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SnI4 and TiI4

plante1999 - 19-2-2011 at 09:54

today i made this experiment : http://81.207.88.128/science/chem/exps/SnI4/index.html

but with some change , i use CHCl3 instead of CS2 ( i made it frome acetone + sodium hypochlorite 4%). i boil it with a tube outside the lab.

now i want to repeat this experiment but in the place of making tin tetraiodide , i want to make titanium tetraiodide ( if it work i will made a youtube video about it , tomorow).

solvent: 95-96% CHCl3
iodine 95-98%
and 1/4 to 1/2inch pellet of 99.999% titanium
but the problem is i need titanium powder for this reaction , i tried to grind it with a file but it is nearly impossible.

thanks!!

[Edited on 19-2-2011 by plante1999]

[Edited on 19-2-2011 by plante1999]

[Edited on 19-2-2011 by plante1999]

[Edited on 19-2-2011 by plante1999]

[Edited on 19-2-2011 by plante1999]

[Edited on 20-2-2011 by plante1999]

plante1999 - 19-2-2011 at 17:05

solvent: 95-96% CHCl3
iodine 95-98%
and titanium powder

Finally I grind the titanium mecanicly with aluminia oxide sand paper.

the powder was very fine and i ad the conssentred iodine solution ( in CHCl3 ) to it at temperature piece and no reation occured ( not like the Sn + I2 reaction , arroun 30 second and it is finish) so i heated it , the titanium make tiny effervescence and nothing more after 2 hour wath do you thing do i need to heat 60degree C with reflux for 1-2hour? or ad a catalist? Al powder ( 2Al + 3I2 -> 2AlI3 --------------------- 3 Ti + 4 AlI3 = 3 TiI4 + 4 Al and the al could be filtered)?

[Edited on 20-2-2011 by plante1999]

hkparker - 19-2-2011 at 18:39

Thanks for drawing my attention to this, hopefully ill do a video on SnI4 for my youtube channel soon.

As for your reaction I'm not so sure it will react. You could try to reflux it but how are you sure iodine solution will attack titanium?, a pretty corrosion resistant metal. As for it displacing aluminum, check the reactivity series. I always though of titanium as pretty noble but it could just be passivation that prevents reactions. Let me know how it goes, cool stuff.

plante1999 - 19-2-2011 at 18:50

titanium is a prety reactive element (think pyro) but the dioxide layer protect it ,brauer said that Ti react with I2 , fast at 200degree C. for the al reactivity sery , brauer said a method with al/ti alloy in iodine solution.

[Edited on 20-2-2011 by plante1999]

blogfast25 - 20-2-2011 at 07:52

Quote: Originally posted by hkparker

Thanks for drawing my attention to this, hopefully ill do a video on SnI4 for my youtube channel soon.

As for your reaction I'm not so sure it will react. You could try to reflux it but how are you sure iodine solution will attack titanium?, a pretty corrosion resistant metal. As for it displacing aluminum, check the reactivity series. I always though of titanium as pretty noble but it could just be passivation that prevents reactions. Let me know how it goes, cool stuff.

Forget the potential series for a minute: that’s very useful for electrochemistry in watery solution but it says very little about reactions like this one.

Plante is correct in saying that titanium is in fact a very reactive metal: it can be made to burn in air for instance. But it passivates very efficiently, protecting the metal against corrosion. Commercial Ti metal dissolves fairly easily in hot conc. HCl, to TiCl3 (aq)…

In the Van Arkel and De Boer crystal bar method, very pure Zr or Ti is obtained by decomposing the resp. tetra iodides (ZrI4 or TiI4) on a hot filament (about 1200 C). New, pure ZrI4 or TiI4 is constantly formed in situ and constantly decomposed to very pure metal at the filament (the I2 is thus constantly being recycled).

TiI4 is a non-ionic material albeit with probably a sizeable heat of formation, which drives the reaction Ti + 2I2 === > TiI4.

I feel TiI4 probably can be made similar to SnI4 but obtaining or making powdered Ti is hard.

plante1999 - 20-2-2011 at 08:17

after testing the Ti react with I2 when refluxed. I will post a video later.

blogfast25 - 20-2-2011 at 09:26

Quote: Originally posted by plante1999

after testing the Ti react with I2 when refluxed. I will post a video later.

