The flammability limits of hydrogen and methane in air were determined experimentally at elevated initial mixture temperatures up to 350°C at atmospheric pressure for upward flame propagation in a conventional steel test tube apparatus. Additionally the extent to which a prolonged exposure (i.e., residence time) of the mixture to elevated temperatures before spark ignition and, consequently, the existence of pre-ignition reactions that may influence the value of the lean and rich flammability limits was also investigated. It was shown that the flammability limits for methane widened approximately linearly with an increase in the initial mixture temperature over the whole range of temperatures tested. These limits were not affected by the length of the residence time before spark ignition. Different behaviour was observed for flammability limits of hydrogen. They were also widened with an increase in the initial temperature but only up to 200°C. In this initial temperature range the limits were not affected by the length of the residence time. However, at initial temperature exceeding 200°C the flammability limits, especially, the rich limits narrowed with an increase in the temperature and were significantly affected by the residence time before spark ignition. The results of detailed chemical kinetic simulation showed that the gas phase reactions of hydrogen oxidation could not be responsible for the substantial drop in the value of the rich limit. It was therefore, suggested that this drop in the value of the rich limit with the increase in the residence time was caused by the relatively low temperature catalytic reactions on the stainless steel surface of the flame tube. Simple method for calculating the hydrogen conversion to water was proposed. The results of calculations are in fair agreement with the experimental evidence.

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