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| MolarMass = 450.288 g/mol | MolarMass = 450.288 g/mol
| Appearance = | Appearance =
| Density = 3.02 g/cm<sup>3</sup>, solid | Density = 3.06 to 3.1 g cm<sup>-3</sup>
| MeltingPt = | MeltingPt =
| BoilingPt = | BoilingPt =
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| Autoignition_notes = }} | Autoignition_notes = }}
}} }}
'''Lead styphnate''' (lead 2,4,6-], C<sub>6</sub>HN<sub>3</sub>O<sub>8</sub>Pb ), whose name is derived from ], is an ] used as a component in ] and ] mixtures for less sensitive ]s.<ref name=Ull>Jacques Boileau, Claude Fauquignon, Bernard Hueber and Hans H. Meyer "Explosives" in Ullmann's Encyclopedia of Industrial Chemistry 2009, Wiley-VCH, Weinheim. {{DOI|10.1002/14356007.a10_143.pub2}}</ref> Lead styphnate varies in color from yellow to brown. '''Lead styphnate''' (lead 2,4,6-], C<sub>6</sub>HN<sub>3</sub>O<sub>8</sub>Pb ), whose name is derived from ], is an ] used as a component in ] and ] mixtures for less sensitive ]s. Lead styphnate is only slightly soluble in ] and ]<ref name=Ull>Jacques Boileau, Claude Fauquignon, Bernard Hueber and Hans H. Meyer "Explosives" in Ullmann's Encyclopedia of Industrial Chemistry 2009, Wiley-VCH, Weinheim. {{DOI|10.1002/14356007.a10_143.pub2}}</ref> Samples of lead styphnate vary in color from yellow to gold, orange, reddish-brown, to brown. Lead styphnate is known in various polymorphs, hydrates, and basic salts. Normal lead styphnate monohydrate, monobasic lead styphnate, tribasic lead styphnate dihydrate, and pentabasic lead styphnate dehydrate as well as α, β polymorphs of lead styphnate exist.


There are two forms of lead styphnate: six-sided ] crystals and small rectangular crystals. Lead styphnate is particularly sensitive to fire and the discharge of ]. When dry, it can be readily detonated by static discharges from the human body. The longer and narrower the crystals, the more susceptible lead styphnate is to static electricity. Lead styphnate does not react with metals and is less sensitive to shock and friction than ] or ]. Lead styphnate is only slightly soluble in ] and ] and may be neutralized by a ] solution. It is stable in storage, even at elevated temperatures. As with other ]-containing compounds, lead styphnate is inherently toxic to humans if ingested i.e. can cause ] poisoning. Two forms of lead styphnate are six-sided ] crystals and small rectangular crystals. Lead styphnate is particularly sensitive to fire and the discharge of ]. When dry, it can readily detonate by static discharges from the human body. The longer and narrower the crystals, the more susceptible lead styphnate is to static electricity. Lead styphnate does not react with metals and is less sensitive to shock and friction than ] or ]. . It is stable in storage, even at elevated temperatures. As with other ]-containing compounds, lead styphnate is toxic owing to ] poisoning.


