Mercury(II) fulminate: Difference between revisions
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| IUPACName = Mercury(II) fulminate | | IUPACName = Mercury(II) fulminate | ||
|SystematicName=Dioxycyanomercury | |SystematicName=Dioxycyanomercury | ||
| OtherNames = Fulminated Mercury | | OtherNames = {{ubl | ||
|Fulminated Mercury | |||
|Bis(fulminato-kappaC)mercury | |||
|Knallquecksilber (German) | |||
|bis[(oxidoazanylidyne)methyl]mercury | |||
}} | |||
|Section1={{Chembox Identifiers | |Section1={{Chembox Identifiers | ||
| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} | | ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} | ||
| Line 29: | Line 34: | ||
}} | }} | ||
|Section2={{Chembox Properties | |Section2={{Chembox Properties | ||
| Formula = | | Formula = {{chem2|Hg(CNO)2}} | ||
| C=2 |Hg=1 |N=2 |O=2 | |||
| Appearance = Grey, pale brown, or white crystalline solid | | Appearance = Grey, pale brown, or white crystalline solid | ||
| Density = 4.42 g/ | | Density = {{val|4.42|u=g/cm3}} | ||
| MeltingPtC = 160 | | MeltingPtC = 160 | ||
| BoilingPtC = 356.6 | | BoilingPtC = 356.6 | ||
| Solubility = slightly soluble | | Solubility = slightly soluble | ||
| | | Solubility1=soluble | ||
| Solvent1=ethanol | |||
| Solubility2=soluble | |||
| Solvent2=ammonia | |||
}} | }} | ||
|Section3={{Chembox Explosive | |Section3={{Chembox Explosive | ||
| Explosive_ref = <ref name="EncycExplosives">{{cite book |last1=Fedoroff |first1=Basil T. |last2=Sheffield |first2=Oliver E. |title=Encyclopedia of Explosives and Related Items |date=1 January 1974 |publisher=Picatinny Arsenal |location=Dover, NJ |pages=F220-221 |url=https://apps.dtic.mil/sti/pdfs/ADA011845.pdf |volume=6 |id=ADA011845, PATR2700 |access-date=5 November 2025 |chapter=F}}</ref> | |||
| ShockSens = High | | ShockSens = High | ||
| FrictionSens = High | {{ubl | ||
| DetonationV = 4250 m/s | |{{val|5|u=cm}} ({{val|2|u=kg}} weight, {{val|20|u=mg}}, Bureau of Mines apparatus) | ||
| REFactor = | |{{val|4|u=in}} ({{val|1|u=lb}} weight, {{val|30|u=mg}}, Picatinny Arsenal apparatus) | ||
}} | |||
| FrictionSens = High (explodes with fiber & steel shoe tests) | |||
| DetonationV = {{ubl | |||
|{{val|3500|u=m/s}} (density = 2.0) | |||
|{{val|4250|u=m/s}} (density = 3.0) | |||
|{{val|5000|u=m/s}} (density = 4.0) | |||
}} | |||
| REFactor = {{val|37|to|50|u=%}} (Trauzl lead block) | |||
}} | }} | ||
|Section4={{Chembox Hazards | |Section4={{Chembox Hazards | ||
| | | Hazards_ref = <ref>{{PubChem|11022444|Mercury(II) fulminate}}</ref> | ||
| GHSPictograms = {{GHS01}}{{GHS06}}{{GHS08}}{{GHS09}} | |||
| GHSSignalWord = Danger | |||
| HPhrases = {{H-phrases|200|301|311|331|373|410}} | |||
| PPhrases = {{P-phrases|201|202|260|261|262|264|270|271|273|280|281|301+316|302+352|304+340|316|319|321|330|361+364|372|373|380|391|401|403+233|405|501}} | |||
| NFPA-H = 4 | | NFPA-H = 4 | ||
| NFPA-F = 1 | | NFPA-F = 1 | ||
| Line 51: | Line 72: | ||
| AutoignitionPtC = 170 | | AutoignitionPtC = 170 | ||
| AutoignitionPt_notes = | | AutoignitionPt_notes = | ||
| TLV={{val|0.02|u=mg/m3}} | |||
| TLV-TWA={{val|0.01|u=mg/m3}} | |||
| TLV-STEL={{val|0.03|u=mg/m3}} (skin, 15 minute) | |||
| PEL={{ubl | |||
|{{val|0.01|u=mg/m3}} (TWA, 8h) | |||
|{{val|0.04|u=mg/m3}} (ceiling) | |||
}} | |||
| REL={{ubl | |||
|{{val|0.01|u=mg/m3}} (TWA, skin) | |||
|{{val|0.03|u=mg/m3}} (STEL, skin) | |||
}} | |||
| IDLH={{val|2|u=mg/m3}} (as Hg) | |||
| NIOSH_id=0384 | |||
}} | }} | ||
