The composition and structure of complexes that formed in aqueous solutions of trifluoroacetic acid were studied by frustrated multiple total internal reflection IR spectroscopy (FMTIR). Two types of complexes with a molecular structure formed: trimers CF3COOH · (H2O)2 and cyclic tetramers (CF3COOH)2 · (H2O)2, in which the molecules of the components are arranged in pairs. In the range of acid concentrations from 100% to [H2O]/[CF3COOH] = 1: 1, only these tetramers formed, and all added water was bound into these hydrates. In more dilute solutions (up to [H2O]/[CF3COOH] = 2: 1), CF3COOH · (H2O)2 complexes formed along with tetramers; at a double excess of H2O, the components of the solution were completely bound into these trimers. In dilute solutions (from 0 to 3.6 M CF3COOH), the acid is completely dissociated into H5O 2 + and CF3COO– ions hydrated with water molecules. In the range of medium concentrations (from 3.6 M to [H2O]/[CF3COOH] = 2: 1), the solutions contain both these ions and CF3COOH · (H2O)2 dihydrates. For this range of compositions of the CF3COOH−H2O system, the concentrations of H5O 2 + ions and CF3COOH · (H2O)2 dihydrates were calculated.
Russian Journal of Physical Chemistry B – Springer Journals
Published: May 29, 2018
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