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In organic chemistry, the class of S N 1 (nucleophilic substitution unimolecular) reactions consists of first-order reactions. For example, in the reaction of aryldiazonium ions with nucleophiles in aqueous solution, ArN + 2 + X − → ArX + N 2, the rate equation is = [+], where Ar indicates an aryl group. [23]
Chemical kinetics. 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.
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 ...
Law of mass action. In chemistry, the law of mass action is the proposition that the rate of a chemical reaction is directly proportional to the product of the activities or concentrations of the reactants. [1] It explains and predicts behaviors of solutions in dynamic equilibrium. Specifically, it implies that for a chemical reaction mixture ...
This has the same form as an equation for a straight line: = +, where x is the reciprocal of T. So, when a reaction has a rate constant obeying the Arrhenius equation, a plot of ln k versus T −1 gives a straight line, whose slope and intercept can be used to determine E a and A respectively. This procedure is common in experimental chemical ...
The Van 't Hoff equation relates the change in the equilibrium constant, Keq, of a chemical reaction to the change in temperature, T, given the standard enthalpy change, ΔrH⊖, for the process. The subscript means "reaction" and the superscript means "standard". It was proposed by Dutch chemist Jacobus Henricus van 't Hoff in 1884 in his book ...
In chemical kinetics, the overall rate of a reaction is often approximately determined by the slowest step, known as the rate-determining step (RDS or RD-step[1] or r/d step[2][3]) or rate-limiting step. For a given reaction mechanism, the prediction of the corresponding rate equation (for comparison with the experimental rate law) is often ...
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 ...