The behaviour of thallium(III) during jarosite precipitation

The behaviour of thallium(III) under the general conditions employed for jarosite precipitation in the zinc industry was investigated in a series of laboratory experiments. Thallium(III) does not appear to form end-member jarosite-type compounds, MTl3(SO4)2(OH)6, where M is Na, K, NH4, etc. In acid solutions at pH > 0.7, the thallium(III) hydrolyzes to Tl2O3; in more strongly acid media, two K–Tl(III) sulphate phases crystallize at temperatures < 90 °C. The K–Tl(III) sulphate phases were investigated by chemical and X-ray diffraction analyses and by thermogravimetry. Although end-member Tl(III) analogues of jarosite-type compounds could not be synthesized, it is possible to incorporate significant amounts of Tl(III) in potassium jarosite (KFe3(SO4)2(OH)6), and over 20 at.% substitution of Tl(III) for Fe(III) was achieved. The presence of Tl(III) in the potassium jarosite structure was confirmed by microscopic methods, electron microprobe analyses and X-ray absorption near-edge structure (XANES) spectroscopy. The Tl(III)-bearing species forms rapidly, and excess Fe(III) precipitates as nearly Tl-free potassium jarosite which envelops the initially formed Tl(III)-bearing potassium jarosite phase.