User:Nippoo/Chemistry

This is just a little page with sections copied from various places along Wikipedia detailing some interesting chemical manufacturing processes (I've rephrased, reformatted or generally cleaned up quite a few of them). I intend to reformat these slightly, test some of them (I'll perhaps give Nitroglycerine and the other explosives a miss!) and stick the finished instructions back on their respective pages if anything needs editing. Mostly, though, it's just a self-reference for my own viewing pleasure.

Explosives

These chemicals generally fall under a few other categories but are mostly used as explosives so I'll leave them here.

Nitroglycerine

Required chemicals / apparatus

• HNO₃ (nitric acid)
• H₂SO₄ (sulphuric acid)
• Glycerol
• Salt-ice bath
• 1000mL beaker
• Jug of ice water
• Glass burette
• Separatory funnel
• Glass rod
• Thermometer
• Safety equipment, minimally including heavy leather gloves, impact-resistant goggles, hearing protection, and face shield.

Synthesis

As with other reactions that pose the risk of explosion, synthesis should not be performed in an enclosed area. Nitroglycerine is prepared by nitration of glycerol (also known as glycerin).

First, you must create a nitrating solution. Slowly mix 200 ml of 98 to 100% nitric acid with 300 ml of 98-100% sulphuric acid into a 1000 ml beaker which is submersed in a salt-ice bath. Make sure to cool down the mixture to 10 °C before the next step.

Next, add 112 ml of glycerol, which has previously been cooled to 15 °C, very slowly (i.e. drop by drop using a burette suspended over the beaker) to the nitrating solution. Slowly stir it, with extreme care not to tap the stirring device against the side of the beaker, as the impact of the stirring rod against the container has been known to create enough pressure to detonate the nitroglycerin. Carefully monitor the temperature while adding the glycerol; the temperature should never rise above 20 °C and should be kept below 15 °C as a safety precaution. If the temperature starts rising, stop adding glycerol and stir slowly until the temperature goes back down.

Keep a jug of ice water nearby and if at any time the temperature rises above 20 °C or red fumes are noticed, carefully dump the solution into the ice water immediately. Once all of the glycerol has been added, let the mixture cool down to 15 °C and let it stand for 15 minutes. Then pour this mixture into a large container containing an equal amount of water at room temperature. Add this mixture to a separatory funnel. The nitroglycerine will settle onto the bottom of the funnel.

Drain out the nitroglycerine layer and then add to a clean funnel, with plenty of water at approximately 38 to 45 °C and wait for it to separate. Then, drain out the nitroglycerine layer again. Repeat the washing process above with a 4% sodium carbonate solution instead of water. Then wash with water again three more times. Give it one more wash with a concentrated sodium chloride solution and then test with litmus for acidity. It should be neutral or it will explode. Keep washing until it tests neutral with litmus.

Trinitrotoluene / TNT

Required chemicals / apparatus

• HNO₃ (nitric acid)
• H₂SO₄ (sulphuric acid)
• Toluene
• Salt-ice bath
• 500mL beaker
• 600mL beaker
• Glass pipette or burette
• Separatory funnel
• Buchner funnel
• Glass rod
• Thermometer
• Safety equipment, minimally including heavy leather gloves, impact-resistant goggles, hearing protection, and face shield.

Synthesis

As with other reactions that pose the risk of explosion, synthesis should not be performed in an enclosed area. TNT is also created by nitrating toluene.

Prepare a nitrating solution of 160 mL of 95% sulphuric acid and 105 mL of 75% nitric acid in a 500-mL beaker set in a salt-ice bath. Mix the acids very slowly to avoid the generation of too much heat. Allow the mixture to cool to room temperature. Slowly add the nitrating solution dropwise, with a pipette or burette, to 115 mL of toluene in a 600-mL beaker while stirring rapidly. Maintain the temperature of the beaker during the addition at 30-40 °C by using either a cold water or salt-ice bath. The addition should require 60-90 minutes. After the addition, continue stirring for 30 minutes without any cooling, then let the mixture stand for 8-12 hours in a separatory funnel. The lower layer will be spent acid and the upper layer should be mononitrotoluene. Drain the lower layer and keep the upper layer.