|Section5={{Chembox Related | |||
| Related_ref = | |||
| OtherAnions = {{ubl | |||
|[[Mercury(II) cyanide]] | |||
|[[Mercury(II) thiocyanate]] | |||
}} | |||
| OtherCations = {{ubl | |||
|[[Potassium fulminate]] | |||
|[[Silver fulminate]] | |||
}} | |||
| OtherFunction = | |||
| OtherFunction_label = | |||
| OtherCompounds = | |||
}} | |||
}} | }} | ||
'''Mercury(II) fulminate''' | '''Mercury(II) fulminate''' is a [[primary explosive]] with the chemical formula {{chem2|Hg(CNO)2}}. When recrystallized from water it exists as the [[hemihydrate]] {{chem2|2 Hg(CNO)2*H2O}}. The anyhydrous form is obtained by recrystallization from ethanol.<ref name="EncycExplosives"/>{{rp|F217}} It is highly sensitive to [[friction]], heat and [[shock (mechanics)|shock]] and is mainly used as a trigger for other explosives in [[percussion cap]]s and [[detonator]]s. Mercury(II) cyanate, though its chemical formula is identical, has a different atomic arrangement, making the [[cyanate]] and [[fulminate]] [[Ion#Anions and cations|anionic]] [[isomer]]s. | ||
First used as a [[priming composition]] in small copper caps beginning in the 1820s, mercury fulminate quickly replaced [[flint]]s as a means to ignite [[black powder]] charges in [[Muzzleloader|muzzle-loading]] [[firearm]]s. Later, during the late 19th century and most of the 20th century, mercury fulminate became widely used in [[Primer (firearms)|primers]] for [[Cartridge (firearms)|self-contained rifle and pistol ammunition]]; it was the only practical detonator for firing projectiles until the early 20th century.<ref name=wisniak/> Mercury fulminate has the distinct advantage over [[potassium chlorate]] of being non-corrosive, but it is known to | First used as a [[priming composition]] in small copper caps beginning in the 1820s, mercury fulminate quickly replaced [[flint]]s as a means to ignite [[black powder]] charges in [[Muzzleloader|muzzle-loading]] [[firearm]]s. Later, during the late 19th century and most of the 20th century, mercury fulminate became widely used in [[Primer (firearms)|primers]] for [[Cartridge (firearms)|self-contained rifle and pistol ammunition]]; it was the only practical detonator for firing projectiles until the early 20th century.<ref name=wisniak/> | ||
Mercury fulminate has the distinct advantage over [[potassium chlorate]] of being non-corrosive, but it is known to attack aluminum and magnesium strongly, and brass, bronze, copper, and zinc slowly when dry; when wet it immediately reacts with aluminum and magnesium and strongly attacks brass, bronze, copper and zinc when.<ref name="EncycExplosives"/> Today, mercury fulminate has been replaced in primers by more efficient chemical substances. These are non-corrosive, less toxic, and more stable over time; they include [[lead azide]], [[lead styphnate]], and [[Tetrazene explosive|tetrazene]] derivatives. In addition, none of these compounds requires mercury for manufacture, supplies of which can be unreliable in wartime.<ref name="Weingart">{{cite book |last1=Weingart |first1=George W. |title=Pyrotechnics |pages=10 |edition=2nd |url=https://archive.org/details/Pyrotechnics_by_G._Weingart_2nd_ed._Corrected/page/n23/mode/2up |access-date=5 November 2025 |date=1947 |quote=Calomel [Hg<sub>2</sub>Cl<sub>2</sub>] is made in this country and sold in normal times at about 65 cents a pound, but due to the scarcity of mercury and the great demand for it in the manufacture of detonating caps the price has recently advanced to several dollars per pound.}}</ref> | |||
