Methyl nitrate

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Methyl nitrate
Methyl Nitrate Structural Formulae V.1.svg
Methyl Nitrate Ball and Stick.png
Methyl Nitrate Space Fill.png
Names
IUPAC name
Methyl nitrate
Other names
nitric acid methyl ester, nitrooxymethane
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.009.039 OOjs UI icon edit-ltr-progressive.svg
PubChem CID
UNII
  • InChI=1S/CH3NO3/c1-5-2(3)4/h1H3 Yes check.svgY
    Key: LRMHVVPPGGOAJQ-UHFFFAOYSA-N Yes check.svgY
  • InChI=1/CH3NO3/c1-5-2(3)4/h1H3
    Key: LRMHVVPPGGOAJQ-UHFFFAOYAP
  • [O-][N+](=O)OC
Properties
CH3NO3
Molar mass 77.04 g/mol
AppearanceLiquid
Density 1.203 g/cm3, liquid
Melting point −82.3 °C (−116.1 °F; 190.8 K) [1]
Boiling point 64.6 °C (148.3 °F; 337.8 K) (explodes) [1]
Explosive data
Shock sensitivity High [2]
Friction sensitivity High [2]
Detonation velocity 6300 m s−1 at ρ=1.217 g cm−3 [2]
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
Toxic, High Explosive
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Methyl nitrate is the methyl ester of nitric acid and has the chemical formula CH3NO3. It is a colourless explosive volatile liquid.

Contents

Synthesis

It can be produced by the condensation of nitric acid and methanol: [3]

CH3OH + HNO3 → CH3NO3 + H2O

A newer method uses methyl iodide and silver nitrate: [4]

CH3I + AgNO3 → CH3NO3 + AgI

Methyl nitrate can be produced on a laboratory or industrial scale either through the distillation of a mixture of methanol and nitric acid, or by the nitration of methanol by a mixture of sulfuric and nitric acids. The first procedure is not preferred due to the great explosion danger presented by the methyl nitrate vapour. The second procedure is essentially identical to that of making nitroglycerin. However, the process is usually run at a slightly higher temperature and the mixture is stirred mechanically on an industrial scale instead of with compressed air.

Electrolytic production methods have been reported involving electrolyzing sodium acetate and sodium nitrate in acetic acid. [5]

Methyl nitrate is also the product of the oxidation of some organic compounds in the presence of nitrogen oxides and chlorine, namely chloroethane or di-tert-butyl ether, while also producing nitromethane. [6] Oxidation of nitromethane using nitrogen dioxide in an inert atmosphere can also yield methyl nitrate. [7]

Explosive properties

Methyl nitrate is a sensitive explosive. When ignited it burns extremely fiercely with a gray-blue flame. Methyl nitrate is a very strong explosive with a detonation velocity of 6,300 m/s, [8] like nitroglycerin, ethylene glycol dinitrate, and other nitrate esters. The sensitivity of methyl nitrate to initiation by detonation is among the greatest known, with even a number one blasting cap, the lowest power available, producing a near full detonation of the explosive.[ citation needed ]

Despite the superior explosive properties of methyl nitrate, it has not received application as an explosive due mostly to its high volatility, which prevents it from being stored or handled safely.

Safety

As well as being an explosive, methyl nitrate is toxic and causes headaches when inhaled.

History

Methyl nitrate has not received much attention as an explosive, but as a mixture containing 25% methanol it was used as rocket fuel and volumetric explosive under the name Myrol in Nazi Germany during World War II. This mixture would evaporate at a constant rate and so its composition would not change over time. It presents a slight explosive danger (it is somewhat difficult to detonate) and does not detonate easily via shock. [9] [10]

According to A. Stettbacher, the substance was used as a combustible during the Reichstag fire in 1933. [11] Gartz shows in a recent work that only methyl nitrate with its production and explosion potential can represent the famous and mysterious "shooting water" from the German Feuerwerkbuch ("fireworks book") of about 1420 [12] (the oldest technical text in German language, handwritten in Dresden and later printed in Augsburg). [13]

An extract of the text from the 1420 Feuerwerkbuch is as follows (written in Early New High German):

"Wildu mit wasser schyessen // daß du kein pulfer prauch // est vnd sterker und waiter // mit schewst dann als du daß aller // pest pulfer hast das yemann gehab // en mag und ye gemacht wurd so ny // salpeter und distillier den mit wasser // vnd nym oleo benedicto dazu auch … // … vnd zunt sie an mit sinnen das du davon kommen magst … // …mit disem wasser schewst du dreytousent schrit weit … // … es ist gar köstlich…"

