Mercury(II) chloride: Difference between revisions

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'''Mercury(II) chloride''' (or '''mercury bichloride'''{{citation needed|reason=BIchloride would be HgHCl2|date=July 2023}}, '''mercury dichloride'''), historically also known as '''sulema''' or '''corrosive sublimate''',<ref name=EB1911>{{cite EB1911 |wstitle=Corrosive Sublimate |volume=7 |page=197}}</ref> is the inorganic [[chemical compound]] of [[Mercury (element)|mercury]] and [[chlorine]] with the [[chemical formula|formula]] HgCl₂, used as a laboratory [[reagent]]. It is a white crystalline [[solid]] and a molecular compound that is very toxic to humans. Once used as a treatment for [[syphilis]], it is no longer used for medicinal purposes because of [[mercury toxicity]] and the availability of superior treatments.

== Properties ==

Mercuric chloride exists not as a salt composed of discrete ions, but rather is composed of linear triatomic molecules, hence its tendency to [[Sublimation (chemistry)|sublime]]. In the crystal, each mercury atom is bonded to two chloride [[ligand]]s with Hg–Cl distance of 2.38&nbsp;Å; six more chlorides are more distant at 3.38&nbsp;Å.<ref>Wells, A.F. (1984) Structural Inorganic Chemistry, Oxford: Clarendon Press. {{ISBN|0-19-855370-6}}.</ref>

Its solubility increases from 6% at {{convert|20|C}} to 36% at {{convert|100|C}}.

Mercuric chloride is occasionally used to form an [[amalgam (chemistry)|amalgam]] with metals, such as [[aluminium]].<ref>{{cite journal|doi=10.15227/orgsyn.092.0013|title=Synthesis of 4,4-Dimethoxybut-1-yne|journal=Organic Syntheses|volume=92|pages=13–25|year=2015|last1=Deng|first1=James|first2=Yu-Pu|last2=Wang|first3=Rick L.|last3=Danheiser|doi-access=free}}</ref> 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)₃ and hydrogen gas. [[Halocarbon]]s react with amalgamated aluminium in the [[Barbier reaction]]. These alkylaluminium compounds are [[nucleophilic]] and can be used in a similar fashion to the Grignard reagent. Amalgamated aluminium is also used as a [[Redox|reducing agent]] in organic synthesis. Zinc is also commonly amalgamated using mercuric chloride.

==History==

===Discovery of the mineral acids===

Around 900, the authors of the Arabic writings attributed to [[Jabir ibn Hayyan]] (Latin: Geber) and the Persian physician and alchemist [[Abu Bakr al-Razi]] (Latin: Rhazes) were experimenting with [[sal ammoniac]] (ammonium chloride), which when it was distilled together with [[vitriol]] (hydrated [[sulfates]] of various metals) produced [[hydrogen chloride]].<ref>{{Cite book|last=Kraus|first=Paul|author-link=Paul Kraus (Arabist)|year=1942–1943|title=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|publisher=[[Institut Français d'Archéologie Orientale]]|location=Cairo|oclc=468740510|isbn=9783487091150}} vol. II, pp. 41–42; {{cite book|last=Multhauf|first=Robert P.|author-link=Robert P. Multhauf|year=1966|title=The Origins of Chemistry|location=London|publisher=Oldbourne|oclc=977570829}} pp. 141-142.</ref> It is possible that in one of his experiments, al-Razi stumbled upon a primitive method to produce [[hydrochloric acid]].<ref>{{cite journal <!-- Citation bot bypass-->|last1=Stapleton|first1=Henry E.|author1-link=Henry Ernest Stapleton|last2=Azo|first2=R.F.|last3=Hidayat Husain|first3=M.|year=1927|title=Chemistry in Iraq and Persia in the Tenth Century A.D.|journal=Memoirs of the Asiatic Society of Bengal|volume=VIII|issue=6|pages=317–418|oclc=706947607|url=http://www.southasiaarchive.com/Content/sarf.100203/231270}} p. 333. The relevant recipe reads as follows: "Take equal parts of sweet salt, Bitter salt, {{transliteration|ar|Ṭabarzad}} salt, {{transliteration|ar|Andarānī}} salt, Indian salt, salt of {{transliteration|ar|Al-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 ({{transliteration|ar|sakhr}}) instantly." (p. 333) For a glossary of the terms used in this recipe, see p. 322. German translation of the same passage in {{cite book|last1=Ruska|first1=Julius|author1-link=Julius Ruska|date=1937|title=Al-Rāzī's Buch Geheimnis der Geheimnisse. Mit Einleitung und Erläuterungen in deutscher Übersetzung|series=Quellen und Studien zur Geschichte der Naturwissenschaften und der Medizin|volume=VI|location=Berlin|publisher=Springer}} p. 182, §5. An English translation of Ruska 1937's translation can be found in {{cite book|last1=Taylor|first1=Gail Marlow|date=2015|title=The Alchemy of Al-Razi: A Translation of the "Book of Secrets"|publisher=CreateSpace Independent Publishing Platform|isbn=9781507778791}} pp. 139–140.</ref> However, it appears that in most of these early experiments with [[chloride]] [[Salt (chemistry)|salts]], 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.<ref>{{harvnb|Multhauf|1966|loc=p. 142, note 79}}.</ref>

