KClO3 to KClO4 Substitution

[BlueComet24]

I found a composition that interests me because it claims to be a blue fire comp without any kind of copper salt. The composition is as follows:

15 KNO3

28 KClO3

14 K2SO4

14 Sulfur

This composition seems quite unsafe as it's listed, due to the presence of a chlorate and sulfur. I was wondering if the chlorate could be substituted with perchlorate? I've heard that blue flames require cooler temperatures, so I'm thinking the higher-temperature burning of the KClO4 might ruin the blue flame, turning it white.

Another of my concerns is any kind of incompatibility or other hazard with potassium sulfate, as this is a chemical that I'm unfamiliar with.

Lastly, I have my doubts that the blue color produced would be very rich or vibrant, but rather more like a sulfur flame.

I found this comp on pyrodata: http://pyrodata.com/compositions/Blue-fire-composition-6

[Mumbles]

Firstly, I have serious doubts if that formula will burn blue. If you replaced the potassium sulfate with copper sulfate, there'd be a possibility.

 

Secondly, I'm glad you recognize the issue of chlorate and sulfur in the same formula. Perchlorate and sulfur is better, though still somewhat sensitive. If you try it, be careful and work in small doses.

[schroedinger]

No copper sulfate is nothing you can use to substitute.

 

First copper sulfate gives a pale green flame, not blue (even in presence of Cl).

 

Also there are more reasons why copper sulfate is ot used commercially first it is expensive 2nd it use only available as penta hydrate the anhydrate absorbs water from air and third it is a salt made of a strong acid and weak base, what results in a acidic salt.

 

The incompability of chlorate and sulfur relies comes from left over acid traces in the sulfur, a problem that is solved today. But this doesn't mean that it would be good idea to use sulfur and chlorate together. It still is a very sensitive comp if mixed.

But in combination with copper sulfate it will turn into a deathmix.

[Fulmen]

Source:

rec.pyrotechnics. Composition from "Magic With Chemistry"[7], chapter "colored fires"

 

Doesn't sound like a credible source, does it. Personally I wouldn't even bother, if you could get a decent blue without copper I think it would be common knowledge by now.

[Arthur]

The economical method for blues uses copper. Other elements have possibilities to produce blues, BUT at silly prices. Even so the chemistry has to be well controlled or the blues can go greenish.

[lloyd]

Schroedinger and his cat posted:

"Also there are more reasons why copper sulfate is ot used commercially first it is expensive...."

---------------

Y'know, I agree with everything you posted about copper sulfate, except for that bit. I can buy a 50lb sack of it (of good purity) at any local "feed'n'seed" for under $75. That's pretty INexpensive, as pyro chemicals go. (It is used in the ag community as an algae and weed killer for ponds, and for certain water conditioning systems... called "bluestone" in that vernacular.)

 

There are some formulae in which it's safe to use. The trick is knowing which ones. But since it doesn't contribute the copper ion as easily as would other more-common pyro-coppers, it's really not worth the price, at any price.

 

LLoyd

[Mumbles]

I wouldn't be worried of it's acidity either. A 5% solution has a pH around 4.5, which isn't much to write home about. Less extreme than a 5% solution of sodium bicarbonate or oxalate, which people use without a thought. The real issue lies in it's oxidation potential. In the presence of most metals we work with, and some tool materials, the copper sulfate will corrode the metal.

[BlueComet24]

I find it a bit surprising that CuSO4 can be purchased for use in ponds, considering that it's "very toxic to aquatic organisms", according to its MSDS, and "may cause long-term adverse effects in the aquatic environment". It seems that a target pesticide (algaecide or herbicide) that can readily biodegrade into harmless chemicals would be superior.

Well, I'm not surprised that this comp probably wouldn't produce a decent blue flame, but still a bit disappointed. Based on its source and the lack of a binder and information regarding stars, I'm thinking that it's not a star comp, but rather something like a flare or Bengal fire comp. I believe that it's a fairly old composition because of the combination of chlorate and sulfur, and that its source has another blue fire comp that calls for mercury (I) chloride.

It sounds like copper salts are the way to go. My goal here is to eventually make shells with charcoal streamers and blue stars. I want the blue to be close to true blue or aquamarine, not a pale blue (I've been told getting the shade right is a challenge). It sounds like I'll probably need to get CuO or CuBenz and parlon or red gum if I want to do this. I want to avoid ammonium perchlorate because of its incompatibility with so many things, so I'll use a KClO4-based comp. I'm thinking Pihko #2.

