Barium sulfide
{{Short description|Chemical compound}}
{{distinguish|Barium sulfate}}
{{chembox
| Watchedfields = changed
| verifiedrevid = 443414470
| ImageFile = NaCl polyhedra.png
| ImageSize =
| IUPACName =
| OtherNames =
| Section1 = {{Chembox Identifiers
| InChI = 1/Ba.S/q+2;-2
| ChEBI_Ref = {{ebicite|correct|EBI}}
| ChEBI = 32590
| SMILES = [Ba+2].[S-2]
| InChIKey = CJDPJFRMHVXWPT-UHFFFAOYAO
| StdInChI_Ref = {{stdinchicite|correct|chemspider}}
| StdInChI = 1S/Ba.S/q+2;-2
| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}}
| StdInChIKey = CJDPJFRMHVXWPT-UHFFFAOYSA-N
| CASNo = 21109-95-5
| CASNo_Ref = {{cascite|correct|CAS}}
| PubChem = 6857597
| EINECS = 244-214-4
| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}}
| ChemSpiderID =5256933
| UNII = TV3U2GEW4H
| Gmelin = 13627
}}
| Section2 = {{Chembox Properties
| Formula =
| Ba=1 | S=1
| MolarMass = 169.39 g/mol
| Appearance = white solid
| Density = 4.25 g/cm3 {{RubberBible87th}}
| MeltingPt_notes =
| BoilingPt = decomposes
| Solubility = 2.88 g/100 mL (0 °C)
7.68 g/100 mL (20 °C)
60.3 g/100 mL (100 °C) (reacts)
| SolubleOther = insoluble in alcohol
| RefractIndex = 2.155
}}
| Section3 = {{Chembox Structure
| CrystalStruct = Halite (cubic), cF8
| SpaceGroup = Fm3m, No. 225
| Coordination = Octahedral (Ba2+); octahedral (S2−)
| LattConst_a =
}}
| Section7 = {{Chembox Hazards
| GHSPictograms = {{GHS07}}{{GHS09}}
| GHSSignalWord = Warning
| HPhrases = {{H-phrases|315|319|335|400}}
| PPhrases = {{P-phrases|261|264|271|273|280|302+352|304+340|305+351+338|312|321|332+313|337+313|362|391|403+233|405|501}}
| LD50=226 mg/kg humans
| NFPA-H = 2
| NFPA-F = 3
| NFPA-R = 2
}}
| Section8 = {{Chembox Related
| OtherAnions = Barium oxide
Barium selenide
Barium telluride
Barium polonide
| OtherCations = Beryllium sulfide
Magnesium sulfide
Calcium sulfide
Strontium sulfide
Radium sulfide
| OtherFunction =
| OtherFunction_label =
| OtherCompounds =
}}
}}
Barium sulfide is the inorganic compound with the formula BaS. BaS is the barium compound produced on the largest scale.{{Greenwood&Earnshaw2nd|paage=678}} It is an important precursor to other barium compounds including barium carbonate and the pigment lithopone, ZnS/BaSO4.Holleman, A. F.; Wiberg, E. "Inorganic Chemistry" Academic Press: San Diego, 2001. {{ISBN|0-12-352651-5}}. Like other chalcogenides of the alkaline earth metals, BaS is a short wavelength emitter for electronic displays.{{cite conference|last1=Vij|first1=D. R.|last2=Singh|first2= N. |title=Optical and electrical properties of II-VI wide gap semiconducting barium sulfide|journal=Proceedings of SPIE |year=1992|volume=1523 |conference=Conf. Phys. Technol. Semicond. Devices Integr. Circuits, 1992|pages= 608–612|doi=10.1117/12.634082|bibcode=1992SPIE.1523..608V}} 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).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 {{Webarchive|url=https://web.archive.org/web/20110813075857/http://www1.chem.leeds.ac.uk/delights/texts/Demonstration_21.htm |date=2011-08-13 }} 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:
:{{chem2|BaSO4 + 2C → BaS + 2CO2}}
and also:
:{{chem2|BaSO4 + 4C → BaS + 4CO}}
The 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.{{Ullmann |doi=10.1002/14356007.a03_325.pub2|title=Barium and Barium Compounds|year=2007|last1=Kresse|first1=Robert|last2=Baudis|first2=Ulrich|last3=Jäger|first3=Paul|last4=Riechers|first4=H. Hermann|last5=Wagner|first5=Heinz|last6=Winkler|first6=Jochen|last7=Wolf|first7=Hans Uwe|isbn=978-3527306732}}
According to Harvey (1957),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. 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.{{cite journal|last1=Smet|first1=Philippe F.|last2=Moreels|first2=Iwan|last3=Hens|first3=Zeger|last4=Poelman|first4=Dirk|title=Luminescence in Sulfides: A Rich History and a Bright Future|journal=Materials|volume=3|issue=4|year=2010|pages=2834–2883|issn=1996-1944|doi=10.3390/ma3042834|bibcode=2010Mate....3.2834S|doi-access=free|hdl=1854/LU-1243707|hdl-access=free}}{{Cite web |title=History of Luminescence from Ancient to Modern Times |author=Hardev Singh Virk |work=ResearchGate |date=2014 |access-date=6 March 2021 |url= https://www.researchgate.net/publication/259713568}} The phosphorescence of the material obtained by Casciarolo made it a curiosity.{{cite web| url = http://www.zeno.org/Lemery-1721/A/Lapis+Boloniensis| title = Lapis Boloniensis| publisher = www.zeno.org| access-date = 2011-01-03| archive-date = 2012-10-23| archive-url = https://web.archive.org/web/20121023034505/http://www.zeno.org/Lemery-1721/A/Lapis+Boloniensis| url-status = live}}{{cite book | url = https://books.google.com/books?id=K25AAAAAcAAJ&pg=PA458 | title =Trait℗e universel des drogues simples | author1 = Lemery, Nicolas | year = 1714 }}{{cite book | url = https://books.google.com/books?id=jAYAAAAAQAAJ&pg=PA411| title =Recreations in mathematics and natural philosophy .. | author1 = Ozanam, Jacques | author2 = Montucla, Jean Etienne | author3 = Hutton, Charles | year = 1814 }}
Preparation
A modern procedure proceeds from barium carbonate:{{cite book|author1=P. Ehrlich|chapter=Alkaline Earth Metals|title=Handbook of Preparative Inorganic Chemistry, 2nd Ed. |editor=G. Brauer|publisher=Academic Press|year=1963|place=NY, NY|volume=2pages=937}}
:{{chem2|BaCO3 + H2S -> BaS + H2O + CO2}}
BaS crystallizes with the NaCl structure, featuring octahedral Ba2+ and S2− centres.
The observed melting point of barium sulfide is highly sensitive to impurities.
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.