Sciencemadness Discussion Board

Does nitroammonium exist ? or similar cations ?

DubaiAmateurRocketry - 28-10-2013 at 08:21

NH4 ammonia very common, and hydroxyl ammonium is also famous.

Hydroxyl ammonium cation in energetic materials, although not as energetic as the ammonium cation, it could help a lot with the oxygen balance.

So will Nitroammonium cation, if it exist. I cant find much about it on the internet.. Maybe a direct nitration of NH3 and N2O5 ? I am not that well in chemistry.

Hydroxyl ammonium cation
....H
H-N-H-O
....H

Nitro ammonium cation also exist, i found on a paper that a structure of this ... does exist
....R
H-N-NO2
....R

So I wonder if

....H
H-N-NO2
....H

Exists.

Or a fully nitrated ammonium cation ? :p

If nitroammonium cation does exist, it would not only be oxygen positive cation, which is rare, I also expect higher density than the normal ammonium salt.

I still havent found any paper about it ?

If there is can any one provide me ?

[Edited on 28-10-2013 by DubaiAmateurRocketry]

vulture - 28-10-2013 at 08:32

Quote:

I still havent found any paper about it ?

If there is can any one provide me ?



While I have no quirks with discussing obscure or theoretical substances, your attitude gets dangerously close to spoonfeeding.

Please provide some references or proof of search effort.

DubaiAmateurRocketry - 28-10-2013 at 08:49

Quote: Originally posted by vulture  
Quote:

I still havent found any paper about it ?

If there is can any one provide me ?



While I have no quirks with discussing obscure or theoretical substances, your attitude gets dangerously close to spoonfeeding.

Please provide some references or proof of search effort.


I apologize, however, I really can not find enough information I want about it.

VladimirLem - 28-10-2013 at 09:07

Ammonium DiNitramide - it contains two nitrogroups - H4N4O4, meltable, high dense: 1.82
is a good propelland, (afaik) moderate-good explosive and of course positive in OB (good oxidizer)

i dont know if the mono-nitro version exists/is-stable/whatever...

i only found this: LINK

DraconicAcid - 28-10-2013 at 09:15

Quote: Originally posted by VladimirLem  
Ammonium DiNitramide - it contains two nitrogroups - H4N4O4, meltable, high dense: 1.82
is a good propelland, (afaik) moderate-good explosive and of course positive in OB (good oxidizer)

i dont know if the mono-nitro version exists/is-stable/whatever...

i only found this: LINK


That link can't be correct- it shows one ammonium ion, and two neutral H2NNO2 molecules.

woelen - 28-10-2013 at 10:09

The dinitramide ion exists, you can consider it as derived from ammonia, with two H-atoms replaced by -NO2 and the last H-atom split off. The molecule HN(NO2)2 is not stable, but salts of this are stable. The potassium salt K[N(NO2)2] exists and is perfectly stable at room temperature. The ammonium salt also exists, NH4[N(NO)2].

Even a home chemist can make this chemical at home, the only real problem being the necessity to perform a reaction at -40 C or so. I tried this reaction, but I do not have the equipment for maintaining a reaction vessel at -40 C for a long time. I also have no access to dry ice, so I abandoned the project. I still have the chemicals, needed for that (potassium sulphamate and fuming nitric acid, both home-made). Maybe I pick up the project again at a later time.

http://www.ijcce.ac.ir/ijcce/ArticlePPDF/200827110.pdf

DraconicAcid - 28-10-2013 at 12:02

Quote: Originally posted by woelen  
The dinitramide ion exists, you can consider it as derived from ammonia, with two H-atoms replaced by -NO2 and the last H-atom split off. The molecule HN(NO2)2 is not stable, but salts of this are stable. The potassium salt K[N(NO2)2] exists and is perfectly stable at room temperature. The ammonium salt also exists, NH4[N(NO)2].


