Post by Anders Hoveland on Feb 2, 2011 20:02:28 GMT -8
Tetrazene
VOD: 1500 to more than 4000 m/s (depending on how it is initiated)
Density: 1.7 g/cm3.
Lead block test: 155cm3 /10g.
Structure: (HN4C)--N=N--N(NH2)--C(=NH)NH2 * H2O
Tetrazene is slightly more impact-sensitive than mercury fulminate. In contact with fire, it readily explodes, producing large amounts of black smoke. Nitrate and perchlorate salts of tetrazene are much more powerful. A mixture of tetracene and mannitol hexanitrate
( in a 4/6 ratio) will give a powerful brisant primary that detonates from moderate heat.
Tetrazene is a colorless pale yellow, fluffy material with slight hygroscopic properties.
It is almost insoluble in water, alcohol, ether, and benzene.
It is stable at normal temperatures when wet or dry, but decomposes in boiling water. Tetrazene is sensitive to friction, shock, and flame. Its brissance is maximized when it has not been compacted; when pressed enough, its sensitivity is reduced or destroyed, which is known as dead pressing. Tetrazene is not suited for blasting caps or alone as an explosive since it does not detonate itself very efficiently. It is best suited for booster charges or in blasting caps mixed with other explosives. It should be detonated by another explosive charge, otherwise if just ignited, it will undergo a lower velocity detonation.
It is prepared by reacting sodium nitrite with an aminoguanidine salt dissolved in acetic acid at 30–40 °C.
Preparation:
Prepare a solution of 34 g of aminoguanidine bicarbonate and 12.5 mL of glacial acetic acid with 2500 mL of water in a 3-liter Florence flask. Gently warm the flask on a steam bath and shake periodically until everything is completely dissolved into solution. The solution should be filtered to remove any impurities that may have not dissolved, then cooled to 30º C by running cold water from the faucet over the flask. It is necessary to filter the solution if there are impurities present. Add 27.6 g of sodium nitrite to the solution while swirling to dissolve it. Set the flask aside at room temperature for 3 or 4 hours then shake it vigorously to start precipitation of the product. Let the flask stand for another 20 hours. After standing, decant as much of the solution off as possible and drown the remaining crystals with water. Decant and drown with water several more times to wash the crystals. Filter the washed crystals to collect them and thoroughly wash again with water. Dry the product at room temperature and store in a sealed glass container to keep out the moisture.
Related Chemistry:
Reaction of tetrazene with a strong base causes the compound to hydrolyze into "triazonitrosoaminoguanidine", which is far more sensitive and dangerous.
(they still do not know the exact structure of this other compound, but it has an azide group in it) This compound can be reacted with Copper Acetate to form a copper-complex salt, which can then with react with a solution of hydrochloric acid to form 5-azido tetrazole in 85% yield.
Treatment of aminoguanidine bicarbonate with sodium nitrite and excess HCl solution makes guanylazide, whereas treatment with a solution of acetic acid and sodium nitrite forms mostly the tetrazene, with a structure (HN4C)-N=N-NH-(CN4H), where the (CNH4) is a tetrazole ring. Guanylazide reacts with sodium hydroxide to form sodium azide, but reacts with a weak base, or weak acid, to form 5-aminotetrazole. 5-aminotetrazole will react with nitrogen dioxide to form 5-nitrotetrazole, which is somewhat acidic and forms nitrotetrazolate salts with bases such as ammonia.
Tetrazene has an enthalpy of formation of +45.2
Preparation of Aminoguanidine:
100 grams (1 mole) of nitroguanidine and 370 g (5 moles) of zinc dust are ground together, then enough water (about 400 mL.) is added with stirring with to form a thick paste. The paste is transferred to a 2 liter beaker surrounded by an ice bath. A solution of 60 g (1 mole) of glacial acetic acid in 75 mL of water is cooled to 5° in another 2 L beaker, which is surrounded by an ice bath. The paste of nitroguanidine and zinc dust, cooled to 5°, is added slowly with strong stirring. The temperature of the reaction mixture is kept between 5° and 15°C . A total of about 500g of brocken ice is added to the mixture periodically if and when the mixture becomes too warm or too viscous and difficult to stir. The addition of the paste should be done over a span of at least 3 hours.
The mixture is then slowly warmed to 40degC on a water bath with more stirring. The temperature is kept at 40C for 5 more minutes. The solution is then quickly separated from the insoluble material by filtration in a large funnel, and the caked material is vacuum-sucked dry. The residue is then placed in the 2-L beaker, washed well with 500mL of water, and then separated from the liquid by filtration. The residue is also washed twice more with 600-mL of water. and placed in a 2L round-bottomed flask. 100 g of ammonium chloride is added, and the solution stirred until it dissolves. The ammonium chloride prevents the coprecipitation of zinc salts when sodium bicarbonate is added to the solution to precipitate the aminoguanidine as the bicarbonate. If the solution is not clear at this step, it should be filtered.
