Lindemann Mechanism
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Lindemann Mechanism
In chemical kinetics, the Lindemann mechanism (also called the Lindemann–Christiansen mechanism or the Lindemann–Hinshelwood mechanism) is a schematic reaction mechanism for unimolecular reactions. Frederick Lindemann and J.A. Christiansen proposed the concept almost simultaneously in 1921, and Cyril Hinshelwood developed it to take into account the energy distributed among vibrational degrees of freedom for some reaction steps. It breaks down an apparently unimolecular reaction into two elementary steps, with a rate constant for each elementary step. The rate law and rate equation for the entire reaction can be derived from the rate equations and rate constants for the two steps. The Lindemann mechanism is used to model gas phase decomposition or isomerization reactions. Although the net formula for a decomposition or isomerization appears to be unimolecular and suggests first-order kinetics in the reactant, the Lindemann mechanism shows that the unimolecular reaction step i ...
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Chemical Kinetics
Chemical kinetics, also known as reaction kinetics, is the branch of physical chemistry that is concerned with understanding the rates of chemical reactions. It is to be contrasted with chemical thermodynamics, which deals with the direction in which a reaction occurs but in itself tells nothing about its rate. Chemical kinetics includes investigations of how experimental conditions influence the speed of a chemical reaction and yield information about the reaction's mechanism and transition states, as well as the construction of mathematical models that also can describe the characteristics of a chemical reaction. History In 1864, Peter Waage and Cato Guldberg pioneered the development of chemical kinetics by formulating the law of mass action, which states that the speed of a chemical reaction is proportional to the quantity of the reacting substances.C.M. Guldberg and P. Waage,"Studies Concerning Affinity" ''Forhandlinger i Videnskabs-Selskabet i Christiania'' (1864), 35P. W ...
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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. Te ...
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Cyclopropane
Cyclopropane is the cycloalkane with the molecular formula (CH2)3, consisting of three methylene groups (CH2) linked to each other to form a ring. The small size of the ring creates substantial ring strain in the structure. Cyclopropane itself is mainly of theoretical interest but many of its derivatives are of commercial or biological significance. History Cyclopropane was discovered in 1881 by August Freund, who also proposed the correct structure for the substance in his first paper. Freund treated 1,3-dibromopropane with sodium, causing an intramolecular Wurtz reaction leading directly to cyclopropane. The yield of the reaction was improved by Gustavson in 1887 with the use of zinc instead of sodium. Cyclopropane had no commercial application until Henderson and Lucas discovered its anaesthetic properties in 1929; industrial production had begun by 1936. In modern anaesthetic practice, it has been superseded by other agents. Anaesthesia Cyclopropane was introduced into cli ...
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Isomerization Reactions
In chemistry, isomerization or isomerisation is the process in which a molecule, polyatomic ion or molecular fragment is transformed into an isomer with a different chemical structure. Enolization is an example of isomerization, as is tautomerization. When the isomerization occurs intramolecularly it may be called a rearrangement reaction. When the activation energy for the isomerization reaction is sufficiently small, both isomers will exist in a temperature-dependent equilibrium with each other. Many values of the standard free energy difference, \Delta G^\circ, have been calculated, with good agreement between observed and calculated data. Examples and applications Alkanes Skeletal isomerization occurs in the cracking process, used in the petrochemical industry. As well as reducing the average chain length, straight-chain hydrocarbons are converted to branched isomers in the process, as illustrated the following reaction of ''n''-butane to ''i''-butane. :\overset -> \ov ...
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Steady State (chemistry)
In chemistry, a steady state is a situation in which all state variables are constant in spite of ongoing processes that strive to change them. For an entire system to be at steady state, i.e. for all state variables of a system to be constant, there must be a flow through the system (compare mass balance). A simple example of such a system is the case of a bathtub with the tap running but with the drain unplugged: after a certain time, the water flows in and out at the same rate, so the water level (the state variable Volume) stabilizes and the system is in a steady state. The steady state concept is different from chemical equilibrium. Although both may create a situation where a concentration does not change, in a system at chemical equilibrium, the net reaction rate is zero (products transform into reactants at the same rate as reactants transform into products), while no such limitation exists in the steady state concept. Indeed, there does not have to be a reaction at all ...
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Farrington Daniels
Farrington Daniels (March 8, 1889 – June 23, 1972) was an American physical chemist who is considered one of the pioneers of the modern direct use of solar energy. Biography Daniels was born in Minneapolis, Minnesota on March 8, 1889. Daniels began day school in 1895 at the Kenwood School and then on to Douglas School. As a boy, he was fascinated with Thomas Edison, Samuel F. B. Morse, Alexander Graham Bell, and John Charles Fields. He decided early that he wanted to be an electrician and inventor. He attended Central and East Side high schools. By this point he liked chemistry and physics, but equally enjoyed “Manual Training." In 1906, he entered the University of Minnesota, majoring in chemistry and adding to the usual mathematics and analytical courses some courses in botany and scientific German. He was initiated into the Beta Chapter of Alpha Chi Sigma in 1908. He sometimes worked summers as a railroad surveyor. He took his degree in chemistry in 1910. The foll ...
