Tommy
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Ammonium dinitramide
Hi,
i've seen several methods for preparing this compound. One method is to react ammonium nitrourethane and dinitrogen pentoxide, but an easier way is to
create potassium dinitramide first by nitrating potassium sulphamate and combining it with ammonium sulfate.
Has anybody made it sucessfully?
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DeAdFX
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I remember reading a thread on Dinitriamides on the explosives and weapons forum. The person who made it was sucessful in creating the potassium salt
(unknown about the NH4 variant) and burned it with sugar. THe mixture was similar to Potassium Chlorate and Sugar. I guess if you have a procedure
and the right chemicals you shouldn't have too much of an issue.
It would be in your best intrest to go to the explosives and weapons forum and look for that thread and or person. Mainly because I am a secondary
source and going off from memory isn't the greatest.
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kazaa81
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here maybe there is the post you were talking about :
posted by Alchmist on July 22nd, 2002
Potassium & Ammonium Nitramide
Hello all,
The other night I dreamed I made Potassium Dinitramide (KDN) and Ammonium Dinitramide at home and it worked. Here are the details of my dream.
Precursors are:
70.35 grams of Sulfamic Acid, this can be bought at most hardware stores as grout and tile cleaner.
53 grams of Potassium Hydroxide, I got mine at a industrial cleaning supply house. I do NOT know if Sodium Hydroxide will work as yet!
264 ML of 95% Ethanol, mine was home made.
45 ML of 90-95% Nitric acid, again home made.
16 ML of 98% Sulfuric Acid, hardware store drain cleaner.
Approx. 10 ML of Acetone from the hardware store.
100 ML of 99% Isopropyl Alcohol.
DRY ICE as needed!
Step 1 otassium salt of Sulfamic Acid
Procedure:
Prepare a suspension by adding 70.35 grams of sulfamic acid into 50 milliliters of water. Prepare a second mixture by dissolving 44 grams of potassium
hydroxide into 50 milliliters of water. Thereafter, add the potassium hydroxide solution to
the sulfamic acid suspension with rapid stirring. After which, pour the entire mixture into 214 milliliters of 95% ethanol while stirring the ethanol.
After which, filter-off the precipitated potassium salt of sulfamic acid, wash with 50 milliliters of 95% ethanol, several times using the same
washing portion, and then vacum or air-dry the product. After the product has been sufficiently dried, grind it up into a fine powder for use in step
2.
Step 2reparation of potassium dinitramide
Place 45 milliliters of 90% nitric acid into a beaker, and then add 16 milliliters of 98% sulfuric acid. Thereafter, cool the acid mixture to -30
Celsius by mean of a dry ice/acetone bath.
Then, carefully, and gradually add 17 grams of the potassium salt of sulfamic acid (prepared in step I), in 500-milligram portions, to the nitrating
acid mixture over a period of about 20 minutes. During the addition, rapidly stir the nitrating acid mixture and maintain its temperature at -30
Celsius. After the addition(20 minutes), immedially pour the entire reaction mixture into a beaker filled with 150 grams of crushed ice and 150
millilitcrs of water. Immediatly thereafter, place this ice water mixture into a dry ice/acetone bath, and then rapidly add 9 grams of a cold
potassium hydroxide solution prepared by dissolving 9 grams of potassium hydroxide into 20 milliliters of ice-cold watcr. During the potassium
hydroxide addition, rapidly stir the reaction mixture while keeping its temperature below 0 Celsius. Note. the solution should tum a greenish-yellow
color. After the addition of the potassium hydroxide, place the reaction mixture into rotary evaporator, and evaporate-off the water under vacuum
until dry solid remains. If rotary evaporator is unavailable, place reaction mixture into a shallow pan, and then blow air over the surface until dry
solid remains. When dry solid remains, recover the dry solid, and then mix with 10 milliliters of acetone, and then add 100 milliliters of isopropyl
alcohol. Then stir the mixture rapidly for several minutes. After which, place the mixture into a clean rotary evaporator, and evaporate-off the
acetone, and some of the isopropyl alcohol under vacuum. If a rotary evaporator is unavailable, place the mixture into a distillation apparatus, and
carefully distill-off the acetone and some of the isopropyl alcohol. Once the acetone has been removed, stop the evaporation, and then cool the
mixture to room temperature. When the acetone is removed, the KDN will
precipitate. Thereafter, filter-off the precipitated KDN, and then vacuum dry or air-dry the product. The result will be about
10.7 grams of relatively pure KDN.
