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Author: Subject: Chlorine
darkflame89
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[*] posted on 14-8-2004 at 00:38


That precipitate mentioned must have been the NaCl precipitating out of the solution due to the ultra high concentration of chloride ions. You could try again with a higher concentration of NaCl or a higher concentration of HCl(which i doubt).



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[*] posted on 14-8-2004 at 05:59


When i used the words "i have NEVER seen" i was trying to imply that although i thought it theoretically possible for a precipitate to form, my observations supported that it were not probable (at least with common salt and acid).

The salt solution i was using was saturated at room temperature (crystals forming on the surface) and my HCL measures sg1.1+-.01 which corresponds to ~20-24%HCl.

Saturation at 20*C NaCl is 35.9g per 100g H2O or 35.9% this corresponds to .614mol per 100g H2O of Cl- at saturation.

My HCl at an approx concentration of 22% would give a chloride concentration of .603mol per 100g H2O and so irrespective of the amount added could never bring the concentration of chloride ions above the saturation value of .614mol per 100g H2O! :cool:

Of course it might be possible to precipitate NaCl if using a higher concentration of acid - not likely to be obtained OTC (at least in my area) unless purchased from lab supplies!
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[*] posted on 21-8-2004 at 11:46
Chlorine?


Not sure I want to call it a complete success but I am running the generator now. The output is not nearly as I hoped it would be. I am using 5 liters of liquid which is now been adjusted to mostly HCl. Secondly, I feel I do not have complete gastight seals so i baught some better adhesive. I will try it out later this afternoon and wait til it cures(24 hours). I definately notice the odor but it must be small amounts because it does not even burn my eyes! I am running at 8.3 amps for crying out loud:mad::o! I will give it 20 more minutes to overcome the volume of liquid.

Could use unglazed pottery as a diaphragm to concentrate chloride ions at the anode. Most pottery would need a run with epson salts to fill some pores with Mg(OH)2. This may help me control the CL2 and channel it where I need it. Sure would be nice to be able to make homemade hypochlorites and chlorinate chloroform etc. etc:D

[Edited on 8/21/2004 by chloric1]




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mad.gif posted on 21-8-2004 at 12:41
Nevermind


Project abandoned! Power supply shorted out!:mad::mad::mad:!! That was a $100 supply! I thought it had current overload protection. I will have to buy another supply. So, no electrolysis or electronic expereiments for at LEAST a month maybe more. :(:(

I finding out that chemistry is more satisfying in books than in real life! Might just chunk all my gear and stick to the books only! I will just sign up for a chemistry program at the University and experience that way. I surrender:(:(




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[*] posted on 21-8-2004 at 13:06


Either way, that sounds expensive.

John W.
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[*] posted on 21-8-2004 at 13:52
Tell me about it


I would try to sell what I could. I just cant dump nay of my chems.

As far as chlorine goes I think I will just set up ground glassware and use hydrochloric acid with permanganate. I only have about 50% of my ground glassware and I really can't use it yet. IT cost so much if I break something, I am down for weeks or even months:o! I maybe just want to go to a University or work in a lab that way I can damage someone elses property:D




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[*] posted on 22-8-2004 at 02:09


KMnO4 + HCl, MnO2 + HCl, TCCA + HCl, these work just fine, for reasons of availability I prefer the latter method.

Not dripping the HCl ON, but running it to the bottom is advised with TCCA.

Pitch is a perfect sealant for these gasgenerators. PLASTILIN works well as a quickfix - good to have some by hand I learned.




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[*] posted on 22-8-2004 at 09:28
Chlorine


I am sure the comment was only in p****d off mod, but please do not go to university to damage someone elses equipment because other people, especially technicians, also use the equipment and if it is left damaged they can be in danger.
One example of many is someone boiled the 2 gallon acetone recovery still dry out of hours (I plug it into a standard time so after 11/2 hours it turns of if I have forgotten about it and only ever run it to just below half full). They made an attempt to clean some of the black stuff in there and refilled it to set it up for another run. It was obvious thing were not right, after emptying the flask you could see the bottom of the flask had a ring of cracks and looking like a shattered windscreen. Luckily they did not do me for harrisment and threatening behavior after I explained to them against the wall that
1) If you do not know what you are doing do not do it
2) They put me in serious danger
3) There was enough solvent there, if it caught fire, to trash the whole of the labs.
4) The most important was, if the labs were trashed I would be out of a job. There is no way that the place would be refitted as labs because of all rules, regs and costs.
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[*] posted on 26-8-2004 at 18:52


I realize Cl2 is toxic, but just how much. Say about 100 L of Cl2 at 1 atm blows out of an apparatus and is dispersed equally throughout a .5 acre lot how dangerous is it to breath the air there, or is it dispersed too much to be dangerous? I'm not expecting to blow out 100 L of chlorine, but just hypothetically.



