Sciencemadness Discussion Board - The true mad science, hydrogen azide distillation

The true mad science, hydrogen azide distillation

plante1999 - 1-12-2013 at 16:09

WARNING
Never ever try this experiment if you want to keep your life expectancy long. The fallowing synthesis deal with EXTREMELY toxic material, similar toxicity to hydrogen cyanide. EXTREMELY sensitive explosive with high power and powerful mucous irritant.

Today I did my most mad project ever, the synthesis of hydrogen azide. During all the synthesis I had two winter coat, a face shield, rubber and leather gloves. There was an acrylic blast shield between me and the reaction most of the time.

8 ml of sulphuric acid and 12 ml of water where mixed, and added to 6 g of sodium azide in 15 ml of water. the mixture was distilled using a short path. The reaction flask was flame heated in a water bath keep at 40-60 C during most of the reaction. At start the mixture that was clear took an orange concentration, the distillation which took about 1 h and half, was kept as low as possible to get the distillate. When the water bath was at 40 I got the first drops in the receiving flask. When distillate stopped to come off at 60 The azide solution was discarded and the hydrazoic acid was measured. The yield was 3 ml of a soft pink liquid with a VERY pungent smell that make someone out of breath the first time he smells it.

I did not test the product yet, however I'm up to take suggestions.

Side point: My apparatus was very improvised if compared to what it should had been, the short path had a teflon tape plug instead of the head thermometer due the lack of one. Since the clamp was very rusted, it was "pressed" in place to keep the apparatus in place. I won't keep the product for long, so if anyone have something that he would like I test, ask for it.

Some detail left behind intentionally.

[Edited on 2-12-2013 by plante1999]

[Edited on 2-12-2013 by plante1999]

Brain&Force - 1-12-2013 at 16:25

This is crazy awesome. I wouldn't even think of trying this, even in a well-controlled environment. However Wikipedia says hydrazoic acid is colorless, not light pink. Could you have any sources of contamination in the setup (possibly iron(III) or manganese(II))?

I can't think of any ideas for hydrogen azide use. Perhaps you could make some uncharacterized metal azide salt out of it?

Oh, and happy 1500th post plante1999!

bismuthate - 1-12-2013 at 16:30

Well to test it you could mix a mg amout with sodium or NaOH and dissolve that in water then mix with CuSO4 (use conc. solutions) and watch for a brown percpitate. Awesome experiment for your 1500th post!

[Edited on 2-12-2013 by bismuthate]

[Edited on 2-12-2013 by bismuthate]

[Edited on 2-12-2013 by bismuthate]

BlackDragon2712 - 1-12-2013 at 17:28

badass! what about trying to perform a schmidt reaction?

The_Davster - 1-12-2013 at 18:21

Do it anhydrous.

A very nice way to do this is to warm a mix of dry stearic acid and dry NaN3. The stearic forms a melt and the HN3 distills nicely and if you are crazy you can collect it neat, or it can be distilled into a non-aqueous solvent making it nice for non-aqueous reactions. And only sometimes does the whole apparatus choose to detonate....

[Edited on 2-12-13 by The_Davster]

plante1999 - 1-12-2013 at 18:26

If one donates enough that I can do it safely, I will.

And of course test the undiluted acid.

I have believe in the fact that the orange coloration comes from adole condensation from stabilizer in one or two of the reactants.

Schmidt reaction, I will try to find what I need.

Thanks, it was just a great add-on that it was my 1500th post.

I doubt mixing such a reactive chemical with sodium is a good idea, and I don't own sodium.
[Edited on 2-12-2013 by plante1999]

[Edited on 2-12-2013 by plante1999]

[Edited on 2-12-2013 by plante1999]

The_Davster - 1-12-2013 at 18:30

Did you measure a concentration from the distillate?

plante1999 - 1-12-2013 at 18:34

No, but by the smell it should be more then 10%. At the moment I only have access to one of these 10$ cheap Chinese 0.01 g scale, I doubt my measurement will be accurate. I guess a 0.001 cheap one could do the trick.

The_Davster - 1-12-2013 at 18:36

You could titrate it. Phenolphthalein should be a decent indicator for the endpoint.

plante1999 - 1-12-2013 at 18:41

I will, I will make stock solutions, and by the end of the week it will be titrated.

blargish - 1-12-2013 at 20:44

Plante... You are absolutely nuts

. This is pretty awesome though, good on ya!

APO - 2-12-2013 at 01:00

On another thread, (one I actually started) we discused methods of alkali metal production, where in fact azide production came up. Although, instead of being distilled, the Hydrogen Azide was absorbed into an Etheral layer as soon as it was produced. It gives considerably higher yield of final product, and can be perfomed at quite a low temperature, so it can be done MUCH less dangerous than distillation (considering that very little fumes are present and the risk of spontaneous detonation is almost non existant at low enough temperatures). Not to mention you can calculate precise concentration much easier since the percentage of affinity that Hydrogen Azide has for Ether over water is known to high accuracy. Also, it's very easy to make Etheral Hydrogen Azide ANHYDROUS just by drying it over a simple dessicant followed by filtering.

