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Author: Subject: NHN synthesis not working
wessonsmith
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[*] posted on 18-2-2020 at 14:27


Quote: Originally posted by Rosco Bodine  
There is no contradiction in what you have observed. The concentration of a reaction mixture and rate of addition, generally are inversely proportional and act counter to increasing crystal size while temperature increase promotes larger crystals.

Greater dilution, slower addition, longer reaction time, higher temperature, and more turbulence to keep precipitates suspended instead of forming "sand dunes" on the bottom of the reactor promotes crystal growth to larger size, and generally the reverse of those factors results in much smaller crystals.

You could try 90 C and see what results at half the concentration with half rate of addition and 4 times longer reaction time with increased turbulence if needed...to see if there is any difference. But a disadvantage is that yield can suffer when a reaction is not being optimized for yield but for a specific physical form for the product. So what is an optimal synthesis can be a tradeoff to find what is most practical.

[Edited on 2/18/2020 by Rosco Bodine]


I think 90C would be pushing the safety limit for hydrazine. Here is a study that was done on NHN. They tried both 65C and 25C and documented the results.

https://www.amazon.com/clouddrive/share/sRTDsJNM9rHNa7FPQ9gh...
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Rosco Bodine
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[*] posted on 18-2-2020 at 16:07


Temperatures well exceeding 90C won't likely be a problem for aqueous hydrazine.

It is used industrially as a boiler water oxygen scavenger, and superheated under pressure in steam plants.

Personally I would have no huge fear issue running it into a complexation reaction mixture even at 95C.


Sigma pump it into the reactor, microaddition stream through a capillary well below the surface and it will complex and be sequestered before air exposure degrades it.


[Edited on 2/19/2020 by Rosco Bodine]
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wessonsmith
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[*] posted on 18-2-2020 at 16:28


Quote: Originally posted by Rosco Bodine  
Temperatures well exceeding 90C won't likely be a problem for aqueous hydrazine.

It is used industrially as a boiler water oxygen scavenger, and superheated under pressure in steam plants.

Personally I would have no huge fear issue running it into a complexation reaction mixture even at 95C.


Sigma pump it into the reactor, microaddition stream through a capillary well below the surface and it will complex and be sequestered before air exposure degrades it.


[Edited on 2/19/2020 by Rosco Bodine]


I might experiment with a higher temp. As it stands now, the NHN I produce at the 65-70c range has excellent properties. In my detonators and as the small particle size energetic for my plastic. I can't imagine it can get any better, but perhaps.
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Rosco Bodine
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[*] posted on 18-2-2020 at 20:01


So continuing this "stream of consciousness" ....I can offer this idea ...

Tris semicarbazide manganese perchlorate is another possible compound that might be interesting. I have investigated *zero* references about this speculated material.

Maybe form a solution of calcium perchlorate by reacting Calcium Hydroxide in excess with Ammonium Perchlorate and heating to drive off byproduct Ammonia, filter to obtain solution of Calcium Perchlorate. Mix solution of Calcium Perchlorate with solution of Manganese Sulfate and filter precipitated Calcium Sulfate from solution of Manganese Perchlorate. React solution of Manganese Perchlorate with 3 equivalents of Semicarbazide to form Tris Semicarbazide Manganese Perchlorate.

That would be the perchlorate analog of the nitrate variant described in attached patent US6127564


Attachment: US6127564 Semicarbazide Manganese Complex.pdf (79kB)
This file has been downloaded 280 times



[Edited on 2/19/2020 by Rosco Bodine]
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wessonsmith
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[*] posted on 19-2-2020 at 07:29


Quote: Originally posted by Rosco Bodine  
So continuing this "stream of consciousness" ....I can offer this idea ...

Tris semicarbazide manganese perchlorate is another possible compound that might be interesting. I have investigated *zero* references about this speculated material.

