My experiences with chlorate from bleach!

[CodeMason]

I had the strangest dream last night, it was surprisingly vivid, and this mornign I was able to perfectly recall everything that happened in my slumberous hallucination. Here is what happened in my dream:
I went down to the local supermarket and bought myself a two litre container of bleach. On the label it read "46 g/L sodium hypochlorite, 4 g/L sodium hydroxide", which is 4.6% NaOCl and .4% NaOH. I poured about a litre (half the volume of the container) of the bleach into my all-purpose cooking pot and brought it to the boil over the stove. I let it boil strongly for about an hour, taking care to make sure it didn't all bubble over, until I had 15% of the original volume. The colour of the solution had changed from clear to light green (indicating the presence of Cl). I let it cool, and then added 80ml of a supersaturated solution of KCl (diet salt, sodium-free salt) in water. I stirred this for a while, then poured it out into a largish glash jar. At first, the results seemed spectacular. A fluffy white cloud of crystals had precipitated in the solution, yields appeared better than AP using 6% peroxide. I was quite pleased. I placed the jar into an ice bath and let it cool to 0°C. No noticable increase in yield was observed, the fluffy cloud has simply settled to the bottom of the beaker. I then poured it through a coffee filter paper and to my dismay, the crystals appeared to vanish. Where did they go? Did they react with the cellulose in the filter paper? Doubtful. Where the crystals I originally saw merely an illusion created by them being highly hydrated? Very likely. Still, I left the filter paper to dry. A thin layer of crystals were present, about 1-2 grams worth of chlorate. This is a shocking yield from 1 litre of bleach. I ignited the filter paper and it burned like touch paper. Bah! All that work (well, it was only a dream after all) for one measly peace of touch paper. What's my conclusion: If you think you're going to make chlorate by the bleach + KCl method, unless you have pure, crystalline NaOCl, FORGET ABOUT IT, the method sucks. No wonder the government isn't concerned about people making explosives from Chlorox. http://theforum.virtualave.net/ubb/smilies/smile.gif
My next experiments, er..., I mean dreams, dealing with home chlorate manufacture will be the Kurt Saxon method and the calcium hypochlorite method (off to the pool store I go. Well, it is available at the supermarket, but it's either in massive bucketloads of the stuff or small amounts for big $$$.) On that note, can the now more readily available trichloro isocyanuric acid be used? Wouter Visser's page seems to indicate that it can, and I have heard rumours that chlorobenzene type mothballs can also be used to make chlorates. Keep it real.

[EventHorizon]

I used the whole gallon and boiled down until it gave 1.3 g/cc per the directions I had at the time, then added the Sodium free salt. It was quite sometime ago that I did this. Final product was about 5g as I recall. I just burned it with sugar which was a little slower than with pyro grade KClO3.

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[CodeMason]

That yield sounds consistant with mine, as I didn't measure density, I just boiled it down to 15% of original volume, and a gallon contains 3.78 litres, if I remember correctly. 5g is still a horrible yield considering how annoying it is to distill bleach.

[CodeMason]

Perhaps this process could be used to form more valuable substances, such as chlorate salts of urea and hexamine. Then a yield of 5g wouldn't be so terrible, if only for experimentation purposes.

[nbk2000]

5 grams from a gallon is horrible. I know you're dealing with a dilute (5%) solution, but there should be more than 5 grams worth in there.

Are you guys boiling the solution down to 1.3 AFTER the first crystallization? Because you can keep repeating the process for several times, getting crystals each time.

So maybe the reasons your yeilds suck is because you're only doing it once, instead of 5 times.

You can avoid that hassle though by using the calcium hypochlorite instead.

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[CodeMason]

nbk, I'm using that in my next experiment, even if I have to buy the expensive stuff. I expect very high yeilds.

[EventHorizon]

Yea, something doesn't seem right. My stoicheometry is VERY rusty cause I came up with like 311g KClO₃ from 1 gallon bleach and 189.53g KCl. http://theforum.virtualave.net/ubb/smilies/frown.gif

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PGP ID 0x147CEF54

[This message has been edited by EventHorizon (edited October 07, 2001).]

[Hex]

I guess we're lucky over here in the UK, where you can buy 57% sodium chlorate wedkiller dirt-cheap down at every garden centre. The fire suppressant is water soluble, so it's a piece of piss to precipitate out potassium chlorate if you can get hold of KCl (diet salt over here always has NaCl in it)
This was my first proper bit of home chemistry, many years ago....(sigh)In my youthful ignorance, I used to mix it with sulphur and charcoal, and sealed up my pipe bombs by flattening the ends with a hammer! Fuck knows how I made it past my early teens with all limbs still attached.

[tvs17]

Some years ago I also tried this method. Can't remember yields anymore, but they where not as bad as described here I think(if I remember well).

