While I have asked questions about Nickel Nitrate hexahydrate synthesis. Today I finally worked up the guts to do it. My first attempt ended in a
runaway almost immediately. I will put all the details of what I did.
I first put in 20 grams of nickel metal (cut into tiny pieces). The metal was 99.96% pure. The next thing I did was add 6ml of 35% hydrogen peroxide.
I saw no reaction. I then poured 30 ml of 70% nitric acid (which had cleared up from all NO2 pollution BEAUTFULLY! It was clear as water) and I added
the acid to the flask.
I used a 100ml boiling flask, and the result was a very violent reaction of a massive cloud of fumes and acid spilling out. Thankfully my spidey
senses warned me immediately of the danger and I put the flask down very quickly and ran back. I did all this in my balcony and sealed the door. No
fumes entered my place.
Cleaning the mess was hectic, but nothing bicarbonate water couldn't do...
At any rate, I collected what nickel metal pieces I could (there is still more that I will sweep up later). I cleaned the flask up and put another 20
grams of metal, added the acid first (I will need to make more nitric acid soon). Then I put the flask into position to insert it into my reflux
column (which I had coolant flowing through already) and put in, drop wise, 2.5 ml of hydrogen peroxide. I had another ultra violent reaction, but I
managed to put it into the column quickly so no spillage happened. But I saw the column go red with the NO2 fumes, but I could not smell any.
I let it boil in a water bath for 2.5 hours, and then I took it out of the water bath and let it boil for 15 minutes, turned off the heat (my heating
mantle's heat settings are useless if I have no way of inserting the thermometer into the solution) and then boiled it again for another 15 minutes
before turning off the heat and ending the experiment.
It's cooling now and I will let it cool outside an ice bath for a few more hours. I posted pictures of my result. Do I have nickel nitrate? Do I need
to filter this? There is still some unreacted nickel metal that I can salvage for later.
If I cannot get the hexahydrate from it, can I still use this solution as is for NHN/Nickel Hydrazine Nitrate synthesis?
ManyInterests - 10-12-2021 at 20:51
I think I did it! After several hours of drying and cooling at room temperature this is what happened (pictured below).
I would call this a success. Albeit I'll need to remove the unreacted nickel metal at the bottom and find a way to scoop out all the nickel nitrate.
Syn the Sizer - 10-12-2021 at 21:33
Yah, just filter it, reduce the volume a bit and crystallize it should be good.
I like the colour of nickel nitrate ManyInterests - 10-12-2021 at 22:07
By reduce the volume a bit, you mean boil it down some more? Also when filtering, how do I remove any unwanted stuff? Nickel nitrate is super soluble
in water.
Edit: Also yes, Nickel nitrate is a colorful thing. NHN is also beautiful in how purple it is.
I just need to master freebasing hydrazine... or making a distillation of azeotropic hydrazine. I think after my experiences with distillation the 2nd
option sounds much easier.
[Edited on 11-12-2021 by ManyInterests]fredsci93 - 10-12-2021 at 22:34
You shouldn’t have much in the way of contaminants (given you had pure nickel metal) so you could boil to obtain a wet solid mixture/slurry to
filter with gravity or with a vacuum pump, or you could instead desiccate the solid mix to dryness if there are only a insignificant amount of
contaminates.
Hydrazine distillation is quite complex since it must be performed in an inert environment to prevent oxidation of the hydrazine, freebasing isn’t
as horrific, it's a little difficult since it generates lots of hydrazine fumes and heat but it only takes half an hour or soBedlasky - 10-12-2021 at 22:36
What do you mean by unwanted stuff? You have just nickel nitrate in solution. Unreacted nickel can be removed by magnet (put magnet to the bottom of
flask (from outside ofcourse) and pour solution in to the beaker. Nickel will be atracted to the magnet, so it will stay in the flask).
I think that distilling hydrazine is unnecessary and dangerous. Nickel hydrazine nitrate is very sensitive explosive, so be very careful with that
stuff.ManyInterests - 10-12-2021 at 22:44
Quote:
What do you mean by unwanted stuff? You have just nickel nitrate in solution. Unreacted nickel can be removed by magnet (put magnet to the bottom of
flask (from outside ofcourse) and pour solution in to the beaker. Nickel will be atracted to the magnet, so it will stay in the flask).
You can't see it from the photos, but there is some unreacted nickel metal in the bottom of the flask. Or maybe it's gone and has reacted while I
wasn't looking. If that is the case, that is good.
In the case of making hydrazine hydrate... OK I'll just freebase it. I will cover the container that I will freebase it in to prevent as much of the
fumes from coming out as possible, and do it outside.
Quote:
Nickel hydrazine nitrate is very sensitive explosive, so be very careful with that stuff.
