The oxidation of n-decane/oxygen/nitrogen is studied at stoichiometric conditions of 1000 ppm fuel in the Princeton variable pressure flow reactor at temperatures of 520-830 K and pressures of 8 and 12.5 atm. The overall oxidative reactivity of n-decane is observed in detail to show low temperature, negative temperature coefficient (NTC) and hot ignition regimes. Detailed temporal speciation studies are performed at reactor initial temperatures of 533 K and 740 K at 12.5 atm pressure and 830 K at 8 atm pressure. Significant amounts of large olefins are produced at 830 K, at conditions of transition from NTC to hot ignition behavior. The predictions using available chemical kinetic models for n-decane oxidation are compared against each other and the experiments. Only the kinetic models of Westbrook et al., Ranzi et al., and Biet et al. capture the NTC behavior exhibited by n-decane. However, each of these models yields varying disparities in the mechanistic predictions of major intermediate species, including ethylene and formaldehyde. Analyses of the Westbrook et al. model are compared with the new data. The predicted double-peaked species yield of ethylene, a behavior not found for the other models or in the experimental observations results from deficiencies in the C(2) chemistry. Mechanistic validation information about fuel oxidation chemistry is also provided by the measurement of various larger carbon number alkene isomers at 830 K and 8 atm. The modeling analysis suggests that in addition to n-alkyl beta-scission chemistry, alkyl peroxy radical chemistry contributes significantly to the formation of these alkenes. Specific reaction pathways and rate constants which affect the computation of these observations are discussed. (C) 2011 The Combustion Institute. Published by Elsevier Inc. All rights reserved.