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4-Stroke
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[*] posted on 19-11-2024 at 12:12
Cheapest Source of Chlorine


Hello. I am wondering what the cheapest source of chlorine is. It seems like calcium hypochlorite and TCCA are most often used by amateurs to generate chlorine. They both are, however, expensive. Where I live, TCCA costs about $8 per kilogram (when bought in 10kg tubs, the largest size available in Canadian Tire), and calcium hypochlorite costs about $5 per kilogram (when bought in 18kg tubs, also the largest size available). Calcium hypochlorite is a little cheaper, but requires more hydrochloric acid, so the cost comes out pretty much equal. Muriatic acid costs about $16 per 4L. Both TCCA and Ca(OCl)2 have around ~50% chlorine available by mass, so the total cost per kg of chlorine gas generated is close to $20 per kilogram. Even when bought in bulk (>1000kg), TCCA costs about $1 per kg, and so does Ca(OCl)2. But that still is expensive. If only there was a way to convert chloride ions into chlorine ions... Oh wait there is :D. But while electrolysis is the preferred industrial method for chlorine generation, it is hard to perform for an amateur on any useful scale. Sodium hypochlorite cells are available on Alibaba for reasonably cheap, but all of them are meant for chlorinating pools, and thus have a very low output concentration (around 0.8%). Concentrating large amounts of it is not an easy task. Moreover, about 4kW/h is required for each kg of chlorine generated. Electricity is not always available (or even if it is, accesses to tens of thousands of watts is not easy to get regardless). And even if one manages to produce enough concentrated sodium hypochlorite, HCL is still required to generate chlorine gas (which at a price of $4 per liter for a 31.45% solution defeats the whole purpose of generating cheap chlorine). I wanted to know, is there any process that uses heat (molten salt electrolysis?) to produce chlorine? Considering that wood contains about 5kW/h of "power" per kilogram, is readily available for free if one lives near a forest, and the efficiency of direct heat transfer from combustion is significantly higher than that of gasoline engines, generators, transformers, and electrolytic cells, it seems very lucrative (if viable). If only it was possible to convert a kilo of wood into a kilo of chlorine... :o
So, is it?




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[*] posted on 19-11-2024 at 12:53


The cheapest and more available source to generate chlorine gas, are the one you mentioned in the beginning: TCCA and hypochlorite.

Another way is the oxidation of HCl with manganese dioxide or potassium permanganate.




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[*] posted on 19-11-2024 at 13:16


you can use the weldon process to recycle the MnO2 after reaction with Hcl it forms the weldon mudd. MnCl2 +2CaOH heating to 55C and bubling air throught it forms Caliummanganite CaMnO3 it reacts like KMnO4 with HCl no heating only droping it in the acid. This process was used from 1865 to somewhat late 1920s. The CaCl2 is essecial for the process it helps desolfe the manganchloride the more CaCl2 the more % yield less works faster but less yield. Somewhere i have an table how much hours but i think it was less then 12hours for 90%
If you have an Kipp you can make with this methode great amounts of Chlorine and you only need CaOH as for regeneration and HCl for the Chlor generation.And they wrote the Weldon process give 35% Chlorine calculated form HCl the older MnO2 methode only 32% or 30% not sure.

[Edited on 19-11-2024 by Alkoholvergiftung]
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[*] posted on 19-11-2024 at 14:50


The main advantage of TCCA over hypochlorite is that the rate of release of chlorine gas is pretty much constant. Hypochlorite generates too much chlorine in the beginning and the rate decays rapidly; it is basically a series of puffs of gas. Another advantage is that the residue (cyanuric acid) has low solubility in water and is easily filtered off.

Check out Leonid Lerner's Small-Scale Synthesis of Laboratory Reagents with Reaction Modeling and Bretherick's Handbook of Reactive Chemical Hazards. The former has a procedure in chapter 15. The latter is exactly what it says.

The downside of electrolysis is hydrogen: it is inflammable and there's too much of it. I chlorinated naphthalene some ten years ago by electrolysing a solution of hydrochloric acid, with ethanol as solvent for naphthalene. It worked fine, there was a yellow oil (chloronaphthalenes plus addition products due to ethanol) at the bottom, but the hydrogen flowing still bothered me.

Perhaps there is a photocatalyst for the decomposition of HCl that could be regenerated by heating alone. Something that takes up hydrogen and leaves chlorine free, with the regeneration process combining the hydrogen with air to form water and leaving the something ready for another run. I don't remember seeing one like that, unfortunately.

Be careful and don't poison yourself or your neighborhood with chlorine gas. It wasn't fun in WWI and it isn't now.




