Pyrotechnical - 2021-06-29
Enjoy
05:50 You must put it in a desiccator afterwards, then it solidifies.
It'll solidify in your flask or beaker on it's own if you use a high concentration nitric acid. I had to break a beaker yesterday to get it out. Make sure to continue heating for several hours, otherwise it can give off NOx in your dessicator.
Alot of ppl say the same about silver fulminate and c2n14 but videos I have seen show counter to the literature. Maybe it was put like that to refrain people from making them.
Ive played with the perchlorate version a few times. Ive made it with nice, pure twice recrystallized nickle perchlorate, and China bought hydrazine hydrate. Same findings, its nowhere near as sensitive as a few papers ive read have said. Its sensitive sure, but they make it sound like silver fulminate levels of sensitivity. I dont make it anymore. I make and use alot of nhn though. I love that beautiful lilac colored powder.
@Hugo Stiglitz china, ebay has sellers once and a while, bonanza does sometimes too
@Hugo Stiglitz id sell you a few hundred ml of 64% if youd want. If youre in the US
@Pyrotechnical I didn't even see your video it was a good source of info. Question would a higher purity of hydrazine still work?
@K0ester I might take you up on that offer that's very generous and I am in the US
Yeah any percentage will work
The amorphous nickel nitrate was bizarre. It behaved like amorphous sulfur. Wonder what was going on there?
no clue maybe it just wasn’t fully dry. What perplexed me was that when I went to redissolve it was no longer soluble. Part of it redissolved but there was a decent amount of solid light green precipitate.
14:14
*gets cut off by extremely loud music*
yeah the music got shifted somehow lol
Philouz Louis - 2021-07-09
Hi nice video and attempts,
Usually the HNO3 when sufficiently concentrated will turn nickel metal into Ni(NO3)2 with evolution of heat and NxOy fumes... I used to do so when playing with Ni(N2H4)3(NO3)2 more than 20 years ago.
No need of H2O2... Dextrine has no use because of the low sensitivity of the pink complex.
You can crush it when dried (or if you are scared by making it wet again with a little methanol or ethanol and allowing it to dry...it then becomes very fine powder clayish like after evaporation.
NiHN is said to be unreliable for detonation in small quantities and was therefore not used in detonators instead of Hg fulminate. It only detonates in high quantity under its own confinement or when confined...the stronger the better. Several wrapping into aluminium foil give sufficient confinement to allow for a strong deflagration/detonation when external heating is applied.
I have circumvented that default unreliability by admixing 2 parts NiHN with 1 part of Ag2C2.xAgNO3 (white/pale grey silver acetylide double salt/silver acetylide nitrato complex (SADS-SANC). The both compounds are synergetic... SANC provides a very strong sensitivity to flame/heat/shock/friction (VOD SADS-SANC in the range of 3,5 km/s) and possible detonation even in the open... NiHN provides a slight tempering of friction sensitivity, a high VOD (velocity of detonation arround 7km/s) and VODG (volume of detonation gases).
Both compounds form a pinkish clay like unsoluble powder...and are stable on storage for years in the dark at ambiant temperature 15-30°C and remains serviceable... sunlight is not optimum for SADS-SANC because it generates black metallic Ag and becomes then more sensitive to friction.
Could it be possible that by mixing H2O2 and HNO3 with Ni you got partial oxydation to the Ni(3+) stage? So into your mix you had Ni(2+) and Ni(3+)? This may explain your pale green goo when trying to concentrate...
Maybe also that it heated too much/strongly thus generating some Ni(NO2)2, Ni(OH)NO3?
Crystals of hydrated Ni(NO3)2 are deep emerald green and hygroscopic.
It is strange you didn't got a near 100% yield... since the complex is really unsoluble vs hydrazine or vs Ni(NO3)2. We me it was quantitative and I exhausted my hydrazine with water ethanolic saturated solution of Ni(NO3)2...until green solution shine as upper layer after mixing and sedimentation of the solid.
I did the Co(NO3)2 orange-brown variant displaying comparable properties and a putative Cu(NO3)2 (Cu(2+) is too oxydant for hydrazine and turns it mostly into H2O vapor, reduced Cu or Cu2O and N2... but eventually I got a part with a pale turquoise blue precipitate that spontaneously took fire onto the filter paper leaving a very small amount of the merely dry pale blue precipitate...it showed energetical properties burning with a fierce white-electric blue flame).
The reaction of N2H4 with AgNO3 or AgNO2 said following books to form AgN3 only generates a black-silver mirror heat and bubbles.
About your Ni nitrate goo, maybe you should try to dissolve it in the minimum amount of water and add ethanol or isopropyl alcohol... usually those pushes ionic forms out of water.
If too soluble even into pure ethanol ... then add some diethyl ether...that should do the trick.
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For the second part... why the hell do you destroy your valuable nitrate... simply add sodium carbonate solution in slight excess... to precipitate NiCO3, filter and water wash the precipitate, suck it dry, put it into a beaker and then put perchloric acid onto it drop by drop until no more bubbles do form... you then have Ni(ClO4)2 (unless you had also Ni3(+)).
The Ni(II)H4P2 is following literature very sensitive to shock even in solution... the glass rod hitting the walls is reputed to be able to detonate it wet. A decade ago, there was a publication about various energetic hydrazine complexes of Ni, Co, Zn, ... nitrates and perchlorates... they were able to test for the NiH4P2 it was the more powerful and sensitive but not excessively sensitive.
