Trinitromethane Explained

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 (1830–1908).[1] [2] In 1900, it was discovered that nitroform can be produced by the reaction of acetylene with anhydrous nitric acid.[3] 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.[4]

Acidity

Trinitromethane as a neutral molecule is colorless. It is highly acidic, easily forming an intensely yellow anion, (NO2)3C. The pKa of trinitromethane has been measured at 0.17 ± 0.02 at 20 °C, which is remarkably acidic for a methane derivative.[5] 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.[6]

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.

Notes and References

  1. For biographical information about Leon Nikolaevich Shishkov, see The Free Dictionary
  2. See:
    • Chichkoff . Léon . Note sur le nitroforme . Comptes rendus . 1857 . 45 . 144–146 . Note on nitroform . French.
    • Schischkoff . L. . Ueber das Nitroform . Annalen der Chemie . 1857 . 103 . 3 . 364–366 . On nitroform . German. 10.1002/jlac.18571030316 . 97319556 .
    • Abstracted in: Schischkoff . L. . On nitroform . The Chemical Gazette . 1857 . 15 . 448 .
    • Abstracted in: Schischkoff . L. . On nitroform . Philosophical Magazine . 1858 . 15 . 302 . 4th series.
  3. The Italian chemist Adolfo Baschieri discovered that nitroform (Italian: nitroformio) could be produced from acetylene (acetilene) and nitric acid (acido nitrico).
  4. A. A. . Gakh . J. C. . Bryan . M. N. . Burnett . P. V. . Bonnesen . Synthesis and structural analysis of some trinitromethanide salts . Journal of Molecular Structure . 2000 . 520 . 1–3 . 221–228 . 10.1016/S0022-2860(99)00333-6 . 2000JMoSt.520..221G .
  5. S. S. . Novikov . V. I. . Slovetskii . S. A. . Shevelev . A. A. . Fainzilberg . Spectrophotometric Determination of the Dissociation Constants of Aliphatic Nitro Compounds . Russian Chemical Bulletin . 1962 . 11 . 4 . 552–559 . 10.1007/BF00904751 .
  6. Electronic structures of trifluoro-, tricyano-, and trinitromethane and their conjugate bases . J. . Cioslowski . S. T. . Mixon . E. D. . Fleischmann . Journal of the American Chemical Society . 1991 . 113 . 13 . 4751–4755 . 10.1021/ja00013a007 .