A study was made of the material balance for the fatty acid methyl ester (biodiesel) synthesis from sunflower oil using potassium hydroxide as the catalyst. A factorial design of experiments and a central composite design have been used to evaluate the influence of operating conditions on the process material balance. The responses chosen were the biodiesel yield and the yield losses due to triglyceride saponification and methyl ester dissolution in glycerol, while the variables studied were temperature, initial catalyst concentration and the methanol: vegetable oil molar ratio. The biodiesel yield increased and therefore the yield losses decreased by decreasing catalyst concentration and temperature. However, the methanol: sunflower oil molar ratio did not affect the material balance variables significantly. Second-order models were obtained to predict the biodiesel yield and both yield losses. Within the experimental range studied, these models largely matched the results from the experiments. (c) 2006 Elsevier Ltd. All rights reserved.