Methyl nitrate

This is the most explosive of the nitrate esters. Not only will it bum in an atmosphere of oxygen, nitric oxide or nitrogen dioxide, but also it can support a stationary decomposition flame which can be stabilized on a burner [122]. At low pressures the various zones of the decomposition flame are clearly separated and the early stages show strong formaldehyde bands in emission. 

The fuel molecule breaks down in the pre-heat zone to give methoxy radicals 

In a static system, the decomposition can proceed in three ways, explosion, chemiluminescent reaction and decomposition without glow [131]. The glow which is probably due to excited formaldehyde is detectable even when the nitrate is diluted between 10 and 10 times with inert gas. 

A careful study of self-heating during the spontaneous ignition of methyl nitrate vapour has given results in very satisfactory agreement with the predictions of thermal explosion theory [132(a), (b)]. 

The simplest nitrate ester is methyl nitrate, which has the chemical structure CH3ONO2. The decomposition process is given byT l 

The first two reaction steps are endothermic however, the overall reaction is exothermic and the final flame temperature is 1800 K. The observed pressure dependence of the burning rate follows a second-order rate law the overall activation energy is consistent with the oxidation reaction by NO2 being the slowest and hence the rate-controlling step. 

Submitted by Alvin P. Black and Frank H. Babers. Checked by John R. Johnson and II. B. Stevenson. 

In a flask cooled in an ice bath, are mixed 425 g. (300 cc. 4.6 moles) of c.p. nitrous-free, concentrated nitric acid (sp. gr. 1.42) (Note 1) and 550 g. (300 cc.) of C.P. concentrated sulfuric acid (sp. gr. 1.84). In a second flask, also cooled in an ice bath, 92 g. (50 cc.) of c.p. concentrated sulfuric acid is added to 119 g. (150 cc. 3.7 moles) of pure methyl alcohol (Note 2) while the temperature is maintained below io°. 

One-third of the cold nitric-sulfuric mixture is placed in each of three 500-cc. Erlenmeyer flasks (Note 3), and each portion is treated separately with one-third of the methyl alcohol-sulfuric acid mixture, with constant shaking and thorough mixing (Note 4). The temperature is allowed to rise fairly rapidly to 40° and kept at this point by external cooling. During the addition of the methyl alcohol-sulfuric acid, most of the ester separates as an almost colorless oily layer above the acid. The time required for completion of the reaction is two to three minutes for each flask. The reaction mixtures are allowed to stand in the cold for an additional fifteen minutes but not longer. The lower layer of spent acid is separated promptly and poured at once into a large volume of cold water (about 11. for each portion) to avoid decomposition which quickly ensues with copious evolution of nitrous fumes. 

The combined ester layers are washed with two 25-cc. portions of ice-cold salt solution (sp. gr. 1.17) (Note 5). A small quantity (8-10 drops) of concentrated sodium hydroxide solution is added to the second wash liquid until it has a faintly alkaline reaction to litmus. The ester is washed free of alkali with ice-cold salt solution and finally washed with two 15-cc. portions of ice water (Note 6). The product is treated with 10-15 g. of anhydrous calcium chloride and allowed to stand with occasional shaking for an hour at o°. It is then decanted onto a fresh 5-g. portion of the drying agent and after standing for one-half hour is filtered. The crude ester without further purification (Note 7) may be used directly for most synthetic purposes, such as the preparation of phenylnitromethane (p. 73). The yield is 190-230 g. (66-80 per cent of the theoretical amount). The crude ester should be used promptly and not stored. 

Colored specimens of nitric acid may be treated with a small quantity of urea (about 1-2 g. per 100 cc.), but this is unnecessary unless the acid is appreciably colored. 

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V-aminoindoles from, 4, 361 Cinnoline, 3,4-diphenyl-synthesis, 3, 42 Cinnoline, 3-hydroxy-synthesis, 2, 92 tautomerism, 3, 4 Cinnoline, 4-hydroxy-tautomerism, 3, 4 Cinnoline, 4-methyl-nitration, 3, 21... 

Furan-2-carbonyl chloride, 5-alkyl-3,4-dichloro-synthesis, 4, 690 Furancarboxamides rotational isomerism, 4, 543 Furan-2-carboxylic acid, 5-acetylamino-ethyl ester reactions, 4, 647 Furan-2-carboxylic acid, amino-properties, 4, 708 Furan-2-carboxylic acid, 5-bromo-nitration, 4, 603, 711 Furan-2-carboxylic acid, 3-methyl-methyl ester bromination, 4, 604 Furan-2-carboxylic acid, 5-methyl-nitration, 4, 602... 