Dissolve one-half of the previously prepared mononitrotoluene and 60 mL of 95% sulphuric acid in a 500-mL beaker set in a cold water bath. Prepare a nitrating solution of 30 mL of 95% sulfuric acid very slowly and 36.5 mL of 95% nitric acid in a 100-mL beaker. Preheat the beaker of mononitrotoluene to 50°C. Add the nitrating acid to the beaker of mononitrotoluene drop by drop while stirring rapidly (with a pipette or burette). Regulate the rate of addition to keep the temperature of the reaction between 90-100 °C. The addition will require about 1 hour. After the addition, continue stirring and maintaining the temperature at 90-100 °C for 2 hours. If the beaker is allowed to stand, a layer of dinitrotoluene will separate. It is not necessary to separate the dinitrotoluene from the acid in this step.

While stirring the beaker of dinitrotoluene, heated to 90 °C, slowly add 80 mL of 100% fuming sulphuric acid, (containing about 15% SO3), by pouring from a beaker. Prepare a nitrating solution of 40 mL of 100% sulfuric acid, with 15% SO3, and 50 mL of 99% nitric acid. Very slowly add the nitrating acid to the beaker of dinitrotoluene, with a pipette or burette, drop by drop while stirring rapidly. Regulate the rate of addition to keep the temperature of the reaction between 100-115 °C. It may become necessary to heat the beaker after three-quarters of the acid has been added in order to sustain the 100-115 °C temperature. The addition will require about 90-120 minutes.

Maintain the stirring and temperature at 100-115 °C for 2 hours after the addition is complete. Allow the beaker to sit undisturbed for 8-12 hours. It should form a solid mass of trinitrotoluene crystals. Pour the contents of the beaker over a Buchner funnel without any filter paper to collect the bulk of the crystals, save the acidic filtrate as well. Break up the collected crystals and wash them with water to remove any excess acid. Add the collected acid and wash filtrates to a large volume of water, this will cause any remaining trinitrotoluene to precipitate. Decant off as much of the water as possible and combine these crystals with the previous ones on the funnel. Drown the crystals in a large volume of water, filter to collect them, and wash several times with water (by adding them to a beaker of water, heating the water enough to melt the crystals while stirring rapidly).

Repeat the melting and stirring with a fresh batch of water three or four times to wash thoroughly. After the last washing, granulate the trinitrotoluene by allowing it to cool slowly under hot water while continuing to stir. Filter to collect the crystals and allow to dry.

The TNT can be further purified by recrystallizing it from ethyl alcohol, (by dissolving the crystals in 60 °C ethyl alcohol and allow the solution to cool slowly. A second method of purification is to digest the TNT in 5 times its weight of 5% sodium bisulfite solution heated to 90 °C while stirring rapidly for 30 minutes. Wash the crystals with hot water until the washings are colourless, then allow the crystals to granulate as before.

Acetone peroxide

Required chemicals / apparatus

• 3% H₂O₂ (hydrogen peroxide)
• 2-Propanone / Acetone
• H₂SO₄ (sulphuric acid)
• Glass thermometer
• Glass eyedropper
• Glass beaker
• Ice bath / Dry ice (CO₂)
• Safety equipment, minimally including heavy leather gloves, impact-resistant goggles, hearing protection, and face shield.

Synthesis

As with the reactions that pose the risk of explosion, synthesis should not be performed in an enclosed area.

Before beginning the synthesis procedure, you should put the hydrogen peroxide and 2-Propanone in a refrigerator for several hours. This will speed up the procedure.

Once several hours have passed, prepare an ice bath for the glass beaker. Pouring a small amount of water around the beaker with plenty of ice seems to work well, as the cold water will surround the beaker better than the ice alone.