I have scribbled notes in the back of my first-year text from 1989, in which I wondered if it was possible to make this (I proposed reacting NaNH2 with NO2Cl). I'm glad to hear that more learned chemists considered the substance, and succeeded.

caterpillar - 28-10-2013 at 12:50

Quote: Originally posted by woelen  


Even a home chemist can make this chemical at home, the only real problem being the necessity to perform a reaction at -40 C or so. I tried this reaction, but I do not have the equipment for maintaining a reaction vessel at -40 C for a long time. I also have no access to dry ice, so I abandoned the project.


Dry CaCl2, mixed with snow (crushed ice) is a good cooling agent- this mixture decreases temperature down to -50 Celsius.

vulture - 28-10-2013 at 12:59

Quote:

Dry CaCl2, mixed with snow (crushed ice) is a good cooling agent- this mixture decreases temperature down to -50 Celsius.



Did you get this to work? I tried once and couldn't get below -36 C.

deltaH - 28-10-2013 at 13:20

@DubaiAmateurRocketry

Nitramide is a well known material. It can be prepared from nitrocarbamates (the existence of nitrocarbamates was more of a surprise to me!).

Anyhow, as pointed out, dinitramides are more useful.

As is usual with nitro anything, the acidity goes up significantly because of the electron withdrawing effect of the nitro group, hence why dinitramide is an anion and it's conjugate acid would be highly acidic.

When it comes to novel oxidisers (a pet hobby of mine as well), the real challenge always comes in the cation when considering salts, because it's very hard to build in a nitro group there and have enough remaining basicity.

The anions are of course easy. Things like the trinitromethanide and dinitramide are the classic. So for example, in the US they favour hydrazinium nitroformate as the next smokeless oxidant, while Europe favours ammonium dinitramide.

Coming back to oxygen rich cations, I would favour NO+
For example a hypothetical nitrosonium trinitromethanide salt.

The interesting thing is that while nitronium trinitromethanide (the NO2+ version) simply forms tetranitromethane of course, BUT molecular modelling done by deltaG suggests that nitrosotrinitomethane has too weak a ON-C bond and will always formally be the salt NO+C(NO2)3-. This means unlike tetranitromethane, it will be a solid and so potentially a crazy powerful novel oxidant.

The only problem is that it would probably be hypergolic in contact with most functionalized fuels, though maybe it can be coated with a thin layer of synthetic wax?

Incidentally, NOClO4 is a well known nitrosonium salt and also a crazy powerful hypergolic oxidant.

The downside is that the perchlorate version would make HCl during combustion and the desire here is for smokeless high performance oxidants.

Long story short, I'd put my money on the hypothetical NO C(NO2)3 for your fondness for novel and oxidants :) though of course this is all academic and probably completely impractical!

[Edited on 28-10-2013 by deltaH]

DubaiAmateurRocketry - 29-10-2013 at 07:47

Sorry if I did not correctly ask the question, I was not asking about dinitramide.

I mean the Ammonium cation. subsituding an H with NO2, so it is still a cation, and with a [NO3]- it would make a very oxygen positive, and maybe energetic oxidizer.

can we add a H+ To nitramide to make nitroammonium cation ? or is it only alkyl that can change R-NH2 to R[N+]H3?

If so..

I have another guess.

Hydroxylamine's structure is same as Nitramide, except the OH became NO2, and because hydroxylamine + HNO3 = Hydroxylammonium nitrate, does that mean the nitro derivative of hydroxylamine, nitramide + HNO3 can make nitroammonium nitrate ? [H3N-NO2]+ [NO3]-


DubaiAmateurRocketry - 29-10-2013 at 11:14

I also wonder why Hydroxyl-ammonium cation is so rarely used in explosives.

Often high nitrogen salts are oxygen negative, and Hydroxyl-ammonium cation could help with that, while it gives higher density.

I think higher density and oxygen balance for more gas production is more important than the one hydrogen used for the hydroxyl bond.

deltaH - 29-10-2013 at 11:32

Quote: Originally posted by DubaiAmateurRocketry  
I also wonder why Hydroxyl-ammonium cation is so rarely used in explosives.

