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Author: Subject: Heavy-Metal Chlorite & Sulfur
Rhodanide
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[*] posted on 20-11-2017 at 06:00
Heavy-Metal Chlorite & Sulfur


Yesterday, I combined 1 part Sulfur powder to 2 parts Silver Chlorite powder.
I then "diapered" the mixture until it was homogeneous. Tapping it lightly with a stick caused it to deflagrate. I did it this way because the last time I did it, I added a much larger portion of each to an evaporating dish, and stirred it with a glass rod. It went up with a violent "whoosh" of flame, and covered my hand in Silver vapor. As much as it was painful, it was frightening and quite surprising. Have any of you had experience with this mixture? Are there any practical uses for it?
Thanks.
-T/R

[Edited on 20-11-2017 by Tetra]




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[*] posted on 21-11-2017 at 07:30


It's *any* chlorite and sulphur...not just heavy metals.

Years ago, I got hold of a small amount (<100g) of NaClO2 and mixed that with sulphur with a mortar and pestle.
Moments later there was a whooooosh of orange flame and I instinctively threw the mortar in the air. Almost burned the sh*t out of my hand, and scared the very same out of my brother who was sitting just a few feet way NOT expecting a fireball in his front room.

Yes, I know it was dumb not to have tested small amounts first.

Lesson to be learned here is that chlorites and sulphur are not good bed fellows.




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[*] posted on 22-11-2017 at 00:01


Sodium chlorite indeed is very sensitive with sulphur (and also with red phosphorus and powdered sugar), but heavy metal chlorites are even more sensitive. I have done tests with Pb(ClO2)2 and AgClO2 and these are even more sensitive than NaClO2. Mixing reductors with these salts is nearly impossible without having spontaneous ignition of the mix. Some metal chlorites are said to be explosive, even on their own, but I have not experienced such a thing personally.

Sodium chlorite is interesting stuff and can be used for many interesting experiments, but it is something which must be handled with care.




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[*] posted on 22-11-2017 at 13:32


A green little chemist,
on a green little day,
mixed some green little chemicals,
in a green little way.
Now the green little grasses tenderly wave
oe'r the green little chemist's
green little grave.

A mortar and pestle is not a sensible way to mix explosives.

Incidentally, in my day, we used chlorates.
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[*] posted on 27-11-2017 at 10:07


Quote: Originally posted by unionised  
A green little chemist,
on a green little day,
mixed some green little chemicals,
in a green little way.
Now the green little grasses tenderly wave
oe'r the green little chemist's
green little grave.


That's cute.




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[*] posted on 4-12-2017 at 02:39


Into the case of Na or K chlorate/S/C type of black powder...

I had success into stabilizing the mix by adding a few % of ultrafine unsoluble carbonate (Ba, Sr, Ca...yeah it induces some color... should have tried Li2CO3 for very beautiful red flame color)... CuCO3 is not for long term storage because sooner or later some Cu(2+) is formed and it is not very stable towards chlorates.

Some unsoluble hydroxydes or oxydes may be used aswel for the stabilization purpose...
The idea is to block any H2SO4 formation by catching any formed SO2, SO3 or residual acidity onto the surface of the S... if some ClO2 or Cl2O3 or Cl2O5 is formed it can also be absorbed/neutralized by the basic media (carbonate/hydroxyde/ or both)

Chlorites are a bit like chlorates so this method may be valuable to reduce sensitivity and allow for a "safer" handling... but always keep in mind that hypochlorites / chlorites and chlorates are very dangerous stuffs and very potent oxydizers despite some stabilization... a spontaneous ignition is always possible due to a local overheating, uncomplete homogeneisation of the stabilizator... better never store for long nor in larger quantity than a few grams... also never in a hard recipient or hermetically sealed one... always imagine the worst case scenario of a suddent blast/fire.




