Calcium hypoclorite and fuel oils

[Lameiras]

Some questions about calcium hypoclorite where made in this forum, but not about the mixture of it with fuel oils.
It’s a very common swimming poll chlorinate agent and also a strong oxidizer. Seems that the commercial versions are composed of Ca(ClO)2 around (65%) and 35% of water, in weight.
It can be heated (not at very height temperatures), to extract the water. This process leave the Ca(ClO)2 crystals dry and porous. Then if a mixture is made with fuel oils like kerosene, vegetable oil etc... it burns extremely fast, like a flash powder. Seems that Ca(ClO)2 is fast to give up it’s oxygen under these conditions. If this mixture is contained, it’s ignition produce a loud and powerful explosion. Much more powerful than the standard black powder for sure. It is also a very "sensitive" mixture(about the same "sensibility" of the black powder).
I have searched but haven’t found anything about this particular kind of mixture. It’s extremely easy to obtain the ingredients and to prepare; and it can be used as an explosive of course. I have read about the production of chlorates through the thermal decomposition of hypoclorites but it is complicated processes if compared with use of the dry comercial Ca(ClO)2 as the oxidizer. Also there is the possibility of prepare the mixture right before the use.
My questions are: Is this a viable low explosive? Are the risks acceptable? There are ways to reduce its "sensibility" and increase the powerful at the same time?

[mongo blongo]

Black powder is sensitive??? :eek: :rolleyes:

[blindreeper]

Exactly my thought mongo, besides why bother with such a mixture when chlorites are know to be unstable?

I have read about the production of chlorates through the thermal decomposition of hypoclorites but it is complicated processes if compared with use of the dry comercial Ca(ClO)2 as the oxidizer.

True but there are far greater things you can do with chlorate than that of hyporchlorites :rolleyes:

[Axt]

He is more then likely refering to flame sensitivity.

At least I found his post intersting enough, if it acts the way as its told. You could fart around converting the hypochlorite to chlorate to get a handful of powder for your trouble, or you could pour oil over hypochlorite and get kilograms for no work at all. Now which is more useful?

I cant think of another liquid fueled BP equivalent, so it has some merit. Although I always assumed such a mix would spontaneously combust.

[nbk2000]

How are you setting it off? I'm assuming you mean with a detonator, and not just straigh fuse, correct?

This isn't exactly a new idea, since hypochlorite/naptha is a known explosive that we've discussed before. It's just another oxidizer/fuel explosive.

[Lameiras]

Detonator.
I have tried with many kinds of common fuels including naptha. And I have observed that with liquid and more volatiles fuels like kerosene the mixture burns faster and its explosion is more powerful. That’s because a liquid fuel is easily absorbed by the porous and dry Ca(ClO)2 grains, which create an enormous contact surface. So it’s not necessary to break the grains or use solvents to mixture a solid fuel. Another observation is that if the grains have to be braked it’s better to do this before the heating process. I think its increase the porosity.
Volatiles fuels like kerosene have obvious disadvantages. Makes the mixture even more sensitive to flames, it can evaporate fast… Anyway this is not a mixture to be stored.
Heaviest oils are better fuels if the mixture will be stored.
I have never observed spontaneous ignition with the dry Ca(ClO)2…

[nbk2000]

At what temperature do you heat your hypochlorite, and for how long?

[Axt]

Therefore doesnt burn but detonates, your choice of words and comparisons with blackpowder completely threw me off.

What sized charge and type of explosive is being used to detonate the mix?

[Lameiras]

The heating temperature should be around 100 C. It should be heated for 20 – 30 minutes. This is a draw of the heating device that I use:
http://paginas.terra.com.br/arte/12367895/D.htm
It’s important to keep the Ca(ClO)2 layer thickness under 0,5 cm to avoid overheating points, that may cause self decomposing.
I use to mixture 0,1 ml of oil for each gram of dry Ca(ClO)2.
The comparisons with black powder or flash powder are to give an idea of how it reacts in open air. If a proportion like 0,1 ml/g is used the reaction in open air is very fast and the light that it produces is extremely strong, may cause blindness for a few seconds.
About the ignition device, I use an improvised one. It’s more like a detonator I think. Consists in a filament of steel confined in a small recipient with a few grams or mg of something like flash powder for example. Draws to give an idea: http://paginas.terra.com.br/arte/12367895/d2.jpg
http://paginas.terra.com.br/arte/12367895/C.jpg

[nbk2000]

Now, just to clarify, the material does NOT spontaneously ignite when mixed, correct? Some formulations of HTH (calcium hypochlorite) with organic fuels spontaneously ignite/explode when mixed, either instantly or after a short delay.