Doebner-von Miller synthesis, 2, 466 hydrazination, 2, 238 NMR, 2, 120 Quinoline, 5-methyl-nitration, 2, 50, 318 Quinoline, 6-methyl-mercuration, 2, 321 N-oxide... 

Quinolinium 2-dicyanomethylene-1,1,3,3-tetracyanopropanediide dimensions, 2, 110 Quinolinium iodide, 1-alkyl-Ladenburg rearrangement, 2, 300 Quinolinium iodide, 1-methyl-Ladenburg rearrangement, 2, 300, 335 Quinolinium iodide, [l-methyl-4-[3(5)-pyrazolyl]-blood sugar level and, 5, 291 Quinolinium perchlorate, 1-ethoxy-hydroxymethylation, 2, 300 Quinolinium perchlorate, 1-methyl-nitration, 2, 318 Quinolinium salts alkylation, 2, 293 Beyer synthesis, 2, 474 electrophilic substitution, 2, 317 free radical alkylation, 2, 45 nitration, 2, 188 reactions... 

Methyl nitrate [598-58-3] M 77,0, b 65 /760mm, d 1.2322, d 1,2167, d 5 1,2032. Distd at -80°. The middle fraction was subjected to several freeze-pump-thaw cycles. VAPOUR EXPLODES ON HEATING. 

CH3N03 METHYL-NITRATE -122.358 3.0626E-01 8.2197E-06 -30.17 74 C2H5F FLUOROETHANE -262.745 1.7117E-01 2.2082E-05 -209.53... 

Methyidichloroarsine Methylene glycol dinitrate Methyl ethyl ketone peroxide, >50% alpha-Methylglucoside tetranitrate alpha-Methylglycerol trinitrate Methyl nitramine (dry) metal salts of Methyl nitrate Methyl nitrite... 

A number of other gases can undergo reactions that produce decomposition flames—for instance, ethylene, ethylene oxide, methyl nitrate, ethyl nitrate, and hydrazine (CCPS 1993). 

Methyl Nitrate (Methylnitrat or Salpetersaure-methylester in Ger), CH3.0N02 mw 77.04,... 

Inasmuch as methyl nitrate is very sensitive to mechanical action, it was found much safer to use it in methanol soln. Such solns, called Myrol, may be obtained directly in the methyl nitrate manufg process, since all that is necessary is to use an excess of methanol. One of the most suitable solns proved to be an azeotropic mixt consisting of about 75% methyl nitrate and 25% methanol. This mixt has a bp of 57.5°. Myrols contg at least 25% methanol will not evaporate to leave 100% methyl nitrate... 

Romer (Ref 1) calls Myrol a mixt contg 73% methyl nitrate and 27% technical methanol contg 4% w. Tschinkel (Ref 3) states that Myrol consisted of 80 wt % methyl nitrate and 20 wt % methanol... 

Following are some props of methyl nitrate-methanol mixts vel of deton ranging from 2400—4900 to 7500—8200m/sec, gas vol about 8732/kg, Qe 1640—1700kcal/kg, power and brisance — comparable to those of NG, sensitivity to shock — comparable to that of DNB, and toxicity — comparable to that of aliphatic... 

Myrol Explosives. Methyl nitrate (qv) and its mixts with methanol, benz, NB, etc found extensive application by Ger in WWII as ingredients of numerous liq, plastic and solid propints and expls. Some of these mixts were known as Ersatzsprengatoffe (substitute expls)... 

In the case of liq expls and propints, Myrol (methyl nitrate plus methanol) was used either by itself or in mixts with liqs such as benz, MNB, etc. For use as a plastic expl or propint, Myrol was treated with small quantities of NC to form a soft jelly. As a solid expl or propint, it was treated with 25-30% NC to form a hard jelly, or was mixed with the usual sol ingredients of dynamites, sUch as kieselguhr, sawdust, inorganic nitrates, lignin, etc... 

Methyl Nitrate. See in this Vol under Methyl Nitrate... 

Houle et al, Development of Mono nit rotoluene and Methyl Nitrate Monitors for Army Ammunition Plants , DPG-TR-C985P (1975) 28) P. 

It is interesting to mention here that Dewar and Storch (1989) drew attention to the fact that ion-molecule reactions often lack a transition state barrier in theoretical calculations related to the gas phase, but are known to proceed with measurable activation energy in solution. Szabo et al. (1992) made separate calculations at the ab initio Hartree-Fock 3/21 G level for the geometry of the nitration of benzene with the protonated methyl nitrate by two mechanisms, not involving solvent molecules. Both calculations yielded values for the energy barriers. 

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