The unselective nature and ubiquitous deactivation of Bronsted acids in aldol condensations have precluded their practical use and unequivocal mechanistic assessments. H-2 and a Pt function are used here to confer stability by scavenging unsaturated intermediates to form stable products, thus allowing kinetic, spectroscopic, and isotopic assessments of elementary steps and their kinetic relevance, confirmed by density functional theory (DFT), for acetone condensation on microporous and mesoporous aluminosilicates (FER, TON, MFI, BEA, FAU, MCM-41). The selective titration of protons with 2,6-ditert-butyl pyridine during catalysis shows that condensations occur exclusively on protons; the number of titrants required to suppress reactivity measures accessible sites and allows reactivity to be rigorously reported as turnover rates. Infrared spectra show that H -bonded acetone is present at saturation coverages during condensation catalysis. Taken together with rates that depend linearly on acetone pressure and with the absence of HID kinetic isotope effects, these data indicate that condensation turnovers are mediated by the kinetically -relevant formation of a C-C bond via reactions of H -bonded acetone with another acetone molecule, a conclusion confirmed by DFT-derived free energies along the reaction coordinate. Measured rate constants reflect free energy differences between this transition state and its relevant precursors, a H -bonded and a gaseous acetone. These rate constants (per H+) depend sensitively on size and shape of the confining voids among aluminosilicates of similar acid strength but diverse framework structure. Confinement effects are mediated by van der Waals contacts and are accurately described by energies derived from Lennard-Jones potentials of DFT-derived transition state structures; these energies are ensemble -averaged over all accessible configurations and T -site locations in each aluminosilicate framework. These energy descriptors replace incomplete metrics based solely on the sizes of voids and transition states, which fail to capture differences in reactivity among different confining frameworks. (C) 2016 Published by Elsevier Inc.