==Preparation== | ==Preparation== | ||
Mercury(II) fulminate is prepared by dissolving | Mercury(II) fulminate is prepared by dissolving mercury in [[nitric acid]] and adding [[ethanol]] to the solution. [[Edward Charles Howard]] is credited with first preparing it in 1800.<ref>{{cite journal |title=On a New Fulminating Mercury |author=Edward Howard |journal=[[Philosophical Transactions of the Royal Society of London]] |year=1800 |volume=90 |issue=1 |pages=204–238 |doi=10.1098/rstl.1800.0012 |s2cid=138658702}}</ref><ref name=wisniak>{{cite journal | last=Wisniak | first=Jaime | title=Edward Charles Howard. Explosives, meteorites, and sugar | journal=Educación Química | publisher=Universidad Nacional Autonoma de Mexico | volume=23 | issue=2 | year=2012 |language=en| issn=0187-893X | doi=10.1016/s0187-893x(17)30114-3 | pages=230–239| doi-access=free }}</ref> However, [[Johann Kunckel]] had discovered the compound more than a century before in the [[17th century]].<ref>{{cite web |title=300 years after discovery, structure of mercury fulminate finally determined |url=https://phys.org/news/2007-08-years-discovery-mercury-fulminate.html |website=Phys.org |access-date=19 February 2025 |date=August 24, 2007}}</ref> The [[crystal structure]] of this compound was determined only in 2007.<ref>{{cite journal |author1=W. Beck |author2=J. Evers |author3=M. Göbel |author4=G. Oehlinger |author5=T. M. Klapötke | title = The Crystal and Molecular Structure of Mercury Fulminate (Knallquecksilber) | year = 2007 | journal = [[Zeitschrift für anorganische und allgemeine Chemie]] | volume = 633 | issue = 9 | pages = 1417–1422 | doi = 10.1002/zaac.200700176| doi-access = free }}</ref> | ||
| title = On a New Fulminating Mercury | |||
| author = Edward Howard | [[Silver fulminate]] can be prepared in a similar way, but this salt is even more unstable than mercury fulminate; it can explode even under water and is impossible to accumulate in large amounts because it detonates under its own weight.<ref>{{Cite web |title=The Sciences - Fulminating Substances |author= |website=Scientific American |date=11 June 1853 |url= https://www.scientificamerican.com/article/fulminating-substances-1853-06-11/}}</ref> | ||
| journal = [[Philosophical Transactions of the Royal Society of London]] | |||
| year = 1800 | Another preparation method is through reaction of the sodium salt of nitromethane with an aqueous solution of [[mercury(II) chloride]] ({{chem2|HgCl2}}) at {{convert|0|C|F}} to form a white precipitate of mercuric nitromethanate. This is digested with warm, dilute [[hydrochloric acid]] (HCl) to produce mercury(II) fulminate.<ref name="EncycExplosives"/>{{rp|F219}} | ||
| volume = 90 | |||
| issue = 1 | |||
| pages = 204–238 | |||
| doi = 10.1098/rstl.1800.0012 | |||
| s2cid = 138658702 | |||
}}</ref><ref name=wisniak>{{cite journal | last=Wisniak | first=Jaime | title=Edward Charles Howard. Explosives, meteorites, and sugar | journal=Educación Química | publisher=Universidad Nacional Autonoma de Mexico | volume=23 | issue=2 | year=2012 |language=en| issn=0187-893X | doi=10.1016/s0187-893x(17)30114-3 | pages=230–239| doi-access=free }}</ref> However, [[Johann Kunckel]] had discovered the compound more than a century before in the [[17th century]].<ref>{{cite web |title=300 years after discovery, structure of mercury fulminate finally determined |url=https://phys.org/news/2007-08-years-discovery-mercury-fulminate.html |website=Phys.org |access-date=19 February 2025 |date=August 24, 2007}}</ref> The [[crystal structure]] of this compound was determined only in 2007.