Are commercial pigments reliable references for the analysis of paintings?

When paintings are examined by spectroscopic techniques, building a robust database is of major importance, in order to compare the analyses with reliable references and to correctly understand the results. The database, which is usually homemade, should include carefully chosen commercial pigments, which should be as pure as possible and should correspond to the expected formula or composition of the historical pigments. Unfortunately, sometimes no correspondence between the names of the pigments used by companies and the actual composition of some of the colors is ascertained. In some cases, the composition is in fact made up of different chemical compounds; in others the presence of extenders is revealed, for example gypsum and calcite. In this paper some cases studies are discussed, regarding commercial pigments analysed by infrared spectroscopy, thermal analysis, X-ray diffraction and X-ray fluorescence. The results highlighted the importance of checking the purity of commercial pigments and excluding any extraneous compounds while interpreting the results of analytical survey of paintings.