Sciencemadness Discussion Board - protonatation/deprotonation of molecules

protonatation/deprotonation of molecules

underground - 19-2-2014 at 23:27

There is a way to protonate or deprotonate the amine group of some molecules to forms salts. The idea is to protonate/deprotonate some molecules to form denser salts for better performance and OB. But how it can be done actually ?

For example i was thinking to deprotonate a molecule (like nitroguanidine) making it to behave like an anion (-1), Then with an aluminum cation (+3), add 3 molecules of nitroguanidine to it to make the aluminum nitroguanidine salt with 1 aluminum molecule and 3 nitroguanidine molecules, i guess it will be powerful. On the other hand, protonation of nitroguanidine can form salts like nitroguanidine nitrate / perclorate e.t.c.

[Edited on 20-2-2014 by underground]

Metacelsus - 20-2-2014 at 05:52

It's not that easy. Deprotonation of guanidine will create an extremely strong base, as guanidine is a base already. The pKa will be around 35. Protonation is much easier.

How would you plan to prepare the aluminum salt? It will not be easy. You would probably need aluminum hydride, and even that may not work.

underground - 20-2-2014 at 06:27

What about nitroguanidine, as i said above ?

DubaiAmateurRocketry - 20-2-2014 at 08:21

nitroguanidine seems much easier.

I recently got interested into Dinitrourea and dinitroguanidine's salts. I wonder if the hydroxylammonium salt of them exist since the ammonium salt's density is pretty horrible. Hydroxylammonium would give much better oxygen balance, density, and hydrogen bonds at same time.

underground - 20-2-2014 at 09:06

Quote: Originally posted by DubaiAmateurRocketry

nitroguanidine seems much easier.

I recently got interested into Dinitrourea and dinitroguanidine's salts. I wonder if the hydroxylammonium salt of them exist since the ammonium salt's density is pretty horrible. Hydroxylammonium would give much better oxygen balance, density, and hydrogen bonds at same time.

That is true, but in practice how you can do that ? protonane and deprotonate molecules ?

DubaiAmateurRocketry - 20-2-2014 at 09:35

Quote: Originally posted by underground

Quote: Originally posted by DubaiAmateurRocketry

That is true, but in practice how you can do that ? protonane and deprotonate molecules ?

I am not an expertise in chemistry. However if you shows me a structure of an molecule, I could tell you which hydrogen is acidic and can form salts.

Guanidine it self is hard be an anion and the reason has already been explained by Cheddite Cheese. When a compound have a lot of electron withdrawing group(for EM nitro group is most common), then the polar bonded hydrogen atoms could be deprotonated.

[Edited on 20-2-2014 by DubaiAmateurRocketry]

underground - 20-2-2014 at 10:27

I am talking about nitroguanidine and not Guanidine. Guanidine indeed it is a strong base

DraconicAcid - 20-2-2014 at 10:40

Well, the Merck Index doesn't give a pKa for nitroguanidine (and googling gives a number of widely varying values), but it does say it is soluble in aqueous alkalis (but not carbonates). This suggests that it can be deprotonated in aqueous solution, and reaction of this solution with a metal salt *may* give precipitation of the metal nitroguanidate(?). I wouldn't bother trying aluminum, though, since that would most likely give a stubborn gel of aluminum hydroxide. A transition metal with an affinity for nitrogen may work better.

This is purely theoretical, of course- I have no experience with nitroguanidine.

underground - 20-2-2014 at 22:39

It is really difficult to find any information for this chemical, google does not have almost nothing about that.

Nitroguanidine nitrate (NGN) it is said that it is more powerful than HMX!! With a little search, in this topic, the last one post, it is said:

Quote: Originally posted by VladimirLem

I read about DiNitroGuadinine and NitroGuadinineNitrate and both can be made by the nitration of nitroguanidine (NGN needs only 60% HNO3 and DNG needs 100%+H2SO4/oleum)...but i dont want to waste such many H2SO4 on DNG and dont want to make oleum (to expensive and much much work - and fucking dangerous btw)

other question, there is not much information about NGN...only some translation that says it would be more powerful than DNG or ammoniumdinitroguanidine...can this be?

Also an another post form Ral123 about NGN

Quote: Originally posted by Ral123

Nitroguanidine nitrate-the legend says it's more powerful then HMX and it's the poor man's elite explosives equivalent. Density about 2, velocity about 9300 and a guy has ripped a whole in a concrete wall with some of it

If it wasn't acidic and with doubtful storage stability, I'd be making some for blast cap base charges and mini boosters.

