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Author: Subject: nitroglycerin
hightechstuff
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Hi ScienceGeek,
Thanks for the info. I figured the haze was water. I dessicated the NG in a petri dish with a sodium chloride solution for 12 hours which obviously didn't remove all the water. It seems I have a potential problem on my hands then. Should I deflag the preparation immediately or do you think it would be safe to store for a week or so? I believe the H2SO4 is the culprit for my impurity problem as well. Is their a way to purify my drain cleaner acid? Is their a way to purify my ammonium nitrate? Purchasing technical grade sulfuric and nitric acids is expensive I'm trying hard to avoid it but it may be the only way to do it right.
Fulmen
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Actually I think you're in good company, Sobreros first batch of NG was also described as olive-colored

Any metal salts should be easy to wash out with water, other than that I don't know. Davis does not mention anything about instability or potential causes, but I won't guess if this is an omission or if there really isn't anything that can cause instability.
S.C. Wack
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Drain cleaner? Technical grade materials too much?
For nitroglycerin?

Call me a crazy old crank, but...well you can probably guess where I'm at with this.

Just for hahas, drop an oxidizer in your drain cleaner (that many here think is pure as snow except for the color) and see what happens on heating for a while. I suggest Cr+6, because of the nice green color of Cr+3, compared to the less dramatic change with permanganate. The most favored brand here (Rooto) will reduce a lot of chromate, and thus isn't even fit for cleaning glassware. I sure as fuck wouldn't use it to make unstable explosives, but I'm just an anal overly-cautious wet blanket.

"You're going to be all right, kid...Everything's under control." Yossarian, to Snowden
a_bab
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10 ml of NG is roughly 15 grams.

5 grams are able to vaporise your palm to the forearm bones and possibly blind you.

I'd get rid of it ASAP; even burning it may cause it to explode.

If ordering reagent grade acids is avoidable, just ask yourself: "what do I need my NG for?"

It's something you make, make sure you don't miss the additional headache, ddt it and you go for the next on the list
pdb
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Hi a_bab, do you think of someone in particular ?

Yes, I'm the one who lost one hand and one eye with approx 10ml of NG when a runaway took place at the end of the synthesis, although the temperature was so far under control (<15°C).
Zinc
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Did you use HNO3/H2SO4 or XNO3/H2SO4? And did it first start to give off NO2 and heat up or did it just explode for no apparent reason?

The_Davster
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So sorry to hear of your accident, pdb. Like Zinc, I would be interested in hearing more about what caused your accident.

IIRC you are more active on roguesci than here, is there a thread there where you posted details that could be linked to?

pdb
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The_Davster: No, I didn't give any details. My memories of this event are focused on the "after" story rather than the "before" one, and thus are bad memories. However, I've been reading a lot since (and before) about NG and in particular reports of manufactoring accidents over the world, but didn't reached any satisfactory conclusion. Some accidents remain uncleared, mine is such...
Fulmen
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I took a peak in Urbanski, and I really can't find any reason for this batch to be dangerous. Not saying it isn't, I just can't see why.

The commercial product is usually yellowish (of straw yellow colour) or pale brown depending on the purity of the original raw materials and on the conditions of manufacture.

Acidity affects stability, but no other sources for instability is mentioned. I agree that reagents of unknown purity are ill-suited for explosive manufacture, but as far as I can tell there's not much cause for concern:

Acids for nitrating glycerine must be as pure as possible. Nitric acid (sp. gr. 1.50) should not contain more than 1% N204. Sulphuric acid (sp. gr 1.84) and oleum (20-25%) should be virtually free from lead sulphate which is liable to be present in old installations constructed of lead, and also from sulphates of iron, as these substances hinder the separation of nitroglycerine and acid.

The sulphates could make it harder to remove all traces of acid, but a litmus test will reveal that.
a_bab
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Hi pdb, long time no see.

Well, that was a general statement, although I did think of you. It could happen to anyone.

hightechstuff
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Hi Everyone,
Thanks for your input. Please excuse the delay. My post was put in detritus and I figured that was the end of my posting here. Since then it was merged with another NG post.

