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Author: Subject: Nitromethane, nitroethane, nitropropane synthesis via industrial route
Melgar
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[*] posted on 20-4-2010 at 17:15


Yeah, it turns out oxidizing EtNH2 does not in fact give you nitroethane. It gets you acetaldehyde or acetic acid depending on how much oxidizer you add. Decarboxylating beta alanine or alanine is a decent way to get ethylamine though. And glycine should be able to be decarboxylated just as easily to form methylamine. Gee, an OTC way to easily make methylamine? I wonder who might possibly be interested in that?

I guess the plan for the propane/nitric acid reactor is still on then.
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[*] posted on 20-4-2010 at 17:40


Appearently my suggestion to you has fallen on deaf ears so once again repeat myself in hopes that you read it this time. Yes you can oxidise amines using a combination of acetone and oxone which forms the active species DMDO.

Do a search around for Tetrahedron Letters,Vol.27,No.21,pp 2335-2336,1986

A new synthesis of nitro compounds using dimethyldioxirane(DMDO)


Abstract:
Quote:
Dimethyldioxirane oxidizes primary amines to nitro compounds in a facile, mild, high yield process.

Here we report that aliphatic and aromatic primary amines are rapidly and efficiently oxidized to nitro compounds by dimethyldioxirane, DMDO. Indeed a survey of some general methods for the preparation of nitro compounds (2) suggests to us that the use of DMDO may be the method of choice. The conditions used are exceedingly mild and give the nitro compound as a solution in acetone. Table 1 summarizes our results with some representative amines.

Table 1. Oxidation of amines with Dimethyldioxirane(DMDO) (modified to fit)
Amine ==> Product = Yield (%)
n-Butylamine ==>1-Nitrobutane = 84%
sec-Butylamine ==> 2-Nitrobutane = 81%
tert-Butylamine ==> 2-Methyl-2-nitrobutane = 90%


I have the paper somewere but I ca not be bothered to look for a reference for someone that can not be bothered to read my post. You can see the yeilds are pretty good and the reagents are avalible.

The other suggestion that wizzed right on by was the use of a ketone to perform the decarboxylation. There are reports that use Carvone which can be isolated from some essential which it is by far the primary componate of. Look around and you will find some references for it.



[Edited on 21-4-2010 by Sedit]





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[*] posted on 20-4-2010 at 20:28


Quote: Originally posted by Sedit  
Appearently my suggestion to you has fallen on deaf ears so once again repeat myself in hopes that you read it this time. Yes you can oxidise amines using a combination of acetone and oxone which forms the active species DMDO.

Do a search around for Tetrahedron Letters,Vol.27,No.21,pp 2335-2336,1986

A new synthesis of nitro compounds using dimethyldioxirane(DMDO)


Abstract:
Quote:
Dimethyldioxirane oxidizes primary amines to nitro compounds in a facile, mild, high yield process.

Here we report that aliphatic and aromatic primary amines are rapidly and efficiently oxidized to nitro compounds by dimethyldioxirane, DMDO. Indeed a survey of some general methods for the preparation of nitro compounds (2) suggests to us that the use of DMDO may be the method of choice. The conditions used are exceedingly mild and give the nitro compound as a solution in acetone. Table 1 summarizes our results with some representative amines.

Table 1. Oxidation of amines with Dimethyldioxirane(DMDO) (modified to fit)
Amine ==> Product = Yield (%)
n-Butylamine ==>1-Nitrobutane = 84%
sec-Butylamine ==> 2-Nitrobutane = 81%
tert-Butylamine ==> 2-Methyl-2-nitrobutane = 90%


I have the paper somewere but I ca not be bothered to look for a reference for someone that can not be bothered to read my post. You can see the yeilds are pretty good and the reagents are avalible.

The other suggestion that wizzed right on by was the use of a ketone to perform the decarboxylation. There are reports that use Carvone which can be isolated from some essential which it is by far the primary componate of. Look around and you will find some references for it.



[Edited on 21-4-2010 by Sedit]

Gee, a reaction with a chemical that can be produced at yields of about 3% if I'm lucky... yeah, sorry if I seem to be ignoring all the pain-in-the-ass syntheses, but I want enough nitroalkanes to be able to use them for solvents and small engine fuels and such, and if I have to order $100 worth of chemicals for every 100 mL I can make, it's not worth it to me.

