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Author: Subject: NHN synthesis not working
MineMan
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[*] posted on 29-11-2021 at 19:09


Quote: Originally posted by ManyInterests  
Quote:
Ask the pbn3 guy, he is active on another form


Which forum? He would be the perfect person to ask as his videos on NHN synthesis are the best I have ever seen. His yields are none too shabby either. If I can get one singular good yield of NHN on my first attempt it'll be the only attempt I need to do.

Quote:

I have used the following approach with success.
Use an excess of nickel so that your acid is mostly consumed by the reaction.
Add approximately 10 mls of 35% peroxide for every 100 mls of 70 % nitric acid.
Heat until a reaction is observed then reflux at that temperature untill the reaction ceases.
Upon cooling you should get a good crop of nickel nitrate crystals.
Be aware that you will generate copious quantities of nitrogen dioxide.
You can get a second crop of crystals by boiling down the remaining solution, but be aware that the vapour will contain nickel nitrate.


That sounds good. And I am aware of the gasses released, which is why I always do these things outdoors. I will also try to to boil it down further as well, but the nickel nitrate in the air sounds quite nasty so I will need to be extra careful with that.

Just one additional question: When you say use an excess of nickel. How much of an excess are we talking about? Say hypothetically I did want to use 10ml of peroxide and 100ml of HNO3, how much nickel would you put in there?


He responds to his YouTube comment.
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ManyInterests
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[*] posted on 10-12-2021 at 15:38


So I am running a nickel nitrate synthesis and it has been running for 2 hours as well as of writing this.

I had a runaway at the first attempt. I used 20 grams of nickel metal, added 6ml of hydrogen peroxide, and then I added 30ml of nitric acid (around half my supply) and it almost immediately had a runaway. Thankfully I managed to put the small flask down and I cleaned the spill. I managed to recover 12 grams of the nickel metal (the others are still on the ground, I'll sweep them off later). I tried again with another 20 grams of nickel metal, 31ml of nitric acid, and around 2.5 ml of hydrogen peroxide (35%). I added the acid to the metal first, and I added the hydrogen peroxide afterward, and it reacted quite violently with it. Thankfully I managed to put the flask in the reflux column right away. The column bulbs filled with NO2 gasses, but no spill happened.

I submerged the boiling flask in a beaker full of water and I have been boiling the water for 2 hours now.

I don't see any more bubbling in the flask. Does that mean the reaction is done? I don't see any supernate. There is still quite a bit of metal in the flask.

Is the green liquid nickel nitrate? Can I use that liquid directly in the hydrazine in order to make NHN?
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[*] posted on 10-12-2021 at 21:11


I think I did it! Below are posted the pictures of my nickel nitrate The first two are of when I took it off the heat, and the third is when it cooled (no ice bath. All room temp).

The question now is getting my nickel nitrate out of the boiling flask!

Nickelnitrate1.jpg - 2.4MBNickelNitrate2.jpg - 2MBNickelNitrate3.jpg - 2MB
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fredsci93
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[*] posted on 10-12-2021 at 22:25


Quote: Originally posted by ManyInterests  
Is the green liquid nickel nitrate? Can I use that liquid directly in the hydrazine in order to make NHN?


The green solution is Nickel nitrate for sure, as for using the solution directly for making NHN, NHN's synth is quite pH dependant so if the solution still contains nitric acid then it's not suitable, not sure about what the hydrogen peroxide could do to the NHN, it could possibly form nickel oxides/peroxides along with Nickel (iii), so I would avoid peroxide contamination.
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[*] posted on 10-12-2021 at 22:37


I had another person post that I should try to reduce the volume some more. So tomorrow I'll put the little flask on the boil for another 10 or 15 minutes until it is completely dry. There will still be some unreacted nickel metal in my flask, but I can remove them later.

I am not too worried about the peroxide. There was barely any in there, and I am sure it is all used up. (I put in 2 ml, and not more than 2.5ml of 35%. This was actually far too strong a peroxide. When I do this again I need to dilute it to down to 30 or 15% even). Boiling a solution is a sure way of destroying the peroxides in it.

I believe it will be much easier to dry it completely. I hope the pH would drop by then. If it doesn't, what can I do to lower it? would adding a dab of baking soda help?

