Any mixture of combustibles has specific lower and upper flammability limits. These limits are a function of the pressure, temperature and composition.
These limits are often shown in flammability diagrams for which an example can be found in the work by Bee and Börner.
Percentage reading on combustible air monitors should not be confused with the LFL concentrations. Explosimeters designed and calibrated to a specific gas may show the relative concentration of the atmosphere to the LFL—the LFL being 100%. A 5% displayed LFL reading for methane, for example, would be equivalent to 5% multiplied by 4.4%, or approximately 0.22% methane by volume at 20 degrees C. Control of the explosion hazard is usually achieved by sufficient natural or mechanical ventilation, to limit the concentration of flammable gases or vapors to a maximum level of 25% of their lower explosive or flammable limit.
Upper flammability limit (UFL): Highest concentration (percentage) of a gas or a vapor in air capable of producing a flash of fire in the presence of an ignition source (arc, flame, heat). Concentrations higher than UFL or UEL are "too rich" to burn. Operating above the UFL is usually avoided for safety because air leaking in can bring the mixture into combustibility range.
Flammability limits of mixtures of several combustible gases can be calculated using Le Chatelier's mixing rule for combustible volume fractions
x
i
{\displaystyle x_{i}}
:
L
F
L
mix
=
1
∑
i
x
i
L
F
L
i
{\displaystyle LFL_{\text{mix}}={\frac {1}{\sum _{i}{\frac {x_{i}}{LFL_{i}}}}}}
and similar for UFL.
Usually atmospheric air supplies the oxygen for combustion, and limits assume the normal concentration of oxygen in air. Oxygen-enriched atmospheres enhance combustion, lowering the LFL and increasing the UFL, and vice versa; an atmosphere devoid of an oxidizer is neither flammable nor explosive for any fuel concentration (except for gases that can energetically decompose even in the absence of an oxidizer, such as acetylene). Significantly increasing the fraction of inert gases in an air mixture, at the expense of oxygen, increases the LFL and decreases the UFL.
Controlling gas and vapor concentrations outside the flammable limits is a major consideration in occupational safety and health. Methods used to control the concentration of a potentially explosive gas or vapor include use of sweep gas, an unreactive gas such as nitrogen or argon to dilute the explosive gas before coming in contact with air. Use of scrubbers or adsorption resins to remove explosive gases before release are also common. Gases can also be maintained safely at concentrations above the UEL, although a breach in the storage container can lead to explosive conditions or intense fires.
Dusts also have upper and lower explosion limits, though the upper limits are hard to measure and of little practical importance. Lower flammability limits for many organic materials are in the range of 10–50 g/m3, which is much higher than the limits set for health reasons, as is the case for the LEL of many gases and vapours. Dust clouds of this concentration are hard to see through for more than a short distance, and normally only exist inside process equipment.
Flammability limits also depend on the particle size of the dust involved, and are not intrinsic properties of the material. In addition, a concentration above the LEL can be created suddenly from settled dust accumulations, so management by routine monitoring, as is done with gases and vapours, is of no value. The preferred method of managing combustible dust is by preventing accumulations of settled dust through process enclosure, ventilation, and surface cleaning. However, lower flammability limits may be relevant to plant design.
Situations caused by evaporation of flammable liquids into the air-filled void volume of a container may be limited by flexible container volume or by using an immiscible fluid to fill the void volume. Hydraulic tankers use displacement of water when filling a tank with petroleum.
The flammable/explosive limits of some gases and vapors are given below. Concentrations are given in percent by volume of air.
Bee, A.; Börner, M. (2023). "Laminar Burning Speeds and Flammability Limits of CH4/O2 Mixtures With Varying N2 Dilution at Sub-Atmospheric Conditions" (PDF). Combustion Science and Technology. 195 (8). Taylor & Francis: 1910--1929. doi:10.1080/00102202.2021.2006191. https://elib.dlr.de/146343/1/Bee%20B%C3%B6rner%20Laminar%20Burning%20Post%20Print%2000102202.2021_Postprint.pdf
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Morrell, Robert W. (1931). Oil Tankers (Second ed.). New York: Simmons-Boardman Publishing Company. pp. 305&306.
Note that for many chemicals it takes the least amount of ignition energy halfway between the LEL and UEL.
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Kim, Dennis K.; Klieger, Alexandra E.; Lomax, Peter Q.; Mccoy, Conor G.; Reymann, Jonathan Y.; Sunderland, Peter B. (14 September 2018). "An improved test method for refrigerant flammability limits in a 12 L vessel". Science and Technology for the Built Environment. 24 (8): 861–866. Bibcode:2018STBE...24..861K. doi:10.1080/23744731.2018.1434381. ISSN 2374-4731. S2CID 139489210. https://doi.org/10.1080/23744731.2018.1434381