This is not true. While all explosives must be treated with the utmost respect, NHN is famously friction and impact insensitive. This is why I was so
obsessed with wanting to make some. I did see a video where someone made a batch that did go off with solid hammer blow. But in all others I've seen
people pound the living hell out of it and scrape it with little reaction. This is not to say I will be playing football with the stuff. Quite to the
contrary. But it's currently the safest primary known.fredsci93 - 10-12-2021 at 22:58
On the sensitivity, it's going to go off if you hit it with a hammer most times (I use a honking 2kg sledge hammer just for context), it's definitely
safer than a majority of primaries that i've worked with, treat it similarly to ETN (it's slightly more sensitive than ETN and is especially more
friction sensitive), so "very sensitive" is a stretch, but it's always important to be vigilant and careful. it is definitely less sensitive than most
primarys when it comes to heat sensitivity as it can be deflagrated in 0.5g+ "piles" without detonation (at least as far as I have noted) however that
all changes in confinement where it has a very low DDT. (It's also not the "safest primary" but it's definitely one of the safest, and potentially the
safest when complicated/expensive energetics are excluded)
[Edited on 11-12-2021 by fredsci93]ManyInterests - 11-12-2021 at 07:47
I've worked with the ETN that I made. I tried several (tiny) bits and tried to get them to go off with a regular hammer. I pounded that stuff HARD and
it didn't go off at all. This is what convinced me that hand pressing it into a plastic detonator (made from a ballpoint pen body). I plan on putting
in the ETN, giving it a slow but solid press with a wooden dowel, add the NHN, press again, then the black powder/nitrocellulose as an ignition
mixture before inserting my electric match and sealing the whole thing with hot glue
My electric match is made of an actual pair of cardboard matches that I wrap with nichrome wire (I experimented with various thicknesses. From 0.25mm
to 0.08mm I honestly think the 0.25mm might be better than the others. But I wanted to test 0.2mm to see if that one maintains firmness while also not
needing as much current to set off). Since the match head already technically has the pyrogen, I wonder if I need black powder or nitrocellulose at
all in the end.fredsci93 - 11-12-2021 at 12:30
For my det caps I use a centrifuge tube with 500mg melt cast ETN at the Bottom, 200mg ETN in the middle and 200mg NHN on top. Nichrome thickness
isn’t crucial for me, I use a little lead battery or a little lithium cell both capable of +35A so just about any nichrome is fine, and even thin
copper wire or steel wire. Steel wire is actually my wire of choice since if you get galvanised steel wire it bursts into flames when you run current
through it which makes it very effective.
You probably need gunpowder to set it off, I use permangnate/sulfur/silicone downstream of the e-fuse to set off the NHN since the e-fuse alone is not
great at setting off the NHN.ManyInterests - 11-12-2021 at 13:50
I tested my gunpowder out (I made with the wet method, but it wasn't 100% successful) I need a jet of flame to get it to go off, but my electric
matches did manage to make it go off as well. I think .3 grams of black gunpowder that surrounds the e-match should be sufficient.
How do you melt cast ETN? I heard of melt casting, but I have no idea how to do it. What I planned on doing was following the Improvised Munitions
Guide on making detonators. Their guideline is 1 gram of secondary (they used picric acid and RDX. Others have used PETN with similar amounts. They
made no mention of ETN as these guides were written decades ago before ETN was a viable option) and .5 to .75 grams of primary. The closest I could
find to NHN in terms of powder was DDNP, which they specified that 0.5 grams was necessary.
I never built a blasting cap before. I did make a nitrocellulose filled cap as well as chlorate/sugar mixture, both went off well (albeit I put them
in a saw-dust filled 5 gallon bucket, so I did not see the explosion), I realize that a true blasting cap like this would be significantly more
powerful.
I don't have any lithium cells, but I do have lots of alkaline batteries and battery packs. I made my own 12 volt battery pack with C cells and a 15
volt with D cells. These will set off any e-match. The current they provide might not match an equivalent lithium cell, but they will still fire up
any wire.
Speaking of which, I learned a lot about wires for e-matches. I had no idea you could use galvanised steel! That stuff is everywhere where I live. But
I'm basically stuck with nichrome as I have a lifetime supply of that. I need to use what I got right now and not spend more money.
One other thing about hydrazine to nickel nitrate mixture. What are the ideal proportions? Like how many grams of nickel nitrate in solution to
hydrazine? WessonSmith's video (he used commercially purchased hydrazine monohydrate though) used around 60 grams of nickel nitrate (far more than I
am willing to use!) with 700ml of water with dextrine added and around 8ml of hydrazine monohydrate.
Chemplayer's video on freebasing hydrazine was crystal clear. I will probably make a surplus if I need to. but is a surplus of hydrazine OK, or do I
need to saturate it with nickel nitrate in order to get some NHN?ManyInterests - 11-12-2021 at 16:42
OK so I attempted to freebase some hydrazine... but I am pretty sure something was off. It is possible that my hydrazine sulfate was far too
contaminated with sodium sulfate. I added around 30 grams of sodium hydroxide gradually to 40 grams of hydrazine sulfate, with 110ml of ethanol added.