I do appreciate the help, but considering the title of the thread is about a SPECIFIC reaction, your response was off-topic.
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[*] posted on 20-4-2010 at 20:36


If one wants to get pissy about things the thread was started about someones death wish to aquire Nitroethane and you then brought up the topic of Ethylamine oxidation stating that it was impossible to do and I showed you otherwise.

Sorry if something is off topic from the direction you took it in but hey.... have fun with your rocket-engine...er... I mean nitroethane factory.


BTW: The persulfate + acetone production of DMDO yeilds about 3%... Maybe if one stops envisioning death traps they will see if there are other ways out there to make it. Considering that DMDO is only made that way because every lab has the materials on hand im SURE you can find higher yeilding DMDO synthesis.

[Edited on 21-4-2010 by Sedit]





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[*] posted on 21-4-2010 at 03:09


Indeed, there are other related oxidation routes based on persulfate, peroxide, or ozoned O2/air.

or low cost I suspect that the hot tube reaction of ethanol and ammonia over a catalyst is cheaper than decarboxylating amino acids. You get a mixture of the mono, di, and tri amines, but using a largish excess of NH3 enhances the mono amine ration while the di and tri amines can be recycled back into the feed stream. There's at least on thread on this method around here.

That brings up one disadvantage of the alkane nitration route. You want short contact times, a few tenths of a second, which generally means fairly high gas flow rates. And you want high propane to nitric acid ratios to minimise by products and exothermic feedback. This means you'll have a lot of propane coming out of the back end of the condenser, propane that should be recycled back into the feed stream to boost yields based on alkane consumption; and this means pumping it back into the input.


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[*] posted on 21-4-2010 at 20:49


Quote: Originally posted by not_important  
That brings up one disadvantage of the alkane nitration route. You want short contact times, a few tenths of a second, which generally means fairly high gas flow rates. And you want high propane to nitric acid ratios to minimise by products and exothermic feedback. This means you'll have a lot of propane coming out of the back end of the condenser, propane that should be recycled back into the feed stream to boost yields based on alkane consumption; and this means pumping it back into the input.

You don't have to dilute with propane. They do it in industry because it's really easy to just feed any unreacted propane back in through the front, but diluting with water or N2 works well too. Also, operating the reaction at lower pressures lowers the reaction speed, which requires a lower flow rate.

The oxygen in the air would increase the reaction rate, and also produce stuff like ethanol, propanol, acetaldehyde, acetic acid, formaldehyde, etc. At some point, I'd probably try adding oxygen to the system then see how feasible it is to separate out the different products. It may not be very feasible, in which case I'd stick to propane and nitric acid.

[Edited on 4/22/10 by Melgar]
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[*] posted on 22-4-2010 at 20:36


you wouldnt catch me making a propane bomb thats for sure.

if I wanted nitro I would buy it or at a pinch I would use silver nitrite.

ketene was more than enough fun for this poor little bee.

I think you will find that you can make nitroethane from henry of nitromethane and formaldehyde.

dehydrate too nitroethylene then use a cat to reduce the double bond.




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[*] posted on 23-4-2010 at 06:04


Quote: Originally posted by Ephoton  
you wouldnt catch me making a propane bomb thats for sure.

if I wanted nitro I would buy it or at a pinch I would use silver nitrite.

ketene was more than enough fun for this poor little bee.

I think you will find that you can make nitroethane from henry of nitromethane and formaldehyde.

dehydrate too nitroethylene then use a cat to reduce the double bond.

Interesting reaction. Distilling nitroethanol seems a bit dangerous, and I don't have any nitromethane (though I could probably get it if I tried). My latest proposal is actually pretty safe though. It only operates at 10-20 psi and uses only 1/4 inch tubing for the reactants, so there's not too much danger of explosive reactions. This wouldn't be a bomb, (ie, a closed, pressurized vessel) since it wouldn't be closed, so not as much danger. Anyway, I'll see if I can use it for other reactions too. The molten aluminum should do a good job of conducting heat around and preventing hot spots, plus, it'd absorb or release energy at its melting temperature, which is also a good temperature for this reaction.

