
doi: 10.1002/kin.20609
AbstractThree 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 SN2 reactions of alkyl halides with ionic and neutral nucleophiles. The three methods consist of (1) half‐life dependence of kapp, (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. © 2011 Wiley Periodicals, Inc. Int J Chem Kinet 44: 2–12, 2012
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