Fulmen,
I emulsified the NG with water using a magnetic stirrer and was able to remove a small layer of unknown white/brown sludge after the separation. However. the NG still remained yellow in color. Obviously whatever the contaminant, it is not soluble in water.

S.C. Wack,
I completely agree. Use $#it = get$#it. I figured I'd nitrate what I believed to be a small amount of glycerin and see what comes out. Obviously not a pure form of NG however it seems fairly stable..... for NG.... You know.

I don't plan on making NG ever again. I just wanted to see if it could be made with AN and drain cleaner which I confirmed. I did however follow your suggestion on the Rooto H2SO4 and it did seem to clear up the acid to a point. Here is what I did...

I poured 200ml of "Rooto drain cleaner" into a 1000ml beaker containing 50ml of 30% H2O2. After about an hour of reacting, the acid appeared as a clear oily substance versus the yellowish cloudy substance.

I then boiled this mixture down to 200ml to obtain the original H2SO4 concentration. The preparation is now clear accept for a few suspended, small, grayish globules of ????

This acid "seems" to be much cleaner than the original drain cleaner form however I would like to also remove the grey material which I believe to be some kind of metal. What would be the best way to filter this acid?

Subsequently I have also devised a way to clean up the ammonium nitrate. Here is my procedure.

In a flask I created a high concentration of AN solution using water. I added fertilizer grade AN prills to the water until the remaining prills would not dissolve. I then took the murky liquid and filtered it three times at room temperature creating a clear solution.

The AN prills I have don't appear to have a calcium coating however I may be wrong. The sludge removed from filtering is a brownish white sludge.

I then took the clear solution and boiled it under vacuum on a hot plate until the solution was devoid of water. The concentration was poured into a dish, solidified and ground into powder. The final product now appears to be fairly pure ammonium nitrate.

pdb,
Damn! That sucks. Sorry to hear about your experience with NG. You seem to be taking it well though and moving on with your life. Good for you! I truly wish you the best.

Thanks Again!
hightechstuff
Zinc
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Today I tried to make NG (again). I mixed 75 ml of H2SO4 with 50 g NH4NO3. After it cooled down to around 15 C I started to slowly add 12.5 ml of glycerin After I added all the glycerin I waited around 15 min and then diluted the mixture with water. I could see that there is some other liquid that doesn't mix with water in it but it never collected on top or at the bottom. I diluted the mixture more and separated one part of it and neutralized. Still no NG. This is the third time it happened!! Does anyone know why?

There is one possibility why it happened. Somewhere I have read that iron or lead sulfate dissolved in sulfuric acid might cause difficulties in the separation of NG from the spent acid. I used boiled down acid from a old car battery.

Boomer
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" ... from a old car battery."

That's it, you want a new (or at least still good) battery, fully charged. Discharged = acid is mostly present as sulfate.
Bert

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Here in the US, you can buy a 5 gallon carton of NEW 30% battery electrolyte at many auto/truck parts stores, probably for less than \$20.00. An old electric deep fryer from a garage sale makes a useable sand bath for dehydrating acid with a large Pyrex beaker or coffee pot set in it on a layer of sand. A 1,000 watt unit set at 450 F. has been seen to concentrate a 4.5 liter batch of 30% electrolyte to a specific gravity of 1.8 in less than 24 hours.
Zinc
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Yes I have heard that it is also available in my country. I searched but didn't find it yet. I will continue looking.

Bert

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Mood: " I think we are all going to die. I think that love is an illusion. We are flawed, my darling".

Look where the parts and batteries for large trucks are sold. Diesel trucks have LOTS of batteries, and they are generally not the sealed units used in passenger cars. Hence the need for their mechanics to be able to maintain electrolyte levels-
StevenRS
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I have a problem. I ran out of nitric acid, so I will improvise. If I were to use KNO3 and Sulfuric to make Nitroglycerin, would the ratios be 5 ml glycerin, 30g KNO3, and 46 ml H2SO4? Someone tell me if I did my math right.