If you're looking to get into energetics, Hydrazanium Azide and Ammonium Azide are pretty interesting.

[Edited on 2-12-2013 by APO]

Boffis - 2-12-2013 at 07:20

I Second APOs comments, when I need hydrazoic acid I simply run a sodium azide solution through an Amberlite resin column (H+) form. When I have finished the column can be regenerated with HCl. This off course gives you only dilute aqueous acid but no lost fingers or eyeballs!

The acid then be neutralised with what you want

plante1999 - 2-12-2013 at 09:20

I do not have a really proper glass set-up, far from having resin column, although it is very viable for low concentration of hydrazoic acid.

APO, Sodium azide will decompose to nitrogen and metallic sodium pretty vigourously when heated in nitrogen.

"Plante... You are absolutely nuts

. This is pretty awesome though, good on ya!"

Awesome but deadly, had been a while since I had done some mad thing, guess this one is in the top of the mad experiment done by member here ha ha. Absolutly nuts... Maybe a bit.

DraconicAcid - 2-12-2013 at 09:23

Quote: Originally posted by plante1999

Awesome but deadly, had been a while since I had done some mad thing, guess this one is in the top of the mad experiment done by member here ha ha. Absolutly nuts... Maybe a bit.

Just make sure you keep posting- a sudden silence from your end will fill us all with dread.

plante1999 - 2-12-2013 at 09:27

I'll make sure to post at least time to time for the upcomings years, and since I started chemistry I asked someone I know well to make an account and tell if something happened... Not that a fear it, but it is a possibility.

DJF90 - 2-12-2013 at 10:45

Deary me... where do I start.

What you have done is very stupid and totally irresponsible. You're too caught up in trying to do the most outrageous/dangerous stuff that you're forgetting to do GOOD science. Not only is this a hazard to yourself, but also those around you, and you have to consider them too.

Before this starts to sound like a brainless rant, lets start with some literature, viz the attached excerpt from Inorganic Syntheses Vol 1. Read the two preparations there, and see where you made the stupid mistakes. I'm not saying you shouldn't have tried to make hydrogen azide solution, but at least do it in as safe a way possible.

If you can't work out what I'm getting at, let me spell it out for you; The experiment you've performed is fairly likely to have generated a very concentrated (and hence explosive) solution of hydrogen azide. It boils at 37 *C. Water doesn't boil until significantly higher. You've collected stuff boiling up to 60 *C. What do you think most of that is..?

They provide a procedure for generating a dilute aqueous solution, and you would have done well to have followed that. It is infinitely safer than what you have done. I think you should consider how badly things could have gone for you; you was lucky this time but maybe not the next.

Quote:

I Second APOs comments, when I need hydrazoic acid I simply run a sodium azide solution through an Amberlite resin column (H+) form. When I have finished the column can be regenerated with HCl. This off course gives you only dilute aqueous acid but no lost fingers or eyeballs!

Actually you can generate 50% HN3 aqueous solutions with IERs. Its not recommended (10-15% is considered safe for freshman labs) but at least possible.

[Edited on 2-12-2013 by DJF90]

Attachment: Hydrogen azide - Inorg Synth Vol 1.pdf (308kB)
This file has been downloaded 1195 times

papaya - 2-12-2013 at 11:47

Uhhh, and this guy judges me in another thread

Nice work, but what are you going next with it? I would like to listen on ammonium azide synthesis and properties from you, also could you just for fun take a small drop of it (far from main container) and throw a KMnO4 crystal into it - will it explode or not high enough concentration ? You mentioned it's smell - you're still alive ? :O

blogfast25 - 2-12-2013 at 11:53

Quote: Originally posted by papaya

Uhhh, and this guy judges me in another thread

You suffer from long toe syndrome and of a vindictive kind too.

Stop talking rubbish as you've repeatedly done and people won't treat you as a 'kewl'.

And if you can't take criticism take up knitting: science isn't for you.

APO - 2-12-2013 at 13:44

Plante, I think you misunderstood me, INSTEAD of being distilled to separate the Hydrogen Azide from the mixture, it is absorbed into a layer of Ether. Thus, it can be cooled as the reaction that forms Hydrogen Azide takes place, since no heating for distillation is needed. Ultimately it is MUCH safer as I described.

Another method that involves a still much safer distillation approach is here.

plante1999 - 2-12-2013 at 13:52

"What you have done is very stupid and totally irresponsible. You're too caught up in trying to do the most outrageous/dangerous stuff that you're forgetting to do GOOD science."

Stupid, I would not say so, totally irresponsible, probably. I have done good science for a while... Trying to do the most dangerous/outrageous stuff I can, Totally agreed, and you already know the reason why, and this is why you are involving yourself into this.

"If you can't work out what I'm getting at, let me spell it out for you"

I may be mad, but not stupid, far from that, you know me better then that.

" I think you should consider how badly things could have gone for you; you was lucky this time but maybe not the next. "

I, honestly considered it before doing the experiment.

