“Nitromethane”的意思、由来-开放百科全书

Nitromethane is an organic compound with the chemical formula {{chem|CH|3|NO|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 pharmaceuticals, pesticides, explosives, fibers, and coatings.^[28] 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.

Preparation

Nitromethane is produced industrially by combining propane and nitric acid in the gas phase at 350–450 °C (662–842 °F). This exothermic reaction produces the four industrially significant nitroalkanes: nitromethane, nitroethane, 1-nitropropane, and 2-nitropropane. The reaction involves free radicals, including the alkoxyl radicals of the type CH₃CH₂CH₂O, which arise via homolysis of the corresponding nitrite ester. These alkoxy radicals are susceptible to C—C fragmentation reactions, which explains the formation of a mixture of products.^[13]

Laboratory methods

It can be prepared in other methods that are of instructional value. The reaction of sodium chloroacetate with sodium nitrite in aqueous solution produces this compound:^[14]

Uses

The principal use of nitromethane is as a stabilizer for chlorinated solvents, which are used in dry cleaning, semiconductor processing, and degreasing. It is also used most effectively as a solvent or dissolving agent for acrylate monomers, such as cyanoacrylates (more commonly known as "super-glues").^[13] It is also used as a fuel in some forms of racing.

It can be used as an explosive, when gelled with several percent of gelling agent. This type of mixture is called PLX. Another used mixtures are ANNM and ANNMAl – explosive mixtures of ammonium nitrate, nitromethane and aluminium powder.

Reactions

Acid-base properties

Nitromethane is a relatively acidic carbon acid. It has a pK_a of 17.2 in DMSO solution. This value indicates an aqueous pK_a of about 11.^[15] The reason of that being so acidic is due to the resonance structure below:

It is slow to deprotonate. Protonation of the conjugate base O₂NCH₂^-, which is nearly isosteric with nitrate, occurs initially at oxygen.^[16]

Organic reactions

In organic synthesis nitromethane is employed as a one carbon building block.^[17]^[18] Its acidity allows it to undergo deprotonation, enabling condensation reactions analogous to those of carbonyl compounds. Thus, under base catalysis, nitromethane adds to aldehydes in 1,2-addition in the nitroaldol reaction. Some important derivatives include the pesticides chloropicrin (Cl₃CNO₂), beta-nitrostyrene, and tris(hydroxymethyl)nitromethane, ((HOCH₂)₃CNO₂). Reduction of the latter gives tris(hydroxymethyl)aminomethane, (HOCH₂)₃CNH₂, better known as tris, a widely used buffer. In more specialized organic synthesis, nitromethane serves as a Michael donor, adding to α,β-unsaturated carbonyl compounds via 1,4-addition in the Michael reaction.

As an engine fuel

Nitromethane is used as a fuel in motor racing, particularly drag racing, as well as for radio-controlled models^[13] (such as cars, planes and helicopters). In this context, nitromethane is commonly referred to as "nitro", and is the principal ingredient for fuel used in the "Top Fuel" category of drag racing.

The oxygen content of nitromethane enables it to burn with much less atmospheric oxygen.

The amount of air required to burn {{convert|1|kg|lb|abbr=on}} of gasoline is {{convert|14.7|kg|lb|abbr=on}}, but only {{convert|1.7|kg|lb|abbr=on}} of air is required for 1 kg of nitromethane. Since an engine's cylinder can only contain a limited amount of air on each stroke, 8.6 times more nitromethane than gasoline can be burned in one stroke. Nitromethane, however, has a lower specific energy: gasoline provides about 42–44 MJ/kg, whereas nitromethane provides only 11.3 MJ/kg. This analysis indicates that nitromethane generates about 2.3 times the power of gasoline when combined with a given amount of oxygen.

Nitromethane can also be used as a monopropellant, i.e., a fuel that burns without added oxygen. The following equation describes this process:

Nitromethane has a laminar combustion velocity of approximately 0.5 m/s, somewhat higher than gasoline, thus making it suitable for high-speed engines. It also has a somewhat higher flame temperature of about {{convert|2400|C|F}}. The high heat of vaporization of 0.56 MJ/kg together with the high fuel flow provides significant cooling of the incoming charge (about twice that of methanol), resulting in reasonably low temperatures

Nitromethane is usually used with rich air–fuel mixtures because it provides power even in the absence of atmospheric oxygen. When rich air–fuel mixtures are used, hydrogen and carbon monoxide are two of the combustion products. These gases often ignite, sometimes spectacularly, as the normally very rich mixtures of the still burning fuel exits the exhaust ports. Very rich mixtures are necessary to reduce the temperature of combustion chamber hot parts in order to control pre-ignition and subsequent detonation. Operational details depend on the particular mixture and engine characteristics.

A small amount of hydrazine blended in nitromethane can increase the power output even further. With nitromethane, hydrazine forms an explosive salt that is again a monopropellant. This unstable mixture poses a severe safety hazard and the Academy of Model Aeronautics does not permit its use in competitions.^[19]

In model aircraft and car glow fuel, the primary ingredient is generally methanol with some nitromethane (0% to 65%, but rarely over 30%, and 10–20% lubricants (usually castor oil and/or synthetic oil). Even moderate amounts of nitromethane tend to increase the power created by the engine (as the limiting factor is often the air intake), making the engine easier to tune (adjust for the proper air/fuel ratio).

