Sciencemadness Discussion Board - NHN synthesis not working

NHN synthesis not working

Pages: 1 2

ManyInterests - 13-1-2023 at 19:09

so i tried making NHN for first time, and when i add the nickel nitrate to the hydrazine freebase a green precipitate forms. i know its supposed to be a purple color and this is not purple. how do i fix this. BTW i was not using the hexahydrate i was using the raw nickel nitrate from making it, im guessing this is the problem but im not sure. also the green precipitate does NOT redisolve into solution. it just kinda sits there. one more note is that i used H2O2 in the nickel nitrate synthesis and maybe converting the "NHN" to some sort of other nickel salt.

I had that problem when I was first making NHN. The green is most likely nickel (II) oxide. What happened for me at the time is that my hydrazine sulfate wasn't actually hydrazine sulfate at all, but almost completely sodium sulfate.

What was the process you used to make hydrazine sulfate? Or did you buy it?

I should update my notes and post them here for getting hydrazine sulfate done correctly and my NHN notes.

Raid - 15-1-2023 at 10:08

ok, yeah it was nickel 2 oxide, so i bought some hydrazine sulfate which its kinda expensive (100g for 20$) and i tried to make it and got really bad yields. how do i fix the bad yield?

Raid - 15-1-2023 at 10:09

Also Manyinterests, do you happen to have a PDF or a method of synthesis that gives good yields?

ManyInterests - 15-1-2023 at 13:33

I tried to find the video that I found most informative, but it seems to be off youtube! Good thing I downloaded it!

I'll have to post my notes here:

Quote:

355 ml pool bleach (or 250 ml regular bleach selection)
75 ml 50% H2SO4 (add 37.5ml 98% H2SO4 to 37.5ml super cold water)
47.8 g NAoh
34.1 g urea (30ml or 40ml of distilled water to dissolve. use absolute minimum and make sure water is warm.)
0.75 g gelatine (takes 15 ml of warm water to dissolve this)
122 ml HCI

Dissolve urea and geltin seperately in the minimum water necessary (use distilled) be very careful not to use excess water. Then pour them into the same container. Keep it cold and handy.

Get the fan started (this is where the deadly gasses start to form). Add the ice-cold bleach to ice bath (keep it super cold) and then add NAoh slowly to it while stir vigerously (remove from ice bath and put on mantel) Do let let temperature rise above 20C.

Add the urea and gelatine to the container.., this is where the foaming starts. Be SUPER careful. After foam starts to subside cover with foil or cling wrap to prevent hydrazine gas from escaping. Heat to 85 celsius for 5 minutes

Once solution is clear the hydrazine is ready. Remove from heat and put on another ice bath. It will still be fuming so be ultra careful.

After cooling, keep in ice bath. Add the HCI dropwise (BE VERY CAREFUL HERE! Also optional). Let it cool for a few minutes, then add H2SO4 and stir for a few minutes. At this point it will cause the hydrazine sulfate to percipitate. Cool down to 15 celsius and you can do the vacuum filteration after it is nice and cold for a while. (do not cool down to below 10C. We don't want the sodium sulfate that will percipitate at this point).

Put bleach in bottom of flask to neutralize any hydrazine that slips past. Neutralize further with dilute solution of calcium hypochlorite or sodium hypochlorite (the same bleach you used to make it). Dry for several days before storing in tupperware

This is for the hydrazine sulfate. Yes they are personal notes with personal reminders.

For my NHN synth here are the notes of my 2 last synths

Quote:

synthesis on (DATE REDACTED)

30.15 grams of hydrazine sulfate
18.43 grams of sodium hydroxide
105ml of 95% ethanol (put 55ml first, then the 30 ml later and finally 25ml)

and 40ml of nickel nitrate solution that I made (with indeterminate amount of dextrin)

as of writing. Filtered and added around 250ml of ice cold distilled water and 100ml of 95% ethanol. Filtration is taking a while. Hopefully it will come out dextrinated and require no crushing.

