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Author: Subject: Ethylene diamine perchlorate
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[*] posted on 18-10-2010 at 15:29
1-Amino,2-Nitro Ethane


Quote: Originally posted by Rosco Bodine  

NH4ClO4 + HCHO ---> CH2=NH(HClO4) + H2O

CH3NO2 + CH2=NH(HClO4) ----> CH2NO2CH2NH2(HClO4)
[Edited on 18-10-2010 by Rosco Bodine]


This is potentially a good idea!

It should be noted that aldehydes actually disproportionate upon reaction with salts of ammonia. Also note that NH4ClO4 is one of the least soluble ammonia salts.

To perform the reaction, formaldehyde could be slowly added over the period of 1h, in several small additions, to a 60% alcohol solution of ammonium perchlorate and nitromethane.

There should be doubts about whether this could work, however. CH2O reacts with ammonia salts, the reaction can be written as:
(2)CH2O + NH4ClO4 ==> CH3NH2*HClO4 + HCO2H

Also note that methylene imine quickly loses ammonia and condenses into hexamine. Whether a solution of hexamine and ammonia could be used in an addtion reaction with nitromethane is not known.

Whether CH3NO2 could react with the intermediate imine (not shown) before it gets reduced is doubtful. It is, however, more likely that such an addition reaction could take place under alkaline conditions.

Nitromethane only reacts to form addition compounds through its "aci-form", and this tautomer only dominates under alkaline conditions. Formaldehyde actually disproportionates into methyl formate ester under very strongly alkaline conditions (sodium methoxide). Michael reactions, of the type between CH2O and CH3NO2, usually require a strong base to catalyze them.

Ammonium "nitromethanate" could possibly exist under normal pressure. Cold anhydrous NH3 would be bubbled into liquid nitromethane cooled to (minus) -25degC.
The salt of hydrazine and nitromethane, which is a liquid mixture, is mentioned on wikipedia: "With nitromethane, hydrazine forms an explosive salt..." The explanation is ellaborated upon in another forum: "nitromethane proton is "acidic" enough to be removed by a relatively weak base such as hydrazine (indeed forming a salt) and thus can act as an acid." http://webcache.googleusercontent.com/search?q=cache:20uotFw...

The formation of the salt of ammonia and nitromethane will probably raise the boiling point of the ammonia, in the same way that NH3 can be handled as a liquid in the form of concentrated NH4OH. This "salt"/ liquid mixture, may react with formaldehyde in a Michael reaction to form the desired product, NH2CH2CH2NO2. The formaldehyde, in this case, should be solid trioxane dissolved in an excess of pure alcohol, and the resulting solution very slowly added to the NH3-CH3NO2 mixture.

However, nitromethane is known to react with formalin (CH2O) under alkaline conditions to form Tris(hydroxymethyl)nitromethane (not sure if this reaction requires heat). To summarize, CH2O and CH3NO2 may react to form an undesirable byproduct under basic conditions, while
CH2O and ammonia condense together into hexamine, or under acidic conditions, will form undesirable byproducts . It is unknown what product(s) would form if CH2O was added to a mixture of ammonia and nitromethane. Not having any formalin, this reaction cannot be investigated by me.

If too much CH2O present, it likely will react with the imine before the imine has a chance to react with CH3NO2.

NH4+ and CH2O ==> CH2=NH2+

CH2=NO2- and CH2=NH2+ ==> O2NCH2CH2NH2

[Edited on 19-10-2010 by AH-Poster]
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[*] posted on 18-10-2010 at 15:51


Actually I have my own strong skepticism that it would work, however it does seem plausible so it continues to be intriguing. Yes nitromethane is reactive towards formaldehyde ....however the formaldehyde is reactive also towards the ammonium and it would seem more favorably so in acidic medium. So I thought
the formation of the methyleneimine might be preferential ...and that then the
nitromethane would couple directly with it. It was my thinking that solubility might drive this route for a reaction in aqueous methanol particularly if the desired product had low solubility as its perchlorate salt....the product desired may simply drop out of solution as fast as it was formed. Of course there are a whole lot of "ifs" there .....but sometimes such things do occur.

