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Gaseous sulfur species play a major role in high temperature corrosion of pulverized coal fired furnaces. The prediction of sulfur species concentrations by 3D-Computational Fluid Dynamics (CFD) simulation allows the identification of furnace wall regions that are exposed to corrosive gases, so that countermeasures against corrosion can be applied. In the present work, a model for the release of sulfur and chlorine species during coal combustion is presented. The model is based on the mineral matter transformation of sulfur and chlorine bearing minerals under coal combustion conditions. The model is appended to a detailed reaction mechanism for gaseous sulfur and chlorine species and hydrocarbon related reactions, as well as a global three-step mechanism for coal devolatilization, char combustion, and char gasification. Experiments in an entrained flow were carried out to validate the developed model. Three-dimensional numerical simulations of an entrained flow reactor were performed by CFD using the developed model. Calculated concentrations of SO2, H2S, COS, and HCl showed good agreement with the measurements. Hence, the developed model can be regarded as a reliable method for the prediction of corrosive sulfur and chlorine species in coal fired furnaces. Further improvement is needed in the prediction of some minor trace species.