Sciencemadness Discussion Board - NHN synthesis not working

Here is the NHN synthesis video.

https://youtu.be/rPxdDSUGxo4

Any particular reason you add the second solution of nickel simultaneously with the hydrazine? Also whats the best method for making the hydrazine solution?

wessonsmith - 12-1-2020 at 14:55

Here is the NHN synthesis video.

https://youtu.be/rPxdDSUGxo4

Any particular reason you add the second solution of nickel simultaneously with the hydrazine? Also whats the best method for making the hydrazine solution?

The reason for the separate Nickel / Hydrazine additions is to prevent an over-concentration of nickel vs hydrazine. It's essential to produce it the way I do; otherwise, you won't get the beautiful free-flowing powder.

Unfortunately, I haven't been able to produce hydrazine in a concentrated enough form to make NHN. I bought my Hydrazine monohydrate from eBay.

LardmanAttack - 16-1-2020 at 01:37

So I was successfully able to make NHN by adding the concentrated nickel solution to the hydrazine solution. It's performance as an explosive isn't great, so i'll likely test out the dextrinated method to see how much it improves from there. Nonetheless I am satisfied that it worked.

[Edited on 16-1-2020 by LardmanAttack]

ShotBored - 16-1-2020 at 10:05

My experience working with Nickel catalysts was that a green solution indicates the presence of Nickel (II) species. So you successfully reduced the nickel metal but if you had the formation of Nickel (II) Hydroxide (from the NaOH/Hydrazine solution) then that would easily dissolve in acidic conditions like you saw. Had the same thing happen to me when I was making a Tetrakistriethylphosphite Nickel complex.

wessonsmith - 16-1-2020 at 11:49

So I was successfully able to make NHN by adding the concentrated nickel solution to the hydrazine solution. It's performance as an explosive isn't great, so i'll likely test out the dextrinated method to see how much it improves from there. Nonetheless I am satisfied that it worked.

[Edited on 16-1-2020 by LardmanAttack]

Was your NHN a fine powder or was in chunks / large grains? Also, did you use a 65C reaction temp?

[Edited on 16-1-2020 by wessonsmith]

XeonTheMGPony - 17-1-2020 at 05:26

Was your NHN a fine powder or was in chunks / large grains? Also, did you use a 65C reaction temp?

[Edited on 16-1-2020 by wessonsmith]

Off topic:

Where did you get your grenade fuses from? been trying to find such things for ages

wessonsmith - 17-1-2020 at 05:33

Quote: Originally posted by XeonTheMGPony

Was your NHN a fine powder or was in chunks / large grains? Also, did you use a 65C reaction temp?

[Edited on 16-1-2020 by wessonsmith]

Off topic:

Where did you get your grenade fuses from? been trying to find such things for ages

https://www.cannonfuse.com/store/pc/American-Visco-Cannon-Fu...

I use the green

LardmanAttack - 18-1-2020 at 13:35

Quote: Originally posted by ShotBored

My experience working with Nickel catalysts was that a green solution indicates the presence of Nickel (II) species. So you successfully reduced the nickel metal but if you had the formation of Nickel (II) Hydroxide (from the NaOH/Hydrazine solution) then that would easily dissolve in acidic conditions like you saw. Had the same thing happen to me when I was making a Tetrakistriethylphosphite Nickel complex.

Wow, that actually makes a lot of sense, I don't even know how I didn't think of that, I guess next time, I'll filter it off and put it in a freezer to extract the majority of the NaOH and NaSO4 before using.

XeonTheMGPony - 19-1-2020 at 08:01

I use the green

Sorry I meant the grenade style fuze.

wessonsmith - 19-1-2020 at 08:04

Quote: Originally posted by XeonTheMGPony

I use the green

Sorry I meant the grenade style fuze.

If you mean the fuse heads that are from used M67 Practice Grenades that I repurposed in my videos.

https://www.oldsargesdropzone.com/index.php?main_page=produc...

XeonTheMGPony - 19-1-2020 at 09:34

Sadly do not ship to Canada, guess I'll have to make the shit from scratch! Use the old Japanese hit initiators.

wessonsmith - 20-1-2020 at 12:37

A light dusting of NHN powder at the bottom of an open plastic container. Watch how the single spark slowly falls and ignites the powder. 960 FPS. Even launches the heavy wooden chair off the ground.

https://www.youtube.com/watch?v=eeRUnAByyYs

[Edited on 20-1-2020 by wessonsmith]

Rosco Bodine - 17-2-2020 at 11:35

To avoid the requirement for hydrazine hydrate, I am thinking it may be workable to convert more commonly available hydrazine sulfate to hydrazine nitrate, precipitating and filtering out the sulfate value as the low soluble calcium salt, or alternately the barium salt, or perhaps strontium salt, to leave hydrazine nitrate in solution.

