The flammability envelope was experimentally determined up to the point of vapor saturation for four flammable liquids: methanol, ethanol, acetonitrile, and toluene. The experimental apparatus consisted of a 20-L spherical chamber with a centrally located 10 J fuse wire igniter. The liquid was injected and vaporized into the chamber via a septum and a precision syringe. Nitrogen and oxygen were mixed from pure components using a precision pressure gauge. Pressure versus time data were measured for each ignition test. Flammability was defined as any ignition resulting in an increase in pressure of 7% over the initial pressure, as per ASTM E 918-83. All data were obtained at an initial temperature of 298 K and 1 atm. The experimental values of the LFL agreed well with published values. Limiting oxygen concentrations (LOC) were also determined-although these were somewhat lower than published values. The calculated adiabatic flame temperature (CAFT) method was used to model the data using a threshold temperature of 1200 K. A reasonable fit of the flammability envelope was obtained, although this could be improved with a higher threshold temperature. (c) 2007 Elsevier Ltd. All rights reserved.