Mercury(II) chloride(ormercury bichloride[citation needed],mercury dichloride), historically also known assulemaorcorrosive sublimate,[2]is the inorganicchemical compoundofmercuryandchlorinewith theformulaHgCl2,used as a laboratoryreagent.It is a white crystallinesolidand a molecular compound that is very toxic to humans. Once used as a treatment forsyphilis,it is no longer used for medicinal purposes because ofmercury toxicityand the availability of superior treatments.
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| Names | |
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| IUPAC names
Mercury(II) chloride
Mercury dichloride | |
| Other names
Mercury bichloride
Corrosive sublimate Abavit Mercuric chloride Sulema (Russia) TL-898 Agrosan Hydrargyri dichloridum (homeopathy) | |
| Identifiers | |
3D model (JSmol)
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| ChemSpider | |
| ECHA InfoCard | 100.028.454 |
| EC Number |
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| KEGG | |
PubChemCID
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| RTECS number |
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| UNII | |
| UN number | 1624 |
CompTox Dashboard(EPA)
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| Properties | |
| HgCl2 | |
| Molar mass | 271.52 g/mol |
| Appearance | colorless or white solid |
| Odor | odorless |
| Density | 5.43 g/cm3 |
| Melting point | 276 °C (529 °F; 549 K) |
| Boiling point | 304 °C (579 °F; 577 K) |
| 3.6 g/100 mL (0 °C) 7.4 g/100 mL (20 °C) 48 g/100 mL (100 °C) | |
| Solubility | 4 g/100 mL (ether) soluble inalcohol,acetone,ethyl acetate slightly soluble inbenzene,CS2,pyridine |
| Acidity(pKa) | 3.2 (0.2M solution) |
| −82.0·10−6cm3/mol | |
Refractive index(nD)
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1.859 |
| Structure | |
| orthogonal | |
| linear | |
| linear | |
| zero | |
| Thermochemistry | |
Std molar
entropy(S⦵298) |
144 J·mol−1·K−1[1] |
Std enthalpy of
formation(ΔfH⦵298) |
−230 kJ·mol−1[1] |
Gibbs free energy(ΔfG⦵)
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-178.7 kJ/mol |
| Pharmacology | |
| D08AK03(WHO) | |
| Hazards | |
| Occupational safety and health(OHS/OSH): | |
Main hazards
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Highly toxic, corrosive. |
| GHSlabelling: | |
   
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| Danger | |
| H300+H310+H330,H301,H314,H341,H361f,H372,H410 | |
| P201,P202,P260,P264,P270,P273,P280,P281,P301+P310,P301+P330+P331,P303+P361+P353,P304+P340,P305+P351+P338,P308+P313,P310,P314,P321,P330,P363,P391,P405,P501 | |
| NFPA 704(fire diamond) | |
| Flash point | Non-flammable |
| Lethal doseor concentration (LD, LC): | |
LD50(median dose)
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32 mg/kg (rats, orally) |
| Safety data sheet(SDS) | ICSC 0979 |
| Related compounds | |
Otheranions
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Mercury(II) fluoride Mercury(II) bromide Mercury(II) iodide |
Othercations
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Zinc chloride Cadmium chloride Mercury(I) chloride |
Except where otherwise noted, data are given for materials in theirstandard state(at 25 °C [77 °F], 100 kPa).
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Synthesis
editMercuric chloride is obtained by the action ofchlorineon mercury or onmercury(I) chloride.It can also be produced by the addition ofhydrochloric acidto a hot, concentrated solution of mercury(I) compounds such as thenitrate:[2]
- Hg2(NO3)2+ 4 HCl → 2 HgCl2+ 2 H2O + 2 NO2
Heating a mixture of solidmercury(II) sulfateandsodium chloridealso affords volatile HgCl2,which can be separated bysublimation.[2]
Properties
editMercuric chloride exists not as a salt composed of discrete ions, but rather is composed of linear triatomic molecules, hence its tendency tosublime.In the crystal, each mercury atom is bonded to two chlorideligandswith Hg–Cl distance of 2.38 Å; six more chlorides are more distant at 3.38 Å.[3]
Its solubility increases from 6% at 20 °C (68 °F) to 36% at 100 °C (212 °F).
