Abstract. The disadvantages of the usual linear least-squares analysis of first-and second-order kinetic data are described, and nonlinear least-squares fitting is recommended as an alternative.
Keywords. Kinetics, Graduate Education/Research, ReactionsA common task in chemical kinetics is to extract the rate constant from the time dependence of concentrations. We first consider a reaction where reactant A is converted to product B, as in eq 1, and where the rate of reaction (rate of product formation or rate of reactant disappearance) is proportional to the concentration of reactant A, as in eq 2. Such a reaction is said to follow firstorder kinetics, because the rate is proportional to only one concentration.Alternatively, the rate may also be proportional to the concentration of another species C with proportionality constant k', as in eq 3. However, if C is a catalyst, so that its concentration remains constant, or if C is in large excess, so that its depletion is negligible, its concentration does not deviate from its initial concentration [C] 0 , and eq 3 can be simplified to eq 2 by setting k'[C] 0 equal to k. Such a reaction is said to follow pseudo-first-order kinetics, and k is often called a rate coefficient, rather than a rate constant, because its value changes with [C] 0 . In either case the solution to eq 2 is given by eq 4, where [A] 0 is the initial concentration of A.