Translated:

"Do you want to shoot with water // so that you don't need powder // and stronger and further // you shoot than the very // best powder somebody might have had ever // and was made ever // so take salpetre and distill it with water // and also take oleo benedicto (the oil of Benedicus) // and ignite it with the intention that you may get off ... with this water you will shoot threethousand foot // it is so delicious"

Structure

The structure of methyl nitrate has been studied experimentally in the gas phase (combined gas-electron diffraction and microwave spectroscopy, GED/MW) and in the crystalline state (X-ray diffraction, XRD) (see Table 1). [4]

Gas phase structure of methyl nitrate determined by gas electron diffraction Methylnitrat.svg
Gas phase structure of methyl nitrate determined by gas electron diffraction
Solid-state structure of methyl nitrate determined by X-ray diffraction Methylnitrat XRD.png
Solid-state structure of methyl nitrate determined by X-ray diffraction

In the solid state there are weak interactions between the O and N atoms of different molecules (see figure).

Table 1: Structural parameters of methyl nitrate Bond lengths in Å , angles in °
Parameter
XRDGED/MW
C–O1.451(1)1.425(3)
N–OC1.388(1)1.403(2)
N–Oterminal1.204(1)1.205(1)
C–O–N113.3(1)113.6(3)
Oterminal-N-Oterminal128.6(1)131.4(4)

Related Research Articles

<span class="mw-page-title-main">Ester</span> Compound derived from an acid

In chemistry, an ester is a compound derived from an acid in which the hydrogen atom (H) of at least one acidic hydroxyl group of that acid is replaced by an organyl group. Analogues derived from oxygen replaced by other chalcogens belong to the ester category as well. According to some authors, organyl derivatives of acidic hydrogen of other acids are esters as well, but not according to the IUPAC.

<span class="mw-page-title-main">Explosive</span> Substance that can explode

An explosive is a reactive substance that contains a great amount of potential energy that can produce an explosion if released suddenly, usually accompanied by the production of light, heat, sound, and pressure. An explosive charge is a measured quantity of explosive material, which may either be composed solely of one ingredient or be a mixture containing at least two substances.

<span class="mw-page-title-main">Nitroglycerin</span> Chemical compound

Nitroglycerin (NG), also known as trinitroglycerin (TNG), nitro, glyceryl trinitrate (GTN), or 1,2,3-trinitroxypropane, is a dense, colorless, oily, explosive liquid most commonly produced by nitrating glycerol with white fuming nitric acid under conditions appropriate to the formation of the nitric acid ester. Chemically, the substance is an organic nitrate compound rather than a nitro compound, but the traditional name is retained. Discovered in 1847 by Ascanio Sobrero, nitroglycerin has been used as an active ingredient in the manufacture of explosives, namely dynamite, and as such it is employed in the construction, demolition, and mining industries. It is combined with nitrocellulose to form double-based smokeless powder, which has been used as a propellant in artillery and firearms since the 1880s.

<span class="mw-page-title-main">Nitric acid</span> Highly corrosive mineral acid

Nitric acid is the inorganic compound with the formula HNO3. It is a highly corrosive mineral acid. The compound is colorless, but samples tend to acquire a yellow cast over time due to decomposition into oxides of nitrogen. Most commercially available nitric acid has a concentration of 68% in water. When the solution contains more than 86% HNO3, it is referred to as fuming nitric acid. Depending on the amount of nitrogen dioxide present, fuming nitric acid is further characterized as red fuming nitric acid at concentrations above 86%, or white fuming nitric acid at concentrations above 95%.

<span class="mw-page-title-main">TNT</span> Impact-resistant high explosive

Trinitrotoluene, more commonly known as TNT, more specifically 2,4,6-trinitrotoluene, and by its preferred IUPAC name 2-methyl-1,3,5-trinitrobenzene, is a chemical compound with the formula C6H2(NO2)3CH3. TNT is occasionally used as a reagent in chemical synthesis, but it is best known as an explosive material with convenient handling properties. The explosive yield of TNT is considered to be the standard comparative convention of bombs and asteroid impacts. In chemistry, TNT is used to generate charge transfer salts.

<span class="mw-page-title-main">Ammonium nitrate</span> Chemical compound with formula NH4NO3

Ammonium nitrate is a chemical compound with the formula NH4NO3. It is a white crystalline salt consisting of ions of ammonium and nitrate. It is highly soluble in water and hygroscopic as a solid, although it does not form hydrates. It is predominantly used in agriculture as a high-nitrogen fertilizer.