The mix you describes only ignites after being exposed to an ingition source like a flash charge, correct?

[Lameiras]

Correct. If the mixture is made like I have described the materials does not spontaneously ignite when mixed. The mixture must be completely free of water. (the fuel and the Ca(ClO)2). Once the mixture is made it must not be exposed to height temperatures. And only substances that are not soluble in water must compose the fuel. Oils, which contains substances like glycols etc, must NOT be used. Only pure oils must be used, the kitchen soy oil for instance.

[metafractal]

This might have some merit, as long as you make sure that the products are completely dry, as Lameiras suggested. However, he did not stress how important this was. My only experience with hypochlorites/fuel oils was when I added some viscous hydrocarbon (sorry, cant remember exactly what it was) to damp calcium hypochlorite. After about fifteen seconds, large volumes of thick, white, highly irritating smoke were formed. After about ten minutes, the mixture burst into bright orange flames.

[FragmentedSanity]

Lo all :)
Just wondering if this is classified as High or Low order? The flash charge initiation sounds like its a low order mix that can burn fast enough to undergo DDT

Its been said that the mix dosent combust spontaneously, but will it iginite by being heated or does it need a flame?

my gnome's (kewlish I know) experiments with calcium hypoclorite + feul mixes have always been unpredictable.

But my gnome tells me that he always used the hydrated calcium hypoclorite and usually break fluid as a fuel. This mix is well known and talked about so I wont rehash old stuff, the point I was getting to was that the mixture's behaviour was dramatically affected by the weather - namely the ambient tempreature. On a hot day ignition is almost immediate upon contact - whereas on a cold day the mix can remain totally inert until a heat source is introduced to kick start the reaction.

If by drying the calcium hypoclorite and using the right fuel we get a reliable mix it would be even easier than AP and totally OTC from the supermarket!

(edited to remove the offending initials - Whats up with that? is it a new rule I missed - I have signed pretty much every post the same way since Ive been here - just curious not trying to step on any toes)

[blindreeper]

FragmentedSanity, I think this is being used as a HE, and it would be easier than AP, granted. But for it to be an effect HE you need a detonator such as AP :rolleyes:
And don't end a post with your username/abbreviation of username!

[Lameiras]

Once the mixture is done, if heated it may ignite. The ignition by heating depends on which kind of fuel oil is used and in how the heating is done. If a more volatile oil is used, it will evaporate during a slow heating process, the mixture will lose the fuel and it will probably not ignite. If the heating process is fast, the temperature may increase a lot before the fuel evaporation that will cause the ignition. If more heavy oil is used as fuel, the temperature of the mixture will increase during a slow or fast heating and the ignition will occur.
The temperature of ignition depends on which kind of oil is used as fuel. Assuming the fast heating.
The calcium hypoclorite must be heated in a controlled temperature BEFORE the oil addition. Once heated the temperature of the Ca(ClO)2 grains or powder must decrease until it gets at least under 45 C to do the mixture with oils.
I have tested oil for breaks. It must not be used in this kind of mixture because it is not pure oil. It contains glycols and other substances that may cause the spontaneous ignition.

[green beret]

This has really caught my attention, it is unbelievably simple, and requires only the tiniest charge to set it off. If he is using only a few grams or milligrams of Flash (?) then a small amount of AP will surely do it.

Just to summarise;

1. Dry Calcium hypochlorite at 100 C for 20-30 minutes
2. Mix with a pure oil
3. Insert detonator and fire

I am assuming that between two and three there would be some time required for full absorbtion of the oil, and that confinement would help.

Lamerias, what type of confinement do you use, if any, and do you mix the oil in by hand, or simply let it absorb. Also, were you using flash to set it off, or some type of primary, because you said "Something like flashpowder for example", just dosent seem too clear thats all.

Good work though, it seems this explosive may be quite useful.

