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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:
The rate for a bimolecular gas-phase reaction, A + B → product, predicted by collision theory is [6] = = ()where: k is the rate constant in units of (number of molecules) −1 ⋅s −1 ⋅m 3.
The rate expression for an elementary bimolecular reaction is sometimes referred to as the law of mass action as it was first proposed by Guldberg and Waage in 1864. An example of this type of reaction is a cycloaddition reaction. This rate expression can be derived from first principles by using collision theory for ideal gases. For the case ...
The order of reaction is an empirical quantity determined by experiment from the rate law of the reaction. It is the sum of the exponents in the rate law equation. [10] Molecularity, on the other hand, is deduced from the mechanism of an elementary reaction, and is used only in context of an elementary reaction.
The rate law for this reaction is: = [] This form shows that the rate-determining step does not involve CO. Instead, the slow step involves two molecules of NO 2. A possible mechanism for the overall reaction that explains the rate law is: 2 NO 2 → NO 3 + NO (slow) NO 3 + CO → NO 2 + CO 2 (fast)
the reaction rate is described by = [] [], where 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 k 2 ≤ ~10 10 M −1 s −1. For ...
As an example, consider the gas-phase reaction NO 2 + CO → NO + CO 2.If this reaction occurred in a single step, its reaction rate (r) would be proportional to the rate of collisions between NO 2 and CO molecules: r = k[NO 2][CO], where k is the reaction rate constant, and square brackets indicate a molar concentration.
where A is the reactant and S is an adsorption site on the surface and the respective rate constants for the adsorption, desorption and reaction are k 1, k −1 and k 2, then the global reaction rate is: = = where: r is the rate, mol·m −2 ·s −1