Modeling the Thermal Properties of Mixtures with Hydrogen Bonding Fluids: Intra-Molecular Association and Dimerization of Organic Acids
The prediction of thermodynamic properties of highly non-ideal mixtures of associated fluids is of major importance for the rational design of industrial chemical processes involving such systems. Hydrogen bonding is one of the most important interactions in such mixtures and may occur between molecules of the same fluid (inter- molecular self-association), of different fluids (inter- molecular cross-association) and between groups of the same molecule (intra- molecular association). The latter may also be an important contribution to the overall hydrogen bonding. Furthermore, in mixtures with organic acids, a peculiar association behavior, which arises from the simultaneous formation of two hydrogen bonds between two molecules, is observed. The bond angle is almost linear introducing reduced ring strain and stabilizing the dimer. The formation of stable dimers results in the termination of the chain reaction and usually the formation of higher oligomers is rare in systems without other associating compounds.
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