p2np not dissolving, my first synthese.

[enzym]

Hi, i just failed my first synthesis. ( AMF AI/Hg)
scaled down by 1/2 of everything ( compare to the :how-to-video, so 5grams of p2np)
i think my amalgam was wrong, ( i've read the thread from gpatreon about amalgation)
but is it normal that my p2np in IPA and water solution became mushy ? ( first it wouldnt mix , with the COLD ipa,) i added the GAA just before i put it in amalgam.
then the mixture, did gas but was not bubling and little heating ( tried it to heat up the sollution in heating mantle but not a succes.
then i added the Naoh sollution and it became in the flask a brownish grey bubbling upper layer, and a dark almost black bottom layer.
Also i used demineralised watter instead of destilled.
any help ? any tricks ?
and need i to worry about mercury so much ( im over proteckting my self from it, i did like 4 clothes changes, 2 douche's, 100X washed my heands, ...
Grt.

 

[Never to sleep]

Upon adding P2NP to IPA you obtain a solution with crystals still floating in it. The solubility of P2NP in IPA is limited but the subsequent addition of GAA accounts for this. You are right about adding the GAA just before mixing with it with the amalgam. Once the GAA is added and the solution is heated moderately to increase solubility, you should obtain a transparent yellow/gold colored solution with no cloudiness.

This might depend on reagents and conditions in which the reaction was done, but from my experience upon adding the P2NP solution, mild immediate bubbling/simmering occurs. If you see no bubbles at all when a nitrostyrene (P2NP) is added to the reducing agent (Al/Hg - the amalgam) it is a sign that the reduction has failed. The bubbles are a result of H₂ gas being generated which is essential for the reduction to work.

Once the alkaline solution is added the H₂O is partially sucked up by the NaOH leading to layer separation where the alcohol moves into the upper layer. Slight bubbling is expected since the NaOH also reacts with residue from the amalgam. I should point out that the layer separation might not occur immediately. In my experience depending on the conditions it might take ~30 min - 1 h for the layers to separate. The upper layer layer should be transparent and colorless or yellow to orange colored (if impure). The grey color as you point out hints residual Al from the amalgam being stuck in the upper layer. You may have used too much Hg salt causing the amalgam to over saturate. It's actually not so straight forward to weight the salt. Make sure you're using a precision scale for this. I've seen instances where people accidentally added too much of the salt because their scale was not sensitive enough.

Distilled H₂O is not strictly necessary in this reaction although advised. Even if you had used drinking H₂O this should not hinder the reaction enough for it to fail so I don't think this is not your main issue.

If I was you I would look for a source of purer Al foil / powder. Check that I'm truly weighting the proper amount of the Hg salt. I would switch to using distilled H₂O to be sure. Switch to chemically pure NaOH instead of technical. And primarily I would recrystallize the P2NP from EtOH. Also it's pretty important, how long you form the amalgam. Do not leave it to react for extended periods of time as you form it. Once you can no longer see through the flask with the amalgam as it has become grey and you see bubbles rapidly evolving that is the perfect time for you to add the P2NP, make sure to have it ready at that exact point instead of attempting to heat and dissolve it for another few minutes.

Now the most important part - NEVER, EVER UNDER ANY CIRCUMSTANCES PUT A FLASK CONTAINING ANYTHING MERCURY RELATED CLOSE TO YOUR HEATING MANTLE AGAIN. Or anything metal (like spatulas, laboratory stands...). The Hg vapor will react with anything metal (with the exception of pure Fe). It's not so much about touching the solution than the vapor that is released in this reaction as it does in-fact releases a significant amount of hot Hg vapor especially as it heats up upon adding the P2NP. You have effectively just contaminated your heating mantle with Hg for eternity. Under the round cover on which you put the flask in the heating mantle is a bunch of foam which is an extremely porous material. Porous materials absorb Hg in their matrix and slowly release it overtime. I would advise you to replace that heating mantle otherwise you will be continuously poisoning yourself with Hg vapor. This reaction must be done in a fume hood or outside. Ventilate the entire room for the next few days at least. Speaking from personal experience Hg is not something you want to fuck with. The invisible vapor contaminates nearly everything if you are not super careful and really it's unavoidable altogether. Switching clothes is essentially useless as it becomes contaminated with Hg anyways. Don't put yourself under the impression that you can wash it off with H₂O or in a washing machine. You can't.

