The Race of Reactions: A Narrative Review of Chemical Kinetics from Waage and Guldberg's Affinity to Femtochemistry
Abstract
Chemical kinetics---the study of reaction rates and their mechanisms---transformed chemistry's question from what reacts to how fast and by what path, and its history runs from affinity's tables to the femtosecond camera. This article presents a narrative review of the field's canonical line: Waage and Guldberg's 1864 rate law, van't Hoff's 1884 Etudes, Arrhenius's 1889 activation energy, Lindemann's 1922 unimolecular mechanism, Semenov's 1934 chain reactions, Eyring's 1935 activated complex, Hinshelwood's kinetics, Laidler's and Houston's syntheses, Steinfeld and colleagues' dynamics text, and Zewail's 1988 femtochemistry. The synthesis is organized around three themes: laws, in which rate laws, orders, and the Arrhenius equation quantified reaction speed; mechanism, in which elementary steps, activated complexes, and chain reactions resolved how reactions proceed; and ultrafast, in which femtosecond spectroscopy photographed transition states in flight. It is concluded that kinetics converted reaction rates into molecular movies---and that its frontier, single-molecule and quantum-state-resolved chemistry, continues the camera's zoom.
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