Well, I just got the titanium tubing, so we'll see how hard this is to build.
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[*] posted on 23-4-2010 at 06:14


good luck brother.
yes you need a special solvent to distill nitroethanol
to stop detanation from hotspots but the right solvent
and a vac and it can be distilled.

also I belive one can condense nitroethanol with an aldehyde

to recive the nitroalkene with an alcohol group on the terminal carbon of the propane chain.

this I belive though I am not sure can be dehydrated moving
the double bond in the secondary position to the terminal
position much like drones post on rhodium about dehydration

of cinnamic alcohol.

http://www.erowid.org/archive/rhodium/chemistry/cinnamyl.txt

REAGENT = Phosphoric acid
Ref = JACS 57; 1935; 151, 155



[Edited on 23-4-2010 by Ephoton]




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[*] posted on 24-4-2010 at 19:46


Thanks for the link! If this falls through, I'll definitely give it a shot. I haven't had time to build this thing yet, plus I want to contain the molten aluminum in an iron pipe, which means I have to run the titanium tube through the end caps, which means I have to drill holes in the end caps that are exactly straight, which means I need a drill press, which means I have to wait until the machine shop opens on monday. Also, I need to connect this titanium tube, which appears to be old USSR military stock, to 1/4 inch stainless steel tubing... not quite sure what that'll involve, but I'm sure I can figure something out...
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[*] posted on 25-4-2010 at 20:59


Quote: Originally posted by Melgar  
I'll post a quick sketch of the proposed reactor, since the design isn't exactly obvious. The whole thing would be behind thick plexiglass, in case there's some sort of nasty reaction, although the narrow tubing should prevent too much from reacting at a time. The pressure is controlled by changing the propane tank temperature. Initially, it would be best to have diluted HNO3, as that would slow down the reaction.

Also, I got offered a deal on .25 inch titanium tubing, and I went for it. So looks like l'm getting set to actually build this thing. And FYI, I am a mechanical engineer, so I really am qualified to design stuff like this. I would discourage anyone else from building a contraption like this too, however I have a piece of paper that says I know what I'm doing. :p


You know this sort of apparatus could probably be made portable as part of an integrated system for synthesis ......
maybe even you could install everything in an RV. All of this seems strangely familiar somehow, like deja vu .....maybe it reminds me of a TV show or something , I just can't be sure. Possibly if I listen to some music it will come to me :D

http://www.youtube.com/watch?v=S9XEGBrA99E&fmt=18
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[*] posted on 25-4-2010 at 22:15


Quote: Originally posted by Rosco Bodine  
Quote: Originally posted by Melgar  
I'll post a quick sketch of the proposed reactor, since the design isn't exactly obvious. The whole thing would be behind thick plexiglass, in case there's some sort of nasty reaction, although the narrow tubing should prevent too much from reacting at a time. The pressure is controlled by changing the propane tank temperature. Initially, it would be best to have diluted HNO3, as that would slow down the reaction.

Also, I got offered a deal on .25 inch titanium tubing, and I went for it. So looks like l'm getting set to actually build this thing. And FYI, I am a mechanical engineer, so I really am qualified to design stuff like this. I would discourage anyone else from building a contraption like this too, however I have a piece of paper that says I know what I'm doing. :p


You know this sort of apparatus could probably be made portable as part of an integrated system for synthesis ......
maybe even you could install everything in an RV. All of this seems strangely familiar somehow, like deja vu .....maybe it reminds me of a TV show or something , I just can't be sure. Possibly if I listen to some music it will come to me :D

http://www.youtube.com/watch?v=S9XEGBrA99E&fmt=18

Cops? Breaking Bad? Not sure what show you're talking about exactly. Though, partial oxidation/nitration in a titanium tube is a pretty cool, versatile reaction. I mean, even just partial oxidation of propane should give me isopropyl alcohol, ethanol, methanol, propanol, and the corresponding aldehydes, ketones, and carboxylic acids. Separating them seems like it'd be a bitch though.
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[*] posted on 26-4-2010 at 03:52


Nitromethane is easy to make.

Nitroethane is somewhat more difficult.

Naturally, if you were using Nitropropenyl benzenes as starting materials, instead of hoping to produce them as end products, your quest would be easier.

C6H6-CH=C(NO2)CH3+C6H6-CH2-NH2+heat-->C6H6-CH=N-CH2-C6H6+CH3CH2NO2(Gas)

Shulgin suggests this approach for the isolation of Myristicin Aldehyde....A material hard to find in nature. As a byproduct, it seems to produce Nitroethane in very high yield. It distills off as it is formed, in the hot reaction mixture.

