OVERCOMING PROBLEMS OF DENSITY AND THICKNESS MEASUREMENTS IN FTIR VOLATILE DETERMINATIONS: A SPECTROSCOPIC APPROACH

Abstract

The Beer–Lambert law is traditionally used to determine water and carbon concentrations in glasses from their infrared (IR) spectra. In practice, this method requires estimation of the thickness and density of the glass as well as the calibration of the molecular absorptivities of the species concerned. All of these parameters can be sources of practical difficulties and analytical uncertainty. These weaknesses in the application of the Beer–Lambert law have been overcome by an empirical analysis of the infrared spectra. Using a set of 292 spectra obtained on 113 natural and experimental tholeiitic glasses (SiO2 48.5–51 wt%; water contents 0–4000 ppm H2O), it can be shown that the thickness–density (ρ d) product of a glass sample can be directly and reliably inferred from its IR spectrum. This allows the Beer–Lambert law to be rewritten. The new form no longer requires thickness or density estimations to determine volatile contents. Moreover, if needed, the thickness of the glass slab can also be accurately determined from the IR spectra. This new method is developed for quantitative determination of water concentrations in MORB glasses but can also be applied to any minor species (carbon, sulfur, etc.) provided it is active in the IR domain and that a suitable independent frequency of IR absorption can be identified. Precision is about 60 ppm H2O on O–H− contents. This method, tested on natural and experimental MORB-type glasses, can be applied to any chemical composition provided a set of reference spectra is available.