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{{chembox |
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| verifiedrevid = 444008044 |
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| verifiedrevid = 444009183 |
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| ImageFile = Mercury Chloride.jpg |
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| ImageFile = Mercury Chloride.jpg |
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| ImageFile1 = Calomel-2D.png |
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| ImageFile1 = Calomel-2D.png |
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| IUPACName = Dimercury dichloride |
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| IUPACName = Dimercury dichloride |
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| OtherNames = Mercurous chloride<br/>Calomel |
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| OtherNames = Mercury(I) chloride<br/>Mercurous chloride<br/>] |
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| Section1 = {{Chembox Identifiers |
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|Section1={{Chembox Identifiers |
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| CASNo = 10112-91-1 |
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| CASNo = 10112-91-1 |
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| CASNo_Ref = {{cascite|correct|CAS}} |
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| CASNo_Ref = {{cascite|correct|CAS}} |
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| PubChem = |
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| Gmelin = 25976 |
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| UNII_Ref = {{fdacite|changed|FDA}} |
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| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
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| UNII = J2D46N657D |
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| PubChem = 24956 |
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| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
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| ChemSpiderID = 16740467 |
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| ChemSpiderID = 16740467 |
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| ChEBI_Ref = {{ebicite|correct|EBI}} |
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| ChEBI_Ref = {{ebicite|correct|EBI}} |
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| ChEBI = 33050 |
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| ChEBI = 33050 |
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| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}} |
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| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}} |
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| StdInChIKey = ZOMNIUBKTOKEHS-UHFFFAOYSA-L |
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| StdInChIKey = ZOMNIUBKTOKEHS-UHFFFAOYSA-L |
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| SMILES = ClCl |
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| SMILES = ClCl |
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| StdInChI_Ref = {{stdinchicite|correct|chemspider}} |
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| StdInChI_Ref = {{stdinchicite|correct|chemspider}} |
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| StdInChI = 1S/2ClH.2Hg/h2*1H;;/q;;2*+1/p-2 |
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| StdInChI = 1S/2ClH.2Hg/h2*1H;;/q;;2*+1/p-2 |
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| RTECS = OV8750000 |
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| RTECS = OV8750000 |
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| EINECS = 233-307-5 |
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| EINECS = 233-307-5 |
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| UNNumber = 3077 keshav |
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| UNNumber = 3077 |
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| Section2 = {{Chembox Properties |
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|Section2={{Chembox Properties |
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| Formula = Hg<sub>2</sub>Cl<sub>2</sub> |
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| Formula = Hg<sub>2</sub>Cl<sub>2</sub> |
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| MolarMass = 472.09 g/mol |
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| MolarMass = 472.09 g/mol |
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| Appearance = White solid |
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| Appearance = White solid |
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| Density = 7.150 g/cm<sup>3</sup> |
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| Density = 7.150 g/cm<sup>3</sup> |
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| MeltingPtC = 383 |
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| MeltingPt = 525 °C (triple point) |