Often high nitrogen salts are oxygen negative, and Hydroxyl-ammonium cation could help with that, while it gives higher density.

I think higher density and oxygen balance for more gas production is more important than the one hydrogen used for the hydroxyl bond.


Hydroxylamine is a kinetically and thermodynamically excellent reducing agent making its use with oxidising anions problematic. However, I believe hydroxylammonium nitrate solutions are being researched as monopropellants, requiring a catalyst to make it go, but that's just because you have all that water around that quenches it, so the decomposition has to proceed at much lower temperatures, hence the need for a catalyst (similar to hydrogen peroxide).

Possibly hydroxylammonium perchlorate is stable enough to isolate as a solid, but again, having the chlorine there takes away from it being a 'uber' oxidant... ideally one doesn't want the HCl formed in a next gen oxidant.

Hydroxylammonium trinitromethanide is a maybe? As I said before, hydrazonium trinitromethanide is favoured by the US in terms of its next gen oxidant research, though this stuff is more of a solid monopropellant.

Hydroxylammonium dinitramide is probably a no go.

So in this case, you have the problem of finding a sufficiently inert anion that isn't a hypervalent halogen.

[Edited on 29-10-2013 by deltaH]

DubaiAmateurRocketry - 29-10-2013 at 11:55

Quote: Originally posted by deltaH  
Quote: Originally posted by DubaiAmateurRocketry  
I also wonder why Hydroxyl-ammonium cation is so rarely used in explosives.

Often high nitrogen salts are oxygen negative, and Hydroxyl-ammonium cation could help with that, while it gives higher density.

I think higher density and oxygen balance for more gas production is more important than the one hydrogen used for the hydroxyl bond.


Hydroxylamine is a kinetically and thermodynamically excellent reducing agent making its use with oxidising anions problematic. However, I believe hydroxylammonium nitrate solutions are being researched as monopropellants, requiring a catalyst to make it go, but that's just because you have all that water around that quenches it, so the decomposition has to proceed at much lower temperatures, hence the need for a catalyst (similar to hydrogen peroxide).

Possibly hydroxylammonium perchlorate is stable enough to isolate as a solid, but again, having the chlorine there takes away from it being a 'uber' oxidant... ideally one doesn't want the HCl formed in a next gen oxidant.

Hydroxylammonium trinitromethanide is a maybe? As I said before, hydrazonium trinitromethanide is favoured by the US in terms of its next gen oxidant research, though this stuff is more of a solid monopropellant.

Hydroxylammonium dinitramide is probably a no go.

So in this case, you have the problem of finding a sufficiently inert anion that isn't a hypervalent halogen.

[Edited on 29-10-2013 by deltaH]


I like your idea of

Hydroxylammonium Nitroformate.

[NH3OH]+ [C(NO2)3]-
CH4N4O7
Molar mass:184.0655
Oxygen balance : +26.1 which is exactly 2 times higher than Hydrazine nitroformate.

I would also expect Hydroxylammonium nitroformate, and hydroxylammonium dinitramide to be more stable than the ammonium or hydrazine salts.

In my opinion, i would favor no carbon atoms, and therefore I am also think hydroxylammonium dinitramide would be a good one. However it might be less energetic than the nitroformate salt

[NH3OH]+ [N(NO2)2]-
N4H4O5
Molar mass 140.05582
Oxygen balance 34.3 (same as ammonium perchlorate while being chlorine free)

What do you think of the reaction that i stated in the pictures ? is it possible at all ?

I wish we can have an almost oxygen balanced stable Cation, so we can just use something like a nitrate for its anion which is cheap and simple. I recently find tetrazoles interesting however their stability is a problem.


[Edited on 29-10-2013 by DubaiAmateurRocketry]

woelen - 29-10-2013 at 13:27

I can tell from experience that hydroxylammonium ion is dangerous in combination with strongly oxidizing ions, even in solution.

