Handling TiCl4
Michael Yuan Feng
to compare my techniques with someone else's to find areas for
improvement.
-Mike Feng
Robert Toreki
Not sure what your application/apparatus might be, but it is no big
deal for an experienced chemist. Lots of groups there at MIT that know how to
handle it, so if you want any help or are unsure consult with one of them and
I'm sure someone would be happy to run though it with you or watch over your
shoulder.
Basically, the stuff I've used comes from Aldrich in a SureSeal (tm)
bottle. More commonly referred to as a sure...it's sealed (wink-wink) bottle.
Aldrich will supply literature with the recommended procedures which are
analogous to those below. You can use a cannula transfer, although most
people use a syringe for small amounts. I'll do the syringe one.
Wear a good set of latex/rubber gloves when working with this. In
truth, not great threat to someone who know what he is doing, but the stuff
makes lots of HCl fumes when it hits moist air. Fume hood and usual
precautions recommended. Inject into the bottle as much nitrogen as volume of
TiCl4 you are going to withdraw. Then tilt the bottle, withdraw more TiCl4
than you will take, remove gas bubbles from the syringe and squirt the excess
back into the bottle. Return the bottle to an upright position and withdraw
the syringe; quickly connect to Intramedic tubing or get it under the N2
counterflow from your apparatus and inject. Some may inevitably get on your
gloves; don't panic and things will be fine. It is just a little HCl and it
won't burn through your gloves for some time and the hood will take care of
the fumes.
Most common error in using Sure Sealed bottles involves having gas
pressure in the wrong place. If too much pressure has gotten into the bottle,
having any bubbles left in the syringe will cause the liquid to squirt out
once the needle is withdrawn from the bottle. Likewise, withdrawing the
needle when the bottle is inverted (liquid around sure seal with gas pressure
above) can cause liquid to spurt through the opening and spray out all over
your benchtop, body, etc.
Care of your sure seal bottle: Put Parafilm (tm) over the top
immediately after dispensing to plug the hole and put the outer cap back on
(and then more parafilm). These things usually only last a couple of times so
some people prefer to pop the seal off and wire down a rubber septum (using a
funnel flushing N2 to ensure air exclusion). Other misc tips include putting
the bottle in a clamp that you can rotate -- that way you don't end up
dropping it. Also (for fun things like t-butyl lithium), having a plastic
container to drop the bottle into to contain spills etc. if something goes
mega wrong is another good idea. Lastly, use a disposable syringe since the
stuff makes TiO2 plugs in your needle bores if not cleaned immediately.
Anyway, there's the long version. If I forgot anything or there are
other alternatives, constructive criticism is welcome. Good luck.
Bill Newcomb
<good description of a syringe transfer>
> Most common error in using Sure Sealed bottles involves having gas
>pressure in the wrong place. If too much pressure has gotten into the bottle,
>having any bubbles left in the syringe will cause the liquid to squirt out
>once the needle is withdrawn from the bottle. Likewise, withdrawing the
The easiest way to avert this kind of disaster is to draw some of the gas
from the bottle into your syringe, after, of course, getting the quantity of
liquid measured correctly. Use a long needle and hold the syringe so that
the luer lok points up. This avoids the problem of having liquid in the
needle to splash around while you're moving the syringe, and reduces the
tendency of needles to clog before they are done being used. Also be sure to
rinse everything as soon as possible, first with inert solvent, then with
something like dilute HCl in the case of metal halides.
>needle when the bottle is inverted (liquid around sure seal with gas pressure
>above) can cause liquid to spurt through the opening and spray out all over
>your benchtop, body, etc.
> Care of your sure seal bottle: Put Parafilm (tm) over the top
>immediately after dispensing to plug the hole and put the outer cap back on
>(and then more parafilm). These things usually only last a couple of times so
>some people prefer to pop the seal off and wire down a rubber septum (using a
>funnel flushing N2 to ensure air exclusion). Other misc tips include putting
>the bottle in a clamp that you can rotate -- that way you don't end up
>dropping it. Also (for fun things like t-butyl lithium), having a plastic
>container to drop the bottle into to contain spills etc. if something goes
>mega wrong is another good idea. Lastly, use a disposable syringe since the
>stuff makes TiO2 plugs in your needle bores if not cleaned immediately.
> Anyway, there's the long version. If I forgot anything or there are
>other alternatives, constructive criticism is welcome. Good luck.
All good points, although I wouldn't have thought to warn about not turning
the bottles upside down. I guess I've seen far too many sure seals that look
like swiss cheese:-)
Aldrich now makes a nifty cap with some kind of a septum-valve combination
on it, that screws directly onto sure-seal bottles. If you use sure-seal
stuff a lot I would recommend looking into it, although I haven't tried it
myself (I'm doing spectrscopy this year, thus not much handling of
chemicals).
Good luck from me too.
--
~/.oo
Magdi N Azer
Methanol to prevent TiO2 deposition in the needle. That way I could use it again
Magdi N. Azer
ma...@uxh.cso.uiuc.edu
Greg Cook|xxxxxx
> Does anyone out there have experience handling TiCl4? I'd like
> to compare my techniques with someone else's to find areas for
> improvement.
I routinely use TiCl4 and find that other than copious amounts of fumes,
handling it is not that difficult.
I usually grab the old crusted up bottles from our stockroom's "used
chemical shelf" and distill it fresh. If you want GOOD TiCl4, distill
it under nitrogen from copper powder. This will take care of any HCl
that is present. I use plain old bantamware flasks and a short path
distillation apparatus and just store the TiCl4 in my receiving flask.
It will last a week or more with a rubber septum, although the septum
does qet quite brittle after a while.
I have found that using it neat works the best for me. I have tried
making solutions in toluene and the solutions turn brown. It may be
good, but I haven't trusted it.
-----------------------------------------------------------------------
Gregory R. Cook gc...@horus.cem.msu.edu
Department of Chemistry cook...@student.msu.edu
Michigan State University co...@msucem.BITNET
Dave Blackburn
(Greg Cook|xxxxxx) writes:
>
>I have found that using it [TiCl4] neat works the best for me. I have tried
>good, but I haven't trusted it.
>
>-----------------------------------------------------------------------
>Gregory R. Cook gc...@horus.cem.msu.edu
>Department of Chemistry cook...@student.msu.edu
>Michigan State University co...@msucem.BITNET
Initial addition of TiCl4 to toluene generates an orange complex,
which is probably (h6-tol)TiCl3(+) Ti2Cl9(-), a pretty nifty complex.
Reference: C. Floriani et. al., J. C. S. Chem Comm, 1989, p. 1747 for the
hexamethylbenxene complex, can also be made from dimethylacetylene.
After a week or so you probably have gook from the rubber septum though.
The original poster was interested in making smokes, and probably doesn't
care, but TiCl4 can be tamed nicely by adding THF to this solution and
crashing it out with pentane as TiCl4*2THF, a stable (except to water) yellow
solid. (Inorg Synth, 1982 vol 21 pg. 135)
Three Cheers for Sci.Chem.Organometallic!!!!!
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