Thermodynamic characterization of weak association equilibria accompanied with spectral overlapping by a SVD-based chemometric method

A singular value decomposition (SVD)-based chemometric method is used fur d econvolution of spectral information obtained from a single sample containi ng an equilibrium system with spectral overlapping at different temperature s. The output of analysis is the association constants at each temperature, thermodynamic parameters and the component spectral profiles. Thermodynami c characterization of charge-transfer complex formation between chloranil a nd some aromatic hydrocarbons are used as a model system for weak associati on equilibria and strong component spectral overlapping. The approach can b e successfully applied for studying equilibrium systems, which cannot be tr eated with classical methods like Benesi-Hildebrand method due to the prese nce of systematic errors. (C) 2001 Elsevier Science B.V. All rights reserve d.