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Author: Subject: Chlorine
Organikum
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Chlorine

Dont say I am nuts, but I searched and found no thread dedicated to this useful compound.

Lets open the competition:
We want chlorine - dry - clean - and in serious amounts from all over the world freely available starting chemicals.

Extra bonus if no H2SO4 is needed for drying! And pleaze not the stoneold KmNO4/MnO2 recipes.....
New ways! Transmutation rulez!

[Edited on 4-15-2004 by Polverone]

Irgendwas is ja immer
DDTea
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Chlorine is easy and cheap to produce in the lab, but is not the easiest to dry without H2SO4. Normally, I would suggest NaCl + H2SO4 + KMnO4...but, we're talking innovation now.

Of course, you could simply add NaOCl to HCl...that's the way I've always generated Chlorine (my KMnO4 is too precious for this). Alternately, you could electrolyse HCl.

These would be the cheapest ways to actually produce Cl2, and any other way seems like it would be unnecessarily costly. Drying the gas is another issue.
BromicAcid
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In place of sodium hypochlorite I usually use calcium hypochlorite. Also I have made chlorine gas by the reaction of HCl(aq) with H2O2(aq). Too bad both of those methods produce chlorine contamainated with water. As does the electrolysis of salt water. You could always do electrolysis of a molten chloride but the temperatures would be unacceptable most of the time, on the plus side you really wouldn't have to worry about a water contaminate.

Shamelessly plugging my attempts at writing fiction: http://www.robvincent.org
Organikum
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molten chloride

The Cl2 produced this way is told be rather impure - this states at least my old chem-engineering book.

I read about electrolysis of NaCl saturated with conc. HCl. Anybody tried this?

All electrolytic methods suffer from the electrode problem: Who can afford platinium electrodes or platimium coated titanium electrodes, I not.
Graphite/coal works, but for how long do the electrodes stand the chlorine attack and how does this attack contaminate the Cl2?

HCl and H2O2: Concentrations, temperatures? Pleaze...?
Organikum
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trichloroisocyanuric acid

Any way to kick the chloride (dry preferrred) from this OTC compound? This would be nice - isocyanuric acid is a very useful compound and if this works one can get two goodies by one shot.....
(ok, the one goodie is a nastie goodie...)
unionised
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Deacon's reaction;
4 HCl+ O2 --> 2 Cl2 +2 H2O
Needs a hot catalyst IIRC.
Polverone
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Cl2 from TCCA

Not dry, unfortunately! But I stumbled across a patent some time ago - GB 1401120 - that stated chlorine gas could be produced by mixing trichloroisocyanuric acid with sodium chloride solution and then heating or simply reducing pressure over the solution. It would still need drying.

I mentioned in another thread that according to a journal article I read, dry Cl2 could be produced by heating dry calcium hypochlorite with cobalt salts (or cobalt/iron salts) as a catalyst.

Anhydrous CuCl2 will release dry Cl2 when heated (probably not useful on a very large scale).

[Edited on 7-1-2004 by Polverone]
Pyrovus
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Not completely on topic, but the method of heating the copper (II) salt also works to produce fluorine. According to Reference Book of Inorganic Chemistry (Wendell M Latimer, Joel H Hildebrand) "the cupric halides decompose according to the equation: 2 CuX2 -> 2CuX + X2. Cupric fluoride decomposes around 500°C, and the chloride and bromide at somewhat lower temperatures." Unfortunately the book doesn't say what at rate this reaction occurs, so it might not necessarily be terrible useful.
KABOOOM(pyrojustforfun)
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 Quote: Cupric fluoride decomposes around 500°C, and the chloride and bromide at somewhat lower temperatures
but I'm pretty sure CuCl<sub>2</sub> decomposes @ 993°C!

Theoretic
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Decomposition of nitrogen trichloride...
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Bleaching powder is Ca(OCl)2. We had a big jar of Ca(OCl)2 that was used for swimming pools. That was over 20 years ago and I haven't seen any Ca(OCl)2 in stores that sell pool supplies in the last 20 years. The pool "chlorine" sold now is usually trichlorotriazinetrione.
Organikum
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bleaching powder

MERCK:
Improperly called " chloride of lime" or "calcium oxychloride". A relatively unstable chlorine carrier in solid form; a complex chemical compd of indefinite composition, presumably consisting of varying proportions of Ca(OCl)2 , CaCl2 , Ca(OH)2 and H2O in its molecular structure. Maximum available chlorine content approaches 39%. Commercial products usually range between 24% and 37% of available chlorine.

Available at every better sorted drugstore where I live.

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Geomancer
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IIRC, bleaching powder has other crap in it, too. The 'net seems to think calcium chloride. I have a big jug of stuff in my basement that claims to be 68% hypochlorite. It's called "Shock It". I bought it a couple of years ago, but I think it should still be available in the US. I suspect the impurities are the hydroxide and chloride, but I'm not sure. It generates chlorine well enough, though. The same company makes an enhanced product with (I think) a 75% concentration.
Mumbles
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76% actually i believe. I've heard that the other 24%/32% was water in the hypochlorite's crystal structure. It wouldn't suprise me if there was Calcium Chloride and Hydroxide in it though. I am assuming it is made the same way that NaOCl(caustic soda with Chlorine bubbled in).

