《Physical Chemistry 7ed 物理化学（第七版）》教师用书 Peter Atkins-Julio de Paula -Instructors Solution Manual-Chap25.pdf

25 The rates of chemical reactions Solutions to exercises Discussion questions E25.1(b) The determination of a rate law is simplified by the isolation method in which the concentrations of all the reactants except one are in large excess. If B is in large excess, for example, then to a good approximation its concentration is constant throughout the reaction. Although the true rate law might be ν = k [A][B], we can approximate [B] by [B]0 and write ν = k [A] k = k [B]0 [25.8] which has the form of a first-order rate law. Because the true rate law has been forced into first-order form by assuming that the concentration of B is constant, it is called a pseudofirst-order rate law. The dependence of the rate on the concentration of each of the reactants may be found by isolating them in turn (by having all the other substances present in large excess), and so constructing a picture of the overall rate law. In the method of initial rates, which is often used in conjunction with the isolation method, the rate is measured at the beginning of the reaction for several different initial concentrations of reactants. We shall suppose that the rate law for a reaction with A isolated is ν = k [A]a ; then its initial rate, ν0 a is given by the initial values of the concentration of A, and we write ν0 = k [A] . Taking logarithms 0 gives: log ν0 = log k + a log[A]0 [25.9] For a series of initial concentrations, a plot of the logarithms of the initial rates against the logarithms