Nanocalorimeters based on a micromachined hotplate platform were characterized for potential applications in catalyst screening and reaction mechanism studies The nanocalorimeters were designed to limit heat loss to the surroundings resulting in a small heat capacity (50 nJ K-1) and thermal time constant (1 ms) This greatly increases the sensitivity of the device allowing reaction heat flows on the order of <1 mu W to be measured in air The Pt catalyzed combustion of hydrogen in air was used as a model reaction A relatively-simple heat and mass transfer model was developed which accurately described the data from the microscale system and the rate-limited and mass transfer-limited regimes of the ignition traces were clearly distinguished An average activation energy of 48 +/- 4 kJ mol(-1) was determined for the Pt catalyzed combustion of hydrogen in air However unique rapid temperature programmed calorimetry methods convincingly demonstrate that the activation energy is influenced by kinetic phase transitions which also result in reaction rate bistabilities and oscillations (C) 2010 Elsevier B V All rights reserved