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[*] posted on 4-12-2017 at 09:24


Mixes with chlorites are more sensitive than mixes with chlorates. Mixes with chlorates already are quite sensitive, the same mixes with chlorites are so sensitive that they cannot be kept around at all safely.

Hypochlorite-based mixes are even more sensitive, e.g. if you take solid Ca(ClO)2 and mix this with a flammable solid or liquid, then usually the mix ignites spontaneously after a while, due to slow reaction and self-heating of the mix.




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[*] posted on 4-12-2017 at 17:26


Quote: Originally posted by woelen  
Mixes with chlorites are more sensitive than mixes with chlorates. Mixes with chlorates already are quite sensitive, the same mixes with chlorites are so sensitive that they cannot be kept around at all safely.

Hypochlorite-based mixes are even more sensitive, e.g. if you take solid Ca(ClO)2 and mix this with a flammable solid or liquid, then usually the mix ignites spontaneously after a while, due to slow reaction and self-heating of the mix.

True...and I know HOCl > HOClO > HOClO2 regarding reactivity/oxydizing power... that was not my point... but we agree that hypochlorites/chlorites/chlorates are fierce molecules when it comes to mixing with other stuffs... and extreme caution must be taken for handling... storage is unadvisable especially for hypochlorite/chlorite... some of my chlorate based BP are stable for decades now...and this thanks to CaCO3 (pulverized blackboard chalk) or to Magnesia (MgCO3.Mg(OH)2) (for accrobatic gymnastic... I did practice 7 years)

Stability is enhanced by the basic media (thus a higher pH).
==> Hypochlorites are relatively stable into basic media but unstable into acidic media.
==> Chlorites are relatively stable into neutral media but unstable into acidic media and quite stable into basic media.
==> Chlorates are stable into neutral media, very stable into basic media and unstable into acidic media...

Known facts (self experienced)
1) NaClO3/C or KClO3/C is quite hard to ignite without S...
2) same occurs with NaClO3/Al or KClO3/Al...
3) or NaClO3/Wax... NaClO3/Oils.
4) or KClO3/SiC (yes carborundum fine mesh... I did try it in april this year) very very hard to ignite.
When traces of S are added ignition is much easier in all the above cases...
So the triggering of sensitivity comes from S and its oxydation products...

If you take a closer look at the reactions of hypochlorite, chlorite or chlorate with the reducers that induces troubles...
There is a common patern...
==> all are acid generators/ acid anhydrides generators...

What do I mean?
==> Hydrocarbons lead to oxoacids (carboxylic acids) prior to carbonic acid but this requires a quite high temperature already about the same as the liberation of the oxygen from its oxo-salt...
==> S leads to SO2 and SO3 what are acid anhydrides...S oxydizes spontaneously and superficially into the air
==> P leads to P2O3 and P2O5... just like S, P does it but more readily...depending onto the allotrope P may inflame spontaneously into the air... what S doesn't do.
==> As/Sb/Se... to As2O3, As2O5, Sb2O3, Sb2O5, SeO2

Such acid anhydrides may set hypochlorite anhydride (Cl2O), chlorite anhydride (Cl2O3) or chlorate anhydride (Cl2O5) or derived ClO2 free... by trans-anhydridi-fication reaction.
Salt 1 + Anhydride 2 <==> Anhydride 1 + salt 2

It is obvious that unstability occurs with the non-metal elements what are acid generators via oxydation to acid anhydride...
==>Most metal elements turns into oxydes that are basic and don't help the decomposition reaction the way acid oxydes do

Predictions:
1) Probably that Br2 and I2 will aswel cause troubles upon time... Br2 by forming oxydes of Br and I2 by forming I2O3, I2O5 and I2O7...
2) Probably that B will cause more unstability than Al... because Al is essentially a basic oxyde generator while B is a generator of boric acid anhydride (B2O3)

The special case of NH4(+)
NH4(+) is the conjugated acid of a mild base as such it is a weak acid hence it favourises the sensitization/decomposition of chlorate/chlorite/hypochlorite mixes...
But ... this is mostly true if under the form of a salt
==> NH3 will not cause such troubles nor NH4OH what also contains NH4(+) but associated with the very strong base OH(-).
==> hypochlorite will maybe decompose NH4OH into N2 bubbles but the reaction will be relatively smooth and will have nothing to do with a fire/blast/deflagration/detonation.