The question I have in my mind now is making the hydrazine hydrate from my hydrazine sulfate. I made about 60 grams of the sulfate (and I probably have a decent amount of sodium sulfate contamination). I've been people put sodium hydroxide and ethanol to draw it out. But I have also been thinking of distilling my hydrazine with the hydroxide and some water to make a 64% azeotrope.

I've seen pyrotechnical science do that on his youtube channel. He stated the amount of sulfate and hydroxide, but didn't say how much water he put in.
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[*] posted on 10-12-2021 at 22:48


If the nickel nitrate is fully dried then the pH will not be a problem, I would strongly dissuade hydrazine distillation considering the conditions required, for freebasing it I turned to chemplayers sodium azide synth (https://www.bitchute.com/video/wWKcMMoAgeVP/), the procedure is as follows, 1mol eq sodium hydroxide mixed with 1mol eq hydrazine sulphate in ~200ml/mol ethanol (1mol hydrazine sulfate would need 200ml, 0.5mol would need 100ml etc) cooled with an ice bath, after the sodium hydroxide dissolves and reacts add another mol equivalent of sodium hydroxide and let react. After everything has reacted decant the solution through a coffee filter while retaining the solids, add more ethanol to the solids and filter to extract the final amounts of hydrazine. there are other methods involving calcium hydroxide or barium hydroxide, however this one is the easiest and cheapest.
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[*] posted on 11-12-2021 at 07:54


OMG, I had downloaded that video ages ago specifically for the hydrazine sulfate freebasing. I totally forgot I had it.

Since it is ultra snowy and cold outside where I live. I can do the hydrazine freebasing outside. The ambient coolness will help in keeping the reaction temperature low (I will still bring an icebath anyway).

I guess to that ethanol-hydrazine solution I just add the nickel nitrate solution made with distilled water? With some dextrin added, obviously.

Edit: The Nickel nitrate is rock solid. This is quite dry. I seriously doubt there is any nitric acid left.

[Edited on 11-12-2021 by ManyInterests]

[Edited on 11-12-2021 by ManyInterests]
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[*] posted on 11-12-2021 at 12:20


Yea, just add the nickel nitrate in water to the ethanol solution, the concentrations aren’t crucial, I actually just made up the concentrations for my NHN synth based on what "felt right" 10-20% nickel nitrate in water seemed to work well, I didn’t add any dextrin but from what I've heard it's very beneficial to do so.
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[*] posted on 11-12-2021 at 14:46


Well I ran into one complication... the nickel nitrate is so rock solid in the boiling flask that I cannot remove it. I will need to remove it by adding boiling hot water into the flask directly. I don't know how much to add since I cannot weigh my final yield. so I'll have to eyeball this one.

The dextrin is very useful because it allows the final NHN to be collected via a talcum powder consistency instead of hard chunks.

Right now I need to make pure guess work. I put in 20 grams of nickel metal. Not all of it reacted and turned to nickel nitrate. I will put in around 200mg of dextrin. As the percentage of dextrin should be a minimum of 0.1% to 1%. Play it safe and conservative and it should turn out mine.

Time to freebase some hydrazine...
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[*] posted on 11-12-2021 at 16:17


Ok, so I added around 30 grams of sodium hydroxide (in portions. Temp never went above 10C) and added around 110 ml of 95% ethanol. I stirred it constantly for around 20 minutes and left it for another 30 minutes now. there is a lot of liquid, but is colored very milky white and not clear at all even after letting it set for a while.

Is this still hydrazine hydrate? I am really not sure if I succeeded or what here.
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[*] posted on 11-12-2021 at 18:36


Ok I saw some clear hydrazine hydrate. But when I poured it in, the same milky white stuff got into my flask. After cooling it in the freezer and adding even more ethanol.

I still didn't get any clear hydrate. I eventually decided... it might still be hydrazine hydrate. It might still work! I boiled some distilled and dextrinated water to free up the nickel nitrate, and the nitrate was quite dark green. But I noticed I had a LOT of unreacted nickel metal. I mean a lot... I will need to add an excess of nitric acid next time in order to get more nickel nitrate. But I did get around 210ml of very dark green nickel nitrate.