[Edited on 19-4-2008 by StevenRS]
Sickman
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 Quote: Originally posted by StevenRS I have a problem. I ran out of nitric acid, so I will improvise. If I were to use KNO3 and Sulfuric to make Nitroglycerin, would the ratios be 5 ml glycerin, 30g KNO3, and 46 ml H2SO4? Someone tell me if I did my math right. [Edited on 19-4-2008 by StevenRS]

StevenRS,

You need to be very, very well informed and prepared, before making any attempt at making NG. Not only that, but you need to be willing to lose your body parts/body part functions and your life for that matter, depending on the amount you plan on making and the material(s) that make up your reaction vessel.

NG synthesis is very hazardous and makes me question wether or not the risks are actually worth it. Nitric esters like ETN or PETN are far more predictable (safety wise) in their synthesis, and in my opinion are a more profitable pursuit than NG. I'm not saying this to mean that NG isn't a very useful explosive to mankind, and that it's hazardous manufacture cannot be carried out, but think about the lives destroyed, disrupted, torn apart, and simply wasted, because of the accidental detonation of NG during it's manufacture and handling.

Don't think that accidents will never happen to you! That's how accidents happen most of the time!

The dangers of synthesis aside, you need to go back and reread my postings in the thread entitled "Nitration Calculations".

To double check your above math you will need to double check your reactants. Ask yourself is my KNO3 anhydrous? Have I taken any steps to insure and confirm this fact. Ask yourself is my sulfuric acid anhydrous? What about your glycerin. It very likely contains some water even if it is just a little.

The truth is the more you know about your reactants (what you are actually using), the more you will be able to accurately predict the products and yields for the reaction.

Water is one of the products of NG synthesis (wether or not your reactants are anhydrous or not) and if your reactants themselves contain water you need to figure this into your balanced equation as well, so that when you end up with a lower yield of NG than expected you will know why.

NG is a trinitrate, so you will need three NO3 groups per one glycerin molecule. In other words you will need three moles of anhydrous KNO3 per every one mole of anhydrous glycerin. During the manufacture of NG 3 moles of H2O is produced for every one mole NG. This will heavily dilute your acids if they are not in excess.

You will also need to be practical. To acheive a high yield you will need an excess of NO3 groups in the reaction zone to increase the likelyhood that each hydroxyl group on each glycerin molecule (there are three on each one) will be replaced with an NO3 group.

Besides having a balanced equation to work with, part of being practical is knowing how much heat is liberated during the reaction and how this can trigger a runaway reaction among other factors. Ask yourself questions like: will I need to use an ice bath to moderate the reaction or perhaps a dry ice/acetone bath to cool the reactants and products. Would some form of stirring be appropriate during the reaction? How long does the reaction take to go to completion and how does temperature and acid concentration effect this? What about addition rates? How will I plan ahead for a worse case scenario (accidental detonation)? What precations have I taken and what steps will I take if a runaway is detected or some other hazard?

If you have done the math correctly and honestly and truly know your reactants and products along with their properties and hazards. If you have been practical in designing your experiment to counteract the factors working against good yields for the end product (NG) and taken every measure to insure your own safety and well being and those of others as well. If you are willing to suffer the potential damage or loss of life or function during an unexpected event. If everything is in place, then I think it is very possible, you may end up with a very decent yield, and possibly a rewarding experiance, if the unknowns keep their distance and leave you without any ill effects. Otherwise, do yourself a favor and leave NG alone.

[Edited on 20-4-2008 by Sickman]
StevenRS
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Thank you for the advice and warnings, I will be making a small (but still dangerous amount) of 10ml. I have a magnetic stirrer, and a large amount of water to dump the reaction into if it goes bad. I have prepared along time for this, I just wanted to make sure I had my ratios right. I believe I do. All the ratios I posted are for anhydrous chemicals, I have already figured the difference for my chemicals, and still use a little extra. I also have decided to use a greater excess of H<sub>2</sub>SO<sub4</sub> to make the mix more fluid and easier to stir.