==Preparation== ==Preparation==
The first preparation of a lead styphnate has never been substantiated but it is thought that it could have been discovered by Peter Griess in 1874. The first well established preparation of anhydrous normal lead styphnate was by Edmund Herz in 1919, through the reaction of magnesium styphnate with lead acetate in the presence of nitric acid. <ref>{{cite journal|author=J.R. Payne|title=Thermochmistry of lead styphnate|journal=Thermochimica Acta, |year=1994|url=http://www.sciencedirect.com/science/article/pii/0040603194850038 |doi=10.1016/0040-6031(94)85003-8}}</ref> Lead styphnate can be synthesized in various polymorphs and basic salts. Normal lead styphnate monohydrate, monobasic lead styphnate, tribasic lead styphnate dihydrate, and pentabasic lead styphnate dehydrate as well as α, β polymorphs of lead styphnate exist. Although never substantiated, lead styphnate may have been discovered by ] (of ] fame) in 1874. In 1919, Edmund Herz first established a preparation of anhydrous normal lead styphnate by the reaction of magnesium styphnate with lead acetate in the presence of nitric acid.<ref>{{cite journal|author=J.R. Payne|title=Thermochmistry of lead styphnate|journal=Thermochimica Acta, |year=1994|url=http://www.sciencedirect.com/science/article/pii/0040603194850038 |doi=10.1016/0040-6031(94)85003-8}}</ref><ref>{{cite journal|author=Jacques Boileau, Claude Fauquignon, Bernard Hueber and Hans H. Meyer|title=Explosives|journal=Ullmann's Encyclopedia of Industrial Chemistry|year=2009|url=http://onlinelibrary.wiley.com/doi/10.1002/14356007.a10_143.pub2/abstract;jsessionid=E8C6E1AD587F31EFF3957D89EF442B20.f01t01|doi=10.1002/14356007.a10_143.pub2}}</ref>


:(C<sub>6</sub>N<sub>3</sub>O<sub>8</sub>}MgH<sub>2</sub>O + Pb(CH<sub>3</sub>CO<sub>2</sub>)<sub>2</sub> → (C<sub>6</sub>N<sub>3</sub>O<sub>8</sub>}PbH<sub>2</sub>O + Mg(CH<sub>3</sub>CO<sub>2</sub>)<sub>2</sub>
:<math>C_{6}HN_{3}O_{8}Mg(H_{2}O) + Pb(CH_{3}COO)_{2} \longrightarrow C_{6}HN_{3}O_{8}Pb(H_{2}O) + Mg(CH_{3}COO)_{2}</math>

Lead styphnate can be produced by the reaction of the magnesium styphnate salt with lead acetate. The presence of agents can promote the formation of specific crystalline forms.<ref>{{cite journal|author=Jacques Boileau, Claude Fauquignon, Bernard Hueber and Hans H. Meyer|title=Explosives|journal=Ullmann's Encyclopedia of Industrial Chemistry|year=2009|url=http://onlinelibrary.wiley.com/doi/10.1002/14356007.a10_143.pub2/abstract;jsessionid=E8C6E1AD587F31EFF3957D89EF442B20.f01t01|doi=10.1002/14356007.a10_143.pub2}}</ref>


==Structure== ==Structure==
Normal lead styphnate forms a monohydrate crystal. The α and β polymorphs are both monoclinic crystals. The lead atoms are seven coordinate and are paired via oxygen bridges. The water molecule is coordinated to the metal and is also hydrogen-bonded to the anion. Many of the Pb-O distances are short, indicating some degree of covalency. The styphnate ions lie in approximately parallel Normal lead styphnate exists as α and β polymorphs, both being monoclinic crystals. The lead centres are seven0coordinate and are bridged via oxygen bridges. The water molecule is coordinated to the metal and is also hydrogen-bonded to the anion. Many of the Pb-O distances are short, indicating some degree of covalency. The styphnate ions lie in approximately parallel
planes linked by Pb atoms. <ref>{{cite journal|author=Pierce-Butler, M.A.|title=The structure of the lead salt of 2,4,6-trinitro-1,3-benzenediol monohydrate (alpha-polymorph)|journal=Acta. Cryst.|year=1984|url=http://scripts.iucr.org/cgi-bin/paper?S0108270184003036|doi=10.1107/S0108270184003036}}</ref><ref>{{cite journal|author=Pierce-Butler, M.A.|title=Structures of the barium salt of 2,4,6-trinitro-1,3-benzenediol monohydrate and the isomorphous lead salt (beta-polymorph)|journal=Acta. Cryst.|year=1982|url=http://scripts.iucr.org/cgi-bin/paper?S0567740882010966|doi=10.1107/S0567740882010966}}</ref> planes linked by Pb atoms.<ref>{{cite journal|author=Pierce-Butler, M.A.|title=The structure of the lead salt of 2,4,6-trinitro-1,3-benzenediol monohydrate (alpha-polymorph)|journal=Acta. Cryst.|year=1984|url=http://scripts.iucr.org/cgi-bin/paper?S0108270184003036|doi=10.1107/S0108270184003036}}</ref><ref>{{cite journal|author=Pierce-Butler, M.A.|title=Structures of the barium salt of 2,4,6-trinitro-1,3-benzenediol monohydrate and the isomorphous lead salt (beta-polymorph)|journal=Acta. Cryst.|year=1982|url=http://scripts.iucr.org/cgi-bin/paper?S0567740882010966|doi=10.1107/S0567740882010966}}</ref>