I read your reply before you edited it, and I had in fact read a few reference, such as Brauer preparation, Ullmann's encyclopedia, and inorganic syntheses, the same you provided me in another time.

Please, do not make this thread derail and go to detritus by arguing with each others.

[Edited on 2-12-2013 by plante1999]

DJF90 - 2-12-2013 at 14:24

Quote: Originally posted by plante1999

I have done good science for a while... Trying to do the most dangerous/outrageous stuff I can, Totally agreed, and you already know the reason why, and this is why you are involving yourself into this.

Agreed, you generally do good science. But not this. Far from it. I am involving myself in this because it is an excessively dangereous method and I'd like to try and prevent yourself and others foolish enough to follow in these footsteps from a serious accident. Theres only one of you, and if you get seriously damaged, not even the best surgeon may be of help.

If you were doing good science you would have read the references and taken note of the following line (which appears in both!):

Quote:

The contents of the flask are heated to boiling (very important!), and 90 ml. of 40% H2SO4 is added dropwise.

.

You see... I don't have a problem with you preparing HN3, but not if you're going to ignore important instructions such as these. Doing so is negligent. These experienced chemists do not make such comments for the fun of it.

Quote: Originally posted by plante1999

I may be mad, but not stupid, far from that, you know me better then that.

" I think you should consider how badly things could have gone for you; you was lucky this time but maybe not the next. "

I, honestly considered it before doing the experiment.

If you had honestly considered it, you would have followed the literature method to the letter. You did not. These seemingly small details could mean the difference between death and performing a successful synthesis. Perhaps you will re-evaluate your risk assessment next time.

Quote: Originally posted by plante1999

I read your reply before you edited it, and I had in fact read a few reference, such as Brauer preparation, Ullmann's encyclopedia, and inorganic syntheses, the same you provided me in another time.

I only edited my post to include the attachment which I had forgotten. You already have the Inorg Synth prep, and that tallies against you once again on the negligence front. You had access to two preps that both tell you to heat before dropwise addition of acid, yet you did not. I'm starting to feel like a broken record...

plante1999 - 2-12-2013 at 14:45

"I'm starting to feel like a broken record..."

You are not. I made a variation of the first Brauer preparation.

Hexavalent - 2-12-2013 at 14:47

Quote: Originally posted by plante1999

I may be mad, but not stupid, far from that, you know me better then that.

Apparently not, if you are willing to attempt this experiment using your "improvised" equipment and comparative minimal experience. I would not even consider this preparation without significantly longer periods of training and outside of a proper laboratory using proper equipment.

Quote: Originally posted by plante1999

" I think you should consider how badly things could have gone for you; you was lucky this time but maybe not the next. "

I, honestly considered it before doing the experiment.

Again, apparently not, if you prepared a significantly more concentrated, and extremely dangerous, solution of this compound than you had intended.

Quote: Originally posted by plante1999

I read your reply before you edited it, and I had in fact read a few reference, such as Brauer preparation, Ullmann's encyclopedia, and inorganic syntheses, the same you provided me in another time.

Reading a few references is not sufficient for synthetic chemistry, least not for compounds of this nature. You must look at each one critically, appreciate and evaluate its content, and design your own experiment accordingly. I feel that your attitude towards your work is too laid back, arrogant and simply not acceptable, if you choose to work with these kinds of compounds. You claim to have done proper science, but your attitude here strongly shows otherwise.

To summarise, do not attempt experiments that are clearly too dangerous for someone of your experience, skill level and equipment availability, and do not show your arrogance. I've learnt this lesson myself, and it's done me a world of good.

[Edited on 2-12-2013 by Hexavalent]

plante1999 - 2-12-2013 at 14:52

"Again, apparently not, if you prepared a significantly more concentrated, and extremely dangerous, solution of this compound than you had intended."

It was intended to be concentrated, read Brauer prep. one.

"To summarise, do not attempt experiments that are clearly too dangerous for someone of your experience, skill level and equipment availability, and do not show your arrogance. I've learnt this lesson myself, and its done me a world of good."

Equipment availability, agreed it was far from required, as for skill and experience, from someone saying that I'm arrogant, show your not fully maturity.

DJF90 - 2-12-2013 at 15:13

Brauer does indeed give instructions along these lines, but they mention it is dangerous and that the liquid obtained is potentially explosive. The synthesis in that case is intended for chemists wanting to study the properties of the pure comound HN3. From an amatuer chemistry perspective, we're more interested in utilising the acid for reactions and salt formations, any improvement on safety at the expense of concentration should be taken.

You did not need to prepare such a concentrated form, and if it really was necessary, ion exchange resin would probably be the best way to go. A dilute 3% solution obtained from the Inorg Synth prep would have served your needs, but you're too cavalier to settle for that. I'm hoping you'll wise up sooner than later, or it may cost you dearly.

Don't take this as an attack; like I mentioned previously I think its good you're following your interests ,but please do it safely. I'd recommend that you start making risk assessments before doing practical work.

