Abstract
This work aims to evaluate the infrared spectroscopic methods for the study of the structural properties of liquid alcohols – specifically how many alcohol molecules and how many hydroxyl groups do not participate in hydrogen bonds as donors. They are known as monomer fractions and free hydroxyl group fractions, respectively, in the community of chemical engineering thermodynamics. The infrared spectra processing methodologies for the extraction of free hydroxyl groups/monomer fractions in 1-alcohol solutions at various temperatures and their assumptions are discussed extensively in a comprehensive manner. The application of these methods addresses the surprising conclusion of literature experimental data that indicated identical behavior of methanol and ethanol in terms of liquid structural properties over a wide range of temperatures. A discrepancy is observed in data regarding saturated liquid methanol and ethanol, which shows that methanol indeed exhibits a stronger association than ethanol, as expected, at higher temperatures. The difficulties in the interpretation of liquid alcohol infrared spectra are further demonstrated in the case of 1-octanol, where evidence indicates that an association scheme which considers branched clusters is more consistent, especially in the region of low free hydroxyl fractions.
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