Applications
editThe main application of mercuric chloride is as acatalystfor the conversion ofacetylenetovinyl chloride,the precursor topolyvinyl chloride:
- C2H2+ HCl → CH2=CHCl
For this application, the mercuric chloride is supported on carbon in concentrations of about 5 weight percent. This technology has been eclipsed by the thermal cracking of1,2-dichloroethane.Other significant applications of mercuric chloride include its use as adepolarizerin batteries and as a reagent inorganic synthesisandanalytical chemistry(see below).[4] It is being used in plant tissue culture for surface sterilisation of explants such as leaf or stem nodes.
As a chemical reagent
editMercuric chloride is occasionally used to form anamalgamwith metals, such asaluminium.[5]Upon treatment with an aqueous solution of mercuric chloride, aluminium strips quickly become covered by a thin layer of the amalgam. Normally, aluminium is protected by a thin layer of oxide, thus making it inert. Amalgamated aluminium exhibits a variety of reactions not observed for aluminium itself. For example, amalgamated aluminum reacts with water generating Al(OH)3and hydrogen gas.Halocarbonsreact with amalgamated aluminium in theBarbier reaction.These alkylaluminium compounds arenucleophilicand can be used in a similar fashion to the Grignard reagent. Amalgamated aluminium is also used as areducing agentin organic synthesis. Zinc is also commonly amalgamated using mercuric chloride.
Mercuric chloride is used to removedithianegroups attached to a carbonyl in anumpolungreaction. This reaction exploits the high affinity of Hg2+for anionic sulfur ligands.
Mercuric chloride may be used as a stabilising agent for chemicals and analytical samples. Care must be taken to ensure that detected mercuric chloride does not eclipse the signals of other components in the sample, such as is possible ingas chromatography.[6]
History
editDiscovery of the mineral acids
editAround 900, the authors of the Arabic writings attributed toJabir ibn Hayyan(Latin: Geber) and the Persian physician and alchemistAbu Bakr al-Razi(Latin: Rhazes) were experimenting withsal ammoniac(ammonium chloride), which when it was distilled together withvitriol(hydratedsulfatesof various metals) producedhydrogen chloride.[7]It is possible that in one of his experiments, al-Razi stumbled upon a primitive method to producehydrochloric acid.[8]However, it appears that in most of these early experiments withchloridesalts,the gaseous products were discarded, and hydrogen chloride may have been produced many times before it was discovered that it can be put to chemical use.[9]
One of the first such uses of hydrogen chloride was in the synthesis of mercury(II) chloride (corrosive sublimate), whose production from the heating ofmercuryeither withalumand ammonium chloride or with vitriol and sodium chloride was first described in theDe aluminibus et salibus( "On Alums and Salts" ).[10]This eleventh- or twelfth-centuryArabic alchemicaltext is anonymous in most manuscripts, though some manuscripts attribute it toHermes Trismegistus,and a fewfalsely attributeit to Abu Bakr al-Razi.[11]It was translated intoHebrewand two timesinto Latin,with one Latin translation byGerard of Cremona(1144–1187).[12]
In the process described in theDe aluminibus et salibus,hydrochloric acid started to form, but it immediately reacted with the mercury to produce mercury(II) chloride. Thirteenth-century Latinalchemists,for whom theDe aluminibus et salibuswas one of the main reference works, were fascinated by the chlorinating properties of mercury(II) chloride, and they eventually discovered that when the metals are eliminated from the process of heating vitriols, alums, and salts, strongmineral acidscan directly be distilled.[13]
Historical use in photography
editMercury(II) chloride was used as a photographic intensifier to produce positive pictures in thecollodion processof the 1800s. When applied to a negative, the mercury(II) chloride whitens and thickens the image, thereby increasing the opacity of the shadows and creating the illusion of a positive image.[14]
Historical use in preservation
editFor the preservation of anthropological and biological specimens during the late 19th and early 20th centuries, objects were dipped in or were painted with a "mercuric solution". This was done to prevent the specimens' destruction by moths, mites and mold. Objects in drawers were protected by scattering crystalline mercuric chloride over them.[15]It finds minor use in tanning, and wood was preserved bykyanizing(soaking in mercuric chloride).[16]Mercuric chloride was one of the three chemicals used for railroad tie wood treatment between 1830 and 1856 in Europe and the United States. Limited railroad ties were treated in the United States until there were concerns over lumber shortages in the 1890s.[17]The process was generally abandoned because mercuric chloride was water-soluble and not effective for the long term, as well as being highly poisonous. Furthermore, alternative treatment processes, such ascopper sulfate,zinc chloride,and ultimatelycreosote;were found to be less toxic. Limited kyanizing was used for some railroad ties in the 1890s and early 1900s.[18]
Historic use in medicine
editMercuric chloride was a common over-the-counter disinfectant in the early twentieth century, recommended for everything from fighting measles germs[19]to protecting fur coats[20]and exterminating red ants.[21] A New York physician, Carlin Philips, wrote in 1913 that "it is one of our most popular and effective household antiseptics", but so corrosive and poisonous that it should only be available by prescription.[22]A group of physicians in Chicago made the same demand later the same month. The product frequently caused accidental poisonings and was used as a suicide method.[23]
It was used to disinfect wounds byArab physicians in the Middle Ages.[24]It continued to be used by Arab physicians into the twentieth century, until modern medicine deemed it unsafe for use.
Syphiliswas frequently treated with mercuric chloride before the advent ofantibiotics.It was inhaled, ingested, injected, and applied topically. Both mercuric-chloride treatment for syphilis and poisoning during the course of treatment were so common that the latter's symptoms were often confused with those of syphilis. This use of "salts of white mercury" is referred to in theEnglish-languagefolk song"The Unfortunate Rake".[25]
Yawswas treated with mercuric chloride (labeled as Corrosive Sublimate) before the advent ofantibiotics.It was applied topically to alleviate ulcerative symptoms. Evidence of this is found in Jack London's bookThe Cruise of the Snarkin the chapter entitled "The Amateur M.D."
Between 1901 and 1904 the US Marines Hospital Service quarantined and engaged in an extensive disinfection program of San Francisco's Chinatown, forcing the closure of over 14,000 rooms and eviction of thousands of Chinese whose dwellings were rendered toxic and uninhabitable from the disinfection program. Long-term mercury pollution is still a concern for construction workers in Chinatown to this day.[26]
Historic use in crime and accidental poisonings
edit- In 1613, whilst imprisoned in the Tower of London,Thomas Overburywas poisoned with an enema of mercury sublimate.[27]The following trial saw the downfall of the murderers,Robert Carrand his wife,Frances.
- In Volume V ofAlexandre Dumas'Celebrated Crimes,he recounts the history ofAntoine François Desrues,who killed noblewoman Madame de Lamotte with "corrosive sublimate."[28]
- In 1906 in New York, Richard Tilghman died after mistaking bichloride of mercury tablets forlithium citrate.[29]
- ActorLon Chaney's estranged wife Cleva attempted suicide by swallowing mercuric chloride in 1913. Although the attempt failed, the toxic effects ruined her singing career.[30]
- In a highly publicized case in 1920, mercury bichloride was reported to have caused the death of 25-year-old Americansilent filmstarOlive Thomas.While vacationing in France, she accidentally (or perhaps intentionally) ingested the compound, which had been prescribed to her husbandJack Pickfordin liquid topical form to treat his syphilis. Thomas died five days later.[31][32]
- Mercuric chloride was used byMadge Oberholtzerto commit suicide after she was kidnapped, raped and tortured byKu Klux KlanleaderD.C. Stephenson.She died from a combination of mercury poisoning and thestaph infectionthat she suffered when Stephenson bit her during the assault.[33]
- Ana María Cires, a young wife of Uruguayan writerHoracio Quiroga,committed suicide by poison. After a violent fight with Quiroga, she ingested a fatal dose of "sublimado", or mercury chloride. She endured great agony for eight days before dying on December 14, 1915.[34]
- Ruth L. Truffant's death was called a suicide after she died frombichloride of mercurypoisoning on 26 April 1914.[35][36]
Toxicity
editMercury dichloride is a highly toxic compound,[37]both acutely and as a cumulative poison. Its toxicity is due not just to its mercury content but also to its corrosive properties, which can cause serious internal damage, including ulcers to the stomach, mouth, and throat, and corrosive damage to the intestines. Mercuric chloride also tends to accumulate in the kidneys, causing severe corrosive damage which can lead toacute kidney failure.However, mercuric chloride, like all inorganic mercury salts, does not cross theblood–brain barrieras readily as organic mercury, although it is known to be a cumulative poison.