Then react the hydrazine nitrate solution with a soluble nickel salt like nickel acetate or nickel nitrate. The soluble nickel salt could be gotten from the commonly available nickel basic carbonate, dissolved in acetic or nitric acid.

What are the kinetics of the reaction and favorable reaction pH value I do not know, but it would seem pH could probably be adjusted basic using aqueous ammonia that would gradually escape from the reaction mixture or be bound to any excess nitrate value. If such a different reaction scheme is workable it would eliminate need for freebase hydrazine as a required precursor and simplify the process for providing an alternative to that less common and more expensive reagent.

wessonsmith - 17-2-2020 at 11:46

To avoid the requirement for hydrazine hydrate, I am thinking it may be workable to convert more commonly available hydrazine sulfate to hydrazine nitrate, precipitating and filtering out the sulfate value as the low soluble calcium salt, or alternately the barium salt, or perhaps strontium salt, to leave hydrazine nitrate in solution.

Then react the hydrazine nitrate solution with a soluble nickel salt like nickel acetate or nickel nitrate. The soluble nickel salt could be gotten from the commonly available nickel basic carbonate, dissolved in acetic or nitric acid.

What are the kinetics of the reaction and favorable reaction pH value I do not know, but it would seem pH could probably be adjusted basic using aqueous ammonia that would gradually escape from the reaction mixture or be bound to any excess nitrate value. If such a different reaction scheme is workable it would eliminate need for freebase hydrazine as a required precursor and simplify the process for providing an alternative to that less common and more expensive reagent.

pH 6-7 for the entire reaction. It would be an interesting idea to try.

[Edited on 17-2-2020 by wessonsmith]

Rosco Bodine - 17-2-2020 at 11:50

Maybe a magnesium acetate buffering could facilitate the near neutral reaction.

Ha! I'll bet Microtek is already trying this to see !

With too many of the ancient wizards that visit here dropping like flies at the end of worldly mission, hopefully in rapture in a lover's arms departing, their angel arrives ..

Until that time for me ...somebody has to take up the slack around here for all the wizards apprentices. :cool:

Every Good Boy Deserves Favour.jpg - 30kB

Additionally I am thinking that if the contemplated scheme would work, the addition of aqueous ammonia, or perhaps NaOH instead, would probably be the needed component for hydrazine freebasing in situ to subsequently provide complexation of a soluble nickel salt to form the low solubility Tris hydrazine nickel nitrate. This would require something in excess of 3 equivalents of NH3 or NaOH to form NH4NO3 or NaNO3 byproduct and 3 equivalents of free hydrazine hydroxide in situ.

The scheme would probably work best to do the hydrazine nitrate plus ammonia or NaOH in one pot, and then to that mixture in excess of theory, gradually add the nickel nitrate solution.

On second thought, the reverse order of addition may work better because of oxidation losses of the free hydrazine. It should work either way, either order of addition, but a benefit of adding the hydrazine value to the nickel nitrate solution would be the free hydrazine would be sequestered by complexation bound to the nickel, and not be vulnerable to air oxidation that destroys hydrazine. Hydrazine is an active reducing agent and has a high affinity for Oxygen of the air, or dissolved oxygen in water which is exactly why it is used as an Oxygen scavenger in boiler water in steam plants.

In my minds eye, the reaction would likely proceed okay in the more basic range probably some above 7 pH, but not too much basic because then the base would displace the complexed nickel from the nitrate instead of the complexed nickel staying where it is desired. It would likely be a reversible equilibrium there where pH could be manipulated to a "sweet spot" value optimum for best yield of the tris hydrazine nickel as the nitrate desired.

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

wessonsmith - 18-2-2020 at 05:19

The only caveat for this new direction in NHN production would be if it also can be done at an elevated temperature. To properly make NHN one needs a temp range of 65-70°C.

Rosco Bodine - 18-2-2020 at 10:03

Those temps or even higher should be no issue for nitrates or hydrazine.

Not sure about how the solubilities or reactivity might play well or not play well together, but it is possible that density improvement for the NHN could occur in a reaction mixture in the presence of a chelating agent like glycine or in the presence of a competing complexing agent like ammonia which should gradually be displaced by the lower solubility higher mole weight hydrazine complex. Exploiting some interesting equilibrium shifts in the reaction mixture could enable a slowing of the formation of the NHN that could result in larger mesh crystals having higher bulk density.

wessonsmith - 18-2-2020 at 10:59

Those temps or even higher should be no issue for nitrates or hydrazine.

