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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 ...
In the equation, k B and h are the Boltzmann and Planck constants, respectively. Although the equations look similar, it is important to note that the Gibbs energy contains an entropic term in addition to the enthalpic one. In the Arrhenius equation, this entropic term is accounted for by the pre-exponential factor A.
Entropy of activation determines the preexponential factor A 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 A = (ek B T/h) exp(ΔS ‡ /R),
However, the Arrhenius equation was derived from experimental data and models the macroscopic rate using only two parameters, irrespective of the number of transition states in a mechanism. In contrast, activation parameters can be found for every transition state of a multistep mechanism, at least in principle.
The equation follows from the transition state theory, also known as activated-complex theory. If one assumes a constant enthalpy of activation and constant entropy of activation, the Eyring equation is similar to the empirical Arrhenius equation , despite the Arrhenius equation being empirical and the Eyring equation based on statistical ...
The activation energy may be used to characterize the kinetic rate parameter of a given reaction through application of the Arrhenius equation. The Evans–Polanyi model assumes that the pre-exponential factor of the Arrhenius equation and the position of the transition state along the reaction coordinate are the same for all reactions ...
For a single rate-limited thermally activated process, an Arrhenius plot gives a straight line, from which the activation energy and the pre-exponential factor can both be determined. The Arrhenius equation can be given in the form: k = A exp ( − E a R T ) = A exp ( − E a ′ k B T ) {\displaystyle k=A\exp \left({\frac {-E_{\text{a ...
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. The pre-exponential ...