Trinitromethane

Trinitromethane^[1]
Names
	IUPAC name Trinitromethane
	Other names Nitroform
Identifiers
CAS Number	517-25-9 ;
3D model (JSmol)	Interactive image; anion: Interactive image;
ChemSpider	10157 ;
ECHA InfoCard	100.007.489
EC Number	208-236-8;
PubChem CID	10602; anion: 11355947;
UNII	Q5IR4EM1R0 ;
CompTox Dashboard (EPA)	DTXSID3060160 ;
	InChI InChI=1S/CHN3O6/c5-2(6)1(3(7)8)4(9)10/h1H Key: LZGVDNRJCGPNDS-UHFFFAOYSA-N ; InChI=1/CHN3O6/c5-2(6)1(3(7)8)4(9)10/h1H; anion: InChI=1S/CN3O6/c5-2(6)1(3(7)8)4(9)10/q-1 Key: LVFFNJCUYJXEAZ-UHFFFAOYSA-N;
	SMILES C([N+](=O)[O-])([N+](=O)[O-])[N+](=O)[O-]; anion: C(=[N+]([O-])[O-])([N+](=O)[O-])[N+](=O)[O-];
Properties
Chemical formula	CHN3O6
Molar mass	151.04 g/mol
Appearance	Pale yellow crystals
Density	1.469 g/cm3
Melting point	15 °C (59 °F; 288 K)
Solubility in water	44g/100ml at 20 °C
Acidity (pKa)	0.25 (see text)
Hazards
	Occupational safety and health (OHS/OSH):
Main hazards	Oxidant, Explosive (esp. in contact with metals), Corrosive.
NFPA 704 (fire diamond)	3 1 4 OX
Related compounds
Related compounds	Hexanitroethane; Octanitropentane; Tetranitromethane
	Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). verify (what is ?) Infobox references

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 Leon Nikolaevich Shishkov [ru] (1830–1908).^[2]^[3] In 1900, it was discovered that nitroform can be produced by the reaction of acetylene with anhydrous nitric acid.^[4] 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.^[5]

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Trinitromethane as a neutral molecule is colorless. It is highly acidic, easily forming an intensely yellow anion, (NO₂)₃C⁻. The pK_a of trinitromethane has been measured at 0.17 ± 0.02 at 20 °C, which is remarkably acidic for a methane derivative.^[6] 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.^[7]

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.

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As found by British chemists Hurd and Starke during WWII, trinitromethane reacts with paraformaldehyde, giving trinitroethanol.^[8] This compound is a solvent to nitrocellulose and a precursor to high explosives such as trinitroethylorthoformate and trinitroethylorthocarbonate.

[1]
Budavari, Susan, ed. (1996). The Merck Index: An Encyclopedia of Chemicals, Drugs, and Biologicals (12th ed.). Merck. ISBN 0911910123., 9859.
[2]
For biographical information about Leon Nikolaevich Shishkov, see The Free Dictionary
[3]
See:
- Chichkoff, Léon (1857). "Note sur le nitroforme" [Note on nitroform]. Comptes rendus (in French). 45: 144–146.
- Schischkoff, L. (1857). "Ueber das Nitroform" [On nitroform]. Annalen der Chemie (in German). 103 (3): 364–366. doi:10.1002/jlac.18571030316. S2CID 97319556.
- Abstracted in: Schischkoff, L. (1857). "On nitroform". The Chemical Gazette. 15: 448.
- Abstracted in: Schischkoff, L. (1858). "On nitroform". Philosophical Magazine. 4th series. 15: 302.
[4]
The Italian chemist Adolfo Baschieri discovered that nitroform (Italian: nitroformio) could be produced from acetylene (acetilene) and nitric acid (acido nitrico).
- Baschieri, A. (1900). "Sul comportamento dell' acetilene con alcuni ossidanti" [On the behavior of acetylene with some oxidizers]. Atti della Reale Accademia dei Lincei. 5th series (in Italian). 9 (part I): 391–393. See p. 392.
- Abstracted in German in: Baschieri, A. (1900). "Über das Verhalten des Acetylens gegen einige Oxydationsmittel" [On the behavior of acetylene towards some oxidizers]. Chemisches Zentralblatt. 5th series (in German). 4 (part II): 528.
- See also: Nieuwland, Julius A.; Vogt, Richard R. (1945). The Chemistry of Acetylene. New York City, New York, USA: Reinhold Publishing Corp. p. 158.
[5]
Gakh, A. A.; Bryan, J. C.; Burnett, M. N.; Bonnesen, P. V. (2000). "Synthesis and structural analysis of some trinitromethanide salts". Journal of Molecular Structure. 520 (1–3): 221–228. Bibcode:2000JMoSt.520..221G. doi:10.1016/S0022-2860(99)00333-6.
[6]
Novikov, S. S.; Slovetskii, V. I.; Shevelev, S. A.; Fainzilberg, A. A. (1962). "Spectrophotometric Determination of the Dissociation Constants of Aliphatic Nitro Compounds". Russian Chemical Bulletin. 11 (4): 552–559. doi:10.1007/BF00904751.
[7]
Cioslowski, J.; Mixon, S. T.; Fleischmann, E. D. (1991). "Electronic structures of trifluoro-, tricyano-, and trinitromethane and their conjugate bases". Journal of the American Chemical Society. 113 (13): 4751–4755. doi:10.1021/ja00013a007.
[8]
British Abstracts: Series A. 1951.

