Replacement for calcium plumbate and formaldehyde in a reaction

[Inserttext12]

Hello everyone, I've been looking through the first edition of The Chemical Formulary, and I ran across this very interesting self ingniting "match" and I thought it would be fun to recreate but the formula contains Calcium Plumbate, which isn't possible to purchase and isn't pheasibly synthesized. So I'm wondering if there's a more common chemical I can replace it with, as I understand it, it's purpose in the formula is as retardant to slow down the reaction. While I can obtain formaldehyde easily, I'd rather not use it in a smoke generating compound as I don't know if it's toxic when burned.

 

Formula:

-Potassium Chlorate 35

- Calcium Plumbate 3.7

- Sulfur 0.9

- Benzoyl Peroxide 3.7

- Powdered Glass 14.2

- Hexamethylene Tetramine 42.5

- Glue Solution sufficent to bind

- Formaldehyde 0.5

 

Any help would be greatly appreciated

[tti82phys]

It seems to me that calcium plumbate is just a "mixed salt" of calcium oxide and lead dioxide, Ca₂PbO₄ = 2CaO^.PbO₂. In that case, the lead dioxide in it will also act as an oxidizer because it releases O₂ when heated. I've seen it mentioned many times that lead dioxide has uses in match chemistry. The calcium oxide part seems to be just to keep the mixture alkaline to prevent accidental ignition for no obvious reason (that can happen when sulfur and chlorates are mixed).

 

Maybe just add an equivalent amount of calcium carbonate in the mix to replace the calcium plumbate? The amount of PbO₂ in that "recipe" doesn't look large enough to be necessary (for having enough of a source of oxygen in the mix).

[cmjlab]

Self igniting as in spontaneously? Or like a strike anywhere? I know for a fact that you can make a "strike anywhere" style mix with far less exotic chemicals (I had a safety incident where I burned my hand making ematch - ignited by a wire rubbing on the side of the container where there was some dried composition). That particular mix only had 2 chemicals, and the wire filled the role of "crushed glass" to ignite the substance with very little friction.

 

*Edit* my saving grace was that I only had 10 grams of working material, and nothing else pyrotechnic out for the fire to spread. Still led to 2d degree burns, dead fingernails, and a whole lot of pain!

 

Was also completely my fault for getting complacent and removing my gloves because they were "in the way", otherwise all of the injuries could have been avoided in the first place.

Edited December 12, 2022 by cmjlab

[tti82phys]

Just had to add that the formaldehyde in the mixture is almost certainly meant to form a polymer with the hexamethylene tetramine, with benzoyl peroxide acting as a radical initiator. This causes the mixture to solidify to some rigid shape. So the properties of formaldehyde when combusted aren't relevant when considering the reaction products formed from the final matchheads when ignited.

[Inserttext12]

It seems to me that calcium plumbate is just a "mixed salt" of calcium oxide and lead dioxide, Ca₂PbO₄ = 2CaO^.PbO₂. In that case, the lead dioxide in it will also act as an oxidizer because it releases O₂ when heated. I've seen it mentioned many times that lead dioxide has uses in match chemistry. The calcium oxide part seems to be just to keep the mixture alkaline to prevent accidental ignition for no obvious reason (that can happen when sulfur and chlorates are mixed).

 

Maybe just add an equivalent amount of calcium carbonate in the mix to replace the calcium plumbate? The amount of PbO₂ in that "recipe" doesn't look large enough to be necessary (for having enough of a source of oxygen in the mix).

The one synthesis I found of it says the two are baked at is memory serves in a 700c furnace and exposed to a mixture of oxygen and nitrogen gas.

[Inserttext12]

Self igniting as in spontaneously? Or like a strike anywhere? I know for a fact that you can make a "strike anywhere" style mix with far less exotic chemicals (I had a safety incident where I burned my hand making ematch - ignited by a wire rubbing on the side of the container where there was some dried composition). That particular mix only had 2 chemicals, and the wire filled the role of "crushed glass" to ignite the substance with very little friction.