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| BoilingPt = 383 °C (sublimes) |
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| MeltingPt_notes = (sublimes) |
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| Solubility = 0.2 mg/100 mL |
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| Solubility = 0.2 mg/100 mL |
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| SolubleOther = insoluble in ], ] |
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| SolubleOther = insoluble in ], ] |
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| SolubilityProduct = 1.43{{e|−18}}<ref name="crc">{{cite book |author1=John Rumble |title=CRC Handbook of Chemistry and Physics |date=June 18, 2018 |publisher=CRC Press |isbn=978-1138561632 |pages=5–188|edition=99 |language=English}}</ref> |
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| RefractIndex = 1.973 |
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| RefractIndex = 1.973 |
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| MagSus = −26.0·10<sup>−6</sup> cm<sup>3</sup>/mol |
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| Section3 = {{Chembox Hazards |
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|Section5={{Chembox Hazards |
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| ExternalMSDS = |
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| ExternalSDS = |
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| GHSPictograms = {{GHS07}}{{GHS09}} |
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| EUIndex = 080-003-00-1 |
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| GHSSignalWord = Warning |
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| EUClass = Harmful ('''Xn''')<br/>Dangerous for the environment ('''N''') |
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| HPhrases = {{H-phrases|302|315|319|335|410}} |
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| RPhrases = {{R22}}, {{R36/37/38}}, {{R50/53}} |
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| PPhrases = {{P-phrases|261|264|270|271|273|280|301+312|302+352|304+340|305+351+338|312|321|330|332+313|337+313|362|391|403+233|405|501}} |
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| SPhrases = {{S2}}, {{S13}}, {{S24/25}}, {{S46}}, {{S60}}, {{S61}} |
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| NFPA-H = 3 |
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| NFPA-H = 3 |
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| NFPA-F = 0 |
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| NFPA-F = 0 |
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| NFPA-R = 0 |
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| NFPA-R = 0 |
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| FlashPt = Non-flammable |
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| FlashPt = Non-flammable |
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| LD50 = 210 mg/kg (rat, oral)<ref>{{IDLH|7439976|Mercury compounds (as Hg)}}</ref> |
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|Section3={{Chembox Structure |
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| CrystalStruct = tetragonal |
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| Section8 = {{Chembox Related |
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|Section4={{Chembox Thermochemistry |
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| DeltaHf = −265 kJ·mol<sup>−1</sup><ref name=b1>{{cite book |last=Zumdahl |first=Steven S. |title =Chemical Principles 6th Ed.| publisher = Houghton Mifflin Company| year = 2009| isbn = 978-0-618-94690-7|page=A22}}</ref> |
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| Entropy = 196 J·mol<sup>−1</sup>·K<sup>−1</sup><ref name=b1/> |
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|Section8={{Chembox Related |
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| OtherAnions = ]<br/>]<br/>] |
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| OtherAnions = ]<br/>]<br/>] |
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| OtherCations = ] |
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| OtherCompounds = ] |
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'''Mercury(I) chloride''' is the ] with the formula Hg<sub>2</sub>Cl<sub>2</sub>. Also known as '''calomel''' (a mineral form, rarely found in nature) or '''mercurous chloride''', this dense white or yellowish-white, odorless solid is the principal example of a ](I) compound. It is a component of ]s in ].<ref>{{Housecroft2nd|pages=696–697}}</ref><ref>{{cite book | author = Skoog, Douglas A., F. James Holler and Timothy A. Nieman | title = Principles of Instrumental Analysis | edition = 5th | publisher = Saunders College Pub. | year = 1998 | pages = 253–271 | isbn = 0030020786}}</ref> |
