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Author: Subject: Converting TiO2 to TiCl4 ?
blogfast25
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[*] posted on 1-10-2013 at 14:10


Hmmm.. I seriously wonder if such a Ti(SO4)2 can exist, and how it would be synthesised. Surely a Ti<sup>4+</sup> must have too strong a central electric field to be able to exist in watery solution and would hydrolyse immediately?

[Edited on 1-10-2013 by blogfast25]




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watson.fawkes
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[*] posted on 1-10-2013 at 17:26


Quote: Originally posted by blogfast25  
I seriously wonder if such a Ti(SO4)2 can exist, and how it would be synthesised.
Here's what Kirk-Othmer says.
Quote:
Titanium(IV) sulfate can be prepared by the reaction if titanium tetrachloride with sulfur trioxide dissolved in sulfuryl chloride. [...] It is readily hydrolyzed by moisture and, when heated, changes first to titanyl sulfate [...] and then to TiO2.
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blogfast25
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[*] posted on 2-10-2013 at 08:56


I was thinking of treating anhydrous TiF4 with anhydrous H2SO4 as a displacement reaction.

One thing's for sure: there are other references to Ti(SO4)2 but so far I haven't found any references to its properties. One mentions a nonahydrate but that's GOTTA be nonsense.

Hydrothermal hydrolysis of titanyl sulphate is the basis of the 'sulphate process' for the production of TiO2 from Ilmenite and H2SO4.

And I remain deeply sceptical re the cited green colour: not a single (IV) compound in Group IV b is coloured.

[Edited on 2-10-2013 by blogfast25]




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Chemosynthetic
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[*] posted on 12-11-2013 at 12:39


Well, I lost my old password, so I haven't been able to post, but I was hoping plante1999 would share more of his experiences about the pyrosulfate, titanium dioxide, and sodium chloride method of TiCl4 production. I am curious if he could offer advice on estimation of the mixed melting point, or how he came to conclusion that TiCl4 was produced rather than the liberation of SO3 from the pyrosulfate, which decomposes near its MP.
http://www.inorganicventures.com/advice/fusion-titanium-diox...

I just have not found a reference to this technique and would like to try it, but would prefer a citation of some kind or more info first.
Edit- spoke too soon:
www.sciencemadness.org/talk/viewthread.php?tid=20234

[Edited on 12-11-2013 by Chemosynthetic]
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bismuthate
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[*] posted on 4-12-2013 at 18:02


Would Al or Ga trichlorides (or monochlorides) react with TiO2 to form TiCl4?

[Edited on 5-12-2013 by bismuthate]




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blogfast25
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[*] posted on 5-12-2013 at 13:38


Not at RT, no. TiO2 has a very high Enthalpy of Formation, it is, in other words, very, very stable. At high temperatures and with continuous removal of the TiCl4 it might be possible:

4 AlCl3 + 3 TiO2 < === > 2 Al2O3 + 3 TiCl4 would be pulled to the right if you distilled off the TiCl4, continuously. Not for the faint of heart...

Neither AlCl nor GaCl are particularly stable or practical to work with.




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NAILA2
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[*] posted on 17-11-2015 at 20:35


Anyone please send to paper or journal about synthesis of titanium tetracloride ?
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blogfast25
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[*] posted on 18-11-2015 at 10:44


Quote: Originally posted by NAILA2  
Anyone please send to paper or journal about synthesis of titanium tetracloride ?


Look up 'Kroll Process'.




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[*] posted on 13-7-2019 at 12:59


I found a patent that uses any titanium salt to produce an alkali chlorotitanate that are thermally decomposed at relative low temperatures producing TICl4. Probably a easier method of synthesis, I guess. I have attached the patent below.


Attachment: Titanium tetrachloride from alkali chlorotitanates.PDF (475kB)
This file has been downloaded 402 times

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[*] posted on 14-7-2019 at 05:17


4NaCl + 2SiO2 +2CaSO4+TiO2 ------> TiCl4 + 2CaSiO3 + 2Na2SO4 Temp>1000C
or
2CaCl2 + 2SiO2 +TiO2 ------> TiCl4 + 2CaSiO3 Temp>1000C
second one is better, no CaTio3
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