To make Ammonium Dinitramide mix a solution of KDN in water, with a solution of Ammonium Sulfate in water. Stir for several minuites then addl
Isopropyl Alcohol and continue to stir for several more minutes ! Then filter off the Potassium Sulfate and let the Ammonium Dinitamide air dry. Then
redisollve in Isopropyl again and air dry a secound time!
*** If you try this please give me your feed back on how it worked for you.
*** MEGA, this would be a good one for your sight!
P.S., this is almost a exact copy of U.S. pat. # 5,976,483. I used the same quanities as they did. I wanted it to be like there's for my first test.
One change was to use Acetone in the freezing bath. The only point here though is to get the temp. to -30 degree's C.
The important factors seem to be the temp's and VERY good stirring! A good mechanical stirer would be a benifit here!
See the pat. for even more details.
This stuff is great and I think better than or as good as Chlorate and Perchlorate!
More later!!!
[ July 23, 2002, 03:31 PM: Message edited by: Alchemist ]
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AndersHoveland
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Ammonium dinitramide, with the structure NH4[+] [-]N(NO2)2, is an energetic oxidizing salt which has been investigated for use in propellents. It is,
however, significantly more sensitive to detonation than ammonim perchlorate during combustion. Ammonium dinitramide with aluminum powder has about an
11% higher specific impulse than ammonium perchlorate.
Below are five different preparation routes for the compound:
Preparation A
17g potassium sulfamate was added in small portions (0.5- 1 g ) to a mixture of 16mL 98% concentrated sulfuric acid and 45 mL fuming nitric acid, with
continual stirring of the mixture. The mixture was kept between (minus) -35 and -45 degC, using an ice bath consisting of dry ice and methylene
chloride. (The reaction temperature need only be below -25 degC, if care is taken to avoid overheating) The viscocity increased as the reaction
proceeded, and potassium bisulfate precipitated. Dinitramidic acid is not stable under acidic conditions so the pH must subsequently be raised to
avoid decomposition. A solution of cold potassium hydroxide was slowly added to the reaction mixture, again with constant stirring, with the mixture
still cooled in the ice bath. The temperature was not allowed to rise above 0degC. The solution becomes a greenish yellow color, indicating that the
acids in solution are nearly neutralized. Further solution of potassium hydroxide was added until the pH reached 8 (weakly basic).
The reaction mixture allowed to evaporate until dry. The dry powder remaining was extracted with acetone, then 100mL pure isopropyl alcohol was added
to the acetone solution. The mixture is again allowed to evaporate. As the acetone first evaporates out, the potassium dinitramide will precipitate
out of the isopropyl alcohol. The crystals were filtered from the solution and dried in an oven at 70 degC. 10.7 grams (60% yield) of potassium
dinitramide is obtained from this procedure. The crystals melt at 130.5 degC.
1g potassium dinitramide and 1g ammonium sulfate were individually dissolved in two separate portions of 2mL water each. The two solutions were then
mixed, resulting in a white precipitate of potassium sulfate. 20mL of isopropyl alcohol was added to the solution, then the potassium sulfate was
filtered out. The remaining solvent that passed through the filter was evaporated under reduced pressure. The product from the evaporation was
slightly moist. It was next dissolved in more isopropyl alcohol. This solution was poured into petroleum ether, at which point ammonium dinitramide
precipitated out. The precipitate was filtered out and dried at 50degC. 0.68 grams ammonium dinitramide is obtained from this procedure (80% yield).