<ref>{{cite journal |author1=W. Beck |author2=J. Evers |author3=M. Göbel |author4=G. Oehlinger |author5=T. M. Klapötke | title = The Crystal and Molecular Structure of Mercury Fulminate (Knallquecksilber) | year = 2007 | journal = [[Zeitschrift für anorganische und allgemeine Chemie]] | volume = 633 | issue = 9 | pages = 1417–1422 | doi = 10.1002/zaac.200700176| doi-access = free }}</ref> | |||
[[ | ===Intermediates=== | ||
The oxidation and nitration of ethanol with nitric acid proceeds through a multitude of intermediate compounds before reaching mercury fulminate; [[acetaldehyde]] ({{chem2|CH3CHO}}), [[nitroso]]acetaldehyde ({{chem2|CH2(NO)\sCHO)}}, isonitrosoacetaldehyde ({{chem2|CH(\dNOH)\sCHO}}), isonitrosoacetic acid ({{chem2|CH(\dNOH)\sCOOH}}), nitroisonitrosoacetic acid ({{chem2|C(NO2)(\dNOH)\sCOOH}}), formo[[nitrolic acid]] ({{chem2|O2H\sCH\dNOH}}), and fulminic acid ({{chem2|C\dNOH}}) are first formed. The last reacts with mercury to produce the fulminate.<ref name="EncycExplosives"/>{{rp|F219}} | |||
==Decomposition== | ==Decomposition== | ||
The thermal decomposition of mercury(II) fulminate can begin at temperatures as low as 100 | The thermal decomposition of mercury(II) fulminate can begin at temperatures as low as {{convert|100|C|F}}, though it proceeds at a much higher rate with increasing temperature.<ref>{{cite journal|doi=10.1098/rspa.1933.0040|title=Thermal decomposition and detonation of mercury fulminate|first1=W. E. |last1=Garner|first2=H. R. |last2=Hailes |journal=Proceedings of the Royal Society of London|volume=139|issue=1–3|year=1933|pages=1–40|bibcode=1933CP....334..128S|doi-access=free}}</ref> | ||
A possible reaction for the decomposition of mercury(II) fulminate yields [[carbon dioxide]] gas, [[nitrogen]] gas, and a combination of relatively stable mercury salts. | It may be decomposed with relative safety by reaction with ten times its weight of 20% [[sodium thiosulfate]] solution. This may evolve some toxic [[cyanogen]] gas.<ref name="EncycExplosives"/> | ||
:4 Hg(CNO) | |||
:Hg(CNO) | A possible reaction for the decomposition of mercury(II) fulminate yields [[carbon dioxide]] gas, [[nitrogen]] gas, and a combination of relatively stable mercury salts.{{cn|date=November 2025}} | ||
:Hg(CNO) | :{{chem2|4 Hg(CNO)2 -> 2 CO2 + N2 + HgO + 3 Hg(OCN)CN}} | ||
:2 Hg(CNO) | :{{chem2|Hg(CNO)2 -> 2 CO + N2 + Hg}} | ||
:{{chem2|Hg(CNO)2 -> Hg([[cyanate|O\sC\tN]])2 or Hg([[isocyanate|N\dC\dO]])2}} | |||
:{{chem2|2 Hg(CNO)2 -> 2 CO2 + N2 + Hg + [[mercury(II) cyanide|Hg(CN)2]]}} | |||
==See also== | ==See also== | ||
| Line 91: | Line 138: | ||
==External links== | ==External links== | ||
{{Commons | * {{Commons inline|Mercury(II) fulminate}} | ||
{{Mercury compounds}} | {{Mercury compounds}} | ||
Latest revision as of 19:02, 18 November 2025
Mercury(II) fulminate is a primary explosive with the chemical formula Template:Chem2. When recrystallized from water it exists as the hemihydrate Template:Chem2. The anyhydrous form is obtained by recrystallization from ethanol.[1]Template:Rp It is highly sensitive to friction, heat and shock and is mainly used as a trigger for other explosives in percussion caps and detonators. Mercury(II) cyanate, though its chemical formula is identical, has a different atomic arrangement, making the cyanate and fulminate anionic isomers.
