| Pages:
1
2 |
plante1999
International Hazard
Posts: 1936
Registered: 27-12-2010
Member Is Offline
Mood: Mad as a hatter
|
|
synthesis of Ti and Zr halide
recently y made a conc. solution of TiCl3 bi disolving 98%titanium in 37%HCl
2Ti+6HCl->2TiCl3+3H2
and a solution of zirconyl chloride
Zr+4HCl->ZrCl4+2H2
Witch will react with water:
ZrCl4+H2O->ZrOCl2+2HCl
and i want to make
TiF3(insolube titanium salt)
ZrOF2(zirconyl fluoride)
ZrF4(zirconium tetrafluoride)
i have for fluoranating agent:
NaF
but i can made other fluoride, but i think ammonium fluoride is a best fluoraniting agent forTiF3 and ZrF4 but i dont know a way to make ammonium
fluoride.
thanks!
|
|
|
DDTea
National Hazard
Posts: 940
Registered: 25-2-2003
Location: Freedomland
Member Is Offline
Mood: Degenerate
|
|
I would think that hydrofluoric acid would be a better fluorinating agent than ammonium fluoride or ammonium bifluoride simply because it is a liquid.
I would dissolve the oxides of the metals into an HF solution.
However, since I don't like working with HF, I wouldn't *really* recommend this. Fluorinations can be nasty, especially when YOU happen to get
fluorinated!
"In the end the proud scientist or philosopher who cannot be bothered to make his thought accessible has no choice but to retire to the heights in
which dwell the Great Misunderstood and the Great Ignored, there to rail in Olympic superiority at the folly of mankind." - Reginald Kapp.
|
|
|
DJF90
International Hazard
Posts: 2266
Registered: 15-12-2007
Location: At the bench
Member Is Offline
Mood: No Mood
|
|
I think that was the whole point of the metathesis DDTea...
I dont know much about the fluorides of these compounds, but if TiF3 is insoluble, mixing your TiCl3 solution with a saturated solution of NaF should
precipitate out your desired material. I can't help you with the other two however. Be careful with these materials - they may be hydrolysable
fluorides.
|
|
|
plante1999
International Hazard
Posts: 1936
Registered: 27-12-2010
Member Is Offline
Mood: Mad as a hatter
|
|
after mixing naf to TiCl3 a layer of with crystal ave been produce, i thinks its sodium exachlorotitanate because of the yellow solution and
precipitate. I ave realy horror of HF.
but after reading titanium trifchloride for fluoro complex with ammonium fluoride, and after some heating the broduct becaume
TiF3 and ammonium chloride and other nasty thing.
tis is simmilar when zirconnium.
I think for makking(NH4)3ZrF7 heating zirconium in ammonium bifluoride.
I know that about all titanium compound is hydrolised in water.
TiF3:insoluble blue matter witch is wery hard to attak.
Zrf4:insoluble white matter witch is wery hard to attak principale componan of ziblan glass verry corrosiun resistan.
[Edited on 28-12-2010 by plante1999]
Attachment: 30122929-Titanium-Compounds-Inorganic.pdf (441kB)
This file has been downloaded 847 times
Attachment: 30123025-Zirconium-and-Zirconium-Compounds.pdf (313kB)
This file has been downloaded 784 times
Attachment: 30127583-Fluorine-Compounds-Inorganic-Zirconium.pdf (50kB)
This file has been downloaded 539 times
[Edited on 28-12-2010 by plante1999]
[Edited on 29-12-2010 by plante1999]
|
|
|
blogfast25
International Hazard
Posts: 10562
Registered: 3-2-2008
Location: Neverland
Member Is Offline
Mood: No Mood
|
|
For TiF3 there is a really interesting patent that I’ve been meaning to try but haven’t gotten round to yet:
http://www.wipo.int/pctdb/ja/ia.jsp?ia=IB2008%2F055559&I...
