Calorimetry, has been used in order to identify the runaway behavior of 2-methylpyridine-N-oxidation (2-picoline-N-oxidation). Experiments were performed in an Automatic Pressure Tracking Adiabatic Calorimeter (APTAC), employing 2-methylpyridine-N-oxide (2-picoline-N-oxide) with or without catalyst, 2-methylpyridine-N-oxide, hydrogen peroxide, 2-methylpyridine (2-picoline) and catalyst, and 2-methylpyridine, hydrogen peroxide and catalyst. Approximately 16.5 g of aqueous solutions were used in 100 ml closed glass cells in all but one measurement. Measurements were performed isothermally or employing the Heat-Wait-Search (HWS) technique. During reaction runaway, any excess of hydrogen peroxide and the produced 2-methylpyridine-N-oxide decompose releasing non-condensable gases and raising the pressure. it was found that the reaction runaway is condition-sensitive. Catalyst, the presence of 2-picoline and/or its N-oxide, affect hydrogen peroxide and/or 2-picoline-N-oxide decomposition rates. Further research accompanied by analytical measurements of the gas and liquid phase would provide indications in regard to the decomposition mechanisms followed in those cases. (C) 2009 Elsevier Ltd. All rights reserved.