Trinitromethane
{{chembox
| Verifiedfields = changed
| verifiedrevid = 470616111
| ImageFile = trinitromethane.svg
| ImageFile1 = Trinitromethane-3D-vdW.png
| ImageSize =
| Name = Trinitromethane
| Reference = {{Merck12th|id=9859}}.
| IUPACName = Trinitromethane
| OtherNames = Nitroform
| SystematicName =
| Section1 = {{Chembox Identifiers
| index1_label = anion
| InChI = 1/CHN3O6/c5-2(6)1(3(7)8)4(9)10/h1H
| StdInChI_Ref = {{stdinchicite|correct|chemspider}}
| StdInChI = 1S/CHN3O6/c5-2(6)1(3(7)8)4(9)10/h1H
| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}}
| StdInChIKey = LZGVDNRJCGPNDS-UHFFFAOYSA-N
| CASNo_Ref = {{cascite|correct|CAS}}
| CASNo = 517-25-9
| UNII_Ref = {{fdacite|correct|FDA}}
| UNII = Q5IR4EM1R0
| EC_number = 208-236-8
| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}}
| ChemSpiderID = 10157
| PubChem = 10602
| PubChem1 = 11355947
| SMILES = C([N+](=O)[O-])([N+](=O)[O-])[N+](=O)[O-]
| InChI1=1S/CN3O6/c5-2(6)1(3(7)8)4(9)10/q-1
| InChIKey1 = LVFFNJCUYJXEAZ-UHFFFAOYSA-N
| SMILES1 = C(=[N+]([O-])[O-])([N+](=O)[O-])[N+](=O)[O-]
}}
| Section2 = {{Chembox Properties
| Formula = CHN3O6
| MolarMass = 151.04 g/mol
| Density = 1.469 g/cm3
| Appearance = Pale yellow crystals
| MeltingPtC = 15
| BoilingPt =
| Solubility = 44g/100ml at 20 °C
| pKa = 0.25 (see text)
}}
| Section3 =
| Section4 =
| Section5 =
| Section6 =
| Section7 = {{Chembox Hazards
| MainHazards = Oxidant, Explosive (esp. in contact with metals), Corrosive.
| NFPA-H = 3
| NFPA-F = 1
| NFPA-R = 4
| NFPA-S = OX
}}
| Section8 = {{Chembox Related
| OtherCompounds = Hexanitroethane
Octanitropentane
Tetranitromethane
}}
}}
Trinitromethane, also referred to as nitroform, is a nitroalkane and oxidizer with chemical formula HC(NO2)3. It was first obtained in 1857 as the ammonium salt by the Russian chemist {{Ill|Leon Shishkov|lt=Leon Nikolaevich Shishkov|ru|Шишков, Леон Николаевич}} (1830–1908).For biographical information about Leon Nikolaevich Shishkov, see [https://encyclopedia2.thefreedictionary.com/Leon+Nikolaevich+Shishkov The Free Dictionary]See:
- {{cite journal |last1=Chichkoff |first1=Léon |title=Note sur le nitroforme |journal=Comptes rendus |date=1857 |volume=45 |pages=144–146 |url=https://babel.hathitrust.org/cgi/pt?id=mdp.39015035405979&view=1up&seq=154 |trans-title=Note on nitroform |language=French}}
- {{cite journal |last1=Schischkoff |first1=L. |title=Ueber das Nitroform |journal=Annalen der Chemie |date=1857 |volume=103 |issue=3 |pages=364–366 |url=https://babel.hathitrust.org/cgi/pt?id=uva.x002457949&view=1up&seq=378 |trans-title=On nitroform |language=German|doi=10.1002/jlac.18571030316 |s2cid=97319556 |url-access=subscription }}
- Abstracted in: {{cite journal |last1=Schischkoff |first1=L. |title=On nitroform |journal=The Chemical Gazette |date=1857 |volume=15 |page=448 |url=https://books.google.com/books?id=xQcAAAAAMAAJ&pg=PA448}}
- Abstracted in: {{cite journal |last1=Schischkoff |first1=L. |title=On nitroform |journal=Philosophical Magazine |date=1858 |volume=15 |page=302 |url=https://books.google.com/books?id=1bZJAQAAMAAJ&pg=PA302 |series=4th series}} In 1900, it was discovered that nitroform can be produced by the reaction of acetylene with anhydrous nitric acid.The Italian chemist Adolfo Baschieri discovered that nitroform (Italian: nitroformio) could be produced from acetylene (acetilene) and nitric acid (acido nitrico).