I mixed them for about 20 minutes and let them sit in an ice bath (covered with plastic wrap) for almost an hour now and the liquid is milky white
with no clear liquid out there. I added more ethanol and the ethanol solution is still very milky white.
Was my hydrazine sulfate a dude or what?Bedlasky - 12-12-2021 at 01:01
Sodium sulfate is insoluble in ethanol.fredsci93 - 12-12-2021 at 01:28
First off, One can melt cast ETN by submerging the ETN in a boing water bath, I put 500mg ETN in the centrifuge tube and lowered that into the boiling
water (not actively being heated, just water from my kettle put in a beaker) after 30s the centrifuge tube was taken out and cooled to yield the melt
cast ETN.
My detonators are meant for setting off secondarys and plastic explosives, the power from ~900mg powerful explosives is sufficient for setting off
secondarys and plastic explosives (plastic ETN and Plastic RDX/keto-RDX) however you would probably need a larger amount of explosives to set off a
tertiary like ANFO.
The galvanised wire I'm talking about is the threaded/rope stuff they use in bike breaks and stuff like that.
The best proportions are near molar 3:1 hydrazine to nickel nitrate hexahydrate (BY MOL), with a slight excess of hydrazine (5% max), for hydrazine
sulphate the mass ratio works out to 1.34:1 hydrazine sulphate to nickel nitrate hexahydrate (BY WEIGHT) and for hydrazine hydrate (80%) it works out
to ~0.64:1 hydrazine hydrate to nickel nitrate hexahydrate (BY WEIGHT)
For your hydrazine freebasing you used 0.307mol hydrazine sulphate and 0.750mol sodium hydroxide, which means you used an excess of sodium hydroxide,
this is undesirable since sodium hydroxide dissolves in ethanol, I would recommend reacting this solution with 12.6g sodium bicarbonate (0.15mol) over
an hour or so (you might want to use an excess) to convert any sodium hydroxide to insoluble sodium carbonate otherwise the sodium hydroxide will
react with the NHN and make useless nickel hydroxides.
After that filter it through a coffee filter and you should be golden, unless the hydrazine sulphate is just fucked.Fantasma4500 - 12-12-2021 at 02:52
there was a man back in the time of r0guesci who purified his ETN by melt-casting
he lived in alaska
one day he just stopped posting
nobody knew exactly where he lived
its hard to tell how much is too much action for molten ETN, but one thing is for sure its very powerful stuff, ive seen just half a gramme of it turn
a half liter soda can into fine shreds
and maybe 50 milligrammes of it snapping a hot knife in half when pressed against it
so in that you would be dealing with molten ETN, which some friction or pressing
would be nice if someone would set up some experiments for liquid ETN, with some powerful blast shields and remote controlling for friction/shock
sensitivity
now to stick to the topic, i always flush chemical compounds with solvents that the salt isnt soluble in, to pull out all the water, because when you
try to dry something using heat, the solubility increases and you end up with awful chunks (which you can easily crush with a round-bottomed jar,
using circular motions- ive found) but flushing it with acetone or similar low boiling/high vapor pressure solvent greatly reduces the time you spend
on dealing with it and gives a better final product
sadly it appears nickel nitrate is soluble in EtOH and i cant find anything on ethanol
ether maybe? you can dump some gasoline in a distillation flask and contract some very low boiling stuff, it seemed a decent portion was at all the
way down to 40*C, this should be great for flushing the nickel nitrate.ManyInterests - 12-12-2021 at 08:19
Good stuff.
This is the liquid nickel nitrate (using distilled water with some dextrin added).
I wasted a lot of it in the failed NHN synthesis. So I will need to make more today. How does it look though?
EDIT: There was a LOT of unused nickel metal in my flask. The next time I will use an excess of nitric acid (I don't got much left. So I need to make
a touch more... if my current nickel nitrate solution is insufficient), and just boil it to completely destroy all remains of nitric acid in it. This
stuff has zero nitric left as the nickel nitrate was rock solid. Thankfully it was quite water soluble and I was able to rinse it out almost
immediately.
[Edited on 12-12-2021 by ManyInterests]fredsci93 - 12-12-2021 at 11:49
it looks a little more turquoise that one would expect, probably has some nickel hydroxide, what's the pH?
This is my nickel nitrate dissolved in waterManyInterests - 12-12-2021 at 13:41
I think it might be too dark... I might need to dilute it more. I am making another batch to use up all remaining nitric acid I have. (I am reusing
the unreacted nickel metal from the last synthesis. Seems like you can get a LOT of nickel nitrate from a bit of nickel metal!).
The pH appears to be slighly acidic. I think it is 4 on the pH scale, but I could be mistaken. Here is the picture.
