A motored engine study using premixed charges of fuel and air at a wide range of diesel-relevant equivalence ratios was performed to investigate autoignition differences among surrogates for conventional diesel fuel, gas-to-liquid (GTL) diesel fuel, and biodiesel, as well as, n-heptane. Experiments were performed by delivering a premixed charge of vaporized fuel and air and increasing the compression ratio in a stepwise manner to increase the extent of reaction while monitoring the exhaust composition via Fourier transform infrared (FTIR) spectrometry and collecting condensable exhaust gas for subsequent gas chromatography/mass spectrometry (GC/MS) analysis. Each fuel demonstrated a two-stage ignition process, with a low-temperature heat release (LTHR) event followed by the main combustion, or high-temperature heat release (HTHR). Among the three diesel-relevant fuels, the magnitude of LTHR was highest for GTL diesel, followed by methyl decanoate, and conventional diesel fuel last. FTIR analysis of the exhaust for n-heptane, the conventional diesel surrogate, and the GTL diesel surrogate revealed that LTHR produces high concentrations of aldehydes and CO while producing only negligible amounts Of CO2. Methyl decanoate differed from the other two-stage ignition fuels only in that there were significant amounts Of CO2 produced during LTHR; this was the result of decarboxylation of the ester group, not the result of oxidation. GUMS analysis of LTHR exhaust condensate for n-heptane revealed high concentrations of 2,5-heptanedione, a di-ketone that can be closely tied to species in existing autoignition models for n-heptane. GUMS analysis of the LTHR condensate for conventional diesel fuel and GTL diesel fuel revealed a series of high molecular weight aldehydes and ketones, which were expected, as well as a series of organic acids, which are not commonly reported as products of combustion. The GC/MS analysis of the methyl decanoate exhaust condensate revealed that the aliphatic chain acts similarly to n-paraffins during LTHR, while the ester group remains intact. Thus, although the FTIR data revealed that decarboxylation occurs at significant levels for methyl decanoate, it was concluded that this occurs after the aliphatic chain has been largely consumed by other LTHR reactions. (c) 2007 The Combustion Institute. Published by Elsevier Inc. All rights reserved.