Abstract
The effect of temperature on self-association of octan-1-ol, octan-2-ol, and octan-3-ol has been studied by two-dimensional (2D) Fourier-transform (FT) near-infrared (NIR) correlation spectroscopy. The comparison of the results for a series of alcohols provided information on the molecular mechanism of self-association process that could not be obtained from analysis of the data for a specific alcohol. The 2D correlation analysis of the dynamic spectra of alcohols reveals that the mechanism of temperature-induced changes in self-association is complex and proceeds through the intermediate species. A careful examination of the asynchronous spectra in the region of the monomer band exhibit different patterns for particular alcohols. This observation indicates that the form and relative populations of the associates strongly depend on the molecular structure of the alcohol. Analysis of the power spectra provides evidences that an average size of the associates is reduced on increasing temperature. The same trend is observed upon branching. The present results show that the degree of self-association decreases in the order octan-1-ol>octan-2-ol>octan-3-ol.
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