If it is too acidic, what can I do to resolve that issue? More water or what?
fredsci93 - 12-12-2021 at 14:04
the pH looks alright, you could remove the cloudiness with a filtration which would improve the colour, it doesn’t look to concentrated to me, do
you have any idea how much nickel is dissolved?ManyInterests - 12-12-2021 at 14:21
I didn't write it down, but I believe around 8 grams or so were fully reacted. The other bits have some tarnish on them, so I assume they were
partially reacted, but not fully.
I am running another synthesis. I added 8 grams of the previously used nickel metal to 14 ml of nitric acid. I also added around 4ml of slighly
diluted hydrogen peroxide (I put in 2.5ml of my 35% and added another 1.5 ml of water. It still reacted quite violently, but I was expecting it and
well prepared for it).
I'm glad that at least the pH is good. You did tell me that the pH is important when it comes to NHN synthesis...
All I need now is to make some good hydrazine sulfate. I hope my next batch will be the last I will need to make.
Edit: Hydrazine question: I realize the answer might probably be no but... I am guessing that after making the hydrazine after adding the hydroxide,
bleach, and urea/gelatin and heating for 5 minutes at 85C is not good enough, but can it be used immediately after the addition of hydrochloric acid
and sulfuric acid?
[Edited on 12-12-2021 by ManyInterests]fredsci93 - 12-12-2021 at 15:19
Edit: Hydrazine question: I realize the answer might probably be no but... I am guessing that after making the hydrazine after adding the hydroxide,
bleach, and urea/gelatin and heating for 5 minutes at 85C is not good enough, but can it be used immediately after the addition of hydrochloric acid
and sulfuric acid?
[Edited on 12-12-2021 by ManyInterests]
Heating at 85C for ~5mins or when the amount of bubbling is very low is the norm for a hydrazine sulphate synth and works well, any longer and you
will start to lose yield.
You should let the solution cool fully before neutralising with sulphuric and hydrochloric since otherwise the solution will overheat and there may
also be some effect on the amount of hydrazine that forms.
Also for the freebasing you need to use 40g hydrazine sulphate to 24.5g sodium hydroxide, it's important to use a very slight excess of hydrazine salt
as if any sodium hydroxide is left in the ethanol it will screw over the reaction, if the hydrazine sulphate is impure then I recommend passing the
ethanolic hydrazine solution over sodium bicarbonate to remove any sodium hydroxide (if the hydrazine sulphate was only 90% then 2.5g of sodium
hydroxide will not be able to react and will simply dissolve into the ethanol).ManyInterests - 12-12-2021 at 15:54
That's good. One thing I need to mention is that once I add the gelatine/urea solution and start heating (I cover it completely and I am always
stirring with the stir bar) is that it takes quite a while to get to 85C.
Do I start the timer for 5 minutes as soon as it hits near 85C or do I stop once it gets there? I think this is where I am losing out. I did let it
cool down completely in an ice bath (still covered with plenty of plastic wrap) until it is around 15C or so before adding the acids, wherein the
temperature goes up to around 30C. then I let it cool down to 15/13C before immediately vacuum filtering. I don't see that much sulfate percipitate,
but when I start filtering it shows up immediately.
I'm trying to find out where I am going wrong with this. Am I adding the acid too fast or what?
Edit: I am guessing that mixing the sodium hydroxide with the hydrazine sulfate first before adding any ethanol is a must. I used 95% denatured
ethanol, and I chilled it in the fridge, is this correct?
[Edited on 12-12-2021 by ManyInterests]fredsci93 - 12-12-2021 at 18:07
Your synth technique sounds fine, probably something weird making it fail.
As for the freebasing you should add sodium hydroxide to the hydrazine sulphate in ethanol slowly, if you add the two dry then add ethanol you will
get more hydrazine fumes and it will be more dangerous. (95% ethanol works fine) ManyInterests - 12-12-2021 at 18:29
That sounds good.
You know what? I'll try to freebase the remaining 20 grams of hydrazine sulfate that I have. Who knows? Maybe it might work. Nothing ventured nothing
gained.
I'm done with my second nickel nitrate synthesis. I've decided that after my reactio nis done. I heat the flask until complete dryness. That way no
more acids remain and I don't have to worry about drying the stuff on the frit. I can just hydrate it from the flask straight and add it to my supply.
I.Just.Want.One.NHN.Synthesis!
Edit: wow. I had no idea you could get that much nickel nitrate from such small amounts of nickel metal. I guess the purity really did make a major
difference!
[Edited on 13-12-2021 by ManyInterests]fredsci93 - 12-12-2021 at 19:46
yea, 20g scale is good and would make ~10g NHN, add 12.2g sodium hydroxide to 20g hydrazine sulphate in ~50ml ethanol and let react for a half hour
with stirring and cooling, then filter through a coffee filter, wash the solids well with ethanol. The filtrate should be good but if you have any
suspicions about the purity of the hydrazine sulphate then you can pass it over some sodium bicarbonate.ManyInterests - 12-12-2021 at 20:31
You know what? I had no idea you could filter this stuff! Everywhere I looked they hydrazine would appear as a fairly clear (or slighly cloudy ethanol
solution).