It relies on the synthesis of (NH4)2Ti(OH)F4 which is insoluble and after drying is fired at 550C to TiF3, NH3, NH4F and water. If you start from
TiCl3 its even easier…
For ZrF4, treat zirconyl chloride (ZrOCl2.8H2O) in solution with a stoichio amount of NH4F or NH4HF2 to precipitate the poorly soluble (NH4)2ZrF6.
Drying and glowing at about 700C leaves behind the ionic and very stable ZrF4.
plante1999: what is your interest (end purpose) of these fluorides? TiF3 is a potential route to metallic Ti, via reduction with Mg
or Ca. That's MY interest in BOTH these fluorides...
NaF is a poor fluorinating agent because it's not very water soluble but can be converted to NH4F quite easily by dry distillation of NaF (s) + NH4Cl
(s) === > NaCl (s) + NH4F (g)
That's not going to work, I think. But reacting ZrO2 slurry with concentrated NH4HF2 solution probably does. Dangerous though!
[Edited on 28-12-2010 by blogfast25]
|
|
|
blogfast25
International Hazard
Posts: 10562
Registered: 3-2-2008
Location: Neverland
Member Is Offline
Mood: No Mood
|
|
Just to sign up for email notifications...
|
|
|
blogfast25
International Hazard
Posts: 10562
Registered: 3-2-2008
Location: Neverland
Member Is Offline
Mood: No Mood
|
|
Here are my notes on proposed OWN method, based on said patent. Like stated, I’ve not put it into practice yet:
Dissolve freshly precipitated, pure, dried but not calcined TiO2 in excess NaHSO4 (or ammonium bisulphate?), adjust pH using strong ammonia to as high
as possible (pH = 4 to 5?) without precipitation of TiO2, to a standard solution of about 5 M.
Add equivalent amount of NH4F to convert TiO2+ to TiF62-. Measure temperature at this point! Scrubbing off gases with slaked line is a MUST!
Add excess Fe or Zn, to reduce Ti (+IV) to Ti (+III), forming (NH4)3TiF6.
Add equivalent amount of NH4Cl to form (NH4)2(Fe,Zn)Cl4
Add NH4OH to precipitate (NH4)2Ti(OH)F4 and HF is formed. Scrubbing of the off gases with slaked lime is a MUST!
Filter, wash and dry. Calcine to TiF3
Note that Zn2+ forms a stable ammonium complex, Zn(NH3)42+:
http://www.chemguide.co.uk/inorganic/complexions/aquanh3.htm...
Thus adding NH4Cl may not be necessary in the case of Zn, simple washing of the Ti (+III) complex precipitate with ammonia may do the trick. Test for
Zn by neutralising/alkalising.
In this case, assume in addition to:
(NH4)3TiF6 + H2O --> (NH4)2Ti(OH)F4 + HF + NH4F
Also so to take place:
HF + NH3 --> NH4F
and:
1/2 Zn2+ + 2 NH3 --.> 1/2 Zn(NH3)42+
Solubility of ZnF2.4H2O is 1.52 g/100 ml.
Overall reaction:
(NH4)2TiF6 (aq) + 1/2 Zn (s) + 3 NH3 (aq) + H2O (aq) --> (NH4)2Ti(OH)F4 (s) + NH4F (aq) + 1/2 Zn(NH3)4F2 (aq)
Filter, wash, dry and calcine precipitate to TiF3...
[Edited on 28-12-2010 by blogfast25]
|
|
|
plante1999
International Hazard
Posts: 1936
Registered: 27-12-2010
Member Is Offline
Mood: Mad as a hatter
|
|
thanks im doing this for rechearch about :
fluoride glass ,conductive corrosion ressitan conductive glass (for anode in fluoraniting agent fluoride it the best think)
fluoro complex of titanium and zirconium
i think zirconium or titanium is a best reductan than zinc.
thanks you very much.