Yes, you do that.

plante1999 - 20-2-2011 at 17:29

here a qick review of the video that i will made . (this is only a 14 day trial)I will re-try to make it in 14day ( I REALY NEED TO IMPROUVE MY WAY TO MAKE TiI4). also it as some missing parts.
as you can see at the end it is not like I2 its is dark violet brown-red , with some heating no I2 vapor form but a very dense darck red-brown fume are formed at high temperature)

<iframe sandbox title="YouTube video player" width="480" height="390" src="http://www.youtube.com/embed/JX1jCrbdivM" frameborder="0" allowfullscreen></iframe>

plante1999 - 20-2-2011 at 18:22

sorry for the double post.

here how i made my solvent , i take very long time to make an usable amount of solvent. I know it is the same music but the first video will be delleted in 14day , so....

<iframe sandbox title="YouTube video player" width="480" height="390" src="http://www.youtube.com/embed/u8vfuqzG8l8" frameborder="0" allowfullscreen></iframe>

hkparker - 20-2-2011 at 23:16

I did a video on SnI4 if anyone wants to see, its on my channel.

Jor - 21-2-2011 at 05:16

Plante1999, I can't see your video on TiI4, because it is private.

plante1999 - 21-2-2011 at 05:21

i will change that take note this is just a report of the experiment not the final guide.

blogfast25 - 21-2-2011 at 08:36

Yes, you seem to have made TiI4. But your claim of seeing TiI4 vapour is dubious: it has a boiling point of 377 C.

Have you tried hydrolysing some of it?

[Edited on 21-2-2011 by blogfast25]

plante1999 - 21-2-2011 at 08:46

i will do tonight. 99 post!!

plante1999 - 21-2-2011 at 09:51

sorry for the double post
this ismy 100th post!

my hot plate haet to 900degree C so....but with amiante sheat it it to 500 degree c.

in 13 day i will improuve my methode , i am in working of a self made ( glass bowing with already made glass part) appartus for making TiI4 , TiCl4 and many other inorganic titanium syntesis.

blogfast25 - 21-2-2011 at 14:03

'amiante' (wonderful word!) = asbestos.

plante1999 - 21-2-2011 at 14:06

sorry for the mistake . i hydrolise te TiI4 and after 2minute a ligth yellow solution is formed i will lets it hydrolise more time.

blogfast25 - 21-2-2011 at 14:39

Interesting test could be to add some NaF solution to TiI4, you should get TiF4! Dry mixing TiI4 with NaF should also yield TiF4 with some mild heating: TiI4 + 4 NaF ---> TiF4 + 4 NaI, driven by the higher HoF of TiF4.

plante1999 - 21-2-2011 at 15:22

yes this woul be a good idee but in wath solvent do you think i should use?

blogfast25 - 22-2-2011 at 10:22

Try heating an intimate dry mix. TiF4 is highly prone to hydrolysis (HF alert!) so separting the NaI and TiF4 may be difficult unless there exists an aprotic solvent for NaI...

Lambda-Eyde - 22-2-2011 at 11:49

Acetone?

blogfast25 - 22-2-2011 at 12:55

If NaI is soluble in acetone (is it?) then heating an intimate mix of TiI4 with NaF in a closed reactor, followed by leaching out the NaI with acetone could indeed be a way to make small amounts of TiF4 (quite a nasty substance from what little I've read about it...)

[Edited on 22-2-2011 by blogfast25]

Lambda-Eyde - 22-2-2011 at 13:07

Well, it's the basis for the Finkelstein reaction, so that would make sense.

blogfast25 - 22-2-2011 at 13:38

Interesting Lambda-Eyde, never heard of that one before...

plante1999 - 22-2-2011 at 16:50

This is a plan of the apparatus i will make for making majority of Ti and Zr compound (i made just Zr and Ti compound. it will cost arround 5dollar us , for all glass reflux it is cheap.

[Edited on 23-2-2011 by plante1999]

plante1999 - 23-2-2011 at 05:17

sorry for the double post , if i made TiCl4 i can reacting it with HF :

TiCl4 + 4NaF -> 4NaCl + TiF4

and i am in working to find a way to make some TiCl4 with the apparatus i described at my last post.

