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BleedingLips
August 6th, 2002, 08:05 AM
February 2, 1999

New Nitrogen Ion Carries Warning: Handle With Care

By MALCOLM W. BROWNE

For a century, chemists doubted that such a substance could exist, but
scientists at an Air Force laboratory have created a freakish form of
nitrogen believed to be one of the most violently explosive substances ever
made.

To the acclaim of many other scientists, a team of chemists headed by Dr.
Karl O. Christe and Dr. William W. Wilson at the Air Force Research
Laboratory at Edwards Air Force Base, Calif., reported their achievement
at a recent meeting of the American Chemical Society.

The new compound is a positively charged ion, or molecular fragment,
consisting of five nitrogen atoms chemically bonded to each other in a V
pattern. It is so sensitive and explosive, the magazine Chemical &
Engineering News reported, that a few tiny grains of the substance
accidentally detonated, destroying part of the apparatus being used to
analyze it.

The newly synthesized allotrope, or form, of nitrogen (N5 ) is only the
third such form of the element ever discovered.

Nitrogen in its most common, gaseous form, consisting of two atoms of
the element chemically bound to each other (N2 ), makes up four fifths of
the earth's atmosphere and is quite stable and chemically unreactive. This
form of nitrogen was identified in 1772.

The next allotrope of nitrogen to be discovered was the azide ion (N3 ),
containing three bound nitrogen atoms, which was synthesized in 1890.
Azides combined with metals as salts are unstable and explosive; lead
azide, for example, has been used commercially to detonate high
explosives, and sodium azide is the explosive used to inflate automobile air
bags.

To chemically bind increasing numbers of nitrogen atoms to one another
requires enormous energy, and chemical theorists had predicted that
nitrogen allotropes with more than three nitrogen atoms would be so
unstable they could not exist.

Dr. Christe's team, however, has confounded the experts.

Over four months, his group succeeded in synthesizing a salt in which the
positive ion consists of five nitrogen atoms and the negative ion consists of
an arsenic atom with six fluorine atoms. The group obtained proof of the
substance's chemical composition using laser spectroscopy, but after the
analysis was completed, several grains of the white crystalline powder
exploded, demolishing the sample chamber.

The material is so dangerous to handle that only a handful of laboratories
would be able to perform Dr. Christe's synthesis, chemists said.

Dr. Steven H. Strauss of Colorado State University at Fort Collins, who is
familiar with Dr. Christe's work, said in an interview that even the most
experienced chemists regard the synthesis of an allotrope with five nitrogen
atoms as astonishing.

"Just having shown that this substance can exist even temporarily is a
gigantic achievement," he said. "Theorists who may have considered this
type of compound impossible will have to do some recalculating."

Dr. Christe is known for another tour de force in chemistry: the first
successful separation, in 1986, of pure fluorine from a fluorine compound
using chemical reactions alone. Fluorine, a poisonous pale yellow gas, is
normally prepared by passing a current of electricity through molten
fluoride salts. Fluorine is the most violently reactive of all elements, and it
can be separated from its compounds only with the help of large amounts
of energy. Most chemists had believed that chemical separation of
elemental fluorine was probably impossible.

Dr. Christe works at the propulsion division of the Air Force laboratory at
Edwards Air Force Base, and his research, some of it secret, is financed
by the Air Force, the Defense Advanced Research Projects Agency and
the National Science Foundation.

He said in an interview that the new nitrogen allotrope was likely to find
uses, but he declined to say what they would be. However, the material is
such a powerful oxidizing agent that it explosively rips water molecules
apart.

Dr. Christe said that the latest goal of his group was to synthesize an
all-nitrogen salt consisting of a positive ion of five nitrogen atoms bound to
a negative ion of five nitrogen atoms. Such a compound, containing 10
mutually linked nitrogen atoms, would be extremely difficult if not
impossible to synthesize, but it would probably pack stupendous chemical
energy that might be released with great explosive force.

Interesting links:
<a href="http://www.llnl.gov/str/June01/Manaa.html" target="_blank">http://www.llnl.gov/str/June01/Manaa.html</a>
<a href="http://www-cms.llnl.gov/buckyballs/research_proj.html" target="_blank">http://www-cms.llnl.gov/buckyballs/research_proj.html</a>

kingspaz
August 6th, 2002, 08:17 AM
wonder how he managed the elemental fluorine by chemical means...

PrimoPyro
August 6th, 2002, 04:40 PM
???

The commercial method is simple electrolysis of fluoride salts, either in water or in a polar aprotic solvent (though I doubt common DMSO or DMF could be used due to low solubility) to release elemental fluorine.