I was hoping that Nicodem may propose an alternative route as he mentioned using the Michael reaction. Paraformaldehyde is what I have on hand and
will doubtlessly convert some of it to methylamine perchlorate as I have no doubt that simpler well known reaction will work. I was simply intrigued by the considered and described possibility that the same unsaturated methyleneimine intermediate in that known reaction might combine directly with nitromethane leading to a possibly even more energetic derivative.

That last reaction equation which you show is not balanced.

For that last reaction you mean 3 CH2O rather than 2 CH2O
and the balanced reaction would actually be

3 CH2O + 2 NH4ClO4 ----> CH3NH2*HClO4 + H2O + HCO2H + CH2=NH*HClO4

If that does happen, then a methylamine perchlorate mixed product or double salt is possible if the methyleneimine does indeed conjugate with the CH3NO2.

[Edited on 19-10-2010 by Rosco Bodine]
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[*] posted on 19-10-2010 at 09:47


Quote: Originally posted by Rosco Bodine  

You just lost me there ...where is the final CH3 coming from ?

As for the other .... ( amending the bond symbol for methyleneimime )

Never mind that. With all those methyls and methylenes I mistakenly believed you are presenting a new reaction using methylamine.
Quote:
Possibly the shorter chain would not cyclize and the reaction would proceed if the formaldehyde was added gradually or there was simultaneous addition so formaldehyde was not present in excess ?

No, the disubstitution Mannich reaction on nitromethane is the consequence of the inherent property of nitroalkanes which tautomerize more easily when they are RCH2CH2NO2 or R2CHNO2 compared to nitromethane (for example, compare the pKa of nitromethane and nitroethane to see the difference). So, once the monosubstituted Mannich product forms, it will be a much better substrate for another Mannich reaction compared to nitromethane itself. The initial product of monusubstitution is an amine and can efficiently participate as bifunctional substrate for the Mannich, thus leading toward cyclization or oligomerization. Essentially, you can forget about forming 2-nitroethylamine this way. If you check the references above, you can see that enough effort was already put into this and it does not work. The only route that actually worked was alkylating ammonia with nitroethene via Michael reaction.

Quote: Originally posted by AH-Poster  
To perform the reaction, formaldehyde could be slowly added over the period of 1h, in several small additions, to a 60% alcohol solution of ammonium perchlorate and nitromethane.

There should be doubts about whether this could work, however. CH2O reacts with ammonia salts, the reaction can be written as:
(2)CH2O + NH4ClO4 ==> CH3NH2*HClO4 + HCO2H

... ...

Instead of diving in idle speculation and off road wilderness, why don't you put some effort and actually read the preceding posts and the references provided? You were already explicitly told to change your ways several times. Don't you think it is about time you change? Why do you insist in ignoring theory and literature? Such attitude can cost a chemist his life and this forum does not promote carelessness or ignorance.




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[*] posted on 19-10-2010 at 11:54


Thanks Nicodem,

Yeah, if the reaction continues for the ( first ) Mannich base, as is likely, rather than it dropping out of solution as a salt ....then the hoped reaction fails and a more complex product results. Oh well, it wasn't a totally dumb idea and it was fun while it lasted :D
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[*] posted on 25-11-2010 at 12:33
aminoacetonitrile perchlorate ....exist?


Further contemplation has been done about a possible similar compound which may have potential usefulness as an energetic perchorate, and with regards to this hypothetical
compound, I also welcome any thoughts from you all.

The organic perchlorate being contemplated is "glycine nitrile" perchlorate, or aminoacetonitrile perchlorate

NH2CH2CN-HClO4

proposed synthetic route

NH2CH2CN-HCl + NaClO4 ----> NaCl + NH2CH2CN-HClO4

Perhaps for the hydrochloride precursor is possible to use a method using TCCA and glycine, reacted in aqueous medium for a half hour at 5C and basic conditions as per description on page 3 of attached paper, reaction following the example
details on page 5 as for the conversion of phenylalanine to phenylacetonitrile: The synthesis could be simplified as there would be no need for isolation of the aminoacetonitrile hydrochloride.

