proton may be atta ...
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Free-energy Relationship
In physical organic chemistry, a free-energy relationship or Gibbs energy relation relates the logarithm of a reaction rate constant or equilibrium constant for one series of chemical reactions with the logarithm of the rate or equilibrium constant for a related series of reactions. Free energy relationships establish the extent at which bond formation and breakage happen in the transition state of a reaction, and in combination with kinetic isotope experiments a reaction mechanism can be determined. Free energy relationships are often used to calculate equilibrium constants since they are experimentally difficult to determine. The most common form of free-energy relationships are linear free-energy relationships (LFER). The Brønsted catalysis equation describes the relationship between the ionization constant of a series of catalysts and the reaction rate constant for a reaction on which the catalyst operates. The Hammett equation predicts the equilibrium constant or react ...
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