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Dornier 335A
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Melting whistle mix
I have discovered something interesting about one particular whistle mix composition. Potassium chlorate and sodium benzoate in a 75 to 25 ratio by
weight has surprisingly high ignition temperature (approximately 400°C) and starts to melt much earlier, at around 310°C.
In this molten state, the whistle mix turns out to be a powerful primary explosive. It detonates violently when confined in just a few layers of
aluminium foil, turning the foil into fine powder. Small amounts detonated against thin aluminium plates showed that it is superior to both silver
acetylide double salt and nano-Armstrong's mixture. This is 4 mg detonated against a 0.11 mm thick aluminium plate (hole is 16 mm in diameter):
After that I detonated 30 mg of the molten mix on an aluminium can to compare it to the same amount of ETN.
Here are the results:
Whistle mix:
ETN:
As you can see, the liquid whistle mix displays extraordinary brisance. The solid powder mix doesn't behave like this at all, so it's obvious that the
homogeneity and lower activation energy of the liquid is the key here. I guess the molten mixture behaves almost like an organic chlorate. I'm
thinking about Blaster's old thread about ethyl perchlorate. He showed its extreme brisance, and it would certainly explain my results if the whistle mix is acting in a
similar fashion.
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papaya
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Very interesting, unfortunately there's no safe way to prepare such a mixture in more than few mg scale, or ? Anyway, must serve a good demonstration!
Nice channel btw!
[Edited on 2-3-2014 by papaya]
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Zyklon-A
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Have you seen this?
[Edited on 2-3-2014 by Zyklonb]
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Rosco Bodine
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Fulminating mixtures exist and evidently this is another one. There are obscure mentions of a few such mixtures in mostly the old literature. Here
is another one reported in a thread where some others are discussed.
http://www.sciencemadness.org/talk/viewthread.php?tid=13283&...
That is the only reference I ever saw to the mixture of potassium ferricyanide with ammonium nitrate being a fulminating mixture and I never tested it
by experiment.
But it would suggest that possibly the same could occur with ammonium perchlorate. There are likely a few of these type mixture that can DDT and it
is the ones that do it in small quantity that are most interesting.
[Edited on 3-3-2014 by Rosco Bodine]
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Bert
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All of the whistle mixes made with Chlorate are a bit too touchy for use in a modern factory setting- And if compacted, some are cap sensitive HE's.
The idea of MELTING those mixes makes my hair stand up. Interesting performance, wouldn't want to depend on it.
Rapopart’s Rules for critical commentary:
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Anatol Rapoport was a Russian-born American mathematical psychologist (1911-2007).
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Varmint
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Obvious next step is to allow it to cool and solidify, then attempt ignition (perhaps detonation?) with fuse or a tiny purpose-built squib.
DAS
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Bert
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KClO3: MP 356 C decomposes 400 C
Ba(ClO3)2: MP 414 C decomposes ?
NaClO3: MP 248 C decomposes 250 C (let's not try that one...)
Sodium benzoate: MP 300 C decomposes 450 C, auto ignition 500 C
Sodium salycilate: MP 200 C decomposes (?) C, auto ignition 337 C
Potassium Hydrogen Terephthalate: MP 295 C, auto ignition (?)
Potassium benzoate: MP ~123 C, auto ignition >950 C (Oooh, I think we have a candidate!)
Potassium salicylate: MP ? auto ignition ?
Copper benzoate: MP ? auto ignition ?
Gallic acid: MP 250 C auto ignition ?
Potassium 2, 4 dinitrophenolate: eh, let's not!
So, I'm going to dig out some Barium chlorate and Potassium benzoate... Just because.
[Edited on 3-3-2014 by Bert]
[Edited on 3-3-2014 by Bert]
Rapopart’s Rules for critical commentary:
1. Attempt to re-express your target’s position so clearly, vividly and fairly that your target says: “Thanks, I wish I’d thought of putting it
that way.”