<span class="mw-page-title-main">Nitric oxide</span> Colorless gas with the formula NO

Nitric oxide is a colorless gas with the formula NO. It is one of the principal oxides of nitrogen. Nitric oxide is a free radical: it has an unpaired electron, which is sometimes denoted by a dot in its chemical formula. Nitric oxide is also a heteronuclear diatomic molecule, a class of molecules whose study spawned early modern theories of chemical bonding.

Nitromethane, sometimes shortened to simply "nitro", is an organic compound with the chemical formula CH
3NO
2. It is the simplest organic nitro compound. It is a polar liquid commonly used as a solvent in a variety of industrial applications such as in extractions, as a reaction medium, and as a cleaning solvent. As an intermediate in organic synthesis, it is used widely in the manufacture of pesticides, explosives, fibers, and coatings. Nitromethane is used as a fuel additive in various motorsports and hobbies, e.g. Top Fuel drag racing and miniature internal combustion engines in radio control, control line and free flight model aircraft.

<span class="mw-page-title-main">Dinitrogen pentoxide</span> Chemical compound

Dinitrogen pentoxide is the chemical compound with the formula N2O5. It is one of the binary nitrogen oxides, a family of compounds that only contain nitrogen and oxygen. It exists as colourless crystals that sublime slightly above room temperature, yielding a colorless gas.

<span class="mw-page-title-main">Nitration</span> Chemical reaction which adds a nitro (–NO₂) group onto a molecule

In organic chemistry, nitration is a general class of chemical processes for the introduction of a nitro group into an organic compound. The term also is applied incorrectly to the different process of forming nitrate esters between alcohols and nitric acid. The difference between the resulting molecular structures of nitro compounds and nitrates is that the nitrogen atom in nitro compounds is directly bonded to a non-oxygen atom, whereas in nitrate esters, the nitrogen is bonded to an oxygen atom that in turn usually is bonded to a carbon atom.

<span class="mw-page-title-main">Nitro compound</span> Organic compound containing an −NO₂ group

In organic chemistry, nitro compounds are organic compounds that contain one or more nitro functional groups. The nitro group is one of the most common explosophores used globally. The nitro group is also strongly electron-withdrawing. Because of this property, C−H bonds alpha (adjacent) to the nitro group can be acidic. For similar reasons, the presence of nitro groups in aromatic compounds retards electrophilic aromatic substitution but facilitates nucleophilic aromatic substitution. Nitro groups are rarely found in nature. They are almost invariably produced by nitration reactions starting with nitric acid.

<span class="mw-page-title-main">Methyl nitrite</span> Chemical compound

Methyl nitrite is an organic compound with the chemical formula CH
3ONO. It is a gas, and is the simplest alkyl nitrite.

<span class="mw-page-title-main">Ethyl nitrate</span> Chemical compound

Ethyl nitrate is the ethyl ester of nitric acid and has the chemical formula C2H5NO3. It is a colourless, volatile, explosive, and extremely flammable liquid. It is used in organic synthesis with use as a nitrating agent and as an intermediate in the preparation of some drugs, dyes, and perfumes. Like nitroglycerin, it's a vasodialator.

<span class="mw-page-title-main">Ethylene glycol dinitrate</span> Chemical compound

Ethylene glycol dinitrate, abbreviated EGDN and NGC, also known as Nitroglycol, is a colorless, oily, explosive liquid obtained by nitrating ethylene glycol. It is similar to nitroglycerine in both manufacture and properties, though it is more volatile and less viscous. Unlike nitroglycerine, the chemical has a perfect oxygen balance, meaning that its ideal exothermic decomposition would completely convert it to low energy carbon dioxide, water, and nitrogen gas, with no excess unreacted substances, without needing to react with anything else.

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.

<span class="mw-page-title-main">Erythritol tetranitrate</span> Chemical compound

Erythritol tetranitrate (ETN) is an explosive compound chemically similar to PETN, though it is thought to be slightly more sensitive to friction and impact.

<span class="mw-page-title-main">Methylammonium nitrate</span> Chemical compound

Methylammonium nitrate is an explosive chemical with the molecular formula CH6N2O3, alternately CH3NH3+NO3−. It is the salt formed by the neutralization of methylamine with nitric acid. This substance is also known as methylamine nitrate and monomethylamine nitrate, not to be confused with methyl nitramine or monomethyl nitramine.