==Properties== ==Properties==
Lead styphnate has a crystal density of 3.06 to 3.1 g cm -3. It has a heat of formation of -835 kJ mol-1. The loss of water leads to the formation of a sensitive anhydride with a density of 2.9 g cm-3. Lead styphnate as a monohydrate comes in gold, orange or reddish-brown monoclinic crystals. The reason for the various colors has not been successfully explained. <ref>{{cite journal|author=Robert Matyáš, Ji í Pachman|title=Primary Explosives|journal=Springer Science & Business Media|year=2013|url=http://link.springer.com/book/10.1007%2F978-3-642-28436-6|doi=10.1007/978-3-642-28436-6}}</ref> Lead Styphnate has a detonation velocity of 5.2 km/s and an explosion temperature of 265-280°C after five seconds.<ref>{{cite journal|author=Hyman Henkin, Russell McGill |title=Rates of Explosive Decomposition of Explosives. Experimental and Theoretical Kinetic Study as a Function of Temperature|journal=Ind. Eng. Chem.|year=1952|url=http://pubs.acs.org/doi/abs/10.1021/ie50510a054|doi=10.1021/ie50510a054}}</ref> Its heat of formation is -835 kJ mol-1. The loss of water leads to the formation of a sensitive anhydrous maaterial with a density of 2.9 g cm<sup>-3</sup>. The variation of colors remains unexplained.<ref>{{cite journal|author=Robert Matyáš, Ji í Pachman|title=Primary Explosives|journal=Springer Science & Business Media|year=2013|url=http://link.springer.com/book/10.1007%2F978-3-642-28436-6|doi=10.1007/978-3-642-28436-6}}</ref> Lead Styphnate has a detonation velocity of 5.2 km/s and an explosion temperature of 265-280°C after five seconds.<ref>{{cite journal|author=Hyman Henkin, Russell McGill |title=Rates of Explosive Decomposition of Explosives. Experimental and Theoretical Kinetic Study as a Function of Temperature|journal=Ind. Eng. Chem.|year=1952|url=http://pubs.acs.org/doi/abs/10.1021/ie50510a054|doi=10.1021/ie50510a054}}</ref>
<!-- something messed up here:C<sub>6</sub>N<sub>3</sub>O<sub>8</sub>}PbH<sub>2</sub>O → Pb(CN)<sub>2</sub> + 4 CO<sub>2</sub> + 1/2 H<sub>2</sub> + H<sub>2</sub>O-->
==Decomposition Reaction==
:<math>C_{6}N_{3}O_{8}PbH(H_{2}O) \longrightarrow Pb(CN)_{2} + 4CO_{2} + 1/2 H_{2} + H_{2}O</math>