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'''Mercury(I) chloride''' is the ] with the formula Hg<sub>2</sub>Cl<sub>2</sub>. Also known as the ] ]<ref name=EB>{{cite EB1911|wstitle=Calomel}}</ref> (a rare mineral) or '''mercurous chloride''', this dense white or yellowish-white, odorless solid is the principal example of a ](I) compound. It is a component of ]s in ].<ref>{{Housecroft2nd|pages=696–697}}</ref><ref>{{cite book |last1=Skoog |first1=Douglas A. |first2=F. James |last2=Holler |first3=Timothy A. |last3=Nieman | title = Principles of Instrumental Analysis | edition = 5th | publisher = Saunders College Pub. | year = 1998 | pages = 253–271 | isbn = 978-0-03-002078-0}}</ref> |
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==History== |
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==History== |
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The name calomel is thought to come from the ] καλός ''beautiful'', and μέλας ''black''. This name (somewhat surprising for a white compound) is probably due to its characteristic ] reaction with ], which gives a spectacular black coloration due to the finely dispersed metallic ] formed. It is also referred to as the mineral ''horn quicksilver'' or ''horn mercury''. Calomel was taken internally and used as a laxative and disinfectant, as well as in the treatment of syphilis, until the early 20th century. |
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The name calomel is thought to come from the ] ''καλός'' "beautiful", and ''μέλας'' "black"; or ''καλός'' and ''μέλι'' "honey" from its sweet taste.<ref name=EB/> The "black" name (somewhat surprising for a white compound) is probably due to its characteristic ] reaction with ], which gives a spectacular black coloration due to the finely dispersed metallic ] formed. It is also referred to as the mineral ''horn quicksilver'' or ''horn mercury''.<ref name=EB/> |
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Calomel was taken internally and used as a laxative,<ref name=EB/> for example to treat ] in 1801, and disinfectant, as well as in the treatment of syphilis, until the early 20th century. Until fairly recently,{{when|date=February 2018}} it was also used as a horticultural fungicide, most notably as a root dip to help prevent the occurrence of ] amongst crops of the family ].<ref>Buczacki, S., ''Pests, Diseases and Disorders of Garden Plants'', Collins, 1998, pp 449-50. {{ISBN|0-00-220063-5}}</ref> |
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Mercury became a popular remedy for a variety of physical and mental ailments during the age of "]." It was used by doctors in America throughout the 18th century, and during the revolution, to make patients regurgitate and release their body from "impurities". ], a famed physician in colonial Philadelphia and signatory to the ], was one particular well-known advocate of mercury in medicine and famously used calomel to treat sufferers of ] during its outbreak in the city in 1793. Calomel was given to patients as a purgative until they began to salivate. However, it was often administered to patients in such great quantities that their hair and teeth fell out.<ref>{{cite journal | title = Heavy Metal Medicine | last = Koehler | first = Christopher S. W. | journal = Today's Chemist at Work | issn = 1062-094X | volume = 10 | pages = 61–65 | issue = 1 | date = January 2001 | publisher = ] | url = http://pubs.acs.org/subscribe/journals/tcaw/10/i01/html/01chemch.html | accessdate = 2009-02-02}}</ref> Shortly after yellow fever struck Philadelphia, the disease broke out in Jamaica. A war of words broke out in the newspapers concerning the best treatment for yellow fever; bleeding or calomel. Anecdotal evidence indicates calomel was more effective than bleeding.<ref>{{cite book| title = Recollections of a Georgia Loyalist | last = Johnston| first = Elizabeth Lichtenstein | pages = 82–83 | publisher = The Bankside Press | 1901}}</ref> |
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Mercury became a popular remedy for a variety of physical and mental ailments during the age of "]". It was prescribed by doctors in America throughout the 18th century, and during the revolution, to make patients regurgitate and release their body from "impurities". ] was a well-known advocate of mercury in medicine and used calomel to treat sufferers of ] during its outbreak in ] in 1793. Calomel was given to patients as a ] or ] until they began to salivate and was often administered to patients in such great quantities that their hair and teeth fell out.<ref> |
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{{cite journal |
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| title = Heavy Metal Medicine |
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| last = Koehler | first = Christopher S. W. |
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| journal = Today's Chemist at Work |
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| issn = 1062-094X |
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| volume = 10 |
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| pages = 61–65 |
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| issue = 1 |
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| date = January 2001 |
