The BLEVE (boiling liquid expanding vapor explosion) effect that involves the formation of a fireball occurs at the engulfment by fire of a tank with a highly flammable liquid or a liquid gas. Heating of the tank causes elevation of the liquid phase temperature and pressure inside the tank. A partial rupture of the dry tank walls is possible, with the formation of a rarefaction wave propagating into the liquid phase. An evaporation wave moves after the rarefaction wave and cause a rapid increase of pressure, exceeding the initial pressure before depressurization. Rapid violent destruction of the tank occurs. The mechanism of a BLEVE initiation is considered using Van der Waals isotherms. The following criterion for the possibility of a BLEVE was formulated. If the final state is located on an unstable part of the Van der Waals isotherm, a BLEVE takes place. Limiting values of the temperatures for overheating of certain highly flammable liquids and liquid gases (propane, n-butane, n-pentane, isopentane) were calculated using the proposed method, and were found to be in good agreement with experimental data available in the literature. (C) 2015 Elsevier Ltd. All rights reserved.