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[*] posted on 19-11-2024 at 18:02


I admit to being surprised at the question.
Chlorine is already one of the cheapest chemicals to make. And the prices you have quoted for HCl, TCCA and Ca(OCl)2 are already very reasonable. The cost of glassware to do the reaction are greater than your material cost by a significant margin.
And it is not like a significant quantity of Cl2 is usually needed.

A much bigger concern than cost is producing (and neutraising) it safely. If someone is cutting costs to this degree, I wonder how many other corners are being cut.
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[*] posted on 19-11-2024 at 19:31


Regarding your “free wood as fuel” idea, this raises the problem that while the wood may be “free” for you in the short term, you’re not considering the externalities. It may not cost you anything to cut down and burn up a whole forest, but by doing so you’ve had a significant impact on the local environment, and you’ve put a lot of CO2 into the air that contributes to global warming. When you factor in the costs of the consequences of climate change- damage to infrastructure, impacts on ecosystems and food chains, agriculture, and human health- burning “free” fuel suddenly starts to look a lot less appealing. Now compare your tree-guzzling monstrosity to a solar powered facility. Sure, the required solar panels are going to have an upfront cost and there will be some environmental impact from extracting the materials needed to make them, but once it’s built, you’d have virtually no operating cost and break even in no time, essentially turning salt into chlorine using sunlight, without any need to raze a forest.

But regardless of all the above, I agree with J. These are very cheap chemicals. You’re going to have a hard time saving money against readily available commodity chemicals that are produced on an industrial scale. If you think they’re too expensive, just work on a smaller scale.




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[*] posted on 19-11-2024 at 20:20


Quote: Originally posted by 4-Stroke  
I wanted to know, is there any process that uses heat (molten salt electrolysis?) to produce chlorine? Considering that wood contains about 5kW/h of "power" per kilogram, is readily available for free if one lives near a forest, and the efficiency of direct heat transfer from combustion is significantly higher than that of gasoline engines, generators, transformers, and electrolytic cells, it seems very lucrative (if viable). If only it was possible to convert a kilo of wood into a kilo of chlorine... :o
So, is it?


You can mix sodium chloride and a metal oxide e.g., iron, strongly heat, and there should be the release of at least some chlorine.

High temperature interactions of metal oxides with NaCl

Edit: Problem with link.

[Edited on 20-11-2024 by Precipitates]
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[*] posted on 19-11-2024 at 21:37


Quote: Originally posted by j_sum1  
I admit to being surprised at the question.
Chlorine is already one of the cheapest chemicals to make. And the prices you have quoted for HCl, TCCA and Ca(OCl)2 are already very reasonable.

Exactly. 4-stroke, I'm using the same materials as you, ie muriatic acid and TCCA from crappy tire. I've tried the hypochlorite, but as bnull notes, the TCCA is just so much more civilised that it's more than worth the slight additional outlay.
I'm not exactly wealthy but with the crappy tire feedstock I could constantly churn out as much chlorine as I'm comfortable being responsible for, for fewer $-per-week than I typically spend on chocolate and cheesy snacks.
How cheap could you possibly want it?
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[*] posted on 20-11-2024 at 00:30


As a hobby chemist I don't count the cost of generating chlorine,
as it's not expensive for the quantities that I use.

My priorities are safety and convenience.
(Both HCl and TCCA should be stored in a ventilated space)
Large volumes of chlorine can be controllably produced in not-too-large glassware, which helps at clean-up time.
Dilute sodium thiosulphate solution in a spray bottle helps with clean-up.

My main concern when generating and using chlorine is that I waste a lot,
which requires gas scrubbing or polluting the air




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[*] posted on 20-11-2024 at 00:53


Or from another perspective...
The cost of sulfuric acid to dry chlorine is greater than the reagents to produce it.
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[*] posted on 20-11-2024 at 11:40


Quote: Originally posted by palico  
The cheapest and more available source to generate chlorine gas, are the one you mentioned in the beginning: TCCA and hypochlorite.

Another way is the oxidation of HCl with manganese dioxide or potassium permanganate.
I know it's the most available, but I am looking for the cheapest. But yes, it seems like you are right so far. But I wonder why Ca(ClO)2 and TCCA cost about the same industrially even though one has significantly more available chlorine.
The main problem with oxidizing HCl is the price and the reusability of the MnO2 (as well as the inefficiency of the conversion).