I'm going to try this tomorrow. I need to get a few disposable jars and funnels since I really don't want to reuse stuff that was in contact with
hydrazine...
And 10 grams? That's a lot. More than any yield I've seen! If I can get 10 grams that is a lifetime supply as far as I am concerned.
BTW, thanks for all the help. I really appreciate this.
Edit: Ok, so add 50ml of ethanol, and slowly (like 2 grams at a time?) of sodium hydroxide and stir for a few minutes before adding more. That'll take
about 15 minutes of constant stirring to get it all in. I'll keep stirring for 30 minutes, albeit I cannot hand stir with a covered container. I think
I might have caught a whiff of the strangely sweet smell of hydrazine when I was working on it yesterday, but the smell was extremely faint and it
could have been my anxiety making me sense things that weren't there.
[Edited on 13-12-2021 by ManyInterests]fredsci93 - 13-12-2021 at 01:18
Yea, I only filtered it after my mix wouldn’t settle out, but it cleaned up the product alot.
That procedure would work perfectly, and after all sodium hydroxide additions and the 30mins of stirring filter the solids, wait for ~20mins for most
of the ethanol to pass through and wash the solids with 20-30ml ethanol, wait another ~20 mins and perform one final wash with 20ml ethanol, let it
fully filter over 20mins.
The filtrate is now ready to be brought up to 60-65C (you don’t strictly need a water bath, but it would help if you don’t have a great hot plate)
then mix in the nickel nitrate/dextrin solution quickly with stirring (I used a 10ml syringe, but you could also just dump it in), let the mix stir
for a minute or so before hot filtering the NHN (hot filtration is very important, it gives a much better product).
Then you can wash and dry the NHN, I used a steam bath for drying it because I'm impatient, also if you don’t fully dry the product it becomes
incredibly weak
Also, I got a whiff of hydrazine when I was making hydrazine sulphate a year or two ago, it smells very similarly to ammonia IIRC
[Edited on 13-12-2021 by fredsci93]ManyInterests - 13-12-2021 at 07:55
In that case I probably didn't smell hydrazine and was just imagining it. I did smell my ammonia (common household cleaner, 6% solution) and it didn't
anything like what I thought I smelled.
Nitrogen Dioxide is still my biggest bane. I made some fuming nitric acid (now sitting in my freezer in a bag full of carbonate and bicarbonate to
clear up) and I got some nasty bit of nitrogen dioxide in my lungs. It isn't the worst time, but I wonder why I used my one-neck boiling flask instead
of two... I got got another whiff of that when blowing into my end product with a long straw. I know that fuming nitric fumes a lot more than regular
nitric acid... but WOW, that stuff smokes like a chimney!
OK. So I'll recap once again. Stir for 30 minutes while adding, wait for 20 minutes, filter, pour more ethanol, wait another 20 minutes, filter, etc,
etc.
I hope it works this time.
I can put my NHN in a glass baking pan and wait however long it needs to dry out. What I normally do when drying it is put several layers of paper
towel on it to draw out the moisture. I won't hand press or anything. I don't want to have any of my end result be inextractable because it was stuck
to some paper towel.
fredsci93 - 13-12-2021 at 12:09
Paper towels are my usual choice but they Usually take days to fully dry the NHN, steam bath works very well though ManyInterests - 13-12-2021 at 13:07
I measured out my supply. Turned out I just have 9.6 grams of sulfate. I'll just half the hydroxide and ethanol and hopefully I'll make it work.
Also I added water to my 2nd batch of nickel nitrate crystals. They were not 100% dry, but I did manage to dilute them with 80ml of dextrinated water.
I took a pH reading after adding it to my other supply.
I think the reason why it's so dark is because it could stand to use a little more water. That will also cause the pH to drop if it is too acid. What
do you think?
Edit: on another reagent note. My fuming nitric acid synthesis appears to be a great success. I took my nitric acid out of the freezer and took a
gravity scale measurement... it came back at 1.518! Granted it was at zero C, maybe even less. I need to wait for it to reach room temp again before
doing another reading, but given the pure silky white fumes, I think I am looking at a nice Keto-RDX synthesis.
[Edited on 13-12-2021 by ManyInterests]
[Edited on 13-12-2021 by ManyInterests]ManyInterests - 13-12-2021 at 15:18
Yeah this doesn't seem like it's working. While freebasing I mixed for 30 minutes before letting it settle for another 35 minutes. The stuff is very
murky and when I poured it into a filter I had to squeeze the filter paper in order to get anything.
I was told I needed to put some water in to start. I squirted 2ml of distilled water to see it would do anything.
Well, that finishes my supply of hydrazine sulfate... I need to make more. This time try to use HCI to reduce the amount of sodium sulfate and
hopefully extract as much hydrazine sulfate as possible.