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[*] posted on 26-8-2004 at 19:23


I would say that would be quite dangerous. I should convert to ppm and compare to the accepted threshold but I know that would be dangerous.

A liter or two over a .2 sq acre area is excessive as I've had 'spills' this size, the clouds kill the grass at this level in areas and some trees, it will hurt your eyes, make you cough, and possibly cause permanate damage if you are not quick to act.

But can someone give a more specific answer. 100 L over .5 acres would seriously seem like trouble to me.




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[*] posted on 26-8-2004 at 20:36


I did some very rough calculations and if you have a 30m x 30m plot and 1 mol (22.4 L) Cl2 is distributed equally through a height of 2 m, that would be roughly 40 mg/cubic meter. Which would make 1 L only 2 mg/ cubic meter. I don't know how harmful 2 mg/cubic meter. If your property was half the size I calculated then it would be around 4 mg/cubic meter. Are you sure you only had one liter of this stuff, 4 mg/cubic meter doesn't sound that bad, as I read the lowest lethal concentration (LCLO) in humans was 2530 mg/cubic meter, although I may be mistaken. Here's here's the msds with Othe LCLO msds:

http://ptcl.chem.ox.ac.uk/MSDS/CH/chlorine.html

[Edited on 27-8-2004 by Mendeleev]




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[*] posted on 26-8-2004 at 22:28


Chlorine is toxic - yes, but it is to handle easily with good ventilation. A room in the basement without window would be a bad place though to do these experiments.

To kill oneself with chlorine is a hard task, one runs away before it kills you - the stuff hurts.
In WWI chlorine could only be successfully used as a war-gas because they were shooting with machine-guns above so nobody could get up and out of the trenches.

Most gas is evolved during the disassembling of the generator/drying setup. A additional inlet on the generator where a aquarium-airpump or similar can be connected and the system purged before disassemblation circumvents this problem and is advised.

The positive point of chlorines toxity/smell is that you know soon when you have a leak. Have some pitch or PLASTILIN or clay by hand and solve the problem in seconds. Forget hot-glue or other glues and silicone.

Chlorine is easily scavenged OVER lye. All in all it is good to work with, better than with dry HCl. Of course the setup needs some testing and trying - these things never work perfect on first shot.




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[*] posted on 19-9-2004 at 10:33
Contemplation


Well, I have gotten over my hissy fit and had some time to contemplate. I realize I will have to redisgn my apparatus. I may go smaller scale and try a divided cell so I don't have an electrical short. Next time I will use a porous ceramic as a membrane. Aluminum oxide is chemically inert but suffers alkaline attack I think. Hmmm! most ceramics do have some action with alkalies and phosphoric acid. What to choose?:o:o



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[*] posted on 19-9-2004 at 19:54
I had a nice idea typed up....


but it seems my username expired :( Here we go again.

Consider the following.

2H3BO3 + 3Ca(OCl)2 ---> 3Cl2 + 3H2O + Ca3(BO3)2 (solubility anyone?)

One mixes the powdered chems well, puts into standard 2L gas generator, and initiates the reaction with a bit of water. This way should have a much higher Cl2:reactant volume ratio than methods using HCl (max ~37%?)
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[*] posted on 26-9-2004 at 12:46


The best method I is TCCA + dil. HCl.
Using the tabs for swimmingpool desinfection as is, is great.

No heating up.
No suckback.
The tabs dissolve not too fast, so everything stays under control.

Ahhh,goverment takes it away and industry gives better things back.

Love it.

ORG :D




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[*] posted on 26-9-2004 at 13:22


stygian,

A good attempt, but if you count oxygens you'll see they dont balence.

The reason is that you are trying to turn chlorine in oxidation state +1 in hypochlorite into oxidation state 0 in chlorine without a reducing agent. The only way it would work would be to partially decompose the hypochlorite into chloride but then all you are really doing is making HCl a different way.

Using Ca(OCl)Cl , or a mixture of hypochlorite and salt in some water and adding sulphuric acid could work, but then you have the heating problems Organikum was talking about. Volume of gas generator shouldnt be much of an issue unless you are making massive amounts.
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[*] posted on 26-9-2004 at 13:39


Hypochlorites (bleaching powder) and dil. H2SO4 (battery acid 38%) works fine.

Its just that 1 mol hypochlorite provides just one mol Cl2, but TCCA and HCl provide 3 mol Cl2 per 1 mol TCCA and 3 mol HCl.
And the slowl dissolving tablets make TCCA so very nice.