Note: I believe some hydrazine fumes were created. No harm was done. But this is something you need to be extremely aware of. It is possible that gravity filtration is the superior choice in this case, as vacuum filteration doesn't seem to be doing this fast enough. You employed emergency protocols of flushing that ethanolized hydrazine down the toliet. No harm happened. You will be A-OK.

Further note: Actually no, it was likely not hydrazine. Hydrazine has an ammonia scent and you know ammonia. It did smell like ethanol, but it might have contained it. So your reaction was still good as it prevented any possible problem.

result was extremely finely powdered stuff. Just perfect!

Final yield after drying: 11.88 grams

Next synthesis (and hopefully final): (DATE REDACTED)

39 grams of hydrazine sulfate (all my remaining supply).
23.9 grams of sodium hydroxide
150ml of 95% ethanol (with 75ml added first, followed by the rest).

75 to 80ml of nickel nitrate solution.

This time no vacuum filteration (and outside!). Do it purely via gravity. Also in two containers as you will be putting in alot more stuff this time.

Gravity filtration takes hours when washing with the 250ml of water and 110 ml of ethanol.

Final yield after drying: 15.72 grams

Extra note on this one. The burn is not as quick. There might be something off with this batch. Some testing is required when making blasting caps with it. If the 2nd batch successfully detonates a booster like ETN then it is good enough. Testing is needed to see its power in confinement. If it goes DDT in a pen body with similar power, then that is all good and well. If it can set off a booster then it won't matter, but until then, the first batch is vastly superior.

It could have been the choice of filteration.

To do: Do another filteration of the batch (now separated into two bits) via vaccuum filteration. Give it plenty of both water and alcohol.

Further notes after drying from second cleaning. Situation has improved. Perhaps not as much as the first batch, but still significantly better. For future synthesis. Follow the first method. It is possible that too much ethanol was used, or that too much/too little nickel nitrate.

Final yield after cleaning and tests is 13.25 grams.

NOTEs: Next time DO NOT dextrinate it. It is unnecessary and might actually make it impossible to go full DDT.

FURTHER NOTES FOR SCIENCEMADNESS: Do not use plastic pen bodies as detonator caps. They won't work!

Yes I know I have some anxiety notes written there. But it was a result of the discussion with Mineman and Laboratory of Liptakov on these forums when it comes to disposing of the left over liquid.

At any rate, I have a gas mask now, so the issue will not repeat.

Raid - 15-1-2023 at 14:48

thanks!

Raid - 15-1-2023 at 15:13

also i forgot to ask if you think methanol would work for the reaction medium in place of ethanol, i have never seen it done but i think it might work.

ManyInterests - 15-1-2023 at 20:04

That is a subject of experimentation! I am not sure. I know that Chemplayer tested both 95% ethanol and isopropyl alcohol (I don't know what percentage, but safe to say it was probably 99% or 91%) and he said that ethanol was best.

I've never seen anyone use methanol for this. If you want to dare giving it a try, please do and report your findings!

Edit: for my hydrazine notes. I forgot to change his. The HCl (hydrochloric acid) is NOT optional. All synths I've done that didn't use it were failures. use the HCl first to neutralize the solution before cooling and adding the sulfuric acid.

[Edited on 16-1-2023 by ManyInterests]

Raid - 17-1-2023 at 06:24

ok, ill try methanol today! and ill come back here and report my findings

Raid - 18-1-2023 at 05:33

Ok, I tried methanol and it works. the yield seems is a bit lower but Im guessing that's because of the lower concentration of methanol I'm using. so I'm going to say that its a safe bet to use methanol in place of ethanol, just use higher concentration for better yields.

ManyInterests - 18-1-2023 at 21:11

Great! Can you list the reagents and the amounts and the steps you took? I know I sound a bit obsessive, but I like using the forums as well as open lab notes (for both myself and for future chemists).