One of the first such uses of hydrogen chloride was in the synthesis of mercury(II) chloride (corrosive sublimate), whose production from the heating of [[mercury (element)|mercury]] either with [[alum]] and ammonium chloride or with vitriol and sodium chloride was first described in the {{lang|la|[[De aluminibus et salibus]]}} ("On Alums and Salts").<ref>{{harvnb|Multhauf|1966|pp=160–163}}. On the {{lang|la|De aluminibus et salibus}}, see further {{cite journal|last1=Ferrario|first1=Gabriele|date=2004|title=Il Libro degli allumi e dei sali: status quaestionis e prospettive di studio|journal=Henoch|volume=26|issue=3|pages=275–296}}, {{cite book|last1=Ferrario|first1=Gabriele|date=2007|chapter=Origins and Transmission of the Liber de aluminibus et salibus|editor1-last=Principe|editor1-first=Lawrence|editor1-link=Lawrence M. Principe|title=Chymists and Chymistry: Studies in the History of Alchemy and Early Modern Chemistry|location=Sagamore Beach|publisher=Science History Publications|pages=137–148}} See also more briefly {{cite journal|last1=Ferrario|first1=Gabriele|date=2009|title=An Arabic Dictionary of Technical Alchemical Terms: MS Sprenger 1908 of the Staatsbibliothek zu Berlin (fols. 3r–6r)|journal=Ambix|volume=56|issue=1|pages=36–48|doi=10.1179/174582309X405219|pmid=19831258 |s2cid=41045827 }} pp. 40–43, and the sources cited in {{harvnb|Ferrario|2009|loc=p. 38, note 5}}. See also {{cite journal|last1=Moureau|first1=Sébastien|date=2020|title=Min al-kīmiyāʾ ad alchimiam. The Transmission of Alchemy from the Arab-Muslim World to the Latin West in the Middle Ages|journal=Micrologus|volume=28|issue=|pages=87–141|hdl=2078.1/211340|url=http://hdl.handle.net/2078.1/211340}} pp. 106–107.</ref> This eleventh- or twelfth-century [[Alchemy in the medieval Islamic world|Arabic alchemical]] text is anonymous in most manuscripts, though some manuscripts attribute it to [[Hermes Trismegistus]], and a few [[Pseudepigrapha|falsely attribute]] it to Abu Bakr al-Razi.<ref>{{harvnb|Moureau|2020|pp=106–107}}. On the false attribution to al-Razi, see {{harvnb|Ferrario|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 the {{lang|la|Liber secretorum Bubacaris}}, an interpolated paraphrase of al-Razi's {{transliteration|ar|Kitāb al-Asrār}}.</ref> It was translated into [[Hebrew]] and two times [[Latin translations of the 12th century|into Latin]], with one Latin translation by {{nowrap|[[Gerard of Cremona]] (1144–1187)}}.<ref>{{harvnb|Moureau|2020|pp=106–107}}.</ref>

In the process described in the {{lang|la|De aluminibus et salibus}}, hydrochloric acid started to form, but it immediately reacted with the mercury to produce mercury(II) chloride. Thirteenth-century Latin [[Alchemy|alchemists]], for whom the {{lang|la|De aluminibus et salibus}} was 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, strong [[mineral acids]] can directly be distilled.<ref>{{harvnb|Multhauf|1966|pp=162–163}}.</ref>

Mercury(II) chloride was used as a photographic intensifier to produce positive pictures in the [[collodion process]] of 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.<ref>Towler, J. (1864). [http://albumen.conservation-us.org/library/monographs/sunbeam/chap18.html Stereographic negatives and landscape photography]. Chapter 28. In: [http://albumen.conservation-us.org/library/monographs/sunbeam/index.html The silver sunbeam: a practical and theoretical textbook of sun drawing and photographic printing. ] Retrieved on April 13, 2005.</ref>