Maybe form a solution of calcium perchlorate by reacting Calcium Hydroxide in excess with Ammonium Perchlorate and heating to drive off byproduct Ammonia, filter to obtain solution of Calcium Perchlorate. Mix solution of Calcium Perchlorate with solution of Manganese Sulfate and filter precipitated Calcium Sulfate from solution of Manganese Perchlorate. React solution of Manganese Perchlorate with 3 equivalents of Semicarbazide to form Tris Semicarbazide Manganese Perchlorate.

That would be the perchlorate analog of the nitrate variant described in attached patent US6127564
[Edited on 2/19/2020 by Rosco Bodine]


Interesting. Here is a link to a PDF of experiments done on various NHN analogs.
https://www.amazon.com/clouddrive/share/pI2jIvnYirlhkCnj1ioc...

[Edited on 19-2-2020 by wessonsmith]
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Rosco Bodine
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[*] posted on 19-2-2020 at 12:49


That linked paper seems familiar ....:D

http://www.sciencemadness.org/talk/viewthread.php?tid=1778&a...

Pasteurized Sunglasses.bmp - 1.6MB
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wessonsmith
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[*] posted on 19-2-2020 at 13:11


Quote: Originally posted by Rosco Bodine  
That linked paper seems familiar ....:D

http://www.sciencemadness.org/talk/viewthread.php?tid=1778&a...


Great minds think alike:)
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Rosco Bodine
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[*] posted on 19-2-2020 at 13:26


Hindsight is 20/20 and what da ya know .....
looking back it is like deja vu all over again....
and here we are in 2020 for real
Hindsight is like a time machine for sure :D

https://www.youtube.com/watch?v=Rp20xUdx62Q Out Of The Blue - APP

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Rosco Bodine
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[*] posted on 19-2-2020 at 14:44


Mixed complexes and complex double or multiple salts are likely possible in this class of compounds where it might be interesting to first form an ammonium complex in solution and then add the desired substituent complexing agent of higher molecular weight which should in part or completely displace the ammonium. Methylamine, glycine, betaine, hydrazine, semicarbazide, carbohydrazide, aminoguanidine, ethanolamine, ect, should act in this way when added alone or in combination, and interesting products should be precipitated having compositions that would depend on the ratio of substitutents added.
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[*] posted on 20-2-2020 at 11:30


Quote: Originally posted by wessonsmith  
Here is the NHN synthesis video.

https://youtu.be/rPxdDSUGxo4


Hi Wessonsmith, has this been deleted? Just tried to check it out and no luck.
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[*] posted on 20-2-2020 at 12:49


Quote: Originally posted by B(a)P  
Quote: Originally posted by wessonsmith  
Here is the NHN synthesis video.

https://youtu.be/rPxdDSUGxo4


Hi Wessonsmith, has this been deleted? Just tried to check it out and no luck.


it's back up. I take down my videos to stay under the radar. Please download anything you like.
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[*] posted on 20-2-2020 at 13:25


Quote: Originally posted by wessonsmith  
Quote: Originally posted by B(a)P  
Quote: Originally posted by wessonsmith  
Here is the NHN synthesis video.

https://youtu.be/rPxdDSUGxo4


Hi Wessonsmith, has this been deleted? Just tried to check it out and no luck.


it's back up. I take down my videos to stay under the radar. Please download anything you like.


Great thanks so much! Another excellent video.
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Rosco Bodine
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[*] posted on 21-2-2020 at 06:47


Quote: Originally posted by wessonsmith  
Quote: Originally posted by B(a)P  
Quote: Originally posted by wessonsmith  
Here is the NHN synthesis video.

https://youtu.be/rPxdDSUGxo4


Hi Wessonsmith, has this been deleted? Just tried to check it out and no luck.


it's back up. I take down my videos to stay under the radar. Please download anything you like.


