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Author: Subject: KCl+O3--->KClO3
Zyklon-A
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[*] posted on 20-12-2013 at 14:48
KCl+O3--->KClO3


I have asked this question at least twice, but haven't got an answer, so I'll start a new topic.
I have been trying to oxidise chlorides for a while now, and I think it could be done with ozone.
Desolve 334 g KCl in 1 liter of water, get a homemade O3 generator and bubble O3 through it. You should get over 400 g of KClO3 if it works.
But would it work?




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plante1999
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[*] posted on 20-12-2013 at 14:56


No.



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Zyklon-A
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[*] posted on 20-12-2013 at 15:00


So it just will not work? Why?




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bismuthate
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[*] posted on 20-12-2013 at 15:15


I believe that this would happen.
2KCl+2O3==>Cl2+2KO3
Although I'm not sure.
EDIT actualy I don't believe that happens but I do know KCl is oxidised to release Cl2.

[Edited on 20-12-2013 by bismuthate]




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blogfast25
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[*] posted on 20-12-2013 at 15:15


Quote: Originally posted by Zyklonb  
So it just will not work? Why?


Reaction kinetics are wholly unfavourable. No more favourable than KCl +3/2 O2 === > KClO3

This really belongs in 'beginnings'.




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Zyklon-A
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[*] posted on 20-12-2013 at 15:25


Yes, that is half of the reaction that I was thinking of: KCl+O3-->Cl2+KO3. KO3+H2O--> KOH. Cl2+KOH--> KClO3. (Note: the reactions are unbalanced).



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Zyklon-A
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[*] posted on 20-12-2013 at 15:29


I just thought, ''O3 is a powerful oxidizer, it might work''. Feel free to put it in 'beginnings'.

[Edited on 20-12-2013 by Zyklonb]




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20-12-2013 at 16:06
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[*] posted on 20-12-2013 at 16:26


Bubbling Cl through NaOH would be more efficient if that is the overall effect you were going for (Implied by the reaction you showed).



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Zyklon-A
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[*] posted on 20-12-2013 at 16:42


Ya, I know, I don't have Cl2.



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Pyro
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[*] posted on 20-12-2013 at 16:49


make it...
HCl+TCCA, HCl+Ca(OCl)

PS:Hardly anybody has Cl2. a 454g cylinder costs 325EUR at aldrich!

[Edited on 21-12-2013 by Pyro]




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bismuthate
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[*] posted on 20-12-2013 at 16:58


Or just add HCl to plain old bleach or battery MnO2.



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Zyklon-A
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[*] posted on 20-12-2013 at 17:21


Quote: Originally posted by Pyro  
make it...
HCl+TCCA, HCl+Ca(OCl)

PS:Hardly anybody has Cl2. a 454g cylinder costs 325EUR at aldrich!

[Edited on 21-12-2013 by Pyro]

Crap, that is expensive.




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Zyklon-A
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[*] posted on 20-12-2013 at 17:25


Are you sure the HCl and NaOCl works, I've heard that it doesn't work or is impure.



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[*] posted on 20-12-2013 at 18:01


It does work and impurities won't matter much.



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[*] posted on 20-12-2013 at 18:07


I'm no expert, but I love reading about O3, so thought I'd chime int. ozone rarely adds on as a whole. in most rxn's one oxygen gets used leaving O2 to roam free or decaying to standard O2. so "IF" any reaction was to be seen with (aq) KCl it would likely proceed in single oxygen addition steps.

http://en.wikipedia.org/wiki/Ozone
...."It is also unstable at high concentrations, decaying to ordinary diatomic oxygen (with a half-life of about half an hour in atmospheric conditions): 2 O3 → 3 O2"...

http://en.wikipedia.org/wiki/Ozonide
inorganic: ..." They are very sensitive explosives that have to be handled at low temperatures in an atmosphere consisting of an inert gas"...