Random - 2-12-2013 at 15:23

Extremly dangerous chemical. There is description on rhodium mirror that after preparation of it the chemist had a very strong headache even while using fume hood and all safety equipment. Personally I would have to think more than twice to attempt this.

I have the feeling that you don't value your life enough plante.. It is not always a matter or life or death to deal with but also a matter of staying phiyically handicapped from your mistakes and having to continue to live.

Very strong acute toxins are pretty straightforward but then again life should be respected and strong explosives in small amounts won't kill you but leave you as a handicap.

plante1999 - 2-12-2013 at 20:37

Well it seams I was doing it safer then him as after the synthesis I only had very very slight headache. I was washing the exit gas in Basic solution. The worst time was when I dismantled the apparatus.

Handicapped or really badly hurt would mess my life so much that I would probably finish myself honestly, in this case a tablespoon of azide should had done the trick, and it was near...

"You did not need to prepare such a concentrated form, and if it really was necessary, ion exchange resin would probably be the best way to go. A dilute 3% solution obtained from the Inorg Synth prep would have served your needs, but you're too cavalier to settle for that"

True, true and True.

"Don't take this as an attack"

I never did, I take theses as advises.

Next time I will make a table for the pros and the cons of my synthesis/madness ha ha.

-----------------------------

I was not obligated at all to make it that concentrated, nor to make it all. It was overly dangerous but well though contrary to the popular believe. I am someone generally quite wise for my age but there is stuff I have hard time to, especially when I got nothing else then my own intelligence to provide reflections. I do not pretend that it was intelligent, the synthesis was definitely not, but the chemist however is not slow or stupid, at all. I could have done something else, but I did not as I was looking for something, something I am looking all day long, and you know what it is DJF90.

science takes balls

quantumchromodynamics - 3-12-2013 at 01:17

I realize that I am a nobody with no posts; however, I congratulate the experimental science and sheer balls it took to attempt this reaction, let alone submit it for review! New experience has created new shared knowledge. Certainly there are more standard and less suicidal ways this particular reaction could have been done, but that was not the point. To me, the point was to push a boundary and learn from experience. Bravo! Real scientists are voraciously curious. Curiosity drives us. Sometimes curiosity makes us do stupid things. Ask any cat. It takes balls to be truly and experimentally curious. Imagine the first Vikings striking out on shitty rafts just to see what the hell was in the West. The list of stupid things people have done just out of curiosity is endless. Frankly, I would rather blow myself up in some chemistry experiment, or get sucked into an electromagnetic space/time vortex, or mind wiped by a rail gun capacitor EMP, than die old and bored, whining about my fair share of government cheese.

phlogiston - 3-12-2013 at 12:43

If you are seeking to risk your life or health with your experiments, at least do something that counts. Not just in our little mad scientist community, but preferably to humanity at large. Come with something monumental or you will just be another Darwin award.

e.g. sign up for the One way trip to mars, a scientist could be useful.

Top 10 Scientists Killed or Injured by Their Experiments

vulture - 3-12-2013 at 13:46

I'm taken aback by the negative responses in this thread.

Quote:

If you are seeking to risk your life or health with your experiments, at least do something that counts. Not just in our little mad scientist community, but preferably to humanity at large. Come with something monumental or you will just be another Darwin award.

Get off your high horse. When is the last time you did something monumental?

I don't understand how people can chastise plante for not doing proper research while at the same time expressing concern that others might get hurt trying to replicate what he did. Clearly you don't hold others up to the same standard.

Yes, this experiment is dangerous. But as long as you're not endangering others and are fully aware of the danger to yourself, I see no harm. What happened to complaining about the nanny state?

subsecret - 3-12-2013 at 15:14

I agree with vulture. Knowing the danger and not putting other people at risk is all that the experimenter needs to do.

Fantastic but dangerous experiment. Good work.

The_Davster - 3-12-2013 at 17:41

Quote: Originally posted by vulture

I'm taken aback by the negative responses in this thread.

Quote:

100% agreed.

Lets not turn into chemicalforums where when someone uses nitric acid at home, the board collectively wets itself.

plante1999 - 3-12-2013 at 19:22

Especially since the name of the forum is science madness. So, anyone got something he would want I try?

blogfast25 - 4-12-2013 at 06:46

Quote: Originally posted by vulture

What happened to complaining about the nanny state?

DOWN with the nanny state!

woelen - 4-12-2013 at 08:08

An interesting experiment with your HN3 would be to make some ClN3 from it. This is a colorless gas, but it is yellow in solution. It only dissolves a little bit in water, but dissolves better in organic solvents, such as CCl4 and CHCl3. Such solutions can be used for substituting azide groups for hydroxyl groups in organic compounds.

If you have HN3, dissolved in water, then add some of the solution (10%, not more concentrated!) to a solution of NaClO (5% active chlorine is OK). You get a yellow solution and production of a colorless gas. The simplest experiment you can do is bubble this colorless under water with dish washing soap and ignite the bubbles, sticking at the surface of the water. You will be really amazed by the incredible powerful BANGs from even small bubbles, especially if you keep in mind that the gas explodes unconfined!

