IR-spectroscopic studies of hydrogen-bonding solutions: Lineshape analysis of ethanol plus hexane system

IR (infrared) line shapes of OH stretching bands in hydrogen-bonding states of ethanol-hexane solutions have been examined using a theoretically rigorous Voigt function, instead of the commonly used empirical Lorentz-Gauss equation. An efficient and numerically-stable computer code with the Voigt function has been developed in order to analyze hydrogen-bonding effects in IR absorption spectra. Although the Voigt function is not an analytically-closed form, a numerical computer subroutine, with only three adjustable parameters for each IR band (or peak), provides a unique solution in a least-squares analysis of the line shapes. On the other hand, the Lorentz-Gauss equation is an analytical function with four adjustable parameters for each IR peak. However, this function makes non-linear least-squares analyses almost impossible due to the existence of strong correlations among the parameters. Example analyses, using the ethanol-hexane system, are given. The degree of hydrogen-bonding associations of ethanol and an effective IR-absorbance coefficient for hydrogenbonded clusters have been estimated, and results are quite reasonable, compared with those in the literature. (c) 2007 Elsevier Ltd. All rights reserved.