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In chemistry, the rate law or rate equation for a chemical reaction is a mathematical equation that links the rate of forward reaction with the concentrations or pressures of the reactants and constant parameters (normally rate coefficients and partial reaction orders). For many reactions, the initial rate is given by a power law such as
where and express the concentration of the species and usually in moles per liter (molarity, ). The exponents and are the partial orders of reaction for and and the overall reaction order is the sum of the exponents. These are often positive integers, but they may also be zero, fractional, or negative. The order of reaction is a number which quantifies the degree to which the rate of a chemical reaction depends on concentrations of the reactants. In other words, the order of reaction is the exponent to which the concentration of a particular reactant is raised. The constant is the reaction rate constant or rate coefficient of the reaction. Its value may depend on conditions such as temperature, ionic strength, surface area of an adsorbent, or light irradiation. If the reaction goes to completion, the rate equation for the reaction rate applies throughout the course of the reaction.
Elementary (single-step) reactions and reaction steps have reaction orders equal to the stoichiometric coefficients for each reactant. The overall reaction order, i.e. the sum of stoichiometric coefficients of reactants, is always equal to the molecularity of the elementary reaction. However, complex (multi-step) reactions may or may not have reaction orders equal to their stoichiometric coefficients. This implies that the order and the rate equation of a given reaction cannot be reliably deduced from the stoichiometry and must be determined experimentally, since an unknown reaction mechanism could be either elementary or complex. When the experimental rate equation has been determined, it is often of use for deduction of the reaction mechanism.
The rate equation of a reaction with an assumed multi-step mechanism can often be derived theoretically using quasi-steady state assumptions from the underlying elementary reactions, and compared with the experimental rate equation as a test of the assumed mechanism. The equation may involve a fractional order, and may depend on the concentration of an intermediate species.
A reaction can also have an undefined reaction order with respect to a reactant if the rate is not simply proportional to some power of the concentration of that reactant; for example, one cannot talk about reaction order in the rate equation for a bimolecular reaction between adsorbed molecules: