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Author: Subject: The holy-grail rocket fuel oxidizer
Theoretic
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[*] posted on 3-10-2004 at 07:52
The holy-grail rocket fuel oxidizer


I once seen this (by Organikum):
"es, I remember a thread that I started at The Forum a while back, "Holy Grail Oxidizer"? That included instructions on how to prepare [NF4+][ClO4-]. This was promptly dismissed by nbk2000, who then gave me a lesson on the basic fundamentals of chemistry. *sarcastic tone of voice* "Chemistry isn't just 1+1. Quit talking out of your ass". Perhaps sometime soon I shall repost that, here."

That was two years ago. :) Now I decide to make the topic that nearly didn't get created. This topic is about the most powerful (oxidizing power for weight) oxidizer you can think of, for use in rocket fuel. NF4ClO4 is one candidate. I have two candidates: peroxygen difluoride O2F2 and peroxynitryl ozonide NO3O3 (PONO). The PONO would be made through HNO3 + H2O2 => HNO4, HNO4 + SO3 => NO3HSO4, NO3HSO4 + heat => (NO3)2S2O7, 3O2 + electric discharge => 2O3, 4NaOH + 4O3 => 4NaO3 + 2H2O + O2, (NO3)2S2O7 + 2NaO3 => 2NO3O3 + Na2S2O7.




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[*] posted on 3-10-2004 at 10:57


Are you sure that the ion NF4(+) exists? I'd think a positive nitrogen-fluoride ion if it exists would be more like HNF3..but I've never heard of it and it sounds....weird.
As do NaO3, I've only heard of NaO2, sodium superoxide.

I'd go for N2O4, it is used today in rocketry. Fluorine is a strong oxidiser, but it requires a cetain kind of fluels to be efficient.
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[*] posted on 3-10-2004 at 12:10


The NF4+ ion is isoelectronic with CF4 and BF4-. However, it is less stable than these two latter species, and is more difficult to obtain, as it involves inducing NF3 to lose an electron and accept a F atom. It resembles the nitronium ion, NO2+, which exists only in combination as a salt of the strongest oxy-acids, e.g. perchlorate, and nitrate as solid N2O5. In fact, [NO2]+[ClO4]- is easier to come by than the NF4+ species.

I have also heard of a ClF6+ ion being obtained, but it would not be easy as it similarly requires ClF5 to lose an electron and accept a F atom.

John W.
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[*] posted on 3-10-2004 at 15:01
Oxidizer


Depends on the fuel being burned. I'll go with NH4ClO4 as the most powerful, practical,
rocket fuel oxidizer. NASA's NH4ClO4 / Al / binder used in the shuttle's solids is probably
still the most versatile.




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[*] posted on 3-10-2004 at 17:55


I've never heard of sodium ozide either but it probably exists, although I am sure of rubidium and cesium ozides. Their larger carion size may well stabilize the ozide same as they can stabilize the triiodide anion.



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[*] posted on 4-10-2004 at 07:14


What is the actual electronic structure of the 'ozide' [O3]- ?? I can't figure a way to make this work...



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[*] posted on 4-10-2004 at 08:38


Quote:
Ozone forms compounds with the alkali and alkaline earth metals. These compounds contain the trioxide (1-), O3-. As we would expect from the lattice stability arguments, it is the larger cations, such as cesium, that form the most stable trioxides. It has been shown that the trioxide (1-) is also V-shaped, so the molecular orbital diagram should be similar to trioxygen itself. Thus, the additional electron in the anion should enter the pi anti-bonding orbital. This arrangement would reduce the pi bonding to one-half, or one-fourth, per oxygen-oxygen bond. Experimental measurments have shown this to be the case. The oxygen-oxygen bond length is 135 pm in the trioxide (-1) ion, slighlty longer then the 128 pm bond in trioxygen itself.


Quote from Descriptive Inorganic Chemistry 3rd editoin, Geoff Rayner-Canham; Tina Overton

It's odd to think that it's still V-shaped. Initially I thought that it would have instead formed something anologous to the azide anion, an oxygen atom carrying the negative charge bonded to the oxygen atom central which has a bond and a partial bond to the terminal oxygen. However being V-shaped this is not the case.

Edit: Forgot to cite my quote

[Edited on 10/4/2004 by BromicAcid]




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thumbup.gif posted on 4-10-2004 at 10:37


Potassium, sodium and tetramethylammonium ozonides have been obtained. The ozonide ion ia a radical ion, like the superoxide.
As for NH4ClO4 as the most powwrful oxidizer, consider this.
1) N2 + 3H2 => 2NH3 + energy RELEASED

2) Cl2O7 + H2O => 2HClO4 + energy RELEASED

3) NH3 + HClO4 => NH4ClO4 + energy RELEASED

All that energy released that could be released in the engine. Of course, you wouldn't use H2 and Cl2O7, but NO2ClO4/NF4ClO4 are MUCH better (and reasonably stable also).

What are the nation's thoughts about the peroxonitryl ion? :P Is there a reason to prevent it from a reasonably stable existence?




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[*] posted on 5-10-2004 at 00:34


PENTACHLOROBENZOIC ACID look like a high one.
http://www.orgsyn.org/orgsyn/prep.asp?prep=cv5p0890
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[*] posted on 5-10-2004 at 08:28


A high one of what?
Can you tell us why this is a 'holy grail oxidiser'?
I cant see why.




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[*] posted on 5-10-2004 at 09:48
Other oxidizers


Theoretic, I'm not doubting you on the other oxidizers mentioned.
I've never seen a synthesis on them. Quite frankly, this was the 1st
time I heard of them.