The stirring is continued, and 100 g. (1.3 moles) of sodium bicarbonate is added. The aminoguanidine bicarbonate begins to precipitate after a few minutes, and the solution is then placed in a refrigerator for 8 hours. The precipitate is collected by filtration with a funnel. The cake is removed to a 500mL beaker and mixed with 200-mL of a 5% solution of ammonium chloride and filtered. It is again washed with 400-mL of distilled water. Finally, the solid is pressed down on the against the filter paper on the funnel; the cake is broken up with a spatula and washed while on the funnel with a total of 400mL of 95% ethanol and then with 200mL of ether. After air drying, the aminoguanidine bicarbonate should weigh about 90 g. (60% yield). It is a white solid, melting (with some decomposition) at 172°C. It should not be recrystallized from hot water, since decomposition will occur. The aminoguanidine bicarbonate from this procedure is pure enough to be used for the tetrazene preparation.
invented a sort of hybrid between TACC and tetrazene. Coppric perchlorate Cu(ClO4)2 is dried and then mixed with tetrazene using absolute methanol as a solvent. my guess is that the resulting adduct has two tetrazene molecules complexed to each copper ion.
This complex salt is called tetrazine coppric perchlorate, which will be refered to as TZCP
in this post.
using a 4g charge detonated between two copper plates (a variation of the lead block test),
TZCP outperforms plain tetrazene, as expected. more advantageous than any increase in power is the fact that coppric perchlorate is much easier to make than tetrazene, so it serves as an easy to prepare filler to stretch a given quantity of pure tetrazene into a somewhat larger quantity of TZCP. It should be noted that TZCP failed to match an equivalent ammount of a tetrazine+xylitol-pentanitrate (in a 3/1 ratio). It is unknown whether the results would differ is larger samples had been tested, since it is to be suspected that TZCP would detonate more efficiently if the diameter of the sample had been greater
NaClO4 + NH4Cl --> NaCl + NH4ClO4 (NH4ClO4 is much less soluble than sodium perchlorate)
2NH4ClO4 + CuCO3 --> Cu(ClO4)2 + H2O + 2NH3 + CO2 (solution is heated)
VOD: 1500 to more than 4000 m/s (depending on how it is initiated)
Density: 1.7 g/cm3.
Lead block test: 155cm3 /10g.
Structure: (HN4C)--N=N--N(NH2)--C(=NH)NH2 * H2O
Tetrazene is slightly more impact-sensitive than mercury fulminate. In contact with fire, it readily explodes, producing large amounts of black smoke. Nitrate and perchlorate salts of tetrazene are much more powerful. A mixture of tetracene and mannitol hexanitrate
( in a 4/6 ratio) will give a powerful brisant primary that detonates from moderate heat.
Tetrazene is a colorless pale yellow, fluffy material with slight hygroscopic properties.
It is almost insoluble in water, alcohol, ether, and benzene.
It is stable at normal temperatures when wet or dry, but decomposes in boiling water. Tetrazene is sensitive to friction, shock, and flame. Its brissance is maximized when it has not been compacted; when pressed enough, its sensitivity is reduced or destroyed, which is known as dead pressing. Tetrazene is not suited for blasting caps or alone as an explosive since it does not detonate itself very efficiently. It is best suited for booster charges or in blasting caps mixed with other explosives. It should be detonated by another explosive charge, otherwise if just ignited, it will undergo a lower velocity detonation.
It is prepared by reacting sodium nitrite with an aminoguanidine salt dissolved in acetic acid at 30–40 °C.
Preparation:
Prepare a solution of 34 g of aminoguanidine bicarbonate and 12.5 mL of glacial acetic acid with 2500 mL of water in a 3-liter Florence flask. Gently warm the flask on a steam bath and shake periodically until everything is completely dissolved into solution. The solution should be filtered to remove any impurities that may have not dissolved, then cooled to 30º C by running cold water from the faucet over the flask. It is necessary to filter the solution if there are impurities present. Add 27.6 g of sodium nitrite to the solution while swirling to dissolve it. Set the flask aside at room temperature for 3 or 4 hours then shake it vigorously to start precipitation of the product. Let the flask stand for another 20 hours. After standing, decant as much of the solution off as possible and drown the remaining crystals with water. Decant and drown with water several more times to wash the crystals. Filter the washed crystals to collect them and thoroughly wash again with water. Dry the product at room temperature and store in a sealed glass container to keep out the moisture.
