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Author: Subject: What to do with a barrel of bleach
ldanielrosa
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What to do with a barrel of bleach

I just committed to buying a drum full of 12% hypochlorite from someone who's moving and closing his roof cleaning business. He sold it as a severe loss due to time constraints.

This caught my interest because several experiments use hypochlorite. It's readily available and not too expensive, but I'm a bit manic with it and use it up way too fast. I'm already thinking about chloroform, chlorate, and hydrazine. What other applications could I bend this to?
Detonationology
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Hypochlorite degrades over time. Store in a cool, dark place. You named the three things that came to my mind when I read the title. You could always dilute and use in in the washroom

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DraconicAcid
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Great for all kinds of oxidation. Ferrate, perhaps?

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BromicAcid
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 Quote: Originally posted by DraconicAcid Great for all kinds of oxidation. Ferrate, perhaps?

That's where my mind would go, hot hypochlorite can do miraculous things. Whenever I would look through Mellor's and come across a high oxidation state compound it seemed like one of the preps always used hypochlorite.

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Aqua_Fortis_100%
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Bleach is a cheap and great oxidizing agent.

Here in Brazil is difficult to find 12% stuff, OTC is mostly 2-3%. I found 12% variety only in chemical store and in 25 L bottle, it has a tiny hole in the cap, I think is just to release any excess pressure from the bottle as the hypochlorite degrades.

Chlorate from bleach is a lot of work, managing liters of solution to get crappy yeilds of it, much better and elegant is the electrochemical route to chlorate, even with very improvised apparatus. The same goes for chloroform, except for the electrochemical way, since probably one could make some nasty chloroacetones by trying electrolysis (better with calcium hypochlorite).

Vast range of organic oxidations could be made with it too. Hydrazine sulfate synthesis is the first that comes to mind, and its a interesting way to use your bleach. Thinking about how much hydrazine sulfate you can make with 5 gallons of concentrated stuff, now imagine a yield from DRUM of it! Related compounds, like semicarbazide*HCl can be made too. All of these are nice precursors to many interesting compounds (many of it energetic compounds like azides, tetrazoles, nitrotriazolone, etc).

Another interesting thing is that strong acidic hypochlorite, could dissolve most noble metals, its very agressive oxidizing chemical. There is a Brazilian patent (portuguese) that claims using it with HCl to leach platinum metal group metals from extinct ceramic car catalysts.

Talking about ferrates I wonder if they could be used just like Fenton's reagent to oxidize contaminants / destroying organic compounds and make safer the disposing of waste chemicals in environment.

[Edited on 19-2-2016 by Aqua_Fortis_100%]

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That patent sounds interesting.
If you had a plausible way of extracting Pt from waste catalytic converters then you would have something quite valuable there.

Aqua_Fortis_100%
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 Quote: Originally posted by j_sum1 That patent sounds interesting. If you had a plausible way of extracting Pt from waste catalytic converters then you would have something quite valuable there.

Actually this is a method used by some amateurs do to remove PMG from catalytic converters.. This is very interesting since is a nice OTC substitute for chlorate/HCl oxidizing mix. Most results from amateurs experiments in this field come from Gold Refining Forum, they have entire threads focusing on leaching PMG out of catalytic honeycombs and other materials.

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ave369

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 Quote: Originally posted by BromicAcid That's where my mind would go, hot hypochlorite can do miraculous things.

Not hot, if you want to make ferrates! The worst enemy of ferrate synthesis is heat. Ferrates are synthesized in ice-cold solution.

Smells like ammonia....
ldanielrosa
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I hadn't thought of ferrate yet. Thanks. I'm supposed to go pick it up tomorrow. I needed time to get loading ramps, a winch, and another body to muscle a 250+ kg load into my truck.

I don't have ready access to waste catalytic converters. Local laws keep wrecking yards from releasing them.
chemplayer..
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Some ideas which might lend themselves to 'industrial scaling':

1. Hydrazine sulfate from bleach/urea/sodium hydroxide/sulfuric acid.
2. Anthranilic acid from bleach/phthalimide/sodium hydroxide.
3. Chloroform via haloform process.
4. Manganese dioxide via manganese sulfate/bleach/sodium hydroxide - store up all that oxidising power!

ldanielrosa
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Idea #4 is new to me, and very interesting. Do you have a link for this?
unionised
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Quote: Originally posted by ave369
 Quote: Originally posted by BromicAcid That's where my mind would go, hot hypochlorite can do miraculous things.

Not hot, if you want to make ferrates! The worst enemy of ferrate synthesis is heat. Ferrates are synthesized in ice-cold solution.

In a very real sense.
But, in another much more real sense, no.
Here's what the WIKI page says about making ferrates
"Georg Ernst Stahl (1660 – 1734) first discovered that the residue formed by igniting a mixture of potassium nitrate (saltpetre) and iron powder dissolved in water to give a purple solution Edmond Frémy (1814 – 1894) later discovered that fusion of potassium hydroxide and iron(III) oxide in air produced a compound that was soluble in water. "
The solutions are unstable when hot, but the salts themselves are OK.
ave369

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The slag method of making ferrates works, but is low-yield and impractical. Above 198 deg. C dry potassium ferrate starts to decompose. This is somewhat higher than the temperature of its decomposition in solution, but still low.