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Keith J
Keith may refer to: People and fictional characters * Keith (given name), includes a list of people and fictional characters * Keith (surname) * Keith (singer), American singer James Keefer (born 1949) * Baron Keith, a line of Scottish barons in the late 18th century * Clan Keith, a Scottish clan associated with lands in northeastern and northwestern Scotland Places Australia * Keith, South Australia, a town and locality Scotland * Keith, Moray, a town ** Keith railway station * Keith Marischal, East Lothian United States * Keith, Georgia, an unincorporated community * Keith, Ohio, an unincorporated community * Keith, West Virginia, an unincorporated community * Keith, Wisconsin, a ghost town * Keith County, Nebraska Other uses * Keith F.C., a football team based in Keith, Scotland * , a ship of the British Royal Navy * Hurricane Keith, a 2000 hurricane that caused extensive damage in Central America * ''Keith'' (film), a 2008 independent film directed by Todd Kessler * ' ...
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Dinitrogen Pentoxide
Dinitrogen pentoxide is the chemical compound with the formula , also known as nitrogen pentoxide or nitric anhydride. It is one of the binary nitrogen oxides, a family of compounds that only contain nitrogen and oxygen. It exists as colourless crystals that melt at 41 °C. Its boiling point is 47 °C, and sublimes slightly above room temperature, yielding a colorless gas.Peter Steele Connell The Photochemistry of Dinitrogen Pentoxide'. Ph. D. thesis, Lawrence Berkeley National Laboratory. Dinitrogen pentoxide is an unstable and potentially dangerous oxidizer that once was used as a reagent when dissolved in chloroform for nitrations but has largely been superseded by nitronium tetrafluoroborate (). is a rare example of a compound that adopts two structures depending on the conditions. The solid is a salt, nitronium nitrate, consisting of separate nitronium cations and nitrate anions ; but in the gas phase and under some other conditions it is a covalently-bo ...
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RRKM Theory
The Rice–Ramsperger–Kassel–Marcus (RRKM) theory is a theory of chemical reactivity. It was developed by Rice and Ramsperger in 1927 and Kassel in 1928 (RRK theory) and generalized (into the RRKM theory) in 1952 by Marcus who took the transition state theory developed by Eyring in 1935 into account. These methods enable the computation of simple estimates of the unimolecular reaction rates from a few characteristics of the potential energy surface. Assumption Assume that the molecule consists of harmonic oscillators, which are connected and can exchange energy with each other. * Assume the possible excitation energy of the molecule to be , which enables the reaction to occur. * The rate of intra-molecular energy distribution is much faster than that of reaction itself. * As a corollary to the above, the potential energy surface does not have any "bottlenecks" for which certain vibrational modes may be trapped for longer than the average time of the reaction Derivatio ...
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Order Of Reaction
In chemistry, the rate law or rate equation for a reaction is an equation that links the initial or forward reaction rate with the concentrations or pressures of the reactants and constant parameters (normally rate coefficients and partial reaction orders). For many reactions, the initial rate is given by a power law such as :v_0\; =\; k mathrmx mathrmy where and express the concentration of the species and usually in moles per liter (molarity, ). The exponents and are the partial ''orders of reaction'' for and and the ''overall'' reaction order is the sum of the exponents. These are often positive integers, but they may also be zero, fractional, or negative. The constant is the reaction rate constant or ''rate coefficient'' of the reaction. Its value may depend on conditions such as temperature, ionic strength, surface area of an adsorbent, or light irradiation. If the reaction goes to completion, the rate equation for the reaction rate v\; =\; k cex cey applies throug ...
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Molecularity
In chemistry, molecularity is the number of molecules that come together to react in an elementary (single-step) reactionAtkins, P.; de Paula, J. Physical Chemistry. Oxford University Press, 2014 and is equal to the sum of stoichiometric coefficients of reactants in the elementary reaction with effective collision ( sufficient energy) and correct orientation. Depending on how many molecules come together, a reaction can be unimolecular, bimolecular or even trimolecular. The kinetic order of any elementary reaction or reaction step is ''equal'' to its molecularity, and the rate equation of an elementary reaction can therefore be determined by inspection, from the molecularity. The kinetic order of a complex (multistep) reaction, however, is not necessarily equal to the number of molecules involved. The concept of molecularity is only useful to describe elementary reactions or steps. Unimolecular reactions In a unimolecular reaction, a single molecule rearranges atoms, forming ...
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Peter Atkins
Peter William Atkins (born 10 August 1940) is an English chemist and a Fellow of Lincoln College at the University of Oxford. He retired in 2007. He is a prolific writer of popular chemistry textbooks, including ''Physical Chemistry'', ''Inorganic Chemistry'', and ''Molecular Quantum Mechanics''. Atkins is also the author of a number of popular science books, including ''Atkins' Molecules'', ''Galileo's Finger: The Ten Great Ideas of Science'' and ''On Being''. Career Atkins left school (Dr Challoner's Grammar School, Amersham) at fifteen and took a job at Monsanto as a laboratory assistant. He studied for A-levels by himself and gained a place, following a last-minute interview, at the University of Leicester. Atkins studied chemistry there, obtaining a BSc degree in chemistry, and a PhD degree in 1964 for research into electron spin resonance spectroscopy, and other aspects of theoretical chemistry. Atkins then took a postdoctoral position at UCLA as a Harkness Fellow of ...
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