[nbk2000]

This would be a good use for the vacuum packaging. By vacuum packing it, you keep the hypochlorite in an anhydrous state, allowing you to store it pre-mixed in a ready to use state with minimal risk of premature ignition from moisture absorbtion. :)

[Lameiras]

100 C is a good temperature to dehydrate it because if the temperature is higher the Ca(ClO)2 may auto decompose. I am not sure about the exactly temperature for auto decomposition to occur, but since the process works in a lower temperature it’s better to proceed in that way.
Once dehydrated, the mixture is done by dropping the oil over the grains or powder and mixing with a spoon, for instance. The absorption is fast and It will be ready immediately.
Observing the grains mixed with oil through this simple process it’s possible to see that some grains absorb more oil then others. Some remain completely dry. Considering this fact and observing the auto decomposition of Ca(ClO)2 by heat, it’s possible to imagine that the grains with excess of fuel reacts producing the necessary heat to decompose the “dry” grains. This decomposition causes an injection of oxygen that oxidizes this excess of fuel in the neighbour’s grains.
I have tried to mix dry grains (fuel less) with grains that exceeded in fuel. The reaction in open air was the same(all the fuel was consumed), a little slower thought.
About the confinement, it can be made of any material that has the proper thermal-mechanical resistance. I have tried with successes cylinders made of cardboard, PVC pipes even metal pipes. With cardboard or paper it good to add two or three layers of aluminium foil on the internal surface. That’s because the Ca(ClO)2 may oxidize the cellulose reducing the mechanical resistance of recipient.
Te mixture will ignite if exposed to a fast and intense heat process. The flashpowder can produce heat quickly and intensity. More than what is necessary to ignition, make it’s explosion more effective. The mach powder can also be used to ignition, with worst results. For it to be more effective, as wrote in a post, it will need a detonator.
Vacuum packaging is a very good Idea!

[green beret]

Thanks Lameiras, you have provided some good information. Do you think thermite would be quick enough to detonate it? Also, unless I get around to doing it first, would AP work well?
I really like the idea of the Vacuum packaging too.

[Lameiras]

Yes. I think that both thermite and AP could work.
I guess I forgot to mention others important observations which I have made.
I mentioned that the dry Ca(ClO)2 grains are porous, they absorb the fuel which makes the contact surface between the substances enormous. However, because of the thermal decomposition of fuel less grains in the mixture with grains exceeding in fuel, and it’s consequently oxygen liberation, the smaller grains are more effective the reaction is. The oxygen injections from decomposed fuel less grains need to travel shortly distances to reach the grains exceeding in fuel. Consequently the oxygen reaches them faster.
The process to reduce the size of grains should take place before the hating as mentioned.
About the possible fuels, in fact, there are many with many kinds of effects. Every pure hydrocarbon or mixture of pure hydrocarbons may be used. Substances that are Ca(ClO)2 solvents such as water must not be used. Substances that are soluble in water must not be used since them can bring water with them and they could also works both as solvent and fuel for Ca(ClO)2, such ethanol, glycols etc… This will cause a spontaneous reaction.
Ammonium nitrate must no be mixed with calcium hypoclorite. If the both substance are not absolutely dry, a violent reaction with a short delay after mixed will occur resulting in explosion.

[Desmikes]

Can you ignite such comp by a drop or two of some acidic liquid? Does anyone have any experimental data showing how the substitution of nitromethane for pure hydrocarbons affects the final product.

[green beret]

Thats interseting, the fact that mixing AN with calcium hypochlorite will produce an explosion, its pretty unlikely thats it a detonation of the AN though. You could mix in some primary with the AN and then combine it with the hypochlorite. Not that it would be very useful though. Maybe for some type of impact grenade?

Lamerias, as soon as I get some hypochlorite, I will do some testing to see how AP and thermite work as detonators for this mix.

[Lameiras]

Desmikes, until now I only observed ignition of the pure Calcium hypoclorite through heat. It decomposes as I have mentioned. But I have never got a sufficient fast decomposing reaction of pure Ca(ClO)2 to use as a viable explosive. The only experiment that I have made in which the pure Ca(ClO)2 exploded was when put abut 5 g of it to dry in a microwave over a glass plate. After 3 minutes it exploded violently producing a loud noise and converting the plate in thousands of pieces.
Dropping acids over pure Ca(ClO)2 will cause a violent reaction on the local where the droops hit the crystals. Dropping over Ca(ClO)2 mixed with fuel may cause ignition.
About the experimental data, I don’t have. Are you talking about mixture nitromethane with Ca(ClO)2?
About the mix with AN, the Ca(ClO)2 produce a strong reaction even by contact of the solid crystals as mentioned. Di or Trichloro-S-Triazinetrione also produces a reaction but it not so violent and it have to be solved in weather to occur quickly. I don’t know if the AN is working as a catalyser to decompose the Ca(ClO)2 which is a much less stable compound or if it’s reacting as well. The reaction is so violent that even if oil is mixed to avoid the direct contact of Ca(ClO)2 crystals with AN crystals, it occurs very slowly.
An idea would be put Ca(ClO)2 and AN in separated plastic bags. Dispose the bags as alternated layers inside a cylindrical recipient and an explosive charge in the end. Or even do the same with bags of ANFO and “CHFO” to obtain more energy.
The same kind of phenomenon occurs by mixing sulphur and Ca(ClO)2. Sulphur is also a fuel. It’s a less violent reaction thought. The same idea could be tried using sulphur. As well with many others substances which possible have this behaviour when mixed with Ca(ClO)2.
Here where I live, bromines are not used as swimming poll chemicals so it’s not that easy for me to get some, however it is logical to suppose that brome compounds would work as well.
By the way, here there is a page with a short description of Ca(ClO)2 industrial production processes and it’s advantages as disinfectant and oxidizer agent . http://www.altairchimica.com/eng/prodotti.htm

