Associative Behavior of Benzyl Alcohol in Carbon Tetrachloride Solutions

Self-association of benzyl alcohol in carbon tetrachloride has been studied by infrared absorption spectroscopic measurements in the fundamental OH-stretching vibration region. Infrared spectra were acquired at 30, 40, and 50 °C for varying alcohol molalities, the highest concentration being 0.2 mol...

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Bibliographic Details
Published in:The journal of physical chemistry. B 1997-08, Vol.101 (35), p.6960-6969
Main Authors: Førland, Geir M, Liang, Yizeng, Kvalheim, Olav M, Høiland, Harald, Chazy, Annick
Format: Article
Language:English
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Summary:Self-association of benzyl alcohol in carbon tetrachloride has been studied by infrared absorption spectroscopic measurements in the fundamental OH-stretching vibration region. Infrared spectra were acquired at 30, 40, and 50 °C for varying alcohol molalities, the highest concentration being 0.2 mol/kg. The spectra were collected in a data matrix and analyzed by multivariate resolution methods in order to determine the numbers of different components present in the solution and to find the spectra and concentration profiles of each component. The result indicates that the spectral variance can be described by three components, free alcohol monomers, open chain oligomers, and cyclic oligomers. The resolved spectra show one sharp band at 3620 cm-1 for the component representing the hydroxyl group of free alcohol molecules and one broad band at 3300 cm-1 for the component representing the hydroxyl groups of cyclic alcohol aggregates. The component representing the hydroxyl groups of open chain aggregates appears with two absorption bands, one broad and asymmetric band at 3500 cm-1 and a smaller band at 3600 cm-1. The small band at 3600 cm-1 is connected to the hydroxyl group situated at the “free-end” of the chain, while a broad and asymmetric band at 3500 cm-1 is connected to the hydroxyl groups situated inside and at the “bound-end” of the chain. The average number of alcohol monomers in the H-bonded aggregates decreases with increasing temperature in the solution. It was equal to 4 for open chain aggregates at 30 °C and equal to 3 at 40 and 50 °C. The corresponding numbers for the cyclic aggregates were 7 at 30 °C and 6 at 40 and 50 °C. The calculated concentration profiles show that the alcohol monomers are the dominating component throughout the concentration range investigated and that there are more open chain oligomers than cyclic aggregates present.
ISSN:1520-6106
1520-5207
DOI:10.1021/jp9704527