The crystals have a melting point of 91 degC.
Note
Maximum yields of dinitramidic acid were obtained when he mole ratios of sulfuric to nitric acid are 2 : 7, with a nitration time between 23-25
minutes.
Preparation B
Alternatively, ammonium sulfamate may be used in the nitration, and ammonium hydroxide can then be used to neutralize the mixture. This more direct
procedure, however, gives only a 40% yield, and the ammonium dinitramide will contain ammonium nitrate impurities, which lowers the observed melting
point to 86degC.
Sulfamic acid has the formula HOSO2NH2, and its salts can be prepared from the pyrosulfate (K2S2O7) with dry NH3 gas, or by direct reaction between
SO3 and NH3 (reaction is extremely violent!)
Preparation C
Into a 250 mL Erlenmeyer flask combine 3 g of potassium dinitramide and 3 g of finely powdered ammonium sulfate. Add 100 mL of isopropyl alcohol and
heat the flask, while stirring, until all of the solids dissolve. Place the flask in a cold water bath to precipitate the byproduct of potassium
sulfate. Filter to remove the crystals of sulfate and gently heat the filtrate to concentrate it to a fraction of its volume. Pour the concentrate
into a beaker containing an excess of petroleum ether to precipitate ammonium dinitramide. Filter to collect the crystals and dry them in an oven at
50 C.
Preparation D
Prepare a mixture of 7.5 g of ammonium N-nitrourethane suspended in 200 mL of methylene chloride. Cool this mixture to -50 C in an acetone-dry ice
bath. Prepare a second mixture of 45 mL of dinitrogen tetroxide in 200 mL of dry methylene chloride. Cool this mixture to -78 C in an acetone-dry ice
bath. Bubble ozone into the second mixture, while stirring, until it is a dark blue color. While bubbling the ozone allow the mixture to warm up to
-30 C. The mixture will now consist of dinitrogen pentoxide in methylene chloride.
Combine the two mixtures and let them sit for 1 hour. During this time the temperature of the reaction mixture is allowed to warm to -30 C. Bubble
ammonia gas into the mixture to raise the pH to 10. Filter to collect any insoluble material and add it to a beaker containing 150 mL of acetonitrile.
Stir the acetonitrile mixture for 20 minutes before filtering to remove any remaining undissolved impurities.
The filtrate is poured into a 2.5cm by 10cm column containing 230-400 mesh silica gel. The ammonium dinitramide is eluted by adding acetonitrile. The
resulting eluted filtrate is concentrated to 30 mL and treated with 30 mL of chloroform to precipitate pure ammonium dinitramide. The crystals are
filtered to collect them and allowed to dry. Final yield is about 4 g or 60%.
Preparation E
Prepare a mixture of 8.8 g of hydrofluoric acid and 40 g of ethylnitrate in 300 mL of dry nitromethane. Place this mixture in a salt-ice bath and cool
to 10 C. Slowly add 100 g of boron trifluoride to the mixture while keeping the temperature between 10 and 15 C. A few minutes after the addition
filter to collect the crystals of nitronium tetrafluorate that form. Wash the crystals with two 400 mL portions of a 1:1 mixture of methylene chloride
and nitromethane, and then with one 400 mL portion of methylene chloride.
Place the nitronium tetrafluorate crystals into a beaker containing 400 mL of methylene chloride. Cool the contents to -78 C in an acetone-dry ice
bath. Bubble 35 g of anhydrous ammonia into the beaker over a period of 2 hours while stirring. Continue stirring the mixture for 12 hours while
allowing it to warm to room temperature. Filter to collect the solid material and wash it with 400 mL of methylene chloride. Add the crystals to 150
mL of acetone and stir for 1 hour. Add 150 mL of ethyl acetate to the mixture and filter to remove any undissolved material. Gently heat the filtrate
solution to dryness to obtain crude ammonium dinitramide. The ammonium dinitramide can be purified by recrystallizing from n-butanol. Final yield is
about 5.5 g or 21% yield.
