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Nonconventional versus conventional application of pseudo‐first‐order kinetics to fundamental organic reactions
Author(s) -
Parker Ver D.,
Hao Weifang,
Li Zhao,
Scow Russell
Publication year - 2012
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.20609
Subject(s) - chemistry , nucleophile , kinetics , alkyl , halide , reaction rate constant , hydride , thermodynamics , computational chemistry , organic chemistry , catalysis , hydrogen , physics , quantum mechanics
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 N 2 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. © 2011 Wiley Periodicals, Inc. Int J Chem Kinet 44: 2–12, 2012