Common side effects of acute mercuric chloride poisoning include burning sensations in the mouth and throat, stomach pain, abdominal discomfort, lethargy, vomiting of blood, corrosive bronchitis, severe irritation to the gastrointestinal tract, and kidney failure. Chronic exposure can lead to symptoms more common with mercury poisoning, such as insomnia, delayed reflexes, excessive salivation, bleeding gums, fatigue, tremors, and dental problems.
Acute exposure to large amounts of mercuric chloride can cause death in as little as 24 hours, usually due to acute kidney failure or damage to the gastrointestinal tract. In other cases, victims of acute exposure have taken up to two weeks to die.[38]
References
edit- ^abZumdahl, Steven S. (2009).Chemical Principles 6th Ed.Houghton Mifflin Company. p. A22.ISBN978-0-618-94690-7.
- ^abcChisholm, Hugh,ed. (1911)..Encyclopædia Britannica.Vol. 7 (11th ed.). Cambridge University Press. p. 197.
- ^Wells, A.F. (1984) Structural Inorganic Chemistry, Oxford: Clarendon Press.ISBN0-19-855370-6.
- ^Matthias Simon, Peter Jönk, Gabriele Wühl-Couturier, Stefan Halbach "Mercury, Mercury Alloys, and Mercury Compounds" in Ullmann's Encyclopedia of Industrial Chemistry 2006: Wiley-VCH, Weinheim.doi:10.1002/14356007.a16_269.pub2
- ^Deng, James; Wang, Yu-Pu; Danheiser, Rick L. (2015)."Synthesis of 4,4-Dimethoxybut-1-yne".Organic Syntheses.92:13–25.doi:10.15227/orgsyn.092.0013.
- ^Foreman, W. T.; Zaugg, S. D.; Faires, L. M.; Werner, M. G.; Leiker, T. J.; Rogerson, P. F. (1992). "Analytical interferences of mercuric chloride preservative in environmental water samples: Determination of organic compounds isolated by continuous liquid-liquid extraction or closed-loop stripping".Environmental Science & Technology.26(7): 1307.Bibcode:1992EnST...26.1307F.doi:10.1021/es00031a004.
- ^Kraus, Paul(1942–1943).Jâbir ibn Hayyân: Contribution à l'histoire des idées scientifiques dans l'Islam. I. Le corpus des écrits jâbiriens. II. Jâbir et la science grecque.Cairo:Institut Français d'Archéologie Orientale.ISBN9783487091150.OCLC468740510.vol. II, pp. 41–42;Multhauf, Robert P.(1966).The Origins of Chemistry.London: Oldbourne.OCLC977570829.pp. 141-142.
