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Obtaining the complex optical constants n and k via quantitative absorption measurements in KBr pellets

Reflectance (emittance) spectroscopy, especially at infrared wavelengths, continues to grow in utility as an analytical technique for contact, standoff, and remote sensing. The reflectance spectra of solids, however, are complex, depending on many parameters, even for the same material. Granule or powder particle size, crystal morphology, layer thickness, and substrate material all affect the spectral distribution of reflected light. However, such phenomena can all be modeled if the optical constants n(ν) and k(ν) are available. If the quantitative absorption coefficient K(ν) is known, the k value can be obtained via the relation k(ν) = 2.303K(ν)/4πν. The absorption coefficient can in turn be derived from a simple KBrpellet infrared absorption measurement, provided the pellet mass ratio is prepared quantitatively. The method requires the pellet’s mass and diameter, along with the analyte mass fraction and density. In this paper we demonstrate the requisite experimental details in preparing the pellets, as well as methods to reduce light scattering in order to obtain more quantitative values. Theoretical methods to derive the related optical constants will also be detailed, in particular the assumptions used to obtain the scalar refractive index n. Ideally, this value is known or measured separately, but in some cases we have found that it can be approximated (first approximation) for most organic chemicals by n~1.5 at the shortest wavelength. The results are presented for a couple of species.