[Edited on 28-12-2010 by plante1999]
[Edited on 28-12-2010 by plante1999]
[Edited on 28-12-2010 by plante1999]
|
|
|
blogfast25
International Hazard
Posts: 10562
Registered: 3-2-2008
Location: Neverland
Member Is Offline
Mood: No Mood
|
|
Quote: Originally posted by plante1999  | thanks im doing this for rechearch about :
fluoride glass ,conductive corrosion ressitan conductive glass (for anode in fluoraniting agent fluoride it the best think)
fluoro complex of titanium and zirconium
i think zirconium or titanium is a best reductan than zinc.
thanks you very much.
|
If you get some results, will you please report back? I for one would be most interested... 
|
|
|
plante1999
International Hazard
Posts: 1936
Registered: 27-12-2010
Member Is Offline
Mood: Mad as a hatter
|
|
do you think its possible to electraly make ZrF4?
and when my rechearch will by finished y will post a tread named''synthesys of Zr/Ti Cconductive glass for anode making''
it will probably doped with tin oxde cobalt oxide or other corosion resistan conductive oxide.
|
|
|
Mixell
Hazard to Others
Posts: 449
Registered: 27-12-2010
Member Is Offline
Mood: No Mood
|
|
I'm intended to make TiF3 as well as StF2. Both of the metal halides will be formed by dissolving the corresponding metal carbonate in hydrofluoric
acid, the reaction will be executed in a fairly good ventilated environment, so is there any danger in doing so?
|
|
|
plante1999
International Hazard
Posts: 1936
Registered: 27-12-2010
Member Is Offline
Mood: Mad as a hatter
|
|
like y said erlier i have horror of HF and titanium carbonate doesn exist in book.
|
|
|
plante1999
International Hazard
Posts: 1936
Registered: 27-12-2010
Member Is Offline
Mood: Mad as a hatter
|
|
| Quote: Originally posted by blogfast25 | For TiF3 there is a really interesting patent that I’ve been meaning to try but haven’t gotten round to yet:
http://www.wipo.int/pctdb/ja/ia.jsp?ia=IB2008%2F055559&I...
It relies on the synthesis of (NH4)2Ti(OH)F4 which is insoluble and after drying is fired at 550C to TiF3, NH3, NH4F and water. If you start from
TiCl3 its even easier…
For ZrF4, treat zirconyl chloride (ZrOCl2.8H2O) in solution with a stoichio amount of NH4F or NH4HF2 to precipitate the poorly soluble (NH4)2ZrF6.
Drying and glowing at about 700C leaves behind the ionic and very stable ZrF4.
plante1999: what is your interest (end purpose) of these fluorides? TiF3 is a potential route to metallic Ti, via reduction with Mg
or Ca. That's MY interest in BOTH these fluorides...
NaF is a poor fluorinating agent because it's not very water soluble but can be converted to NH4F quite easily by dry distillation of NaF (s) + NH4Cl
(s) === > NaCl (s) + NH4F (g)
That's not going to work, I think. But reacting ZrO2 slurry with concentrated NH4HF2 solution probably does. Dangerous though!
[Edited on 28-12-2010 by blogfast25] |
wath is the apparatus should bi used for dry distllation of ammonium fluoride?
|
|
|
Mixell
Hazard to Others
Posts: 449
Registered: 27-12-2010
Member Is Offline
Mood: No Mood
|
|
Oh,sorry, I meant strontium carbonate and titanium dioxide.
|
|
|
blogfast25
International Hazard
Posts: 10562
Registered: 3-2-2008
Location: Neverland
Member Is Offline
Mood: No Mood
|
|
| Quote: Originally posted by Mixell | | I'm intended to make TiF3 as well as StF2. Both of the metal halides will be formed by dissolving the corresponding metal carbonate in hydrofluoric
acid, the reaction will be executed in a fairly good ventilated environment, so is there any danger in doing so? |
Hydrofluoric acid is one of the most toxic substances you'll find in any laboratory. It's both a contact poison and kills almost instantly upon
inhalation. Read up on it. For a REAL scare story go to the Wiki entry on HF and look for a link about the use of HF in... car wash
chemicals!
|
|
|
blogfast25
International Hazard
Posts: 10562
Registered: 3-2-2008
Location: Neverland
Member Is Offline
Mood: No Mood
|
|
Brauer (see our library at the root of this site) describes a simple apparatus with a platinum cooler but the platinum is a little overkill I think.