If the quantity of 2-propanone in your posession is sufficient, it may be desirable to utilize it in a more effective form of cold bath for the reaction. Instead of an ice bath, one may substitute a container filled with 2-propanone, cooled by small amounts of CO₂ in solid form (dry ice). This mixture can be cooled to temperatures very well below the normal freezing point of water, thus making it possible to more easily restrict the temperature of the reaction.The cooling is acheived by placing the CO2 in small amounts at a time into the solution and allowing them to sublime, thus cooling the 2-Propanone. However, be extremely careful with this cold bath! 2-Propanone is very flammable and will irritate skin and eyes. Also, since the bath is cooled to well below water's freezing point, touching the liquid could cause instant freeze burns and/or frostbite. Never touch this solution with unprotected skin!

For a safer synthesis, you may choose to skip the step of concentrating the peroxide and use the 500mL 3% H₂O₂ as is in the actual reaction. It is highly recommended that amateurs not attempt to concentrate it down to below 150 mL as hydrogen peroxide of that concentration can easily ignite.

Put 500mL H₂O₂ in a glass beaker, and slowly boil it down to about 100-250mL. Keep the temperature below 302 °F (150 °C) to prevent boiling. Do not raise the temperature past 212 °F (100 °C). The goal is to lightly boil away the water in the H₂O₂, leaving a purer form of H₂O₂. Once you have concentrated the H₂O₂, take it off of the heat and allow it to cool.

Do not allow the solution to evaporate to leave less than 80 mL as the peroxide could spontaneously combust. If any solution remains after the experiment it should be diluted in a litre of water otherwise it risks combustion.

Put the H₂O₂ into the beaker in the ice bath, and add 60mL chilled 2-Propanone. Measure the temperature of the liquids with a thermometer and wait for it to drop to around 40 °F (4.4 °C). Using a glass eyedropper, slowly add 15mL H₂SO₄. Monitor the temperature closely while adding the H₂SO₄, if the temperature gets around 50 °F (10 °C), quit adding the H₂SO₄. Failure to quit adding the H₂SO₄ when the temperature rises will cause to solution to stop producing AP. There will be a slight temperature rise during the addition of H₂SO₄; this is why the adding of the H₂SO₄ must be done slowly. If the H₂SO₄ is added too quickly, it will not have time to create the proper peroxysulfuric acid; in this scenario you will not produce any precipitate.

When all of the H₂SO₄ has been added, stir the mixture for about 15 minutes. After 15 minutes, place the reaction mixture into a refrigerator for about 24 hours. A white crystalline solid will result. This crystalline mass can then be filtered out with filter paper. When the crystalline mass has been filtered, pour 400mL of water over it to wash the acid residue away. Set the crystalline mass out to dry. The crystalline mass is tricycloacetone peroxide. If you did the reaction above 50 °F (10 °C), you will have the very unpleasant dicycloacetone peroxide remaining.

This final crystalline mass is very sensitive when dry (its friction sensitivity can be as low as .1NM). Proper care must be taken with the final crystalline mass, as it is highly unstable.

For safety, separate the crystalline mass onto paper plates at 1 gram per plate; this will greatly reduce the risk of explosion. If a problem were to occur, the one gram on one of the plates would be less likely to hurt you.

Storing acetone peroxide is not recommended, because it quickly sublimes. But if it must be stored, it is recommended that it is stored under water and in a container without a cap with threads, as opening it could result in an explosion from crystalized acetone peroxide.

Cyclonite / RDX

Required chemicals / apparatus

For standard method

• HNO₃ (nitric acid)
• Hexamine
• NAHCO₃ (sodium bicarbonate)
• 500mL beaker
• Glass thermometer
• Glass rod
• Safety equipment, minimally including heavy leather gloves, impact-resistant goggles, hearing protection, and face shield.

For E method

• NH₄NO₃ (ammonium nitrate)
• C₄H₆O₃ or (CH₃CO)₂O (acetic anhydride)
• Paraformaldehyde
• BF₃ (Boron trifluoride)
• Standard laboratory equipment
• Safety equipment, minimally including heavy leather gloves, impact-resistant goggles, hearing protection, and face shield.

