In chemical kinetics, a reaction rate constant or reaction rate coefficient ( k {\displaystyle k} ) is a proportionality constant which quantifies the rate and direction of a chemical reaction by relating it with the concentration of reactants. For a reaction between reactants A and B to form a product C,
where
A and B are reactants C is a product a, b, and c are stoichiometric coefficients, the reaction rate is often found to have the form:
r = k [ A ] m [ B ] n {\displaystyle r=k[\mathrm {A} ]^{m}[\mathrm {B} ]^{n}}
Here k {\displaystyle k} is the reaction rate constant that depends on temperature, and [A] and [B] are the molar concentrations of substances A and B in moles per unit volume of solution, assuming the reaction is taking place throughout the volume of the solution. (For a reaction taking place at a boundary, one would use moles of A or B per unit area instead.) The exponents m and n are called partial orders of reaction and are not generally equal to the stoichiometric coefficients a and b. Instead they depend on the reaction mechanism and can be determined experimentally. The sum of m and n gives the overall order of reaction.
Elementary steps For an elementary step, there is a relationship between stoichiometry and rate law, as determined by the law of mass action. Almost all elementary steps are either unimolecular or bimolecular. For a unimolecular step
the reaction rate is described by r = k 1 [ A ] {\displaystyle r=k_{1}[\mathrm {A} ]} , where k 1 {\displaystyle k_{1}} is a unimolecular rate constant. Since a reaction requires a change in molecular geometry, unimolecular rate constants cannot be larger than the frequency of a molecular vibration. Thus, in general, a unimolecular rate constant has an upper limit of k1 ≤ ~1013 s−1. For a bimolecular step
the reaction rate is described by r = k 2 [ A ] [ B ] {\displaystyle r=k_{2}[\mathrm {A} ][\mathrm {B} ]} , where k 2 {\displaystyle k_{2}} is a bimolecular rate constant. Bimolecular rate constants have an upper limit that is determined by how frequently molecules can collide, and the fastest such processes are limited by diffusion. Thus, in general, a bimolecular rate constant has an upper limit of k2 ≤ ~1010 M−1s−1. For a termolecular step
the reaction rate is described by r = k 3 [ A ] [ B ] [ C ] {\displaystyle r=k_{3}[\mathrm {A} ][\mathrm {B} ][\mathrm {C} ]} , where k 3 {\displaystyle k_{3}} is a termolecular rate constant. There are few examples of elementary steps that are termolecular or higher order, due to the low probability of three or more molecules colliding in their reactive conformations and in the right orientation relative to each other to reach a particular transition state. There are, however, some termolecular examples in the gas phase. Most involve the recombination of two atoms or small radicals or molecules in the presence of an inert third body which carries off excess energy, such as O + O2 + N2 → O3 + N2. One well-established example is the termolecular step 2 I + H2 → 2 HI in the hydrogen-iodine reaction. In cases where a termolecular step might plausibly be proposed, one of the reactants is generally present in high concentration (e.g., as a solvent or diluent gas).
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