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[1] [1]
Budavari, Susan, ed. (1996). The Merck Index: An Encyclopedia of Chemicals, Drugs, and Biologicals (12th ed.). Merck. ISBN 0911910123., 9859.

[2] [2]
For biographical information about Leon Nikolaevich Shishkov, see The Free Dictionary

[3] [3]
See:
Chichkoff, Léon (1857). "Note sur le nitroforme" [Note on nitroform]. Comptes rendus (in French). 45: 144–146.

Schischkoff, L. (1857). "Ueber das Nitroform" [On nitroform]. Annalen der Chemie (in German). 103 (3): 364–366. doi:10.1002/jlac.18571030316. S2CID 97319556.

Abstracted in: Schischkoff, L. (1857). "On nitroform". The Chemical Gazette. 15: 448.

Abstracted in: Schischkoff, L. (1858). "On nitroform". Philosophical Magazine. 4th series. 15: 302.

[4] Chichkoff, Léon (1857). "Note sur le nitroforme" [Note on nitroform]. Comptes rendus (in French). 45: 144–146.

[5] Schischkoff, L. (1857). "Ueber das Nitroform" [On nitroform]. Annalen der Chemie (in German). 103 (3): 364–366. doi:10.1002/jlac.18571030316. S2CID 97319556.

[6] Abstracted in: Schischkoff, L. (1857). "On nitroform". The Chemical Gazette. 15: 448.

[7] Abstracted in: Schischkoff, L. (1858). "On nitroform". Philosophical Magazine. 4th series. 15: 302.

[4] [4]
The Italian chemist Adolfo Baschieri discovered that nitroform (Italian: nitroformio) could be produced from acetylene (acetilene) and nitric acid (acido nitrico).
Baschieri, A. (1900). "Sul comportamento dell' acetilene con alcuni ossidanti" [On the behavior of acetylene with some oxidizers]. Atti della Reale Accademia dei Lincei. 5th series (in Italian). 9 (part I): 391–393. See p. 392.

Abstracted in German in: Baschieri, A. (1900). "Über das Verhalten des Acetylens gegen einige Oxydationsmittel" [On the behavior of acetylene towards some oxidizers]. Chemisches Zentralblatt. 5th series (in German). 4 (part II): 528.

See also: Nieuwland, Julius A.; Vogt, Richard R. (1945). The Chemistry of Acetylene. New York City, New York, USA: Reinhold Publishing Corp. p. 158.

[9] Baschieri, A. (1900). "Sul comportamento dell' acetilene con alcuni ossidanti" [On the behavior of acetylene with some oxidizers]. Atti della Reale Accademia dei Lincei. 5th series (in Italian). 9 (part I): 391–393. See p. 392.

[10] Abstracted in German in: Baschieri, A. (1900). "Über das Verhalten des Acetylens gegen einige Oxydationsmittel" [On the behavior of acetylene towards some oxidizers]. Chemisches Zentralblatt. 5th series (in German). 4 (part II): 528.

[11] See also: Nieuwland, Julius A.; Vogt, Richard R. (1945). The Chemistry of Acetylene. New York City, New York, USA: Reinhold Publishing Corp. p. 158.

[5] [5]
Gakh, A. A.; Bryan, J. C.; Burnett, M. N.; Bonnesen, P. V. (2000). "Synthesis and structural analysis of some trinitromethanide salts". Journal of Molecular Structure. 520 (1–3): 221–228. Bibcode:2000JMoSt.520..221G. doi:10.1016/S0022-2860(99)00333-6.

[6] [6]
Novikov, S. S.; Slovetskii, V. I.; Shevelev, S. A.; Fainzilberg, A. A. (1962). "Spectrophotometric Determination of the Dissociation Constants of Aliphatic Nitro Compounds". Russian Chemical Bulletin. 11 (4): 552–559. doi:10.1007/BF00904751.

[7] [7]
Cioslowski, J.; Mixon, S. T.; Fleischmann, E. D. (1991). "Electronic structures of trifluoro-, tricyano-, and trinitromethane and their conjugate bases". Journal of the American Chemical Society. 113 (13): 4751–4755. doi:10.1021/ja00013a007.

[8] [8]
British Abstracts: Series A. 1951.

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[4]

[5]

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Trinitromethane

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Acidity

Nitroform salts

Condensation with formaldehyde

References