Inorganic Syntheses, Volume VI

Edited by Eugene G. Rochow

Copyright © 1960 by McGraw-Hill Book Company, Inc.

52 INORGANIC SYNTHESES

16. TITANIUM (111) CHLORIDE

(Titanium Trichloride)

Hz+ 2H
+
H T i c 1 4 4 Tic13 HCI +
+
Ti 3TiC14 + 4TiC13
+
TiC13 HC1- Tic14 +Hz +
SUBMITTED BY T. R. INGRAHAM,* K. W. DOWNES,*AND P. MARIER*
CHECKED B Y z. z. HUGUS,J R . , AND
~ STANLEY STEIGERt

Titanium trichloride has been prepared by reducing tita-

nium tetrachloride with metals such as aluminum,l anti-
mony, lead, sodium amalgam,2 and t i t a n i ~ mand
, ~ also by
reduction with hydrogen.4 Hydrogen reduction is pre-
ferred to metal reduction in producing a pure product
because the low volatility and the tendency to dispropor-
tionation of titanium trichloride make the clean separation
of titanium trichloride from other metal chlorides difficult.
The procedure here described utilizes a closed Pyrex-glass
apparatus into which titanium tetrachloride is fed at its
vapor pressure a t room temperature, and from which tita-
nium trichloride is recovered as a fine brownish-purple pow-
der. The hydrogen required for the arc-induced reduction
is continuously regenerated over warm metallic titanium
from the hydrogen chloride product of the arc reactione5
The apparatus is simple to construct and operates almost
continuously, unattended, to produce about 1g. of titanium
trichloride per hour.
Procedure
The apparatus is shown in Fig. 7. It is constructed
principally of 25-mm. Pyrex-glass tubing with packless Hoke
* Mines Branch, Department of Mines and Technical Surveys, Ottawa,
Canada; published with the permission of the director.
t University of Minnesota, Minneapolis, Minn.
 T I T A N I U M ( I I I ) CHLORIDE 53

valves number 482,7 and 9, joined to the Pyrex by a brass-

to-Pyrex seal. One valve, 7, serves to control the access of
titanium tetrachloride, 5, to the system; the other, 9, seals
the system from vacuum, helium, and hydrogen sources.

8
3
10 4

FIG.7. Apparatus for the preparation of Ticla.

KEL-F gasket seals are used in the valves. When it is
necessary to open the apparatus for the discharge of prod-
uct, a Pyrex-glass pipe fitting with a Teflon gasket, 16, is
used.
The electrode section of the apparatus, 12, is its most
critical part. It consists of Pyrex tubing reduced from
25 mm. to 6.5 & 1.0 mm. i.d. over a length of 11 1 mm.
Tungsten electrodes are sealed into the Pyrex in such a way
that the space through which the arc passes is 22 5 5 mm.
in length. The top electrode is placed deeper within the
constricted zone than the bottom electrode, to aid in direct-
ing the reaction product downward through the arc. In
this way, the rapidly expanding gases from the arc force the
titanium trichloride product, 13, preferentially in the direc-
tion of the collection container, 14.
54 INORGANIC SYNTHESES

High voltages to produce the required arc within the gas

are provided by a Tesla coil leak tester, 11, connected to
one electrode. The other electrode is grounded. For long
operations, it is convenient to remove the outer casing of
the Tesla leak tester to assist in the dissipation of heat. A
titanium coupon, 3, of dimensions 1 by 15 by 120 mm. is
used for the regeneration of hydrogen and is heated by an
external tube furnace, 10, fitted with suitable controls to
maintain a temperature of 460 k 10". Hydrogen absorp-
tion by the titanium does not occur at the temperatures and
pressures of the operation.
To begin a run, the apparatus is evacuated to a pressure
of mm. of mercury and checked for leaks. When the
apparatus is found to be free from leaks and from any mois-
ture introduced during construction, helium is admitted
through 1,and an opening is made with a torch at 2 through
which the titanium coupon is placed at 3. It should be
clean and free of surface oxide coatings. The system is
then sealed with a torch at 2 and an opening made at 4.
Through this opening, against a gentle countercurrent of
helium, 50 ml. of purified titanium tetrachloride is admitted
to the apparatus at 5. The opening at 4 is then sealed with
a torch, the helium supply cut off, and the titanium tetra-
chloride frozen with liquid air." When freezing is com-
plete, the apparatus is thoroughly evacuated through 6,
and then valve 7 is closed. The titanium tetrachloride at
5 is then melted rapidly and brought to room temperature.
While this is taking place, hydrogen is admitted through 8
to 4 t 2 mm. of mercury with the use of a McLeod gage,
then valve 9 is closed and the furnace 10 surrounding the
titanium is brought up to 460 _+ 10". When this tempera-
ture is attained, the Tesla coil is started, and valve 7 is
opened to admit titanium tetrachloride vapor to the sys-
tem. This results immediately in the production of finely
powdered titanium trichloride which collects on the inside
of orifice 12 and is blown down the tube by the circulating
* Because of its lower freezing temperature, helium is preferred to argon.
 TITANIUM(IIII) CHLORIDE 55