Do this experiment on a very small scale, use face protection and hand protection. The gas may explode without apparent reason! I have done this experiment once myself, IIRC the description lingers around on sciencemadness somewhere in an old thread. I used an aqueous solution of NaN3 which I added to slightly acidified bleach. With your HN3 the experiment should run much smoother.

-------------------------------

I do agree with vulture, but I really hope, however, that you will remain safe and healthy. Doing potentially dangerous chemistry is not a no go in my opinion (I also sometimes do, as the above experiment shows), but be VERY careful and always think about what can go wrong and if things go wrong what can be done to alleviate the consequences of this. For me the line is where experiments can go wrong in such a way that they permanently damage my body, such that I get handicapped for the future. It is not worth such an offer. But DJF90 also had a very good remark: there is only one plante1999. It would be a really sad thing if this person would be severely damaged or even die.

Random - 4-12-2013 at 13:22

Before attempting ClN3 synthesis read this:

http://www.lateralscience.co.uk/oil/

Then decide for yourself. Woelen seems quite experienced dealing with extremly dangerous stuff such as handling smaller quantities of this or HCN easily but he is woelen after all. I mean just check his experiments on the site.

I wouldn't be surprised with him playing with phosgene or something even worse than that but I can't say that is for everyone. He has a lot of experience and caution, something a younger chemist might lack.

Story with Klute and H2S is also something I'm not gonna forget so easily. He would have died if he didn't inject himself with LAB GRADE nitrite iirc.

[Edited on 4-12-2013 by Random]

plante1999 - 4-12-2013 at 13:44

Nitrogen trichloride and chlorine are not the same thing, funnily, I had already did experiments with chlorine azide before Woelen mentionned it.

woelen - 5-12-2013 at 01:12

@Random: You are referring to the compound NCl3, I am talking about ClN3. Both are dangerous compounds, but I think NCl3 is somewhat more dangerous, because it is a liquid and hence inherently much more concentrated. I never made NCl3 in more than microquantities (and with micro I mean really micro, droplets of at most 0.5 mm diameter). I would feel really uncomfortable if I had a ml of NCl3.

ClN3 also is very dangerous, like NCl3 it can explode apparently without reason. Don't look at it too angrily, it may hit back at you by exploding! In my experiments with ClN3 I was really amazed by the power of its explosions. A bubble of only 1 ml of gas, when ignited, gives an impressively loud BANG!

Random - 5-12-2013 at 08:16

I know it's not the same compound woelen but seems similar. It should be an example of what explosives are able to cause. Care should be taken with both of these compounds.

plante1999 - 5-12-2013 at 18:16

Yes of course, but it is not like if they seamed really stable...

I won't be able to titrate this week, but still take suggestions.

Lateral Science is (Mostly) Fiction!!!

bfesser - 5-12-2013 at 18:30

Quote: Originally posted by Random

Before attempting ClN3 synthesis read this: http://www.lateralscience.co.uk/oil/ Then decide for yourself.

Quote: Originally posted by bfesser

Please, not that Lateral Science site again! Just so you're aware, that site is heavily fictional. The proprietor came around here a few <del>weeks</del> [months] ago advertising for his new novel (you may find the post in Detritus

. I caution you to be skeptical of anything you read on that website! It can be tricky to sort out the factual information from the rest of it.

watson.fawkes - 5-12-2013 at 18:49

bfesser, did you even bother read the page in question before your own internal fulminating humors detonated and splattered all over the board? There's nothing on that page that's more recent than a century and a half except a quotation from a 1929 Encyclopedia Brittanica article. There's absolutely nothing remotely controversial about it.

Yeah, we get it. You don't like the site. But all you're proving is that your personal opinion is nothing but prejudice in this case.

Quoting the entirety of the above post for the record.
Title: Lateral Science is (Mostly) Fiction!!!

Quote: Originally posted by bfesser

Quote: Originally posted by Random

Before attempting ClN3 synthesis read this: http://www.lateralscience.co.uk/oil/ Then decide for yourself.

Quote: Originally posted by bfesser

. I caution you to be skeptical of anything you read on that website! It can be tricky to sort out the factual information from the rest of it.

<hr/>bfesser moderator expellendus est

bfesser - 5-12-2013 at 19:13

Yes, I've read it. Stop quoting me.

Tetrakis - 5-12-2013 at 23:06

First post.

What you have done was extremely stupid. No fume hood, improvised distillation equipment, insufficient shielding, and you allowed yourself to breathe HN3 gas? That smell that took your breath away could have seriously injured or killed you had the vapor been more concentrated or were you less lucky. If the distillate had detonated, you would have not only been injured but you and your surroundings sprayed with HN3 solution. What shocks me even more is that you have been encouraged by well wishers on this board. I feel that the board lacks a safety culture... open benzene and bromine distillations came to mind while reading this thread. Do you even have a serious plan for its safe disposal? This kind of behavior is exactly why the general public fears amatuer chemistry. Frankly I do not understand why someone would celebrate risking their lives to make a useless, dangerous chemical that has already been thoroughly studied and reported...

