
Peculiar Rate Laws, Bond Dissociation Energies, and Relative Reactivities
Yale professor Michael McBride continues Freshman Organic Chemistry II (CHEM 125B) with a lecture on what unusual kinetic behavior reveals about reaction mechanisms. He starts with fractional kinetic orders, showing how they can indicate dissociation of a dominant aggregate into a smaller reactive species, and an apparent negative kinetic order that arises from competition with a second-order process, leading to spontaneous deracemization of chiral crystals. He then examines bond dissociation energies, questioning the standard claim that tertiary, secondary, and primary radical stability explains the usual ordering, and argues the differences may instead lie in the alkanes themselves. The lecture closes with the Hammond Postulate, McBride's account of how chemists predict relative reaction rates by locating transition states closer to starting materials for more exothermic reactions. Recorded in spring 2011 as part of Open Yale Courses, the talk moves through three clearly marked chapters of close mechanistic reasoning.