Sciencemadness Discussion Board - Titanium hydroxide?

Titanium hydroxide?

Ramblesthegoat - 27-5-2012 at 15:44

Hi guys, I was just messing around with some titanium(III) chloride and reacted it with some some sodium bicarbonate. I'm not positive, but I think that the reaction is something along the lines of...

TiCl3+NaHCO3--->Ti(OH)3+CO2+3NaCl

The blackish blue hydroxide decomposes pretty quickly into titanium dioxide and water. I just wanted to know if you guys think I'm right or not, and if not, what compound i have made and what reaction went on. Also, while i'm here, are there any other interesting titanium reactions/experiments that I should try out? I'm quite interested in the chemistry of titanium.

plante1999 - 27-5-2012 at 16:15

If you are interested titanium chemistry you may want to U2U me. You are actually making titanium III oxide hydrate, Which then react with water/disproportionate to hydrous titanium dioxide.

General equation (without water ligant/water of hydratation):

2TiCl3 + 6NaHCO3 -) 2Ti(OH)2O + 6CO2 + 6NaCl + H2

Ramblesthegoat - 27-5-2012 at 16:22

Quote: Originally posted by plante1999

If you are interested titanium chemistry you may want to U2U me. You are actually making titanium III oxide hydrate, Which then react with water/disproportionate to hydrous titanium dioxide.

General equation (without water ligant/water of hydratation):

2TiCl3 + 6NaHCO3 -) 2Ti(OH)2O + 6CO2 + 6NaCl + H2

That actually makes a lot of sense, because i was pretty sure that hydrogen was coming off, but when i tried to fill a test tube with it it wouldn't combust. I'm guessing that that's because of all the CO2.

plante1999 - 27-5-2012 at 16:42

Quote: Originally posted by Ramblesthegoat

Quote: Originally posted by plante1999

Dilute ammonia do a better job for production of hydrous titanium dioxide from titanium III chloride, in bonus It will only make hydrogen gas, no CO2.

blogfast25 - 28-5-2012 at 07:53

Yes, I've seen Ti(OH)3.nH2O too from TiCl3(aq) + alkali. It goes from black to white quite quickly. Solutions of TiCl3 that I kept for years, well stoppered and in the dark, eventually all cleared: presumably to titanyl (IV) chloride.

Plante, can you post more details about your method for TiCl4? TiO2 + pot. pyrosulphate + NaCl?

plante1999 - 31-5-2012 at 03:34

Quote: Originally posted by blogfast25

Plante, can you post more details about your method for TiCl4? TiO2 + pot. pyrosulphate + NaCl?

I'm actually making it, in 1 day I will post it.

blogfast25 - 31-5-2012 at 08:50

Good. Look forward to it.

plante1999 - 3-6-2012 at 06:16

It is know that early titanium dioxide plant used conc. H2SO4 to dissolve titanium dioxide/iron oxide ore. This process made at high temperature produced Titanyl sulphate. Then the sulphate was hydrolysed to get purified hydrous titanium dioxide. Last stage of the process was the calcination of the hydrous oxide.

Why titanium IV sulphate was not produced was becaude of the ''presence'' of water in the H2SO4 since the real disolving agent for the titanium dioxide was the sulphur trioxide.

Making sodium pyrosulphate by heating sodium hydrogen sulphate (pool chem) at 400 degree celcius is a relatively easy process to get the pyrosulphate. Mixing the pyrosulphate with titanium dioxide would produce Titanium IV sulpate in equilibrium with the titanium dioxide. Adding NaCl to the melt will make the reaction go to competition since titanium IV chloride is volatile at 500-600 degree Celsius (the temperature required).

2Na2S2O7 + TiO2 + 4NaCl -) 4Na2SO4 + TiCl4

A borosilicate glass apparatus is suitable for the reaction take note that the flask will be hard to clean after the reaction. Heating can be done with a bunsen or a propane torch.

[Edited on 3-6-2012 by plante1999]

blogfast25 - 3-6-2012 at 08:17

Quote: Originally posted by plante1999

Making sodium pyrosulphate by heating sodium hydrogen sulphate (pool chem) at 400 degree celcius is a relatively easy process to get the pyrosulphate. Mixing the pyrosulphate with titanium dioxide would produce Titanium IV sulpate in equilibrium with the titanium dioxide. Adding NaCl to the melt will make the reaction go to competition since titanium IV chloride is volatile at 500-600 degree Celsius (the temperature required).

2Na2S2O7 + TiO2 + 4NaCl -) 4Na2SO4 + TiCl4

A borosilicate glass apparatus is suitable for the reaction take note that the flask will be hard to clean after the reaction. Heating can be done with a bunsen or a propane torch.

[Edited on 3-6-2012 by plante1999]

I worked in a TiO2 factory (sulpuric acid process) as a chemist (first 'real' job!) some 25 years ago.

I've dissolved commercial TiO2 (Anatase, in this case) by fusing with NaHSO4, in my lab.

But have you actually made TiCl4 by adding NaCl to the mix? It sounds likely possible, as the automatic removal of the volatile TiCl4 pushes the equilibrium to the right.

