The ketonization of acetic acid is investigated over HZSM-5 via a combination of temperature programmed techniques (TP), IR, and reaction kinetics. TP experiments demonstrate the generation of stable acyl intermediates that require higher temperatures to facilitate CC coupling with a second acetic acid molecule. Near exclusive selectivities for the ketonization reaction devoid of significant sequential aldol condensation are observed at temperatures ranging from 270-330°C. The ratedetermining step is proposed to involve the interaction of an acyl group with a second acid, with an apparent reaction order of 1.6. This order can be explained by a second order rate-determining step that is reduced as a result of acid-derived surface species. Isotope labeling experiments reveal that the rate-determining step is the formation of the CC bond rather than the activation of the second acid. The rate of reaction per gram scales with the concentration of Brønsted sites present, with the exchange of Brønsted sites with Na resulting in a corresponding drop in activity. The ketonization reaction exhibits a-0.46 order with respect to water, but this loss in activity is accompanied by a significant increase in catalyst stability.