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Band Analysis of Temperature-Dependent Near-Infrared Spectra of Oleic Acid in the Pure Liquid State by the Analytic Geometric Approach

Volume 57, Number 12 (Dec. 2003) Page 1539-1550

Koashi, Katsue; Iwahashi, Makio; Ozaki, Yukihiro

The applicability of the band-stripping and complementary matching method has been demonstrated by the analysis of temperaturedependent near-infrared (NIR) absorption spectra in the 7500-6500 cm - 1 region of oleic acid ( cis -9-octadecenoic acid) in the pure liquid state. This method is based on first derivative-second derivative pair (D1-D2) plots and a new concept called the complementary band, cBDi, created by subtracting all the rest of the bands, exclusive of the ith estimated band, eBDi, from an experimental spectrum. The degree of coincidence of both band shapes provides a suitable measure for the quality of fit for each individual component band. It has been confirmed from the present analysis of the NIR spectra of oleic acid measured over a temperature range of 16-79 °C that the change of the peak intensity of the component band at around 6915 cm-1 due to the first overtone of an O-H stretching vibration of the monomer has two transition points around 35 and 55 °C. Moreover, the present study has provided new insight into the analysis of temperature-dependent spectral variations of oleic acid. Among the three temperature ranges, 16-35 °C, 35-55 °C, and 55-79 °C, in the first range the band near 6915 cm-1 shows a slight increase and in the second range it has a linear intensity change with a slope of 0.002 a.u./°C. In the third range, a rapid increase of the peak intensity is observed. This band exists even at 15 °C (just below the melting point) and shows a shift from 6910 to 6915 cm-1 and a band narrowing from 85 to 80 cm-1 (full width at half-height) over a temperature range of 16 to 79 °C. Furthermore, it has been found that there are two broad bands at around 6835 and 6778 cm-1.