Methyl nitrate

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Methyl nitrate
Methyl nitrate Methyl Nitrate Structural Formulae V.1.svg
Methyl nitrate
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).
Yes check.svgY  verify  (what is  Yes check.svgYX mark.svgN ?)

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 [ citation needed ]). The Feuerwerkbuch describes it as follows (written in Early New High German): [13]

Wilt du mit wasser schiessen
das du denne kain puluer brvchest
vnd stercker vnd wyter mit schüssest
denne ob du das best puluer hettest
das ye gemachet ward so
nyme salpeter vnd distillier das zu wasser
vnd den swebel zu öl
vnd salarmoniack ouch zu wasser
vnd nym oleum benedictum ouch darzu
näch gewichte als du wol hören wirst
vnd wenn du das wasser zusammen bringen machst
so nym sechß tail salpeterwassers
zway tail swebelöls
zway tail salarmoniakwasser
zway tail de oleo benedicto
vnd lad die büchß vast wol
mit clotz vnd mit stain vnd güß
die wasser in die büchs
ain zechen tail des rors
hinder dem clotzen
vnd zünd si an mit zunder das
du dauon kommen mügest vnd lug
das die büchß vast starck sy
vnd mit disem wasser schüssest du
mit ain gemainer buchß
ob drwtusent schrytt wytt
es ist aber gar kostlichen.

Translation:

Do you want to shoot with water,
so that you need no powder
and blast farther and wider
than if you had the best powder
that anyone had made? Well,
take saltpeter and distill it with water,
add sulfur to oil,
sal ammoniac to water,
and you'll need chrism oil there, too,
in careful proportions seen below.
And when you bring it all together,
well, take six parts saltpeter water,
two parts sulfur oil,
two parts sal ammoniac water
and two parts chrism.
Load the gun tight and well,
with bricks and stones; and pour
the water in the gun,
a tenth of the barrel,
behind the bricks;
and set it off with forethought that
you can 'scape the blast: for
the gun is fastened strong.
With this water you shall shoot
in a common gun
perhaps three thousand paces far.
It is a veritable delight.

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)

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. ↑ Nibler (13 Jan 2005). "[No title]" (PDF). Feuerwerkbuch. Section (222). Archived from the original (PDF) on 15 Jan 2022.. The cited document compares two scribal versions; the quote here is from the Freiburger Manuscript #362 (on the left in the cite). For more context, see or (in German) .
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