Nonconventional versus conventional application of pseudo-first-order kinetics to fundamental organic reactions

Article abstract of DOI:10.1002/kin.20609

Three new analysis procedures for pseudo-first-order kinetics are introduced and applied to eight different fundamental organic reactions. The reactions belong to the following classes: nitroalkane proton transfer, formal hydride ion transfers from NADH model compounds, and S_N2 reactions of alkyl halides with ionic and neutral nucleophiles. The three methods consist of (1) half-life dependence of k_app, (2) sequential linear pseudo-first-order correlation, and (3) revised instantaneous rate constant analysis. Each of the three procedures is capable of distinguishing between one- and multistep mechanisms, and the combination of the three procedures provides a powerful strategy for differentiating between the two mechanistic possibilities. The data from the eight reactions chosen as examples clearly show how the procedures work in practice.