As a note from a friend I would advise you to avoid Hg entirely and opt towards a reduction with NaBH₄ instead. I understand its sad to hear this after you've just obtained all the reagents but its a fair point.

Since I know you likely won't listen to this advice I will also provide another to help you reduce this contamination a fair bit. The best lab wear for this reaction is a plastic raincoat which won't absorb Hg. You can easily wash it off (outside) with H₂O. This also protects most of your clothes from absorbing high amounts of Hg, especially if you're working outside. Hg is also absorbed by retina in your eyes which brings me to another point. During the entire reaction you should wear a respirator even if you're working outside.

 

[Never to sleep]

Oh yeah and also NEVER THINK ABOUT WASHING THE RESIDUE FROM THIS REACTION DOWN THE DRAIN. The Hg salt might get reduced in your plumbing into Hg and poison you with vapor overtime. This gets significantly worse if you live in an area where buildings share drainage. You might not only poison yourself but other people. It might a also end up being a disaster if you have metal pipes for drainage. The Hg will cling onto them and corrode them. Even if you use PVC tubing wherever your drainage leads, whoever looks after it won't like the fact that Hg ions are contaminating H₂O, even city H₂O purifying facilities have problems removing the Hg from the H₂O which you release there in the stream. This might end up coming back to you in the future.

The only "proper" way that is somehow ethical is to store all the waste from this reaction in glass reagent bottles with a tight seal (otherwise once again the Hg will release vapor and continue to poison you overtime). Once you are ready to deal with the waste pour it in a much larger glass container (perhaps a large reagent bottle). Make sure it does not go above half the height of whatever container you are using. Because of the next step, avoid plastic. Then add non-azeotropic HNO₃ (above 68% concentration). Do this outside or in a well ventilated area. The reaction upon adding the acid is very violent due to the basicity of the waste from residual NaOH which is a strong base and so a vigurous acid-base reaction occurs (add the acid slowly, make sure it does not bubble over the container). Once all the base has been neutralized and no more bubbling occurs continue adding more acid to reach a pH of about 5. Afterwards swirl the bottle gently to mix everything. Seal it and let it stand for a day or two. Because the Hg ions originated from a reduction reaction your solution does contain some mercury(I) nitrate as a result of the reduction from mercury(II) nitrate. For the next step all of the nitrate must be of the +2 oxidation state. This can be done by heating at high temperatures (which I completely advise against as explained above) or by exposing the solution to a strong source of UV light for a few days (keep in mind that UV light is damaging to any forms of life including humans, when working with it wear appropriate goggles to block the light otherwise you might become blind in a moment (not a joke). You have just converted all residual Hg ions into the highly reactive Hg nitrate salt of the +2 oxidation state (the same one you use to create the amalgam). It is dissolved in solution. Measure the pH again. Now add a subtle base like sodium carbonate until pH = 8. You will eventually reach a point in which the pH no longer changes due to your base being a weak one. This is referred to as a buffer solution and it is required for the next step. Now take sodium sulfide and dissolve some in H₂O to create a solution. Pour the solution into the vessle containing the now basic solution. Precipitation of mercury sulfide occurs notable as a black mass which is insoluble in H₂O. You now have to add the solution until no more precipitate forms. This becomes hard to see as the solution turns dark black. You can either immediately test for the presence of any remaining Hg ions by pouring some of the solution a separate flask with separate sodium sulfide solution and transferring a small portion of the precipitate solution from the very top (which is the most clear) using a pipette into the flask. If you clearly see more black precipitate forming you must continue adding the solution. Otherwise you can seal the container and return in a day or two. Most of the mercury sulfide will have settled at the bottom due to gravity. Then you can continue adding the solution and see whether more precipitate forms. Once no more precipitate forms you filter the entire solution through approximately 1 cm thick layer of celite (diatomecious earth). This is the only way to filter the fine particles of mercury sulfide from the solution. Done, now you can dispose of the solution with no risk whatsoever.

I think it has become pretty clear by this point why you should not pour this down the drain. Water purification plants have exactly this same issue which is why they don't tolerate people pouring Hg down the drain very well.