Take a look at this link:
http://huizen.dds.nl/~wfvisser/EN/chlorate_EN.html#thermal

[CodeMason]

That's the method I used, tvs.

[10fingers]

Code Mason, the problem may have been the sodium hydroxide in the bleach. Get some with only sodium hypochlorite listed as an ingredient. I have noticed some brands like Clorox are putting sodium hydroxide in their bleach. Usually the cheaper brands contain only sodium hypochlorite.
I have tried this method several times and it works fine. IIRC it usually yields 2 or 3 ounces,(50 to 75 gms)per gallon of bleach.
I have not had good results with the other method using calcium hypochlorite, swimming pool chlorinator.

[BoB-]

You probably dumbed your yeild down the sink, since there will always be some water in the hypochlorite, the chlorate dissolves in the water present, you have to cool the solution to about 0deg. F. to make the crystals precipitate.



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It lets you to blame someone else.

[CodeMason]

Hrmm, yes, you're probably right. Because this reaction relies on the formation of an acid intermediate right? Forseeing a possible problem, at the supermarket I tried to find a hydroxide free bleach but to no avail. I'll look harder next time. http://theforum.virtualave.net/ubb/smilies/smile.gif

[CodeMason]

BoB-, I did that, quote from my original post:
<ul>I placed the jar into an ice bath and let it cool to 0°C. No noticable increase in yield was observed, the fluffy cloud has simply settled to the bottom of the beaker.[/list]

[nbk2000]

Try using liquid pool chlorinator instead of household bleach. It doesn't have any hydroxide, and is 10% hypochlorite, not the 5% of the household type. 2 gallons costs less than $3.
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Expect the worst and you'll never be disappointed.

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[This message has been edited by nbk2000 (edited October 09, 2001).]

[Anthony]

BoB- said 0*F which is -17.78*C

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[nbk2000]

I'm pretty sure he meant 0C/32F, ice water bath temperature.

Otherwise you'd have to stick it in the deep freeze.

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[Kdogg]

I am erie about trying this one.

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Monkeyman

[CodeMason]

nbk, that brings me back to one of my original questions. Will trichloro isocyanuric acid work as well?

I have only found two brands containing HTH in my local supermarket, one is this little tub of 500g that costs like $30 (AUS mind you), and then there's a 20kg tub of the stuff for $50. I can tell you, there are certain fertilizers I'd rather waste my money on! However there are rows and rows of trichloro isocyanuric acid. The reasons people like this is that for pools it is a superior chlorinator (higher available chlorine content), and it is less likely to explode like HTH did when mixed with common ingredients. Wouter Visser's site on chlorates, a veritable goldmine for home manufacturers, seems to indicate that it can, but makes no direct reference to it being useful. Its byproduct, cyanuric acid, can be made into an incredibly powerful primery explosive by forming a salt of it, and mixing this with a solution of sodium azide.

[BoB-]

My bad homies, according to Wouter Vissers' page its 0deg.C

[CodeMason]

KIPE also says 0 celcius.

[nbk2000]

I've never seen anything about trichloro being useful for anything other than pools, so I wouldn't bother with it.

$30 for a pound?! Holy shit! At that rate, by the 20K for $50. That much should get you at least a couple of kilos of chlorate.

I don't know about australia, but in the US, you can by water softener crystals (KCl) for $8/50 pounds. A lot cheaper than grocery store salt-substitute.

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[firebreether]

Where would you get water softener crystal from?

PS I would think that you should get a much bigger yield than a few g from 1 L, I have never tried it but that sounds shitty.

[SafetyLast]

In the US it is sold at Wal-Mart K-Mart and a couple other marts along with any hardware store.
It comes in 40Lb. bags that are blue or yellow.
the salt is little ovaliod chunks.
I also think that a better yield could be attained from the chlorox bleach method.

[10fingers]

CodeMason, I didn't notice this before but that procedure you used is unusual.
The one I use is to place 63 grams potassium chloride into 1 gallon of bleach. Then boil this down until the density is 1.3. You can use a battery tester for this. I have found them to be inconsistent though so I just boil the solution down to about 1/3 it's original volume. You will begin to see some crystals forming on the surface as the solution becomes saturated. At this point I remove if from the heat and put the whole thing in the freezer. Many crystals will form and settle out. Filter them out of the solution and rinse with a small amount of cold water. You can boil down the liquid again to get another crop of crystals.

[This message has been edited by 10fingers (edited October 17, 2001).]

[CodeMason]

10fingers, it seems that your method is the unusual one, I followed step by step Wouter Visser's procedure (the generally accepted one). What yield do you get from yours?