Synthesis (standard method)

As with other reactions that pose the risk of explosion, synthesis should not be performed in an enclosed area.

Add 335 mL of 100% nitric acid, free of nitrogen oxides in a 500-mL beaker. Cool the acid to below 30 °C. Add 45 g of hexamine in small portions, while stirring the mixture. (During the addition toxic fumes will be produced. Perform this in a fume cupboard). During the addition the temperature must be kept between 20 °C to 30 °C.

After the hexamine has dissolved, slowly heat the mixture to 55 °C while stirring. Keep the mixture between 50-55 °C for 5 minutes, while continuing to stir. Now cool the mixture to 20 °C then let sit for 20 minutes. Slowly dilute the mixture with four times its volume of cool water to precipitate the RDX from solution. Most of the RDX will precipitate in several hours; after 24 hours there will be no additional precipitation of RDX. Filter the RDX which precipitated from the mixture and add 1 L of 5% sodium bicarbonate solution to adjust the pH to neutral. Dry the pH balanced RDX at room temperature; after drying the RDX is ready to use.

If RDX of higher purity is desired, recrystalize from acetone.

Synthesis (E method)

This way of synthesizing RDX is called the "E method" (named so by Ebele) and has a different approach to the synthesis. Again, synthesis should not be performed in an enclosed area.

The precursors for this method of synthesis are ammonium nitrate, acetic anhydride and paraformaldehyde. No nitric acid is needed. The yield of the process is 60 - 65%, although it can be as high as 80% on small scale production. The Boron trifluoride is also needed as the catalyst that reduces the quantity of by-products.

Warm 260 ml of acetic anhydride to 60 - 65°C and add 0,4% of Boron trifluoride (BF₃). Slowly add 105 g of ammonium nitrate while stirring. Remove the source of heat and keep the temperature 60 - 65°C. Slowly add paraformaldehyde (be careful because toxic and flammable fumes are released).

After the reaction has stopped put the product into distilled water to precipitate the crystals of RDX.

Methyl ethyl ketone peroxide

Required chemicals / apparatus

• 40mL 27.5% H₂O₂ solution (hydrogen peroxide)
• 25mL CH₃COCH₂CH₃ (methyl ethyl ketone - sold as a solvent in shops) [beware - this will dissolve most plastics. Use a glass syringe!]
• 5mL 98% H₂SO₄ (sulphuric acid)
• 200mL NaHCO₃ solution
• 2x 100mL beaker
• 300mL beaker
• Glass syringe
• Glass rod
• Standard laboratory equipment
• Safety equipment, minimally including heavy leather gloves, impact-resistant goggles, hearing protection, and face shield.

Synthesis (anhydrous dimeric form - appears as an oily liquid, more stable but more powerful)

As with other reactions that pose the risk of explosion, synthesis should not be performed in an enclosed area.

Place 25mL of methyl ethyl ketone in a 100mL beaker. Place this beaker in an ice bath at temperatures ranging preferrably from -10 to 5°C; the lower end of the described recommended temperature range is preferable. (To achieve this, you can use dry ice) Then, place 40mL of 27.5% H2O2 solution in a 100mL beaker. Place this beaker in an ice bath at temperatures ranging preferably from -10 to 5°C; the lower end of the described recommended temperature range is preferable. Wait for the temperature of both the methyl ethyl ketone and the temperature of the 27.5% H2O2 solution to fall into the recommended temperature range. Then, pour the beaker of methyl ethyl ketone into the beaker of hydrogen peroxide solution. Stir this solution for thirty seconds.

Add 5mL of 98% sulphuric acid slowly, drop by drop, taking care to keep temperatures within the recommended temperature range, into the beaker containing the monomeric methyl ethyl ketone peroxide. If the temperature rises above 5°C, stop adding the sulphuric acid immediately.

After all of the sulphuric acid is added, wait 24 hours. It is highly recommended to attempt to keep the temperatures within the recommended temperature range during the entirety of every step (this is a very common mistake made when attempting to make trimeric acetone peroxide; most will not bother to keep the temperatures around zero degrees Celcius while waiting 24 hours or so for the reaction to complete; the result of that is far less stable acetone peroxide due to lower yields of the trimeric form and higher yields of the dimeric form).