Related Chemistry:
Reaction of tetrazene with a strong base causes the compound to hydrolyze into "triazonitrosoaminoguanidine", which is far more sensitive and dangerous.
(they still do not know the exact structure of this other compound, but it has an azide group in it) This compound can be reacted with Copper Acetate to form a copper-complex salt, which can then with react with a solution of hydrochloric acid to form 5-azido tetrazole in 85% yield.
Treatment of aminoguanidine bicarbonate with sodium nitrite and excess HCl solution makes guanylazide, whereas treatment with a solution of acetic acid and sodium nitrite forms mostly the tetrazene, with a structure (HN4C)-N=N-NH-(CN4H), where the (CNH4) is a tetrazole ring. Guanylazide reacts with sodium hydroxide to form sodium azide, but reacts with a weak base, or weak acid, to form 5-aminotetrazole. 5-aminotetrazole will react with nitrogen dioxide to form 5-nitrotetrazole, which is somewhat acidic and forms nitrotetrazolate salts with bases such as ammonia.
Tetrazene has an enthalpy of formation of +45.2
Preparation of Aminoguanidine:
100 grams (1 mole) of nitroguanidine and 370 g (5 moles) of zinc dust are ground together, then enough water (about 400 mL.) is added with stirring with to form a thick paste. The paste is transferred to a 2 liter beaker surrounded by an ice bath. A solution of 60 g (1 mole) of glacial acetic acid in 75 mL of water is cooled to 5° in another 2 L beaker, which is surrounded by an ice bath. The paste of nitroguanidine and zinc dust, cooled to 5°, is added slowly with strong stirring. The temperature of the reaction mixture is kept between 5° and 15°C . A total of about 500g of brocken ice is added to the mixture periodically if and when the mixture becomes too warm or too viscous and difficult to stir. The addition of the paste should be done over a span of at least 3 hours.
The mixture is then slowly warmed to 40degC on a water bath with more stirring. The temperature is kept at 40C for 5 more minutes. The solution is then quickly separated from the insoluble material by filtration in a large funnel, and the caked material is vacuum-sucked dry. The residue is then placed in the 2-L beaker, washed well with 500mL of water, and then separated from the liquid by filtration. The residue is also washed twice more with 600-mL of water. and placed in a 2L round-bottomed flask. 100 g of ammonium chloride is added, and the solution stirred until it dissolves. The ammonium chloride prevents the coprecipitation of zinc salts when sodium bicarbonate is added to the solution to precipitate the aminoguanidine as the bicarbonate. If the solution is not clear at this step, it should be filtered.
The stirring is continued, and 100 g. (1.3 moles) of sodium bicarbonate is added. The aminoguanidine bicarbonate begins to precipitate after a few minutes, and the solution is then placed in a refrigerator for 8 hours. The precipitate is collected by filtration with a funnel. The cake is removed to a 500mL beaker and mixed with 200-mL of a 5% solution of ammonium chloride and filtered. It is again washed with 400-mL of distilled water. Finally, the solid is pressed down on the against the filter paper on the funnel; the cake is broken up with a spatula and washed while on the funnel with a total of 400mL of 95% ethanol and then with 200mL of ether. After air drying, the aminoguanidine bicarbonate should weigh about 90 g. (60% yield). It is a white solid, melting (with some decomposition) at 172°C. It should not be recrystallized from hot water, since decomposition will occur. The aminoguanidine bicarbonate from this procedure is pure enough to be used for the tetrazene preparation.
invented a sort of hybrid between TACC and tetrazene. Coppric perchlorate Cu(ClO4)2 is dried and then mixed with tetrazene using absolute methanol as a solvent. my guess is that the resulting adduct has two tetrazene molecules complexed to each copper ion.
This complex salt is called tetrazine coppric perchlorate, which will be refered to as TZCP
in this post.
using a 4g charge detonated between two copper plates (a variation of the lead block test),
TZCP outperforms plain tetrazene, as expected. more advantageous than any increase in power is the fact that coppric perchlorate is much easier to make than tetrazene, so it serves as an easy to prepare filler to stretch a given quantity of pure tetrazene into a somewhat larger quantity of TZCP. It should be noted that TZCP failed to match an equivalent ammount of a tetrazine+xylitol-pentanitrate (in a 3/1 ratio). It is unknown whether the results would differ is larger samples had been tested, since it is to be suspected that TZCP would detonate more efficiently if the diameter of the sample had been greater
NaClO4 + NH4Cl --> NaCl + NH4ClO4 (NH4ClO4 is much less soluble than sodium perchlorate)
2NH4ClO4 + CuCO3 --> Cu(ClO4)2 + H2O + 2NH3 + CO2 (solution is heated)