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Author: Subject: Apparatus for generating HF
blogfast25
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[*] posted on 18-9-2015 at 12:45


Quote: Originally posted by Upsilon  


4) Dissolving in molten sodium bisulfate. This looks like the most appealing to me, since sodium bisulfate melts at quite a low temperature, but I'm not sure of the extent to which it will actually dissolve.



Fusion of TiO2 with excess NaHSO4 works but can take a while.

Fusion of TiO2 with excess KOH gives potassium titanate. Hydrolysis of the titanate with water gives insoluble 'Ti(OH)4' but when freshly precipitated this 'titanic acid' dissolves easily in 37 % HCl or 50 % H2SO4.


[Edited on 18-9-2015 by blogfast25]




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[*] posted on 18-9-2015 at 13:23


Quote: Originally posted by blogfast25  
Quote: Originally posted by Upsilon  


4) Dissolving in molten sodium bisulfate. This looks like the most appealing to me, since sodium bisulfate melts at quite a low temperature, but I'm not sure of the extent to which it will actually dissolve.



Fusion of TiO2 with excess NaHSO4 works but can take a while.

Fusion of TiO2 with excess KOH gives potassium titanate. Hydrolysis of the titanate with water gives insoluble 'Ti(OH)4' but when freshly precipitated this 'titanic acid' dissolves easily in 37 % HCl or 50 % H2SO4.


[Edited on 18-9-2015 by blogfast25]


That would require significant temperatures, no? And don't molten hydroxides dissolve glass? In that case I would need to find a suitable vessel for such a thing.
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[*] posted on 18-9-2015 at 13:48


Quote: Originally posted by Upsilon  


That would require significant temperatures, no? And don't molten hydroxides dissolve glass? In that case I would need to find a suitable vessel for such a thing.


Melting points only. Of course you need steel (better even nickel) to fuse with KOH.




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[*] posted on 18-9-2015 at 14:16


Quote: Originally posted by Upsilon  
And don't molten hydroxides dissolve glass? In that case I would need to find a suitable vessel for such a thing.


They do, but, apparently, their effect on porcelain is negligible (I've melted KOH in porcelain crucibles without damage to them). My only case of ruining a porcelain crucible was when I was scraping fused pyrosulfate from it too vigorously.

[Edited on 18-9-2015 by ave369]




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[*] posted on 18-9-2015 at 16:25


Quote: Originally posted by ave369  
Quote: Originally posted by Upsilon  
And don't molten hydroxides dissolve glass? In that case I would need to find a suitable vessel for such a thing.


They do, but, apparently, their effect on porcelain is negligible (I've melted KOH in porcelain crucibles without damage to them). My only case of ruining a porcelain crucible was when I was scraping fused pyrosulfate from it too vigorously.

[Edited on 18-9-2015 by ave369]


Sounds good then. I'd like to note that I mixed some titanium dioxide and highly concentrated KOH solution for the fun of it, and it has been mildly fizzing for hours now. Not really sure what it means but I'll let it keep going.
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[*] posted on 18-9-2015 at 17:34


Quote: Originally posted by Upsilon  

Sounds good then. I'd like to note that I mixed some titanium dioxide and highly concentrated KOH solution for the fun of it, and it has been mildly fizzing for hours now. Not really sure what it means but I'll let it keep going.


I tried that years ago with 50 % NaOH and it didn't put a dent in the TiO2. Let me know what you find.

[Edited on 19-9-2015 by blogfast25]




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[*] posted on 18-9-2015 at 17:44


Forgot to mention that I squirted some weak hydrogen peroxide in there as well. It only seems to fizz when I stir it so it's probably just the peroxide decomposing.
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[*] posted on 22-9-2015 at 08:41


Ok, so my little beaker of titanium dioxide and potassium hydroxide has been sitting for several days now. I still saw solid titanium dioxide at the bottom so I figured I should just pull the plug and free up a beaker. Upon adding concentrated HCl to the mixture to neutralize the KOH, however, it bubbled extremely violently. This is not typical of a regular strong base-strong acid reaction. What's happening here?
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[*] posted on 22-9-2015 at 10:44


Maybe the heating up caused by neutralization kicked hydrogen chloride from the solution. Highly concentrated HCl releases the gas even on slight heating.