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[*] posted on 26-9-2004 at 13:52
Chlorine


Chlorine is toxic - no doubt about that ! Some of it evolves during my
electrolysis of chlorides into chlorates and subsequently perchlorates.
I live in an apartment(flat) and can easily vent the excess Cl2 into the
atmosphere without problems. I can still smell it and at most it's an
irritant ! Just be sensible about how you handle this 1. As for producing
Cl2 for use from electrolysis, you should
fashion a U-shaped apparatus that will not allow the Cl2 to re-combine
with the brine. If you're using NaCl as the chlorine source you should
get chlorine on 1 electrode and a solution of NaOH on the other.




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[*] posted on 26-9-2004 at 14:27


Organikum, the reaction between TCCA and an acid sounds VERY interesting as Calcium Hypochlorite is not available at pool stores where I live. (I've got one kilogram of chlorinated lime, but I have no supplier for it, so I don't want to use it up).
TCCA however can be got quite easily.

Could you write down the equation TCCA + HCl? I know almost nothing about the chemistry of TCCA, only that it somehow slowly produces chlorine or hypochlorite in the water of swimming pools.
Perhaps we should start a thread about the reactions and chemistry of TCCA?

I just don't feel well producing chlorine with a reaction I can't formulate. ;)
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[*] posted on 26-9-2004 at 16:03
No problem...


TCCA and HCl:

C3Cl3N3O3 + 3HCl = 3Cl2 + C3H3N3O3

TCCA: 232,14 g/mol
HCl: 31% muriatic acid contains about 10 mole Cl per liter (5 mole Cl2)

So take at least 350 ml HCl (31%), better more and dilute it to 15-20%. Add this to 250g TCCA and you will get netto/effective after drying and losses 3 mole Cl2 (70,91 g/mol), thats over 200 gram.

When the HCl is icecold outa the freezer then you can dump the acid over the TCCA, as the evolution of the Cl2 is not sooo fast.

Hey, thats the hit, no shit! :D




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[*] posted on 27-9-2004 at 07:40


Thanks a lot, Organikum!

Now I will buy some TCCA when I'm at "The Home store" next time.

However, HCl is only sold at max. 25% concentration where I live and its rather expensive.
I'm sure that sodium hydrogen sulfate will also work to produce Cl2 from TCCA because it's an acidic salt and its solution in water acts like a mixture of dilute sulfuric acid + sodium sulfate.

The reaction should then go as follows:

2 C3N3O3Cl3 + 6 NaHSO4 ----->
2 C3N3O3H3 + 3 Cl2 + 3 Na2SO4

Is this right?
When yes, I now have access to virtually unlimited quantities of Cl2 for my production of chloral hydrate. :cool:

Another idea, perhaps not so related to the topic:
In pool water, TCCA reacts with water to form hypochlorous acid, which serves as the disinfectant.

C3N3O3Cl3 + 3 H2O ----> C3N3O3H3 +
3 HClO

And now my idea: Could this reavtion somehow be used to convert acetone to chloroform using the haloform reaction?
If yes, we all would have a much better synthesis for chloroform which doesn't use such excessive amounts of bleach! :o
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[*] posted on 29-9-2004 at 06:12


Now I've got a kilo of TCCA and it makes lots of greenish bubbles when it's mixed with HCl. :)

However, it doesn't produce chlorine when NaHSO4 soln is added! :o I don't know the reason, but there is only a slight evolution of colorless gas.
I've got no idea what this is!
So my equation with NaHSO4 is wrong.

But, I think that when NaHSO4 soln is mixed with NaCl soln, the resulting soln contains both H3O+ and Cl- Ions and should therefore also work for producing Cl2 from TCCA.
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[*] posted on 29-9-2004 at 06:18


TCCA is practically inert to sulfuric acid in any concentration.
You can of course make HCl in any of the known ways and vent this to the TCCA.

The concentration of the HCl doesnt matter, 25% is ok as written in my last post. HCl shouldnt be expensive anywhere as it is actually a waste product, look around you for sure will be able to localize a cheaper source.




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[*] posted on 29-9-2004 at 08:00


I can get HCl cheaper and in higher concentration, but only via mail order, and there are always the shipping costs.
I prefer using the 25% HCl as it is available from the Home Store.

I have posted the equilibrium reaction of TCCA with water before.
When NaOH is added to TCCA, would the equilibrium be shifted to the right (formation of Hypochlorite)?
I'm going to try this out!
It would be great if this is an alternative source of hypochlorite!
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[*] posted on 29-9-2004 at 08:58


How about aqua regia? The "aqua regia " equilibrium gives you chlorine, like so:
3HCl + HNO3 <=> NOCl + 2H2O + Cl2.
Heating aqua regia should convert most of HCl to Cl2. To get more bang for your buck, use an excess of whichever acid is more available, this will shift the equilibrium to the right.




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