Raid - 19-1-2023 at 09:49

I used your procedure but divided everything by 10 as to not waste reagents if this did not work. And instead of ethanol, I used methanol. the yield was a bit lower then it should have been but I will still say that methanol is a viable replacement for ethanol if your don't care about a gram or two.

but since you asked for the steps here they are.

3.9 grams of Hydrazine Sulfate was added to a 100ml beaker along with 2.39 grams of sodium hydroxide.
After that, i added 15ml of Methanol in the first addition. the solution heated up to the point the Methanol was evaporating so make sure to cover the reaction mixture well. i allowed that to stir on the hot plate for around 30 min until somewhat cool. then i added an extra 10ml of Methanol to make sure i freebased all the Hydrazine. and stirred for an hour. I left it on the hot plate for about a day to make sure all the sulfate salts crashed out. then i pipetted off the supernate and put it in a test tube and heated it up to 65c when i added as little Methanol to the Nickel Nitrate as possible. after the Hydrazine solution heated up to 65c,I slowly added the nickel nitrate solution aver the next 2-3 min. Then i gravity filtered the solution and dried on a hot water bath.

ManyInterests - 21-1-2023 at 02:34

Quote: Originally posted by PINKBOII

I used your procedure but divided everything by 10 as to not waste reagents if this did not work. And instead of ethanol, I used methanol. the yield was a bit lower then it should have been but I will still say that methanol is a viable replacement for ethanol if your don't care about a gram or two.

but since you asked for the steps here they are.

3.9 grams of Hydrazine Sulfate was added to a 100ml beaker along with 2.39 grams of sodium hydroxide.
After that, i added 15ml of Methanol in the first addition. the solution heated up to the point the Methanol was evaporating so make sure to cover the reaction mixture well. i allowed that to stir on the hot plate for around 30 min until somewhat cool. then i added an extra 10ml of Methanol to make sure i freebased all the Hydrazine. and stirred for an hour. I left it on the hot plate for about a day to make sure all the sulfate salts crashed out. then i pipetted off the supernate and put it in a test tube and heated it up to 65c when i added as little Methanol to the Nickel Nitrate as possible. after the Hydrazine solution heated up to 65c,I slowly added the nickel nitrate solution aver the next 2-3 min. Then i gravity filtered the solution and dried on a hot water bath.

Did you cool down all the reagents before mixing? I always cooled everything down and kept it in an ice bath when mixing with also keeping most of the beaker covered with cling film while mixing it. ( I keep only as little as needed uncovered to stir properly while covering everything in order to stop the hydrazine from escaping).

Raid - 24-1-2023 at 08:04

the only thing that i left cool was the freebase hydrazine. after stirring for like an hour I left if to sit for a day to cool to room-temp but I guess you could cool in the freezer for faster synthesis. it also should help the Sulfate contamination.

Raid - 11-3-2023 at 10:32

Does anyone think you could use water for the reaction medium in place of the ethanol?

Accidental Hydrazine Nitrate

Hey Buddy - 23-3-2023 at 15:12

I got really lazy and attempted to make some NHN with nickel nitrate solution still acidified and hydrazine in alcohol. It precipitated white Hydrazine Nitrate in EtOH solution and rejected the nickel which stayed in solution. I thought it was obvious but none the less interesting as there is no hypergolic reaction in the alcohol medium.

ManyInterests - 23-3-2023 at 21:38

Quote:

Does anyone think you could use water for the reaction medium in place of the ethanol?

I really don't see how that would work. Water and ethanol are fairly different solvents and I am not sure if it'll work to freebase hydrazine.

Quote:

I got really lazy and attempted to make some NHN with nickel nitrate solution still acidified and hydrazine in alcohol. It precipitated white Hydrazine Nitrate in EtOH solution and rejected the nickel which stayed in solution. I thought it was obvious but none the less interesting as there is no hypergolic reaction in the alcohol medium.