I know for a fact it's still available in the US. I saw it at the hardware store no more than 3 hours ago. It's made by HTH. "Shock-it" is the normal 68% and "Super Shock-it" is the enhanced one.
chloric1
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Hey Polverone

 Quote: Originally posted by Polverone I mentioned in another thread that according to a journal article I read, dry Cl2 could be produced by heating dry calcium hypochlorite with cobalt salts (or cobalt/iron salts) as a catalyst. [Edited on 1-4-2004 by Polverone]

I have seen this before and I was wondering what conditions are necessary for the catalyst. Preparation,ratios, activation what type of substrate, if any, was the catalyst deposited on. I have a small amount of cobalt sulfate and I could precipitate Co(OH)3 with hypochlorite then warm to 300C to dry to oxide. Then I would soak in Ferric Nitrate with tarce nitric acid and roast it with a large propane torch. This would deposit ferric oxide on cobalt oxide. I could also use both nitates on diatamaceous earth and perform the same roasting. Calcium hypochlorite can be bought for $10-$15 for 5 pounds in spring and summer and I could use this easy method. Also, if you could list the reference.

THanks

In the theater of life its nice to know where the exit doors are located.
Polverone
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It was a homogeneous catalyst. There was no special preparation that I recall. I originally read it in an English translation of The Journal of Applied Chemistry of the USSR, and it was from an issue from the 1950s or early 1960s. Not very specific, I know! I shall try to locate the article again.

[Edited on 1-25-2004 by Polverone]

PGP Key and corresponding e-mail address
kryss
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Cl2 from TCCA

the beauty of using di-chloro- isocyanurates is that they generate Chlorine in Situ, avoiding all the hassle you get with handling Chlorine gas.So eg if its NCl3 your interested in making, you'd mix the DCI with a slightly ammonium salt, and hopefully get your product. IF you make up a solution of it in water over days it'll start smelling of chloramine as it reacts with ammonia in the air so can see no reason why this wouldnt work.
Theoretic
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There's no ammonia in air.
Organikum
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And TCCA is TRI-chloro-isocyanuric acid not DI-chloro btw.....
Organikum
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After doing some exoeriments with bleaching powder and HCl and H2SO4 for producing chlorine with very unsatisfying results btw. I changed to electrolysis of HCl - with even more dissatisfaction.

-> Rolling Stones: I can get no....

F**k!

The chlorine was meant to be used for organic chlorinations (toluene...) and also for anorganic uses (Sn -> SnCl4 etc.).
Anyways, chlorine produced by the above named ways works lousy - or not at all.

Huh?
Thats exactly what I thought.
After exploiting the hypothesis that all chemistry is a fraud - there are many good reasons to believe this, I started over with research and found out.....

.....found out that all above named ways produce chlorine admixed with oxygen/hydrogen. And at least in organic chlorinations already small amounts of oxygen will fuck up the reaction. Also in inorganic chemistry the impurities seem to be at least "unfavorable".

My next try is to make chlorine from the electrolysis of zinc-chloride (actually my first idea - how funny...) which is told to produce chlorine free from oxygen and hydrogen.
We will see.
And I will tell.

Remark: Also impure chlorine is not healthy at all! Cough, cough.......
Proteios
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pah.... lightweights!

before i turned professional.... by far the most fearsome Cl generator i made was.....

1/4 fill a wine making bottle (demijorn) with FeSO4 (cheap, freely available (by the kg!) from garden centres), gurgle common domestic bleach onto this (NaOCl soln). Cl comes off like the clappers. Get yourself a bung and some tubing, a little CaCl2 from drying and u got it made. Cl hardened all the tubing i ever got hold of as a kid. As for how it works..... meh.... never really did figure it out.... but the Fe II goes from green 2 brown..... so there something else going on other than the acidity of the Fe.

basically this outclasses any other Cl gerenator i ever made is the sheer volume of Cl that can be made, the convenience, and the controlability.

Happy hunting!

[Edited on 14-4-2004 by Proteios]

[Edited on 14-4-2004 by Proteios]
t_Pyro
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Proteios: The reaction you stated most probably is a redox reaction between Fe<sup>2+</sup> ions and Cl atoms in the +1 oxidation state. Fe<sup>2+</sup> is oxidised to Fe<sup>3+</sup>, and Cl<sup>+</sup> reduced to Cl. 2Cl->Cl<sub>2</sub>.

My choice of preparation of chlorine would be the electrolysis of concentrated NaCl solution, drying the Cl<sub>2</sub> by passing through a drying tower packed with fused calcium chloride, and collect the gas by the downward displacement of oil, or some other non-reactive liquid. The choice of oil would also be important: if it contains too many double bonds, you might end up chlorinating the oil. Maybe benzene could also be used instead...
Organikum
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I choose the ZnCl2 electrolysis as it produces quite pure Zn which is useful for me in other reactions and - last not least - NaCl electrolysis produces chlorine which is NOT free from oxygen/hydrogen. (after what I read on this subject).

The FeSO4 + bleach is nonsense.
The NaCl electrolysis would work but not for my purposes.

[Edited on 14-4-2004 by Organikum]
Organikum
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Bleaching powder + water + FeSO4:

Doesnt even SMELL like chlorine.

The same bleaching powder + water + H2SO4 produced an instant strong chlorine stench, as did HCl.

Dear Proteios, only teenagers call others "lightweights" and speak like "before I went professional" - those real in the know dont have to show off like this.

Have a nice day, be a little more careful in what you post in future - somebody might get hurt following your "tips".

Irgendwas is ja immer
Organikum
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Ok. Retried it with liquid bleach and some chlorine stench was produced this time. (from FeSO4 and bleach) but no serious amounts. I guess this is the most lousy way to produce impure chlorine known. There was no chlorine visibly evolved - ya know this green/yellow stuff.

Somehow I believe the iron might love to react with the chlorine - doesnt it?

Irgendwas is ja immer
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 Sciencemadness Discussion Board » Fundamentals » Chemistry in General » Chlorine 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