Edit: I think the sweet smell I was smelling while trying to freebase is the ethanol. It does have a sweet scent to it. That's good that I didn't
breath in anything toxic.
Edit2: I will try to see if this works anyway. I double filtered it, sequeezed the stuff out, and I hope what I have is freebase hydrazine and not
just ethanol.
Edit3: Nope it's a giant dud. I need to make more hydrazine sulfate. I'll make one normal sized batch and I hope I will succeed...
[Edited on 13-12-2021 by ManyInterests]
[Edited on 13-12-2021 by ManyInterests]fredsci93 - 13-12-2021 at 15:53
How much ethanol did you use, surely some should pass the filter, my mix was super gloopy and even it filtered in time, also water is not a
requirement, I haven’t heard of adding water to it before. if it can’t filter I would recommend adding ethanol to thin it out.
btw how much sodium hydroxide did you use?
Also you need to be very careful with KetoRDX's synth it is the single hardest nitration I have ever done. It always takes forever and takes huge
amounts of ice, each time I have underestimated it had had to make a dash to the supermarket or service station, and when it fails it shoots Fuming
nitric acid everywhere, it is seriously difficult to control, it's a wonderful product but just keep in mind failure is nearly certain if you let your
guard down for a second, or at any point underestimate how much heat the process generates (temperature monitoring is a must and enough ice for 3-4
SALTED ice baths is required) if the ice isn’t salted or the ice has gone above -10C it is useless and the reaction will slowly heat up while you
wonder what could be wrong until the temp is 20C and the reaction is basically fucked, it's not a fun reaction, but good luck to you, it's a very
interesting product.
(when I made my largest batch not only did I screw it up a bit, it took from 11am to 8pm, due to poor cooling mostly since I assumed a -10C ice bath
could cool a mix down to 0C however the reaction continuously produced heat from DNU decomposition)ManyInterests - 13-12-2021 at 15:55
I used 9.6 grams of sulfate (all my supply) 6.22 grams of sodium hydroxide. I put in 2ml of water first and then around 32ml of pure ethanol.
This is getting really frustrating... I wish I heard of CHP from the start (I am sure making concentrated ammonia and ammonium perchlorate aren't that
hard...). I am committed now to make NHN. I believe my nickel nitrate is perfect. All I need is just one freebased hydrazine! Just one batch!
Edit: I might not do Keto-RDX but regular RDX. I made a beautiful batch of fuming nitric (around and 18 grams of HDN. This is what is so frustrating
about freebasing hydrazine... it should be simpler than the other synthesis I have done, but it is being a giant pain. I realize that RDX is a tough
thing to make, but I am confident in my ability to do it. I made sure my HDN is both dry and acetone free.
I will freeze my nitric acid in a solid block of ice, and make sure I have other ice ready for anything.
[Edited on 14-12-2021 by ManyInterests]fredsci93 - 13-12-2021 at 16:15
First, that's a slight excess of sodium hydroxide you should use 5.9g, not that that was the problem though, if it wasn’t filtering then you need to
thin it out with ethanol, or if filtration is somehow impossible try let the solution sit for a day or so and decant instead.
Also did you add the sodium hydroxide directly to the hydrazine sulphate? I wouldn’t recommend that, it's not great since it causes local heating
maxima at the hydrazine sulphate-sodium hydroxide interface which can decompose the hydrazine or cause some boiling.
I recommend when redoing the reaction using extra ethanol, adding the sodium hydroxide to the hydrazine sulphate in ethanol and using less sodium
hydroxide, for the filtration if it really, really will not filter, calcium sulphate style, then get a diaphragm pump for doing a vacuum filtration or
add even more ethanol (don’t go super crazy but it's not that detrimental if you have a large volume of ethanol).
CHP isn’t easier, it's a fair bit more difficult synthesis and the preparation of the sodium perchlorate starting material is pretty difficult
(unless you have a perchlorate cell) since you need to convert sodium chlorate to perchlorate which takes a very long time and is low yielding, I'd
stick with NHN unless you have a good source of perchlorate
edit: DNH is a bitch to dry from experience, how'd you get it dry?
[Edited on 14-12-2021 by fredsci93]ManyInterests - 13-12-2021 at 16:30
The first thing I did was make a chlorate cell. I have MMO and titanium anodes and cathodes. But at any rate. I will try again, and give it more time.
Right now I am prepping to make more hydrazine sulfate. I will follow your advice and give it a day or so if that's what it means to make it freebase.ManyInterests - 13-12-2021 at 16:32
Quote:
edit: DNH is a bitch to dry from experience, how'd you get it dry?
I left it on a plastic plate with a paper towel underneath it and more paper towels over it. I pressed and squeezed it and replaced the paper towels
as needed. I then left it for several days to try.
When I squeeze my HDN I don't get any wetness on the paper towels at all. I do see the sparkly bits of HDN on it. I dispose of the paper towels by
burning them.