[sauvin]

I'd be very careful to examine the nitromethane proposed for this application. I've seen references to many nitromethane formulations (10%, 25%, etc) whose other major component is methanol. At the same time as not being a chemist, I do know that methanol is extremely popular in "dry gas" products because of its affinity with water.

Does pure nitromethane itself have such affinity?

[Desmikes]

The other day I was playing around making plastic container rockets with 40% gasoline 45% nitromethane and 15% xylene (rough eye approx.), they used to work better and look cooler w/o xylene, but that's not the point. After ripping boxes and launching plastic jugs across my backyard got old I decided to mix the above mixture with some 78% calcium hypochlorite (not the best purity) to watch it burn. I poured enough fuel to get it all wet and felt for temperature change as a safety precaution (that particular Ca(ClO)2 never did react by itself with gasoline before, but I wasn't sure about the nitro and xylene). There was no obvious change within first 20 sec, so feeling satisfied I inserted a fuse but then I felt the T rise. I set the whole thing down and ran a few meters back. It produced LOTS of fumes, kinda like H2O2 + catalyst, except these were heavy, fuel fumes that didn't rise at all. About 20 sec later the O+F mixture violently deflagrated with a slight boom-woosh setting off the entire cloud of fumes that covered near-by area. One cup of reactants resulted in a very impressive 2m wide fireball.
Points/observations/ideas: my Ca(ClO)2 sat for three days in the unsealed container prior to this experiment, it was 22*C outside and very humid; the fumes produced were mostly nitromethane judging from the type and color of the flame but it's kinda hard to say for sure; this would make a simple (NON-detonation) FAE if put inside a narrow and tall case close to the top.

[bloodbob]

*USING THIS THREAD TO TEST POSTING AS REGISTRATION SAID I HAD TO WAIT 2 WEEKS*

Okay I'm assuming those fumes were probably a mixuture of gasoline vapour which cooled and hung low.

Calicum hypochlorite is probably good for smoke mixtures too. When I was younger I made smoke mixtures of the chlorine tablets ( I dunno whats in them it isn't a simple chlorine oxide salt it has nitrogens in I believe ) ground up with sugar when heated produced alot of smoke and a carbon matrix also I noted the isopropanol alcohol + the cholrine tablets produced either CO2 or CO.

[blindreeper]

You wait 2 weeks so you will hopefully read the forum a bit and learn not to post crap or irrelevant garbage

[Blackhawk]

This seems like quite a good discovery, so very simple :D the only problem being with the drying of the hypochlorite, but I will definately try this.
I will probably use Ca(ClO)2 and kerrosene or naptha with innitiation via a slowflash salute or possibly the primary from christmass bon-bon crackers. Will be annoying drying out the hypochlorite but I suppose it is safer than making AP, seems too good to be true, safe easily innitiated HE's with OTC chems that even I of all people have access to.

[xyz]

Let me know how it goes blackhawk, Calcium Hypochlorite is very easy to get hold of around where I live (many people have their own pools).

[Lameiras]

I have also observed that aluminium powder can be a great fuel for the dry Ca(ClO)2. Not pure aluminium powder but a mixture of it with oils. Many proportions could be used. The aluminium increases the reaction energy. The velocity decrease thought. When contained and ignited it provides a more powerful explosion if compared with the mixture of oils only as fuel.
An interesting possibility is to use metallic paints of right brilliance as fuel. The pigment of this kind of paints is usually aluminium powder of the finest kind. The solvent and the vehicle, works as the fuel oils. By passing this paint through a filter for instance, it’s possible to separate some solvent which increase the concentration of aluminium powder.
Another possibility is mixture the dry Ca(ClO)2 and pure oils with flash powders (that not contains sulphur!).