I've just never heard it mentioned or seen anyone doing it.

blogfast25 - 3-6-2012 at 08:58

Interesting *.pdf for those who love titanium:

http://www.saimm.co.za/Journal/v111n11p781.pdf

From Wiki:

”Major success using magnesium at 1000 °C using a molybdenum clad reactor, as reported to the Electrochemical Society in Ottawa.[4] Kroll's titanium was highly ductile reflecting its high purity.”

1000 C?Blimey, must be high pressure to keep that TiCl4 liquid or am I missing something here?

plante1999 - 3-6-2012 at 08:58

Quote: Originally posted by blogfast25

But have you actually made TiCl4 by adding NaCl to the mix? It sounds likely possible, as the automatic removal of the volatile TiCl4 pushes the equilibrium to the right.

I've just never heard it mentioned or seen anyone doing it.

So it seam that I'm the first one that did this process. I did it on a small scale and condensed 0.3ml of the higly fuming liquid (humid air). Only a small amount of water in the pyrosulphate will spoil the reaction.

I made many other organic/inorganic compound of titanium which are hard to make. This is why I am the master of titanium chemistry on this board....

blogfast25 - 3-6-2012 at 13:51

This reaction should also work for SnO2 === > SnCl4.

plante1999 - 3-6-2012 at 13:57

Quote: Originally posted by blogfast25

This reaction should also work for SnO2 === > SnCl4.

Maybe it would work but I'm not familiar with Tin chemistry...
Titanium tetrachloride is a pretty weird stuff.

blogfast25 - 4-6-2012 at 09:24

SnCl4 is quite similar to TiCl4, actually.

Interesting study here on the possibility of using TiCl3 instead of TiCl4 for the magnesiothermic reduction:

http://www.okabe.iis.u-tokyo.ac.jp/japanese/for_students/par...

[Edited on 4-6-2012 by blogfast25]

plante1999 - 4-6-2012 at 13:28

I already read something similar as this but TiCl3 is actually somewhat hard to make anhydrous, which is required for this reaction. TiCl2 does not worth the work but TiCl3 could be use full for the home chemist since it have a mush lower vapor pressure than TiCl4. I would prefer to use (NH4)2TiCl6 and/or the fluoride variant of this compound. From wath I read Tin seam less prone to hydrolysis than titanium, At lest tin II can form stable compound... But probably in similar way to titanium it would form it's anhydrous chloride.

blogfast25 - 5-6-2012 at 05:59

In the Okabe study the TiClx (x = 2, 3) is produced by reducing TiCl4 with Al, Mg or even Ti.

I have a recipe for (NH4)2TiCl6 somewhere. But reducing that with Mg would cause NH4Cl to be blown off. Could (NH4)2TiCl5 (Ti III) exist and could be thermally decomposed to NH4Cl and TiCl3? It sounds plausible..

Here’s a patent (WO/2009/090513) for TiF3, via (NH4)2Ti(OH)F4:

http://patentscope.wipo.int/search/en/WO2009090513 (I have the full text)

The reduction TiF3 + 3/2 Mg → Ti + 3/2 MgF2 may just about run hot enough to produce the reaction products in the liquid state (otherwise preheating will increase the end temperature sufficiently) But fluorides complicate everything safety wise.

SnCl4 is indeed a bit less prone to hydrolysis than its titanium equivalent. Combined with a little water it even forms a hydrate (aka ‘butter if tin’).

[Edited on 5-6-2012 by blogfast25]

plante1999 - 5-6-2012 at 15:09

I found something quite interesting in kirk-othmer encyclopedia. Titanium III fluoride is quite easily made from titanium anhydrous HF gas at 900 degree Celsius, as you know I already made very safely 9%HF sol from sodium hydrogen sulphate and sodium fluoride. Sodium hydrogen sulphate and sodium fluoride in the dry state in a steel equipment will make anhydrous HF when melted. I already did this process some time ago to make anhydrous HF. (Arggg I need to buy again fluoride... It will be the 12time in my life... It is the reagent which I bought the most time...). The reaction of titanium and hydrogen fluoride produce hydrogen which reduce any Ti IV to TiF3.

[Edited on 5-6-2012 by plante1999]

[Edited on 5-6-2012 by plante1999]

[Edited on 5-6-2012 by plante1999]

blogfast25 - 6-6-2012 at 05:31

Quote: Originally posted by plante1999

Titanium III fluoride is quite easily made from titanium anhydrous HF gas at 900 degree Celsius, as you know I already made very safely 9%HF sol from sodium hydrogen sulphate and sodium fluoride.

"quite easily', plante??? Your 9 % HF is still a million miles away from anhydrous HF.

No, the wet procedure to arrive at TiF3 described in various (very similar) patents is much easier (not to mention infinitely safer!) and achievable at the home lab level.

[Edited on 6-6-2012 by blogfast25]

plante1999 - 6-6-2012 at 07:46

I know I was just stating that HF could be made safely, I actualy made anydrous HF from sodium hydrogen sulphate and sodium fluoride.