Explosive properties

Nitromethane was not known to be a high explosive until a railroad tanker car loaded with it exploded on {{#dateformat:June 1, 1958}}.^[20] After much testing, it was realized that nitromethane was a more energetic high explosive than TNT, although TNT has a higher velocity of detonation (VoD) and brisance. Both of these explosives are oxygen-poor, and some benefits are gained from mixing with an oxidizer, such as ammonium nitrate. Pure nitromethane is an insensitive explosive with a VoD of approximately {{convert|6400|m/s|ft/s|abbr=on}}, but even so inhibitors may be used to reduce the hazards. The tank car explosion was speculated to be due to adiabatic compression, a hazard common to all liquid explosives. This is when small entrained air bubbles compress and superheat with rapid rises in pressure. It was thought that an operator rapidly snapped shut a valve creating a "hammer-lock" pressure surge.

Nitromethane can also be mixed with ammonium nitrate, which is used as an oxidizer, to form an explosive mixture known as ANNM. One graphic example of this was the use of nitromethane and ammonium nitrate in the Oklahoma City bombing.

Nitromethane is used as a model explosive, alongside with TNT. It has several advantages as a model explosive over TNT, namely its uniform density and lack of solid post-detonation species that complicate the determination of equation of state and further calculations.

Nitromethane exhaust

Exhaust gas from an internal combustion engine whose fuel includes nitromethane will contain nitric acid vapour, which is corrosive, and when inhaled causes a muscular reaction making it impossible to breathe. The condensed nitric acid-based residue left over in a glow-fueled model engine after a model-flight session can also corrode their internal components, usually mandating use of a combination of kerosene to neutralize the residual nitric acid, and an "after-run oil" (often the lower-viscosity "air tool oil" variety of a popular preservative oil) for lubrication to safeguard against such damage, when such an engine is placed into storage.

Purification

Nitromethane is a popular solvent in organic and electroanalytical chemistry. It can be purified by cooling below its freezing point, washing the solid with cold diethyl ether, followed by distillation.^[21]

See also

References

1. ^{{cite book | title = Nomenclature of Organic Chemistry : IUPAC Recommendations and Preferred Names 2013 (Blue Book) | publisher = The Royal Society of Chemistry | date = 2014 | location = Cambridge | page = 662 | doi = 10.1039/9781849733069-FP001 | isbn = 978-0-85404-182-4| chapter = Front Matter }}
2. ^¹²³⁴Haynes, p. 3.414
3. ^Haynes, p. 5.94
4. ^{{cite web|last1=Reich|first1=Hans|title=Bordwell pKa table: "Nitroalkanes"|url=http://www.chem.wisc.edu/areas/reich/pkatable/|website=University of Wisconsin Chemistry Department|accessdate=17 January 2016}}
5. ^Haynes, p. 6.231
6. ^Haynes, p. 6.231
7. ^Haynes, p. 3.576
8. ^¹²³⁴Haynes, p. 15.19
9. ^Haynes, p. 6.69
10. ^Haynes, p. 5.20
11. ^¹²³⁴⁵{{PGCH|0457}}
12. ^¹²{{IDLH|75525|Nitromethane}}
13. ^¹²³{{ cite encyclopedia | author = Markofsky, S. B. | chapter = Nitro Compounds, Aliphatic | encyclopedia = Ullmann's Encyclopedia of Industrial Chemistry | year = 2000 | publisher = Wiley-VCH | location = Weinheim | doi = 10.1002/14356007.a17_401.pub2 | isbn = 978-3527306732 }}
14. ^{{OrgSynth | author = Whitmore, F. C. | author2 = Whitmore, M. G. | title = Nitromethane | collvol = 1 | collvolpages = 401 | year = 1941 | prep = cv1p0401 }}
15. ^{{cite journal|author=Bordwell, F. G.; Satish, A. V.|title=Is Resonance Important in Determining the Acidities of Weak Acids or the Homolytic Bond Dissociation Enthalpies (BDEs) of Their Acidic H-A Bonds?|journal=Journal of the American Chemical Society|volume=116|issue=20|pages=8885–8889|doi=10.1021/ja00099a004|year=1994}}
16. ^{{cite book|doi=10.1002/9780470166437.ch1|author=Kramarz, K. W.; Norton, J. R.|title=Progress in Inorganic Chemistry|pages=1–65|chapter=Slow Proton-Transfer Reactions in Organometallic and Bioinorganic Chemistry|year=2007|isbn=9780470166437}}
17. ^{{ OrgSynth | author = Dauben, H. J. Jr. | author2 = Ringold, H. J. | author3 = Wade, R. H. | author4 = Pearson, D. L. | author5 = Anderson, A. G. Jr. | author6 = de Boer, T. J. | author7 = Backer, H. J. | title = Cycloheptanone | collvol = 4 | collvolpages = 221 | year = 1963 | prep = cv4p0221 }}
18. ^{{ OrgSynth | author = Noland, W. E. | title = 2-Nitroethanol | collvol = 4 | collvolpages = 833 | year = 1963 | prep = cv5p0833 }}
19. ^{{cite web |url=https://www.modelaircraft.org/files/2015-2016General.pdf |title=AMA Competition Regulations 2015–2016 Part 7. Fuels |author= |page=24 |date=February 15, 2016 |website=www.modelaircraft.org |publisher=Academy of Model Aeronautics |accessdate=April 18, 2014}}
20. ^{{cite web | url = http://www.blet602.org/Historic_accidents/Mt.%20Pulaski_6.1.1958.pdf | author = Interstate Commerce Commission | work = Ex Parte No 213 | title = Accident Near Mt. Pulaski, ILL }}
21. ^{{ cite journal |author1=Coetzee, J. F. |author2=Chang, T.-H. | title = Recommended Methods for the Purification of Solvents and Tests for Impurities: Nitromethane | journal = Pure and Applied Chemistry | year = 1986 | volume = 58 | issue = 11 | pages = 1541–1545 | doi = 10.1351/pac198658111541 | url = http://www.iupac.org/publications/pac/1986/pdf/5811x1541.pdf }}