Mercuric chloride was a common over-the-counter disinfectant in the early twentieth century, recommended for everything from fighting measles germs<ref>{{cite news |author=<!--Staff writer(s)/no by-line.--> |date=1908-01-29 |title=Measles Kills Many Children |url=https://news.google.com/newspapers?nid=2241&dat=19080129&id=dZAlAAAAIBAJ&sjid=BPMFAAAAIBAJ&pg=6284,2248186 |work=The Star and Sentinel |location=Gettysburg, PA |access-date=2021-09-25}}</ref> to protecting fur coats<ref>{{cite news |author=<!--Staff writer(s)/no by-line.--> |date=1914-05-05 |url=https://chroniclingamerica.loc.gov/lccn/sn83045487/1914-05-05/ed-1/seq-31/#date1=1777&index=1&rows=20&words=bichloride+mercury&searchType=basic&sequence=0&state=&date2=1963&proxtext=bichloride+of+mercury&y=0&x=0&dateFilterType=yearRange&page=1 |work=The Day Book |location=Chicago, IL |access-date=2021-09-25|page=31|title=Adventures of Mr. Mouse}}</ref> and exterminating red ants.<ref>{{cite book|title=The American Frugal Housewife|last=Child|first=Lydia Maria|year=832|edition=12th|url=https://www.gutenberg.org/files/13493/13493-h/13493-h.htm#page21|page=21}}</ref>

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.<ref>{{cite news |last=Philips, M.D. |first=Carlin |date=1913-06-15 |title=To Keep Deadly Bichloride of Mercury from Family Medicine Shelves |url=https://chroniclingamerica.loc.gov/lccn/sn85038615/1913-06-15/ed-1/seq-15/ |work=The Times Dispatch |location=Richmond, VA |access-date=2021-09-25}}</ref> 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.<ref>{{cite news |author=<!--Staff writer(s)/no by-line.--> |date=1913-06-23 |title=Want Sale of Bichloride of Mercury Restricted |url=https://chroniclingamerica.loc.gov/lccn/sn83045487/1913-06-23/ed-1/seq-8/ |work=The Day Book |location=Chicago, IL |access-date=2021-09-25}}</ref>

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.<ref>{{cite book |last1=Craddock |first1=Susan |title=City of Plagues |date=2000 |publisher=University of Minnesota Press |page=138}}</ref>

*In 1613, whilst imprisoned in the Tower of London, [[Thomas Overbury]] was poisoned with an enema of mercury sublimate.<ref>{{Cite book |last=Somerset |first=Anne |title=Unnatural Murder: Poison at the Court of James I |publisher=Orion Publishing Group |year=1997 |isbn=978-0753801987}}</ref> The following trial saw the downfall of the murderers, [[Robert Carr, 1st Earl of Somerset|Robert Carr]] and his wife, [[Frances Carr, Countess of Somerset|Frances]].

*In Volume V of [[Alexandre Dumas]]' ''Celebrated Crimes'', he recounts the history of [[Antoine François Desrues]], who killed noblewoman Madame de Lamotte with "corrosive sublimate."<ref>{{cite book |last1=Dumas |first1=Alexandre |author-link1=Alexandre Dumas |date=1895 |title=Celebrated Crimes Volume V: The Cenci. Murat. Derues |url=https://books.google.com/books?id=0vU_AAAAYAAJ&pg=250 |publisher=G. Barrie & sons |page=250 |access-date=30 June 2015 |via=Google Books}}</ref>

*In 1906 in New York, Richard Tilghman died after mistaking bichloride of mercury tablets for [[lithium citrate]].<ref>{{Cite web|url=https://chroniclingamerica.loc.gov/lccn/sn86063756/1906-06-28/ed-1/seq-1/|title = The times and democrat. [volume] (Orangeburg, S.C.) 1881-current, June 28, 1906, Image 1|date = 28 June 1906}}</ref>

*Actor [[Lon Chaney]]'s estranged wife Cleva attempted suicide by swallowing mercuric chloride in 1913. Although the attempt failed, the toxic effects ruined her singing career.<ref>{{cite AV media | title=Mysteries and Scandals – Lon Chaney (Season 3, Episode 34) | publisher=E! | date=2000}}</ref>

