High-temperature spectroscopic study of redox reactions in iron-and arsenic-doped melts

Abstract

Glasses with the basic composition 16Na2O - 10CaO - 74SiO2 doped with iron or with both iron and arsenic were studied by means of high-temperature UV-VIS-NIR spectroscopy. Increasing temperatures led to a shift of the UV absorption edge caused by Fe3+ -charge transfer bands to larger wavelengths. All other bands, especially the Fe2+ absorption band at around 1100 nm, decreased in intensity at higher temperatures. For glasses, solely doped with iron, the temperature dependency of the extinction coefficient was quantitatively determined. Glasses doped with both arsenic and iron showed a different behaviour: the intensity of the bands decreased up to a temperature of 600 to 650 °C and then increased again. This can be explained by the temperature-dependent redox reaction 2Fe3+ + As3+ ⇌ 2Fe2+ + As5+. Increasing temperatures lead to a shift of the reaction to the right. This reaction is in equilibrium at temperatures > 650 °C and gets frozen in at smaller temperatures, depending on the respective iron and arsenic concentrations. The latter is explained by a numerical simulation assuming the redox reactions to be controlled by diffusion.