| Identification | More | [Name]
Titanium tetrachloride | [CAS]
7550-45-0 | [Synonyms]
Tetrachlorotitanium
Titanic chloride
TITANIC CHLORIDE TETRAHYDRATE
TITANIUM(+4)CHLORIDE
TITANIUM ATOMIC SPECTROSCOPY STANDARD (TICL4)
TITANIUM CHLORIDE
TITANIUM(IV) CHLORIDE
TITANIUM(IV) TETRACHLORIDE
(t-4)-titaniumchloride(ticl4
Tetrachlorure de titane
tetrachloruredetitane
tetrachloruredetitane(french)
TiCl4
Titaantetrachloride
Titane
titane(tetrachlorurede)
titane(tetrachlorurede)(french)
Titanio
titanio(tetraclorurodi)
Titanium chloride (TiCl4) (t-4)- | [EINECS(EC#)]
231-441-9 | [Molecular Formula]
Cl4Ti | [MDL Number]
MFCD00011267 | [Molecular Weight]
189.68 | [MOL File]
7550-45-0.mol |
| Chemical Properties | Back Directory | [Appearance]
Colorless liquid. Fumes strongly when
exposed to moist air, forming a dense and persistent
white cloud. Soluble in dilute hydrochloric acid; soluble
in water with evolution of heat; concentrated
aqueous solutions are stable and corrosive; dilute
solutions | [Melting point ]
−25 °C(lit.)
| [Boiling point ]
135-136 °C(lit.)
| [density ]
1.73 g/mL at 20 °C(lit.)
| [vapor pressure ]
50 mm Hg ( 55 °C)
| [refractive index ]
1.61 | [Fp ]
46 °F
| [storage temp. ]
Flammables area | [solubility ]
H2O: soluble
| [form ]
Solution | [color ]
Light yellow to dark brown | [Specific Gravity]
1.726 | [Stability:]
Stable. Reacts with water. Incompatible with moisture, ammonia, amines, alcohols, potassium and other chemically active metals. | [Water Solubility ]
reacts | [Hydrolytic Sensitivity]
8: reacts rapidly with moisture, water, protic solvents | [Sensitive ]
Moisture Sensitive | [Merck ]
14,9478 | [Dielectric constant]
40.0（Ambient） | [Exposure limits]
ACGIH: TWA 50 ppm
OSHA: TWA 25 ppm; STEL 125 ppm
NIOSH: IDLH 2300 ppm | [CAS DataBase Reference]
7550-45-0(CAS DataBase Reference) | [NIST Chemistry Reference]
Titanium tetrachloride(7550-45-0) | [EPA Substance Registry System]
7550-45-0(EPA Substance) |
| Safety Data | Back Directory | [Hazard Codes ]
C,F,Xi | [Risk Statements ]
R36/37/38:Irritating to eyes, respiratory system and skin .
R67:Vapors may cause drowsiness and dizziness.
R65:Harmful: May cause lung damage if swallowed.
R63:Possible risk of harm to the unborn child.
R48/20:Harmful: danger of serious damage to health by prolonged exposure through inhalation .
R34:Causes burns.
R14:Reacts violently with water.
R11:Highly Flammable.
R23:Toxic by inhalation.
R40:Limited evidence of a carcinogenic effect.
R37:Irritating to the respiratory system. | [Safety Statements ]
S26:In case of contact with eyes, rinse immediately with plenty of water and seek medical advice .
S7/8:Keep container tightly closed and dry .
S62:If swallowed, do not induce vomiting: seek medical advice immediately and show this container or label .
S46:If swallowed, seek medical advice immediately and show this container or label .
S45:In case of accident or if you feel unwell, seek medical advice immediately (show label where possible) .
S36/37/39:Wear suitable protective clothing, gloves and eye/face protection .
S24/25:Avoid contact with skin and eyes .