Could the literature be wrong and made a typo... perchlorate instead of chlorate ... or did they made Ni(3+) perchlorate variant (the Ni(3+) is probably way too oxydant for hydrazine or puting the complex on the edge of existance... just like Cu(2+) nitrate?
I have played with N2H4.HNO3 and with N2H4.HClO4 the first is slightly hygroscopic but the second one is much more hygroscopic... both are detonable when dry with a detonator but the second one when preheated in a molten state can detonate very strongly on red heated iron or from shock...
PHZ (PHILOU Zrealone from Science Madness forum)
Pyrotechnical - 2021-07-10
Appreciate the detailed comment!
The goo that was formed was very strange, after attempting to redissolve the goo a good portion of it was insoluble and I was only able to get a portion of it to redissolve. I was baffled as to what this insoluble compound could be because the only thing in the beaker was nickel nitrate and water, only thing I can think of was some kind of reaction from decomposition of the nitrate. I still don’t know what formed or how it formed but it was a green insoluble compound. your guess is as good as mine but I don’t think is had any Ni3+ in there as the solution was a nice emerald green, characteristic of Ni2+ but I can’t confirm any of it.
For making metal perchlorate I usually opt for the carbonate method u described mainly for making silver perchlorate but on this occasion I did not have any carbonate on hand so I just went with the method in the video.
I actually wanted to make a video on some hydrazine salts like the ones you mentioned. I actually came across a mention of hydrazine perchlorate in the book ignition and how it blew up in the dehydrator. Ever since reading that I’ve wanted to synthesize them.
As to why I didn’t get a 100% yield I think some metal ion contamination got in my storage bottle which as been decomposing the hydrazine. I noticed a constant strong pressure build in the storage bottle from the decomposing hydrazine into gases like N2, NH3, H2
Philouz Louis - 2021-07-10
@Pyrotechnical
I have a question for you...don't you have/had another YT channel or more videos a few months/years ago?
Now there are only a few videos but I have the impression I saw you in other videos not so long ago?
Back on topic...
You should redo an attempt at the second part dealing with NiHP and eventually the preparation of HClO4 and Ni(ClO4)2.
Why?
I didn't notice at first because of the strong variations of the sound volume (your voice vs the music) but after you made NiO (and maybe Ni2O3) you used an excess of HCl to make NiCl2...finally you added HClO4 (7%, 17% or 70%?)... you boiled a little the solution...
But this is a bad idea because:
1) You need again to heat the solution to a certain degree to get all HCl out... ideally near dryness.
2) HCl fumes are the most annoying stuf for chemists... it makes all iron or aluminium based material rust deep and fast even monthes after mild exposure AlCl3 and FeCl3 are corrosion catalyst because upon air moisture exposure they set free Al(OH)O, Al(OH)3, Fe(OH)O, Fe(OH)3 and HCl that goes deeper ...so with a minute HCl amount you may and will have a lot of damages all over your lab (material, electronics, lab apparatus, fridge, freezers and furnitures or fixations, etc.)
3) If you don't use a concentrated HClO4 or don't boil off hot enough to get concentrated HClO4... the stronger acid will be HCl and not HClO4... thus HCl will stick arround and HClO4 will volatilize faster or at equal speed... then better use > 50% HClO4 and in excess... ideally azeotropic HClO4 72%.
4) In fact....no HCl is requested if you have Ni, NiO, Ni(OH)2 (btw precipitable from NaOH an Ni nitrate if you had no carbonate) or NiCO3 you can use directly HClO4 to make Ni(ClO4)2 (eventually with the help of H2O2 by regular addition of a few drops... H2O2 decompose catalytically with some metal cations... so its effect will be negligible or strongly reduced if added in a single initial shot...most of the O2 will escape the reactor prior to any reaction with the metal surface... air bubbling or blowing into the solution would be as efficient...the only purpose is to provide oxydation of the Ni surface to make a thin layer of NiO that is dissolved by the HClO4...and the naked Ni attacked again by O2 layer by layer until fully chewed by the acid.
Better use a more direct approach and avoid intermediary contaminating steps.
I think that you got mostly NiHCl and a little NiHP... this may account for the crappy results... of the putative NiHP...
Pyrotechnical - 2021-07-10
Yeah I did have more videos but ended up taking them down to replace them with better videos.
I think your right about not getting fully formed nickel perchlorate, I simply didn’t drive off all the HCl not driving the reaction to completion. That would explain the low sensitivity I observed. I’ll have to try it again with one of the routes you mentioned and observe the results.
Philouz Louis - 2021-07-10
@Pyrotechnical
Thanks for the explanation... but taking the videos down... if I'm not wrong you also took the messages and comments away aswel as some valuable replies from you or followers.
For the next attempt... maybe avoid hard plastic cup and friction from a glass rod (you gave me goose bump)... even if NiHP is wet... you know...just to be on the safe side if some of the remarks from the past literature are right.
Even hard plastic shrapnels may pearce and schred some body parts...especially if flying at speeds superior to mach 10... soft/thin plastic or rubber/silicon may be advisable.
Good luck.
Chemistry of Questionable Quality - 2021-07-29
@Philouz Louis you're definitely right about being able to make the nickel nitrate with strong enough HNO3, I just made 137g. Supposedly the dextrin causes smaller crystals to be formed, but I'm not convinced either. As for the sensitivity of the perchlorate variant, a lot of the concern seems to come from people being idiots. Like the student who lost fingers and an eye when grinding it in a mortar and pestle...