I suppose other Nitro-Alkenes might also be utilized. The important factor being the ability to form a high boiling shiff's base, that allows the Nitro-ethane to be distilled off in pure form.

http://www.erowid.org/library/books_online/pihkal/pihkal132....



[Edited on 26-4-2010 by zed]
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[*] posted on 26-4-2010 at 18:03


Aw, come on. I'm not just interested in making nitroethane for making illegal drugs you know. They're really useful chemicals, all of them. So anyway, what's a good way to coat an iron pipe so you can wrap a nichrome element around it without it shorting? I was going to use this fiberglass woven cloth stuff, since its melting point is well above that of aluminum.
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[*] posted on 26-4-2010 at 19:21


Legality is a regional issue. And, indeed Nitroethane is a useful reagent.

I'm just suggesting there may be more practical ways to produce it.

As Shulgin demonstrated, nitration of an alkene, produces a nitroalkene, which can be easily used to generate nitroethane.

Very handy for producing some benzaldehydes which may not occur in nature, and producing pure nitroethane, which is hard to acquire in some vicinities.

The am unaware of the full range of nitroalkenes that could be used to generate nitroethane. And, I am not aware of every method of producing such nitroalkenes. I'm simply offering that nitroalkenes might under some circumstances, become a reasonable sources of nitroethane.

As do others, I look forward to reading about the results of your experiments in vapor phase nitration.

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[*] posted on 29-4-2010 at 11:26


I have just run through the thread, unfortunately I have nothing vlauable to contribute, but, since I am working in the chemical industry too. I decided to post my thoughts, based on industrial and home experiments.

1 Pressure type reactions at home is suicide and does not worth the risk for a few percent of impure product.

2 Any type of metal with ccHNO3 expect tantalum is attacked by HNO3, this is the major reason the home made HNO3 distilling setups to fall apart during operation:) And I never forget when I was told that "We could save costs If we made the whole nitrating unit of gold":) Apart with the joke, the whole setup should be made of glass.

I also do not understand why are you planning to control the temp with molten metals, It is absolutely impractical, I have a feeling that you have not even tried yet, after your first attempt you will also be of this opinion I guarantee!

Take a Pt100 element and calibrate it in the required region, and measure its resistance during operation, the voltage of your ohm meter does not cause temp increase during the measurement at all if you perform it within seconds.

I am eager to see your results anyway, so report back as soon as you finished, (hopefully not yourself:)
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[*] posted on 29-4-2010 at 20:19


Quote: Originally posted by Jimmymajesty  
I have just run through the thread, unfortunately I have nothing vlauable to contribute, but, since I am working in the chemical industry too. I decided to post my thoughts, based on industrial and home experiments.

1 Pressure type reactions at home is suicide and does not worth the risk for a few percent of impure product.

2 Any type of metal with ccHNO3 expect tantalum is attacked by HNO3, this is the major reason the home made HNO3 distilling setups to fall apart during operation:) And I never forget when I was told that "We could save costs If we made the whole nitrating unit of gold":) Apart with the joke, the whole setup should be made of glass.

I also do not understand why are you planning to control the temp with molten metals, It is absolutely impractical, I have a feeling that you have not even tried yet, after your first attempt you will also be of this opinion I guarantee!

Take a Pt100 element and calibrate it in the required region, and measure its resistance during operation, the voltage of your ohm meter does not cause temp increase during the measurement at all if you perform it within seconds.

I am eager to see your results anyway, so report back as soon as you finished, (hopefully not yourself:)

I've got the heating tube half-built, although I was running into problems electrically isolating the iron outer tube from the heating element. This time I'm going to try furnace cement. If that doesn't work, I may have to try some sort of enamel glaze. I'm also having trouble joining metric and SAE tubing. Anyway, to answer your questions:

1. 150 psi is not THAT high pressure, and wouldn't be that problematic as long as I purchased all components that were rated for this sort of use. Expensive, but possible. Anyway, the literature I was provided with states that there's no need to pressurize this reaction anyway, so I won't.

2. Glass is unreliable at the temperatures I want to use, at least for the reactor area. Also, just because nitric acid can attack virtually any metal, that doesn't mean it will under any conditions. Titanium, for instance, will not corrode even in the presence of aqua regia. It can corrode in the presence of nitric acid, but the nitric acid has to be really pure, and even then it's a rare occurrence. My nitric acid will be diluted to prevent this from happening, and also to moderate the reaction.

