More stuff to not work with...

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Dave
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More stuff to not work with...

Post by Dave » Thu Dec 26, 2019 3:58 pm

For those who are in love with (or at least interested in) "energetic" materials (Hi, Glytch!) I can report the arrival of a small holiday present. After a hiatus of a couple of years, Derek Lowe has written two more blog entries in his "Things I Won't Work With" series... one on high-oxidation-state bromine compounds, and another on molecules which have just too darned much nitrogen and/or nitro groups packed into them,

such as this one Image and also this one Image

Synthesizing these is likened to "spray[ing] as much graffiti on the snouts of salt-water crocodiles as possible." You can probably see why these compounds tend to be referred to by names which reflect their contents... as in "OOH, NO!"

Of the high-oxidation-state bromine compounds, he mentions one whose starting materials include such tasties as redistilled pure hydrogen fluoride, with the author of the synthesis paper suggesting "double vacuum distillation in a metal line to get your HF sufficiently anhydrous for the reaction" which is not something for the faint-hearted (or even the moderately foolish). Lowe comments that "you will at all times want to be suited up like you’re going to going to spay a velociraptor."

Lowe's writing is usually quite a giggle.

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AnotherFairportfan
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Re: More stuff to not work with...

Post by AnotherFairportfan » Thu Dec 26, 2019 5:34 pm

ye-e-a-a-ahhh
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Re: More stuff to not work with...

Post by TazManiac » Thu Dec 26, 2019 8:11 pm

I have a vision of a suited-up figure, mid span of a very high suspension bridge, with a small bottle and eye dropper.

One drop over the edge followed by the tortured silence. Followed by gleeful cackling as the small mushroom cloud roils up from the casm bellow.

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Re: More stuff to not work with...

Post by AnotherFairportfan » Thu Dec 26, 2019 9:55 pm

Anyone here remember "duodec"?

"Doc" Smith was an organic chemist, and the World War 2 section of Triplanetary with Ralph Kinnison running an R&D group at a munitions plant is to some extent autobiographical.

Duodec {"duodecaplatylatomate" in full, i think] was the most powerful explosive in his "Lensman" books written before the atomic bomb.

I believe that it had a molecular structure consisting of twenty-six atoms of nitrogen.
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Re: More stuff to not work with...

Post by Warrl » Thu Dec 26, 2019 10:02 pm

You go ahead and synthesize that. I'll wait over there.... on that other continent...

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Re: More stuff to not work with...

Post by Dave » Thu Dec 26, 2019 10:43 pm

AnotherFairportfan wrote:
Thu Dec 26, 2019 9:55 pm
I believe that it had a molecular structure consisting of twenty-six atoms of nitrogen.
The N26 explosive I recall was from another E.E. Smith story "Spacehounds of IPC", a standalone novel not part of the Lensman universe. It was developed by the natives of Titan... "crystalline, pentavalent nitrogen"... and it was quite violently explosive. Stevens was warned not to take it into atmosphere even on Ganymede as it would destabilize, explode, and destroy his ship.

I don't recall the formula of duodec ever being disclosed in the Lensman series itself, or there being any discussion of it needing cryogenic storage. Smith might well have had the same idea for both series, of course.

I don't think I would want to be the person responsible for doing X-ray crystallography on N26 to confirm its structure... even by remote control. :shock: Would make spray-painting graffiti on a crocodile seem tame.

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Re: More stuff to not work with...

Post by GlytchMeister » Fri Dec 27, 2019 12:37 am

Yes, I saw those! An excellent holiday gift indeed! :D

And 26 nitros?

So far, we’ve only managed 14.

“The most alarming of them has two carbons, fourteen nitrogens, and no hydrogens at all, a formula that even Klapötke himself, who clearly has refined sensibilities when it comes to hellishly unstable chemicals, calls “exciting”.”

But I’ve been looking at ways to use nanostructures to stabilize a N60 fullerene.

Yeah, that’s 60 nitrogens, arranged in a fullerene, with NO carbons OR hydrogens. And not only that, but it has some funky stressed bond angles, adding even MORE energy. Kinda like what you find in hexanitrohexaazaisowurtzitane.

Heeheeheeheehee...

OOH and I wonder if I could co-crystalize it with anything else exciting... anhydrous hydrogen peroxide, perhaps, or maybe even something with fluorine...
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Re: More stuff to not work with...

