Raman Spectroscopy of Water–Ethanol Solutions: The Estimation of Hydrogen Bonding Energy and the Appearance of Clathrate-like Structures in Solutions

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 119; no. 44; pp. 10806 - 10815
• Main Authors: Dolenko, Tatiana A, Burikov, Sergey A, Dolenko, Sergey A, Efitorov, Alexander O, Plastinin, Ivan V, Yuzhakov, Viktor I, Patsaeva, Svetlana V
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 05.11.2015
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/acs.jpca.5b06678

The structure of aqueous alcohol solutions at the molecular level for many decades has remained an intriguing topic in numerous theoretical and practical investigations. The aberrant thermodynamic properties of water–alcohol mixtures are believed to be caused by the differences in energy of hydrogen bonding between water–water, alcohol–alcohol, and alcohol–water molecules. We present the Raman scattering spectra of water, ethanol, and water–ethanol solutions with 20 and 70 vol % of ethanol thoroughly measured and analyzed at temperatures varying from −10 to +70 °C. Application of the MCR-ALS method allowed for each spectrum to extract contributions of molecules with different strengths of hydrogen bonding. The energy (enthalpy) of formation/weakening of hydrogen bonds was calculated using the slope of Van’t Hoff plot. The energy of hydrogen bonding in 20 vol % of ethanol was found the highest among all the samples. This finding further supports appearance of clathrate-like structures in water–ethanol solutions with concentrations around 20 vol % of ethanol.