Edit: One thing I noticed is that I saw no precipitate from my hydrazine sulfate when I added the sulfuric acid. Something must have went wrong.
On a plus note, my HCI is very, very clean.
[Edited on 14-12-2021 by ManyInterests]Triflic Acid - 15-12-2021 at 07:45
Ive had decent success making ethanolic hydrazine from NaOH and N2H6SO4. works quite well. Only thing is that it can often be a pain to get it to
work, becuase of how insoluble hydrazine sulfate is. Also, a mod should probably move this to EngMatTexium - 15-12-2021 at 10:45
You will need a nitrate (say KNO3) and react it with (NH4)2SO4 (from the action of NH3 on aqueous MgSO4, the latter sold as a hydrate under the name
Epsom's Salt), freeze to separate out the sulfate leaving aqueous NH4NO3).
Use a microwave for lab work only, add a solid piece of Nickel metal to dilute H2O2 plus NH4NO3, a piece of activated carbon (burned food as in bread
works) and a bit of NaCl.
Microwave on and off for a few minutes and see if you can any coloration development. Take precaution on exposure to fumes (see Safety comment
below).
If yes, you have Nickel nitrate (or related salt, like Nickel nitrate diammine, Ni(NH3)2(NO3)2 or a hexamine, all of which decompose on heating
releasing NH3 and eventually the nitrogen oxides before the last NH3 leaving just Ni(OH)2, see "Ni(NH3)2(NO3)2—A 3-D Network through Bridging
Nitrate Units Isolated from the Thermal Decomposition of Nickel Hexammine Dinitrate") .
Logic: Anodic corrosion of the Nickel (anode here) introduces Ni++ ions. The NO3- is converted into the powerful nitrating •NO3 radical (see my
prior comments here http://www.sciencemadness.org/talk/viewthread.php?tid=152782...) created from the battery cell electrons acting on H2O2:
where the free ammonia could become captured by nickel ions or escapes.
No exposure to toxic nitrogen oxides or even the need for HNO3.
However, per Wikipedia https://en.wikipedia.org/wiki/Nickel(II)_nitrate on safety to quote:
"Safety
Like other nitrates, nickel nitrate is oxidizing. It is also irritating to the eyes, skin and, upon inhalation of the dust, respiratory tract. It may
cause skin allergy. Nickel nitrate is a carcinogen, along with most other nickel compounds. The nickel ion is also toxic to aquatic organisms."
[Edited on 28-12-2021 by AJKOER]ManyInterests - 30-12-2021 at 18:31
Thank you for that. That sounds like an extremely interesting way to synthesize Nickel Nitrate! When it comes time to buy a new microwave, I'll use my
old one to make a batch of nickel nitrate that way.
The initial process you mentioned of making ammonium nitrate using potassium nitrate and the (NH4)2SO4 is not something I thought of. I did see a
video where someone made ammonium nitrate by mixing azeotropic nitric acid/HNO3 with ammonia water (they used the 6% household concentration. I know a
brand that is 6% ammonia with the rest being water. No other detergents or additives). I didn't think to use straight KNO3 to do that. That would make
the process of obtaining ammonium nitrate much easier, since I will need some for experiments in the future.
The only question I have is this: When you say a dilute H2O2. How dilute are we talking about? 15% 10%? I can experiment with the proportions of the
others, but I will assume that a slight excess of nickel metal would be preferable as to use up all the nitrates in the process. Which is what
happened in my previous nickel nitrate synthesis with the nickel metal + 68% HNO3 + 3ml of 35% H2O2.Texium - 31-12-2021 at 07:22
Alright AJKOER, but have you actually DONE this reaction? Because if not, don’t go talking about it like it’s a known method that will certainly
work! I’d love to see someone try it out, but I have serious doubts that a bit of burnt bread will magically allow you to make nitrate radicals…
Edit: To be clear, this method that AJKOER proposes depends on the formation of nitrate radical from hydrogen peroxide and nitrate anion under these
so-called galvanic conditions. None of the references that he cites as you wade back through his posts actually support this happening. It is pure
conjecture, and unproven.
[Edited on 12-31-2021 by Texium]AJKOER - 31-12-2021 at 08:24
Yes, thank you Texium, as I should I noted a disclaimer.
First, the mechanism noted by Texium which I cited and demonstrated with pictures here http://www.sciencemadness.org/talk/viewthread.php?tid=151055... has worked, but not with the nitrate radical, per se. However, I have use KNO3 in
place of NaCl for the galvanic dissolution of Sterling Silver (as AgCl is insoluble and cannot serve as an electrolyte in the associated
electrochemistry.
"Oxidation of biogenic volatile organic compounds (BVOC) by the nitrate radical (NO3) represents one of the important interactions between
anthropogenic emissions related to combustion and natural emissions from the biosphere. This interaction has been recognized for more than 3 decades,
during which time a large body of research has emerged from laboratory, field, and modeling studies. NO3-BVOC reactions influence air quality, climate
and visibility through regional and global budgets for reactive nitrogen (particularly organic nitrates), ozone, and organic aerosol. Despite its long
history of research and the significance of this topic in atmospheric chemistry, a number of important uncertainties remain."
