For a given coal gasification atmosphere, the reactions between fired alumina-chromia solid solution refractories and alkali (sodium and potassium) with and without sulfur at varying alkali concentrations were thermodynamically calculated using the SOLGASMIX-PV computer program and the results were experimentally confirmed. In addition, the kinetics of alkali diffusion into the refractory were experimentally determined as a function of time and temperature. The results, both experimental and theoretical, show formation of alkali-aluminate (Na₂O⋅Al₂O₃, K₂O⋅Al₂O₃) and β-alumina (Na₂O⋅11Al₂O₃, K₂O⋅11A₂O₃) compounds with formation of several metastable alkali compounds in a coal gasification environment. Sulfur did not appear to affect the reaction products. Alkali distribution into the alumina-chrome refractory is rapid and the formation of the Na₂O⋅Al₂O/K₂O⋅Al₂O₃ compounds cause large volume expansion from the reaction surface which causes poor thermal shock resistance and eventual refractory failure. The hot face of an alumina-chrome refractory in service in an alkali environment will be prone to failure by alkali attack. / Master of Science