megalomania
June 9th, 2003, 05:58 PM
Jumala
Frequent Poster
Posts: 200
From: Germany
Registered: OCT 2000
posted 05-30-2001 12:10 AM
--------------------------------------------------------------------------------
Hallo,
I have scanned receipes and propertys of some nitric esters from an old book (Phokion Naoum 1923)and I would like to post it here.
But to prevent the mods from a nervous breakdown I ask for o.k. because they are some bookpages long. Then I´ll add the text.
Methyl Nitrate
Of the nitric esters of the primary alcohols of the fatty series, methyl nitrate is theoretically the most important on account of its high explosive properties and high energy content, which is on a par with nitroglycerine, to which it is stochiometrically related very closely, as can be seen from table 12. Practically, it has had no importalice äs an explosive up to the present time on account of its great volatility, as well as on account of the danger from fire or explosion of the liquid or vapors in increasing the risk in commercial manufacture or use.
According to Meyer-Jakobsen it has been made commercially for some time for use in the dye industry for methylation, but on account of several disastrous explosions its manufacture was given up.
Preparation.1 Methyl nitrate, like ethyl nitrate, can be obtained by careful distillation of the proper alcohol with moderately strong nitric acid, e.g., of a specific gravity of 1.4. It can also be obtained, like nitroglycerine and nitroglycol, by putting the alcohol into a mixture of concentrated nitric and sulphuric acids, with good yields, while ethyl alcohol and other mono- and polyvalent alcohols con-taining methyl or methylene groups readily undergo oxidation in such a case.
Example. One hundred grams of pure, anhydrous methyl alcohol was added gradually to 630 grams of a mixed acid containing 40 per cent HNO3 and 60 per cent H2SO4, contained in a spherical glass vessel having three openings for a stirrer, thermometer and inlet, the mixture being well cooled, mechanically stirred and maintained at 0 to 10°C., the Operation taking twenty-five minutes. Agitation by compressed air is out of the question on account of the volatility of the ester. The ester separated rapidly in a funnel. It was digested with cold water and then neutralized with a soda solution. There was obtained 196 grams of neutral methyl nitrate, or 81.5 per cent of theory (240.6 grams).
Properties. Methyl nitrate is a colorless, very mobile liquid of a high volatility and strongly aromatic odor, somewhat resembling chloroform. The vapors cause headache when inhaled. It is some-what less viscous than water, and has a specific gravity of 1.21 at 15°C. At ordinary pressures it distils at 65°C. without decomposi-tion. Water dissolves it only slightly at room temperatures. One hundred cubic centimeters of water at 20°C. dissolve 3.85 grams of methyl nitrate. Collodion nitrocotton is dissolved, forming a gelatine, from which the methyl nitrate evaporates very easily.
TABLE 12
Relation of methyl nitrate to nitroglycerine
METHYL NITRATE NITR0G LYCE RIN E
Molecular weight........................... 77 227
Composition: C....................................... •per cent 15.6 'per cent 15.86
H,...................................... 3.9 2.20
0....................................... 62.3 63.44
N....................................... 18.2 18.50
100.0 100.0
Explosive character. The thermo chemical relations of methyl nitrate have already been determined by Berthelot.2 The explosive decomposition is possibly along the line of the following equations:
1. 2(CH3ON02) = CO2 + CO + 3H2O + N2
2. 2(CH3ONO2) = 2CO2 + 2H2O + H2 + N2
The molecule lacks one atom of oxygen for complete combustion. The oxygen balance is therefore —10.39 per cent.
Based on a molecular heat of formation of 39.6 Calories for methyl nitrate Berthelot calculated for 1 kg. of this material at constant volume and with water liquid a heat of explosion of 1609 Calories according to Formula l, and 1616 Calories according to Formula 2. Methyl nitrate has therefore a somcwhat higher energy contcnt than nitroglycerine (1595 Calories), and this makes itself evident also by a slightly higher explosive action. When shot in the lead block with water tamping:
10 grams methyl nitrate gives.................... 615 cc. expansion
10 grams nitroglycerine gives..................... 600 cc. expansion
The expansions are as 102.0:100. The heats of explosion are as 101.0:100, or a satisfactory agreement,
When mixed with kieselguhr or gelatinized with collodion nitro-cotton it shows about the same explosive effect on the lead block as nitroglycerine, namely 320 and 565 cc.
Sensitiveness. Methyl nitrate is extremely sensitive to an initiating Impulse, and when shot with a No. l cap under water tamping, ifc gives approximately the same effecfc äs with a No. 8 cap, in contrast to nitroglycerine, which is more difficult to detonate.
