The present work is a systematic sensitivity study of how inaccuracies in thermochemical data influence important parameters resulting from chemical equilibrium modeling of black liquor combustion and gasification processes. These effects have also been compared with those originating from normal variations in process variables and black liquor composition. Determination of the effects was achieved by performing a large number of equilibrium calculations structured according to statistical designs. Evaluation of the chemical equilibrium model calculations was facilitated by regression analysis. From the results, it can be concluded that uncertainties in thermochemical data of several key components have significant effects on important chemical and physical modeling responses in black liquor combustion and gasification. These effects are in many cases comparable to, or larger than, the effects from variation in fuel and process variables. Experimental redetermination of thermochemical data for Na2S, K2S, and gaseous NaOH is suggested.