You seem proud of what you did, and as a chemist I feel that you have no respect for my field. If you must pursue your death wish, I ask that you stop calling it science.

Tetrakis - 5-12-2013 at 23:11

Quote: Originally posted by quantumchromodynamics

I realize that I am a nobody with no posts; however, I congratulate the experimental science and sheer balls it took to attempt this reaction, let alone submit it for review! New experience has created new shared knowledge. Certainly there are more standard and less suicidal ways this particular reaction could have been done, but that was not the point. To me, the point was to push a boundary and learn from experience. Bravo! Real scientists are voraciously curious. Curiosity drives us. Sometimes curiosity makes us do stupid things. Ask any cat. It takes balls to be truly and experimentally curious. Imagine the first Vikings striking out on shitty rafts just to see what the hell was in the West. The list of stupid things people have done just out of curiosity is endless. Frankly, I would rather blow myself up in some chemistry experiment, or get sucked into an electromagnetic space/time vortex, or mind wiped by a rail gun capacitor EMP, than die old and bored, whining about my fair share of government cheese.

This isn't science. It sounds like science, but there was no hypothesis being tested or question being answered; hydrogen azide has been thoroughly studied and there will be no new answers from this work. It was just a dangerous stunt.

plante1999 - 6-12-2013 at 04:14

I really like these last two posts, you know, if you are scared about people distilling bromine this board is not for you really.

As a chemist, you probably know no everything is obtainable, and some chemicals must be synthesized in house to test some reactions. Having no respect for your field, well that is the best, I believe mostly everyone on this board could say I'm one of the few here that is doing study to become a chemist, and don't be too tempted to think I won't succeed.

I hope you already read older reference work of the 18th century, as that hypotesis thing for every work started at school there is about 60 years now. If you where needing iodine in an experiment and you described its synthesis, would you think an "hypothesis" would be needed? Certainly no, because you know that it will the reported procedure work.

Put your 21th century chem book aside, and read older references.

Have a good day.

[Edited on 6-12-2013 by plante1999]

blogfast25 - 6-12-2013 at 06:16

Quote: Originally posted by Tetrakis

I feel that the board lacks a safety culture... open benzene and bromine distillations came to mind while reading this thread.

[snip]

You seem proud of what you did, and as a chemist I feel that you have no respect for my field. If you must pursue your death wish, I ask that you stop calling it science.

You hardly know this board and are already judging it very superficially, not to mention use an extremely reductionist definition of science.

'No respect for your field'? You pompous git. I'm a qualified chemist and I feel he's MORE than respecting 'my field'.

Quote: Originally posted by Tetrakis

This kind of behavior is exactly why the general public fears amatuer chemistry.

Wrong again. The public fears what they don't understand. Accidents in home labs hardly EVER affect them.

Now please bugger off or present something interesting you did yourself. And don't forget to make it jam packed with hypotheses or else it doesn't count!

[Edited on 6-12-2013 by blogfast25]

bfesser - 6-12-2013 at 06:36

blogfast25, take it easy. There's nothing wrong with a newcomer posting here. Would you rather he junk post in beginnings? [/rhetorical] Down, boy! Down! Sit! Stay!

Tetrakis, while I agree with many of your points, I must assert that you're wrong about this board lacking a safety culture.

vulture - 6-12-2013 at 06:49

Quote:

You seem proud of what you did, and as a chemist I feel that you have no respect for my field. If you must pursue your death wish, I ask that you stop calling it science.

As a chemist I'd strongly wish you'd drop your elitist attitude. Read about Tesla, Nobel and Moore and then quietly reconsider.

There are millions of taxpayer dollars devoted to science without immediate benefit or use.

I would rather call plante's experiment science than the crap which is coming out of the publication mill nowadays.

The_Davster - 6-12-2013 at 06:50

Quote: Originally posted by Tetrakis

I feel that the board lacks a safety culture...

And I feel that the average chemist has his balls in OSHA's purse, and is unable to accurately gauge risk thanks to years of safety indoctrination.

It seems we are at an impasse.

You should direct your eyes to the name of the site "ScienceMADNESS" as well as "The ART and science..."

Picasso painted lots of paintings, because that's what he did, that was his method of expression, through art. Here, synthesis is our art.

Perhaps the facebook group "I fucking love science" would be more your style.

woelen - 6-12-2013 at 07:33

Quote: Originally posted by Tetrakis

First post.

What you have done was extremely stupid. No fume hood, improvised distillation equipment, insufficient shielding, and you allowed yourself to breathe HN3 gas? That smell that took your breath away could have seriously injured or killed you had the vapor been more concentrated or were you less lucky.

I myself would not have done this experiment (at least not in this form), but your way of expressing is simply exaggerating the situation. The single reason for me not doing this experiment myself is the risk of violent explosion. I am not afraid of a whiff of HN3. A single whiff of this will not kill you. HN3 is not a cumulative poison and has no irreversible after effects. That makes a great difference for me.

Quote:

If the distillate had detonated, you would have not only been injured but you and your surroundings sprayed with HN3 solution.