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3. Mention anything you have learned from your target.
4. Only then are you permitted to say so much as a word of rebuttal or criticism.
Anatol Rapoport was a Russian-born American mathematical psychologist (1911-2007).
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Dornier 335A
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I have melted small amounts and let it solidify as small flakes. These burn really quickly and fly away like rockets. I haven't attempted to detonate
them but I could try tomorrow.
Rosco, ammonium nitrate and potassium ferricyanide is certainly not a fulminating mixture. Potassium chlorate and ferricyanide is a
good one but it lacks brisance. I have a video about it here.
Here is another video with some small scale whistle mix tests.
Bert, why barium chlorate instead of potassium chlorate? To get a higher ignition point?
Why not potassium dinitrophenolate and sodium chlorate?
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Praxichys
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What's with the term fulminating mixture?
The fulminate anion is -CNO, which this is clearly not. If anything, it's an archaic term for an "explosive mixture" or a "detonating mixture." You
wouldn't say sal ammoniac or oil of vitriol, so what's with fulminating? This isn't the seventeenth century.
Besides, it's confusing. In the thread Rosco referenced earlier, which contains patents from as early as 1901, the term "fulminate" is used 85 times
and exclusively for metal salts of -CNO. It has been a dead term for "explosive" for at least a hundred years.
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DubaiAmateurRocketry
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Nice!
Why are you grinding potassium chlorate and sodium benzoate ? They both are sparkling soluble in hot water.
KClO3.
57 g/100 mL (100 °C)
Sodium benzoate
62.9 g/100ml (rt)
You can try adding them to boiling water until it stops dissolving more. Then chill the solution. You should end up having them mixed to a new level
than nano. Then melt it and ignite, and tell me what happens! It should be a good primary hehe. You can publish some work on your nano flash powder.
Dornier's flash powder etc is on another level.
[Edited on 3-3-2014 by DubaiAmateurRocketry]
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Dornier 335A
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That would not work very well for two reasons. First, sodium benzoate is way to soluble to precipitate fully when the solution is cooled. Secondly, I
don't think they would mix at all. Wouldn't the two salts just crystallize into large separate crystals when the solution is cooled down? A better
approach is to pour the warm solution into cold ethanol.
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DubaiAmateurRocketry
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Ah yes, potassium chlorate might precepitate out first as the problem, true. Ethanol idea would be good, acetone probably too.
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Rosco Bodine
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What is with the term is the correct use of language.
| Quote: |
The fulminate anion is -CNO, which this is clearly not. If anything, it's an archaic term for an "explosive mixture" or a "detonating mixture." You
wouldn't say sal ammoniac or oil of vitriol, so what's with fulminating? This isn't the seventeenth century.
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No it is not an archaic term for just any explosive mixture, but a particular type of behavior about an explosive mixture
which progresses rapidly from burning to detonation.
| Quote: |
Besides, it's confusing. In the thread Rosco referenced earlier, which contains patents from as early as 1901, the term "fulminate" is used 85 times
and exclusively for metal salts of -CNO. It has been a dead term for "explosive" for at least a hundred years. |
Knowledge can be confusing, and can even cause a headache. You have my sympathy.
Fulminating never was used just exclsuively as a term for "explosive" but is a more general term that could even apply to a strident tirade of
criticism as a verbal communication could be called "fulminating" when the point made severely as a deserved criticism lands home with a "kaboom" of
understanding. The root word I think is latin fulmen or fulminis meaning generally thunder, and the word origin is lost in antiquity.
http://www.latin-dictionary.net/definition/21133/fulmen-fulm...