- ^Stapleton, Henry E.;Azo, R.F.; Hidayat Husain, M. (1927)."Chemistry in Iraq and Persia in the Tenth Century A.D."Memoirs of the Asiatic Society of Bengal.VIII(6): 317–418.OCLC706947607.p. 333. The relevant recipe reads as follows: "Take equal parts of sweet salt, Bitter salt,Ṭabarzadsalt,Andarānīsalt, Indian salt, salt ofAl-Qilī,and salt of Urine. After adding an equal weight of good crystallised Sal-ammoniac, dissolve by moisture, and distil (the mixture). There will distil over a strong water, which will cleave stone (sakhr) instantly. "(p. 333) For a glossary of the terms used in this recipe, see p. 322. German translation of the same passage inRuska, Julius(1937).Al-Rāzī's Buch Geheimnis der Geheimnisse. Mit Einleitung und Erläuterungen in deutscher Übersetzung.Quellen und Studien zur Geschichte der Naturwissenschaften und der Medizin. Vol. VI. Berlin: Springer.p. 182, §5. An English translation of Ruska 1937's translation can be found inTaylor, Gail Marlow (2015).The Alchemy of Al-Razi: A Translation of the "Book of Secrets".CreateSpace Independent Publishing Platform.ISBN9781507778791.pp. 139–140.
- ^Multhauf 1966,p. 142, note 79.
- ^Multhauf 1966,pp. 160–163. On theDe aluminibus et salibus,see furtherFerrario, Gabriele (2004). "Il Libro degli allumi e dei sali: status quaestionis e prospettive di studio".Henoch.26(3): 275–296.,Ferrario, Gabriele (2007). "Origins and Transmission of the Liber de aluminibus et salibus". InPrincipe, Lawrence(ed.).Chymists and Chymistry: Studies in the History of Alchemy and Early Modern Chemistry.Sagamore Beach: Science History Publications. pp. 137–148.See also more brieflyFerrario, Gabriele (2009). "An Arabic Dictionary of Technical Alchemical Terms: MS Sprenger 1908 of the Staatsbibliothek zu Berlin (fols. 3r–6r)".Ambix.56(1): 36–48.doi:10.1179/174582309X405219.PMID19831258.S2CID41045827.pp. 40–43, and the sources cited inFerrario 2009,p. 38, note 5. See alsoMoureau, Sébastien (2020)."Min al-kīmiyāʾ ad alchimiam. The Transmission of Alchemy from the Arab-Muslim World to the Latin West in the Middle Ages".Micrologus.28:87–141.hdl:2078.1/211340.pp. 106–107.
- ^Moureau 2020,pp. 106–107. On the false attribution to al-Razi, seeFerrario 2009,pp. 42–43 and the sources cited there. Moureau 2020, p. 117 stresses that the only Latin work which in the current state of research is known to be a translation of an authentic Arabic work by al-Razi is theLiber secretorum Bubacaris,an interpolated paraphrase of al-Razi'sKitāb al-Asrār.
- ^Moureau 2020,pp. 106–107.
- ^Multhauf 1966,pp. 162–163.
- ^Towler, J. (1864).Stereographic negatives and landscape photography.Chapter 28. In:The silver sunbeam: a practical and theoretical textbook of sun drawing and photographic printing.Retrieved on April 13, 2005.
- ^Goldberg, Lisa (1996)."A History of Pest Control Measures in the Anthropology Collections, National Museum of Natural History, Smithsonian Institution".JAIC.35(1): 23–43.RetrievedApril 17,2005.
- ^Freeman, M.H. Shupe, T.F. Vlosky, R.P. Barnes, H.M. (2003).Past, present and future of the wood preservation industryArchived2005-05-03 at theWayback Machine.Forest Products Journal. 53(10) 8–15. Retrieved on April 17, 2005.
- ^Pg. 19-75 "Date Nails and Railroad Tie Preservation" (3 vol.; 560 p.), published in 1999 by the Archeology and Forensics Laboratory, University of Indianapolis; Jeffrey A. Oaks
- ^Oaks, Jeffrey A."History of Railroad Tie Preservation"(PDF).p. 20-30; p. 64, Table I. Archived fromthe original(PDF)on 2011-07-18.Retrieved2009-01-14.
- ^"Measles Kills Many Children".The Star and Sentinel.Gettysburg, PA. 1908-01-29.Retrieved2021-09-25.