The beaker should by now have two layers; a thick oily layer on the top, and a translucent white, relatively thin liquid on the bottom. The thick oily layer on top is the anhydrous dimeric methyl ethyl ketone peroxide. All traces of acid must now be removed. Pour this beaker into a 300mL beaker. Then slowly add 200mL of NaHCO3 solution. Stir vigorously for five minutes; try to keep the size of the pockets of the oily liquid (the anhydrous dimeric methyl ethyl ketone peroxide) as small as possible when stirring. Most of the anhydrous dimeric methyl ethyl ketone peroxide will now begin to sink to the bottom of the beaker. Extract it with a syringe. Some will also remain on the surface; extract this also with a syringe (it is possible to isolate the anhydrous dimeric methyl ethyl ketone peroxide by decantation, but this process can be very time consuming, frustrating, and you will not be able to harvest nearly as much of the anhydrous dimeric methyl ethyl ketone peroxide as bythe syringe extraction method).

If you wish to further deacidify the anhydrous dimeric methyl ethyl ketone peroxide, place it in an airtight aluminum container, in an ice bath (extremely important!). Leave the methyl ethyl ketone peroxide in the airtight aluminum container until bubbles no longer form. A safer alternative to this process is to add non-crumpled pieces of aluminum foil to the anhdrous dimeric methyl ethyl ketone peroxide (also in an ice bath); however this will often make it difficult to recollect all of the anhdrous dimeric methyl ethyl ketone peroxide, due to it sticking to the pieces of aluminum foil; it can be very difficult to remove from that surface.

Now pour the deacidified anhydrous dimeric methyl ethyl ketone peroxide into an open glass, or plastic (not made of a polyhydrocarbon plastic!). Let it stay in the open at temperatures around 15°C to allow most of the water to evaporate off. Now that the anhydrous dimeric methyl ethyl ketone peroxide is dehydrated, it is ready for use.

Even though it is not recommended to store MEKP for a long time, if need be you can pour the anhydrous dimeric methyl ethyl ketone peroxide into a sealed plastic container (not made of a polyhydrocarbon plastic!) for storage. The reason for sealing it is to prevent loss of anhydrous dimeric methyl ethyl ketone peroxide due to evaporation. The lower the temperatures are during storage, the better, with the exception of temperatures so low that it freezes the anhydrous dimeric MEKP.

Miscellaneous

An example of gallium crystals grown using this technique. Courtesy of Foobar

Gallium

Required chemicals / apparatus

Minimal

• >50g (99.99%+) Ga (gallium)
• Sealable (transparent) plastic container

Recommended

• Cloth
• Temperature-controlled plastic box
• Vibration-damped sandbox

Crystallization

You need to obtain at least 50 grams of highly pure (99.99%+) gallium metal, as impurities rapidly destroy its ability to form large crystals. I say 50 grams because anything less cools too quickly and isn't nearly as visually impressive. This experiment should ideally be performed in a vibration-damped environment just below the melting point of gallium (about 29.7 °C). Put the metal in a sealable transparent plastic container (ideally on top of a sandbox if you want to obtain visually perfect crystals). Melt the gallium completely, then leave it to cool and solidify. Measure the amount of time required for it to completely solidify with a stopwatch. Set a timer for 3/4 of that time, then remelt it, leave it to cool, and when the timer bleeps, tilt the container so that the liquid gallium runs out from underneath the solid gallium, hopefully revealing your crystals. Let the remainder solidify, and you're done.

If it doesn't form crystals, it's being cooled too quickly, or there wasn't a good seed crystal available. To combat the former, lightly insulate the container with some cloth; to combat the latter, swirl the gallium around as it's being melted and stop melting it when there's a small amount of solid mass left inside. If you have access to a precisely temperature-controlled enclosure (around 0.1-0.5 degree precision), this becomes far easier, as you set the enclosure to just below the melting point of gallium and wait.