Note about the Preparation of Nitronium Tetrafluoroborate
Nitronium tetrafluoroborate is a useful nitrating agent which has several advantages over nitric acid. There are also some nitration reactions where
the presence of the nitrate ion would prevent the desired product from forming. Nitronium tetrafluoroborate is a solid ionic compound, with the
formula NO2(+) BF4(-). Nitronium tetrafluoroborate can be prepared by adding a mixture of anhydrous hydrogen fluoride gas and boron trifluoride to a
solution of either highly concentrated nitric acid or nitrogen pentoxide dissolved in nitromethane.
WARNING: Rubber gloves, an apron, and a plastic face mask are strongly recommended. All operations should be carried out in a hood. If hydrogen
fluoride comes in contact with the skin, the contacted area should be thoroughly washed with water and then immersed in ice water while the patient is
taken to rushed to the emergency department. Burns caused by hydrogen fluoride may not be noticed for several hours, by which time serious tissue
damage may have occurred.
Note: Any operations involving liquid hydrogen fluoride must be carried out with equipment resisting hydrogen fluoride, such as fused silica,
polyolefin, monel steel, or teflon. Kel-F grease is recommended for ground-glass joints. Nitronium tetrafluoroborate slowly attacks silicone stopcock
grease, causing air to enter the flask. After completion of the reaction, all equipment should be washed with plenty of water.
A 1-Liter three-necked polyolefin flask is provided with a short inlet tube for nitrogen, a long inlet tube for gaseous boron trifluoride, a drying
tube, and a magnetic stirring bar. The flask is immersed in an ice-salt bath and flushed with dry nitrogen. Under a gentle stream of nitrogen and with
stirring, the flask is charged with 400 ml. of methylene chloride, 41 ml. (65.5 g., 1.00 mole) of red fuming nitric acid (95%), and 22 ml. (22 g.,
1.10 moles) of cold, liquid, anhydrous hydrogen fluoride. 5. It is convenient to condense anhydrous hydrogen fluoride, b.p. 19.5°, from a cylinder
into a small calibrated polyolefin flask immersed in a mixture of dry ice and acetone. As hydrogen fluoride is very hygroscopic, it should be
carefully protected from atmospheric moisture, preferably by maintaining an atmosphere of dry nitrogen over it, otherwise by means of a drying tube.
The hydrogen fluoride is then simply poured into the reaction flask.
Gaseous boron trifluoride (136 g., 2.00 moles) from a cylinder mounted on a scale is bubbled into the stirred, cooled reaction mixture. (The
temperature of the reaction is not critical, but the reaction is slower at higher temperatures because of the lower solubility of boron trifluoride in
the solvent). The first mole is passed in rather quickly (in about 10 minutes). When approximately 1 mole has been absorbed, copious white fumes begin
to appear at the exit, and the rate of flow is diminished so that it takes about 1 hour to pass in the second mole; even at this slow rate, there is
considerable fuming at the exit. After all the boron trifluoride has been introduced, the mixture is allowed to stand in the cooling bath under a slow
stream of nitrogen for 1.5 hours. The mixture is swirled, and the suspended product is separated from the supernatant liquid by means of a
medium-porosity, sintered-glass Buchner funnel. Note that since free hydrogen fluoride is no longer present, filtration can be carried out with glass
or porcelain equipment.