Spraying around of HN3 solution is not good at all, but it is not the end of the world. It is volatile and quickly will evaporate. Plante1999 writes he had a double coat, face protection and double gloves, one pair being big leather ones. The chance of getting his own body sprayed with HN3 is practically zero.
I agree though that detonation of the solution IS a great risk. I think that explosion of 3 ml of HN3 can have devastating effects on your hearing capabilities and if you have the bad luck to have your hand very close at the moment of explosion, I can imagine that it is irreversibly damaged, even when gloved! That is the reason for me not to do this experiment.

Quote:

What shocks me even more is that you have been encouraged by well wishers on this board. I feel that the board lacks a safety culture... open benzene and bromine distillations came to mind while reading this thread.

I have done distillation of bromine myself: http://woelen.homescience.net/science/chem/exps/raw_material...
Of course you need to be careful and you need to know what you are doing, but it definitely can be done in an amateur setting! I would also do a benzene distillation if I had the means to prepare that chemical and wanted to isolate it.

Quote:

Do you even have a serious plan for its safe disposal?

Disposal of HN3 is not a problem at all. Just dilute with a lot of water and pour in excess solution of NaNO2 (ingredient of curing salt), which converts all azide to N2 and then flush down the drain the remaining nitrite-solution. Even if you don't have NaNO2 (which to my opinion should be present in your home lab when you experiment with azides), then I think that strong dilution with a lot of water and then flushing it down the drain (remember, we are talking about 3 ml only) with a bucket more of water is OK. Half-life of HN3 in the environment is low, maybe hours, at most days.

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This kind of behavior is exactly why the general public fears amatuer chemistry. Frankly I do not understand why someone would celebrate risking their lives to make a useless, dangerous chemical that has already been thoroughly studied and reported...

Amateur chemistry very very seldomly leads to accidents which other people besides the experimenter himself notices. When did you hear of an accident in the lab of an amateur chemist, such that other people had to be evacuated or such that a house burned down or something like that? Sometimes you hear such things from people making fireworks or from illegal drug labs who have a solvent fire, but a general home chemist blowing up things, poisoning the area around the house or some other major incident are unknown to me. That is the best evidence for me that there hardly is any need to talk so lowly about amateur chemistry.

Quote:

You seem proud of what you did, and as a chemist I feel that you have no respect for my field. If you must pursue your death wish, I ask that you stop calling it science.

There is no deathwish in plante1999, and I think that he has quite some respect for what you call 'my field'.

Altogether I also am inclined to say that this experiment is beyond what you should do at an amateur level, and in my previous post in this thread I have expressed my concern about plante1999's safety, but the way you respond to this is 'whoaah look at how dangerous this is, he is going to kill himself and he destroys the environment'. We have enough nannies around us already who tell us what we may do and what we may not do.

It would be more interesting to think about modifications of this experiment, such that its risk is reduced. Think of DJF90's remarks, such as assuring that the liquid remains boiling hot, such that a lot of water vapor comes with the HN3. So, not simply dismissing things, but trying to think about improvements of the process is the key to getting people with you and having people listen to you. I can imagine that one day I also try to make some HN3 at low concentration, and then I most likely will remember this thread and implement safety measures, which plante1999 did not think of, but which he now knows about and can implement in the future. We can learn from each other, but only if we provide constructive remarks and not just yell about how dangerous and irresponsible someone has been.

Safety? Yes!
Listening to nannies? No!

[Edited on 6-12-13 by woelen]

phlogiston - 6-12-2013 at 13:58

Quote: Originally posted by vulture

I'm taken aback by the negative responses in this thread.

Quote:

I am sorry if I sounded arrogant at all. Just trying to say it would be such a loss of a young and already very excellent scientist and experimenter (as well as a great human being). Perhaps I misinterpreted it (English is not my native language) but it seemed to me in his first posts that he doesn't place very much value on his life or limbs.
With his talents certainly he should be able to contribute to advancing the real frontiers of science soon (or whatever else he chooses to do). While, indeed, this was a fascinating and brave experiment, it is not worth losing body parts over (but, indeed, everyone should be free to decide otherwise for themselves)

ScienceSquirrel - 6-12-2013 at 15:03

The Victorian period was a great time for amateur science.
Great discoveries were made by amateurs who worked in home labs.
There were disputes but many of them treated their fellow experimenters as gentle men and women.
So when you write; put on your smoking jacket, relax in your arm chair in front of cherry logs burning in the grate, puff your pipe filled with plum tobacco.
There are great discussions on here, this must be the best site for amateur science in the world.
I am off to the mountains of Brittany avec ma meuf et notre chatte, mais I hope I willl be online.
Maybe we could have a thread on Christmas Day?
Happy Christmas on Science Madness from across the world!

bfesser - 6-12-2013 at 15:25

Quote: Originally posted by Tetrakis

First post. What you have done was extremely stupid. … This isn't science. It sounds like science, but...

Hell of a first post! It got the attention of no less than two administrators and three moderators. Welcome to Science Madness!