You could upload the video files to the scipics directory here, if the allowable file types permit this and files aren't too huge.
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[*] posted on 14-1-2021 at 14:09


For what I thought, the hydrazine sulfate, which is acidic as solution, would be neutralized with NaOH to form sodium sulfate and hydrazine (hydrate). When nickel nitrate is introduced as per reactions Mr. Wesson presented, all the other compounds are soluble except NHN, and by this logic, it should form and precipitate out of the solution, and all of the rest will be rinsed away during filtration&washing.
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[*] posted on 14-1-2021 at 16:53


Quote: Originally posted by Fyndium  
For what I thought, the hydrazine sulfate, which is acidic as solution, would be neutralized with NaOH to form sodium sulfate and hydrazine (hydrate). When nickel nitrate is introduced as per reactions Mr. Wesson presented, all the other compounds are soluble except NHN, and by this logic, it should form and precipitate out of the solution, and all of the rest will be rinsed away during filtration&washing.


I have tried this numerous times and could not get it to work.
The only way I could get from hydrazine sulfate to NHN was by reacting the hydrazine sulfate and sodium hydroxide in ethanol in an ice bath. I then used the ethanol/hydrazine solution to react with nickel nitrate dissolved in water following the approach outlined by wessonsmith.
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[*] posted on 15-1-2021 at 04:33


I see. Have you got any idea what reaction mechanism disrupts the formation?
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[*] posted on 15-1-2021 at 11:53


Quote: Originally posted by Fyndium  
I see. Have you got any idea what reaction mechanism disrupts the formation?


I do not. I researched it at length as it seems a far easier approach than trying to extract hydrazine in ethanol due to the low solubility of hydrazine sulfate at the low temperature required.
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[*] posted on 15-1-2021 at 14:09


There must be something else going on, then.

If there is nickel nitrate, sodium sulfate and hydrazine hydrate, the logic would say that the only compound that crashes out of the solution will be nickel hydrazine nitrate, leaving behind a water solution of sodium sulfate.

Would be waste of time to test out that it doesn't work, if you have already done that. On the other hand, chemistry is try and error game. On the other hand, making azeotropic hydrazine does not appear to be too challenging, as it can be done in basic distillation app with NaOH and enough water to balance with the azeotrope amount, simultaneously allowing the reaction to occur, as well. A slight corrosion of flask would not be an issue, like I said in hydrazine topic, as they can basically bought by the kilo from chinese suppliers, presuming you aren't using your most precious and expensive 12-neck jacketed reaction vessel for the job. Also, everyone's got hydrazine sulfate, but not all got hydrazine.
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[*] posted on 28-11-2021 at 19:51


I am necroing this thread in order to clear up any possible questions I have before I start to do my NHN synthesis.

While I haven't tried it yet, I think from all the information I gathered I have a decent idea on freebasing hydrazine sulfate into hydrazine hydrate. But for nickel nitrate I have some questions.

When making the nickel nitrate, I saw everyone reflux it in a boiling flask with nickel metal, nitric acid (65-70%) and hydrogen peroxide (30-35%) for a few hours. They didn't specify what temperature, but from what I've seen it would just below the boiling point of water. I can do this in a hot water bath and monitor it's temperature. When doing this, what signs do I need to look for that it is ready?

From what I've read here, the nickel nitrate must be free of the acids. I've seen people put the stuff in a buchner funnel and drain off the remaining acid/liquid. I also heard that it is really, really hard to remove it this way because of how soluable the nickel nitrate crystals are. I went through several threads on this and I am still not entirely sure.

I did see the Pyrotechnical Science try to heat it to dryness but it formed a goo instead (he was still able to synthesis NHN with it by adding water) and video from the channel PbN3 2 where he just dries it on the buchner funnel and it forms nice blue-ish crystals shortly after cooling. I guess the solution that is made after refluxing the nickel metal, HNO3, and H2O2 can't be used directly?

What would be the ideal way to obtaining/using the nickel nitrate in this situation?
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[*] posted on 29-11-2021 at 00:23


Quote: Originally posted by ManyInterests  
I am necroing this thread in order to clear up any possible questions I have before I start to do my NHN synthesis.

