Recovery of energy from biomass and various waste–derived fuels by combustion has become important due to reduction of detrimental CO2 emissions. Biomass does, however, release significant amounts of chlorine and alkali metals, as e.g. HCl(g), KCl(g), KOH(g) and NaCl(g), into the gas phase during combustion. The alkali chlorides may cause deposits on superheater tubes, which interfere with operation and can lead to corrosion and/or blockage of the gas path. To prevent and diminish the problems mentioned above, better and more detailed knowledge of the reactions between potassium chloride and the tube materials during combustion is needed. These materials commonly contain, among other metals, chromium, which is thought to protect the rest of the material since it forms a very dense but thin oxide layer on the surface of the tube material. It has been suggested that the reaction between solid or partly molten KCl and chromium oxide is the one responsible for starting the complex series of corrosion reactions. In this work, the overall reaction between potassium chloride and chromium was studied through partial reactions with compounds known to participate to the overall reaction or to be formed during it. The reactions were studied in synthetic air by heating sample mixtures in a DTA/TGA (Differential Thermal Analysis/ Thermogravimetric Analysis) apparatus. Selected samples were also studied and analyzed with a scanning electron microscope equipped with an energy dispersive x-ray analyzer (SEM/EDXA). Under the used conditions both potassium chloride and potassium chromate reacted with pure chromium and chromium oxide. In the case of chromium, chromium oxide was formed via the formation of potassium chromate. In reactions including chromium oxide as reactant also potassium dichromate was detected.