And yes, Activated Carbon (as created here by the carbonizing food) is more noble than nickel (and, in fact, in a cell employing HOCl and not H2O2, I
did accomplish the anodic dissolving of Tungsten see http://www.sciencemadness.org/talk/viewthread.php?tid=153380... ), a lab verification with H2O2 is recommend possibly with a bit of Ascorbic acid
(for secondary oxygen REDOX reaction).
On the concentration question, while only the presence (at any concentration) of the respective metals and electrolyte is required, having a small
surface area anode relative to a much larger area cathode will accelerate galvanic based corrosion. The issue with H2O2 as a radical source may take
longer at low concentration, but it is a trade-off of expensive/availability of say H2O2 versus differences in preparation time.
Note: Photolysis based routes using nitrate, NO3-, should be mindful of a breakdown to NO2-,..., albeit, I am not citing this as occurring here in a
galvanic cell setting.
Also, a general disclaimer, my suggested path does not promote any reagents or use of equipment for which I have any financial interests.
[Edited on 31-12-2021 by AJKOER]Texium - 31-12-2021 at 08:34
Stating a lot of facts that are of tangential relevance to your claim, at best, does not mean that your untested method works, or even should work.AJKOER - 31-12-2021 at 09:38
Personally, based on my experience, I suspect Nickel is likely hard to dissolve with any concentration of H2O2 (like Tungsten) and, as such, I would
recommend first experimenting by simply adding a small piece of Ni metal to 6% or higher Chlorine Disinfecting Bleach (neutralized to HOCl see
preparation discussed here http://www.sciencemadness.org/talk/viewthread.php?tid=154302...) and a graphite (or a silver) cathode (with relatively much greater surface area
than the anode) together with much added KNO3. Process in a microwave for several minutes.
Unfortunately, as the Bleach is an equal mix of NaoCl and NaCl (as industrially prepared from Cl2 acting on NaOH), the product will be a mixture of
the aqueous Nickel chloride and Nickel nitrate. However, the nitrate is somewhat more soluble (see https://en.wikipedia.org/wiki/Solubility_table#N) and with the presence of NaCl, the Sodium/Potassium/Nickel chloride should exit first on cooling
leaving Nickel nitrate.
If successful, a workable and cheap prep.
[Edited on 31-12-2021 by AJKOER]Ankit1612 - 17-5-2023 at 09:30
Hi guys,
I have 44.4g nickel in hard chunk form can someone tell me how can i dissolve it in conc. Nitric acid to make Nickel nitrate?
[Edited on 17-5-2023 by Ankit1612]B(a)P - 17-5-2023 at 12:26
He used 10g of Nickel strip which he had purchased from amazon.
Here i've 44.4g of nickel in chunk form, so i'm concern about dissolving it.
By the way, what if i use small amount of 50% h2o2?
will it increase the rate of dissolving Nickel?
I still think it will work. When I make nickel nitrate I use more or less the same method as ManyInterests. I use 50% H2O2. I
also use nickel strips, the reaction is pretty vigorous I don't think the additional surface area of the nickel strips is essential. Why not take a
small piece off the side and try?maldi-tof - 24-5-2023 at 21:42
I obtained recently nickel (ii) nitrate hexahydrate crystals more or less like you did, but I started with nickel metal powder. No fumes (a part from
hydrogen gas) was observed.
The solution after the attack was still strongly acidic. I filter it to remove any unreacted nickel.
I added as well some H2O2 just for the sake of adding it, but i do not think it is mandatory.
After concentration (you need to control the density) you let it crystallize and that's it.
The yield was not the best, but mother liquors can be re-used and you obtain more product from it.Raid - 25-5-2023 at 10:25
That's interesting that no fumes appeared. I have heard that using metal powders opposed to metal chunks can cause a violent reaction and lots of No2
evolution. Herr Haber - 25-5-2023 at 16:38
Mother liquor re-used ? Your nickel nitrate will then certainly contain some HNO3 which might be a problem if you are going to use it in a synth
involving a basic compound.
@Raid: Of course, more surface area, the more violent the reaction. The first time I burned myself with magnesium it wasnt even lit... (HCl + Mg in a
test tube between my knees).
You might want to start by using a chunk of Nickel and keep a few strips or powder to soak up any remaining acid.
I' do this when dissolving silver. I always keep a few sterling teaspoons around to drop in the reactor if I notice most of the silver is gone after
heating. Sometimes I dont do that when I want ultrafine silver powder but then the process is wasteful on copper because the solution will also
contain HNO3.Raid - 26-5-2023 at 05:59
When I make nickel nitrate I use nickel rounds that I bought off of ebay. They work really well and when the reaction is completed I can just take the
unreacted nickel out of the solution.