General One-Pot Procedure for the Preparation of
Nitriles from a-Aminoacids. The reported procedure is
representative: L-Phenylalanine (1.20 g, 7.6 mmol) was
dissolved in an aq solution of 2 N NaOH (3.8 mL) and
treated with TCCA (1.17 g, 5.1 mmol) at 25 °C. After 10
min, when TLC analysis showed the complete absence of the
L-phenylalanine, the reaction mixture was treated with HCl
(15 mL), followed by an aq solution of 3 N HCl (2.5 mL).
After 10 min the mixture was extracted twice with Et2O (15
mL). The organic layers were washed with H2O (10 mL),
dried on Na2SO4, filtered and concentrated in vacuo to yield
2-phenylacetonitrile (20, 0.87 g, 98%). 1H NMR: d = 7.38
(m, 5 H), 3.75 (s, 2 H). 13C NMR: d = 142.1, 129.1, 127.9,
127.8, 117.8, 23.5.

A bit of scientific trivia perhaps is that aminoacetonitrile is a material detected in the far reaches of interstellar space ...... (see link) ........
http://medgadget.com/archives/2008/04/scientists_spot_amino_...

http://www.youtube.com/watch?v=3hEfcawx6Fc&feature=relat...

http://www.youtube.com/watch?v=DNjzzDNIJWw&fmt=18

Attachment: An Insight of the Reactions of Amines with Trichloroisocyanuric Acid.pdf (160kB)
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[Edited on 26-11-2010 by Rosco Bodine]
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[*] posted on 26-11-2010 at 01:12


Sort of OT:

What would happen if NH3 was used under the same conditions? Presumably it would form nitrogen nitrille. (a fancy word for nitrogen gas) I was wondering what makes the formation of Cl-NH2 more favorable in the the hydrazine synthesis, while Cl2-NH (Cl3-N?) is apparently the result of the direct reaction of TCCA.

[Edited on 26-11-2010 by nitro-genes]
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[*] posted on 26-11-2010 at 01:41


Ummm ....
I think for a nitrile there must be a C having a triple bond to N as a CN .....
nitrile being synonymous with cyanide .....right ?

therefore, your nitrogen nitrile would be NCN ??

( because if it was CNN .... then it would be a TV station )

And yes I am a blonde :P , or I used to be long ago before I became a silver :D

Ummm....anyway there is a unusual amount of energy contained (and releasable) from a CN group ....so it seemed like as a fuel component of an energetic organic perchlorate that it may provide excellent performance.

[Edited on 26-11-2010 by Rosco Bodine]
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[*] posted on 26-11-2010 at 08:48


( because if it was CNN .... then it would be a TV station )

Haha, you may have lost your blonde manes, but clearly not your humor! :D

It's been a while since I've done anything even remotely chemistry related. I increasingly tend to write brain-fart-inspired posts and then think about it later, srry about that...
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[*] posted on 26-11-2010 at 09:20


No problem, I have my moments too when things get kind of foggy. I drink way too much coffee just to try to keep from sleeping excessively....I'm like an old lion who wakes up when hungry, eats too much and then goes back to sleep till hungry again.

http://www.youtube.com/watch?v=THWgH85TyJQ Bungle In The Jungle

Anyway .....
what about the speculative and hypothetical cyanoglycine perchlorate ?

Seems worth an experiment and simple enough. It would be great if it is stable and non-hygroscopic.
The stuff could even be a primary and the energy potential there is probably somewhere around that of tetryl or better.

[Edited on 26-11-2010 by Rosco Bodine]
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[*] posted on 1-12-2010 at 21:25


It looks like the actual precursor required for oxidation to aminoacetonitrile would be aminoglycine since the amino is the source of nitrogen for the formation of the nitrile. Glycine would be oxidized to acetonitrile. I have been looking at this for a few days and that is my conclusion. Aminoglycine is mentioned as a component of hair treatments.

It may be interesting also to see what would be the oxidation product of hydantoic acid (ureidoacetic acid) NH2CONHCH2COOH .

[Edited on 2-12-2010 by Rosco Bodine]
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[*] posted on 8-2-2011 at 09:31
Diammonium Hydrazinium Tetraperchlorate


Diammonium Hydrazinium Tetraperchlorate US4053566

This is interesting because of the numerous possible different synthetic routes and the likelihood it is energetic,
along with an absence of literature references to the material. It suggests that other complex double salt perchlorates involving substituted ammonias and/or substituted hydrazines are also possible. For example perhaps a methylamine perchlorate with semicarbazide perchlorate would form an analogous double salt.

Good luck trying to find any further information. It appears this may be obscure or in the realm of purely experimental.