Quote: Originally posted by Alkoholvergiftung  
you can use the weldon process to recycle the MnO2 after reaction with Hcl it forms the weldon mudd. MnCl2 +2CaOH heating to 55C and bubling air throught it forms Caliummanganite CaMnO3 it reacts like KMnO4 with HCl no heating only droping it in the acid. This process was used from 1865 to somewhat late 1920s. The CaCl2 is essecial for the process it helps desolfe the manganchloride the more CaCl2 the more % yield less works faster but less yield. Somewhere i have an table how much hours but i think it was less then 12hours for 90%
If you have an Kipp you can make with this methode great amounts of Chlorine and you only need CaOH as for regeneration and HCl for the Chlor generation.And they wrote the Weldon process give 35% Chlorine calculated form HCl the older MnO2 methode only 32% or 30% not sure.
Thank you! I'll look into this more. Also do you mean that the yield is 35%?

Quote: Originally posted by bnull  
The main advantage of TCCA over hypochlorite is that the rate of release of chlorine gas is pretty much constant. Hypochlorite generates too much chlorine in the beginning and the rate decays rapidly; it is basically a series of puffs of gas. Another advantage is that the residue (cyanuric acid) has low solubility in water and is easily filtered off.
Yes that's true, and also for some reason the hypochlorite costs about the same as TCCA industrially while having much less available chlorine. But why is cyanuric acid's low solubility an advantage? Doesn't it make it harder to remove from the flask? Apart from it's use as a reagent itself (e.g. for making cyanide) what's the point of filtering it out?

Quote: Originally posted by bnull  
The downside of electrolysis is hydrogen: it is inflammable and there's too much of it. I chlorinated naphthalene some ten years ago by electrolysing a solution of hydrochloric acid, with ethanol as solvent for naphthalene. It worked fine, there was a yellow oil (chloronaphthalenes plus addition products due to ethanol) at the bottom, but the hydrogen flowing still bothered me.
Oh yeah I remember when a couple years ago I had an HHO explosion. But I hope it is possible to mitigate the risk using good ventilation.

Quote: Originally posted by bnull  
Perhaps there is a photocatalyst for the decomposition of HCl that could be regenerated by heating alone. Something that takes up hydrogen and leaves chlorine free, with the regeneration process combining the hydrogen with air to form water and leaving the something ready for another run. I don't remember seeing one like that, unfortunately.
Yeah something like that would be perfect form what I need. Considering the price of HCl (or generating it from sulfuric acid) that would make chlorine generation MUCH cheaper. They used to use the Deacon process, but that requires some extreme conditions which would be hard replicate.

Quote: Originally posted by bnull  
Be careful and don't poison yourself or your neighborhood with chlorine gas. It wasn't fun in WWI and it isn't now.
;)

Quote: Originally posted by j_sum1  
I admit to being surprised at the question.
Chlorine is already one of the cheapest chemicals to make. And the prices you have quoted for HCl, TCCA and Ca(OCl)2 are already very reasonable. The cost of glassware to do the reaction are greater than your material cost by a significant margin.
And it is not like a significant quantity of Cl2 is usually needed.

A much bigger concern than cost is producing (and neutraising) it safely. If someone is cutting costs to this degree, I wonder how many other corners are being cut.
I wouldn't say that it is the cheapest, but yes the price is reasonable. But who doesn't want stuff for cheaper?
Yes, the glassware is more expensive, but I already have it.
For me, the cost usually determines the amount I make :D
Can't a gas mask can substitute for most safety precautions (assuming that nobody else is near during the experiment)?

Quote: Originally posted by Texium  
Regarding your “free wood as fuel” idea, this raises the problem that while the wood may be “free” for you in the short term, you’re not considering the externalities. It may not cost you anything to cut down and burn up a whole forest, but by doing so you’ve had a significant impact on the local environment, and you’ve put a lot of CO2 into the air that contributes to global warming. When you factor in the costs of the consequences of climate change- damage to infrastructure, impacts on ecosystems and food chains, agriculture, and human health- burning “free” fuel suddenly starts to look a lot less appealing. Now compare your tree-guzzling monstrosity to a solar powered facility. Sure, the required solar panels are going to have an upfront cost and there will be some environmental impact from extracting the materials needed to make them, but once it’s built, you’d have virtually no operating cost and break even in no time, essentially turning salt into chlorine using sunlight, without any need to raze a forest.
I absolutely do not support razing forests, and that isn't what I'm proposing. I see no damage in going to the forest once in a while and collecting some wood (no need to even chop down trees, just collect some twigs, dead trees, sticks, or even just take some free firewood that is often available here). Plus, even if I got the money to buy the solar panels, where do I put them? I don't own land (yet). About 100Wh per m2 is a reasonable estimate for solar panels during day in the summertime. That means that 100m2 of square panels could make ~2.5kg of chlorine per hour (during sunny summer days). The upfront cost for 100m2 is quite a lot. You also need the land, permissions, chloroalkali cells... Or just go and get some free wood :D

Quote: Originally posted by Precipitates  
You can mix sodium chloride and a metal oxide e.g., iron, strongly heat, and there should be the release of at least some chlorine.