As far as controlling temperatures with molten metal, we'll see how well it works. The molten aluminum will be inside an iron pipe, so it shouldn't be that hard to deal with. One reason I wanted to use molten aluminum is because the reaction is exothermic and I wanted it to be able to deal with varying amounts of heat as I adjusted the reaction parameters. The other reason is because it conducts heat really well, and so would be nearly ideal for keeping the entire reaction tube at a constant temperature.

Anyhow, I can think of a bunch of ways to repurpose this equipment if the reaction doesn't work, so I don't feel as bad about the possibility of it not working so well.

Also, industry (at least in the developed world) is FAR more cautious than a home experimenter needs to be. For one, there's the whole liability thing. But the main reason is that in industry, they're dealing with tons of chemicals and if a reaction got out of control, well, it's easy to see how a disaster with a huge death toll could ensue. With my setup, even a catastrophic failure wouldn't be that dangerous provided I took the necessary precautions and did it outside.

Anyway, glad to have the feedback, since it makes me think critically about my own design. :)
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[*] posted on 29-4-2010 at 21:03


I think that molten Al, at 660+ C, is too hot for this purpose; I believe that temperatures above 500 C cause more side reactions.

This process can be done in ferrous alloy by first coating the tube interior with fused alkali nitrates, so exotic alloys are not needed. The industrial guys aren't using tantalum.

The product yields are reasonable, especially considering the low cost of the reactants and that most of the products can be useful to the amateur.
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[*] posted on 29-4-2010 at 21:06


Quote:
With my setup, even a catastrophic failure wouldn't be that dangerous provided I took the necessary precautions and did it outside.


Watch the most recent episode of Mythbusters. They tryed to make a rocket out of a propane tank to get an idea of that a catastrophic failure of your system would look like.

There would be a huge need for wide open spaces because the resulting "explosion" is pretty large. You can expect a pretty large crater from any failer the system may have even if it wasn't a huge fireball like one would expect.

There is some very useful information to take away from there experiment though because if you watch when the tank ruptured the resulting shockwave extinqished the flame before it had a chance to ignite the propane cloud that formed. This would be the best case but I could not imagine how large the explosion would be if the propane was able to ignite. My guess it would be simular to a Fuel air exploasion judging from the footage that Mythbusters aired.





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[*] posted on 30-4-2010 at 00:10


You can insulate your kanthal wire with calcined Al2O3 elements, or go to the junkyard and dismantle an owen for that purpose.

I do not really worry about the glass being not able to handle high temps, as I went as high as 500°C in my acetaldehyde setup (see acetaldehyde thread) and there were no problems at all at this temp even after hours, when the controller switched on, the glass pipe was take up a dull red colour, and it was made of simple lab quality glass.. borosilicate maybe I dunno.

@ not important, the nitrating unit was designed to nitrate toluene to DNT, the nitrating pots were made of tantalum, IIRC not tantalum plated onto steel, but pure tantalum.

I think you could make usefull quantities of nitro parafins with a well designed setup. But with something that can be recycled e.g.: n-hexane. The advantage with propane that it can be bubbled into nitric acid and the HNO3 content of the gas+nitrating acid mix could be controlled by the temp of the acid.

I would use a glass tube as a reactor packed with Al2O3 granules.
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[*] posted on 30-4-2010 at 09:56


Quote: Originally posted by Sedit  
Watch the most recent episode of Mythbusters. They tryed to make a rocket out of a propane tank to get an idea of that a catastrophic failure of your system would look like.

Do you see an oxygen tank anywhere in my design? No? Ok then. You're comparing apples and oranges. Without a source of oxygen, combustion is limited to the rate the fuel can mix with the air. Also, my propane tank has a regulator on it that limits the pressure to under 20 psi.

Quote: Originally posted by not_important  
I think that molten Al, at 660+ C, is too hot for this purpose; I believe that temperatures above 500 C cause more side reactions.

This process can be done in ferrous alloy by first coating the tube interior with fused alkali nitrates, so exotic alloys are not needed. The industrial guys aren't using tantalum.

The product yields are reasonable, especially considering the low cost of the reactants and that most of the products can be useful to the amateur.