Smells like ammonia....
chemplayer..
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Can't find a reference but from practise we know that mixing hypochlorite and manganese sulfate gives an instant thick dark brown precipitate of MnO2. Some experimentation would be needed to see if it's quantitative and what conditions are best (thinking about it having NaOH would possibly react and create an impurity of Mn(OH)2 in the product).

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ldanielrosa

ldanielrosa
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Two attempts on manganese dioxide:

The first was with a slight excess of bleach, and it seemed to come out well. The result weighed more than quantitative, so I think maybe some moisture and manganese hydroxide. The color is very dark.

The second one I tried adding NaOH to reconvert the chlorine gas back to a mix of NaCl and NaOCl. That one had ugly results. I haven't washed it yet, but the color is wrong. More medium brown. I'm thinking Mn2O3 and Mn(OH)2.

One attempt on potassium chlorate:

The stainless steel pot wasn't so much. It wasn't destroyed either, but it's not pretty. I took it off the heat and dumped it into a plastic bucket. About the color of merlot. I don't think I'll get much out of that one, if anything.
chemplayer...
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I wonder if it's possible, given a mixture of NaOH and NaOCl in solution, to work out how much NaOH specifically there is, and then use an acid to neutralise it selectively leaving just NaOCl which you could then use and improve yields and purity of products?

One idea which springs to mind is to use a 'weak' acid like acetic acid, perhaps keeping the mixture chilled, producing sodium acetate which shouldn't then interfere with subsequent reactions (e.g. manganese II acetate is water soluble so won't precipitate out). Unless of course acetic acid itself undergoes some crazy reaction with hypochlorite... not sure.

The challenge would be how to work out via titration the specific amount of NaOH. I suspect that NaOCl on its own appears strongly basic with a pH test, so doing an acid-base titration might not work. Perhaps adding excess MgSO4 solution to the bleach, filtering the insoluble hydroxide, drying it and weighing it might give an indication (problem might be that filtering and drying the hydroxide is normally a pain in the a).

Just some ideas to share...

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The Volatile Chemist
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Chloroform synthesis I can imagine industrial-style, though certainly just for practicality, not profit. Hydrazine sulfate, though, would probably have better yield and less loss, perhaps for profit on SM. Though I bring this up simply as a way to measure what's worth making mass-scale, as you probably don't need the 10 odd gallons of chloroform you'd get from using half the drum of bleach. Though I suppose I'm forgetting that it's rather concentrated. Perhaps you'd get a better yield than with typical laundry bleach.

aga
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I appear to have a Very large container of 36% sodium hypochlorite.

For no apparent reason i've done nothing with it at all.

The last time i made chloroform i just stuck it in a drawer for a year.

I forget who said it first (IrC IIRC) :-

There is no point making and keeping lots of any potentially dangerous chemicals unless you have an immediate use for them

As it stands, i could make a lot of chloroform and other stuff, but there is no point as i have no immediate need.

Storage of chemicals is a whole other ball-game.

The Volatile Chemist
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Good point, and I suppose that applies to most of the highly oxidized, oxidizing products from most reactions with bleach. So perhaps nothing should be made from the entire barrel of bleach, something I totally would've done...

Amos
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If you work with hexavalent chromium much, hypochlorite can be used to convert chromium(II) hydroxide back to sodium chromate, effectively allowing you to recycle it each time it is reduced.

ldanielrosa
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I keep getting excellent feedback. Thanks, everybody!

aga and The Volatile Chemist, true enough. However, one pint of chloroform takes less space than 4 gallons of bleach. I also may have a use for chloroform in the future- I plan to run a few extractions. I know the stuff isn't pure, but a larger quantity is easier to justify the effort later on. Don't worry, I stabilized it with 1% ethanol.

This is more of a discontinued candy shop item. The bleach is degrading, and taking more space than it should. I'm looking to have fun wasting a hazardous substance that's normally a bit spendy use so inefficiently. Sadly, I may run out of the other ingredients first. I only have 500 grams of manganese sulfate.

So I've given some thought to lead dioxide too. I have a fair amount of lead chloride. The solubility is poor, and that may make the reaction much less efficient.

chemplayer, I may do that out of curiosity. I'm concerned about how long it would take for the Mg(OH)2 to precipitate, and that the remaining solution may become less stable. I'd need to use it immediately for the information to be of use to me.
The Volatile Chemist
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Is that concentration of bleach a viable chlorine gas source? With proper safety precautions and a reasonable reaction set-up, you might try some interesting things with chlorine gas.

Amos
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I wouldn't bother making manganese dioxide out of manganese sulfate; if you browse online it's usually cheaper to buy the former.

 Sciencemadness Discussion Board » Fundamentals » Chemistry in General » What to do with a barrel of bleach Select A Forum Fundamentals   » Chemistry in General   » Organic Chemistry   » Reagents and Apparatus Acquisition   » Beginnings   » Responsible Practices   » Miscellaneous   » The Wiki Special topics   » Technochemistry   » Energetic Materials   » Biochemistry   » Radiochemistry   » Computational Models and Techniques   » Prepublication Non-chemistry   » Forum Matters   » Legal and Societal Issues