 

[Never to sleep]

The bonus part about cleaning up this shitty waste is that you can recover the used mercury in the initial amalgam reaction this way. You can then easily convert the mercury sulfide back into mercury metal which you can then convert into the Hg salt again. I admit the amalgam is pretty OP when you think about it this way since you essentially recover nearly all the mercury which you've used initially. Still reduction with sodium borohydride is the ultimate way for reductive amination.

 

[enzym]

-first thank u for ur input i thank u!
but i forget to mention i used : the chloride version 0.15g.
always weared a 3m half face mask with new gascartridges.
the amalgation i did outside, but the rinsing inside 3x.( in a bucket i kept apart)
and the heating mantle was only used after a while when the solution wont started to react( p2np solution in amalgam)
and the gas did never escaped the condensor. im not happy to hear that my brand new heating jacket is for the trash ... .
also im aware of not to despose the waist down the drain ( thinking about collecting it, and drop it off before a dispose central or something like that).
again thank u about ure input its golden info for me.
-
i dont care about my amalgram didnt worked , or getting some chemicals backs .
the only thing whats botherred me the most is
1: is my brand new heating mantle for the trash?/!
2: so everything in my vented garage is contaminated with mercury? / ( even tho i saw a guy giving the advise in the video topic, that i didnt need to worry about mercury vapors, because of condesor bringing it back to reéaction flask)

 

[Never to sleep]

I understand your concerns regarding the cost of replacing the items. Obviously in the future wear some cheap clothes when doing this reaction.

You are not entirely fucked. According to your description the exposure did not continue for an extended period of time so I have two ideas how you could attempt to remove most of the Hg from your heating mantle and continue using it.

First, the less dangerous way short term would be to put your heating mantle outside under a roofing (in case of rain this will save your mantle if H₂O gets into it it's done for). Like advised don't put it anywhere close to anything metal. Ideally you would dismantle the heating mantle to take out the foam that's inside, disperse it on a plate or something and let it went out like that (make sure the foam doesn't fly of because of wind lmao). If you leave it like that for some 14 days would be my guess a good portion of the Hg will evaporate from the foam without poisoning you. Some will inevitably remain stuck in it but that's not so bad, likely nothing much will happen to you if you frequently ventilate the room in which it is stored. I would avoid putting it in a room with something porous like a carpet under any circumstance otherwise you will fuck it up greatly. Dismantling the mantle is pretty simple. They're actually much simpler in design than people imagine by their appearance. Now this depends on which heating mantle you have but most commonly the casing/cover of the mantle is only attached using a few screws. Take a screwdriver and unscrew them. Now listen closely! Most heating mantles contain a metal wire which is continuously shorted by the circuit board that's usually located at the bottom unit. Depending on the manufacturer this wire might be very short and applying strong force could rip the mount to the circuit board. Once you remove the screws slowly move the unit with the foam away from the circuit board to keep the wires mounted. It is a huge pain to mount them back into place when you rip them out. This will give you enough space to remove the foam on the inside. Again do this slowly, take out small pieces of the foam not to disturb the wires. Once you have removed the foam you can put it separately from the rest of the heating mantle and let it air out the vapor. Reassembling the mantle is exactly the same. You just put the foam back inside and mount everything with the screws. DO NOT WASH THE FOAM WITH ANY LIQUID this will ruin it and make it sticky. Just let it air out dry.

Another way which is more dangerous but does not require disassembly of the mantle is to simply put it outside and heat it to something like 120 °C. Do not let the temperature go much higher otherwise you might reduce any mercury nitrate which had sublimed into the foam into mercury metal which would worsen the situation. Let it run like this for some 3 days is my guess (do this outside hot Hg vapour is ridiculously dangerous).

Any of the methods will likely remove the majority of the Hg vapor from the foam. Also when you put it outside put it somewhere away from where you originally ran the reaction otherwise you might contaminate it further.

Personally I would replace the mantle entirely but I understand this might not be an option for everybody.

I'm happy to hear you wear a respirator when doing this reaction.

Regarding the jacket if you don't want to dispose of it I'd also let it air out outside for some 14 days. This should remove the majority of Hg stuck in the jacket. Not all of it but you should be fine.

As for your garage, went it out for some time frequently and the vapor should again mostly be removed. You don't have to move to a different place because of this fortunately.

