A forensic project is described that is suitable for an undergraduate instrumental methods lab. Accelerants commonly used by arsonists are analyzed by static headspace enrichment followed by gas chromatography. The conditions used for headspace enrichment (e.g., time and temperature) are known to influence the distribution of hydrocarbons extracted from an arson sample. To minimize artifacts associated with headspace enrichment, simplex optimization was used to determine the optimal time and temperature for the various classes of common hydrocarbon accelerants. Both optimal enrichment times and temperatures were determined to be significantly lower than recommended by ASTM procedures for all accelerant classes. The time and temperature ranged from 1 hour at 55 degrees C for lighter fluid (class 1) to 4 hours at 90 degrees C for diesel fuel (class 4).