[lloyd]

"...parlon or red gum..."

-----------

Not either-or. Parlon is a chlorine donor, red gum is not -- only a flame temperature modifying fuel and/or a binder.

 

You must have a chlorine donor to create many colors. (sodium yellow not among them).

 

Lloyd

[schroedinger]

I wouldn't be worried of it's acidity either. A 5% solution has a pH around 4.5, which isn't much to write home about. Less extreme than a 5% solution of sodium bicarbonate or oxalate, which people use without a thought. The real issue lies in it's oxidation potential. In the presence of most metals we work with, and some tool materials, the copper sulfate will corrode the metal.

Well that sounds like apples and pears. Most times it is way easier to oxidize metalls in an acidic enviroment.

 

But bicarbonate and oxalates are alkaline.

[Mumbles]

All I was saying is that sodium bicarbonate and oxalate are well over an order of magnitude less neutral than copper sulfate, but no one bats an eye. AKA it doesn't matter. Most metal fuels we work with are amphoteric and attacked by both acid and base anyway. I really don't see where you're going with any of this.

 

Additionally, the acidity has no influence on the reactivity here. Driving the potentials more negative with mildly acidic pH has no impact on an already spontaneous reaction. Al, Mg, Fe, and Zn all react with copper sulfate on their own at any pH. Lowering the pH doesn't make it any more spontaneous, maybe just an unobservable amount quicker.

 

Anyway, back more on topic. The link in the first post contains a database of formulas. Many were mined without credit from the now defunct Wouter Visser website. Seeing it in context would make it slightly more clear that this is designed to be a colored fire or bengal flare type of composition. I tend to ignore most formulas from the "Magic With Chemistry" source, as they tend to be unreliable, dangerous, and/or non-functional.

 

http://www.pyrocreations.com/pyro_info___other

[BlueComet24]

"...parlon or red gum..."

-----------

Not either-or. Parlon is a chlorine donor, red gum is not -- only a flame temperature modifying fuel and/or a binder.

 

You must have a chlorine donor to create many colors. (sodium yellow not among them).

 

Lloyd

I understand that red gum is a fuel and binder, and parlon can be both those plus a chlorine donor. I just said "either" because I've seen some comps call for only one or the other, but one with a chlorine donor would probably make a much nicer color.

[lloyd]

You'd have to show me something besides a fusee formula that doesn't require a chlorine donor. (and they're SO strontium nitrate-rich as to be useless as star or gerb formulae).

 

I don't believe you can produce any legitimate formulae from legitimate sources that don't have chlorine donors for colored flames -- except for sodium yellows (again).

 

Lloyd

[schroedinger]

Lloyd Mg+Barium sulfate 1:1 gives a deep green flash powder and if bound a green star. Only works with straight mg, mg/al, or al give a white flame.

[lloyd]

Shroe,

There are no "deep" colored flash powders. Believe me when I say that I've made commercial colored flashes for many years (for stage flash pots). Both green and red flames may be made with a large excess of barium or strontium oxidizer, but they're neither 'pure' in color, nor of the hue we like to see in pyro stars And with such 'excess oxidizer' formulae, they are never fast enough to be considered 'flash powders'.

 

Flash powders are not deep (saturated) in color because of the necessary addition of large amounts of metal fuel to make true 'flash powder'. It _always_ whitens the flame to a pastel. (And I comment this way on everyone's colored flashes, not only my own.)

 

Chlorine is necessary to produce the monochloride species in the flame that we treasure for the 'true color' producers in our art.

 

Arguing otherwise is contrary to over a century of colored pyro experience, and contrary to simple chemistry.

 

Lloyd

[gregh]

Sodium Yellows are your favorite aren't they Lloyd?

[BlueComet24]

Lloyd, I assume you like charcoal sparks, which are pretty close in color to sodium yellow, so why do you feel differently about sodium yellows? I just can't believe how much you recommend those beloved sodium yellows on this forum! Ooh, these smiley faces remind me of sodium stars.

Maybe it's that I've never made yellow stars myself, but I really don't see much of a difference between sodium and composite yellows. Do you have a video or picture that does a good job of detailing the difference? As far as I can tell, sodium yellow is like a streetlamp (amber or gold), while composite yellow is more like true yellow (like a lemon). Both are fine by me.

[schroedinger]

Lloyd did you ever try that formula? Single micro mg and reagent grade Ba sullfate make up a 5 g Sample a d vjew it from 100 m distance.