[Edited on 5-12-2017 by PHILOU Zrealone]




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[*] posted on 5-12-2017 at 02:20


Interesting summary and I agree with most of it. Especially your observation of acid-forming elements is interesting in this context. I indeed can imagine that this is the reason why P, S and probably Se and sulfide-containing compounds are so sensitive in combination with these compounds.

Ammonium ions and free ammonia are a special class on its own.

In aqueous solutions, ammonium ions and chlorate ions can coexist without problem. Ammonium ions and chlorite ions also can coexist without problem. Hypochlorites and ammonium ion are not a good combination. This may lead to formation of the very dangerous NCl3.

In the solid state, only ammonium ions and chlorate ions can coexist, but the resulting solid is very dangerous and little provocation (e.g. friction, or slight heating) may set it off. Ammonium chlorite and ammonium hypochlorite cannot exist.

With ammonia, both chlorite and chlorate can coexist. I tested this myself. With hypochlorite you get nitrogen, but also NH2Cl (very pungent smell). Under the right conditions, you also can get hydrazine. Solid hypochlorites (and also hypochlorite-generating compounds like TCCA or Na-DCCA) react extremely violently with ammonia. Just for fun, take 10% or so ammonia and add a pea-sized (not larger!!) chunk of TCCA to it. The TCCA reacts with a loud crackling noise. With 25% ammonia it explodes on contact with the liquid.




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[*] posted on 6-12-2017 at 12:57


Quote:
4) or KClO3/SiC (yes carborundum fine mesh... I did try it in april this year) very very hard to ignite.
When traces of S are added ignition is much easier in all the above cases...
So the triggering of sensitivity comes from S and its oxydation products...


When finally ignited, how energetic was the Silicon carbide/Potassium chlorate/trace ammount of Sulfur mix?! How fine a mesh SiC? I have various SiC abrasive powders for rock polishing, valve grinding & etc., where to begin?


I had never tried adding Sulfur, and did not think anything short of chlorine triflouride was going to get SiC burning... So I learned something new today.


[Edited on 6-12-2017 by Bert]




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[*] posted on 7-12-2017 at 04:47


Quote: Originally posted by Bert  
Quote:
4) or KClO3/SiC (yes carborundum fine mesh... I did try it in april this year) very very hard to ignite.
When traces of S are added ignition is much easier in all the above cases...
So the triggering of sensitivity comes from S and its oxydation products...


When finally ignited, how energetic was the Silicon carbide/Potassium chlorate/trace ammount of Sulfur mix?! How fine a mesh SiC? I have various SiC abrasive powders for rock polishing, valve grinding & etc., where to begin?


I had never tried adding Sulfur, and did not think anything short of chlorine triflouride was going to get SiC burning... So I learned something new today.


[Edited on 6-12-2017 by Bert]

The burning is very white, relatively slow not like KClO3/C/S/CaCO3 mix... (burning last 4-5 times longer) probably because of the molten SiO2... CO2 escapes the system while SiO2 remains there coating the rest of the réactants into molten pyrex glass...

The SiC was greyisch 400 mesh (I had other lower mesh... but I knew it would be too coarse for a good burning.
I did use 4,85555 gr KClO3/1 gr SiC assuming a perfect OB and 50/50 molar mix into Si/C.
KClO3/C would require 6,80215 gr /1 gr
KClO3/Si would require 2,90895 gr /1 gr

Then 10% bw S chozen arbitrary also added afterwards... because ignition didn't happened at first trial with cooking blow torch.