Jor - 15-4-2011 at 05:02

I am also gonna try to make TiI4 this day or tomorrow. I will use dichloromethane instead of chloroform as a solvent (I only have about 60mL of chloroform, I have 350mL CCl4 but thats only more toxic). I see you reflux your chloroform during reaction. Do you know if the reaction also proceeds nicely at RT?
I will be using very fine titanium turnings, but not really a powder.
Because with DCM I can't reach the reflux temp of chloroform I wonder if the reaction will proceed.
In any case I will wash the titanium with 0,1M HCl containing some NaF untill a good amount of H2 evolves, then I will decant, rinse with small amount of water, acetone (or IPA) and finally DCM to activate the material.

[Edited on 15-4-2011 by Jor]

plante1999 - 15-4-2011 at 07:50

if you lets it for 1-4 week it will work at rt( i already have tested it) but if you want to make it in a day or so it should be very hot or refluxing , washing is nessecary. try to dilute as mush you can your solution , and than boil it to get the crystal, or the restion is very hard to see.

good luck!!

Mixell - 2-7-2011 at 16:56

My metals and iodine are going to arrive soon.
I don't have any chloroform, is there any way to perform such reaction(synthesis TiI4, SnI4) without a solvent?
possibly using an excess of iodine and then just boiling the iodine away?
I got a good amount of acetone, but I think it will react with the substance and cannot be used as a solvent...

[Edited on 3-7-2011 by Mixell]

Titanium tetraiodide from Industrial and Engineering Chemistry

The WiZard is In - 4-7-2011 at 09:26

Picked this ref up in Brauer (la book is in the forums library).
He mentions this method among others.

Because this is from a bound volume I had to take a scalpel
to it and remove the pages for scanning. No extra charge.

Mixell - 4-7-2011 at 10:08

Thank you for the post wizard.
I guess its decided, I'll use an excess of iodine. The titanium/iodine mix will be heated in a sealed vessel (with a pop-up stopper) to about 125-130C. After the reaction is completed, the vessel will be heated to 185-200C and all of the excess iodine will be evaporated. And it should leave a quite pure TiI4.
Hope the shipment will arrive soon...

The WiZard is In - 4-7-2011 at 10:31

Quote: Originally posted by Mixell

Thank you for the post wizard.
I guess its decided, I'll use an excess of iodine. The titanium/iodine mix will be heated in a sealed vessel (with a pop-up stopper) to about 125-130C. After the reaction is completed, the vessel will be heated to 185-200C and all of the excess iodine will be evaporated. And it should leave a quite pure TiI4.
Hope the shipment will arrive soon...

I would suggest reading Brauer's Handbook of Preparative
Inorganic Chemistry, p. 1205-09. Titanium (IV), Zirconium (IV)
and Thorium (IV) Iodides. The book can be DL'd. It is in
the library where science is often most mad. Granted his methods
are nuanced... big time!

Mixell - 12-8-2011 at 14:27

After successfully synthesizing SnI4, I'm planning to venture into the more slower reacting metals, such as titanium, tantalum, tungsten and niobium. I;m planning to start with titanium, but I would very much like to replace chloroform with another solvent, like hexane. Is it possible? or the iodine will react with the hexane to form HI and some iodinated derivatives of the hexane with the formula C6I(n)H(14-n)?
Also, after I will be done with the titanium I'm planning to try tungsten, but I didn't found any information on WI6 (as opposed to WCl6) but found some info about WI4 and WI2, which one of this species would be created in a solution of iodine at room temperature?
And finally, as I mentioned, I'm planning to do the reaction at room temperature, I got time (weeks and even more) to wait for it to fully react, but will the reaction proceed at this temperature at all?

blogfast25 - 13-8-2011 at 03:50

I'm not sure whether iodine is capable of halogenating heptane at RT. If so, yields will be poor, I predict. A question for the organikers, I feel...

WCl6 can be synthesised by direct union of the elements but it takes higher than RT temperatures to so so. I strongly suspect this might also be the case for any iodides. WI6 may be a bit of a stretch (no pun intended): to fit 6 quite large iodine atoms 'around' one just barely larger tungsten atom may be pushing it a bit?