gas stream. The powdered titanium trichloride, 13, settles

in the graduated container, 14. Because the powder is elec-
trostatically charged, some of it is attracted to the glass
walls of the vertical tubing. It may be continuously dis-
lodged by a mechanical vibrator, 15.
At the end of a run, when reservoir 14 is filled with tita-
nium trichloride, valve 7 is closed and the gaseous atmos-
phere of the apparatus is removed by pumping through 6.
Helium is then admitted through 1, and clamp 16 loosened.
Against a gentle countercurrent of helium, container 14 is
removed and replaced by a duplicate container, previously
flushed with helium. After the clamps are tightened at 16,
the system is again evacuated to mm. of mercury and
cylinder hydrogen admitted through 8 to 4 2 2 mm. of
mercury. Valve 9 is closed and valve 7 opened. When
the arc is struck again, the reaction is resumed. The run
may be continued without further interruption or attention
until another container has been filled with titanium tri-
chloride, or the titanium or the titanium tetrachloride sup-
ply is exhausted. Occasionally it may be necessary to
replenish the hydrogen in the system when a large amount
of titanium trichloride has been formed, owing presumably
to the adsorption of hydrogen on the finely divided titanium
trichloride.
As an alternative to the injection of hydrogen into the
system at the beginning of an experiment, a solution of
hydrogen chloride in titanium tetrachloride may be substi-
tuted for the titanium tetrachloride. This can be prepared
by the addition of a small amount of water to titanium tet-
rachloride. The amount of the solution used is chosen so
that when the hydrogen is liberated from it during the run,
the pressure of hydrogen in the system will be approxi-
mately the same as that obtained by hydrogen injec-
tions. A convenient method of determining the amount of
hydrogen chloride in the titanium tetrachloride has been
published.'
The yield of titanium trichloride from the arc, based on
56 INORGANIC SYNTHESES

the consumption of metallic titanium, is over 90%. The

titanium trichloride, with the exception of adsorbed hydro-
gen, hydrogen chloride, or titanium tetrachloride, which
may be removed by a vacuum treatment, is pure and free
from titanium dichloride and other metallic chlorides.

Properties
Titanium trichloride, as prepared by this method, is a
brownish-purple powder with a bulk density varying from
0.07 to 0.25 g./cc. The particles vary in size from a few
microns to aggregates of several hundred microns. The
material is very reactive, being immediately hydrolyzed by
moisture and pyrophoric in air. Any transfer or handling
of the powder must be done in a dry box under nitrogen or
an inert gas, if contamination is to be prevented.
Titanium trichloride is stable up to temperatures of about
500". Above this temperature, under vacuum, it dispro-
portionates quantitatively to titanium dichloride and tita-
nium tetrachloride. Some of the dichloride disproportion-
ates to metal under these conditions.

References
1. W. C . SCHUMB and R. J. SUNDSTROM: J . Am. Chem. Soc., 66,596 (1933).
2. 0. PFORDTEN: Liebigs Ann. Chem., 237, 217 (1887).
3. J. D. FAST:2. anorg. u. allgem. Chem., 241, 42 (1939).
4. N. BAEZINGER and R. E. RUNDLE: Acta Cryst., 1, 274 (1948).
5. T. R. INGRAHAM, K. W. DOWNES, and P. MAFXER: Can. J . Chem., 36,
850 (1957).
Proc. Roy. SOC.(London), 204A, 309 (1950).
6. A. D. MCQUILLAN:
Can. J . Chem., 33, 1731 (1955).
7. T. R. TNGRAHAM: