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The Rice–Ramsperger–Kassel–Marcus (RRKM) theory is a theory of chemical reactivity. [1] [2] [3] It was developed by Rice and Ramsperger in 1927 [4] and Kassel in 1928 [5] (RRK theory [6]) and generalized (into the RRKM theory) in 1952 by Marcus [7] who took the transition state theory developed by Eyring in 1935 into account.
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.
It breaks down an apparently unimolecular reaction into two elementary steps, with a rate constant for each elementary step. The rate law and rate equation for the entire reaction can be derived from the rate equations and rate constants for the two steps. The Lindemann mechanism is used to model gas phase decomposition or isomerization reactions.
Using the Eyring equation, there is a straightforward relationship between ΔG ‡, first-order rate constants, and reaction half-life at a given temperature. At 298 K, a reaction with Δ G ‡ = 23 kcal/mol has a rate constant of k ≈ 8.4 × 10 −5 s −1 and a half life of t 1/2 ≈ 2.3 hours, figures that are often rounded to k ~ 10 −4 s ...
The unimolecular nucleophilic substitution (S N 1) reaction is a substitution reaction in organic chemistry. The Hughes-Ingold symbol of the mechanism expresses two properties—"S N " stands for " nucleophilic substitution ", and the "1" says that the rate-determining step is unimolecular .
The Eyring equation (occasionally also known as Eyring–Polanyi equation) is an equation used in chemical kinetics to describe changes in the rate of a chemical reaction against temperature. It was developed almost simultaneously in 1935 by Henry Eyring , Meredith Gwynne Evans and Michael Polanyi .
In a unimolecular elementary reaction, a molecule A dissociates or isomerises to form the products(s) A → products. {\displaystyle {\mbox{A}}\rightarrow {\mbox{products.}}} At constant temperature, the rate of such a reaction is proportional to the concentration of the species A
The E1cB mechanism is just one of three types of elimination reaction. The other two elimination reactions are E1 and E2 reactions. Although the mechanisms are similar, they vary in the timing of the deprotonation of the α-carbon and the loss of the leaving group. E1 stands for unimolecular elimination, and E2 stands for bimolecular elimination.
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