Not sure about how the solubilities or reactivity might play well or not play well together, but it is possible that density improvement for the NHN could occur in a reaction mixture in the presence of a chelating agent like glycine or in the presence of a competing complexing agent like ammonia which should gradually be displaced by the lower solubility higher mole weight hydrazine complex. Exploiting some interesting equilibrium shifts in the reaction mixture could enable a slowing of the formation of the NHN that could result in larger mesh crystals having higher bulk density.

With the current production method I use, Dextrin is used to increase the bulk density of NHN from 0.9 g/cm³ to 1.2 g/cm³ and produces an avg crystal size of 13 µm, which is fairly small. The smaller the crystal size, the better with NHN.

[Edited on 18-2-2020 by wessonsmith]

Rosco Bodine - 18-2-2020 at 11:41

The use of dextrin, gelatin, PVA, methylcellulose other modifiers is done with other primary explosives to produce a range of greater bulk densities and mesh crystal sizes that can be optimized for a particular use. Stirring speed, intensity of turbulence and reaction temperature are also factors affecting crystal size. The same generality is probably true for NHN which is low solubility and tends to form small crystals, that would be even smaller without any dextrin if the dextrin functions similarly as in the precipitation of other primary explosives. If the smaller the better, then lower reaction temperature and not using any dextrin would be "better" if the process for NHN behaves the same as for example lead azide or silver azide, that can even form as extremely fine colloidal particles. Particle size for a particular use is generally an intermediate mesh, and high bulk density, having crystals not too small and not too large.

I would have to review to be sure I remember this right, but I think I recall reading somewhere a figure of 80 microns for NHN being about right...but it could be silver azide on that ...I am not certain.

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

wessonsmith - 18-2-2020 at 12:36

The use of dextrin, gelatin, PVA, methylcellulose other modifiers is done with other primary explosives to produce a range of greater bulk densities and mesh crystal sizes that can be optimized for a particular use. Stirring speed, intensity of turbulence and reaction temperature are also factors affecting crystal size. The same generality is probably true for NHN which is low solubility and tends to form small crystals, that would be even smaller without any dextrin if the dextrin functions similarly as in the precipitation of other primary explosives. If the smaller the better, then lower reaction temperature and not using any dextrin would be "better" if the process for NHN behaves the same as for example lead azide or silver azide, that can even form as extremely fine colloidal particles. Particle size for a particular use is generally an intermediate mesh, and high bulk density, having crystals not too small and not too large.

I would have to review to be sure I remember this right, but I think I recall reading somewhere a figure of 80 microns for NHN being about right...but it could be silver azide on that ...I am not certain.

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

With NHN high temperature is a must. Without high temperature, the NHN produced is amorphous in nature whereas the
materials prepared at 65◦C are granular, free-flowing. 13 µm is the average particle size of NHN according to literature and observation. I used to make NHN without dextrin and it didn't perform as well.

NHN produced at 65°C

NHN produced at 25°C

Rosco Bodine - 18-2-2020 at 14:06

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]

wessonsmith - 18-2-2020 at 14:27

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...

Rosco Bodine - 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]

wessonsmith - 18-2-2020 at 16:28

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.

Rosco Bodine - 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 582 times

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

wessonsmith - 19-2-2020 at 07:29

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]

Rosco Bodine - 19-2-2020 at 12:49

That linked paper seems familiar ....

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

Pasteurized Sunglasses.bmp - 1.6MB

wessonsmith - 19-2-2020 at 13:11

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

That linked paper seems familiar ....

Great minds think alike

Rosco Bodine - 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

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

Rosco Bodine - 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.

B(a)P - 20-2-2020 at 11:30

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.

wessonsmith - 20-2-2020 at 12:49

Quote: Originally posted by B(a)P

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.

B(a)P - 20-2-2020 at 13:25

Quote: Originally posted by B(a)P

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.

Rosco Bodine - 21-2-2020 at 06:47

Quote: Originally posted by B(a)P

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.

Fyndium - 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.

B(a)P - 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.

Fyndium - 15-1-2021 at 04:33

I see. Have you got any idea what reaction mechanism disrupts the formation?

B(a)P - 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.

Fyndium - 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.

ManyInterests - 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?

MineMan - 29-11-2021 at 00:23

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

B(a)P - 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.

ManyInterests - 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?

B(a)P - 29-11-2021 at 12:06

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.

ManyInterests - 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?

B(a)P - 29-11-2021 at 17:03

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.