I did not use the term "fulminate" as applies to the isomer of cyanate described by Liebig, but I used the term "fulminating mixture" two words as a
phrase neither of which words is fulminate. There are other correct usage applications for the word fulminating to decribe the explosive nature of
other explosive compounds and mixtures than applies exclusively to the salt of fulminic acid. Fulminating gold is an example, as is fulminating
silver, neither of which are salts of fulminic acid. For example fulminating silver a distinctly different compound from silver fulminate. Archaic
perhaps, but still correct usage so far as I know. Consult your philosophers' stone regarding this matter and get back to me 
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Rosco Bodine
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Quote: Originally posted by Dornier 335A  |
Rosco, ammonium nitrate and potassium ferricyanide is certainly not a fulminating mixture. Potassium chlorate and ferricyanide is a
good one but it lacks brisance. I have a video about it here. |
I said I haven't tested the mixture reported in the 1891 text.
Have you?
I already knew about the mixture you show in your video, actually knew about it 50 years ago but never experimented with it extensively. There are
several different compounds and/or mixture compositions that will DDT to a low order detonation lacking brisance when unconfined but above a certain
quantity and/or with confinement become brisant when having made the transition to high order detonation. The quantities and conditions vary widely
for what is required to enable that transition.
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Bert
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Anyone seen numbers on (anhydrous) low melting point/eutectic mixtures of Sodium and/or Potassium chlorate and other oxidizers? Ones having MP's
substantially below the decomposition temperatures of the chlorate(s)?
Enquiring minds want to know!
[Edited on 4-3-2014 by Bert]
Rapopart’s Rules for critical commentary:
1. Attempt to re-express your target’s position so clearly, vividly and fairly that your target says: “Thanks, I wish I’d thought of putting it
that way.”
2. List any points of agreement (especially if they are not matters of general or widespread agreement).
3. Mention anything you have learned from your target.
4. Only then are you permitted to say so much as a word of rebuttal or criticism.
Anatol Rapoport was a Russian-born American mathematical psychologist (1911-2007).
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Dornier 335A
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| Quote: Originally posted by Rosco Bodine |
I said I haven't tested the mixture reported in the 1891 text.
Have you?
I already knew about the mixture you show in your video, actually knew about it 50 years ago but never experimented with it extensively. There are
several different compounds and/or mixture compositions that will DDT to a low order detonation lacking brisance when unconfined but above a certain
quantity and/or with confinement become brisant when having made the transition to high order detonation. The quantities and conditions vary widely
for what is required to enable that transition. |
I tested that mixture a while ago. I couldn't get it go ignite, only melt and decompose. With some added magnesium powder, I got a delayed flash
powder. After ignition, it hissed slightly and went poof after a fraction of a second.
K3Fe(CN)6 / KClO3 is one of the more widely known detonating mixtures. When the powders are as homogeneously mixed as
what I showed in my video, 10 mg is enough to self-confine. But it still won't dent an aluminium plate more than slightly even when confined. Yellow
powder behaves similarly for me. I suppose the amounts I have tested could be too small, but at least for other primaries, self-confinement means that
detonation is very close.
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Rosco Bodine
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Mixtures are not as predictable as compounds, but there can be some things done as experiments. For example see what effect is had by using dextrine
to binder the composition into a pellet, working upwards to even a hundred milligrams, or more. Some materials which absolutely will DDT eventually
at a certain weight and geometry and confinement combination, have a minimum amount requirement for DDT that is inconveniently large, which prevents
use of such materials due to lack of economy and for the inconvenient larger scale of the device that would use such materials. A possibly useful
test is to granulate the powder mixture dampened with a binder and press the dried granules and see what its response to initiation by lead azide. If
it has an ability to detonate that should reveal the ability. But it is expected to be limited by minimums for critical diameter and critical mass
just like applies to a compound. WRT the ferricyanide and ammonium nitrate, since no conditions or examples are given, it is difficult to rule out or
dismiss the information as an error based on a spot test where the small quantity may not develop the described detonation, but it could well be an
error in the literature. It wouldn't be the first or last example of a mistake if that turns out to be the case.
[Edited on 4-3-2014 by Rosco Bodine]
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papaya
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Now try with benzoic acid instead of benzoate - you'll be surprized how difficult is it to ignite (I think due to sublimation) even confined (some
20mg) didn't do anything, however a hammer blow gives a sharp crack.