The alkalai is removed from the reaction via absorption into a mercury cathode forming an amalgam which is continuously pumped to prevent solidification. It is perodically discharged and replaced, and the mercury distilled under noble gas to recover the alkalai metal free of oxydation. This type of process also the first industrial process used for manufacturing alkalai metals, before the Downs Process was invented.

But alas, researchers have it easy today. No longer limited like their alchemist ancestors who had to synthesize all their own reagents for experimentation, researchers today just BUY whatever they need from chemical megagiants like S-A or Fisher. There's a certain pride in making EVERYTHING yourself, even if it does take longer.

I think thye just bought a fluorine canister personally, lol. The cooled it with liquid N2.

The concept of Total Synthesis is almost lost to our vocabulary today. How sad.

PrimoPyro

kingspaz
August 6th, 2002, 06:07 PM
from the above article 'Dr. Christe is known for another tour de force in chemistry: the first successful separation, in 1986, of pure fluorine from a fluorine compound using chemical reactions alone'

thats why i was confused! flourine cannot (to my simple knowlegde) be reduced by anything other than electricity.

total synthesis is my speciality by the way :D .....'neccessity is the mother of all invention'.....or somthing like that <img border="0" title="" alt="[Wink]" src="wink.gif" />

PrimoPyro
August 6th, 2002, 11:31 PM
Ah well, it's always possible then that he exploited a complexing mechanism, like Friedel Crafts principals for example, where strong Lewis Acids complex with halogens to form extremely electron hungry species. I am sort of unfamiliar with this region of chemistry, but I don't think that it would be impossible to liberate fluorine chemically from an organic compound at least, using a EWD-lewis acid complex to form a more electronegative entity, which could replace the fluorine through a usual substitution mechanism pathway, and then the complex could be destroyed afterwards.

All speculation though. I have no articles on this.

Glad to hear you like Total Synthesis. I do as well.

Heh, it's not "purely" chemical, but alpha particle bombardment would liberate bipositive fluorine ions that could be led away into a cathode. :p

No? Cheating you say? Well ok, I guess you kinda got me there....but it IS cool, you have to admit. :D

PrimoPyro

<small>[ August 06, 2002, 10:34 PM: Message edited by: PrimoPyro ]</small>

PrimoPyro
August 7th, 2002, 01:19 AM
Jesus Christ! Fucking Duh!

The same analogous reducing system for ALL halides/halates --&gt; halogens.

Halide + Halate --&gt; halogen.

This would have to be a special situation for this to work on fluorides. You would need to exploit solubility. (When do you NOT have to??)

A normal example of this (and hits home hard for meth cooks) is the preparation of iodine from iodide salts. Granted this can of course be done with acid and either hypohalite or hydrogen peroxide, BUT the yields with this method are always much much better, nearly quantitative actually.

NaIO3 + 5NaI +6HCl --&gt; 6NaCl + 3I2 + 3H2O

Now this cannot directly be used for fluorides because we need a more electronegative halide than fluorine and that simply does not exist. But if you were to exploit solubility, you could force such a reaction using sodium fluoride, sodium fluorate, and another acid. The acid choice and solvent are key.

What need be done is choose a solvent and acid that a)both sodium fluoride and sodium fluorate are soluble in, and b)the sodium salt of the acid is not soluble in that particlular solvent.

The sodium salts precipitate out of solution forcing the reaction to proceed to completion. Hell, if you could cheat and start with the dry acids themselves, HF and HFO3, you could use P2O5 to dehydrate them to F2 + H3PO4 (not balanced).

I love figuring these possibilities out.

PrimoPyro

Pu239 Stuchtiger
August 7th, 2002, 01:45 AM
The [FO3-] ion doesn't exist. Only [OF-] exists, and that is very unstable.

How about this?

3HOF + 3HF + P2O5 ----&gt; 2H3PO4 + 3F2

That just seems too simple to be real! :D

<small>[ August 07, 2002, 12:48 AM: Message edited by: Pu239 Stuchtiger ]</small>

PrimoPyro
August 7th, 2002, 01:54 AM
I see you are correct. I have to admit I'm slightly embarrassed, I did not ever realize this. It never occurred to me to consider that.

Hypofluorites can also substitute for fluorates then, if used with strong dehydrating conditions like P2O5.

Halates are just more common. Heh, "Not with fluorine they ain't!"

PrimoPyro

<small>[ August 07, 2002, 12:55 AM: Message edited by: PrimoPyro ]</small>

Marvin
September 28th, 2002, 10:57 PM
Flourine from only compounds, hmm. Maybe if you started from XeF4.....