The dehydrogenation of ethanol via acetaldehyde for the synthesis of acetic acid over a Cu based catalyst in a new process is reported. Specifically, we have studied a Cu on SiO2 catalyst which has shown very high selectivity to acetic acid via acetaldehyde compared to competing condensation routes. The dehydrogenation experiments were carried out in a flow through lab scale tubular reactor. Based on 71 data sets a power law kinetic expression has been derived for the description of the dehydrogenation of acetaldehyde to acetic acid. The apparent reaction order was 0.89 with respect to water and 0.45 with respect to acetaldehyde, and the apparent activation energy was 33.8 kJ/mol. The proposed oxidation of acetaldehyde with hydroxyl in the elementary rate determining step is consistent with these both. Density Functional Theory (DFT) calculations show the preference of water cleavage at the Cu step sites. In light of this, an observed intrinsic activity difference between whole catalyst pellets and crushed pellets may be explained by the Cu crystal size and growth rate being functions of the catalyst particle size and time. (C) 2011 Elsevier B.V. All rights reserved.