S23:Do not breathe gas/fumes/vapor/spray (appropriate wording to be specified by the manufacturer) . | [RIDADR ]
UN 3289 6.1/PG 2
| [WGK Germany ]
2
| [RTECS ]
XR1925000
| [F ]
21 | [TSCA ]
Yes | [HazardClass ]
8 | [PackingGroup ]
II | [HS Code ]
28273990 | [Safety Profile]
Poison by inhalation. A
corrosive irritant to skin, eyes, and mucous
membranes. When heated to decomposition
it emits toxic fumes of Cl-. See also
TITANIUM COMPOUNDS. | [Hazardous Substances Data]
7550-45-0(Hazardous Substances Data) | [Toxicity]
Not found naturally in the environment. Manufactured from
titanium-containing minerals and is used to make metallic titanium, titanium dioxide, and other titanium compounds. An irritant to skin, eyes, mucus membranes, and lungs due to its
interaction with water to form hydrochloric acid, excessive
exposure can result in chemical bronchitus, pneumonia, and
death. Severe burns may result from contact with liquid titanium tetrachloride. Although long term, high dose studies
caused lung tumors in rodents, IARC and other agencies have
not classified titanium tetrachloride for its potential as a human
carcinogen. |
| Hazard Information | Back Directory | [General Description]
A colorless fuming liquid with a pungent odor. Corrosive to metals and tissue. Very toxic by inhalation. | [Reactivity Profile]
TITANIUM TETRACHLORIDE acts as an acid in aqueous solution. During the reduction of TITANIUM TETRACHLORIDE to titanium metal with potassium, an explosion occurred. The system had been heated to 90°C [Walter and Mandell 1967]. Addition directly to tetrahydrofuran caused a violent exothermic reaction [Inorg. Syn., 1982, 21, 135]. Ethylene can polymerize at low pressure if catalyzed by titanium halides. (Sundaram, K. M, M. M. Shreehan, E. F. Olszewski. thylene. Kirk-Othmer Encyclopedia of Chemical Technology. John Wiley & Sons, Inc. 2001.) | [Health Hazard]
This compound is a highly corrosive, acute irritant to the skin, eyes, mucous membranes and the respiratory tract. It is capable of causing death or permanent injury due to exposures encountered in normal use. Even short contact may lead to eye inflammation which may result in corneal opacities. | [Potential Exposure]
Used in the manufacture of titanium salts; mordant dye; titanium pigments; and used as a chemical intermediate for titanium metal; titanium dioxide; as an agent in smoke screens; polymerization catalyst; and iridescent agent in glass and pearl manufacturing. | [Fire Hazard]
Material will react with water to produce hydrochloric acid. TITANIUM TETRACHLORIDE may ignite other combustible materials (e.g., wood, oil, etc.). Flammable, poisonous gases may accumulate in tanks and hopper cars. Runoff to sewer may create fire or explosion hazard. Reacts strongly with water to release hydrochloric acid and heat. Avoid water, moist air. Stable in concentrated aqueous solutions. Avoid contact with moisture; the chemical absorbs moisture from air and evolves dense white fumes. | [First aid]
If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 minutes, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. If victim is conscious, administer water, or milk. Do not induce vomiting. Medical observation is recommended for 24-48 hours after breathing overexposure, as pulmonary edema may be delayed. As first aid for pulmonary edema, a doctor or authorized paramedic may consider administering a drug or other inhalation therapy. | [Shipping]
UN1838 Titanium tetrachloride, Hazard class: 6.1; Labels: 6.1-Poison Inhalation Hazard, 8-Corrosive material, Inhalation Hazard Zone B. | [Incompatibilities]
Violent reaction with water or steam, releasing heat and hydrogen chloride fumes. Contact with moist air releases hydrogen chloride. Attacks many metals in presence of moisture. | [Description]
Titanium ore was first discovered in 1791 in Cornish beach
sands by an English clergyman, William Gregor. The actual
identification of the oxide was made a few years later by
a German chemist, M.H. Klaproth, who gave the metal
constituent of this oxide the name titanium, after the Titans of
Greek mythology. Pure metallic titanium was first produced in
the early 1900s in 1910 by M.A. Hunter at Rensselaer Polytechnic
Institute in cooperation with General Electric
Company.