MineMan - 29-11-2021 at 19:09

Quote:

Ask the pbn3 guy, he is active on another form

Quote:

He responds to his YouTube comment.

ManyInterests - 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?

ManyInterests - 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!

fredsci93 - 10-12-2021 at 22:25

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.

ManyInterests - 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.

fredsci93 - 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.

ManyInterests - 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]

fredsci93 - 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.

ManyInterests - 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...

ManyInterests - 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.

ManyInterests - 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]

S.C. Wack - 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.

ManyInterests - 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?

fredsci93 - 12-12-2021 at 01:44

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.

ManyInterests - 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.

MineMan - 12-12-2021 at 15:21

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.

ManyInterests - 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.

MineMan - 13-12-2021 at 03:14

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.

fredsci93 - 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.

MineMan - 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.

Both are 7kms, for a primary that is quite excellent. Anyways many interests, the doctor is your friend

ManyInterests - 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.

Microtek - 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.

ManyInterests - 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.

fredsci93 - 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]

S.C. Wack - 13-12-2021 at 14:52

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.

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

To properly make NHN one needs a temp range of 65-70°C.

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]

ManyInterests - 13-12-2021 at 21:25

To report what has been happening in my quest to get some NHN... turns out the reason why I failed is because both my first and second hydrazine sulfate synthesis were duds. I am not sure where the process failed. But it turned out I didn't get any hydrazine sulfate at all.

That being said. Tonight i decided to make some hydrazine sulfate and I made a full batch. When I added the sulfuric acid, even though it was already at a 27 or so C, the hydrazine sulfate precipitate immediately began to form. I only let it cool to 18C before beginning filteration. I haven't weighed my yield yet, but I hope I have enough for a good synthesis or two.

That being said, I need to ask this one question... because to me making hydrazine sulfate has not proven to be dangerous... neutralizing the byproducts IS. The first time I did it I poured in a calcium hypochlorite solution into the leftover hydrazine in my bathroom and the fumes were unbearable. It took a long time to clean everything up.

My second time was better, but I wasn't sure if I needed to give it time to fully neutralize, but I did use a lot of bleach mixed with calcium hypochlorite.

The third time... maybe it was because I was using a full batch... my god I think I nearly died! What happened is that I initially poured water, the hydrazine leftovers, and bleach into my glass baking pan that I only use for chemistry now... and then I added a bit more bleach and the solution fizzed. Then I added a good amount of calcium hypochlorite to the thing and mixed it, letting it fizz and fizz and so on.

My pan was too full to add anything else. I figured I would do what I did previously and put it in my bathtub and pour water over it until everything went down the drain... but instead I went to my kitchen sink.

While carrying the thing I didn't smell anything, but the moment I got to my kitchen sink it's almost like being in a gas attack! My eyes teared up and I coughed violently. I turned on the faucet and ran away. I let the thing run for a while before returning and the gasses were still there. Just very isolated. I held my breath before approaching again and made sure the water was pouring away the undissolved calcium hypochlorite. After everything seemed to wash away I was in a bit of a tizz over the whole thing.

I wasn't short of breath or had any of those symptoms. I decided to leave my kitchen sink on and leave my apartment for a long walk. I had no problem breathing, albeit I was worried I was feeling some minor sensation when I took a full breath. I started to salivate a little after around 45 minutes but that stopped after around 20 minutes.

That was one hell of an experience that I hope to never repeat. Someone just told me that the hydrazine byproducts can be flushed down the toilet or drain and the bacteria in the sewer system will take care of it. Is this true? Because disposing of that stuff is the only thing I ever worry about.

fredsci93 - 13-12-2021 at 23:44

It's safe to flush, what happened to you was the solution was too acidic so upon addition of the bleach chlorine started forming, to avoid this you can add sodium carbonate/bicarbonate until bubbling stops before you add bleach. Or you could just leave it acidic, so long as you keep it outside until all the chlorine is liberated.

ManyInterests - 14-12-2021 at 02:50

That was still one hell of an experience. I feel a mild bit of lung burn when I breathe deeply though. It'll heal, but between this and nitrogen dioxide inhalation I really don't want to have any more of these incidents.

I was so fixated on neutralizing the hydrazine I forgot that I put in a lot of acid in it that also needed to be neutralized... because normally whenever I do anything with acid I always add a lot of carbonate even if it is technically safe to pour down the drain as is.

I am glad that it is more likely chlorine than hydrazine. While that is still pretty nasty stuff I would rather deal with a chlorine gas than a hydrazine.

MineMan - 14-12-2021 at 04:20