[Blackhawk]

That is a good idea, first I have to get myself an oven that I don't cook with (a little snack oven thanx Blind), have you observed a critical diameter with your containment? whats the smallest amount you have succesfully 'detonated' (is that the right word for this stuff or is it just fast def) I may try a mix of Ca(ClO)2/KMnO4/Al/Naptha the Al/KMnO4 acting as a flash 'sensetiser' and the naptha as the fuel, I may also det with a small amount of OTC primary instead of relying on DDT. That gives me an idea, may be a use for 40%monomer MEKP (the commercial rubbish), it may prove to be an effective sensetiser in this case (although I will have to try a spontaneous ignition sample first to make sure it is safe)

xyz: Yeah same around here, quite easy and cheap, just buy it from the pool section of franklins I'll document and post results when I do some, but It may be a while, I have to go shopping for tools first ;)

[Lameiras]

I have observed that the geometrical disposition of this mixture inside a closed recipient results in a critical relation between the diameter, the length and the thermal-mechanical resistance of recipient material. Assuming a cylindrical disposition, the critical diameter would be ¾ pol and the maximum length would depend on thermal-mechanic resistance of recipient. If you use more resistant recipients such as metal pipes, you may decrease the diameter and increase the length.
(The distance between the ignition point and the end of the charge can be considered as the length in this case.)
I guess the smallest amount I have successful ‘detonated’ was 5 g contained in a cylindrical recipient with ½ pol diameter and approximately 3 pols length.

[nbk2000]

We here at the Forum use either Imperial or Metric for all units of measure.

A "Pol" is not a unit of measure used by either of these systems. Define what a "Pol" is in these sytems.

Thank you.

[Lameiras]

1 pol = 25,4 mm

½ pol = 12,7 mm
¾ pol = 19,05 mm
3 pols= 76,2 mm

[blindreeper]

So a "pol" is an inch? 1 Pol = 25.4mm = 1 inch?

[Lameiras]

Necessarily. 1 Pol = 1 inch.

Please, I am sorry about this confusion. I am accustomed with the metric system. But for some reason, here where I live the pipes diameters are measured in terms of inches. ("polegadas" in Portuguese. "pol" is the abbreviation).

[Spy]

Nice to meet you Lameiras! I am Brazilian too! if you have a free time send me a e-mail(sidys01@hotmail.com),to give more power to that mixture , puts some potassium nitrate and aluminium powder before putting the oil and mix , its will give good results.

[blindreeper]

Adding KNO3, aluminium or any other exotic chemical defeats the purpose of using Ca(OCl)2. Its meant to be nice and OTC :)

[Lameiras]

Exactly!
The idea is keep it simple. The aluminium paint is a way to add aluminium powder and fuel oils from a common available product.

[30yearstoolate!]

Is it necessary to detonate with AP or other high explosive or can it be achieved with a length of visco fuse. AP would not keep to the simplicity theme.

If a length of fuse would be sufficient to cause the ignition, would this be able to cause a build up of pressure within a confined object [steel pipe or copper tube] to a high enough pressure to explode the container?

If so would it be as powerful as using flash or black powder in the same container.

On a side note: If water is introduced into the reaction would spontaneous ignition occur?

If so then it might be able to be used as a basic depth charge with a small hole in the container. Thus controlable by the diameter of the hole.

[nbk2000]

Seems someone is three years too late. ;) :D

[Lewis]

Seems a pretty dead thread, but hopefully someone knows this:

Are the so called 'chlorine pucks' used in pools pure, or relativley pure calcium hypochlorite? I recently obtained some but not from their original container.

They're largish, white chalky cylinders similar in shape to water paints kids use. Unfortunatley the only test I was able to do on them was expose them to relativley pure H2SO4, with no result.

I no longer have the pucks, but my question is would it be worth stealing some more?

[nbk2000]

They can vary from a low of 15% to a high of 95%+.

So, without knowing exactly what percentage of active chlorine content the tablets have, you're wasting your time.

Quik-Shock HTH is the best to use, as it's very high chlorine content.

Be sure to get the packages from a normal pool retailer who'll have constant turn-over of inventory, otherwise the chemicals may be old. Old=Bad.

[flashpoint]

Well I'll just let you in on a little secret too even know this thread is dead. Cal-Hypo doesn't reguarly come in 'pucks' by the way. The brand name for Cal-Hypo in 'pucks' is Accutab. Most 3" tabs in my area are Tri-Chlor based. You can't mix the two together. Granular Cal-Hypo and Tri-Chlor = Bad. Read the packets of chlorine and make sure you are infact using Calcium Hypochlorite, or you might find your self fucked up :)