ARRHENIUS EQUATION

mathematical expression that describes the effect of temperature on the velocity of a chemical reaction, the basis of all predictive expressions used for calculating reaction-rate constants. In the Arrhenius equation, k is the reaction-rate constant, A and E are numerical constants characteristic of the reacting substances, R is the thermodynamic gas constant, and T is the absolute temperature. The equation is commonly given in the form of an exponential function, k = Aexp(-ERT), and it predicts that a small increase in reaction temperature will produce a marked increase in the magnitude of the reaction-rate constant. The Arrhenius equation was originally formulated by J.J. Hood on the basis of studies of the variation of rate constants of some reactions with temperature. The Swedish chemist Svante Arrhenius, for whom the equation is named, showed that the relationship is applicable to almost all kinds of reactions. He also provided a theoretical basis for the equation by an analogy with the expression for the thermodynamic equilibrium constant. Later, the numerical constants A and E were shown by the collision and transition-state theories of chemical reactions to represent quantities indicative of the fundamental process of chemical reactions; i.e., E represents the energy of activation, and A represents the frequency at which atoms and molecules collide in a way that leads to reaction.