==Applications== ==Applications==
Lead styphnate is mainly used in military and commercial small arm ammunition. It serves as a primary explosive because gun powder will not ignite from a simple impact.<ref>{{cite journal|author=Gray, Theodore |title=Flash Bang|journal=Popular Science |year=2009|url=hhttp://www.periodictable.com/PopSci/2009/10/01/index.html}}</ref> Lead styphnate is also similarly used as primer in micro thruster for small satellite stationkeeping.<ref>{{cite journal|author=Daniel W. Youngner, et al.|title=MEMS Mega-pixel Micro-thruster Arrays for Small Satellite Stationkeeping|journal=Honeywell Technology 14th Annual/USU Conference on Small Satellites|year=2000|url=http://alfven.princeton.edu/papers/MMMAabstext.htm}}</ref> Lead styphnate is mainly used in small arm ] for military and commercial applications. It serves as a ] because gun powder will not ignite upon a simple impact.<ref>{{cite journal|author=Gray, Theodore |title=Flash Bang|journal=Popular Science |year=2009|url=hhttp://www.periodictable.com/PopSci/2009/10/01/index.html}}</ref> Lead styphnate is also used as primer in microthrusters for small satellite stationkeeping.<ref>{{cite journal|author=Daniel W. Youngner, et al.|title=MEMS Mega-pixel Micro-thruster Arrays for Small Satellite Stationkeeping|journal=Honeywell Technology 14th Annual/USU Conference on Small Satellites|year=2000|url=http://alfven.princeton.edu/papers/MMMAabstext.htm}}</ref>


==References== ==References==

Revision as of 23:27, 16 December 2014

Lead styphnate
Names
IUPAC name Lead 2,4,6-trinitrobenzene-1,3-diolate
Other names
  • Lead 2,4,6-trinitro-m-phenylene dioxide
  • 1,3-Benzenediol, 2,4,6-trinitro-, lead(2+) salt (1:1)
  • Lead tricinate
  • Lead trinitroresorcinate
  • Tricinat
Identifiers
CAS Number
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.035.703 Edit this at Wikidata
PubChem CID
UN number 0130
CompTox Dashboard (EPA)
InChI
  • InChI=1S/C6H3N3O8.Pb/c10-5-2(7(12)13)1-3(8(14)15)6(11)4(5)9(16)17;/h1,10-11H;/q;+2/p-2Key: WETZJIOEDGMBMA-UHFFFAOYSA-L
  • InChI=1/C6H3N3O8.Pb/c10-5-2(7(12)13)1-3(8(14)15)6(11)4(5)9(16)17;/h1,10-11H;/q;+2/p-2Key: WETZJIOEDGMBMA-NUQVWONBAY
SMILES
  • c1c(c(c(c(c1(=O)))(=O)))(=O).
Properties
Chemical formula C6HN3O8Pb
Molar mass 450.288 g/mol
Density 3.06 to 3.1 g cm
Explosive data
Shock sensitivity High
Friction sensitivity High
Hazards
NFPA 704 (fire diamond)
NFPA 704 four-colored diamondHealth 4: Very short exposure could cause death or major residual injury. E.g. VX gasFlammability 0: Will not burn. E.g. waterInstability 3: Capable of detonation or explosive decomposition but requires a strong initiating source, must be heated under confinement before initiation, reacts explosively with water, or will detonate if severely shocked. E.g. hydrogen peroxideSpecial hazards (white): no code
4 0 3
Autoignition
temperature
330 °C (626 °F; 603 K)
Except where otherwise noted, data are given for materials in their standard state (at 25 °C , 100 kPa). ☒verify (what is  ?) Infobox references
Chemical compound

Lead styphnate (lead 2,4,6-trinitroresorcinate, C6HN3O8Pb ), whose name is derived from styphnic acid, is an explosive used as a component in primer and detonator mixtures for less sensitive secondary explosives. Lead styphnate is only slightly soluble in water and methyl alcohol Samples of lead styphnate vary in color from yellow to gold, orange, reddish-brown, to brown. Lead styphnate is known in various polymorphs, hydrates, and basic salts. Normal lead styphnate monohydrate, monobasic lead styphnate, tribasic lead styphnate dihydrate, and pentabasic lead styphnate dehydrate as well as α, β polymorphs of lead styphnate exist.