Methyl Nitrate Nitroglycerine
Blasting cap No. l.. 520 cc. (84.5 per cent) 190 cc. (32 per cent)
Blasting cap No. 8.. 615 cc. (100 per cent) 590 cc. (100 per cent)
or after deducting 30 cc. for the No. 8, and 5 cc. for the No. l cap:
Blasting cap No. l... 515 cc. (88 per cent) 185 cc. (33 per cent)
Blasting cap No. 8... 585 cc. (100 per cent) 560 cc. (100 per cent)
The crusher fest also shows similar rclations, which were obtained with 100 grams of the liquid in a sheet lead shell with walls l mm, thick, tamped by thin cork plates, i.e., under slight confinement:
Methyl Nitrate Nilroglycol Nitroglycerine
Compression.............. 24.5 mm. 30 mm. 18.5 mm.
The lower viscosities of methyl nitrate and nitroglycol as compared to nitroglycerine give higher velocities of detonation with the first two, even with a weak confinement.
The sensitiveness also is evidenced by a flame causing detonation Given in a narrow space, a small amount of methyl nitrate in a beaker, when ignited by fuse containing a black powder core, sometimes gives a puff and destruction of the glass into large pieces, Bometimes a brisant detonation and pulverizing of the glass to a fine powder.
In an open dish methyl nitrate ignites immediately when in contact with a flame, and burns quietly with a large, non-luminous flame. The vapors puff readily on ignition, and on heating them to 150°C. they explode. Methyl nitrate is also sensitive to shock, although less so than nitroglycerine and nitroglycol. Under a 2 kg. weight it explodes at a drop of 40 cm. Even when mixed with kieselguhr it is appreciably less sensitive than nitroglycerine.
Velocity of detonation. The velocity of detonation was determined by Berthelot3 at very small diameters. In glass tubes 3 mm. in diameter and 1 mm, wall thickness he found 1890 meters per second, and with 4.5 mm. wall thickness 2480 meters. Nitroglycerine gives only about 1500 meters per second at such small diameters- It is indeed probable that methyl nitrate at larger diameters such as 30 to 40 mm. would give velocities of detonation of far higher magnitudes, such as 6000 to 8000 m/s.
Frequent Poster
Posts: 200
From: Germany
Registered: OCT 2000
posted 05-30-2001 12:10 AM
--------------------------------------------------------------------------------
Hallo,
I have scanned receipes and propertys of some nitric esters from an old book (Phokion Naoum 1923)and I would like to post it here.
But to prevent the mods from a nervous breakdown I ask for o.k. because they are some bookpages long. Then I´ll add the text.
Methyl Nitrate
Of the nitric esters of the primary alcohols of the fatty series, methyl nitrate is theoretically the most important on account of its high explosive properties and high energy content, which is on a par with nitroglycerine, to which it is stochiometrically related very closely, as can be seen from table 12. Practically, it has had no importalice äs an explosive up to the present time on account of its great volatility, as well as on account of the danger from fire or explosion of the liquid or vapors in increasing the risk in commercial manufacture or use.
According to Meyer-Jakobsen it has been made commercially for some time for use in the dye industry for methylation, but on account of several disastrous explosions its manufacture was given up.
Preparation.1 Methyl nitrate, like ethyl nitrate, can be obtained by careful distillation of the proper alcohol with moderately strong nitric acid, e.g., of a specific gravity of 1.4. It can also be obtained, like nitroglycerine and nitroglycol, by putting the alcohol into a mixture of concentrated nitric and sulphuric acids, with good yields, while ethyl alcohol and other mono- and polyvalent alcohols con-taining methyl or methylene groups readily undergo oxidation in such a case.
Example. One hundred grams of pure, anhydrous methyl alcohol was added gradually to 630 grams of a mixed acid containing 40 per cent HNO3 and 60 per cent H2SO4, contained in a spherical glass vessel having three openings for a stirrer, thermometer and inlet, the mixture being well cooled, mechanically stirred and maintained at 0 to 10°C., the Operation taking twenty-five minutes. Agitation by compressed air is out of the question on account of the volatility of the ester. The ester separated rapidly in a funnel. It was digested with cold water and then neutralized with a soda solution. There was obtained 196 grams of neutral methyl nitrate, or 81.5 per cent of theory (240.6 grams).