Finally regarding the use of a reflux condenser. Some vapor still escapes, especially if very cold H₂O is not used. Laboratories handle this by exhausting the vapor outside or into a closed space containing activated carbon. The guy in the video you watched is unfortunately an idiot to think this magically saves him from it. I'm not saying it doesn't help just that it isn't perfect.

People are careless when using Hg but only until they suffer negative health effects. Remember that it bioaccumulates for a loooooong time. Once it enters your bloodstream it has the ability to cross the blood-brain-barrier entering your brain where it might get stuck to your neurons which are high in fat content. Hg due to being highly liphophillic behaves sort of like oil and accumulates in fatty tissues in the body. The half life (meaning how long it takes for half of it to disappear) of Hg in the bloodstream is about 1-2 months and varies by person. The most dangerous part is whatever gets stuck in the brain. The half life of Hg in the brain is approximately a little over 20 years during which it can cause great neurological damage. There is nothing you can do to remove it once it gets stuck in the brain other than taking chelators (prescription only medications). The chelating therapy does affect liver and kidney function so it is used only in serious cases.

I don't want to scare you too much. Most likely if you air out the vapor that got stuck in whatever you should be fine honestly. Just consider this factor in the future.

I wish you the best success in recovering your heating mantle.

 

[Never to sleep]

Oh yeah and I would advise you to apply protection from the vapor which is very cheap but only temporary. You can buy activated carbon (aka activated charchcoal). Put some in a dish preferably or in a glass. Fill a few of them like this and put them anywhere the vapor might reside. Activated carbon is highly effective and adsorbing Hg vapor on it's surface with up to 7% capacity by weight. Even if Hg vapor would remain in the room this will actively continue to remove it. You can then just throw the activated carbon in the trash instead of breathing the vapor into your lungs. I would do this for like the next two months replacing the activated carbon after 2 weeks or so. Do not buy pharmaceutical pills containing the activated carbon, they are ridiculously overpriced. Buy a bulk amount of activated carbon (its very cheap really). And don't use it for anything else in the future. If you do this I think chances of the vapor harming you are very low by that point.

Actually now that I'm thinking about it one could put activated carbon into a drying tube and attach it on top of a reflux condenser when doing this reaction. This would prevent nearly all of the vapor from escaping in my opinion. You guys this actually sounds like a good idea you should do this if using a reflux condenser for this reaction.

 

[Never to sleep]

Finally regarding the reaction. How big of a scale the reaction was? (How much P2NP and Al did you use)? I think I might have an idea what fucked the reaction up in the first place.

 

[enzym]

uhm gonna reply in a quicky, getting ready to go outside.
again thank u for ur imput , everything u said is enterying my lvl of knowledghe.
but i read that only dimethylmercury (Hg(CH 3) 2) and maybe a few others enters the brain barrier ( see Karen Wetterhan poisoning) i thought mercury chloride wouldnt enter the brain.
and in total the highest concentration that can be founded on something is 0.15g ( wich i rinsed , and so on) is it that toxid with all the measurements i have taken ? since my amalgams on my teeths are giving away mercury everythime i chew ( i have read)

and second answer, i divided everything from the ingredients in the video by 2.
so 5 gram p2np and 6g of alluminium household paper ( not cutted with siccors ,since it would stick toghetter, but teared piece by piece so everything has place to connect wxith watter)

i did not read your answer fully, but in a hurry . like i said got to go. in the evening i will have more time .
till then, and again big thx

 

[enzym]

about this carbon on outlet of condesor idea sounds indeed like a good idea.
and by the way i use activated charcoal in my gas protecting mask ( what is the lifetime since the bag is opened ? no one at the store could gfive a good answer

 

[G.Patton]

>by the way i use activated charcoal in my gas protecting mask ( what is the lifetime since the bag is opened ?

It is very depends on intensity of using. Its capacity can be measured by volume of air, which is dumped through the filter. Nobody knows how will you use it. If you'll work in lab everyday with mask, I recommend you to change it every couple months or more frequently.

 

[enzym]

how can i add someone to give their opinion ? i would like to add/ mention 2 members on this topic .
@gpatreon
the other guy i will search

 

[G.Patton]

Who is @gpatreon? lol

In general, I agree with @Never to sleep. In my opinion, you can clean up your lab from Hg and continue with all security measures. In accordance with your reaction load, I don't think that you polluted too much.