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| url = http://pubs.acs.org/subscribe/journals/tcaw/10/i01/html/01chemch.html | access-date = 2009-02-02 |
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}}</ref> |
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Yellow fever was also treated with calomel.<ref name="Johnston1901">{{cite book|last=Johnston|first=Elizabeth Lichtenstein|title=Recollections of a Georgia Loyalist...written in 1836|url=https://archive.org/details/recollectionsag00johngoog|page=|year=1901|publisher=Mansfield & Company|location=New York}} pp. 82-83.</ref> |
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] brought calomel on their expedition. Researchers used that same mercury, found deep in ] pits, to retrace the locations of their respective locations and campsites.<ref>{{Cite news|url=https://io9.gizmodo.com/archaeologists-tracked-lewis-and-clark-by-following-the-1727887223?commerce_insets_disclosure=on|title=Archaeologists Tracked Lewis and Clark by Following Their Trail of Laxatives|last=Inglis-Arkell|first=Esther|work=io9|access-date=2018-11-09|language=en-US}}</ref> |
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==Properties== |
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==Properties== |
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Mercury is unique among the group 12 metals for its ability to form the M–M bond so readily. Hg<sub>2</sub>Cl<sub>2</sub> is a linear molecule. The ] of the ] is shown below: |
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Mercury is unique among the group 12 metals for its ability to form the M–M bond so readily. Hg<sub>2</sub>Cl<sub>2</sub> is a linear molecule. The mineral calomel crystallizes in the ] system, with space group I4/m 2/m 2/m. The ] of the ] is shown below: |
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|<center>]</center>||<center>]</center> |
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|<center>unit cell</center>||<center>distorted octahedral coordination of Hg</center> |
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| unit cell||distorted octahedral coordination of Hg |
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</center> |
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The Hg–Hg bond length of 253 pm (Hg–Hg in the metal is 300 pm) and the Hg–Cl bond length in the linear Hg<sub>2</sub>Cl<sub>2</sub> unit is 243 pm.<ref name = "Wells">Wells A.F. (1984) ''Structural Inorganic Chemistry'' 5th edition Oxford Science Publications ISBN 0-19-855370-6</ref> The overall coordination of each Hg atom is octahedral as, in addition to the two nearest neighbours, there are four other Cl atoms at 321 pm. Longer ] exist. |
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The Hg–Hg bond length of 253 pm (Hg–Hg in the metal is 300 pm) and the Hg–Cl bond length in the linear Hg<sub>2</sub>Cl<sub>2</sub> unit is 243 pm.<ref name = "Wells">Wells A.F. (1984) ''Structural Inorganic Chemistry'' 5th edition Oxford Science Publications {{ISBN|0-19-855370-6}}</ref> The overall coordination of each Hg atom is octahedral as, in addition to the two nearest neighbours, there are four other Cl atoms at 321 pm. Longer ] exist. |
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==Preparation and reactions== |
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==Preparation and reactions== |
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Mercurous chloride forms by the reaction of elemental mercury and mercuric chloride: |
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Mercurous chloride forms by the reaction of elemental mercury and mercuric chloride: |
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::Hg + HgCl<sub>2</sub> → Hg<sub>2</sub>Cl<sub>2</sub> |
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:Hg + HgCl<sub>2</sub> → Hg<sub>2</sub>Cl<sub>2</sub> |
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It can be prepared via ] reaction involving aqueous ] using various chloride sources including NaCl or HCl. |
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It can be prepared via ] involving aqueous ] using various chloride sources including NaCl or HCl. |
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::2HCl + Hg<sub>2</sub>(NO<sub>3</sub>)<sub>2</sub> → Hg<sub>2</sub>Cl<sub>2</sub> + 2HNO<sub>3</sub> |
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:2 HCl + Hg<sub>2</sub>(NO<sub>3</sub>)<sub>2</sub> → Hg<sub>2</sub>Cl<sub>2</sub> + 2 HNO<sub>3</sub> |
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] causes Hg<sub>2</sub>Cl<sub>2</sub> to ]: |
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] causes Hg<sub>2</sub>Cl<sub>2</sub> to ]: |
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::Hg<sub>2</sub>Cl<sub>2</sub> + 2NH<sub>3</sub> → Hg + Hg(NH<sub>2</sub>)Cl + NH<sub>4</sub>Cl |
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:Hg<sub>2</sub>Cl<sub>2</sub> + 2 NH<sub>3</sub> → Hg + Hg(NH<sub>2</sub>)Cl + NH<sub>4</sub>Cl |
