Abstract

The first paper in a series devoted to self-association in neat butanols presents the results of two-dimensional (2D) near-infrared (NIR) correlation analysis of temperature-induced spectral variations of sec -butanol. By taking advantage of resolution enhancement in the 2D correlation spectra, it was possible to identify spectral features due to vibrations of the free and associated OH groups in the first-overtone region. On the basis of a few assumptions, band assignments of the various types of OH bonds have been proposed. The monomer band (near 7100 cm-1) can be resolved into three components; two of them are due to a rotational isomerism (7089 and 7116 cm-1), and the third one is attributed to the free terminal OH groups in linear polymers (7055 cm-1). The presence of the 7055cm-1 band implies that the intensity of the monomer peak cannot be used as a measure of the concentration of the monomer species (except in very diluted solutions). Thus, previous estimations of equilibrium constants and thermodynamic parameters associated with hydrogen-bond dissociation have been subject to unacceptable error. At higher temperatures, a new band near 6550 cm-1becomes visible. This band originates from bended OHO bond, mostly in the cyclic polymers. In order to obtain more detailed information on the complex mechanism of the thermal dissociation of hydrogenbonded sec -butanol in the pure liquid phase, the entire experimental temperature range was divided into narrower ranges, and then 2D correlation analysis was performed for smaller data sets. It has been shown that the variations of population of the polymeric species and the cyclic dimers are faster than the corresponding changes for the monomers. At elevated temperatures an appreciable dissociation of the cyclic species takes place.

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