Properties. Methyl nitrate is a colorless, very mobile liquid of a high volatility and strongly aromatic odor, somewhat resembling chloroform. The vapors cause headache when inhaled. It is some-what less viscous than water, and has a specific gravity of 1.21 at 15°C. At ordinary pressures it distils at 65°C. without decomposi-tion. Water dissolves it only slightly at room temperatures. One hundred cubic centimeters of water at 20°C. dissolve 3.85 grams of methyl nitrate. Collodion nitrocotton is dissolved, forming a gelatine, from which the methyl nitrate evaporates very easily.
TABLE 12
Relation of methyl nitrate to nitroglycerine
METHYL NITRATE NITR0G LYCE RIN E
Molecular weight........................... 77 227
Composition: C....................................... •per cent 15.6 'per cent 15.86
H,...................................... 3.9 2.20
0....................................... 62.3 63.44
N....................................... 18.2 18.50
100.0 100.0
Explosive character. The thermo chemical relations of methyl nitrate have already been determined by Berthelot.2 The explosive decomposition is possibly along the line of the following equations:
1. 2(CH3ON02) = CO2 + CO + 3H2O + N2
2. 2(CH3ONO2) = 2CO2 + 2H2O + H2 + N2
The molecule lacks one atom of oxygen for complete combustion. The oxygen balance is therefore —10.39 per cent.
Based on a molecular heat of formation of 39.6 Calories for methyl nitrate Berthelot calculated for 1 kg. of this material at constant volume and with water liquid a heat of explosion of 1609 Calories according to Formula l, and 1616 Calories according to Formula 2. Methyl nitrate has therefore a somcwhat higher energy contcnt than nitroglycerine (1595 Calories), and this makes itself evident also by a slightly higher explosive action. When shot in the lead block with water tamping:
10 grams methyl nitrate gives.................... 615 cc. expansion
10 grams nitroglycerine gives..................... 600 cc. expansion
The expansions are as 102.0:100. The heats of explosion are as 101.0:100, or a satisfactory agreement,
When mixed with kieselguhr or gelatinized with collodion nitro-cotton it shows about the same explosive effect on the lead block as nitroglycerine, namely 320 and 565 cc.
Sensitiveness. Methyl nitrate is extremely sensitive to an initiating Impulse, and when shot with a No. l cap under water tamping, ifc gives approximately the same effecfc äs with a No. 8 cap, in contrast to nitroglycerine, which is more difficult to detonate.
Methyl Nitrate Nitroglycerine
Blasting cap No. l.. 520 cc. (84.5 per cent) 190 cc. (32 per cent)
Blasting cap No. 8.. 615 cc. (100 per cent) 590 cc. (100 per cent)
or after deducting 30 cc. for the No. 8, and 5 cc. for the No. l cap:
Blasting cap No. l... 515 cc. (88 per cent) 185 cc. (33 per cent)
Blasting cap No. 8... 585 cc. (100 per cent) 560 cc. (100 per cent)
The crusher fest also shows similar rclations, which were obtained with 100 grams of the liquid in a sheet lead shell with walls l mm, thick, tamped by thin cork plates, i.e., under slight confinement:
Methyl Nitrate Nilroglycol Nitroglycerine
Compression.............. 24.5 mm. 30 mm. 18.5 mm.
The lower viscosities of methyl nitrate and nitroglycol as compared to nitroglycerine give higher velocities of detonation with the first two, even with a weak confinement.
The sensitiveness also is evidenced by a flame causing detonation Given in a narrow space, a small amount of methyl nitrate in a beaker, when ignited by fuse containing a black powder core, sometimes gives a puff and destruction of the glass into large pieces, Bometimes a brisant detonation and pulverizing of the glass to a fine powder.
In an open dish methyl nitrate ignites immediately when in contact with a flame, and burns quietly with a large, non-luminous flame. The vapors puff readily on ignition, and on heating them to 150°C. they explode. Methyl nitrate is also sensitive to shock, although less so than nitroglycerine and nitroglycol. Under a 2 kg. weight it explodes at a drop of 40 cm. Even when mixed with kieselguhr it is appreciably less sensitive than nitroglycerine.
Velocity of detonation. The velocity of detonation was determined by Berthelot3 at very small diameters. In glass tubes 3 mm. in diameter and 1 mm, wall thickness he found 1890 meters per second, and with 4.5 mm. wall thickness 2480 meters. Nitroglycerine gives only about 1500 meters per second at such small diameters- It is indeed probable that methyl nitrate at larger diameters such as 30 to 40 mm. would give velocities of detonation of far higher magnitudes, such as 6000 to 8000 m/s.