According to a Dow Chemical research report this is not an actual compound, but is a physical mixture which has been misidentified.
http://oai.dtic.mil/oai/oai?verb=getRecord&metadataPrefi...

An additional patent US3743701 (attached) subsequent to the Dow Chemical report evidently disputes the Dow finding.

Attachment: US4053566 Diammonium Hydrazinium (tetra)Perchlorate.pdf (151kB)
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Attachment: US3743701_DIAMMONIUM_HYDRAZINIUM_TETRAPERC.pdf (378kB)
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Thiokol is the patent holder for what indeed does appear to be an actual compound.

[Edited on 9-2-2011 by Rosco Bodine]
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[*] posted on 9-2-2011 at 12:56


This is some really neat stuff. The diammonium hydrazinium tetraperchlorate isn't all that far out of reach for those with perchlorate salts, esp. pertaining to the first patent.

If the compound is able to sustain detonation it might find use when plasticized since the relatively large amount of binder needed for plasticization could bring the overly-positive oxygen balance into check. Of course, this would then serve to reduce sensitivity (which is probably pretty low anyway since the patent talks about using it as a propellant) as well as increase power but probably reduce brisance.

Decomp seems to be (NH4)2(N2H6)(ClO4)4 --> 2N2 + 6H2O + 2HCl + 5O2 with a whopping oxygen balance of +40.3 wt%!

For that matter, this compound could probably be used to make oxygen candles once the HCl has been scrubbed.





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[*] posted on 9-2-2011 at 13:52


DAHTP could be useful as an energetic oxidizing perchlorate explosive component, especially if compatable with another energetic oxygen deficient perchlorate based explosive fuel in a mixture achieving oxygen balance. It would be a bonus if such a mixture was a nonhygroscopic eutectic....such a composition could be very stable, and dense and powerful. It is good to have valid alternative compositions to the more usual nitration products used as energetic materials.
Of course DAHTP could be an interesting component also with the usual fuels
which might be used with other energetic oxidizers, fuels like nitronaphthalene, dinitrotoluene, ect. It would be my expectation that such mixtures would be
cap sensitive and would be brisant and powerful, although more expensive than more usual nitrate oxidizer based analogues.
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[*] posted on 9-2-2011 at 21:34


If the perchlorate double salt forms in perchloric acid, why not the picrate salt in picric acid? Instead of ammonium perchlorate and perchloric acid, ammonium picrate in picric acid with a halide hydrazine salt. Or is picric too weak of an acid? I don't know much about this sort of chemistry but the TNP anions might be too bulky to "stick." Starting with chlorides might be a bad idea since the reaction might favor chloropicrin... bromopicrin wouldn't be unnecessarily hazardous though.

Diammonium hydrazinium tetrapicrate? That would be quite a compound.

(NH3)2(N2H6)(C6H3N3O7)4 --> 8N2 + 10CO2 + 24CO2 + H2O + 11H2

And with a terrible lack of oxidants, possibly the answer to what to mix with the DAHTP. I wonder if there's a reliable way to estimate the density of such a compound?

By the way, do you think this would favor the water and tend to produce more elemental C to keep the oxygen deficit? Like TNT, I think because of the similar structure and already existent C=C bonds. Hm.

Possibly impossible to manufacture but maybe split it 50/50 and do Diammonium hydrazinium dipicrate diperchlorate... what a mess. Heck, mixing perchloric acid with picric acid sounds like a positively terrible idea.

Theoretically:

(NH3)2(N2H6)(C6H3N3O7)2(ClO4)2 --> 5N2 + 8H2O + 7CO2 + 5C + 2HCl

Or diammonium hydrazinium picrate triperchlorate. I guess anything could exist on paper.

I think the general theme here is that much like a mixture of explosive compounds is usually better than a mix of an explosive and a fuel (NC gelled NG vs. ANFO for instance), molecules made of two explosive ions are usually better than an explosive ion with a metal or something. (Like pentazenium azide vs. NaN3) The main problem is finding the salts which are stable enough to exist for any useful length of time.

[Edited on 10-2-2011 by DougTheMapper]




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[*] posted on 10-2-2011 at 03:07


The OB mixture of DAHTP with Triaminoguandine Perchlorate would be something that comes to mind as a possible candidate mixture. Betaine Perchlorate, Choline Perchlorate, Trimethylamine Perchlorate, and Tetramethylammonium Perchlorate
in OB mix with DAHTP or some complex mixture in specific proportions of these compounds could result in one or more eutectics having desirable properties.