If you have the chemicals, then try adding some solid NaBrO3 to a fairly concentrated solution of NH2OH.HCl. If you do this, then first nothing seems to happen and then after some time (a few tens of seconds), the material suddenly explodes :o . With KBrO3 instead of NaBrO3 there also is an induction period, and then there is a very violent and exothermic reaction, no explosion, but still very violent.
With iodates there is a very violent reaction, without induction time. With chlorite, there also is a very violent reaction without induction time.

In all cases, we are talking about solutions of the hydroxylammonium chloride, not solid chemicals mixed with each other. NH2OH.HClO4 is stable, I once prepared this as a solid chemical. It energetically decomposes when heated. I never made NH2OH.HNO3, but I can imagine that it is stable as well, although slight heating may lead to violent decomposition of this (it will be MUCH more sensitive than NH4NO3).

caterpillar - 29-10-2013 at 16:17

Quote: Originally posted by vulture  
Quote:

Dry CaCl2, mixed with snow (crushed ice) is a good cooling agent- this mixture decreases temperature down to -50 Celsius.



Did you get this to work? I tried once and couldn't get below -36 C.


Negative. I only read table with properties of cooling mixtures like NaCl + snow, H2SO4 + snow and so on. But, according to dear Jared Ledgard (preparatory manual of explosives), -30 Celsius is low enough for aforementioned synthesis.

The_Davster - 29-10-2013 at 18:00

Quote: Originally posted by DubaiAmateurRocketry  


Hydroxyl ammonium cation in energetic materials, although not as energetic as the ammonium cation, it could help a lot with the oxygen balance.



Nope. In (almost) every case where there is the hydroxylammonium and ammonium salt known of an energetic anion the hydroxylammonium is always more dense, higher VOD, and higher pcj. The thing has a pretty nice dipole helping increase density, beyond the increase on OB.

Check out TKX50, its got like 9.7km/s using the hydroxylammonium cation.
Quote: Originally posted by woelen  
The molecule HN(NO2)2 is not stable, but salts of this are stable.


You can acidify dinitramide in the cold and extract into ether giving dilute ethereal solutions of dinitramidic acid. Evaporation leads to explosion or decomposition.

Quote: Originally posted by DubaiAmateurRocketry  
I also wonder why Hydroxyl-ammonium cation is so rarely used in explosives.




Nope. Hydroxylammonium nitrate has been investigated as a rocket fuel. Also many hydroxylammonium salts have been studied as explosives eg. http://onlinelibrary.wiley.com/doi/10.1002/zaac.201100479/ab...

DubaiAmateurRocketry - 30-10-2013 at 05:54

Quote: Originally posted by The_Davster  

Nope. In (almost) every case where there is the hydroxylammonium and ammonium salt known of an energetic anion the hydroxylammonium is always more dense, higher VOD, and higher pcj. The thing has a pretty nice dipole helping increase density, beyond the increase on OB.

Check out TKX50, its got like 9.7km/s using the hydroxylammonium cation.

Nope. Hydroxylammonium nitrate has been investigated as a rocket fuel. Also many hydroxylammonium salts have been studied as explosives eg. http://onlinelibrary.wiley.com/doi/10.1002/zaac.201100479/ab...



Yup thats what ive said, the higher density, OB results in higher performance than the ammonium cation.

I mean its rarely used like, you can often find ammonium, hydrazine salts, of whatever new anion a team foundd, in a paper, but you will rarely see a team trying hydroxyl ammonium cation.

DubaiAmateurRocketry - 30-10-2013 at 05:55

Do you guys think the nitroammonium cation is possible ? few posts up in the picture.

deltaH - 30-10-2013 at 06:47

Quote: Originally posted by woelen  
I can tell from experience that hydroxylammonium ion is dangerous in combination with strongly oxidizing ions, even in solution.

If you have the chemicals, then try adding some solid NaBrO3 to a fairly concentrated solution of NH2OH.HCl. If you do this, then first nothing seems to happen and then after some time (a few tens of seconds), the material suddenly explodes :o . With KBrO3 instead of NaBrO3 there also is an induction period, and then there is a very violent and exothermic reaction, no explosion, but still very violent.
With iodates there is a very violent reaction, without induction time. With chlorite, there also is a very violent reaction without induction time.

