摘要：Metal soaps and resinates are known to be spontaneously formed in artistic paintings, as a product of the reaction between aliphatic and terpenoid acids released by hydrolysis and oxidation of the organic media and certain cations contained in some inorganic pigments. In this paper we present an optimization and the validation of a GC/MS method for the qualitative and quantitative analysis of mixtures of terpenoid acids and aliphatic mono and dicarboxylic acids and metal carboxylates of terpenoid and aliphatic mono and dicarboxylic acids in the same paint microsample. This is based on a two-step analytical approach entailing the subsequent use of two silylating agents, N,O-bis(trimethylsilyl)trifluoroacetamide for the analysis of free acids and metal carboxylates, and 1,1,1,3,3,3-hexamethyldisilazane for the analysis of free acids. The application of this approach is possible because of the good stability at room temperature of the TMS derivatives of aliphatic and terpenoid species, characterized by high boiling points and relatively low vapour pressures. The method was then applied to the characterization of samples collected from two reference paint layers aged for 20 years, a paint sample taken from a pulpit, and sample of the varnish coating of a wooden writing desk, both from the second half of the seventeenth century.
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