This study considers the thermochemistry and kinetics of gamma-valerolactone and pentenoic acid interconversion as well as the decarboxylation of both molecules over amorphous silica alumina. Through microkinetic analysis, macroscopically observed production rates and product distributions are reconciled with a mechanistic description of all chemistries. Ring opening of gamma-valerolactone, cyclization of pentenoic acids, and decarboxylation of either molecule occur in parallel at surface Bmnsted sites through a sequence of proton-mediated elementary steps. Conceptually, this is illustrated as proceeding through gas-phase oxonium and carbenium ions that are stabilized through interactions with deprotonated Bronsted sites and/or the solid oxide lattice. This interpretation provides a rigorous thermochemical foundation for detailed microkinetic analysis, which we employ to regress elementary interaction energies and kinetic parameters moving the field toward a fundamental description of reactivity in acid-catalyzed upgrading of gamma-valerolactone. (C) 2016 Elsevier Inc. All rights reserved.