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Arrhenius plots are often used to analyze the effect of temperature on the rates of chemical 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.
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 ...
At a more advanced level, the net Arrhenius activation energy term from the Arrhenius equation is best regarded as an experimentally determined parameter that indicates the sensitivity of the reaction rate to temperature. There are two objections to associating this activation energy with the threshold barrier for an elementary reaction.
The general form of the Eyring–Polanyi equation somewhat resembles the Arrhenius equation: = ‡ where is the rate constant, ‡ is the Gibbs energy of activation, is the transmission coefficient, is the Boltzmann constant, is the temperature, and is the Planck constant.
The time–temperature shift factor can also be described in terms of the activation energy (E a). By plotting the shift factor a T versus the reciprocal of temperature (in K), the slope of the curve can be interpreted as E a /k, where k is the Boltzmann constant = 8.64x10 −5 eV/K and the activation energy is expressed in terms of eV.
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),
Thus Marcus's theory builds on the traditional Arrhenius equation for the rates of chemical reactions in two ways: 1. It provides a formula for the activation energy, based on a parameter called the reorganization energy, as well as the Gibbs free energy.
Next, the desorption rate for a particular coverage is determined from each curve and an Arrhenius plot of the logarithm of the rate of desorption against 1/T is made. An example of an Arrhenius plot can be seen in the figure on the right. The activation energy can be found from the gradient of this Arrhenius plot. [7]