organic: ..." Organic ozonides are more explosive cousins of the organic peroxides formed by addition reactions of ozone and unsaturated compounds"...

this was just from wiki so its not a comprehensive presentation of all situations and there may be special cases. I love playing with ozone and it has some very interesting reading(IMO). I have built a few O3 cells and still have one for clearing smells from a room (or small experiments). (3 cats = 3 litter boxes ). quite effective.

this may be something of interest, not sure it's long so I didn't read the whole thing: Method of producing at least one of chlorite, chlorine dioxide and chlorate by combining the reactions of ozonation and electrolytic chlorination
http://www.google.com/patents?hl=en&lr=&vid=USPAT681...

the patent describes the oxidation proceeding in incremental steps as mentioned was likely.
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[*] posted on 20-12-2013 at 18:11


In regards to the MnO2 method, I've had problems getting the chlorine to leave the reaction flask - namely, it's too darn heavy. It just sits there. How could this be remedied? I think if I used a smaller reaction flask, that might help.



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[*] posted on 20-12-2013 at 18:19


You need to heat the MnO2 and HCl mix, else it only make a sligth amount.



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Zyklon-A
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[*] posted on 20-12-2013 at 18:21


I would just stick a glass tube through the stopper all the way down, pull the Cl off the bottom of the flask.



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[*] posted on 20-12-2013 at 18:47


Well if you used a second gas as a "carrier" like H2 is used in a marsh test that might help. You could either make the carrier gas in the mixture or you could bubble it through the solution.



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[*] posted on 20-12-2013 at 19:41


Quote: Originally posted by bismuthate  
Well if you used a second gas as a "carrier" like H2 is used in a marsh test that might help. You could either make the carrier gas in the mixture or you could bubble it through the solution.

Given the reaction between hydrogen and chlorine, that would not end well.

@Plante199: In my experience with battery-grade MnO2, it actually makes a lot after a slow start-up time - so much so that it is hard to find a container big enough to contain the overflow. After this, the chlorine just sits there - hence the question.

[Edited on 12-21-2013 by elementcollector1]




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Zyklon-A
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[*] posted on 20-12-2013 at 19:43


Cl2 and H2 is a very reactive mixture.



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[*] posted on 20-12-2013 at 20:07


<a href="http://en.wikipedia.org/wiki/Activation_energy" target="_blank">Activation energy</a> <img src="../scipics/_wiki.png" />

[edit] <a href="http://youtu.be/NN82GoBG98s" target="_blank">Hydrogen and Chlorine Reaction</a> <img src="../scipics/_yt.png" />

[Edited on 21.12.13 by bfesser]




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[*] posted on 20-12-2013 at 23:59


ya I don't think bismuthate was actually suggesting H2, but was using it as an example in a specific setting. the marsh test. but I like the vid bfesser. cool to see the different LED's used and only the UV one worked. I was kinda expecting the blue light to have a chance to pop it.
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[*] posted on 21-12-2013 at 04:14


violet sin is right. I was thinking of a gas like O2 (very easy to generate) or whatever (in this situation) inert gas that is easiest for the experimenter.
bfesser, thats an amazing reaction. I wonder what would happen if you added HCl to Al and MnO2 (or anything else that produces Cl2) perhaps the H2 and Cl2 would form a pyrophoric mix.




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[*] posted on 21-12-2013 at 06:45


Quote: Originally posted by elementcollector1  
@Plante199: In my experience with battery-grade MnO2, it actually makes a lot after a slow start-up time - so much so that it is hard to find a container big enough to contain the overflow. After this, the chlorine just sits there - hence the question.



It's really just a question of quantities: a small amount of Cl2 in a large vessel will of course just displace the air and that's it.

I found years and years ago that with battery crud the graphite is a real problem because it gets everywhere and the mixture foams terribly. Pure MnO2 is cheap as chips and does make a decent Cl generator but as always you have to plan your stoichiometry well to get what you want. Wash your chlorine gas with water to eliminate HCl.




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