Post by Dave » Fri Dec 27, 2019 12:47 am

GlytchMeister wrote:
Fri Dec 27, 2019 12:37 am
OOH and I wonder if I could co-crystalize it with anything else exciting... anhydrous hydrogen peroxide, perhaps, or maybe even something with fluorine...
I think you'd end up with something very interesting. Even at a temperature of absolute zero, the remaining (inescapable) quantum-level vibrations of the atoms would probably be enough to make it undergo... what do the nuclear-weapons guys call it... oh, that's right, "spontaneous disassembly". And a rapid one at that.

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Re: More stuff to not work with...

Post by AnotherFairportfan » Fri Dec 27, 2019 1:01 am

Dave wrote:
Thu Dec 26, 2019 10:43 pm
AnotherFairportfan wrote:
Thu Dec 26, 2019 9:55 pm
I believe that it had a molecular structure consisting of twenty-six atoms of nitrogen.
The N26 explosive I recall was from another E.E. Smith story "Spacehounds of IPC", a standalone novel not part of the Lensman universe. It was developed by the natives of Titan... "crystalline, pentavalent nitrogen"... and it was quite violently explosive. Stevens was warned not to take it into atmosphere even on Ganymede as it would destabilize, explode, and destroy his ship.

I don't recall the formula of duodec ever being disclosed in the Lensman series itself, or there being any discussion of it needing cryogenic storage. Smith might well have had the same idea for both series, of course.
No, he didn't - but he divulged it, and it was printed in a concordance {The Universes of E E Smith} from Advent:Publishers, as i recall
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Re: More stuff to not work with...

Post by Dave » Fri Dec 27, 2019 1:17 am

AnotherFairportfan wrote:
Fri Dec 27, 2019 1:01 am
No, he didn't - but he divulged it, and it was printed in a concordance {The Universes of E E Smith} from Advent:Publishers, as i recall
You're right about the concordance... I happen to have a copy of it on my shelf here.

The entry for duodec describes it as 324 atoms of heptavalent nitrogen, arranged in 12 linked molecules of 27 atoms each. This sentence in the concordance doesn't cite a specific story/page/source for the information, so it's probably a "word of Smith, at a 'con" sort of thing.

This would make duodec slightly different than the pentavalent N26 explosive he used in Spacehounds of IPC.

I suppose this difference in basic physical chemistry clearly rules out any possibility that the Spacehounds universe was somehow the same as the Lensman (Triplanetary-era) universe. In fact, it does valence to the very notion of it.

(Grins, ducks, runs like hell to avoid the explosion of a shock-sensitive nitrogen compound... tossing a handful of Galactic Patrol credits in the general direction of the Pun Jar as he goes...)

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Re: More stuff to not work with...

Post by Atomic » Fri Dec 27, 2019 3:25 am

All righty then, try this one for size. I forget the Sci Fi story name, but basically the good guys (Earthlings) were launching orbital bombs at a planet in the 300 megaton range to cripple the economy. Devastating and enough to bury the factories, mines, etc, under a few hundred meters of dust and rubble when the ground penetrators went off. They did the job, and the bad guys economy collapsed in short order.

The amazing thing was, despite using fusion weapons, the radioactive mess was basically gone a month after the attack! Various neutral or victim of the bad guy parties viewed this with amazement - more so that the Earthlings promptly retreated to their home planet and left the bad guy empire to fully collapse, thus freeing the captive planets, etc.

Long after the fact, the explanation for the extremely short fallout was this: The weapons were being manufactured as they were being launched. A special blend of lithium and bromine isotopes (something like that) with very, very short half-lives degraded into a critical mass on the way down, then detonated when the impact stressed an x-ray generating crystal. No x-rays - no detonation as the critical mass (just barely) continued it's isotope degradation into more modest forms.

Something like that anyway. Uber damage at ground zero, fail safe, and zero fallout after a month to impede repopulation of that area. Heck of a weapon!

How would you like to have been on THAT development team, eh?
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Re: More stuff to not work with...

Post by Just Old Al » Fri Dec 27, 2019 2:42 pm

Atomic wrote:
Fri Dec 27, 2019 3:25 am
How would you like to have been on THAT development team, eh?
I've worked on crazier shit...been there done that had the bar napkins classified...
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Re: More stuff to not work with...