While I haven't tried it yet, I think from all the information I gathered I have a decent idea on freebasing hydrazine sulfate into hydrazine hydrate. But for nickel nitrate I have some questions.

When making the nickel nitrate, I saw everyone reflux it in a boiling flask with nickel metal, nitric acid (65-70%) and hydrogen peroxide (30-35%) for a few hours. They didn't specify what temperature, but from what I've seen it would just below the boiling point of water. I can do this in a hot water bath and monitor it's temperature. When doing this, what signs do I need to look for that it is ready?

From what I've read here, the nickel nitrate must be free of the acids. I've seen people put the stuff in a buchner funnel and drain off the remaining acid/liquid. I also heard that it is really, really hard to remove it this way because of how soluable the nickel nitrate crystals are. I went through several threads on this and I am still not entirely sure.

I did see the Pyrotechnical Science try to heat it to dryness but it formed a goo instead (he was still able to synthesis NHN with it by adding water) and video from the channel PbN3 2 where he just dries it on the buchner funnel and it forms nice blue-ish crystals shortly after cooling. I guess the solution that is made after refluxing the nickel metal, HNO3, and H2O2 can't be used directly?

What would be the ideal way to obtaining/using the nickel nitrate in this situation?


Ask the pbn3 guy, he is active on another form
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[*] posted on 29-11-2021 at 01:04


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.
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[*] posted on 29-11-2021 at 06:22


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?
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[*] posted on 29-11-2021 at 12:06


Quote: Originally posted by ManyInterests  


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?


A large excess, so that you don't have lots of little pieces of metal to separate from your solution at the end of the reaction. So for that volume of acid approximately 80 g of nickel, depending on the size and shape of the pieces of nickel that you have.
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[*] posted on 29-11-2021 at 14:12


So as a general estimate it is 80% nickel metal to the HNO3/Nitric acid. I only have 60 grams of 99.96% pure nickel metal strips so I guess the example amount you mentioned is out of my range. I don't want to make that much NHN anyway.

https://amzn.to/3d0YZnu

This is how my supply of nickel metal looks like. What I did now is cut 20 grams of the strips into tiny chips. I plan on making two batches with 10 grams each. So it would be 10 grams metal to 12.5 ml of HNO3, and 1.25ml of hydrogen peroxide? This is substantially less than what PbN3 2 did at what I believe is 10 grams of metal to 30ml of 68% nitric acid and 10ml of hydrogen peroxide.

But if its a successful synthesis you made, I guess it wouldn't hurt to experiment. Especially since it doesn't require that much HNO3. Worst comes to worse I can always buy more nickel metal from amazon.

And just a safety question for disposal... after making NHN and draining off the liquid. Do I neutralize the remaining liquid with bleach (for the hydrazine) and add sodium bicarbonate (for the acids) and then pour it down the drain? Or is there another safety protocol for that?
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[*] posted on 29-11-2021 at 17:03


Quote: Originally posted by ManyInterests  
So as a general estimate it is 80% nickel metal to the HNO3/Nitric acid. I only have 60 grams of 99.96% pure nickel metal strips so I guess the example amount you mentioned is out of my range. I don't want to make that much NHN anyway.

https://amzn.to/3d0YZnu

This is how my supply of nickel metal looks like. What I did now is cut 20 grams of the strips into tiny chips. I plan on making two batches with 10 grams each. So it would be 10 grams metal to 12.5 ml of HNO3, and 1.25ml of hydrogen peroxide? This is substantially less than what PbN3 2 did at what I believe is 10 grams of metal to 30ml of 68% nitric acid and 10ml of hydrogen peroxide.

But if its a successful synthesis you made, I guess it wouldn't hurt to experiment. Especially since it doesn't require that much HNO3. Worst comes to worse I can always buy more nickel metal from amazon.


It will be easier to dissolve the nickel with an excess of acid, but then you need to deal with the acid in with your nickel nitrate solution. If you use an excess of nickel, then the nickel that is not consumed can be removed and rinsed, then stored for later use.
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