Two forms of lead styphnate are six-sided monohydrate crystals and small rectangular crystals. Lead styphnate is particularly sensitive to fire and the discharge of static electricity. When dry, it can readily detonate by static discharges from the human body. The longer and narrower the crystals, the more susceptible lead styphnate is to static electricity. Lead styphnate does not react with metals and is less sensitive to shock and friction than mercury fulminate or lead azide. . It is stable in storage, even at elevated temperatures. As with other lead-containing compounds, lead styphnate is toxic owing to heavy metal poisoning.

Preparation

Although never substantiated, lead styphnate may have been discovered by Peter Griess (of Griess test fame) in 1874. In 1919, Edmund Herz first established a preparation of anhydrous normal lead styphnate by the reaction of magnesium styphnate with lead acetate in the presence of nitric acid.

(C6N3O8}MgH2O + Pb(CH3CO2)2 → (C6N3O8}PbH2O + Mg(CH3CO2)2

Structure

Normal lead styphnate exists as α and β polymorphs, both being monoclinic crystals. The lead centres are seven0coordinate and are bridged via oxygen bridges. The water molecule is coordinated to the metal and is also hydrogen-bonded to the anion. Many of the Pb-O distances are short, indicating some degree of covalency. The styphnate ions lie in approximately parallel planes linked by Pb atoms.

Properties

Its heat of formation is -835 kJ mol-1. The loss of water leads to the formation of a sensitive anhydrous maaterial with a density of 2.9 g cm. The variation of colors remains unexplained. Lead Styphnate has a detonation velocity of 5.2 km/s and an explosion temperature of 265-280°C after five seconds.

Applications

Lead styphnate is mainly used in small arm ammunition for military and commercial applications. It serves as a primary explosive because gun powder will not ignite upon a simple impact. Lead styphnate is also used as primer in microthrusters for small satellite stationkeeping.

References

  1. ECHA, European Chemicals Agency http://echa.europa.eu/documents/10162/13638/svhc_supdoc_lead_styphnate_en.pdf
  2. Jacques Boileau, Claude Fauquignon, Bernard Hueber and Hans H. Meyer "Explosives" in Ullmann's Encyclopedia of Industrial Chemistry 2009, Wiley-VCH, Weinheim. doi:10.1002/14356007.a10_143.pub2
  3. J.R. Payne (1994). "Thermochmistry of lead styphnate". Thermochimica Acta,. doi:10.1016/0040-6031(94)85003-8.{{cite journal}}: CS1 maint: extra punctuation (link)
  4. Jacques Boileau, Claude Fauquignon, Bernard Hueber and Hans H. Meyer (2009). "Explosives". Ullmann's Encyclopedia of Industrial Chemistry. doi:10.1002/14356007.a10_143.pub2.{{cite journal}}: CS1 maint: multiple names: authors list (link)
  5. Pierce-Butler, M.A. (1984). "The structure of the lead salt of 2,4,6-trinitro-1,3-benzenediol monohydrate (alpha-polymorph)". Acta. Cryst. doi:10.1107/S0108270184003036.
  6. Pierce-Butler, M.A. (1982). "Structures of the barium salt of 2,4,6-trinitro-1,3-benzenediol monohydrate and the isomorphous lead salt (beta-polymorph)". Acta. Cryst. doi:10.1107/S0567740882010966.
  7. Robert Matyáš, Ji í Pachman (2013). "Primary Explosives". Springer Science & Business Media. doi:10.1007/978-3-642-28436-6.
  8. Hyman Henkin, Russell McGill (1952). "Rates of Explosive Decomposition of Explosives. Experimental and Theoretical Kinetic Study as a Function of Temperature". Ind. Eng. Chem. doi:10.1021/ie50510a054.
  9. Gray, Theodore (2009). . Popular Science.
  10. Daniel W. Youngner; et al. (2000). "MEMS Mega-pixel Micro-thruster Arrays for Small Satellite Stationkeeping". Honeywell Technology 14th Annual/USU Conference on Small Satellites. {{cite journal}}: Explicit use of et al. in: |author= (help)

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