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[*] posted on 6-10-2004 at 01:00


CO2.H.C6CL5 + H2O + heat -- CH3 +CO2 + C6(ring) + Cl5.
So whats wrong with the fomulas?

[Edited on 6-10-2004 by tokat]
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[*] posted on 6-10-2004 at 03:15


Hmmm....I'm only a novice but:

--> CH<sub>3</sub> - what is this exactly?
C<sub>6</sub>(ring) - what is this? Sure as hell isn't benzene...could a ring of 6 Carbons with only double bonds between them even exist?
Cl<sub>5</sub> - should be 5Cl (or even 2.5 Cl<sub>2</sub> I guess, though I am sure the reaction wouldn't go like you wrote it.)

It (your pentachlorobenzoic acid) may be a chlorine donor but that is all - not the greatest oxidiser ever. I would wager most nitrates would beat it...
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[*] posted on 6-10-2004 at 06:17


Tokat, we are looking for OXIDISERs, not for some highly chlorinated compounds.
Pentachlorobenzoic acid certainly isn't an oxidiser.




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[*] posted on 6-10-2004 at 22:14


Sorry i thought oxidisers were oygen,clorine,floruine donors,i didn't learn it from chemstiry though.
"CH3 - what is this exactly?" Cann't remember what it is called but mix HCL with carbon to make it.
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[*] posted on 7-10-2004 at 02:26


Tokat:
That kind of question probably belong in the "beginnings" section.

CH3- is a methyl group. It can't exist on it's own, it's always part of a molecule. You cannot make CH3 by adding HCl to carbon.

Oxidisers are indeed compounds with the ability to accept electrons. Things like sulfur and chlorine are oxidisers too, but weaker since they have lower electronegativity and higher atomic weight than oxygen and fluorine.
In pyro / rocketry oxidisers normally contain oxygen as a part of a compound / or a salt with the ability to loose it's oxygen when temperature rises.
Example:
6KNO3--->3K2O, 3KO2, 3N2 and 3O2.
2KClO3---heat--->2KCl+3O2
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[*] posted on 9-5-2013 at 03:46


NF4ClO4?

I heard this salt is not really dangerous or reactive.. but i havent found any melting / boiling points ever.

I saw the decomposition is NF4ClO4 + Heat = NF3 + FClO4
If enough heat is added, both compound will further decompose at not much above room temperature.

2NF3 = F2 + N2F4
2FClO4 = F2 + Cl2 + 2O2

N2F4 further decompose into 2F2 and N2.

so 2 NF4ClO4 = N2 + 4F2 + Cl2 + 2O2

wow.. Flourine and chlorine and oxygen being released !
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[*] posted on 9-5-2013 at 05:14


Quote: Originally posted by KonkreteRocketry  
NF4ClO4?




Do you have any credible references for the existence/synthesis of this compound?

This cannot be analogous to an ammonium salt, as it would require an electron acceptor to yield a cation, like in the case of 'straight' ammonium:

NH3 + H+ === > NH4+

An F+ ion, assuming you could create it, would immediately try and capture an entire electron pair to form F-, which would be almost infinitely more stable than F+ due to the extreme electronegativity of fluorine.

'On paper' something like NF3H+ could be imagined but I've no idea if it has been synthesised. It sounds unlikely because the electron pull of the three F atoms would partially charge the N atom, making it far less attractive for protons.




[Edited on 9-5-2013 by blogfast25]




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[*] posted on 9-5-2013 at 06:27


Quote: Originally posted by blogfast25  
Quote: Originally posted by KonkreteRocketry  
NF4ClO4?




Do you have any credible references for the existence/synthesis of this compound?

This cannot be analogous to an ammonium salt, as it would require an electron acceptor to yield a cation, like in the case of 'straight' ammonium:

NH3 + H+ === > NH4+

An F+ ion, assuming you could create it, would immediately try and capture an entire electron pair to form F-, which would be almost infinitely more stable than F+ due to the extreme electronegativity of fluorine.

'On paper' something like NF3H+ could be imagined but I've no idea if it has been synthesised. It sounds unlikely because the electron pull of the three F atoms would partially charge the N atom, making it far less attractive for protons.




[Edited on 9-5-2013 by blogfast25]


oh, NF4ClO4 is not NF4, its kind of NF3FOClO3

http://en.wikipedia.org/wiki/Fluorine_perchlorate


Structure of NF4ClO4 shall be like.. ignore dots

.....F.................O
F- N - F - O - Cl = O
.....F.................O




[Edited on 9-5-2013 by KonkreteRocketry]

[Edited on 9-5-2013 by KonkreteRocketry]

[Edited on 9-5-2013 by KonkreteRocketry]
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[*] posted on 10-5-2013 at 10:13


Quote: Originally posted by KonkreteRocketry  

Structure of NF4ClO4 shall be like.. ignore dots

.....F.................O
F- N - F - O - Cl = O
.....F.................O


Fluorine creating two bonds?! omg :(

During all these years in chemistry I never saw anything like this...

Sure, NF3 and fluorine perchlorate both exists, but this...

I hope You understand that his formula equals to statement that by mixing water with table salt you get NaH2ClO, or something similar...




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[*] posted on 10-5-2013 at 10:26


The ion NF4(+) does exist.

http://pubs.acs.org/doi/abs/10.1021/ic50052a020

The salt NF4ClO4 also seems to exist. In 1980 it was prepared by K.O. Christe. This person has done research on many REALLY obscure and special chemicals. Just google his name and you will find interesting reads about very weird compounds.

http://oai.dtic.mil/oai/oai?verb=getRecord&metadataPrefi...

[Edited on 10-5-13 by woelen]




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[*] posted on 10-5-2013 at 13:03


Yes, I saw it woelen. That one surprised me a lot.



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