The gooey solid remaining in the flask is transferred to the funnel with the aid of two 50-ml. portions of nitromethane. The solid on the funnel,
nitronium tetrafluoroborate, is washed successively with two 100-ml. portions of nitromethane and two 100-ml. portions of methylene chloride. In order
to protect the salt from atmospheric moisture during the washing procedure, suction is always stopped while the salt is still moist. The moist salt is
transferred to a round-bottomed flask and dried by evaporating the solvent. At the end of the procedure the flask can be gently heated to 40–50°C
(Nitronium tetrafluoroborate is thermally stable up to 170°. Above this temperature it starts to dissociate into nitryl fluoride and boron
trifluoride.) The yield of colorless nitronium tetrafluoroborate is 85–106 g. (64–80%) It is stored in a wide-mouthed polyolefin bottle with a
screw cap. The edge of the cap is sealed with paraffin wax after it is screwed on. Nitronium tetrafluoroborate is very hygroscopic. It is stable as
long as it is anhydrous, but it is decomposed by moisture, and all transfers should be in a dry box.
Nitronium tetrafluoroborate slowly attacks polyethylene and polypropylene, but apparatus made of these materials will last for several preparations of
the salt.
The last part of the procedure can be used to purify nitronium tetrafluoroborate that has picked up water on standing. The impure salt is washed twice
with nitromethane, twice with methylene chloride, and is dried under reduced pressure.
Making Boron Trifluoride BF3
Boron trifluoride is a very toxic gas, which readily reacts with water to form metaboric acid and Fluoroboric acid, which then can further hydrolyze
if excess water is present. It is a strong fluoride ion abductor, meaning it will pull a fluorine atom from many covalent compounds to form the
tetrafluoroborate anion (BF4-), while leaving a positively charged cation. However, boron trifluoride is not as powerful of an abductor as antimony
pentafluoride, as demonstrated by its unreactivity towards trichlorofluoromethane.
Boron trifluoride may be prepared by heating a mixture of boric oxide and calcium fluoride with concentrated sulfuric acid. It may also be prepared by
mixing 5 parts of potassium borofluoride (KBF4) with 1 part finely powdered boric oxide, then heating with concentrated sulfuric acid. The boron
trifluoride, can be collected over mercury. Potassium borofluoride may be produced by heating together 2 parts boric acid, 5 parts CaF2, and 10
parts conc H2SO4. The liquid is then cooled and filtered, and a solution of a potassium salt is added. Potassium borofluoride precipitates out, and
may then be recrystallized from hot water. By this method it can be prepared as anhydrous hexagonal crystals. If it is prepared instead from
hydrofluoric acid, boric acid, and K2CO3, a gelatinous mass forms instead, which however forms cubic octahedral and cubic dodecahedral crystals when
heated to 100degC. Boron trifluoride also results from heating a mixture of boric oxide and calcium fluoride to a white heat in an iron pipe. Heating
solid borofluorides to red heat, boron trifluoride is evolved, leaving behind metal fluorides.
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quicksilver
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What were the source documentation from which these (five above) Ammonium dinitramide synthesis were extrapolated?
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AndersHoveland
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found some interesting information about the dinitramide salt of cesium:
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Cesium dinitramide has a melting point of 87 °C followed by the onset of exothermic decomposition at 175°C. Its density is 3.05 g/cm3.
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hydrazinium dinitramide is highly shock (impact) sensitive and thus has no practical value.
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Hydrazinium nitroformate has a is not as sensitive, having a sensitivity to friction value above 20 Newtons, and sensitivity to shock value above 2
Joules.
Another source describes hydrazinium nitroformate as having a friction sensitivity between 14-36 N, an impact sensitivity of 2-15 Joules. Density:
1.85 g/cm3. Melting with decomposition at 110-124°. The salt may have thermal stability problems above 71°C.
[Edited on 16-2-2012 by AndersHoveland]
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Dany
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Optimization of Ammonium Sulfamate Nitration for the Preparation of Ammonium Dinitramide
CEJEM, 2014, 11(1), 83-97
http://www.wydawnictwa.ipo.waw.pl/cejem/Vol-1-Number-1-2014/...
Dany.
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