First used as a priming composition in small copper caps beginning in the 1820s, mercury fulminate quickly replaced flints as a means to ignite black powder charges in muzzle-loading firearms. Later, during the late 19th century and most of the 20th century, mercury fulminate became widely used in primers for self-contained rifle and pistol ammunition; it was the only practical detonator for firing projectiles until the early 20th century.[2]
Mercury fulminate has the distinct advantage over potassium chlorate of being non-corrosive, but it is known to attack aluminum and magnesium strongly, and brass, bronze, copper, and zinc slowly when dry; when wet it immediately reacts with aluminum and magnesium and strongly attacks brass, bronze, copper and zinc when.[1] Today, mercury fulminate has been replaced in primers by more efficient chemical substances. These are non-corrosive, less toxic, and more stable over time; they include lead azide, lead styphnate, and tetrazene derivatives. In addition, none of these compounds requires mercury for manufacture, supplies of which can be unreliable in wartime.[3]
Preparation
Mercury(II) fulminate is prepared by dissolving mercury in nitric acid and adding ethanol to the solution. Edward Charles Howard is credited with first preparing it in 1800.[4][2] However, Johann Kunckel had discovered the compound more than a century before in the 17th century.[5] The crystal structure of this compound was determined only in 2007.[6]
Silver fulminate can be prepared in a similar way, but this salt is even more unstable than mercury fulminate; it can explode even under water and is impossible to accumulate in large amounts because it detonates under its own weight.[7]
Another preparation method is through reaction of the sodium salt of nitromethane with an aqueous solution of mercury(II) chloride (Template:Chem2) at Template:Convert to form a white precipitate of mercuric nitromethanate. This is digested with warm, dilute hydrochloric acid (HCl) to produce mercury(II) fulminate.[1]Template:Rp
Intermediates
The oxidation and nitration of ethanol with nitric acid proceeds through a multitude of intermediate compounds before reaching mercury fulminate; acetaldehyde (Template:Chem2), nitrosoacetaldehyde (Template:Chem2, isonitrosoacetaldehyde (Template:Chem2), isonitrosoacetic acid (Template:Chem2), nitroisonitrosoacetic acid (Template:Chem2), formonitrolic acid (Template:Chem2), and fulminic acid (Template:Chem2) are first formed. The last reacts with mercury to produce the fulminate.[1]Template:Rp
Decomposition
The thermal decomposition of mercury(II) fulminate can begin at temperatures as low as Template:Convert, though it proceeds at a much higher rate with increasing temperature.[8]
It may be decomposed with relative safety by reaction with ten times its weight of 20% sodium thiosulfate solution. This may evolve some toxic cyanogen gas.[1]
A possible reaction for the decomposition of mercury(II) fulminate yields carbon dioxide gas, nitrogen gas, and a combination of relatively stable mercury salts.Script error: No such module "Unsubst".
See also
References
External links
- ↑ a b c d e Cite error: Invalid
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