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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_\text 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–P ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Physical Chemistry
Physical chemistry is the study of macroscopic and microscopic phenomena in chemical systems in terms of the principles, practices, and concepts of physics such as motion, energy, force, time, thermodynamics, quantum chemistry, statistical mechanics, analytical dynamics and chemical equilibria. Physical chemistry, in contrast to chemical physics, is predominantly (but not always) a supra-molecular science, as the majority of the principles on which it was founded relate to the bulk rather than the molecular or atomic structure alone (for example, chemical equilibrium and colloids). Some of the relationships that physical chemistry strives to resolve include the effects of: # Intermolecular forces that act upon the physical properties of materials ( plasticity, tensile strength, surface tension in liquids). # Reaction kinetics on the rate of a reaction. # The identity of ions and the electrical conductivity of materials. # Surface science and electrochemistry of cel ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Activation Energy
In chemistry and physics, activation energy is the minimum amount of energy that must be provided for compounds to result in a chemical reaction. The activation energy (''E''a) of a reaction is measured in joules per mole (J/mol), kilojoules per mole (kJ/mol) or kilocalories per mole (kcal/mol). Activation energy can be thought of as the 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. ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Enthalpy Of Reaction
The standard enthalpy of reaction (denoted \Delta_ H^\ominus or \Delta H_^\ominus) for a chemical reaction is the difference between total reactant and total product molar enthalpies, calculated for substances in their standard states. This can in turn be used to predict the total chemical bond energy liberated or bound during reaction, as long as the enthalpy of mixing is also accounted for. For a generic chemical reaction :\nu_ \text + \nu_ \text ~+ ~... \rightarrow \nu_ \text + \nu_ \text ~+ ~... the standard enthalpy of reaction \Delta_ H^\ominus is related to the standard enthalpy of formation \Delta_ H^\ominus values of the reactants and products by the following equation: : \Delta_ H^\ominus = \sum_ \nu_p\Delta_ H_^ - \sum_ \nu_r\Delta_ H_^ In this equation, \nu_p and \nu_r are the stoichiometric coefficients of each product p and reactant r. The standard enthalpy of formation, which has been determined for a vast number of substances, is the change of enthalpy ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
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 react ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Reaction Coordinate
In chemistry, a reaction coordinate is an abstract one-dimensional coordinate which represents progress along a reaction pathway. It is usually a geometric parameter that changes during the conversion of one or more molecular entities. In molecular dynamics simulations, a reaction coordinate is called collective variable. These coordinates can sometimes represent a real coordinate system (such as bond length, bond angle...), although, for more complex reactions especially, this can be difficult (and non geometric parameters are used, e.g., bond order). Reaction coordinate is distinct from extent of reaction, a different parameter of reaction progress, which is a measure of the ''composition'' of the reaction system. (Free) energy is often plotted against reaction coordinate(s) to demonstrate in some schematic form the potential energy profile (an intersection of a potential energy surface) associated with the reaction. In the formalism of transition-state theory the re ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
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 reac ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Reaction Rate Constant
In chemical kinetics a reaction rate constant or reaction rate coefficient, ''k'', quantifies the rate and direction of a chemical reaction. For a reaction between reactants A and B to form product C the reaction rate is often found to have the form: r = k(T) mathrmm mathrm Here ''k''(''T'') is the reaction rate constant that depends on temperature, and and are the molar concentrations of substances A and B in moles per unit volume of solution, assuming the reaction is taking place throughout the volume of the solution. (For a reaction taking place at a boundary, one would use moles of A or B per unit area instead.) The exponents ''m'' and ''n'' are called partial orders of reaction and are ''not'' generally equal to the stoichiometric coefficients ''a'' and ''b''. Instead they depend on the reaction mechanism and can be determined experimentally. Elementary steps For an elementary step, there ''is'' a relationship between stoichiometry and rate law, as determined b ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Arrhenius Equation