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===Calomel electrode=== |
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===Calomel electrode=== |
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{{main|Saturated calomel electrode}} |
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{{main|Saturated calomel electrode}} |
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Mercurous chloride is employed extensively in ], taking advantage of the ease of its oxidation and reduction reactions. The calomel electrode is a ], especially in older publications. Over the past 50 years, it has been superseded by the silver/silver chloride (Ag/AgCl) electrode. Although the mercury electrodes have been widely abandoned due to the dangerous nature of ], many chemists believe they are still more accurate and are not dangerous as long as they are handled properly. The differences in experimental potentials vary little from literature values. Other electrodes can vary by 70 to 100 millivolts.{{Citation needed|date=February 2007}} |
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Mercurous chloride is employed extensively in ], taking advantage of the ease of its oxidation and reduction reactions. The calomel electrode is a ], especially in older publications. Over the past 50 years, it has been superseded by the silver/silver chloride (Ag/AgCl) electrode. Although the mercury electrodes have been widely abandoned due to the dangerous nature of ], many chemists believe they are still more accurate and are not dangerous as long as they are handled properly. The differences in experimental potentials vary little from literature values. Other electrodes can vary by 70 to 100 millivolts.{{Citation needed|date=February 2011}} |
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===Photochemistry=== |
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===Photochemistry=== |
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Mercurous chloride decomposes into ] and elemental mercury upon exposure to UV light. |
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Mercurous chloride decomposes into ] and elemental mercury upon exposure to UV light. |
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::Hg<sub>2</sub>Cl<sub>2</sub> → HgCl<sub>2</sub> + Hg |
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:Hg<sub>2</sub>Cl<sub>2</sub> → HgCl<sub>2</sub> + Hg |
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The formation of Hg can be used to calculate the number of photons in the light beam, by the technique of ]. By utilizing a light reaction in the presence of ] and ], ], ] and ] is produced. |
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The formation of Hg can be used to calculate the number of photons in the light beam, by the technique of ]. |
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::2HgCl<sub>2</sub> + (NH<sub>4</sub>)<sub>2</sub>C<sub>2</sub>O<sub>4</sub> + Light → Hg<sub>2</sub>Cl<sub>2</sub><sub>(s)</sub> + 2 + 2CO<sub>2</sub> |
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{{anchor|Eder reaction}}By utilizing a light reaction in the presence of ] and ], mercury(I) chloride, ] and ] are produced. |
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This particular reaction was discovered by J.M. Eder (hence the name '''Eder reaction''') in 1880 and reinvestigated by W. E. Rosevaere in 1929<ref>{{Cite journal | title = The X-Ray Photochemical Reaction between Potassium Oxalate and Mercuric Chloride | author = W. E. Roseveare | journal = ] | year = 1930 | volume = 52 | issue = 7 | pages = 2612–2619 | doi = 10.1021/ja01370a005}}</ref> |
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:2 HgCl<sub>2</sub> + (NH<sub>4</sub>)<sub>2</sub>C<sub>2</sub>O<sub>4</sub> {{overset|Light|→}} Hg<sub>2</sub>Cl<sub>2(s)</sub> + 2 + 2 CO<sub>2</sub> |
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This particular reaction was discovered by J. M. Eder (hence the name '''Eder reaction''') in 1880 and reinvestigated by W. E. Rosevaere in 1929.<ref>{{Cite journal |last=Roseveare |first=W. E. | title = The X-Ray Photochemical Reaction between Potassium Oxalate and Mercuric Chloride | journal = ] | year = 1930 | volume = 52 | issue = 7 | pages = 2612–2619 | doi = 10.1021/ja01370a005}}</ref> |
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==Related mercury(I) compounds== |
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==Related mercury(I) compounds== |
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], Hg<sub>2</sub>Br<sub>2</sub>, a light yellow, whereas ], Hg<sub>2</sub>I<sub>2</sub>, is greenish in colour. Both are poorly soluble. ] is unstable in the absence of a strong acid. |
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], Hg<sub>2</sub>Br<sub>2</sub>, is light yellow, whereas ], Hg<sub>2</sub>I<sub>2</sub>, is greenish in colour. Both are poorly soluble. ] is unstable in the absence of a strong acid. |
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==Safety considerations== |