I started heating and stirring the solution to 65C and began to add the nickel nitrate. the solution turned from milky white to a light green. It did not turn into the beautiful purple color, but instead remained that way. I do see some minor NHN formation at the absolute bottom ( there is some purple there. I don't think it can be anything else) But there does appear to be some other solid forming. I do not know what it is. But I don't think it is nickel hydrazine nitrate.

My first synthesis... well. I need to try again later. I need to practice freebasing hydrazine, or making better hydrazine sulfate as I think it was mostly sodium sulfate.

Edit: I added calcium hypochlorite and some of my 10% sodium hypochlorite solution to the stuff. The goop and the liquids turned black. I assume this is because of the hydrazine contents. I also poured sodium bicarbonate water on them to remove any possible acids. I hope this will render them safe when I throw them away.


[Edited on 12-12-2021 by ManyInterests]
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[*] posted on 11-12-2021 at 21:38


It's easy to determine, without chemicals, indicators etc., whether a sulfate is hydrazine or sodium; with a blowtorch, test tube, and about 15 seconds.



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[*] posted on 11-12-2021 at 22:42


Quote:
It's easy to determine, without chemicals, indicators etc., whether a sulfate is hydrazine or sodium; with a blowtorch, test tube, and about 15 seconds.


I have a barbique lighter but no test tubes. Is that sufficient?
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[*] posted on 12-12-2021 at 01:44


Quote: Originally posted by ManyInterests  

Edit: I added calcium hypochlorite and some of my 10% sodium hypochlorite solution to the stuff. The goop and the liquids turned black. I assume this is because of the hydrazine contents. I also poured sodium bicarbonate water on them to remove any possible acids. I hope this will render them safe when I throw them away.
[Edited on 12-12-2021 by ManyInterests]


Shame about the synth going sour, on another note, I think the black color is due to nickel oxide peroxide since it can form in the presence of basic hypohalide ions.
btw Calcium hypochlorite should render everything safe if you leave everything overnight.
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[*] posted on 12-12-2021 at 08:25


That's good. I left it out overnight as the winds were very blustery and I didn't want to touch any of the stuff. There is still some green in it. But I am not too worried. I will pour a little more calcium hypochlorite and wrap the thing in multiple overlapping garbage bags before throwing them out. The first rule of home chemistry: Be safe and responsible.
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[*] posted on 12-12-2021 at 15:21


Quote: Originally posted by ManyInterests  
That's good. I left it out overnight as the winds were very blustery and I didn't want to touch any of the stuff. There is still some green in it. But I am not too worried. I will pour a little more calcium hypochlorite and wrap the thing in multiple overlapping garbage bags before throwing them out. The first rule of home chemistry: Be safe and responsible.


What a boring and unadventurous rule. I for one like to take life by the horns.
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[*] posted on 12-12-2021 at 16:13


Quote:
What a boring and unadventurous rule. I for one like to take life by the horns.


Well that rule prevents chemical burns, amputated fingers and burned lungs. It's the reason why I want to make NHN instead of something much easier (and far more dangerous) like TATP and HMTD.
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[*] posted on 13-12-2021 at 03:14


Quote: Originally posted by ManyInterests  
Quote:
What a boring and unadventurous rule. I for one like to take life by the horns.


Well that rule prevents chemical burns, amputated fingers and burned lungs. It's the reason why I want to make NHN instead of something much easier (and far more dangerous) like TATP and HMTD.


You should follow LL. CHP I believe is better than NHN from what I read. LL is a hero a round here. I am named my firstborn after him.
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[*] posted on 13-12-2021 at 03:34


Quote: Originally posted by MineMan  


You should follow LL. CHP I believe is better than NHN from what I read. LL is a hero a round here. I am named my firstborn after him.


CHP is a good energetic, but from what I've seen it's worse than NHN in terms of raw power (det velocity, ect), although I haven’t compared the two directly. CHP in general seems like a more "useful" explosive since it can reach max density more easily is less impact sensitive etc, but NHN is more powerful.
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[*] posted on 13-12-2021 at 07:20


Quote: Originally posted by fredsci93  
Quote: Originally posted by MineMan  


You should follow LL. CHP I believe is better than NHN from what I read. LL is a hero a round here. I am named my firstborn after him.