In all cases, we are talking about solutions of the hydroxylammonium chloride, not solid chemicals mixed with each other. NH2OH.HClO4 is stable, I once prepared this as a solid chemical. It energetically decomposes when heated. I never made NH2OH.HNO3, but I can imagine that it is stable as well, although slight heating may lead to violent decomposition of this (it will be MUCH more sensitive than NH4NO3).


Interesting. I think the important thing here is to distinguish between kinetically fast oxidant anions and inhibited (non labile) ones. For example, ClO4- is theoretically a good oxidant, but kinetically inert at low temperatures. That is why perchlorate salts are a little more stable and safer to handle.

I would imagine that dinitramide is kinetically uninhibited, just like bromates and hypochlorites and the like, so I would say that these are a no go with all but the most kinetically inert of cations... like ammonium.

Hydroxylammonium cation IS NOT kinetically inactive... it is REACTIVE, so solid hydroxylammonium nitrate is a NO NO in my opinion and trying to isolate solid hydroxylammonium dinitramide is simply crazy... but I'm not as worried about that one as it would probably react almost instantly in solution long before you attempt to isolate anything :)

The dangerous ones are the ones that are half and half, stable enough to isolate in solid form, but not necessarily stable ;)

Hydroxylammonium nitroformate is exactly in such a category!

[Edited on 30-10-2013 by deltaH]

DubaiAmateurRocketry - 8-11-2013 at 05:31

Quote: Originally posted by deltaH  
Quote: Originally posted by woelen  
I can tell from experience that hydroxylammonium ion is dangerous in combination with strongly oxidizing ions, even in solution.

If you have the chemicals, then try adding some solid NaBrO3 to a fairly concentrated solution of NH2OH.HCl. If you do this, then first nothing seems to happen and then after some time (a few tens of seconds), the material suddenly explodes :o . With KBrO3 instead of NaBrO3 there also is an induction period, and then there is a very violent and exothermic reaction, no explosion, but still very violent.
With iodates there is a very violent reaction, without induction time. With chlorite, there also is a very violent reaction without induction time.

In all cases, we are talking about solutions of the hydroxylammonium chloride, not solid chemicals mixed with each other. NH2OH.HClO4 is stable, I once prepared this as a solid chemical. It energetically decomposes when heated. I never made NH2OH.HNO3, but I can imagine that it is stable as well, although slight heating may lead to violent decomposition of this (it will be MUCH more sensitive than NH4NO3).


Interesting. I think the important thing here is to distinguish between kinetically fast oxidant anions and inhibited (non labile) ones. For example, ClO4- is theoretically a good oxidant, but kinetically inert at low temperatures. That is why perchlorate salts are a little more stable and safer to handle.

I would imagine that dinitramide is kinetically uninhibited, just like bromates and hypochlorites and the like, so I would say that these are a no go with all but the most kinetically inert of cations... like ammonium.

Hydroxylammonium cation IS NOT kinetically inactive... it is REACTIVE, so solid hydroxylammonium nitrate is a NO NO in my opinion and trying to isolate solid hydroxylammonium dinitramide is simply crazy... but I'm not as worried about that one as it would probably react almost instantly in solution long before you attempt to isolate anything :)

The dangerous ones are the ones that are half and half, stable enough to isolate in solid form, but not necessarily stable ;)

Hydroxylammonium nitroformate is exactly in such a category!

[Edited on 30-10-2013 by deltaH]


Well, I dont think its too much, Hydroxylammonium perchlorate can be easily prepared and isolated by ion exchanging.

https://docs.google.com/viewer?url=patentimages.storage.goog...

deltaH - 8-11-2013 at 06:38

Yes DubaiAmateurRocketry, that's what I said in my first paragraph, perchlorate salts are particularly non labile an anion, so tend to produce safer salts (but not necessarily safe enough). It's just the others that are potentially too unstable to be safe and practical for dry use.