When i first time did that to try formula, i was amazed by how deep colored the flash was.

[lloyd]

I don't know exactly why I hate sodium yellows, I just do. They remind me of 'puke' instead of 'pretty'.

 

For others, the benefit of 'optical' yellow is that it can be precisely tuned to any shade you wish.

 

Shroe, yes, I've made it 'for fun', and I've even made a few ounces of it for a customer who demanded it (and later regretted it). My impression was then that it's a paltry, washed-out, barely sickly greenISH, compared to a good chlorine induced green. My opinion -- YMMV. But my opinion is shared by most of the pyros who've ever seen chlorine-free color comps, and pretty much all the professional pyros who've written about it.

 

As an aside; even though it's magnesium-fueled, the stuff is hard to ignite, because the barium sulfate requires a lot of energy to break down - like a melting point of ~1350 C for the sulfate vs ~592C for Ba(NO3)2, and MUCH higher amounts of waters of hydration than for the more-common oxidizers.

 

So, in addition to its poor color saturation, it can be VERY hard to ignite, and also result in 'duds', due to poor ignition.

 

I located an on-line copy of Don Haarmon's PGI bulletin #46 (1985) article about the use of sulfates in general, which was scanned (with subsequent minor errors): http://parazite.nn.fi/roguesci/index.php/t-4136.html

 

Lloyd

Edited February 6, 2016 by lloyd

[schroedinger]

That wonders me, i always got a clear dark green from it, not a pastell color. For me it always was what i would call a "true" green, compared to nitrate green, it is a little bit darker green and not a bright brilliant green. But thats propably just point of view.

 

But you also got the deep sounding boom compared to the 7/3 pitched boom?

[lloyd]

Oh, it explodes well, if you can get it to light. Yep -- it makes a nice 'boom'.

 

Keep in mind, I spent most of my professional career making close-proximity fireworks. You don't get 100-meter viewing ranges with that stuff, and proximity to a bright fire changes color impressions.

 

It's entirely possible to make deeply-saturated colors for close viewing, but the color must be immensely more color saturated to look 'pure' at 10 meters than it does at 100. As light level increases, the eye does not respond linearly to color intensity.

 

Lloyd

[Mike]

Yes, it really need some distance, in close proximity it is just greenish.

 

But why do you say if you can get it to light? Simpel visco or black match lights it reliable.

[lloyd]

Sometimes it needs to take fire from things that don't 'dwell' on fire on it for so long.

 

I've seen commercial e-matches fail to ignite sulfate compositions, which is one reason why we didn't ever make them (except on that one specific demand).

 

Lloyd

[Eyegasm]

Hello. I'm brand new in this community and thought I would look around a little. Then I saw this again. I have seen this recipe before with the same ingredients. I never tried it though. A friend of mine said he was going to try it with an added sodium bicarbonate moderator to raise (and stabilize ) the pH with regard to the sulphur added. He also mentioned not to use flowers of sulphur. The problem was he had a nasty car wreck a week later and had more important things on his mind. Later he gave up Pyro completely after someone he knew lost a hand playing with really dangerous stuff. I always wondered if it would amount to a viable recipe for a "fast" flash powder or maybe even find use in blasting as an alternative to fulminate. However knowing what I do about Chloride and Sulphur I personally would not try it outside of a lab and no batch more than 200mg.

[Seymour]

I'm assuming you mean chlorate, not chloride?

 

Adding bicarbonate, or other bases can serve to prevent the acids forming and then remaining which are the culprit for spontaneous ignition, but it does not prevent chlorate and sulfur compositions from being very sensitive.

 

The reality is that no one has ever demonstrated to me that any mix with chlorate and sulfur is necessary. There is always an alternative. Chlorate/Sulfur/Dye/Bicarbonate has been used for coloured smoke, but you can use lactose instead of sulfur for the same effect.

 

Yes some explosive mixtures can be made that are extremely violent in very small quantities and some people use them for breaking tiny crossettes, but this is a very small niche that only the extremely experienced should ever attempt, and even then I am sure there are ways of doing it without the chlorate/sulfur mixture.

 

As for fulminate, this is really a topic for the HE section of the forum, but I will risk breaking the rules to point out that there are much safer alternatives than both fulminate and flash powders of extreme brissance for this purpose. While we all risk injury in this hobby, most times people lose hands they are handling things that also fit in to the category of "there are way safer ways to do it".

 

PS, Welcome to the forum

Edited March 7, 2016 by Seymour