If I go too low though, I'm left with a lot of unreacted "reactants". I can alloy the aluminum with zinc to lower the melting point if needed though. And how are the tubes coated in fused alkali nitrates? Sodium and potassium nitrate both decompose below 400 C.

Jimmy - Two other advantages of propane: 1) You're a lot more limited in the products you end up with, making separation easier. 2) Propane is cheap. A barbecue-sized tank is about 4.5 gallons and costs around $20. Any other relatively pure hydrocarbon besides methane is going to cost the average person a lot more.

Anyway, the titanium tube is in place, so I plan to try that first. If it had been glass, I probably would have broken it by now. :-P
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[*] posted on 30-4-2010 at 13:04


Quote: Originally posted by Melgar  
Quote: Originally posted by Sedit  
Watch the most recent episode of Mythbusters. They tryed to make a rocket out of a propane tank to get an idea of that a catastrophic failure of your system would look like.

Do you see an oxygen tank anywhere in my design? No? Ok then. You're comparing apples and oranges. Without a source of oxygen, combustion is limited to the rate the fuel can mix with the air. Also, my propane tank has a regulator on it that limits the pressure to under 20 psi.


WTF are you talking about now? Im compairing apples to fucking apples so chill with the tude my freind...

I am making mention to what it would look like in the case that your PROPANE tank ruptured. It you even bothered to look up what I was talking about you would not be getting so damn mouthy. No source of oxygen? Hmmm let me breath for a second.... oh yeh there it is.

Now with your little kiddie attitude out of the way lets get down to the basic point I was making:mad:


In the event that your rig catches fire rupturing of the Propane tank, regulator or not, is a real possibility. Albeit most of the times these are provided with a fail safe mechanism to relieve the pressure in the event this tank catches on fire the most you will get its one hell of a flame thrower. BUT since im talking about worst case senerio and why this should be done far away from any dwellings what so ever, if it did go off full force the explosion is going to be VERY large.

I would love to see you pull this off and produce a very nice writeup of it because it would open the doors to many other vapor phase reactions as well. However I do see a large case of ones Ego getting in the way of there common sense so I guess we will just have to wait and see where this thread ends up at. Finished product or just alot of hot air.

[Edited on 30-4-2010 by Sedit]





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[*] posted on 30-4-2010 at 13:51


Ah... you mentioned a rocket so I assumed an oxygen tank was part of the equation... it would have to be in order to make a rocket. Which I guess could explain why their rocket didn't work. I'm trying to think how my system could fail like that though. After all, the tank would need to be heated really hot in order to rupture and a steel tank would dissipate heat pretty quickly if it was only being heated in one spot for instance. Even if somehow the nitric acid spilled all over it and ate through it, all that would happen is propane shooting out at 80 psi or so. Again, a flamethrower but no explosion. I suppose high explosives could also do that to a propane tank, but there won't be any in the vicinity. Unless you count nitromethane, but that's harder to detonate than NH4NO3. I suppose the risks would be similar to having a barbecue on a propane grill then...
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[*] posted on 30-4-2010 at 14:01


I'd just avoid the whole issue and place the tank a ways away from the apparatus..

I'll be interested to hear how it works, good luck.
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[*] posted on 30-4-2010 at 14:28


I agree with 497 theres no real reason to have the main tank anywhere near the system and it could be feed in remotely with no issues at all allowing for a much safer working for something like this. Even having it seperated by a wall would be of no concern and increase safety alot. My main concern was not so much the propane being the fuel for a fire that caused a rupture but the produced nitroalkanes could very well reach extremely high temperatures very quickly in the event that things went very wrong.

On the show they where trying to bust a myth that a propane tank in a garage that caught fire acted like a rocket and shot into the air. They where unable to replicate this myth for reasons just like you stated there is no oxygen. They even thinned the bottom of the tank and placed it directly on top of the burner and once again all they got was a tank rupture and a huge cloud of LP which DID NOT ignite. The force of the explosion blew out the ignition source so the LP just hung there in a cloud. I couldnt imagine the result if this was able to find ignition. Non the lest I could imagine that the shockwave from the tank rupture along could very well break some windows from a good distance.







Knowledge is useless to useless people...

"I see a lot of patterns in our behavior as a nation that parallel a lot of other historical processes. The fall of Rome, the fall of Germany — the fall of the ruling country, the people who think they can do whatever they want without anybody else's consent. I've seen this story before."~Maynard James Keenan
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