Sciencemadness Discussion Board - synthesis of Ti and Zr halide

synthesis of Ti and Zr halide

plante1999 - 27-12-2010 at 23:45

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 - 28-12-2010 at 01:38

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!

DJF90 - 28-12-2010 at 04:42

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 - 28-12-2010 at 07:50

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)
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Attachment: 30123025-Zirconium-and-Zirconium-Compounds.pdf (313kB)
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Attachment: 30127583-Fluorine-Compounds-Inorganic-Zirconium.pdf (50kB)
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[Edited on 28-12-2010 by plante1999]

[Edited on 29-12-2010 by plante1999]

blogfast25 - 28-12-2010 at 08:24

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)

Quote: Originally posted by plante1999

I think for makking(NH4)3ZrF7 heating zirconium in ammonium bifluoride.
[Edited on 28-12-2010 by plante1999]

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 - 28-12-2010 at 08:25

Just to sign up for email notifications...

blogfast25 - 28-12-2010 at 08:31

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 - 28-12-2010 at 08:53

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 - 28-12-2010 at 10:32

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 - 28-12-2010 at 11:05

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 - 28-12-2010 at 12:06

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 - 28-12-2010 at 12:29

like y said erlier i have horror of HF and titanium carbonate doesn exist in book.

plante1999 - 28-12-2010 at 12:38

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)

Quote: Originally posted by plante1999

I think for makking(NH4)3ZrF7 heating zirconium in ammonium bifluoride.
[Edited on 28-12-2010 by plante1999]

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 - 28-12-2010 at 13:03

Oh,sorry, I meant strontium carbonate and titanium dioxide.

blogfast25 - 28-12-2010 at 13:21

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 - 28-12-2010 at 13:27

Quote: Originally posted by plante1999

wath is the apparatus should bi used for dry distllation of ammonium fluoride?

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 - 28-12-2010 at 13:29

Quote: Originally posted by plante1999

do you think its possible to electraly make ZrF4?

I doubt it but have no knowledge of Zr/F electrochemistry worth reciting...

blogfast25 - 28-12-2010 at 13:31

Quote: Originally posted by Mixell

Oh,sorry, I meant strontium carbonate and titanium dioxide.

TiO2 with HF gives you TiF4, a nasty chemical that will fume off HF in certain circumstances. TiF3 is much safer.

blogfast25 - 28-12-2010 at 13:39

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 - 28-12-2010 at 13:42

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 - 28-12-2010 at 13:44

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 - 28-12-2010 at 13:51

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 - 28-12-2010 at 14:02

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 - 28-12-2010 at 14:05

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 - 28-12-2010 at 14:06

NaF is dangerous if ingested, its not like I'm going to drink the solution...

plante1999 - 28-12-2010 at 14:08

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?

heat titanium in HCl and take the TiCl3 with NaF WILL PRODUCE SODIUM HEXACHLOROTITANATE.

Mixell - 28-12-2010 at 14:14

And what about doing it in cold temperatures? But the yield will be quite low...

[Edited on 28-12-2010 by Mixell]

plante1999 - 28-12-2010 at 14:20

Quote: Originally posted by Mixell

sodium hexachlorotitanate should be soluble (if I'm not mistaken), and the titanium fluoride should sink to the bottom of the flask as it is insoluble.

10ml for 35% TiCl3 you get this visible result0.02g of TiF3
undisolvend NaF
yellow sodium hexachlorotitanate

i dont know where is the F2 ion but i think it maked HF.

Mixell - 28-12-2010 at 14:21

And if the sodiumhexachlorotitanate will be formed (in a solution) you will still have half of the titanium turned into TiF3.
Anyway, I'm going to bed, goodnight to you all...

plante1999 - 28-12-2010 at 14:35

Quote: Originally posted by blogfast25

Quote: Originally posted by plante1999

wath is the apparatus should bi used for dry distllation of ammonium fluoride?

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.

i dont find the ducument could you help me to find?

[Edited on 28-12-2010 by plante1999]

Jor - 29-12-2010 at 05:37

Talking about titanium halides, i have been wanting to prepare some TiCl3.6H2O. How oxidation sensitive is this? I was thinking of dissolving some (1g) titanium powder in hot conc. HCl, followed by evaporation. I read somewhere that at some point one must saturated the solution with HCl gas, and then cool, wich will result in the desired compound crystallising as purple crystals. 3 questions though, for anyone having experience with it's preparation:
To what volume should the solution be evaporated before being saturated with HCl-gas (ml solution per gram of Ti).
How oxidation sensitive is this compound. Do I have to work under inert gas constantly or is it not that oxidation sensitive?
Can I also extract the chloride with a solvent, such as ether, followed by easy evaporation (maybe addition of a little ethanol to also easily evaporate the water in the ether as the azeotrope).

