Ignition below autoignition limit

The autoignition temperature is the minimum temperature required for self-sustained combustion in the absence of an external ignition source. The value depends on specified test conditions. Tht flammable (explosive) limits specify the range of concentration of the vapor in air (in percent by volume) for which a flame can propagate. Below the lower flammable limit, the gas mixture is too lean to burn above the flammable limit, the mixture is too rich. Additional compounds can be found in National Fire Protection Association, National Fire Protection Handbook, 14th ed., 1991. 

However, to focus attention on the potential hazards always associated with the use of flammable and especially highly flammable substances, some 560 gases and liquids with flash points below 25° C and/or autoignition temperature below 225°C have been included in the text, their names prefixed with a dagger. The numerical values of the fire hazard-related properties of flashpoint, autoignition temperature and explosive (flammability) limits in air where known are given in the tabular Appendix 2. Those elements or compounds which ignite on exposure to air are included in the text, but not in the Table. 

The complex and incompletely understood phenomena of cool flames and then-close relationship with autoignition processes is discussed in considerable detail. As the temperature of mixtures of organic vapours with air is raised, the rate of autoxidation (hydroperoxide formation) will increase, and some substances under some circumstances of heating rate, concentration and pressure will generate cool flames at up to 200° C or more below their normally determined AIT. Cool flames (peroxide decomposition processes) are normally only visible in the dark, are of low temperature and not in themselves hazardous. However, quite small changes in thermal flux, pressure, or composition may cause transition to hot flame conditions, usually after some delay, and normal ignition will then occur if the composition of the mixture is within the flammable limits. 

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