High temperature interactions of metal oxides with NaCl
[Edited on 20-11-2024 by Precipitates]
Thank you! Do you by any chance have access to the article, because I can only read the abstract :(. Sounds promising it it produces useful amounts of chlorine. How much does it have to be heated?

Quote: Originally posted by paulll  
Exactly. 4-stroke, I'm using the same materials as you, ie muriatic acid and TCCA from crappy tire. I've tried the hypochlorite, but as bnull notes, the TCCA is just so much more civilised that it's more than worth the slight additional outlay.
I'm not exactly wealthy but with the crappy tire feedstock I could constantly churn out as much chlorine as I'm comfortable being responsible for, for fewer $-per-week than I typically spend on chocolate and cheesy snacks.
How cheap could you possibly want it?
Ah nice to see a fellow Canadian! Which province are you in?
I just usually like to make as much as I can (of everything), so cheaper feedstock = more chlorine. Also, TCCA needs less HCl (and has more available chlorine), so it is really more expensive than calcium hypochlorite?
One more question, I remember that in some of them sell a product which is mostly formaldehyde, but I wasn't able to find it here. Is it available where you are?

Quote: Originally posted by Sulaiman  
As a hobby chemist I don't count the cost of generating chlorine,
as it's not expensive for the quantities that I use.

My priorities are safety and convenience.
(Both HCl and TCCA should be stored in a ventilated space)
Large volumes of chlorine can be controllably produced in not-too-large glassware, which helps at clean-up time.
Dilute sodium thiosulphate solution in a spray bottle helps with clean-up.

My main concern when generating and using chlorine is that I waste a lot,
which requires gas scrubbing or polluting the air
I unfortunately don't have the money to not consider the cost of anything I do, so I do consider the cost of chlorine. For me the main priority is price per kilo, but safety is also important (not really convenience). Why do you waste chlorine?

Quote: Originally posted by j_sum1  
Or from another perspective...
The cost of sulfuric acid to dry chlorine is greater than the reagents to produce it.
Sulfuric acid isn't the only thing that can be used to dry it (e.g. CaCl2 works well too), and it can be regenerated as it is just diluted, not used up. Plus, industrially, sulfuric acid is very cheap (about $200 per ton, compared to $1000 for TCCA), so it is a lot cheaper than the chlorine it dries.



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[*] posted on 20-11-2024 at 13:38


Yes i think counted on HCl.
Reaction :6 HCl + MnO₂CaO = MnCl₂ + CaCl₂ + Cl₂ + 3 H₂O
They wrote the Weldon chlorine is purer than with natural MnO2 and CO2 free.
The Calciummagnite is an black water insoluble substance.The higest yield was 6 parts CaCl2 pressent give 95% if you have only CaCl2 1 part to one part MnCl2 pressent you only reach 50% but in an hour.It is the solvent for the CaO and the MnCl

There are two Weldon process this one with Weldon mud and the
Weldon Pechiney's process : Magnesiumoxychlorid=Magnesiumchloride solution mixed with MgO 1,3 part MgO to 1 MgCl2 .Than dryd at 260C after it was dried brocken heated to 300C yield 50% but i dont think thats something for home use.

[Edited on 20-11-2024 by Alkoholvergiftung]
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[*] posted on 20-11-2024 at 18:56


Quote: Originally posted by 4-Stroke  
But why is cyanuric acid's low solubility an advantage? Doesn't it make it harder to remove from the flask? Apart from it's use as a reagent itself (e.g. for making cyanide) what's the point of filtering it out?
You don't have to boil the solution or wait a lifetime until water has gone to discard the stuff. To remove residues from the flask use a solution of an alkaline carbonate or hydroxide.

Quote: Originally posted by 4-Stroke  
For me, the cost usually determines the amount I make :D
The amount should be determined by necessity. It skips the whole hassle of storage, purification if the substance degrades with time, disposal of residues, dealing with accidents. When I need chlorine, I take a chip off the TCCA block and use it. If I were to make chlorine gas and store it, I would need a suitable container and all the precautions that involve safe storage of a toxic gas. The same applies to sulfur chlorides; if you need them, make just enough. You don't cook twenty pounds of pasta at once for the whole month. You cook just enough to eat for a day or two. At least that's my policy.

Edit: You're not thinking about making mustard gas, are you? Ethylene, sulfur chlorides, cheap large scale manufacturing for amateurs, that book on chemical weapons... I find the coincidence quite amusing (but it probably isn't).