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[*] posted on 24-9-2015 at 18:32


Quote: Originally posted by ave369  
Maybe the heating up caused by neutralization kicked hydrogen chloride from the solution. Highly concentrated HCl releases the gas even on slight heating.


Possibly. I ended up dumping it out. I think I'm going to try fusion with sodium bisulfate first; I think it's a good idea to try something easier before I dive into using molten KOH. What's the reaction that goes on with molten bisulfate?
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[*] posted on 24-9-2015 at 22:47


Quote: Originally posted by Upsilon  
[...]Upon adding concentrated HCl to the mixture to neutralize the KOH, however, it bubbled extremely violently. This is not typical of a regular strong base-strong acid reaction. What's happening here?
This certainly is not due to HCl bubbling out of solution. Even if it heats up you won't get enough free HCl (remember, most of it is neutralized by the KOH) to bubble out of solution. Even 30% HCl requires near boiling temperatures for loss of HCl and even then, it contains a lot of water vapor as well.

What actually happened is that the KOH-solution absorbed CO2 from the air. If it is allowed to stand in a beaker for several days, even if this beaker is loosely covered, then it can pick up considerable amounts of CO2. Hydroxide in aqueous solution is very eager to pick up CO2:

2OH(-) + CO2 --> CO3(2-) + H2O

So, your solution of KOH turns into a solution of K2CO3.

If you add acid to such a solution, then the carbonate is converted to carbonic acid, which in turn decomposes to water and CO2:

CO3(2-) + 2H(+) --> H2CO3 --> H2O + CO2




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[*] posted on 25-9-2015 at 08:31


Quote: Originally posted by woelen  
Quote: Originally posted by Upsilon  
[...]Upon adding concentrated HCl to the mixture to neutralize the KOH, however, it bubbled extremely violently. This is not typical of a regular strong base-strong acid reaction. What's happening here?
This certainly is not due to HCl bubbling out of solution. Even if it heats up you won't get enough free HCl (remember, most of it is neutralized by the KOH) to bubble out of solution. Even 30% HCl requires near boiling temperatures for loss of HCl and even then, it contains a lot of water vapor as well.

What actually happened is that the KOH-solution absorbed CO2 from the air. If it is allowed to stand in a beaker for several days, even if this beaker is loosely covered, then it can pick up considerable amounts of CO2. Hydroxide in aqueous solution is very eager to pick up CO2:

2OH(-) + CO2 --> CO3(2-) + H2O

So, your solution of KOH turns into a solution of K2CO3.

If you add acid to such a solution, then the carbonate is converted to carbonic acid, which in turn decomposes to water and CO2:

CO3(2-) + 2H(+) --> H2CO3 --> H2O + CO2


That's it, then. It was definitely sitting uncovered for several days. Thanks for the explanation.
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[*] posted on 26-9-2015 at 23:04


In my school I saw a video of glass etching. What they did, is they poured H2SO4 on NaF and put a glass plate on that container so that HF fumes (:o) can etch it. So they let HF fumes into the air. And it wasn't inside glovebox. Maybe not even in fumehood. And it was video by our chemistry book publisher. Without a single warning of how gaseous HF dangerous is.
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[*] posted on 27-9-2015 at 11:36


I love living right near Seattle, I was able to go there in person and buy a whole bunch of chemicals that would have been a pain to get elsewhere.
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[*] posted on 24-12-2015 at 09:49


Quote: Originally posted by DFliyerz  
I love living right near Seattle, I was able to go there in person and buy a whole bunch of chemicals that would have been a pain to get elsewhere.


Considering the low cost of their chemicals, it still advantageous for me even though I am just under 2000 miles from Seattle pottery supply. The low prices more than compensate for transcontinental shipping. Customer service is above par as well.




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[*] posted on 24-12-2015 at 21:49


Quote: Originally posted by chloric1  

Considering the low cost of their chemicals, it still advantageous for me even though I am just under 2000 miles from Seattle pottery supply. The low prices more than compensate for transcontinental shipping. Customer service is above par as well.


When I went there they said that they get a lot of chemistry hobbyists buying stuff from them, and that some of their sales staff actually used to work in pyrotechnics.
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