- {{cite journal |last1=Baschieri |first1=A. |title=Sul comportamento dell' acetilene con alcuni ossidanti |journal=Atti della Reale Accademia dei Lincei |date=1900 |volume=9 (part I) |pages=391–393 |url=https://www.biodiversitylibrary.org/item/155899#page/397/mode/1up |series=5th series |trans-title=On the behavior of acetylene with some oxidizers |language=Italian}} See p. 392.
- Abstracted in German in: {{cite journal |last1=Baschieri |first1=A. |title=Über das Verhalten des Acetylens gegen einige Oxydationsmittel |journal=Chemisches Zentralblatt |date=1900 |volume=4 (part II) |page=528 |url=https://babel.hathitrust.org/cgi/pt?id=mdp.39015020184084&view=1up&seq=576 |series=5th series |trans-title=On the behavior of acetylene towards some oxidizers |language=German}}
- See also: {{cite book |last1=Nieuwland |first1=Julius A. |last2=Vogt |first2=Richard R. |title=The Chemistry of Acetylene |date=1945 |publisher=Reinhold Publishing Corp. |location=New York City, New York, USA |page=[https://archive.org/details/in.ernet.dli.2015.239313/page/n172 158] |url=https://archive.org/details/in.ernet.dli.2015.239313}} This method went on to become the industrial process of choice during the 20th century. In the laboratory, nitroform can also be produced by hydrolysis of tetranitromethane under mild basic conditions.{{ cite journal | first1 = A. A. | last1 = Gakh | first2 = J. C. | last2 = Bryan | first3 = M. N. | last3 = Burnett | first4 = P. V. | last4 = Bonnesen | title = Synthesis and structural analysis of some trinitromethanide salts | journal = Journal of Molecular Structure | year = 2000 | volume = 520 | issue = 1–3 | pages = 221–228 | doi = 10.1016/S0022-2860(99)00333-6 | bibcode = 2000JMoSt.520..221G | url = https://zenodo.org/record/1259627 }}
Acidity
Trinitromethane as a neutral molecule is colorless. It is highly acidic, easily forming an intensely yellow anion, (NO2)3C− (nitroformate). The pKa of trinitromethane has been measured at 0.17 ± 0.02 at 20 °C, which is remarkably acidic for a methane derivative.{{ cite journal | first1 = S. S. | last1 = Novikov | first2 = V. I. | last2 = Slovetskii | first3 = S. A. | last3 = Shevelev | first4 = A. A. | last4 = Fainzilberg | title = Spectrophotometric Determination of the Dissociation Constants of Aliphatic Nitro Compounds | journal = Russian Chemical Bulletin | year = 1962 | volume = 11 | issue = 4 | pages = 552–559 | doi = 10.1007/BF00904751 }} Trinitromethane easily dissolves in water to form an acidic yellow solution.
There is some evidence that the anion, which obeys the 4n+2 Hückel rule, displays Y-aromaticity, a form of aromaticity disputed among chemists.{{ cite journal | title = Electronic structures of trifluoro-, tricyano-, and trinitromethane and their conjugate bases | first1 = J. | last1 = Cioslowski | first2 = S. T. | last2 = Mixon | first3 = E. D. | last3 = Fleischmann | journal = Journal of the American Chemical Society | year = 1991 | volume = 113 | issue = 13 | pages = 4751–4755 | doi = 10.1021/ja00013a007 | bibcode = 1991JAChS.113.4751C }}
Nitroform salts
Trinitromethane forms a series of bright yellow ionic salts. Many of these salts tend to be unstable and can be easily detonated by heat or impact.
The potassium salt of nitroform, KC(NO2)3 is a lemon yellow crystalline solid that decomposes slowly at room temperatures and explodes above 95 °C. The ammonium salt is somewhat more stable, and deflagrates or explodes above 200 °C. The hydrazine salt, hydrazinium nitroformate is thermally stable to above 125 °C and is being investigated as an ecologically friendly oxidizer for use in solid fuels for rockets.
Condensation with formaldehyde
As found by British chemists Hurd and Starke during WWII, trinitromethane reacts with paraformaldehyde, giving {{ill|trinitroethanol|zh|2,2,2-三硝基乙醇}}.{{Cite book |url=https://books.google.com/books?id=JL0rilW6mMEC&q=Hurd+Starke |title=British Abstracts: Series A. |date=1951 |language=en}} This compound is a solvent to nitrocellulose and a precursor to high explosives such as trinitroethylorthoformate and trinitroethylorthocarbonate.
References
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Further reading
- {{Cite encyclopedia |title=Nitromethanes |encyclopedia=Encyclopedia of Oxidizers |publisher=De Gruyter |last=Schmidt |first=Eckart W. |date=2022 |pages=2820–2832 |doi=10.1515/9783110750294-022 |isbn=978-3-11-075029-4|chapter=Trinitromethane}}