Pre-exponential Factor
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In
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 wh ...
, the pre-exponential factor or A factor is the pre-exponential constant in the
Arrhenius equation 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 1 ...
(equation shown below), an empirical relationship between temperature and
rate coefficient In chemical kinetics a reaction rate constant or reaction rate coefficient, ''k'', quantifies the rate and direction of a chemical reaction. For a reaction between reactants A and B to form product C the reaction rate is often found to have the f ...
. It is usually designated by A when determined from experiment, while Z is usually left for
collision frequency Collision frequency describes the rate of collisions between two atomic or molecular species in a given volume, per unit time. In an ideal gas, assuming that the species behave like hard spheres, the collision frequency between entities of specie ...
. The pre-exponential factor can be thought of as a measure of the frequency of properly oriented collisions. It is typically determined experimentally by measuring the rate constant k at a particular temperature and fitting the data to the Arrhenius equation. The pre-exponential factor is generally not exactly constant, but rather depends on the specific reaction being studied and the temperature at which the reaction is occurring. A=\frac The units of the pre-exponential factor A are identical to those of the rate constant and will vary depending on the order of the reaction. For a first-order reaction, it has units of s−1. For that reason, it is often called frequency factor. According to
collision theory Collision theory is a principle of chemistry used to predict the rates of chemical reactions. It states that when suitable particles of the reactant hit each other with correct orientation, only a certain amount of collisions result in a percept ...
, the frequency factor, A, depends on how often molecules collide when all concentrations are 1 mol/L and on whether the molecules are properly oriented when they collide. Values of A for some reactions can be found at Collision theory#Steric factor. According to
transition state theory In chemistry, transition state theory (TST) explains the reaction rates of elementary chemical reactions. The theory assumes a special type of chemical equilibrium (quasi-equilibrium) between reactants and activated transition state complexes. T ...
, A can be expressed in terms of the
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) which are typically obtained from the temperature dependence of a reaction rate constant, when these data are analyzed ...
of the reaction.


References


IUPAC Gold Book definition of pre-exponential factor
Chemical kinetics {{chemistry-stub