plante1999 - 29-12-2010 at 05:58

Quote: Originally posted by Jor

Talking about titanium halides, i have been wanting to prepare some TiCl3.6H2O. How oxidation sensitive is this? I was thinking of dissolving some (1g) titanium powder in hot conc. HCl, followed by evaporation. I read somewhere that at some point one must saturated the solution with HCl gas, and then cool, wich will result in the desired compound crystallising as purple crystals. 3 questions though, for anyone having experience with it's preparation:
To what volume should the solution be evaporated before being saturated with HCl-gas (ml solution per gram of Ti).
How oxidation sensitive is this compound. Do I have to work under inert gas constantly or is it not that oxidation sensitive?
Can I also extract the chloride with a solvent, such as ether, followed by easy evaporation (maybe addition of a little ethanol to also easily evaporate the water in the ether as the azeotrope).

titaiu trichloride coud be worcker in atmosfere for 5-10m without notice.
take 3ml 35-37% HCl and ad 1gram heat de mixture to boiling,lets it colt to room temp re-boil and re cold. i make this for 2,5hours befor saturation and than use a dessicator bag, the crystal are beautifule i think is the fase A (t ave 4 differant fase witch onli 1 is other than violet.

[Edited on 29-12-2010 by plante1999]

blogfast25 - 29-12-2010 at 07:12

Quote: Originally posted by plante1999

i dont find the ducument could you help me to find?

[Edited on 28-12-2010 by plante1999]

Go here:

http://library.sciencemadness.org/library/index.html

Select: ‘Handbook of Preparative Inorganic Chemistry' by Georg Brauer. You’ll find the NH4F procedure there. I think he trick is to heat the mixture NaF/NH4Cl to only just above the sublimation point of NH4F and to use quite an excess of NaF… The escaping NH4F then drives the equilibrium to the right...

You made solid TiCl3 hydrate? Blimey, I didn’t even know you could! I had several liters of about 0.1 M TiCl3 (from Ti + HCl) and they stayed fine for years but eventually did clear up due to hydrolytic oxidation.

[Edited on 29-12-2010 by blogfast25]

[Edited on 29-12-2010 by blogfast25]

plante1999 - 29-12-2010 at 08:02

but we talk about 1week in very dry environement.

plante1999 - 29-12-2010 at 08:03

and after i store it in dry argon atmosphere.

plante1999 - 31-12-2010 at 16:05

Quote: Originally posted by blogfast25

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...

[Edited on 28-12-2010 by blogfast25]

after reading some of your post i ave find that you want to make the same fluoride than mine so wath is the apparatus you ave used for making the NH4F , After some defeat I ave producted impure wihte crystal from this apparatus, I know this isn a chemist apparatus but it is the only apparatus i could use because i dont ave Pt apparatus(where did you get your apparatus?), A1inch copper end pipe cleaned with HCl with a thick 1/4inch Cu sheet coled withe snow (-20degren centigrade)yea i live in Canada)Befor using this apparatus I used hdpe sheet coled withe snow but the hdpe melted at the 100 degree centigrade needed.

thanks!

blogfast25 - 1-1-2011 at 08:48

Quote: Originally posted by plante1999

I haven’t made any TiF3 or NH4F yet (as I stated above). Instead of NH4F I’ll be using NH4HF2 which is readily available where I am (UK).

But I did have plans for an ‘NH4F distiller’ based on the information on Brauer and one plan did involve a cooled copper pipe as a collector of the sublimed NH4F! What about a small copper reactor (a capped off piece of pipe) with a longer, air or water cooled piece of copper pipe screwed onto it? Heat one end in a sand bath to about 150C, hold the assembly nearly horizontal and the condensed NH4F should be collected in the cool part. Even a transparent and rigid PP (MP ≈ 165C) tube (with rigorous temperature control!) should work…

If your reagents are sufficiently dry you may also get away with a glass assembly like a long test tube, because very dry HF gas doesn’t attack glass. That would certainly be worth investigating on a small scale, possibly sacrificing the test tube if it fails…

What ratio of NaF/NH4Cl did you use?

Did you know you can apparently make NH4HF2 from crystallising NH4F, through loss of ammonia?

2 NH4F (aq) === > NH4HF2 (aq) + NH3 (g)

Or so I’ve been told… :cool:

[Edited on 1-1-2011 by blogfast25]

plante1999 - 1-1-2011 at 13:39

I dont know that we could make NH4HF2 from crystalising NH4F, bu7t i know it is imposible to crystalise pur NH4F from solution.

: I use 2NaFg for 0.75g of NH4Cl

[Edited on 1-1-2011 by plante1999]