Yeah, this is why I was advised to use an excess of nickel metal to use up all the nitric acid. At first I was thinking of find the 'right' balance until I realized it is smarter to just salvage the left over nickel metal for later use.

Raid - 26-3-2023 at 09:52

I have seen a procedure on freebasing hydrazine to hydrazine hydrate with water and I think i'll try it out. It is said to work well as long is a PH is adjusted accordingly.
It is said that hydrazine sulfate in water is acidic with a PH of 3 and you need to all a hydroxyl group to increase its PH to 11. Then it said to filter to get rid of sulfate contamination.
I will probably chill it to 0-5c to make sure sulfate contamination is at a minimum.
Ill report back the results.

Raid - 1-4-2023 at 14:40

ok, i just tried the process i talked about above and it works very well, Its much faster and better then using an alcohol.

ManyInterests - 2-4-2023 at 12:42

Nice!

So let me see if I can possible recreate what you are saying.

Say I would get water (distilled of course) and add some HCl to get the pH to 3, then add some sodium bicarbonate (or sodium hydroxide) to get it to 11, then chill it and then filter it out any solids, then add that water to the hydrazine sulfate and mix to freebase?

After that, of course, it is warming to 40C and adding the room temp nickel nitrate I assume. I was told not to use dextrin anymore and not to heat to 65C.

Am I on the right track?

Raid - 2-4-2023 at 14:01

you don't need to add HCL, the hydrazine sulfate is acidic in water. I used NaOH to get the ph to

Note: I have tested it with heating to 65c but it does not seem to do anything different if you were just to use no heating.
all the patents i have seen say the same thing.

I would also recommend chilling the solution if the freezer for around 5-7 hours (longer if you want) that should precipitate out the sulfate salts and you should get a better and more pure yield.

[Edited on 3-4-2023 by Raid]

Raid - 14-4-2023 at 06:53

After longer and more testing with freebasing using distilled water, I have noticed that when adding the Ni(NO3)2 to the N2H4 it will sometimes produce a non-energetic salt that has all of the same qualities as regular NHN. One of the main differences it that it does not deflagrate like regular NHN, instead it will just burn and some of it will fly away. It will deflagrate with heating under it. I have not tried to detonate it.
I have a few reasons why this would happen most of which could be traced back to my own fault.
The first thing that I have done is add an alcoholic solution of Ni(NO3)2 to the N2H4 in H20, this could have caused the less energetic salt. I will be fixing this mistake later today and reporting on what I find.
Also, when adding the alcoholic solution to the N2H4 it forms a bit of a supernatant that can be easily broken upon mixing the solution. This does not happen when using all EtOH for the reaction medium. I'm guessing that this is caused by the difference in density or water content (most likely density).
If you're wondering if this freebasing technique works well I can say that it does, if your not sure what I'm talking about scroll up and look for where I talk about it. The only downside is that your getting more sulfate contamination with the hydrazine, this can be fixed by chilling it until the sulfates crash out. This has its own problem because the water will freeze if your using a freezer.
The best method I have used is distilling it. This will take out most of the impurities. If you don't want to do any of these then I would recommend buying hydrazine sulfate from Amazon or HiMedia, The prices are cheap for hydrazine sulfate. I got 100g for $16 which I thought was a reasonable price. Store-bought Hydrazine Sulfate is much purer compared to synthesizing it yourself and will reduce the chance of metal contamination by lots. If you don't want to buy it, I would reccomend freebasing the N2H4 and then distilling it untill you get your desired consentration then you can get the sulfate or chloride if desired. This is one of the easiest ways to reduce the contamination of DIY hydrazine sulfate.