[Edited on 21-2-2014 by underground]

Dornier 335A - 21-2-2014 at 00:11

Nitroguanidine nitrate may be powerful, but it's not very stable. It slowly loses HNO₃ in contact with air.

It's made by dissolving nitroguanidine in hot, concentrated nitric acid and allowing it to cool.

underground - 21-2-2014 at 00:33

Quote: Originally posted by Dornier 335A

Nitroguanidine nitrate may be powerful, but it's not very stable. It slowly loses HNO₃ in contact with air.

It's made by dissolving nitroguanidine in hot, concentrated nitric acid and allowing it to cool.

Too bad

I guess this is because of its low basicity due to nitro group. That is why i guess the aminonitoguanidine nitrate is more stable, cause of its amino group, it becames a stronger baze than nitroguanidine.

An another idea, As long as the formation of aminonitroguanidine needs hydrazine, a chemical that i really want to avoid, i was wondering if the amino group can be replaced with other group like methyl group for something like methylnitroguanidine nitrate.

[Edited on 21-2-2014 by underground]

VladimirLem - 21-2-2014 at 04:06

well....what if someone would react NGN with stuff like ammonia or urea ?

would the NGN decomposite to like NG and AN/UN or could that bring a bit more stability and would make the OB of NGN (OB +5%) to nearly zero

DubaiAmateurRocketry - 21-2-2014 at 04:36

underground, it is CH3 on instead of CH there.

underground - 21-2-2014 at 04:50

Quote: Originally posted by DubaiAmateurRocketry

underground, it is CH3 on instead of CH there.

Yea that is true... i forget the number, i will fix it

Quote: Originally posted by VladimirLem

well....what if someone would react NGN with stuff like ammonia or urea ?

would the NGN decomposite to like NG and AN/UN or could that bring a bit more stability and would make the OB of NGN (OB +5%) to nearly zero

I bet AN/UN will be formed...

[Edited on 21-2-2014 by underground]

VladimirLem - 21-2-2014 at 06:50

Quote: Originally posted by underground

Quote: Originally posted by DubaiAmateurRocketry

underground, it is CH3 on instead of CH there.

Yea that is true... i forget the number, i will fix it

Quote: Originally posted by VladimirLem

I bet AN/UN will be formed...

[Edited on 21-2-2014 by underground]

damn

and how about my question you quoted from the other thread - does it seem possible to make first NGN with (60% hno3) and then making DNG with only 95<% HNO3 and maybe a little bit H2SO4? (2 step instead of one step-nitration the same way it works at RDX over HDN)

underground - 21-2-2014 at 07:10

Quote: Originally posted by VladimirLem

damn

Yea it will may be possible but maybe the yelds will not going to be so high

I have also an other question too, adding h2so4 to aminoguanidine nitrate will it yeld to aminonitroguanidine ?

VladimirLem - 21-2-2014 at 09:28

Quote: Originally posted by underground

Quote: Originally posted by VladimirLem

damn

Yea it will may be possible but maybe the yelds will not going to be so high

I have also an other question too, adding h2so4 to aminoguanidine nitrate will it yeld to aminonitroguanidine ?

i have two synthesis files, and both use the Nitroguanidine+hydrazine-way

underground - 21-2-2014 at 10:23

Quote: Originally posted by VladimirLem

i have two synthesis files, and both use the Nitroguanidine+hydrazine-way

I guess there is no other way...

I have also an another more promised idea

Dinitrobiuret itself has a positive OB and a VoD of 8660m/s
Also it can easily give 2 of his hydrogen molecules to any base with a -2 charge. So a diammonium dinitrobiuret can be exist, and i bet it will be really stable with a really high VoD.

[Edited on 21-2-2014 by underground]

Dornier 335A - 21-2-2014 at 11:11

Guanidine nitroformate is another one. It has a detonation velocity like RDX and low impact sensitivity. It can be made by combining a dilute guanidine solution or guanidine carbonate with trinitromethane. OB is -7.6%.

underground - 21-2-2014 at 22:27

Quote: Originally posted by VladimirLem

i have two synthesis files, and both use the Nitroguanidine+hydrazine-way

They usually do the use of zydrazine because i believe theu want to avoid the long way below for making aminonitroguanidine. Also i can not see any reason why this is not going to work

nitroguanidine --(acetic acid+zink)--> aminoguanidine bicarbonate
aminoguanidine bicarbonate --(15% nitric acid)--> aminoguanidine nitrate
aminoguanidine nitrate --(H2SO4)--> aminonitroguanidine
aminonitroguanidine --(nitric acid)--> aminonitroguanidine nitrate

And all of these without any exotic chemicals and dilute nitric acid!!

[Edited on 22-2-2014 by underground]