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PHILOU Zrealone
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Maybe when melting the mix of KClO3/NaO2C-C6H5 turns into a more sensitive mix of KClO3/NaO2C-C6H5/NaClO3/KO2C-C6H5 with a lower Ea due to NaClO3. In
the molten state, the average number of molecules with a sufficient energy to ensure propagation of the reaction is much higher and you spare energy
from the fusion enthalpy...so the propagation of the burning flame front/deflagration-detonation wave is much faster.
Should be good to test KClO3/KO2C-C6H5 and NaClO3/NaO2C-C6H5 and NaClO3/KO2C-C6H5 as comparison
A real sand crushing test, lead block test and VOD determination should be done.
Sand crushing test can also be used to determine the detonation ability (critical mass).
Last but not least maybe try some 3,5-dinitrobenzoate and dinitrophenates. They already display VOD above 6000 m/s so the whistle mix made from those
would be more on the primary side.
PH Z (PHILOU Zrealone)
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Dornier 335A
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Update:
I detonated 0.10 g of the liquid mixture on a 0.5 mm thick steel plate with great results!
I will try with NaClO3 soon. Is there any good way to prepare potassium benzoate? It's solubility is very similar to that of sodium
benzoate which makes it a bit problematic.
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Zyklon-A
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| Quote: | One very common way to make potassium benzoate is by oxidizing toluene.[4]
Another way to synthesize potassium benzoate in the lab setting is by reacting methyl benzoate with potassium thioacetate.[
[4] |
You probably already saw this, but it may help.
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DubaiAmateurRocketry
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That is some impressive result! Does it behave similar if you ignite it without melting?
It would make a good primary, but the thing that this need melting is a problem. However might be overcomed on a re-design of a special detonator for
this.
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PHILOU Zrealone
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| Quote: Originally posted by Dornier 335A | Update:
I will try with NaClO3 soon. Is there any good way to prepare potassium benzoate? It's solubility is very similar to that of sodium
benzoate which makes it a bit problematic. |
Very common organic chemistry ;-)
Take sodium benzoate, acidify it with concentrated mineral acid...benzoic acid will be relatively unsoluble in the water and
cristallize/precipitate/flocculates.
Filter it off and allow it to react with K2CO3, KHCO3 or KOH.
PH Z (PHILOU Zrealone)
"Physic is all what never works; Chemistry is all what stinks and explodes!"-"Life that deadly disease, sexually transmitted."(W.Allen)
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PHILOU Zrealone
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| Quote: Originally posted by Dornier 335A | Update:
I will try with NaClO3 soon. Is there any good way to prepare potassium benzoate? It's solubility is very similar to that of sodium
benzoate which makes it a bit problematic. |
Very common organic chemistry ;-)
Take sodium benzoate, acidify it with concentrated mineral acid...benzoic acid will be relatively unsoluble in the water and
cristallize/precipitate/flocculates.
Filter it off and allow it to react with K2CO3, KHCO3 or KOH.
PH Z (PHILOU Zrealone)
"Physic is all what never works; Chemistry is all what stinks and explodes!"-"Life that deadly disease, sexually transmitted."(W.Allen)
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Dornier 335A
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I came to the same conclusion shortly after posting but thank you anyway PHILOU Zrealone.
Update 2:
The same person who made the 30 mg ETN test performed another, this time identical to my 0.5 mm steel plate test. The results were very similar: 5.5
mm deep dent (whistle mix) vs. 6 mm for ETN, and the maximum angles of the dents were 135° and 130° respectively.
Something of more importance is that the melted, solidified and then crushed mixture can go high order with very little confinement. 10 mg ignited by
a tiny amount of KClO3 and K3[Fe(CN)6] in just a few layers of aluminium foil exploded with a sharp bang. This might
actually have some potential as primary if the sensitivity isn't exceedingly high.
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