In physical chemistry, the Arrhenius equation is a formula for the temperature dependence of reaction rates. The equation was proposed by Svante Arrhenius in 1889, based on the work of Dutch chemist Jacobus Henricus van 't Hoff who had noted in 1884 that the van 't Hoff equation for the temperature dependence of equilibrium constants suggests such a formula for the rates of both forward and reverse reactions. This equation has a vast and important application in determining the rate of chemical reactions and for calculation of energy of activation. Arrhenius provided a physical justification and interpretation for the formula. Laidler, K. J. (1987) ''Chemical Kinetics'', Third Edition, Harper & Row, p. 42 Currently, it is best seen as an empirical relationship.Kenneth Connors, Chemical Kinetics, 1990, VCH Publishers It can be used to model the temperature variation of diffusion coefficients, population of crystal vacancies, creep rates, and many other thermally-induced processe ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Pre-exponential Factor
In chemical kinetics, the pre-exponential factor or A factor is the pre-exponential constant in the Arrhenius equation (equation shown below), an empirical relationship between temperature and rate coefficient. It is usually designated by A when determined from experiment, while Z is usually left for collision frequency Collision frequency describes the rate of collisions between two atomic or molecular species in a given volume, per unit time. In an ideal gas, assuming that the species behave like hard spheres, the collision frequency between entities of speci .... The pre-exponential factor can be thought of as a measure of the frequency of properly oriented collisions. It is typically determined experimentally by measuring the rate constant k at a particular temperature and fitting the data to the Arrhenius equation. The pre-exponential factor is generally not exactly constant, but rather depends on the specific reaction being studied and the temperature at which the rea ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Ronald Percy Bell
Ronald Percy Bell FRS FRSC FRSE (24 November 1907 – 9 January 1996) was a leading British physical chemist who worked in the Physical Chemistry Laboratory at the University of Oxford. Life Ronald Percy Bell was the eldest child of Edwin Alfred Bell and his wife Beatrice Annie (née Ash), teachers at an elementary school. He was born on 24 November 1907 at Willowfield, Court House Road, Maidenhead; he had a brother, Kenneth, and an adopted sister, Margaret. From age 11 Bell attended Maidenhead County Boys’ School, where F. Sherwood Taylor was chemistry master, and a great influence on Bell; from there he went up to Balliol to read chemistry in 1924. Bell obtained a first-class honours degree in 1928. Unusually, he published two papers as sole author in his final year. Bell was awarded an Oxford University senior studentship in 1928 to work with Brønsted in Copenhagen, and in 1930 the Goldsmiths' Company gave him a senior studentship, enabling him to work on the the ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Meredith Gwynne Evans
Meredith Gwynne Evans, FRS (2 December 1904 – 25 December 1952) was a British physical chemist, who made important theoretical contributions in the study of chemical reaction rates and reaction mechanisms. Together with Henry Eyring and Michael Polanyi, Meredith Gwynne Evans is one of the founders of the transition state theory. Early life and education Meredith Gwynne Evans was born in Atherton, a suburb of Manchester, on 2 December 1904 and the son of Frederick George Evans, an elementary schoolmaster from Pembrokeshire, Wales, and his wife, Margaretta Eleanora Williams. He was the eldest son in a family of three sons and one daughter. Evans attended the elementary school at which his father was Headmaster, won a County Scholarship to Leigh Grammar School, and was educated at the University of Manchester. C. E. H. Bawn, Hugh Taylor, Muriel Tomlinson and Harold Hartley, "Obituary notices: Meredith Gwynne Evans, 1904–1952; James William McBain, 1882–1953; Sydney Gle ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Michael Polanyi
Michael Polanyi (; hu, Polányi Mihály; 11 March 1891 – 22 February 1976) was a Hungarian-British polymath, who made important theoretical contributions to physical chemistry, economics, and philosophy. He argued that positivism supplies an imperfect account of knowing as no observer is perfectly impartial. His wide-ranging research in physical science included chemical kinetics, x-ray diffraction, and adsorption of gases. He pioneered the theory of fibre diffraction analysis in 1921, and the dislocation theory of plastic deformation of ductile metals and other materials in 1934. He immigrated to Germany, in 1926 becoming a chemistry professor at the Kaiser Wilhelm Institute in Berlin, and then in 1933 to England, becoming first a chemistry professor, and then a social sciences professor at the University of Manchester. Two of his pupils, and his son John Charles Polanyi won Nobel Prizes in Chemistry. In 1944 Polanyi was elected to the Royal Society. The contributi ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