Into my mineral collection I also have pure crystaline Si... light like charcoal... it must be brittle and much easier to mesh... in a few weeks (when all my stuffs are unpacked into my new living place) I could do a test... pure KClO3/Si vs KClO3/SiC and sulfurated variant.

Edit:
So SiC may be used as a energy rich fuel for chlorate pyrocomposition... but:
-Hard to ignite without ignition help like S.
-May require confinement or large quantities to help ignition
-Require a fine mesh... the higher the mesh the best.
SiC being hard like diamond is not easy to get as fine mesh... finer mesh cost more for that reason.

[Edited on 7-12-2017 by PHILOU Zrealone]




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[*] posted on 7-12-2017 at 11:24


Thanks-

FYI, we have used technical grade (85%) Si in hot igniters, Potassium nitrate was sufficient oxidizer with a few % of fine black powder included when bound with nitrocellulose lacquer and ignited by some medium sized black powder grains pressed into the surface before drying.

A thermite of Lead tetroxide and the same amorphous Silicon was briefly tested, this worked fine with a black powder first fire also- but was too sensitive to impact (and toxic) for our comfort. If you need a shock to flame transducer element for use with shock tube or similar, you might try a pellet of this "red thermite".

Much the same effect as the Si/KNO3 prime was achieved from a water bound prime mixture of Potassium perchlorate, red gum, diatomaceous earth and a bit of fine Aluminum, Vanadium pentoxide, a few % each of charcoal and wood flour to produce a rough, fuzzy surface, with gum Arabic for binding and guar or xanthan gum to control consistency while wet. I would have to dig for the exact %.

That prime may be used with any star mixture that can stand a water bound prime, without producing any sensitive or hygroscopic double replacement products with other oxidizers. Chlorate, nitrate, Potassium or ammonium perchlorate, all good as long as there is no uncoated magnesium or high Mg % magnalium present to react with oxidizers when damped.

The water bound mixture with diatomaceous earth was cheaper and did not involve solvent fumes, so we went with that-

All these compositions function by producing drops of a sticky, molten glassy slag stuck to the surface of a star. These hot slag droplets stay where they are needed, protecting hot spots under them until a fast moving star slows down enough not to be blown out.





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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.

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[*] posted on 8-12-2017 at 14:19


Quote: Originally posted by Bert  
Thanks-

FYI, we have used technical grade (85%) Si in hot igniters, Potassium nitrate was sufficient oxidizer with a few % of fine black powder included when bound with nitrocellulose lacquer and ignited by some medium sized black powder grains pressed into the surface before drying.

A thermite of Lead tetroxide and the same amorphous Silicon was briefly tested, this worked fine with a black powder first fire also- but was too sensitive to impact (and toxic) for our comfort. If you need a shock to flame transducer element for use with shock tube or similar, you might try a pellet of this "red thermite".

Much the same effect as the Si/KNO3 prime was achieved from a water bound prime mixture of Potassium perchlorate, red gum, diatomaceous earth and a bit of fine Aluminum, Vanadium pentoxide, a few % each of charcoal and wood flour to produce a rough, fuzzy surface, with gum Arabic for binding and guar or xanthan gum to control consistency while wet. I would have to dig for the exact %.

That prime may be used with any star mixture that can stand a water bound prime, without producing any sensitive or hygroscopic double replacement products with other oxidizers. Chlorate, nitrate, Potassium or ammonium perchlorate, all good as long as there is no uncoated magnesium or high Mg % magnalium present to react with oxidizers when damped.

The water bound mixture with diatomaceous earth was cheaper and did not involve solvent fumes, so we went with that-

All these compositions function by producing drops of a sticky, molten glassy slag stuck to the surface of a star. These hot slag droplets stay where they are needed, protecting hot spots under them until a fast moving star slows down enough not to be blown out.


Thank you Bert very valuable expériences, informations and compositions :):D




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