Barium sulfide is the inorganic compound with the formula BaS. BaS is the barium compound produced on the largest scale. It is an important precursor to other barium compounds including barium carbonate and the pigment lithopone, ZnS/BaSO4. Like other chalcogenides of the alkaline earth metals, BaS is a short wavelength emitter for electronic displays. It is colorless, although like many sulfides, it is commonly obtained in impure colored forms.
Discovery
BaS was prepared by the Italian alchemist Vincenzo Cascariolo (also known as Vincentius or Vincentinus Casciarolus or Casciorolus, 1571–1624) via the thermo-chemical reduction of BaSO4 (available as the mineral barite).4 It is currently manufactured by an improved version of Cascariolo's process using coke in place of flour and charcoal. This kind of conversion is called a carbothermic reaction:
BaSO4 + 2C → BaS + 2CO2and also:
BaSO4 + 4C → BaS + 4COThe basic method remains in use today. BaS dissolves in water. These aqueous solutions, when treated with sodium carbonate or carbon dioxide, give a white solid of barium carbonate, a source material for many commercial barium compounds.5
According to Harvey (1957),6 in 1603, Vincenzo Cascariolo used barite, found at the bottom of Mount Paterno near Bologna, in one of his non-fruitful attempts to produce gold. After grinding and heating the mineral with charcoal under reducing conditions, he obtained a persistent luminescent material that soon came to be known as Lapis Boloniensis, or Bolognian stone.78 The phosphorescence of the material obtained by Casciarolo made it a curiosity.91011
Preparation
A modern procedure proceeds from barium carbonate:12
BaCO3 + H2S → BaS + H2O + CO2BaS crystallizes with the NaCl structure, featuring octahedral Ba2+ and S2− centres.
The observed melting point of barium sulfide is highly sensitive to impurities.13
Safety
BaS is quite poisonous, as are related sulfides, such as CaS, which evolve toxic hydrogen sulfide upon contact with water. Barium itself is also toxic.
References
Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN 978-0-08-037941-8. 978-0-08-037941-8 ↩
Holleman, A. F.; Wiberg, E. "Inorganic Chemistry" Academic Press: San Diego, 2001. ISBN 0-12-352651-5. /wiki/ISBN_(identifier) ↩
Vij, D. R.; Singh, N. (1992). Optical and electrical properties of II-VI wide gap semiconducting barium sulfide. Conf. Phys. Technol. Semicond. Devices Integr. Circuits, 1992. Proceedings of SPIE. Vol. 1523. pp. 608–612. Bibcode:1992SPIE.1523..608V. doi:10.1117/12.634082. /wiki/Proceedings_of_SPIE ↩
F. Licetus, Litheosphorus, sive de lapide Bononiensi lucem in se conceptam ab ambiente claro mox in tenebris mire conservante, Utini, ex typ. N. Schiratti, 1640. See http://www.chem.leeds.ac.uk/delights/texts/Demonstration_21.htm Archived 2011-08-13 at the Wayback Machine http://www.chem.leeds.ac.uk/delights/texts/Demonstration_21.htm ↩
Kresse, Robert; Baudis, Ulrich; Jäger, Paul; Riechers, H. Hermann; Wagner, Heinz; Winkler, Jochen; Wolf, Hans Uwe (2007). "Barium and Barium Compounds". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a03_325.pub2. ISBN 978-3527306732. 978-3527306732 ↩
Harvey E. Newton (1957). A History of Luminescence: From the Earliest Times until 1900. Memoirs of the American Physical Society, Philadelphia, J. H. FURST Company, Baltimore, Maryland (USA), Vol. 44, Chapter 1, pp. 11-43. ↩
Smet, Philippe F.; Moreels, Iwan; Hens, Zeger; Poelman, Dirk (2010). "Luminescence in Sulfides: A Rich History and a Bright Future". Materials. 3 (4): 2834–2883. Bibcode:2010Mate....3.2834S. doi:10.3390/ma3042834. hdl:1854/LU-1243707. ISSN 1996-1944. https://doi.org/10.3390%2Fma3042834 ↩
Hardev Singh Virk (2014). "History of Luminescence from Ancient to Modern Times". ResearchGate. Retrieved 6 March 2021. https://www.researchgate.net/publication/259713568 ↩
"Lapis Boloniensis". www.zeno.org. Archived from the original on 2012-10-23. Retrieved 2011-01-03. http://www.zeno.org/Lemery-1721/A/Lapis+Boloniensis ↩
Lemery, Nicolas (1714). Trait℗e universel des drogues simples. https://books.google.com/books?id=K25AAAAAcAAJ&pg=PA458 ↩
Ozanam, Jacques; Montucla, Jean Etienne; Hutton, Charles (1814). Recreations in mathematics and natural philosophy . https://books.google.com/books?id=jAYAAAAAQAAJ&pg=PA411 ↩
P. Ehrlich (1963). "Alkaline Earth Metals". In G. Brauer (ed.). Handbook of Preparative Inorganic Chemistry, 2nd Ed. Vol. 2pages=937. NY, NY: Academic Press. ↩
Stinn, C., Nose, K., Okabe, T. et al. Metall and Materi Trans B (2017) 48: 2922. https://doi.org/10.1007/s11663-017-1107-5 Archived 2024-01-01 at the Wayback Machine https://doi.org/10.1007/s11663-017-1107-5 ↩