Titanium tetrachloride is an inorganic compound that is an
important intermediate in the production of titanium metal
and the pigment titanium dioxide. On contact with humid air,
it forms opaque clouds of titanium dioxide (TiO2) and
hydrogen chloride (HCl). Early attempts to isolate titanium
metal from titanium tetrachloride were unsuccessful. The
process was improved and commercialized by William Kroll of
Luxembourg in the 1930s which involved the reduction of
titanium tetrachloride with magnesium in an inert gas atmosphere.
This process remains essentially unchanged today. The
primary use of titanium tetrachloride is for titanium dioxide
used in paints.
The production of titanium metal accounts for only 5% of
annual titanium mineral consumption, with the remainder
being used in the titanium pigment industry. Pigments are
produced using either a sulfate process or a more environmentally
acceptable carbochlorination process that converts
TiO2 into TiCl4. The latter process also supplies the TiCl4
necessary for the production of titanium metal. | [Chemical Properties]
Colorless liquid. Fumes strongly when
exposed to moist air, forming a dense and persistent
white cloud. Soluble in dilute hydrochloric acid; soluble
in water with evolution of heat; concentrated
aqueous solutions are stable and corrosive; dilute
solutions precipitate insoluble basic chlorides. | [Chemical Properties]
Description: Titanium tetrachloride is a noncombustible, colorless to light yellow liquid that fumes in air. Penetrating acrid odor. | [Production Methods]
TiCl4 is used in TiO2 production, the manufacture of artificial
pearls and iridescent glass, and, by the military, to create
smoke screens. | [Hazard]
Toxic by inhalation, strong irritant to skin
and tissue. | [Carcinogenicity]
Rats exposed to 10 mg TiCl4/m3 for 6 h/day, 5 days/week, for
2 years developed rhinitis, tracheitis, hyperplasia, foamy dust
cell accumulation, and alveolar bronchiolization. In addition,
5/150 animals developed squamous cell carcinoma, compared
to 0/156 in the controls. Two of the squamous cell
carcinomas were described as cystic keratinizing lesions,
whose relevance to humans was questioned by the authors.
However, the remaining three squamous cell tumors were
described as microscopic, well-differentiated carcinomas. Therefore, TiCl4 may be regarded as potentially
carcinogenic in the rat. | [Environmental Fate]
Titanium tetrachloride is a colorless to pale yellow liquid with
a strong penetrating odor. If it comes in contact with water, it
rapidly forms hydrochloric acid, as well as titanium
compounds. Titanium tetrachloride is not found naturally in
the environment and is made from minerals that contain titanium.
Titanium tetrachloride is the most toxic of the titanium
compounds and is highly corrosive and unstable and
undergoes rapid hydrolysis through a vigorous exothermic
reaction generating a large quantity of heat and hydrolysis
products such as hydrochloric acid and other titanium
compounds including titanium hydroxide, titanium oxychloride,
and titanium dioxide. It may ignite other combustible
materials (e.g., wood, oil, etc.) and produce toxic gases. Runoff
to sewers may create fires or explosion hazards.
Titanium tetrachloride enters the environment primarily as
air emissions from facilities that make or use it in these various
chemical processes or as a result of accidental releases. Its
chemical properties suggest that titanium tetrachloride partitions
to the air underscoring the fact that the most likely route
of human exposure to titanium tetrachloride hydrolysis or its
intermediate products is via inhalation. The hydrochloric acid
may break down or be carried in the air for some distance.
Some of the titanium compounds may settle out to soil or in
water as bottom sediments and remain for many years. Other
titanium compounds, such as titanium dioxide, can also be
found in the air. Consequently, environmental transport of
titanium tetrachloride is negligible in soil and water; however,
the atmospheric transport of the hydrolysis products may be
significant. There is a paucity of data estimating the residence
time for titanium tetrachloride in air or water; however, based
on the compounds’ rapid hydrolysis, residence times are
expected to be in the order of hours. In water, hydrochloric
acid dissociates to the hydrogen and chloride ions, while
titanium dioxide is insoluble in water and may settle out into
the sediments. Titanium tetrachloride released to soils or
sediments is expected to hydrolyze on contact with moisture in
the soil and sediment. However, titanium dioxide is likely to
remain in the soil or settle out to the sediment as it is an inert
compound.