In my last post above immediately before the subject of DAHTP, there is my speculation concerning a nitrile derivative gotten by oxidation of hydantoic acid, also having a perchlorate of potential interest. In an earlier thread regarding glycine nitrate,
http://www.sciencemadness.org/talk/viewthread.php?tid=2642&a...
hydantoic acid was mentioned by Axt in a related interest as an intermediate. And a simple synthesis of the hydantoic acid was described, taken from GB991644. See example 1 of the patent attached. It is also possible that hydantoic acid itself may form an energetic perchlorate, properties also unknown.

Attachment: GB991644 Hydantoic Acid and derivatives.pdf (146kB)
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[Edited on 10-2-2011 by Rosco Bodine]
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[*] posted on 26-9-2011 at 13:02


Here's an interesting find and perhaps a useful method for simultaneously getting the water out and putting the fuel into molecular explosive compositions where otherwise a hydrated oxidizing salt could be problematic. Basically it appears that the water of crystallization can be azeotroped from DMSO solution of the hydrated oxidizer salt and then DMSO of crystallization substitutes for the previous water of crystallization, this substitution resulting in an energetic material instead of what was before a benign hydrated oxidizer salt.

US3463684 DMSO substituted Hydrate Oxidizer Salt Molecular Explosives

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[*] posted on 26-9-2011 at 17:40


That may not be necessary. Organic amine perchlorates tend not to be hygroscopic, and indeed they have much lower solubilities than the corresponding nitrates.
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[*] posted on 26-9-2011 at 18:07


I was thinking more in terms of producing an energetic fuel component for another possible chemically compatible candidate mixture with DAHTP, which could achieve OB for the mixture. Such a DMSO adduct could also possibly be used with other oxidizers in mixture to achieve OB.
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[*] posted on 13-2-2012 at 23:12
Ethylenediamine Perchlorate Picrate


Here's something interesting I found. US2406573 describes that a complex salt can be formed by half neutralization of ethylenediamine to form the monoperchlorate can be followed by another half neutralization with picric acid
resulting in a perchlorate-picrate ethylenediamine salt which has explosive properties. Other similar combination salts may also be possible.

Attachment: US2406573 Ethylenediamine Perchlorate Picrate.pdf (123kB)
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[*] posted on 15-2-2012 at 14:27


Among the similar possible combination salts which might be worth investigation
is a possible Ethylenediamine Hydrazine Tetraperchlorate similar to the DAHTP described in the other patents posted earlier. Ethylenediamine and hydrazine both should displace ammonia from ammonium perchlorate, the ammonia being volatile. Therefore it might be possible to form the speculated Ethylenediamine Hydrazine Tetraperchlorate easily if indeed it does exist as speculated. It would seem possible the result could also be a triperchlorate or other multiple salt as opposed to a tetraperchlorate.

[Edited on 15-2-2012 by Rosco Bodine]
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[*] posted on 16-2-2012 at 13:57


Both hydrazinium di-nitrate and di-perchlorate hydrolyse in water. So it would not be possible to obtain the di-perchlorate by reacting hydrazinium perchlorate with an aqueous solution of perchloric acid.

More information about hydrazinium di-perchlorate:
Quote:

Not only is the monoperchlorate much less energetic as an oxidizer than the hydrazinium diperchlorate, but it is much more sensitive to detonation by shock than the diperchlorate.

Preparation of hydrazinium diperchlorate using sodium perchlorate and hydrazinium dichloride In a reaction vessel equipped with stirring means, a cooling device and inlets for supplying nitrogen and liquid hydrogen fluoride, the following reactants are added; a pulverized and intimately admixed mixture of 2.45 parts by weight of anhydrous sodium perchlorate and 1.05 parts by weight of hydrazinium. dichloride. The mixture is chilled to -80' C., purged with a nitrogen atmosphere, evacuated and 9.88 parts by weight of anhydrous liquid hydrogen fluoride is added to the reaction mixture. The system is brought back to atmospheric pressure by reintroducing nitrogen to the system and the reaction is initiated by allowing the reaction mixture to warm to room temperature. The solvolysis of the hydrazinium dichloride to the fluoride salt is evidenced by the evolution of bubbles of hydrogen chloride gas. The hydrogen fluoride suspension is stirred vigorously for 5 hours and allowed to settle. The insoluble fraction is hydrazinium. diperchlorate and the soluble fraction is principally sodium fluoride, which has a solubility in hydrogen fluoride.