*In a highly publicized case in 1920, mercury bichloride was reported to have caused the death of 25-year-old American [[silent film]] star [[Olive Thomas]]. While vacationing in France, she accidentally (or perhaps intentionally) ingested the compound, which had been prescribed to her husband [[Jack Pickford]] in liquid topical form to treat his syphilis. Thomas died five days later.<ref>{{cite news|url=https://news.google.com/newspapers?id=L0pLAAAAIBAJ&pg=3680,4398473&dq=olive+thomas+mercury&hl=en|title=Bichloride of Mercury Killed Olive Thomas|date=September 15, 1920|work=The Toronto World|page=6|access-date=August 27, 2018}}</ref><ref>Foster, Charles (2000). ''Stardust and Shadows: Canadians in Early Hollywood'', page 257. Toronto, Canada: Dundurn Press, 2000. {{ISBN|978-1550023480}}.</ref>

*Mercuric chloride was used by [[Madge Oberholtzer]] to commit suicide after she was kidnapped, raped and tortured by [[Ku Klux Klan]] leader [[D.C. Stephenson]]. She died from a combination of mercury poisoning and the [[staph infection]] that she suffered when Stephenson bit her during the assault.<ref name="Linder">[http://law2.umkc.edu/faculty/projects/ftrials/stephenson/atatevstprosecution.html Daniel O. Linder, "D.C. Stephenson"], Testimony, ''Famous Trials'', hosted at University of Missouri Law School, Kansas City</ref>

*Ana María Cires, a young wife of Uruguayan writer [[Horacio 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.<ref>{{cite book|last=Brignol|first=José|title=Vida y Obra de Horacio Quiroga|year=1939|publisher=La Bolsa de los Libros|location=Montevido|pages=211–213}}</ref>

*[[Ruth L. Truffant]]'s death was called a suicide after she died from [[bichloride of mercury]] poisoning on 26 April 1914.<ref name="Dies">{{cite news |title=Actress Dies of Poisoning When Heart Balm is Denied |url=https://www.newspapers.com/clip/104488448/ruth-trufant/ |access-date=27 June 2022 |publisher=The Indianapolis Star |date=27 April 1914}}</ref><ref name="Company">{{cite book |title=The American Library Annual: Including Index to Dates of 1914-1915 |date=1915 |publisher=R.R. Bowker Company |location=New York |page=155 |url=https://books.google.com/books?id=OYkfAQAAIAAJ&dq=Ruth+L.+Truffant+actress&pg=PA155 |access-date=27 June 2022}}</ref>

Mercury dichloride is a highly toxic compound,<ref>[[#ToxSum|Mercury (II) chloride, toxicity]]</ref> 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 to [[acute kidney failure]]. However, mercuric chloride, like all inorganic mercury salts, does not cross the [[blood–brain barrier]] as readily as organic mercury, although it is known to be a cumulative poison.

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.<ref>[http://toxnet.nlm.nih.gov/cgi-bin/sis/search/r?dbs+hsdb:@term+@rn+@rel+7487-94-7 "Mercuric chloride"]{{dead link|date=July 2022}} in ''ToxNet: Hazardous Substances'' data bank. National Institutes of Health (2002, October 31). Retrieved on April 17, 2005. See also the [[#PubChem|corresponding entry]] in ''ToxNet''<nowiki>'</nowiki>s successor, ''PubChem''.</ref>

* Agency for toxic substances and disease registry. (2001, May 25). [https://web.archive.org/web/20010718214647/http://www.atsdr.cdc.gov/toxprofiles/tp46.html Toxicological profile for Mercury]. Retrieved on April 17, 2005.

* {{vanchor|PubChem|text=[https://pubchem.ncbi.nlm.nih.gov/compound/24085 "Mercuric Chloride {{pipe}} HgCl₂"] in ''PubChem'' database.}} US National Institutes of Health. Retrieved 19 July 2022. [https://archive.today/20220720043040/https://pubchem.ncbi.nlm.nih.gov/compound/24085 Archived] 20 July 2022.

*[https://www.atsdr.cdc.gov/toxfaqs/tfacts46.pdf ATSDR - ToxFAQs: Mercury]

*[https://web.archive.org/web/20020802220747/http://www.atsdr.cdc.gov/toxprofiles/phs46.html ATSDR - Public Health Statement: Mercury]

*[https://web.archive.org/web/20030802024248/http://www.atsdr.cdc.gov/MHMI/mmg46.html ATSDR - Medical Management Guidelines (MMGs) for Mercury (Hg)]

*[https://web.archive.org/web/20010718214647/http://www.atsdr.cdc.gov/toxprofiles/tp46.html ATSDR - Toxicological Profile: Mercury]