The chemical characteristics of titanium tetrachloride and its
rapid hydrolysis in the presence of water suggest that there is
little potential for bioaccumulation or biomagnification in
aquatic or terrestrial organisms. It is not possible to determine
if there is a potential for bioaccumulation of the compound in
humans. Because of its chemical characteristics and rapid
hydrolysis in the presence of water, however, it is also unlikely
that it would bioaccumulate in the body although its final
hydrolysis product may do so. Hence, titanium tetrachloride is
not considered to be persistent, bioaccumulating, nor toxic. | [Purification Methods]
Reflux it with mercury or a small amount of pure copper turnings to remove the last traces of colour [due to FeCl3 and VCl4], then distil it under N2 in an all-glass system, taking precautions to exclude moisture. Clabaugh et al. [J Res Nat Bur Stand 55 261 1955] removed organic material by adding aluminium chloride hexahydrate as a slurry with an equal amount of water (the slurry being ca one-fiftieth the weight of TiCl4), refluxed it for 2-6hours while bubbling in chlorine, the excess of which is subsequently removed by passing a stream of clean dry air. The TiCl4 is then distilled, refluxed with copper and again distilled, taking precautions to exclude moisture. Volatile impurities are then removed using a technique of freezing, pumping and melting. The titanium tetrachloride 2-tetrahydrofuran complex [Beilstein 17/1 V 33.] M 333.9, has m 126-128o and is easier to handle than TiCl4 [Abrahamson et al. Organometallics 3 1379 1984]. [Baxter & Fertig J Am Chem Soc 45 1228 1923, Baxter & Butler J Am Chem Soc 48 3117 1926.] HARMFUL VAPOURS. | [Toxicity evaluation]
It has been hypothesized that harmful effects of titanium
tetrachloride are due to the vigorous reaction with water from
perspiration on the skin, tears, and moisture in the air resulting
in a severely exothermic reaction. The mechanism of injury is
thought to be a combined thermal and acid burn process.
Initially, there is a thermal burn, which exposes deeper tissue
layers to hydrolysis products such as hydrochloric acid,
furthering the severity of the effects.
The results of a mouse study showed that titanium
tetrachloride was more toxic than hydrochloric acid. It is
speculated that the more severe effects seen from exposure
to titanium tetrachloride compared with hydrochloric acid
is because hydrochloric acid is dissolved in the moisture of
the nasopharynx and trachea remaining in this upper
respiratory area and therefore is physically limited in the
extent of lung penetration. However, in the case of exposure
to titanium tetrachloride, the hydrolysis occurs in several
steps. One of the hydrolysis products, titanium oxide
hydrate, is a particulate that can adsorb the hydrochloric
acid vapors that are also generated during hydrolysis and
carry them into the deeper parts of the lungs and to the
alveoli. However, titanium tetrachloride hydrolysis products
such as titanium oxide hydrate can absorb some of the
hydrochloric acid vapors that are also generated during
hydrolysis and carry them past the upper respiratory spaces
and into the deeper parts of the lungs. This mechanism of
toxicity could potentially explain the second- and thirddegree
burns observed after acute dermal exposure to titanium
tetrachloride. |
| Questions And Answer | Back Directory | [Physical Properties]
Colorless or yellow liquid; penetrating acid odor; absorbs moisture from air; produces dense white fumes; density 1.73 g/mL; freezes at –25°C; boils at 136.5°C; critical temperature 464.8°C; critical pressure 46.6 atm; critical volume 339 cm3/mol; reacts with water forming TiO2 and HCl; soluble in ethanol
| [Uses]
Titanium tetrachloride is used to prepare titanium dioxide and most other titanium compounds. It also is used in making iridescent glass; arificial pearls; and smoke screens. The compound is a polymerization catalyst.
| [Preparation]
Titanium tetrachloride is prepared by heating titanium dioxide or the ores ilmenite or rutile with carbon to red heat in a stream of chlorine. When ilmetite is used, ferric chloride also is produced. Titanium tetrachloride is separated from ferric chloride and other impurities by fractionation.
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