Proton transfer to carbon bases tenors) and from carbon acids (ketones) det
ermines the rare of ketonization and enolization reactions, respectively. K
inetic studies performed over the last two decades have provided absolute r
ate constants and reliable equilibrium constants for a broad range of proto
tropic reactions. Structure-reactivity and free energy relationships now fo
rm a reliable framework to predict the reactivity of the transient species
involved in these fundamental reactions. Comparison of reaction rates in aq
ueous solution with rates achieved by enzymes reveals the striking efficien
cy of the latter.