<img src="http://s3.amazonaws.com/quotefully_production/photos/character/bac870c49a2511e0910f12313b10052d_small" width="100" align="middle" /> "Back off, man. I'm a scientist." — Dr. Peter Venkman</a>

[Edited on 6.12.13 by bfesser]

subsecret - 6-12-2013 at 19:02

Tetrakis, I understand your concern for Plante, and if he were to severely injure himself, well, I would feel bad. You are free to discourage such experiments, though I do support them (as long as it's for science, and to pursue real, non-kewlish home chemistry). Even such a dangerous experiment involved lots of science, and I know that Plante took precautions to protect himself, and was aware of the dangers, thereby making himself fully aware of the risks. He proceeded to conduct the experiment without any bodily injury.

If you had asked me a year ago, I would've censured such an experiment, but I later learned that science is...science. For other references, I am a Darwinist. As for the public outlook on amateur chemistry, we must communicate that, though some of our experiments are dangerous, we take safety precautions. Chemistry can be safe or dangerous, but in the latter case, we "sure as hell" take precautions. Usually.

Tetrakis - 6-12-2013 at 21:44

I apologize for having posted in anger. Let me just say that I have respect for, and support, amateur chemistry. I am not as seasoned a chemist as many who post on this board, and have admiration for their achievements. If one needs hydrogen azide, by all means they should make it. Good chemistry, however, means achieving your synthetic goals while avoiding unnecessary risks. If the goal was to make pure HN3, there were better ways to do it... if I were to make this myself, I would have done it at 1/30th the scale in a short path distillation apparatus with flame-polished glass, and distilled it directly into a thick-walled vessel that I could seal from a distance. I would never put any part of my body near liquid HN3 unless I was sure it was in some sort of reinforced vessel. If you just wanted to obtain some pure HN3, why did you do this reaction on such a large scale? Perhaps you should read about the Texas Tech lab explosion in 2010, where students in an academic lab were maimed while inappropriately handling a large quantity of explosive material.

My mentioning benzene and bromine distillation was unnecessarily vague; I had earlier found an example of a teenager talking about how he had enjoyed walking around with an open container of bromine, and elsewhere on the board I saw an example apparatus (impressive, but still) for high temperature benzoic acid decarboxylation without active ventilation. Benzene isn't acutely toxic, but does have a cumulative carcinogenic effect... I don't think that its unreasonable to expect volatile, toxic liquids to be handled in a more controlled manner. I use or make CO, HCN, HN3, benzene, thallium chloride, etc. all the time, but I spend just as much time planning disposal and workup as I do planning the reactions, constructing apparati, etc.

That being said, I still don't understand why anyone would prepare undiluted HN3. Its a completely impractical form of HN3, which shouldn't be stored for extended periods of time and presents unpredictable dangers. When I work with HN3, I go to great lengths to isolate such reactions from normal waste and digest it appropriately when I'm done. If you need it to make something, why not just generate it in situ? I work with plenty of dangerous materials, but always minimize my risk by avoiding them as much as possible and isolating myself from them when I do need to use or make them.

vulture - 7-12-2013 at 05:59

Quote:

if I were to make this myself, I would have done it at 1/30th the scale in a short path distillation apparatus with flame-polished glass, and distilled it directly into a thick-walled vessel that I could seal from a distance. I would never put any part of my body near liquid HN3 unless I was sure it was in some sort of reinforced vessel.

And you'd be exposing yourself to more risk than plante did. Why? A thick-walled vessel would only cause greater damage if HN₃ exploded. Thinking that a thick-walled vessel can contain a HN₃ explosion, now that is bad risk assessment.

The_Davster - 7-12-2013 at 11:03

I have distilled anhydrous HN3. However on 1/10th gram scale.

It detonated a few times before I was able to collect the pure material. However thanks to the protective gear I had on, only my ego was damaged each time.

Assuming adequate windflow to keep Plante upwind was present, the only potential safety issue here in my eyes is scale and handling. I am convinced his crude armour/face shield would protect from everything(shrapnel) except the pure HN3 going off in his hand. 3g is more than any anti-explosion glove can take, so the way to mitigate this is either to scale down a bit, or to have standoff from handling. This can be achieved simply by handling the collection flask with a clamp around the neck. As explosive energy scales with (cubic or square, I forget), a little standoff is hugely effective. Even a 6" clamp, keeping his hands away from the flask would leave this experiment totally fine in my books. (of course, if collecting this in a testtube, you would not want the clamp around the liquid-containing part, lest the tines turn into shrapnel itself, shrapnel that would be harder to block than glass shrapnel)

Vulture already covered the folly of thick glass.

plante1999 - 7-12-2013 at 11:27

Next time I will probably make trimethylsilyl azide to try the propreties of anh. Hydrogen azide safely with that substitute. Although It would require a good 60$ to buy some trimethylsilyl chloride...

plante1999 - 15-12-2013 at 15:25

I just destroyed the azide in dilute sodium nitrite/ sulphuric acid solution because my scale completely stopped working. I may work back on that project later this year.