Moving on to the theoredical synthesis.
One thing I would like to point out to people is that using the Cl salt of hydrazine (Hydrazine Dihydrochloride or Monohydrochloride) is MUCH better than the sulfate. It will make your end product much better and reduced the chance of getting your Ni(NO3)2 turned in to NiSO4. You may be wondering if this same thing could happen with with the Chloride instead of the Sulfate, In all of my testing with this it takes considerably more Cl ions in solution to convert the Ni(NO3)2 to NiCl2. If your using the Hydrazine Dihydrochloride for the NHN synthesis then having the nitrate converted should not be much of a problem.
I have seen many people on youtube using a synthesis where the N2H4 is added to the Ni(NO3)2, I'm not sure if this is just used to make large batches of NHN or what. If someone could find where they got this synthesis it would be very helpful.
Thanks for reading

[Edited on 14-4-2023 by Raid]

Cubane538 - 31-7-2023 at 11:26

Few days back I made some NHN by adding hydrazine (extracted from hydrazine sulphate and dissolved in ethanol) in Nickel nitrate solution.
When I filtered and dried the product I observed that the colour is violet - blue instead of Liac!!
I also did flame test and it was burning well.
But I'm in confusion wheather it is NHN or something else!!

[Edited on 31-7-2023 by Cubane538]

ManyInterests - 31-7-2023 at 12:39

How fast does it burn? Does it instaneously vanish with a bright flash? Then that is probably good enough.

I need to make more NHN soon, since I am running out. The last time I made it, one of the batches I made seemed sub par. I wonder how well it would work as a cap on its own. I need to test them.

B(a)P - 31-7-2023 at 16:28

I recently saw this on youtube.
https://www.youtube.com/watch?v=enJAVGGTPQ4
Interestingly they use hydrazine sulfate directly (using sodium hydroxide to generate the hydrazine in the solution) with nickel nitrate. I have not tested this approach myself, curious if anyone else has though?

ManyInterests - 31-7-2023 at 16:44

Quote: Originally posted by B(a)P

I recently saw this on youtube.
https://www.youtube.com/watch?v=enJAVGGTPQ4
Interestingly they use hydrazine sulfate directly (using sodium hydroxide to generate the hydrazine in the solution) with nickel nitrate. I have not tested this approach myself, curious if anyone else has though?

That's how I've been doing it all the time. He used Isopropyl alcohol while I used ethanol. It is possible to use methanol as well, but ethanol has the best yields.

When I freebase my hydrazine sulfate with sodium hydroxide and ethanol, I also need to filter out whatever solids that are left behind (my process for hydrazsulfate always has a little sodium sulfate in it). One thing that he is doing that I must do next is add nickel nitrate until I get that excess added and used up all my hydrazine freebase. since I didn't know you could do that (and easily get rid of the surplus, since NHN is water insoluble).

B(a)P - 31-7-2023 at 17:13

Quote: Originally posted by ManyInterests

Quote: Originally posted by B(a)P

Where did they say they used isopropyl alcohol to liberate hydrazine? My understanding was they dissolved hydrazine sulfate in water then added sodium hydroxide to pH 8, heated the solution, then added the nickel nitrate solution. The isopropyl alcohol was used to wash the product.

Cubane538 - 31-7-2023 at 18:17

Quote: Originally posted by ManyInterests

How fast does it burn? Does it instaneously vanish with a bright flash? Then that is probably good enough.

I need to make more NHN soon, since I am running out. The last time I made it, one of the batches I made seemed sub par. I wonder how well it would work as a cap on its own. I need to test them.

Here you can see the video..

Attachment: 20230801_073927~2.mp4 (4.7MB)
This file has been downloaded 154 times

ManyInterests - 31-7-2023 at 20:08

Quote:

I stand corrected. I was confusing videos in my mind with one where Chemplayer freebases hydrazine with IPA and Ethanol in two separate attempts.

I did remember that Raid said he did liberate it with just water. I might do that next time if it is easier. Just keeping in mind that the pH needs to be 8 or thereabouts. I'm probably going to continue to use the old ethanol method since it worked for me quite a few times.

Quote:

Here you can see the video..