For cooling, I am using a homemade forced water/antifreeze cooling system that has several glass spirals in the reaction mix itself, in addition to an ice bath. I have to be careful I don't freeze everything with this!

I have already set everything up, outside, and now I am putting my face shield and gas mask on... Here goes...
Bert

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 Quote: Originally posted by StevenRS Thank you for the advice and warnings, I will be making a small (but still dangerous amount) of 10ml.

Sigh. Damn straight "still dangerous ammount".

Boomer's freezer NG method with sulfuric acid and nitrate
Sickman
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StevenRS,

Don't rely on your magnetic stirrer to get the job done! A KNO3/H2SO4 mixture can get very thick, espeacially below 0 degrees Celsius. Suppose your stir bar stalls out and then you have to try and stir manually around these glass cooling coils. You could have problems.

Make sure you have a backup plan for every possible thing that could go wrong.

A high velocity peice of glass or metal WILL go right through your face shield if it has enough mass (a half gram fragment is all it takes). A one gram fragmnent with a high velocity has proven itself over and over again on the battle field to penetrate body armor and cause lethal wounds. All wounds from such high velocity fragments are well known for causing wounds that bleed profusely and it can be extremely difficult to stop the bleeding. Bleeding to death is a real factor here. Along with blindness and getting your eardrums blown out.

It would be best to design a very robust shield of plexy glass around the entire reaction vessel no less than 3/4 of an inch thick and large enough to shield your entire body and you still might lose a hand reaching over the shield during the synthesis. Ear plugs with a high decibel reduction covered by high decibel ear muffs is smart. Also your eyes are very precious and are worth every effort to protect against high velocity fragments.

10 ml of NG can change your life if you let it! Just ask pdb, a member here who had just such an experiance.

He says and I qoute:

 Quote: Yes, I'm the one who lost one hand and one eye with approx 10ml of NG when a runaway took place at the end of the synthesis, although the temperature was so far under control (<15°C).

and

 Quote: The_Davster: No, I didn't give any details. My memories of this event are focused on the "after" story rather than the "before" one, and thus are bad memories. However, I've been reading a lot since (and before) about NG and in particular reports of manufactoring accidents over the world, but didn't reached any satisfactory conclusion. Some accidents remain uncleared, mine is such...

Like I said "is it really worth it?"
Pulverulescent
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I used a thermometer to mix the reactants when I made nitro and I remember the slight worry that too-vigorous mixing could cause detonation by shock or friction.

In a runaway, with already formed nitro at high temperature, the slightest jar (a thermometer dropping into the mix?) might be enough to set it off.

No one wants to repeat pdb's experience (however heroically he's dealing with it!) so all eventualities should be considered.

If I ever make a liquid explosive again, it'll be nitroglycol!
Its reduced sensitivity certainly commends it!

P
Pulverulescent
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Oh, and drain-cleaner + nitrate salts will have no part in it.
The H2S04 will, hopefully, be the stuff that comes in an amber safe-break bottle.

Or I could try distilling what I've got!

P
Pulverulescent
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Pdb, I should just say I'm not insinuating any bad practise on your part.

Some accidents are inexplicable!

P
StevenRS
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I added an excess of sulfuric acid to the mix to reduce viscosity, and yes, the glass coils would make manual stirring impossible. If the stir-bar stopped, I was prepared to dump it.

But I didn't have to, everything went fine, I now have a decent 5ml of nitroglycerin, completely neutralized, and stored in a plastic bottle.
Definitively worth the effort and worry, but only once, just to say I did it.
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 Sciencemadness Discussion Board » Special topics » Energetic Materials » nitroglycerin Select A Forum Fundamentals   » Chemistry in General   » Organic Chemistry   » Reagents and Apparatus Acquisition   » Beginnings   » Responsible Practices   » Miscellaneous   » The Wiki Special topics   » Technochemistry   » Energetic Materials   » Biochemistry   » Radiochemistry   » Computational Models and Techniques   » Prepublication Non-chemistry   » Forum Matters   » Legal and Societal Issues