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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 ...
In the Arrhenius model of reaction rates, activation energy is the minimum amount of energy that must be available to reactants for a chemical reaction to occur. [1] The activation energy ( E a ) of a reaction is measured in kilojoules per mole (kJ/mol) or kilocalories per mole (kcal/mol). [ 2 ]
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 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.
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]
From the reaction rate's temperature dependence an activation energy is determined, and this activation energy is interpreted as the energy of the transition state in a reaction diagram. The latter is drawn, according to Arrhenius and Eyring, as an energy diagram with the reaction coordinate as the abscissa.
In case of 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. However, advances in experimental and theoretical methods have revealed the existence of deviation from Arrhenius behavior (Fig.1).