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Entropy Of Activation
In chemical kinetics, the entropy of activation of a reaction is one of the two parameters (along with the enthalpy of activation) that are typically obtained from the temperature dependence of a reaction rate constant, when these data are analyzed using the Eyring equation of the transition state theory. The standard entropy of activation is symbolized and equals the change in entropy when the reactants change from their initial state to the activated complex or transition state ( = change, = entropy, = activation). Importance Entropy of activation determines the preexponential factor of the Arrhenius equation for temperature dependence of reaction rates. The relationship depends on the molecularity of the reaction: * for reactions in solution and unimolecular gas reactions *: , * while for bimolecular gas reactions *: . In these equations is the base of natural logarithms, is the Planck constant, is the Boltzmann constant and the absolute temperature. is the ideal gas ...
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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 different from 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 The pioneering work of chemical kinetics was done by German chemist Ludwig Wilhelmy in 1850. He experimentally studied the rate of inversion of sucrose and he used integrated rate law for the determination of the reaction kinetics of this reaction. His work was noticed 34 years later by Wilhelm Ostwald. In 1864, Peter Waage and Cato Guldberg published the law ...
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Boltzmann Constant
The Boltzmann constant ( or ) is the proportionality factor that relates the average relative thermal energy of particles in a ideal gas, gas with the thermodynamic temperature of the gas. It occurs in the definitions of the kelvin (K) and the molar gas constant, in Planck's law of black-body radiation and Boltzmann's entropy formula, and is used in calculating Johnson–Nyquist noise, thermal noise in resistors. The Boltzmann constant has Dimensional analysis, dimensions of energy divided by temperature, the same as entropy and heat capacity. It is named after the Austrian scientist Ludwig Boltzmann. As part of the 2019 revision of the SI, the Boltzmann constant is one of the seven "Physical constant, defining constants" that have been defined so as to have exact finite decimal values in SI units. They are used in various combinations to define the seven SI base units. The Boltzmann constant is defined to be exactly joules per kelvin, with the effect of defining the SI unit ke ...
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Transmission Coefficient
The transmission coefficient is used in physics and electrical engineering when wave propagation in a medium containing discontinuities is considered. A transmission coefficient describes the amplitude, intensity, or total power of a transmitted wave relative to an incident wave. Overview Different fields of application have different definitions for the term. All the meanings are very similar in concept: In chemistry, the ''transmission coefficient'' refers to a chemical reaction overcoming a potential barrier; in optics and telecommunications it is the amplitude of a wave transmitted through a medium or conductor to that of the incident wave; in quantum mechanics it is used to describe the behavior of waves incident on a barrier, in a way similar to optics and telecommunications. Although conceptually the same, the details in each field differ, and in some cases the terms are not an exact analogy. Chemistry In chemistry, in particular in transition state theory, there ...
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Gas Constant
The molar gas constant (also known as the gas constant, universal gas constant, or ideal gas constant) is denoted by the symbol or . It is the molar equivalent to the Boltzmann constant, expressed in units of energy per temperature increment per amount of substance, rather than energy per temperature increment per ''particle''. The constant is also a combination of the constants from Boyle's law, Charles's law, Avogadro's law, and Gay-Lussac's law. It is a physical constant that is featured in many fundamental equations in the physical sciences, such as the ideal gas law, the Arrhenius equation, and the Nernst equation. The gas constant is the constant of proportionality that relates the energy scale in physics to the temperature scale and the scale used for amount of substance. Thus, the value of the gas constant ultimately derives from historical decisions and accidents in the setting of units of energy, temperature and amount of substance. The Boltzmann constant a ...
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Reaction Rate Constant
In chemical kinetics, a reaction rate constant or reaction rate coefficient () is a proportionality constant which quantifies the rate and direction of a chemical reaction by relating it with the concentration of reactants. For a reaction between reactants A and B to form a product C, where :A and B are reactants :C is a product :''a'', ''b'', and ''c'' are stoichiometric coefficients, the reaction rate is often found to have the form: r = k mathrmm mathrm Here 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 reacti ...