[Edited on 21-11-2024 by bnull]




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[*] posted on 20-11-2024 at 20:16


Quote: Originally posted by 4-Stroke  
Thank you! Do you by any chance have access to the article, because I can only read the abstract :(. Sounds promising it it produces useful amounts of chlorine. How much does it have to be heated?


Attachment: High_Temperature_Interactions_of_Metal_Oxides_with_NaCl.pdf (807kB)
This file has been downloaded 11 times

I've no idea how much chlorine it will produce, but from the equations, it looks somewhat promising:

2 NaCl + 1/2 O2 <-> Na2O + Cl2

Chlorine produced will boil off, shifting the equilibrium to the right.

1100-1200K

So it would be better to turn some of that wood into charcoal, which isn't too difficult, just a bit time consuming.
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[*] posted on 20-11-2024 at 21:00


I think you'd have to make an awful lot of chlorine to pay off the equipment you use to generate it in any case, regardless of how it's generated.

I think you could easily regenerate MnO2 by:

MnCl2 (aq) + Na2CO3 (or NaHCO3) >> MnCO3 (s) + 2 NaCl (aq)

MnCO3 + heat + O2 >> MnO2 + CO2

Wiki says the latter reaction gives "a mixture of Mn (II) and Mn (IV) oxides", which is probably still enough to make more chlorine.




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[*] posted on 20-11-2024 at 22:29


Quote: Originally posted by 4-Stroke  

Quote: Originally posted by paulll  
Exactly. 4-stroke, I'm using the same materials as you, ie muriatic acid and TCCA from crappy tire. I've tried the hypochlorite, but as bnull notes, the TCCA is just so much more civilised that it's more than worth the slight additional outlay.
I'm not exactly wealthy but with the crappy tire feedstock I could constantly churn out as much chlorine as I'm comfortable being responsible for, for fewer $-per-week than I typically spend on chocolate and cheesy snacks.
How cheap could you possibly want it?
Ah nice to see a fellow Canadian! Which province are you in?
I just usually like to make as much as I can (of everything), so cheaper feedstock = more chlorine. Also, TCCA needs less HCl (and has more available chlorine), so it is really more expensive than calcium hypochlorite?
One more question, I remember that in some of them sell a product which is mostly formaldehyde, but I wasn't able to find it here. Is it available where you are?

Brit in AB. I understand the warm-and-feelies of maximum efficiency, but as I hinted and Sulaiman elaborated-upon, the chances that you're going to use the chlorine, let alone the reagents, at anything like 100% efficiency are zero. Even if you wanted to set a more reasonable efficiency goal, chlorine is so cheap to make that it's never going to be worth the ballache compared to giving your attention to whatever you're using the chlorine *for*. OTOH, there is very much such a thing as too much chlorine. Priorities are safety and convenience.
Cig-packet calculation for doing it OTC in Canada, the hypochlorite comes in a bit cheaper, especially with those small bags of the stuff, but even figuring-in the annoyance of breaking up TCCA tablets, not worth it; You can get it running comfortably and be free to monitor what you're *doing* with the chlorine for an extended period - maybe even read a book and take in the same rays as your chlorine lol.
Home Hardware do a, I think it was RV Septic Flush? Towing your own toilet is such a popular pastime that it's hard to keep up, but it was in a "gallon" jug that looks like the Klenk's acetone, clear liquid, high formaldehyde and looked not to have anything in it that would be hard to get rid of. I passed it up as I'd just got some from a lab supplier but it is a thing. Look in Home Building Supply, rather than HH.
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[*] posted on 20-11-2024 at 23:53


clearly_not_atara this reaction was used before the weldon process but you need to heat the MnCO3 to 200-300c and the powder was pressed into prills but the brills where to birttl and releases to much chlorine at once and the amount of Chlorine was smaller because of the oxide mix. More HCl needed.
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[*] posted on 21-11-2024 at 01:52


Quote: Originally posted by 4-Stroke  
...Why do you waste chlorine?...

1) due to impatience and/or inattention combined with sub-optimal equipment configurations,
I usually had unreacted gas escaping when bubbling chlorine
2) to compensate for this I put excess TCCA in the gas generator,
because adding TCCA during operation is undesirable,
so I have to waste some of my potential chlorine source whether it is used or not.
3) if reacting with solids the ratio of lost to used chlorine was massive
(sorry, no data but I think more than 10x wasted compared to used due to my poor procedures)

For most of my experiments I'm not really interested in efficiency,
my main concerns are
A) can I do it: cost/safety etc., B) can I test and purify it, C) how do I dispose of my waste.
.............................
I'm having difficulty understanding your requirements because you mention budget constraints, and large scale production of chlorine and ( in another thread) ethylene.
Maybe you could explain your actual requirements?