Attachment: 20230801_073927~2.mp4 (4.7MB)
This file has been downloaded 3 times

I always lit my NHN from the top and not the bottom, but that is some slow burning stuff. I think there is something wrong with it, but sadly I cannot tell what... :\

ManyInterests - 6-4-2024 at 18:28

I need to bump this thread back up due to a series of rather... irritating events. I wanted to make more NHN and since I had been quite experienced in making it and seen numerous setbacks and know how to deal with them, but my last two synthesis, especially my latest, has been a failure and I really don't understand why.

So here are the number of reagents used:

Hydrazine sulfate: 43.25g
95% ethanol: 150ml
sodium hydroxide: 26.4g

I had freebased my hydrazine the same way as I done before. Added the ethanol to the sulfate, mixed it thoroughly, then added the sodium hydroxide (I did it in one fell swoop). Everything was put in the fridge for days so it was ice cold to begin with, and I did it while everything was in an ice bath to keep things cool. The temperature never rose above 9C the whole time.

I mixed in a covered beaker and allowed it to settle, then mixed and such for 35 minutes to allow all the hydrazine to freebase. Then I filtered off the sulfate into a flask and heated it up (also covered) with strong stirring. I need to mention that the heating on my mantle is a bit unpredictable. When it was reaching the 60C the temperature then almost immediately shot up to 75C. Also since I was doing this on a windy day on my balcony, my flask tipped as well, it loosed up the plastic wrap that I was using to seal it and I saw fumes come out (no inhalation, I am fine). But when I added the nickel nitrate solution (I added more water to it, but it is still very emerald green, as pictured).

I am really confused as to what is happening here. My last attempt worked, but it yielded barely 4g. The last successful time I made it was in 2022 and I made two attempts that yielded 11.4g (of excellent quality NHN) and of 15.5g (of poor quality NHN that I had to get rid of) respectively. All other previous successful synthesis of mine also yielded much higher amounts of high quality NHN.

The first times I attempted they failed due to my hydrazine synthesis not working. But when I made the hydrazine sulfate for this they absolutely WERE hydrazine. I am really baffled.

Any thoughts? Any help?

Edit: Maybe I freebased my hydrazine wrong and it was destroyed by the temperature spike?

Edit2: when I added the nickel nitrate to the hydrazine solution It didn't turn torquoise blue. It remained green. Normally in a successful synthesis it would be immediately purple.

Edit3: upon further thing, this probably is a hydrazine issue. Either the original synthesis, or I was too cavalier with the freebasing.

IMG_20240406_222009100 - Copy.jpg - 1.7MB

[Edited on 7-4-2024 by ManyInterests]

[Edited on 7-4-2024 by ManyInterests]

[Edited on 7-4-2024 by ManyInterests]

Sir_Gawain - 6-4-2024 at 20:53

Are you sure the free-basing reaction took place at all? If your reagents are dry and cold enough, the reaction may not start. What’s your source of hydrazine sulfate and nickel nitrate?

ManyInterests - 7-4-2024 at 04:49

Quote: Originally posted by Sir_Gawain

Are you sure the free-basing reaction took place at all? If your reagents are dry and cold enough, the reaction may not start. What’s your source of hydrazine sulfate and nickel nitrate?

That could be my problem. It could have been too cold. All regents were very cold except for the nickel nitrate solution, it was at room temperature.

The Hydrazine sulfate I made myself with the Hoffman rearrangement of urea. The nickel nitrate was purchased from a chemical supplier online. It was Nickel(II)nitrate hexahydrate.

I had successfully made hydrazine sulfate many times before and they all made NHN. At this point I will believe that you are right. No freebasing occurred because everything was too cold.

Edit: This is one aspect that I as unaware would happen. I had no idea that that freebasing needs some decent temperature. I remember being warned that it can get hot and you can lose your hydrazine, I didn't store ingredients in the fridge previously, I think this was the mistake I made this time. Not my nickel nitrate solution being too concentrated or maybe even the temperature spike on the mantle.

[Edited on 7-4-2024 by ManyInterests]

Pages: 1 2