Tetranitromethane

Chembox new
Name = Tetranitromethane
Reference = ["Merck Index", 11th Edition, 9164.]
ImageFileL1 = tetranitromethane.png ImageSizeL1 = 120px
ImageNameL1 =
ImageFileR1 = tetranitromethane 3D.png ImageSizeR1 = 120px
ImageNameR1 =
IUPACName = Tetranitromethane
OtherNames = TNM
Tetan
Section1 = Chembox Identifiers
CASNo = 509-14-8
SMILES = O= [N+] ( [O-] )C( [N+] ( [O-] )=O)( [N+] ( [O-] )=O) [N+] ( [O-] )=O
Section2 = Chembox Properties
Formula = CN₄O₈
MolarMass = 196.04 g/mol
Density = 1.623 g/cm³
MeltingPtC = 13.8
BoilingPtC = 126
Section3 = Chembox Related
OtherCpds = hexanitroethane
octanitropentane

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. [cite journal
author = L. N. Shishkov
title = Sur la constitution de l'acetic fulminique et un nouvelle serie de corps derives de l'acide acetique
journal = Annales de chimie et de physique
year = 1857
volume = 49
issue = 11
pages = 310
url = http://gallica.bnf.fr/ark:/12148/bpt6k347908/f309.table]

Uses

It has been investigated for use as an oxidizer in bipropellant rockets, however its high freezing temperature makes it unsuitable. The explosive sensitivity is low, but would be raised by anti-freezing additives. This makes it effectively unusable. [cite journal
author = J. G. Tschinkel
title = Tetranitromethane as Oxidizer in Rocket Propellants
journal = Industrial and Engineering Chemistry
year = 1956
volume = 48
issue = 4
pages = 732
doi = 10.1021/ie50556a022] 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 fuel to increase the cetane number. [cite journal
author = K. V. Altukhov, V. V. Perekalin
title = The Chemistry of Tetranitromethane
journal = Russian Chemical Reviews
year = 1976
volume = 45
issue = 11
pages = 1052–1066
doi = 10.1070/RC1976v045n11ABEH002759]

Preparation

TNM is a pale yellow liquid that can be prepared by the nitration of acetic anhydride with anhydrous nitric acid. ["Org. Syn. Coll. Vol. III", 1955, 803.]

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. [cite journal
author = F. D. Chattaway
title = A simple method of preparing tetranitromethane
journal = Journal of the Chemical Society
year = 1910
volume = 97
issue =
pages = 2099–2102
doi = 10.1039/CT9109702099] . 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.cite journal
author = K. F. Hager
title = Tetranitromethane
journal = Industrial and Engineering Chemistry
year = 1949
volume = 41
issue = 10
pages = 2168–2172
doi = 10.1021/ie50478a028]

For commercial use a cheaper method starting from acetylene has been used. [cite journal
author = K. J. P. Orton, P. V. McKie
title = The action of nitric acid on unsaturated hydrocarbons. The action of nitric acid on acetylene
journal = Journal of the Chemical Society
year = 1920
volume = 117
issue =
pages = 283–297
doi =10.1039/CT9201700283 ] First, acetylene is reacted with nitric acid containing mercury nitrate, resulting in nitroform (trinitromethane) and a mixture of carbon dioxide and nitrogen oxide as waste gas. The resulting nitroform is converted to TNM by adding sulfuric acid at higher temperatures. With this method a yield of 90% before purification can be reached.Fact|date=September 2008

afety

TNM is an explosive that is sensitive to heat, friction and shock. It is reasonably expected to be a human carcinogen. [ [http://ntp-server.niehs.nih.gov/ntp/roc/eleventh/profiles/s171tetr.pdf NIH substance profile for tetranitromethane] ]

References

External links

* [http://webbook.nist.gov/cgi/cbook.cgi?ID=C509148 WebBook page for CN4O8]