Mixell - 13-8-2011 at 05:01

So probably WI4 is the species that will be produced at this reaction. May be dissolve some iodine in hexane and let it stand for a few days or weeks? If the iodinated species of hexane are colorless, then if the solution will turn colorless or the purple color will faint, then it means that the hexane was iodinated.
Bromination of hexane seems to be quite quick at RT, so I guess iodination will proceed too, seems like chloroform is the better option after all.

[Edited on 13-8-2011 by Mixell]

blogfast25 - 13-8-2011 at 05:13

Yes on the heptane/iodine.

Re. WI4, apparently it decomposes before melting which would suggest low temperature synthesis. What will be your source of tungsten?

Mixell - 13-8-2011 at 05:17

Tungsten powder.
There is also a WI2 species, although I didn't find much information about it.

Morgan - 15-11-2012 at 17:46

Ti + 2 I2 → TiI4
"This reaction can be reversed to produce highly pure films of Ti metal.[4]"
http://en.wikipedia.org/wiki/Titanium_tetraiodide#cite_note-...
Would it be possible to make a thin film of titanium inside of a quartz tube via TiI4 vapor deposition followed by thermal decomposition of the titanium tetraiodide? I wonder if it would stick or react with the quartz in some way?

tetrahedron - 15-11-2012 at 17:56

at the very least the Ti film being a metal probably expands a lot upon heating, stressing the more rigid quartz substrate (if that's the use you have in mind).

Morgan - 15-11-2012 at 18:16

Basically, I just wanted to coat the inside of one of these quartz tubes I have with a very thin film of titanium dioxide ultimately to create some pretty colors playing on the interference of light.
It was just something I thought might be fun to try, anodizing the titanium coating into an artistic "Peter Max" effect if you will.
That is a good point about the coefficient of expansion between SiO2 and Ti.

Morgan - 16-11-2012 at 07:05

Materials and procedure for TiI4 - A major motion picture of glassware.
http://pubs.acs.org/doi/abs/10.1021/ja01201a006

Morgan - 16-11-2012 at 07:15

"The gaseous metal tetraiodide is decomposed on a white hot tungsten filament (1400 °C). As more metal is deposited the filament conducts better and thus a greater electric current is required to maintain the temperature of the filament. The process can be performed in the span of several hours or several weeks, depending on the particular setup."
http://en.wikipedia.org/wiki/File:Titan-crystal_bar.JPG
http://en.wikipedia.org/wiki/Crystal_bar_process

watson.fawkes - 16-11-2012 at 10:28

Quote: Originally posted by tetrahedron

at the very least the Ti film being a metal probably expands a lot upon heating, stressing the more rigid quartz substrate (if that's the use you have in mind).

That's unlikely to be much of a problem in this case. There about a 10^4:1 thickness ratio between the glass and a thin metal film. There will be an interfacial force, still, but that's the stress. The strain will predominantly deform the film (compressing it as it heats up) rather than the glass. The risk is not breaking the glass, but delaminating the film. I would guess that Ti bonds fairly tightly, as its inner layer would partially oxidize and meld with the glass matrix.

Morgan - 16-11-2012 at 19:10

A method of TiO2 deposition on glass, not enough color for my purposes though and a rather involved process.
Lab Report: Dr Charlie Dunnill on chemical vapour deposition
http://www.youtube.com/watch?v=KjjQf12FgUQ
I would like something more like this though it would be nice to produce less kitsch-like colors or isolate a few colors and patterns that work well together.
Anodizing Titanium and Niobium: Science and Art Combined
http://www.youtube.com/watch?v=OzShFSj3xxA#t=1m26s
Loud creations made by vaporizing titanium in a vacuum I believe. Not a route I could afford.
https://www.google.com/search?q=titanium+quartz&hl=en&am...
Titanium films
"There have been many studies which have concluded that the adhesion of metal films to oxide substrates is directly related to the free energy of oxide formation of the deposited material. That being the case, very strong adhesion should occur for titanium to the quartz substrate. A titanium film was sputter deposited on a quartz substrate."
http://ntrs.nasa.gov/archive/nasa/casi.ntrs.nasa.gov/1976001...

[Edited on 17-11-2012 by Morgan]