The pyrolysis and oxidation of all four butanols (n-, sec-, iso- and tert-) have been studied at pressures from 1 to 4 atm and temperatures of 1000-1800 K behind reflected shock waves. Gas chromatographic sampling at different reaction times varying from 1.5 to 3.1 ms was used to measure reactant, intermediate and product species profiles in a single-pulse shock tube. In addition, ignition delays were determined at an average reflected shock pressure of 3.5 atm at temperatures from 1250 to 1800 K. A detailed chemical kinetic model consisting of 1892 reactions involving 284 species was constructed and tested against species profiles and ignition delays. The little-known chemistry of enols is included in this work to explain the temperature dependence of acetaldehyde produced in the thermal decomposition of isobutanol. (C) 2012 The Combustion Institute. Published by Elsevier Inc. All rights reserved.