 

*Edit* my saving grace was that I only had 10 grams of working material, and nothing else pyrotechnic out for the fire to spread. Still led to 2d degree burns, dead fingernails, and a whole lot of pain!

 

Was also completely my fault for getting complacent and removing my gloves because they were "in the way", otherwise all of the injuries could have been avoided in the first place.

Like strick anywhere. Are there any good strike anywhere mixtures you know of that burn fairly slowly (I'm liiking for more smoke and smolder rather than fire and bang).

Edited December 12, 2022 by Inserttext12

[Inserttext12]

Just had to add that the formaldehyde in the mixture is almost certainly meant to form a polymer with the hexamethylene tetramine, with benzoyl peroxide acting as a radical initiator. This causes the mixture to solidify to some rigid shape. So the properties of formaldehyde when combusted aren't relevant when considering the reaction products formed from the final matchheads when ignited.

Thank you very much for that information, I was trying to figure out what the formaldehyde was used for. Do you think another chemical would form a polymer as well? Or is Formaldehyde it? I can safetly work with it, I have a fume hood and all that jazz, I'd just rather use an alternative if there is one.

[Richtee]

Ummm.. sulfur/chlorates should be avoided. The CAN go spontaneously enough... proper balancing and acid free sulfur will help.

 

​Were it I, I’d look up “glusatz” and an Ohio Blue Tip match head.

 

​( in reality..I’d just carry a lighter. I trust visco. )

Edited December 12, 2022 by Richtee

[Inserttext12]

Ummm.. sulfur/chlorates should be avoided. The CAN go spontaneously enough... proper balancing and acid free sulfur will help.

 

​Were it I, I’d look up “glusatz” and an Ohio Blue Tip match head.

 

​( in reality..I’d just carry a lighter. I trust visco. )

Glusatz is unfortunately to fast for what I need this for. I'm trying to recreate a form of incense matches I found.

[cmjlab]

For match compositions, Alexander Hardt's "Pyrotechnics" has a chapter, but the "strike anywhere" comps are energetic by nature. Unfortunately, that's the extent of my knowledge, good luck!

 

Charles

[Inserttext12]

For match compositions, Alexander Hardt's "Pyrotechnics" has a chapter, but the "strike anywhere" comps are energetic by nature. Unfortunately, that's the extent of my knowledge, good luck!

 

Charles

Thank you for that, my bigger issue is, what's the composition the stick, as the few companies that produce incense matches are pretty secretive with their formulas (all I know is that it's paper fiber, charcoal, scents, and a binder, plus most likely something to slow down the burning). I figured it probably would be easier to find a paste that I can put scents into rather than have a composite match but that's just what my odd brain says.

[Inserttext12]

Just had to add that the formaldehyde in the mixture is almost certainly meant to form a polymer with the hexamethylene tetramine, with benzoyl peroxide acting as a radical initiator. This causes the mixture to solidify to some rigid shape. So the properties of formaldehyde when combusted aren't relevant when considering the reaction products formed from the final matchheads when ignited.

Could you theoretically replace that polymer with a calcium hydroxide and sodium silicate polymer?

[tti82phys]

Could you theoretically replace that polymer with a calcium hydroxide and sodium silicate polymer?

Unfortunately I'm not able to answer that, polymer chemistry isn't really my specialty. However, I don't believe there is any practical reason to replace the formaldehyde with anything else.

[Inserttext12]

Unfortunately I'm not able to answer that, polymer chemistry isn't really my specialty. However, I don't believe there is any practical reason to replace the formaldehyde with anything else.

Thank you for the reply, at this point the benzoyl peroxide is the thing holding me back, not the formaldehyde anymore. Ironically formaldehyde opens up all the doors in this reaction, as its also used in the synthesis of Hexamethylene Tetramine (though that one I can just buy)