Gently heating of the NaF/NH4Cl mix (ratio described in Brauer too) in a steel or copper cup or crucible, covered with a water cooled lid made of HDPE
or better PP should do it. You'll need excellent ventilation (fumehood ideally) and a real good, tight fitting (with goggles) dust mask to avoid
inhaling any NH4F...
|
|
|
blogfast25
International Hazard
Posts: 10562
Registered: 3-2-2008
Location: Neverland
Member Is Offline
Mood: No Mood
|
|
I doubt it but have no knowledge of Zr/F electrochemistry worth reciting...
|
|
|
blogfast25
International Hazard
Posts: 10562
Registered: 3-2-2008
Location: Neverland
Member Is Offline
Mood: No Mood
|
|
TiO2 with HF gives you TiF4, a nasty chemical that will fume off HF in certain circumstances. TiF3 is much safer.
|
|
|
blogfast25
International Hazard
Posts: 10562
Registered: 3-2-2008
Location: Neverland
Member Is Offline
Mood: No Mood
|
|
A deadly rinse: The dangers of hydrofluoric acid:
http://www.carwash.com/article.asp?IndexID=4230101
Never work with water soluble fluorides without at least having the best antidote, calcium gluconate jelly, at hand!
|
|
|
Mixell
Hazard to Others
Posts: 449
Registered: 27-12-2010
Member Is Offline
Mood: No Mood
|
|
Well, I think I'll drop the idea of using hydrofluoric acid...
Maybe its possible to add NaF to a boiling solution of (TiO2 dissolved in HCl after the HCl has boiled away) and continue doing so until you get the
solid product?
|
|
|
Mixell
Hazard to Others
Posts: 449
Registered: 27-12-2010
Member Is Offline
Mood: No Mood
|
|
I'm wondering if the toxic fumes them self kill you or the inhalation of the liquid?
Because burns can be avoided, fume inhalation is a bit harder without the proper equipment.
|
|
|
blogfast25
International Hazard
Posts: 10562
Registered: 3-2-2008
Location: Neverland
Member Is Offline
Mood: No Mood
|
|
| Quote: Originally posted by Mixell | Well, I think I'll drop the idea of using hydrofluoric acid...
Maybe its possible to add NaF to a boiling solution of (TiO2 dissolved in HCl after the HCl has boiled away) and continue doing so until you get the
solid product?
|
TiO2 doesn't dissolve in HCl AT ALL!!! You simply don't know enough to be let near ANY soluble fluoride.
|
|
|
Mixell
Hazard to Others
Posts: 449
Registered: 27-12-2010
Member Is Offline
Mood: No Mood
|
|
So is there any acid or a way to make a solution of Ti (lll) ions that later could be added to a solution of NaF?
And may be you could explain to me what is the chief danger of soluble fluorides?
|
|
|
plante1999
International Hazard
Posts: 1936
Registered: 27-12-2010
Member Is Offline
Mood: Mad as a hatter
|
|
| Quote: Originally posted by Mixell | So is there any acid or a way to make a solution of Ti (lll) ions that later could be added to a solution of NaF?
And may be you could explain to me what is the chief danger of soluble fluorides? |
read all the test, and after the knoweldg on this post you showed i think you must not work with fluorine compound you dont know ow it is dengerous.
[Edited on 28-12-2010 by plante1999]
|
|
|
Mixell
Hazard to Others
Posts: 449
Registered: 27-12-2010
Member Is Offline
Mood: No Mood
|
|
NaF is dangerous if ingested, its not like I'm going to drink the solution...
|
|
|
| Pages:
1
2 |
![[*]](images/xpblue/default_icon.gif){kind=icon}