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[*] posted on 21-11-2024 at 11:17


Quote: Originally posted by bnull  
Quote: Originally posted by 4-Stroke  
But why is cyanuric acid's low solubility an advantage? Doesn't it make it harder to remove from the flask? Apart from it's use as a reagent itself (e.g. for making cyanide) what's the point of filtering it out?
You don't have to boil the solution or wait a lifetime until water has gone to discard the stuff. To remove residues from the flask use a solution of an alkaline carbonate or hydroxide.
Wait I might be missing something, but why does the water have to be gone before discarding the stuff?

Quote: Originally posted by bnull  
The amount should be determined by necessity. It skips the whole hassle of storage, purification if the substance degrades with time, disposal of residues, dealing with accidents. When I need chlorine, I take a chip off the TCCA block and use it. If I were to make chlorine gas and store it, I would need a suitable container and all the precautions that involve safe storage of a toxic gas. The same applies to sulfur chlorides; if you need them, make just enough. You don't cook twenty pounds of pasta at once for the whole month. You cook just enough to eat for a day or two. At least that's my policy.
Fair enough. But I am not planning to store the chlorine itself (I don't need a container with trench air freshener blowing up at my home :D), I am only planning to store the TCCA (or whatever else I could use to generate chlorine) and the product (most likely sulfur chloride) which is made out of the chlorine. Your point about the decomposition is a good once, I haven't thought about that much before, so I might actually have to not store much sulfur chloride for long (although, how fast does S2Cl2 really decompose in the dark at low temperatures?). But I need to store TCCA not because I "need" to, but because it is just simply much cheaper to buy it in bulk.

Quote: Originally posted by bnull  
: You're not thinking about making mustard gas, are you? Ethylene, sulfur chlorides, cheap large scale manufacturing for amateurs, that book on chemical weapons... I find the coincidence quite amusing (but it probably isn't).
I'm not planning to "mass-produce" it, that's for sure. Might I purely hypothetically perform a test-tube scale synthesis of it someday? Perhaps. Am I going to start "large scale" production of sulfur mustard? No. As you have already noticed, I am interested in chemical weapons, so I would be dumb of me to pretend like what I am asking is completely unrelated to that, but I am not trying to mass produce mustard gas. And I don't think that accusing me of doing so is very nice. Even if I was some "terrorist", what's even the point of making sulfur mustard? There are so many CWs that are incomparably better than mustard gas. Many of them aren't even much harder to make. I am simply asking what I ask out of curiosity, ok? I really don't want to offend you, bnull, but please don't accuse me of trying to make sulfur mustard.



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[*] posted on 21-11-2024 at 13:28


I'm being forced to use the phone now because of a botched update (thanks, Microsoft), so I'll answer the questions by numbers.

1. I believe solids are usually easier to discard than solutions. It has been my policy for more than twenty years. Solutions are subject to spillage (which may be a mess to clean up) and it is not a good idea to dump everything in the sewers or soil. Calcium chloride and cyanuric acid may alter the population of bacteria in the soil (cyanuric decreases nitrification, for example).

2. TCCA also decomposes. Not as fast as calcium hypochlorite, of course.

3. Oh, come on... Every time I see an organic reagent, I think of all the possible uses (at least those I can remember). When you asked about sulfur chlorides, one of my first thoughts, right after "chlorinations", was "mustard gas". It was so obvious that I thought, "five bucks he'll come up with ethylene next". And you did! :P You, possibly playing Fritz Haber Jr. in the middle of Canada. It was surreal.

No, I'm not accusing you. As for the dumbness, I've shared the world with mankind long enough to understand that there is no "I'm not so dumb" when it comes to doing dumb things. If there is a chance that someone will do something really stupid, someone will certainly do. Detritus has plenty of examples of cooks and kewls and deeply misguided ideas. And what if you were really after the stuff? I wouldn't stop you from receiving a Darwin Award, trust me. What is it to me?

Would you buy one ton of TCCA just because it is cheaper than buying the stuff when needed? Where would you store all that? How can you guarantee the quality of the stuff after time has passed? Would you be able to eventually consume one ton of TCCA before expiry date? The (let's say) fifteen percent more that you pay for an individual (and fresh) TCCA tablet more than covers for all that and the headache you would have with the cheaper one ton.

Again, be careful. If you need help (most probably the "it ain't gonna work like that", Devil's Advocate part), I'm here.

Edit: The update unbotched itself. Weird.

[Edited on 21-11-2024 by bnull]




Quod scripsi, scripsi.