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==Safety considerations== |
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{{main|Mercury poisoning}} |
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{{main|Mercury poisoning}} |
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Mercurous chloride is ], although due to its low solubility in water it is generally less dangerous than its ] counterpart. It was used in medicine as a ] and ] (laxative) in the ] from the early 1830s through the 1860s. Calomel was also a common ingredient in ] powders in Britain up until 1954, causing widespread mercury poisoning in the form of ], which at the time had a mortality rate of 1 in 10.<ref>{{cite book | first = Walter | last = Sneader | title = Drug Discovery: A History | url = http://books.google.com/?id=mYQxRY9umjcC&pg=PA46&lpg=PA46 | pages = 45–46 | publisher = ] | isbn = 0471899801 | year = 2005 | accessdate = 2009-02-02}}</ref> These medicinal uses were later discontinued when the compound's toxicity was discovered. |
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Mercurous chloride is ], although due to its low solubility in water it is generally less dangerous than its ] counterpart. It was used in medicine as a ] and ] (laxative) in the ] from the late 1700s through the 1860s. Calomel was also a common ingredient in ] powders in Britain up until 1954, causing widespread mercury poisoning in the form of ], which at the time had a mortality rate of 1 in 10.<ref>{{cite book | first = Walter | last = Sneader | title = Drug Discovery: A History | url = https://books.google.com/books?id=mYQxRY9umjcC&pg=PA46 | pages = 45–46 | publisher = ] | isbn = 978-0-471-89980-8 | year = 2005 | access-date = 2009-02-02}}</ref> These medicinal uses were later discontinued when the compound's toxicity was discovered. |
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It has also found uses in cosmetics as soaps and ] creams, but these preparations are now illegal to manufacture or import in many countries including the U.S., Canada, Japan and the European Union.<ref>{{cite web |url=http://eur-lex.europa.eu/LexUriServ/LexUriServ.do?uri=CONSLEG:1976L0768:20080424:en:PDF |title=Commission Directive 86/199/EEC, OJ L 149, p. 38 of 3.6.1986}}</ref> A study of workers involved in the production of these preparations showed that the sodium salt of ] (DMPS) was effective in lowering the ] of mercury and in decreasing the urinary mercury concentration to normal levels.<ref>{{cite journal | author = D. Gonzalez-Ramirez, M. Zuniga-Charles, A. Narro-Juarez, Y. Molina-Recio, K. M. Hurlbut, R. C. Dart and H. V. Aposhian | title = DMPS (2,3-Dimercaptopropane-1-sulfonate, Dimaval) Decreases the Body Burden of Mercury in Humans Exposed to Mercurous Chloride | date=1 October 1998| journal = ] | volume = 287 | issue = 1 | pages = 8–12 | url = http://jpet.aspetjournals.org/cgi/content/abstract/287/1/8 | format = free full text | pmid = 9765315 }}</ref> |
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It has also found uses in cosmetics as soaps and ] creams, but these preparations are now illegal to manufacture or import in many countries including the US, Canada, Japan and the European Union.<ref>{{cite web |url=http://eur-lex.europa.eu/LexUriServ/LexUriServ.do?uri=CONSLEG:1976L0768:20080424:en:PDF |title=Commission Directive 86/199/EEC, OJ L 149, p. 38 of 3.6.1986}}</ref> A study of workers involved in the production of these preparations showed that the sodium salt of ] (DMPS) was effective in lowering the ] of mercury and in decreasing the urinary mercury concentration to normal levels.<ref>{{cite journal |author1=D. Gonzalez-Ramirez |author2=M. Zuniga-Charles |author3=A. Narro-Juarez |author4=Y. Molina-Recio |author5=K. M. Hurlbut |author6=R. C. Dart |author7=H. V. Aposhian | title = DMPS (2,3-Dimercaptopropane-1-sulfonate, Dimaval) Decreases the Body Burden of Mercury in Humans Exposed to Mercurous Chloride | date=1 October 1998| journal = The Journal of Pharmacology and Experimental Therapeutics| volume = 287 | issue = 1 | pages = 8–12 | url = http://jpet.aspetjournals.org/cgi/content/abstract/287/1/8 | format = free full text | pmid = 9765315 }}</ref> |
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==References== |
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==References== |
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{{reflist}} |
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<references/> |
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== External links == |
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== External links == |
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{{Commons category|Mercury(I) chloride}} |
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{{Commons category|Mercury(I) chloride}} |
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{{DEFAULTSORT:Mercury(I) Chloride}} |
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{{DEFAULTSORT:Mercury(I) Chloride}} |
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