The catalytic partial oxidation (CPO) and the steam reforming (SR) of acetic acid (HAc) over a 2 wt% Rh/alpha-Al2O3 were investigated in an isothermal annular reactor. The experiments were performed at GHSV values up to 2.0 x 10(6) l(NTP)/kgcat/h by feeding highly diluted HAc/O-2 and HAc/H2O mixtures; temperature was varied from 200 to 850 degrees C, In analogy with the CPO of hydrocarbons, also the CPO of HAc showed a low temperature regime characterized by the oxidation of the acid, while the production of synthesis gas occurred above 450 degrees C. Deep oxidation was observed below 300 degrees C. In between 300 and 450 degrees C, a progressive decline of O-2 conversion was observed (a very unique feature), accompanied by decrease of CO2 production and formation of CO with traces of H-2. C-accumulation was observed starting from 400 degrees C. The data suggest that an increasing fraction of the surface sites was active in an oxygen-lean chemistry. This could be explained by assuming that competitive adsorption displaced oxygen in favor of acetic acid. Dedicated SR tests confirmed that the production of CO and H-2 became significant only above 450-500 degrees C, while the process was hindered, likely by C-poisoning, at lower temperatures. Raman measurements confirmed that at the intermediate temperatures (450 degrees C) the surface was enriched by unsaturated C-species. The TPO profiles after CPO test at 450 degrees C indicated a major peak at 350 degrees C, suggesting the presence of C-species with intermediate reactivity or intermediate proximity to the metal particles, in between the highly reactive CHx fragments on metal sites and the polymeric C-species stored on the support. (C) 2016 Elsevier B.V. All rights reserved.