Chemical Kinetics and Mechanism by M. Mortimer, P.G. Taylor

By M. Mortimer, P.G. Taylor

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The first three successive half-lives are very close in value (approximately 42 s in each case) which is typical of a first-order reaction; thus p = 1 . 22 is therefore referred to as a pseudo-order rate equation; in fact it is pseudo-first-order. 7b. 22. 23) where k< = kRIBr-loPis another pseudo-order rate constant. We have already established that p = 1. 21. 16 dm3 mol-' = s-l It is worth noting that some types of reaction automatically have one reactant in large excess. 26) C#~N2Cl(aq) + H20(1) = C6H@H(aq) + N2(g) + HCl(aq) In this case water is the solvent, as well as a reactant, and it remains in large excess throughout the reaction.

If a single reactant, or a reactant that is not in excess, is almost totally consumed in a reaction then from a kinetic viewpoint the reaction is said to have gone to completion. The instantaneous rate of change of the concentration of a reactant, or a product, at a particular instant in a chemical reaction is equal to the slope of the tangent drawn to the kinetic reaction profile at that time. , have their smallest possible, positive, integer values, then the stoichiometric numbers are defined to be V A = -a, VB = -b, vp = +p and VQ = +q.

4 2N02(g> = 2NO(g>+ 02(g) A preliminary half-life check of the kinetic reaction profile for NO2 shows that the reaction is not first-order. ) To use the differential method it is necessary to propose a plausible rate equation and to do this the simplest proposal is made. Can you suggest what this might be? 3) so that the rate of reaction depends only on the concentration of the reactant NO2 raised to the power of the partial order a. It is important to recognize that the plausible rate equation is only a suggestion.

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