Tetranitromethane

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Tetranitromethane[1]
Tetranitromethane.png Tetranitromethane 3D.png
Identifiers
CAS number 509-14-8 YesY
ChemSpider 13842838 YesY
UN number 1510
KEGG C19300 N
ChEMBL CHEMBL261663 YesY
RTECS number PB4025000
Jmol-3D images Image 1
Properties
Molecular formula CN4O8
Molar mass 196.04 g/mol
Appearance Colorless to pale-yellow liquid or solid
Odor Pungent
Density 1.623 g/cm3
Melting point 13.8 °C (56.8 °F; 286.9 K)
Boiling point 126 °C (259 °F; 399 K)
Hazards
MSDS ICSC 1468
EU Index Not listed
EU classification Oxidising agent O Toxic T
R-phrases R8 R23/24/25 R36/38 R45
S-phrases S17 S45
Main hazards Oxidant, can form explosive mixtures
NFPA 704
Flammability code 1: Must be pre-heated before ignition can occur. Flash point over 93 °C (200 °F). E.g., canola oil Health code 3: Short exposure could cause serious temporary or residual injury. E.g., chlorine gas Reactivity code 2: Undergoes violent chemical change at elevated temperatures and pressures, reacts violently with water, or may form explosive mixtures with water. E.g., phosphorus Special hazard OX: Oxidizer. E.g., potassium perchlorateNFPA 704 four-colored diamond
Related compounds
Related compounds Hexanitroethane
Octanitropentane
Trinitromethane
Except where noted otherwise, data are given for materials in their standard state (at 25 °C (77 °F), 100 kPa)
 N (verify) (what is: YesY/N?)
Infobox references

Tetranitromethane or TNM is an organic oxidizer with chemical formula C(NO2)4. Its chemical structure consists of four nitro groups attached to one carbon atom. In 1857 it was first synthesised by the reaction of sodium cyanoacetamide with nitric acid.[2]

Uses[edit]

It has been investigated for use as an oxidizer in bipropellant rockets; however, its high freezing temperature makes it unsuitable. Highly purified tetranitromethane cannot be made to explode, but its sensitivity is increased dramatically by oxidizable contaminants, such as anti-freezing additives. This makes it effectively unusable as a propellant.[3] In the laboratory it is used a reagent for the detection of double bonds in organic compounds and as a nitrating reagent. It has also found use as an additive to diesel fuel to increase the cetane number.[4]

Preparation[edit]

TNM is a pale yellow liquid that can be prepared in the laboratory by the nitration of acetic anhydride with anhydrous nitric acid (Chattaway's method).[5] This method was attempted on an industrial scale in the 1950s by Nitroform Products Company in Newark, USA, but the entire plant was destroyed by an explosion in 1953.[6]

The first industrial scale production was started in Germany during World War II in an effort to improve the cetane number of diesel fuel. This process improved the original method, which started with acetic acid and nitric acid.[7] Without regard to yield or cost, approximately 10 tons of TNM were produced in a few weeks. However, this production process has not been used again industrially after the end of the war, because of high associated costs.[8]

For commercial use a cheaper method starting from acetylene has been used.[9] First, nitric acid containing mercuric nitrate is reduced by acetylene, resulting in nitroform (trinitromethane) and a mixture of carbon dioxide and nitrogen oxide as waste gas. The nitrogen oxides are valuable and normally recovered as nitric acid in an absorption tower. The resulting nitroform is converted to TNM by adding nitric and sulfuric acid at higher temperatures. With this method a yield of 90% (based on nitric acid) before purification can be reached.[10]

Safety[edit]

Pure TNM is stable and cannot be made to explode, even with the use of 10g of tetryl as a detonator. However, the ability of TNM to detonate is greatly affected by the presence of impurities, even in small quantities. TNM forms extremely powerful explosive mixtures when fuels are added in stochiometric proportions. Many of these mixtures show sensitivity to impact even higher than that of nitroglycerine.[11]

TNM reacts with moisture at elevated pH to produce trinitromethane (nitroform) which reacts easily with metals to form highly unstable and explosive salts.

Tetranitromethane is highly toxic. Absorption of as little as 2.5 mg/kg can cause methemoglobinemia, lung edema, and damage to liver, kidney, and central nervous system. It is reasonably expected to be a human carcinogen.[12]

References[edit]

  1. ^ Merck Index, 11th Edition, 9164.
  2. ^ L. N. Shishkov (1857). "Sur la constitution de l'acetic fulminique et un nouvelle serie de corps derives de l'acide acetique". Annales de chimie et de physique 49 (11): 310. 
  3. ^ J. G. Tschinkel (1956). "Tetranitromethane as Oxidizer in Rocket Propellants". Industrial and Engineering Chemistry 48 (4): 732. doi:10.1021/ie50556a022. 
  4. ^ K. V. Altukhov, V. V. Perekalin (1976). "The Chemistry of Tetranitromethane". Russian Chemical Reviews 45 (11): 1052–1066. doi:10.1070/RC1976v045n11ABEH002759. 
  5. ^ Liang, P. (1941), "Tetranitromethane", Org. Synth. 21: 105 ; Coll. Vol. 3: 803 
  6. ^ Mahoney vs Nitroform Co., 114 A.2d 863 (NJ Appellate Div 1955).
  7. ^ F. D. Chattaway (1910). "A simple method of preparing tetranitromethane". Journal of the Chemical Society 97: 2099–2102. doi:10.1039/CT9109702099. 
  8. ^ K. F. Hager (1949). "Tetranitromethane". Industrial and Engineering Chemistry 41 (10): 2168–2172. doi:10.1021/ie50478a028. 
  9. ^ K. J. P. Orton, P. V. McKie (1920). "The action of nitric acid on unsaturated hydrocarbons. The action of nitric acid on acetylene". Journal of the Chemical Society 117: 283–297. doi:10.1039/CT9201700283. 
  10. ^ Urbanski, Tadeusz (1964). Chemistry and Technology of Explosives I. Pergamon Press. pp. 589–594. LCCN 83002261. 
  11. ^ Urbanski, Tadeusz (1964). Chemistry and Technology of Explosives I. Pergamon Press. p. 593. LCCN 83002261. 
  12. ^ National Toxicology Program (2011). "Tetranitromethane" (pdf). Report On Carcinogens (12th ed.). National Toxicology Program. Retrieved 2012-08-14. 

External links[edit]