B. N. Ull

P.S.: Did you know that we have a Library?
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[*] posted on 21-11-2024 at 14:32


Quote: Originally posted by Alkoholvergiftung  
Yes i think counted on HCl.
Reaction :6 HCl + MnO₂CaO = MnCl₂ + CaCl₂ + Cl₂ + 3 H₂O
They wrote the Weldon chlorine is purer than with natural MnO2 and CO2 free.
The Calciummagnite is an black water insoluble substance.The higest yield was 6 parts CaCl2 pressent give 95% if you have only CaCl2 1 part to one part MnCl2 pressent you only reach 50% but in an hour.It is the solvent for the CaO and the MnCl

There are two Weldon process this one with Weldon mud and the
Weldon Pechiney's process : Magnesiumoxychlorid=Magnesiumchloride solution mixed with MgO 1,3 part MgO to 1 MgCl2 .Than dryd at 260C after it was dried brocken heated to 300C yield 50% but i dont think thats something for home use.
Ah ok, thank you! I don't think that 300°C is really that hard to achieve (sulfuric acid boils at 337°C), so it might actually be viable for home use :D

Quote: Originally posted by Precipitates  
I've no idea how much chlorine it will produce, but from the equations, it looks somewhat promising:

2 NaCl + 1/2 O2 <-> Na2O + Cl2

Chlorine produced will boil off, shifting the equilibrium to the right.

1100-1200K

So it would be better to turn some of that wood into charcoal, which isn't too difficult, just a bit time consuming.
Thank you very much! How did you get access to it? Turning salt into chlorine would really be very cool, and the temperatures are pretty easy to achieve with charcoal. Maybe even wood will work (if well dried and insulated)? But thank you very much for the article :D

Quote: Originally posted by clearly_not_atara  
I think you'd have to make an awful lot of chlorine to pay off the equipment you use to generate it in any case, regardless of how it's generated.
Well, how much is an "awful lot"? Maybe it's within what I am willing to make.

Quote: Originally posted by paulll  
Brit in AB. I understand the warm-and-feelies of maximum efficiency, but as I hinted and Sulaiman elaborated-upon, the chances that you're going to use the chlorine, let alone the reagents, at anything like 100% efficiency are zero. Even if you wanted to set a more reasonable efficiency goal, chlorine is so cheap to make that it's never going to be worth the ballache compared to giving your attention to whatever you're using the chlorine *for*. OTOH, there is very much such a thing as too much chlorine. Priorities are safety and convenience.
Cig-packet calculation for doing it OTC in Canada, the hypochlorite comes in a bit cheaper, especially with those small bags of the stuff, but even figuring-in the annoyance of breaking up TCCA tablets, not worth it; You can get it running comfortably and be free to monitor what you're *doing* with the chlorine for an extended period - maybe even read a book and take in the same rays as your chlorine lol.
Home Hardware do a, I think it was RV Septic Flush? Towing your own toilet is such a popular pastime that it's hard to keep up, but it was in a "gallon" jug that looks like the Klenk's acetone, clear liquid, high formaldehyde and looked not to have anything in it that would be hard to get rid of. I passed it up as I'd just got some from a lab supplier but it is a thing. Look in Home Building Supply, rather than HH.
What do you mean by "maximum efficiency"? Do you mean that if I use 1kg of TCCA and add an excess of HCl I won't get ~900g of Cl2?
I am planning to use the chlorine mostly for making sulfur chlorides, so yes, while chlorine isn't really that expensive compared to other reagents, compared to sulfur, it is multiple times more expensive, so that's why I'm trying to minimize the cost.
Ah ok, thank you very much! I'll check if we have that here because I've been needing formaldehyde for quite a while now and it would be great if I could find a source for it.

Quote: Originally posted by Sulaiman  
Quote: Originally posted by 4-Stroke  
...Why do you waste chlorine?...

1) due to impatience and/or inattention combined with sub-optimal equipment configurations,
I usually had unreacted gas escaping when bubbling chlorine
2) to compensate for this I put excess TCCA in the gas generator,
because adding TCCA during operation is undesirable,
so I have to waste some of my potential chlorine source whether it is used or not.
3) if reacting with solids the ratio of lost to used chlorine was massive
(sorry, no data but I think more than 10x wasted compared to used due to my poor procedures)

For most of my experiments I'm not really interested in efficiency,
my main concerns are
A) can I do it: cost/safety etc., B) can I test and purify it, C) how do I dispose of my waste.
.............................
I'm having difficulty understanding your requirements because you mention budget constraints, and large scale production of chlorine and ( in another thread) ethylene.
Maybe you could explain your actual requirements?
Ah I see. But I hope that when making sulfur chlorides (which I need the chlorine for) the chlorine will be utilized more effectively as even if it is used in excess, the disulfur dichloride can be further converted into sulfur dichloride. The sulfur is also going to be molten, so I think it should react better than a solid would.