Post by Dave » Fri Dec 27, 2019 4:05 pm

Just Old Al wrote:
Fri Dec 27, 2019 2:42 pm
Atomic wrote:
Fri Dec 27, 2019 3:25 am
How would you like to have been on THAT development team, eh?
I've worked on crazier shit...been there done that had the bar napkins classified...
I'd personally prefer to work on the development of that sort of technology from a safe distance. As in, from orbit. Ideally, an orbit around an entirely different planet.

I see some practical and theoretical problems with the approach, though... I can't make the idea sync up terribly well with nuclear physics as I currently understand it.

The practical problem: close-in radiation hazard. The scheme depends on making large amounts (kilograms?) of isotopes with "very, very short half-lives"... and "very short half life" equates to "intensely radioactive". In order for these parent isotopes to decay into bomb-fodder they'd be emitting something... alpha or beta particles, often followed by gamma-ray photons... and probably a great deal of heat as a side effect. They'd be about as healthy to be around as an equivalent amount of corium during the early stages of the Chernobyl meltdown. Even figuring out how to enclose them in some sort of bomb casing would be an interesting challenge.

Then, there's the actual bomb detonation. "Fusion" and "critical mass" are terms that just don't fit together very well in my head. As far as I'm aware, fusion-capable isotopes don't have a critical mass... the fusion process has a critical temperature, up in the hundreds of millions of degrees. It takes an A-bomb to create such temperatures to "ignite" the fusion process in a thermonuclear weapon, and that means long-lived fallout. The energy in small amounts of X-rays is far too little to heat up any known materials to the point where they would begin to fuse.

Now, maybe there's something that could be done with unstable nuclear isomers of some sort... :?:

Of course, if we allow the same sort of authorial license to create new or variant physics that Doc Smith took full advantage of, then all things are possible (and frequently explosive). :D

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Re: More stuff to not work with...

Post by TazManiac » Fri Dec 27, 2019 6:36 pm

:ugeek: C’mon Dave. Yer learning me stuff but yer harsh’n my buzz, maaaan...

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Re: More stuff to not work with...

Post by AnotherFairportfan » Sat Dec 28, 2019 2:12 am

Dave wrote:
Fri Dec 27, 2019 4:05 pm
Of course, if we allow the same sort of authorial license to create new or variant physics that Doc Smith took full advantage of, then all things are possible (and frequently explosive). :D
Yeah. But in what we laughingly call "The Real World", he invented Dunkin' Doughnuts...
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Re: More stuff to not work with...

Post by TazManiac » Sat Dec 28, 2019 5:19 pm

AnotherFairportfan wrote:
Sat Dec 28, 2019 2:12 am
Dave wrote:
Fri Dec 27, 2019 4:05 pm
Of course, if we allow the same sort of authorial license to create new or variant physics that Doc Smith took full advantage of, then all things are possible (and frequently explosive). :D
Yeah. But in what we laughingly call "The Real World", he invented Dunkin' Doughnuts...
Can you 'splain that a bit?

[edit]- This? The effect of bleaching with oxides of nitrogen upon the baking quality and commercial value of wheat flour

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Re: More stuff to not work with...

Post by AnotherFairportfan » Sat Dec 28, 2019 8:18 pm

No - he was a food chemist primarily {as that dissertation would indicate} and he specialised in powders. He apparently had a major hand in developing the mixes Dunkin' used, and he worked out how to make powdered sugar stick to a doughnut.
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Re: More stuff to not work with...

Post by Dave » Sat Dec 28, 2019 10:26 pm

So, you're saying that he was in effect a thionite supplier? :shock:

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Re: More stuff to not work with...

Post by AnotherFairportfan » Sun Dec 29, 2019 1:05 am

Dave wrote:
Sat Dec 28, 2019 10:26 pm
So, you're saying that he was in effect a thionite supplier? :shock:
I've never seen a purple Dunkin Doughnut.

...and i'd rather see than be one...
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Re: More stuff to not work with...

Post by Bookworm » Tue Jan 14, 2020 10:20 pm

AnotherFairportfan wrote:
Sat Dec 28, 2019 8:18 pm
No - he was a food chemist primarily {as that dissertation would indicate} and he specialised in powders. He apparently had a major hand in developing the mixes Dunkin' used, and he worked out how to make powdered sugar stick to a doughnut.
I don't know if that's more fun or less than the Mathematician Tom Lehrer, who apparently invented the Jello Shot while drafted during Korea. (They weren't allowed to have alcohol on base, but they could have food that _contained_ alcohol. So they went off base, and made trays of gelatinized alcohol. )
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