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Chemical kinetics, also known as reaction kinetics, is the branch of physical chemistry that is concerned with understanding the rates of chemical reactions. It is different from chemical thermodynamics , which deals with the direction in which a reaction occurs but in itself tells nothing about its rate.
[A] can provide intuitive insight about the order of each of the reagents. If plots of v / [A] vs. [B] overlay for multiple experiments with different-excess, the data are consistent with a first-order dependence on [A]. The same could be said for a plot of v / [B] vs. [A]; overlay is consistent with a first-order dependence on [B].
Here k is the first-order rate constant, having dimension 1/time, [A](t) is the concentration at a time t and [A] 0 is the initial concentration. The rate of a first-order reaction depends only on the concentration and the properties of the involved substance, and the reaction itself can be described with a characteristic half-life. More than ...
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 ΔG ‡ = 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 ...
Another example is the unimolecular nucleophilic substitution (S N 1) reaction in organic chemistry, where it is the first, rate-determining step that is unimolecular. A specific case is the basic hydrolysis of tert-butyl bromide (t-C 4 H 9 Br) by aqueous sodium hydroxide. The mechanism has two steps (where R denotes the tert-butyl radical t-C ...
A first order reaction depends on the concentration of only one reactant (a unimolecular reaction). Other reactants can be present, but their concentration has no effect on the rate. The rate law for a first order reaction is [] = [], The unit of k is s −1. [14]
Figure 6:Reaction Coordinate Diagrams showing reactions with 0, 1 and 2 intermediates: The double-headed arrow shows the first, second and third step in each reaction coordinate diagram. In all three of these reactions the first step is the slow step because the activation energy from the reactants to the transition state is the highest.
The kinetic order of any elementary reaction or reaction step is equal to its molecularity, and the rate equation of an elementary reaction can therefore be determined by inspection, from the molecularity. [1] The kinetic order of a complex (multistep) reaction, however, is not necessarily equal to the number of molecules involved.