 

[enzym]

i believe u said in the topic u wrote ( about amalgams) that u have information , about the remaining hg in amalgam if not rinsed( but only let the water out) is about 0,0000... in the end product ?
can u confirm this?
my main worry is now hg being in the end product.

 

[G.Patton]

I cannot confirm it by papers, unfortunately. I've got this information from chemist in this forum, who had access to a photoelectric flame photometer. You can check by yourself. Also, Al/Hg method is very common. Dozens tons of amphetamine were synthesized by this method and successfully consumed.

 

[enzym]

What do you mean about checking yourself ( Hg in final product)?
I can only check the purity of the end product by checking the boiling point.
But if boiling point is not achieved at the desired temperature range, the only Thing i know is that its inpure ( could be other impurities from the proces).
I'm not an chemist , every info i adapted is from this forum.

Also i'm so insecure about the Hg residue, here where i live its all/only bmk leukart reaction in mass scale production. and getting a impure product ( they skip a lot of end processes for cleaning, due to less time wasting and more quantity making.
Thats the main reasing i want to make it myself ( even tho it costs me more to do it myself , than buy some shitty wet paste.

Also can i store the(leftover) ipa/aceton sulphur acid solution for further synthesis?
And the storage of Hg chloride would be oke in airtight bottle( at room temperature) ?

And whats the reason why a premixter of the solution IPA, p2np ,H20, GAA cant be used ? ( like maded the night before)

And the main reason for adding the GAA just before solution go's into amalgam ?

thank u.

 

[enzym]

I can believe a lot is produced this way and consumed.( basicly because its so easy to produce , and easy to use alternative's for expensive glasswear,hotplates, mantles... like jars and pots , and using a hot watterbath in the sink)
But the things i have seen on this forum ( dont want to bash on this guy, but yeah he is a hazard for everything/everyone ).
((Making it in the kitchen between his vegetables, used a kitchen knife from the table to pick up his amout of Hg , and then just blow his knife off and give it a sweep with the closed kitchentowel that was available.
solvents drying in the kitchen oven, ...)).

 

[G.Patton]

Yes, exactly
ofc no
yes

You can don't use GAA at all as I said in my tutorial here.

 

[enzym]

will do another synthesis (if im lucky 2) tomorow.
also a big concern of me is mercury in the end product.
will wash my amalgam 2X.
and will use hot IPA to disolve the p2np.

 

[Marvin "Popcorn" Sutton]

Do not use hot IPA. Use it warmed up to 30ºC and stir very well. If p2np still does not dissolve, warm it up a little more but not too much.

 

[enzym]

Oke thank u for the input. in my first synthese/ first try. i used colled IPA and mixed a lot with glass rod, but didnt dissolve ( the p2np). Then i heated it op ( with in the back of my head that IPA boiling point is only 60 degrees),
did a Mcguyver and tried to somehow to heaten it up in the 1L heating mantle ( did it in a 3headed 250ml flask).
Did it on the lowest setting , but i think it was way to hot. ( was my first try using a heating meantle so i dont know the temperature range). It became verry burning in my eyes( so i stopped imideatly, health=more important).
(( the p2np was disolved , but after i removed it from the heating source it became a mushy fluffy solution))
question: is this normal ? or not ? ( the burning alcohol sensation in my eyes)

Again everything is new for me, was my first try with chemicals like p2np.
Tommorow will arive a 2l hotplate (with stearing) from amazon.

 

[enzym]

Also back to my first synthese, the solution ( adding alki to the p2np dissolved amalgam solution) it came with a clear layer on top wich i collected in iPA ratio 50/50.( for further synthese)
but the funny thing is , after i removed top layer, i stirred in the whole mixture and 24h later there is again an light yellow layer on top.

 

[Marvin "Popcorn" Sutton]

What did you get from the two layers (clear and yellow)? Did you acidify it?

 

[enzym]

I dont know yet, i did not acidify it because i wouldnt take the time and effort to put in this failed try ( kept the 2 oil layers apart, will acidify them after my new synthese. then i have already a acid/aceton solution on hand so i dont waiste 3X the time for that. )
(( will acidify ofcourse them not toghetter in 1 mixter!))
And random note: kept the solution again for 24 hours , and another( but tinny and more darken yellowed) upper layer apeared.( this i will throw in waist with other content in beaker)