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Associative Substitution
Associative substitution describes a pathway by which compounds interchange ligands. The terminology is typically applied to organometallic and coordination complexes, but resembles the Sn2 mechanism in organic chemistry. The opposite pathway is dissociative substitution, being analogous to the Sn1 pathway. Intermediate pathways exist between the pure associative and pure dissociative pathways, these are called interchange mechanisms. Associative pathways are characterized by binding of the attacking nucleophile to give a discrete, detectable intermediate followed by loss of another ligand. Complexes that undergo associative substitution are either coordinatively unsaturated or contain a ligand that can change its bonding to the metal, e.g. change in hapticity or bending of a nitrogen oxide ligand (NO). In homogeneous catalysis, the associative pathway is desirable because the binding event, and hence the selectivity of the reaction, depends not only on the nature of the me ...
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Dissociative Substitution
In chemistry, dissociative substitution describes a reaction pathway by which compounds interchange ligands. The term is typically applied to coordination and organometallic complexes, but resembles the SN1 mechanism in organic chemistry. This pathway can be well described by the ''cis'' effect, or the labilization of CO ligands in the ''cis'' position. The opposite pathway is associative substitution, being analogous to SN2 pathway. Pathways that are intermediate between the pure dissociative and pure associative pathways are called interchange mechanisms. Complexes that undergo dissociative substitution are often coordinatively saturated and often have octahedral molecular geometry. The entropy of activation is characteristically positive for these reactions, which indicates that the disorder of the reacting system increases in the rate-determining step. Kinetics Dissociative pathways are characterized by a rate determining step that involves release of a ligand from t ...
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Rate Determining Step
In chemical kinetics, the overall rate of a reaction is often approximately determined by the slowest step, known as the rate-determining step (RDS or RD-step or r/d step) or rate-limiting step. For a given reaction mechanism, the prediction of the corresponding rate equation (for comparison with the experimental rate law) is often simplified by using this approximation of the rate-determining step. In principle, the time evolution of the reactant and product concentrations can be determined from the set of simultaneous rate equations for the individual steps of the mechanism, one for each step. However, the analytical solution of these differential equations is not always easy, and in some cases numerical integration may even be required. The hypothesis of a single rate-determining step can greatly simplify the mathematics. In the simplest case the initial step is the slowest, and the overall rate is just the rate of the first step. Also, the rate equations for mechanisms with a ...
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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) * Keith (gamer), American professional League of Legends player * 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 * '' ...
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Absolute Temperature
Thermodynamic temperature, also known as absolute temperature, is a physical quantity which measures temperature starting from absolute zero, the point at which particles have minimal thermal motion. Thermodynamic temperature is typically expressed using the Kelvin scale, where the unit of measurement is the ''kelvin'' (unit symbol: K). The Kelvin scale uses the same degree interval as the Celsius scale but is offset so that 0 K corresponds to absolute zero. For comparison, a temperature of 295 K corresponds to 21.85 °C and 71.33 °F. Another absolute scale of temperature is the Rankine scale, which is based on the Fahrenheit degree interval. Historically, thermodynamic temperature was defined by Lord Kelvin in terms of a macroscopic relation between Work (thermodynamics), thermodynamic work and Heat, heat transfer as defined in thermodynamics, but the kelvin was redefined by international agreement in 2019 in terms of phenomena that are now understood as man ...
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Planck Constant
The Planck constant, or Planck's constant, denoted by h, is a fundamental physical constant of foundational importance in quantum mechanics: a photon's energy is equal to its frequency multiplied by the Planck constant, and the wavelength of a matter wave equals the Planck constant divided by the associated particle momentum. The constant was postulated by Max Planck in 1900 as a proportionality constant needed to explain experimental black-body radiation. Planck later referred to the constant as the "quantum of Action (physics), action". In 1905, Albert Einstein associated the "quantum" or minimal element of the energy to the electromagnetic wave itself. Max Planck received the 1918 Nobel Prize in Physics "in recognition of the services he rendered to the advancement of Physics by his discovery of energy quanta". In metrology, the Planck constant is used, together with other constants, to define the kilogram, the SI unit of mass. The SI units are defined in such a way that, w ...
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Rate Constant
In chemical kinetics, a reaction rate constant or reaction rate coefficient () is a proportionality constant which quantifies the rate and direction of a chemical reaction by relating it with the concentration of reactants. For a reaction between reactants A and B to form a product C, where :A and B are reactants :C is a product :''a'', ''b'', and ''c'' are stoichiometric coefficients, the reaction rate is often found to have the form: r = k mathrmm mathrm Here 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 reactio ...
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