Temperature Dependences of IR Spectra of Humic Substances of Brown Coal

Abstract

The capabilities of temperature-monitored IR spectroscopy for studying the organic matter and mineral composition of humic substances (HS) were tested. Temperature dependences of the mid-IR spectra of humic substances heated in the air in the range 25–215 °C (298–488 K, with a step of 2.5 °C)—for three commercially available samples isolated from brown coal (leonardite)—were performed. The characteristic bands were identified, and their changes in band maxima positions and intensities were compared. From the viewpoint of interpretation of HS components, the spectra were divided into regions of quartz lattice region (800–260 cm−1), quartz overtone region (1270–800 cm−1), humic substance organic matter region (1780–1270 cm−1), quartz combination region (2800–1780 cm−1), CH-speciation region (3100–2800 cm−1), and hydrogen-speciation region (4000–3100 cm−1) thus selected to contain the dominating type of bands. For the first time, a reversible change in the frequencies of the band maxima in IR spectra upon heating was observed, which can be interpreted as forming structures with a particular order in the studied humic substances in the dry state. For a single sample, both the band-shift scale and the functional dependence of the various bands on temperature differ significantly. The approach differentiates crystalline quartz bands, amorphous silica, and HSOM/surface groups experiencing a different temperature behavior of the band maxima and their intensities. Band-maximum temperature dependence can be considered more stable to changes in experimental conditions than band maxima at a single temperature, thus providing a more detailed HS structure analysis without HS decomposition or destruction.