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[bubbling_beaker]

Hi this post may be too late but i think this will be useful for people who will see this post.
Sorry to say this but it seems you aren’t doing it right, I used to experience the same problems, all attempts i made resulted in failure . but I was really determined and tried a couple of times until I succeeded! (BTW DO NOT use any type of metal pots pan to boil with, Pyrex is best from my experiences, metal ones react and turn the bleach into a thick muck which takes absolutely ages to filterand probably interferes in other aspects too).

If you make sure you take the following into consideration I can almost assure you will get better and at least positive results:

*Boil your Hypochlorite properly when using NaOCl i make sure the yellow colour is made, (lots of NaCl should be precipitating even whilst the soln is boiling)

*Boil your hypochlorite to the right volume (for 1 litre of 5% bleach it should be 140ml)

*Once you have boiled it let your soln cool.
i cool it until it feels cool to the touch. filter, keep the filtrate and discard the salt that remains in your filter (NaCl) then try to use the least amount of water to dissolve your Kcl Make sure you have the stoichiometrically correct amount of KCl-some indicate eg “50% less sodium” usually is a ratio by moles not mass And once the KCl is added to the boiled down bleach, you reboil it and make sure all that precipitated is redissolved then let it cool at room temp, then move it to a fridge or freezer and cool until 0*c less if you want Then filter it through a cloth and squeeze the water out yes just squese mainly KCl and NaCl will dissolve and go through which is the reason why the mass gets slightly smaller and then purify it.

I hope ive made a valuable contribution.
Cheers :D

[scarletmanuka]

My method of making chlorate is from 125g/L NaClO liquid pool chlorine.
At 70C the following occurs 3NaClO--> 2NaCl + NaClO3 (in solution)
And then K+(aq) + ClO3-(aq) --> KClO3(ppt) at 0C
What I do, is heat up 200mL of the chlorinator to boiling point and then add 10gm of KCl in saturated solution( about 120mL). The KClO3 immediately precipitates about 5g KClO3. further boiling and then crystillisation can give about 10gm more. This is a pretty good yeild ie.90% of stoich

[Spy]

hi,
the last time I used that method, I used HTH powder and I had any success , don't understand why that happened!

[blazter]

In my experiments (probably posted before) I used to get approx 40g of crystaline material from 1.5L of standard bleach. The trick to good yeilds in my experience is just to keep it boiling at a good rate until crystals just begin to form at the surface of the hypochlorite/chlorate solution. The theory here is that the solution has reached saturation and the maximum amount of potassium chlorate will precipitate when KCl solution is added. Once the KCl solution is added, the mother liquor was chilled in the freezer for some time and quickly filtered before crystals began redissolving. This procedure always left me with nice white crystals which looked like fish scales. Purity seems to be decent, though the ground crystals always seem to be slightly hydroscopic and would cake in the summer, but become free flowing in the winter when it was drier. Flame test showed a mix of yellow/potassium purple, so there was still a slight bit of Na ion contamination.

[scarletmanuka]

Would it be possible to precipitate KClO3 from NaClO3 solution using KNO3 in any of the above processes, or is the solubility of KNO3 and KClO3 just to close to be of any value. I ask this because KNO3 is dirt cheap and anything precipitated is then likely to be an energetic material.
I was thinking then of maybe doing this in large scale with HTH 85%Ca(OCl)2. ie
add hot saturated Cal hypochlorite solution to hot saturated KNO3 solution
3Ca(OCl)2 + 6KNO3 --> 2KClO3(insolublish) + 3Ca(NO3)2(soluble) + 4KCL(soluble)

[Pyroman]

Last year I tried to make some clhorate from bleach and I was very disapointed with the very low yelds. In that summer I didn´t have the potassium chloride for double decomposition and I never got the sodium chlorate out of the solution after it had been concentrated by boiling and then lowering the temp. to zero degrees celcius. Other cuorious thing that happened, I never get the 1.3 density onthe solution even when it started precipitating on the bottom of pan.Last month I bought two gallons of sodium hipochlorite that contents 13.5% active chlorine and a 100lbs bag of potassium chloride as a soil alcalinity corrector on a farm store, this is a big bag but I can´t found anithing smaller.
This time I boiled the hipochlorite until it has a density about 1.2 and added about 730g of potassium chloride dissolved in a minimum of water at a temperature about 80C. after the adition the density was 1.3. Then temperature was lowered to 0ºC by putting in the freezer after reaching the room temp. and this time I got alot of cristals of potassium chlorate . This cristals was washed with some freezing water and then dried.The portion of solution remaining was concetrated by boiling again and new portion of chlorate was recovered and this procedure was repetead one more time, the total yeld was about 600g. I milled a lot of cristals and added some sugar for test i dropped a few dropsof H2SO4 on it and it catch fire immediatly.