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[*] posted on 21-11-2024 at 14:47


Quote: Originally posted by Alkoholvergiftung  
clearly_not_atara this reaction was used before the weldon process but you need to heat the MnCO3 to 200-300c and the powder was pressed into prills but the brills where to birttl and releases to much chlorine at once and the amount of Chlorine was smaller because of the oxide mix. More HCl needed.

Well, that is the difficulty with cheap, isn't it? You get what you pay for. :P

But I don't quite understand why you would press the powder. Why not just use it as a powder?




Quote: Originally posted by bnull  
you can always buy new equipment but can't buy new fingers.
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[*] posted on 21-11-2024 at 15:47


Quote: Originally posted by bnull  
1. I believe solids are usually easier to discard than solutions. It has been my policy for more than twenty years. Solutions are subject to spillage (which may be a mess to clean up) and it is not a good idea to dump everything in the sewers or soil. Calcium chloride and cyanuric acid may alter the population of bacteria in the soil (cyanuric decreases nitrification, for example).
Yeah fair enough. Though cyanuric acid specifically is pretty useful for making cyanide, while calcium chloride should be pretty safe to just dump somewhere (they put it on the roads anyway).

Quote: Originally posted by bnull  
2. TCCA also decomposes. Not as fast as calcium hypochlorite, of course.
Yes of course, but considering that calcium hypochlorite has a shelf life of ~2 years (I think), TCCA should last for a few years at least.

Quote: Originally posted by bnull  
3. Oh, come on... Every time I see an organic reagent, I think of all the possible uses (at least those I can remember). When you asked about sulfur chlorides, one of my first thoughts, right after "chlorinations", was "mustard gas". It was so obvious that I thought, "five bucks he'll come up with ethylene next". And you did! :P You, possibly playing Fritz Haber Jr. in the middle of Canada. It was surreal.
I've actually asked about making ethylene earlier, even before asking about sulfur chlorides, but you guessed right :P

Quote: Originally posted by bnull  
No, I'm not accusing you. As for the dumbness, I've shared the world with mankind long enough to understand that there is no "I'm not so dumb" when it comes to doing dumb things. If there is a chance that someone will do something really stupid, someone will certainly do. Detritus has plenty of examples of cooks and kewls and deeply misguided ideas. And what if you were really after the stuff? I wouldn't stop you from receiving a Darwin Award, trust me. What is it to me?
Yes, this is definitely true. Many people are very "misguided". But it sure is good to know that I am not one of them :D
But honestly, I don't think that making mustard gas without killing yourself is really that hard. It's not like it's sarin or anything. Just get a gas mask, a hazmat suit, and don't spill it on yourself. I'm pretty sure that only about 1% of those deliberately gassed with it during WWI actually died as a result.

Quote: Originally posted by bnull  
Would you buy one ton of TCCA just because it is cheaper than buying the stuff when needed? Where would you store all that? How can you guarantee the quality of the stuff after time has passed? Would you be able to eventually consume one ton of TCCA before expiry date? The (let's say) fifteen percent more that you pay for an individual (and fresh) TCCA tablet more than covers for all that and the headache you would have with the cheaper one ton.
Oh, if it was only 15% more expensive at the hardware store, I wouldn't even consider buying a ton of it! The problem is, the difference is about 8 times. It costs over $8 per kg in Canadian Tire, while on Alibaba, it is somewhere around a $1 per kg. Yes of course there is also shipping and fees, but it is still way under $2 per kg. That's like five times cheaper. And some supplies have a minimum order even less than a ton (maybe a couple hundred kilos). Yes, there are of course issues with storage and such, but these are solvable. Seal it real well and hide it in a forest, or if you own land, just store it at home (or a shed/storage). A ton of it will take up less space than a fridge.

Quote: Originally posted by bnull  
Again, be careful. If you need help (most probably the "it ain't gonna work like that", Devil's Advocate part), I'm here.
Thank you :D



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[*] posted on 21-11-2024 at 16:09


TCCA for chlorine is very good but be careful. I don't think you should try to heat the Cl2 generator to get a bit more out. And also don't neutralize any of the waste it's not toxic:
https://www.sciencemadness.org/talk/viewthread.php?tid=10975
https://www.sciencemadness.org/talk/viewthread.php?tid=15816...

Here is a summary thread for different chlorine generators:
https://www.sciencemadness.org/talk/viewthread.php?tid=9713
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[*] posted on 21-11-2024 at 20:15


Quote: Originally posted by 4-Stroke  
How did you get access to it?


Sci-Hub :D
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