- ^"Adventures of Mr. Mouse".The Day Book.Chicago, IL. 1914-05-05. p. 31.Retrieved2021-09-25.
- ^Child, Lydia Maria (832).The American Frugal Housewife(12th ed.). p. 21.
- ^Philips, M.D., Carlin (1913-06-15)."To Keep Deadly Bichloride of Mercury from Family Medicine Shelves".The Times Dispatch.Richmond, VA.Retrieved2021-09-25.
- ^"Want Sale of Bichloride of Mercury Restricted".The Day Book.Chicago, IL. 1913-06-23.Retrieved2021-09-25.
- ^Maillard, Adam P. Fraise, Peter A. Lambert, Jean-Yves (2007).Principles and Practice of Disinfection, Preservation and Sterilization.Oxford: John Wiley & Sons. p. 4.ISBN978-0470755068.
{{cite book}}:CS1 maint: multiple names: authors list (link) - ^Pimple, K.D.; Pedroni, J.A.; Berdon, V. (2002, July 09).Syphilis in historyArchived2008-04-30 at theWayback Machine.Poynter Center for the Study of Ethics and American Institutions at Indiana University-Bloomington. Retrieved on April 20, 2008.
- ^Craddock, Susan (2000).City of Plagues.University of Minnesota Press. p. 138.
- ^Somerset, Anne (1997).Unnatural Murder: Poison at the Court of James I.Orion Publishing Group.ISBN978-0753801987.
- ^Dumas, Alexandre(1895).Celebrated Crimes Volume V: The Cenci. Murat. Derues.G. Barrie & sons. p. 250.Retrieved30 June2015– via Google Books.
- ^"The times and democrat. [volume] (Orangeburg, S.C.) 1881-current, June 28, 1906, Image 1".28 June 1906.
- ^Mysteries and Scandals – Lon Chaney (Season 3, Episode 34).E!. 2000.
- ^"Bichloride of Mercury Killed Olive Thomas".The Toronto World.September 15, 1920. p. 6.RetrievedAugust 27,2018.
- ^Foster, Charles (2000).Stardust and Shadows: Canadians in Early Hollywood,page 257. Toronto, Canada: Dundurn Press, 2000.ISBN978-1550023480.
- ^Daniel O. Linder, "D.C. Stephenson",Testimony,Famous Trials,hosted at University of Missouri Law School, Kansas City
- ^Brignol, José (1939).Vida y Obra de Horacio Quiroga.Montevido: La Bolsa de los Libros. pp. 211–213.
- ^"Actress Dies of Poisoning When Heart Balm is Denied".The Indianapolis Star. 27 April 1914.Retrieved27 June2022.
- ^The American Library Annual: Including Index to Dates of 1914-1915.New York: R.R. Bowker Company. 1915. p. 155.Retrieved27 June2022.
- ^Mercury (II) chloride, toxicity
- ^"Mercuric chloride"[dead link]inToxNet: Hazardous Substancesdata bank. National Institutes of Health (2002, October 31). Retrieved on April 17, 2005. See also thecorresponding entryinToxNet's successor,PubChem.
External links
edit
- Agency for toxic substances and disease registry. (2001, May 25).Toxicological profile for Mercury.Retrieved on April 17, 2005.
- "Mercuric Chloride | HgCl2"inPubChemdatabase.US National Institutes of Health. Retrieved 19 July 2022.Archived20 July 2022.
- Young, R.(2004, October 6).Toxicity summary for mercury.The risk assessment information system. Retrieved on April 17, 2005.
- ATSDR - ToxFAQs: Mercury
- ATSDR - Public Health Statement: Mercury
- ATSDR - Medical Management Guidelines (MMGs) for Mercury (Hg)
- ATSDR - Toxicological Profile: Mercury
- International Chemical Safety Card 0979
- National Pollutant Inventory - Mercury and compounds Fact Sheet
- NIOSH Pocket Guide to Chemical Hazards
- Mercury chloride toxicity- includes excerpts from research reports.