The low-temperature oxidation of hydrocarbon fuels has received increasing attention as advanced engines seek to operate in less conventional combustion regimes. Large n-alkanes are a notable component of many real transportation fuels and possess strong reactivity in this important low-temperature range. These n-alkanes have been studied extensively in various canonical kinetic experiments but seldom in systems with strong coupling between low-temperature chemistry, transport, and heat release. To address this issue, the present study investigates self-sustaining n-alkane cool diffusion flames in a counterflow burner. The extinction limits of both hot diffusion flames and cool diffusion flames are measured at atmospheric pressure for a range of n-alkanes from n-heptane to n-tetradecane. It is observed that while these fuels behave similarly for hot flames, the larger n-alkanes are substantially more reactive in the low-temperature cool flame regime. Moreover, ozone addition strongly enhances the low-temperature chemistry to the point where the differences in fuel reactivity are nearly suppressed. The experimental measurements are compared with numerical simulations employing both detailed and reduced chemical kinetic models of various sizes. Although the different kinetic models adequately predict the extinction limits of the hot flames, a large scatter is present in the model results for cool flames, and a general overprediction of the measured cool flame extinction limit is observed for all of the fuels studied. This implies that the cool flame heat release is not well agreed upon by the current chemical kinetic models, despite their capability to reproduce many homogeneous reactor experiments at low temperatures. Furthermore, it is observed that the cool flame heat release is spread over a substantial number of reactions involving large molecules, a trait that makes it particularly difficult to create reduced kinetic models that can accurately describe cool flame behavior. The results of this study suggest that the cool flame platform can provide crucial validation of the coupling between chemistry, transport, and heat release in flames at low temperatures. (C) 2017 The Combustion Institute. Published by Elsevier Inc. All rights reserved.