CHP is a good energetic, but from what I've seen it's worse than NHN in terms of raw power (det velocity, ect), although I haven’t compared the two directly. CHP in general seems like a more "useful" explosive since it can reach max density more easily is less impact sensitive etc, but NHN is more powerful.


Both are 7kms, for a primary that is quite excellent. Anyways many interests, the doctor is your friend :)
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[*] posted on 13-12-2021 at 08:19


CHP sounds very interesting. But I didn't hear about it until fairly recently and was already committed to making NHN. I'll leave it for another time.

I did look up CHP synthesis here, it seems it needs TACP, which I don't have. I also don't have ammonia water at 25%. I am not proficient in concentrating ammonia (never attempted it), and I don't have ammonium perchlorate and never attempted to make it.

I'll chaulk it up to a future project... for now I just want to get this NHN situation dealt with.
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[*] posted on 13-12-2021 at 09:11


When you are dissolving nickel metal in nitric acid, you need to use much more acid (or less of the metal). Depending on the ratio of nitrogen oxides produced in the redox reaction, you require a stoichiometric minimum of 80-120 grams of 70% HNO3 to dissolve 20 g Ni, probably more to account for losses. Also, dispense with the peroxide; it isn't necessary.
I recommend not cooling during the freebasing. It is not an exceedingly exothermic reaction, and excessive cooling will just make it slower. You should look for a copy of Leonid Lerner's "Small Scale Synthesis of Laboratory Chemicals". It is excellent, and specifically covers synthesis of HS and the freebasing and extraction with ethanol.
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[*] posted on 13-12-2021 at 12:04


I guess maybe it was the fact that I kept things too cold is why it didn't freebase correctly? Either way I will try it again today with whatever hydrazine sulfate (as contaminated as it is with sodium sulfate) and try to filter the stuff out when it freebases.
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[*] posted on 13-12-2021 at 12:05


the freebasing gets very hot, so much to that it can occasionally boil, cooling (if not an ice bath then a water bath) is necessary based off what i've seen.

[Edited on 13-12-2021 by fredsci93]
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[*] posted on 13-12-2021 at 14:52


Quote: Originally posted by LardmanAttack  
I'll filter it off and put it in a freezer to extract the majority of the NaOH and NaSO4 before using.


There may be difficulties in getting the NaOH to precipitate. Hydroxide in the alcohol would be pretty bad, not only for the Ni but also the hydrazinate itself. I have to wonder about dissolving the hydrochloride in the minimum amount of hot methanol and adding the appropriate amount of conc. Na methoxide, and filtering maybe after concentrating a bit by distillation, if the hydrazine stays put.

But then again there's a 1955 JCE article with ethanolic nitrate and hydrate, where the desiccated "extremely fine pink powder" exploded while being held (1.5 g in evaporating dish)...maybe it was static...but they suspect it was excess hydrazine or any other reason except static. Maybe the product prepared with minimal water is more sensitive?...I haven't read the Mem. Poudres articles/abstracts where it was so made.

Quote: Originally posted by Microtek  
Why do you use ethanol as the reaction medium? Most reported syntheses I have seen uses aqueous solutions.


But not all.

Quote: Originally posted by wessonsmith  
It's essential to produce it the way I do; otherwise, you won't get the beautiful free-flowing powder.


Quote: Originally posted by wessonsmith  
To properly make NHN one needs a temp range of 65-70°C.


Quote: Originally posted by wessonsmith  
With NHN high temperature is a must.


(and so on...)

This feels dubious. There's a very interesting Chinese article using sonication and no heat, with lots of dirty pictures...some really nifty hexagonal plates and gorgeous hexagonal rods...what they got was quite dependent on several conditions such as additives, concentration of nickel or hydrazine, time digesting, i.e. everything. With increasing heat came increasing size and irregularity.

Quote: Originally posted by Microtek  
Also, dispense with the peroxide; it isn't necessary.


It probably doesn't help with passivation, but is said to prevent ammonium nitrate from forming.

[Edited on 13-12-2021 by S.C. Wack]




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