<span class="mw-page-title-main">Trinitroanisole</span> Chemical compound

Trinitroanisole is a chemical compound that exists as pale yellow crystals with a melting point of 68 °C. It is highly toxic. It is an explosive with a detonation velocity of 7200 meters per second. The compound's primary hazard is a blast of an instantaneous explosion, not flying projectiles or fragments.

<span class="mw-page-title-main">Nitrate ester</span> Chemical group (–ONO2)

In organic chemistry, a nitrate ester is an organic functional group with the formula R−ONO2, where R stands for any organyl group. They are the esters of nitric acid and alcohols. A well-known example is nitroglycerin, which is not a nitro compound, despite its name.

<span class="mw-page-title-main">Water gel explosive</span> Fuel sensitized explosive mixture

A water-gel explosive is a fuel sensitized explosive mixture consisting of an aqueous ammonium nitrate solution that acts as the oxidizer. Water gels that are cap-insensitive are referred to under United States safety regulations as blasting agents. Water gel explosives have a jelly-like consistency and come in sausage-like packing stapled shut on both sides.

References

  1. 1 2 CRC Handbook of Chemistry and Physics (64th ed.). 1983. pp. C–376.
  2. 1 2 3 Meyer, R.; Köhler, J.; Homberg, A. (2007). Explosives (PDF) (6th ed.). Wiley-VCH. p. 212. ISBN   978-3-527-31656-4.
  3. ↑ Black, A. P.; Babers, F. H. (1939). "Methyl nitrate". Organic Syntheses . 19: 64; Collected Volumes, vol. 2, p. 412.
  4. 1 2 Reichel, Marco; Krumm, Burkhard; Vishnevskiy, Yury V.; Blomeyer, Sebastian; Schwabedissen, Jan; Stammler, Hans-Georg; Karaghiosoff, Konstantin; Mitzel, Norbert W. (2019-12-16). "Solid-State and Gas-Phase Structures and Energetic Properties of the Dangerous Methyl and Fluoromethyl Nitrates". Angewandte Chemie International Edition. 58 (51): 18557–18561. doi: 10.1002/anie.201911300 . ISSN   1433-7851. PMC   6916544 . PMID   31573130.
  5. ↑ Fichter, Fr.; Metz, Fritz (January 1935). [10.1002/hlca.193501801137 "Elektrolyse von Nitrat-Acetat-Gemischen"]. Helvetica Chimica Acta (in German). 18 (1): 1005–1007. doi:10.1002/hlca.193501801137. ISSN   0018-019X.{{cite journal}}: Check |url= value (help)
  6. ↑ Shi, Jichun; Wallington, Timothy J.; Kaiser, E. W. (1993). "FTIR product study of the chlorine-initiated oxidation of chloroethane: reactions of the alkoxy radical CH3CHClO". The Journal of Physical Chemistry. 97 (23): 6184–6192. doi:10.1021/j100125a016. ISSN   0022-3654.
  7. ↑ Pagsberg, Palle; Munk, Jette; Anastasi, Christopher; Simpson, Victoria J. (1989). "Reaction of hydroxymethyl radicals with oxygen, nitric oxide, and nitrogen dioxide at room temperature". The Journal of Physical Chemistry. 93 (13): 5162–5165. doi:10.1021/j100350a028. ISSN   0022-3654.
  8. ↑ Friedel, Robert (2021). "Improvised Explosive Device Clearance Good Practice Guide". Basic Chemistry of Explosives and Hazards of Home-Made Explosives and Chemical Precursors Handbook (PDF). Geneva: Geneva International Centre for Humanitarian Demining. p. 175. Retrieved 29 May 2024.
  9. ↑ Meyer, Rudolf (2008). Explosivstoffe. Köhler, Josef., Homburg, Axel. (10., vollst. überarb. Aufl ed.). Weinheim: Wiley-VCH. ISBN   978-3-527-32009-7. OCLC   244068971.
  10. ↑ Koch, Ernst-Christian (2019-06-17). Sprengstoffe, Treibmittel, Pyrotechnika (in German) (2. Auflage ed.). Berlin: De Gruyter. ISBN   978-3-11-055784-8. OCLC   1107346317.
  11. ↑ Stettbacher, A. (1948). Schieß- und Sprengstoffe. Rascher Verlag, Zürich.
  12. ↑ Gartz, Jochen (2007). Vom griechischen Feuer zum Dynamit : eine Kulturgeschichte der Explosivstoffe. Hamburg: E.S. Mittler & Sohn. ISBN   978-3-8132-0867-2. OCLC   153884719.
  13. ↑ "www.feuerwerkbuch.de". www.feuerwerkbuch.de. Retrieved 2020-06-15.
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