Preparation of hydrazinium diperchlorate using potassium perchlorate and hydrazinium dibromide as reactants. In this example the same equipment and procedure is followed as described in before, except that 2.77 parts by weight of anhydrous potassium perchlorate, 1.94 parts by weight of hydrazinium dibromide and 10.65 parts by weight of anhydrous liquid hydrogen fluoride are used as reactants.

US 317459210 (1973)
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[*] posted on 16-2-2012 at 16:00


Agreed, from an aqueous system and ammonia displacement reaction from ammonium perchlorate, a triperchlorate product consisting of Ethylenediamine Diperchorate + Hydrazine Monoperchlorate is about all that would be likely.
And it is unknown if such a triple perchlorate exists or what would be its properties......other than it would likely be highly energetic.
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[*] posted on 12-5-2019 at 12:22


Quote: Originally posted by mnick12  
[...]woelen, interesting expiriments! Have you tried methylamine perchlorate? I was going to attempt this once I get some more conc HCl to make perchloric acid, but money is kinda tight right now. I have a feeling methylamine perchlorate would be pretty soluable, but also could be a good energetic oxidizer when mixed with other fuels.
I just received my order of methylamine (40% in water) and I remembered this thread, so I looked it up again. I have done the experiment with methylamine. Making methylammonium perchlorate is remarkably easy.

I took 2 ml of 40% methylamine in water and added appr. 3 ml of water. The resulting liquid is around 15% of methylamine and has a fairly strong smell, but it is not pungent anymore at this lower concentration. I took appr. 2.5 ml of 50% perchloric acid and added 3 ml water to this to make it more dilute.

Using these amounts, the methylamine is in excess amount. I slowly mixed the liquids (some heat is produced, but not as much as I expected). After mixing, a clear and colorless liquid is obtained. No crystals are formed.

I poured the liquid in a petri dish and put this aside in a dry warm place without dust (40 C or so). The next day, I had a nice amount of crystalline mass, which I scraped off the glass and crushed somewhat. Then I put the petri dish on the same place for another day. After that I had a perfectly dry snow-white solid.

I assured in this experiment that I had excess methylamine. On drying, the methylamine evaporates, together with the water, and simply disappears. This allows me to prepare a nice dry solid. If there is some excess HClO4, then you will get an ugly sticky and humid mess, which never gets dry. HClO4 does not evaporate (like H2SO4) and is very hygroscopic. You can easily check whether you have excess methylamine. If the liquid has a "yummy" smell, then there is free methylamine :D
The white salt is totally odourless.

Next, I tried ignition of this compound. It is comparable with the ethylene diamine complex, described at the start of this thread. The color of combustion, however is a beautiful blue.

I also tried a small amount of this material in a test tube (only 10 mg or so, DO NOT SCALE UP!). Put it in a test tube, and then heat the test tube in the flame of a bunsen burner. The material starts to fizzle a little, and then suddenly it decomposes with a blue flame and a kind of whistling noise. After cooling down of the test tube, I added some water. On addition of the water, very dense fumes are formed in the test tube (I think due to formation of HCl).

I have a camera which can make high speed movies at 1000 frames per second. I'll try to make a movie with this camera of the decomposition reaction. Lighting is a difficult thing, however, with such high frame rates, the base/background lighting must be such that you get a meaningful image at at most 1/1250 seconds expposure time.




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[*] posted on 12-5-2019 at 13:57


Wont the excess MeNH2 absorb CO2 from air and form some methylamine bicarbonate?



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[*] posted on 13-5-2019 at 11:36


@ woelen
All about perchlorates + some fuel (or anything) in interesting. Because here can be something for replace classic primary substances. But I am afraid, that methylamine (commerce solution 40%) can be difficult available. Also HCLO4 is not some easily available. OIf course, that both compound is possible prepare. Any way, very easy reaction and clear result. I think, that testing on Anvil is necessary for basic properties.... :cool:...LL




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