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Elemental sulphur combustion is traditionally used to generate SO2 to produce sulphuric acid that is consumed in chemical industries, but is now also being considered as an energy vector for power generation. Despite the fact that sulphur combustion has been practiced for decades, there are limited reaction mechanisms for its combustion chemistry, which is critical for the optimization of the sulphuric acid production process to maximize efficiency and reduce cost. In this paper, a detailed reaction mechanism is developed and validated with different sets of experimental data from lab‐scale and industrial plant studies. The reaction mechanism is used to conduct sulphur furnace simulations, where the effects of feed air/sulphur ratio and oxygen enrichment of air stream on furnace temperature and the concentrations of SO2, SO3, and O2 are investigated. The dominant reaction pathways in sulphur combustion, particularly for the production of SO2 and SO3, are identified. It was found that the feed air/sulphur ratio monitors the furnace temperature and can be used to obtain the desired O2/SO2 ratio at the furnace exit for the optimal operation of catalytic converter (for SO2 oxidation to SO3) that follows the furnace in the sulphuric acid plant. Moreover, high oxygen enrichment above 35% (while maintaining the desired O2/SO2 ratio at the furnace exit) significantly increased the furnace capacity through reduced total gas flow (thus decreasing blower energy requirement and equipment size). The developed reaction mechanism provides a method to obtain optimized furnace parameters to achieve high efficiency and reduced costs in sulphuric acid plants. [ABSTRACT FROM AUTHOR]