7705-07-9 Usage
Uses
Used in Chemical Synthesis:
Titanous chloride is used as a strong reducing agent for various chemical reactions, enabling the synthesis of different compounds.
Used in Catalysts:
It serves as a catalyst in Α-olefin polymerization, a process that produces polymers with specific properties.
Used in Azo Dye Analysis:
Titanous chloride is used as the titrant in azo dye analysis, a method for determining the concentration of azo dyes in a sample.
Used in Gas Chromatography Tandem Mass Spectrometry:
Titanium Chloride (≥12% HCl Solution) is used in the optimized gas chromatography tandem mass spectrometry for the quantification of 1,1''-sulfonylbis[2-(methylthio)ethane] in human urine.
Used in Environmental Applications:
As a powerful reducing agent, titanous chloride can reduce nitrate to ammonia and separate sulfur when boiled with aqueous SO2. It is used in aqueous solutions for the estimation of nitro groups, ferric ions, per-salts, etc., and for removing stains in the laundering industry (stripper).
Physical and chemical properties
It appears as deep purple crystal and can be easily subject to deliquescence. Its chemical formula is TiCl3. It has a molecular weight of 154.26. It has a relative density is 2.64, a melting point of 440 °C (decomposition) and the boiling point of 660 °C (106 × 133.322 Pa). It is easily soluble in water and slightly soluble in ethanol with both the solutions exhibiting purple color. Upon heating, the solution will be turned into a blue with further returning back to purple after cooling down. It is unstable and will be faded after standing in the air for a long time with precipitation of metatitanic acid (H2TiO3) precipitate. It can be dissolved in hydrochloric acid and insoluble in ether. Being dissolved in HCl solution will generate titanium tetrachloride tetrahydrate TiCl3 ? 4H2O, which is unstable in the air. It will be subject to decomposition under 440 ℃. In the air, it can be oxidized to Ti (Ⅳ) with moisture being able to accelerate the oxidation process, which must be stored in CO2 atmosphere. The purple TiCl3 ? 6H2O salt prepared by electrolysis of dilute HCl solution of TiCl4 is more stable.
Preparation: it can be obtained through the interaction between the hydrochloric acid solution of titanium tetrachloride and stannous chloride or alternatively through the hydrogen reduction of the hydrochloric acid solution of titanium tetrachloride.
Applications: (1) it can be used for azo dye analysis titration solution for colorimetric determination of copper, iron, vanadium and so on. (2) In synthetic chemistry, it can be used as the reducing agent of tetravalent chromium and an important component of Ziegler-Natta catalyst [Al (C2H5) 3TiCl3], the catalyst can be used for olefin polymerization.
Image 1 the chemical structure of the titanium trichloride.
Chemical reaction
Titanium trichloride has lively chemical nature, being able to react with a variety of elements or compounds: upon heating and oxidation in O2 gas, it will sometimes undergo combustion and generate TiCl4 and TiO2; in H2 gas stream, it will be reduced to TiCl2; and will react with water vapor at 600 ℃ to generate TiOCl and HCl; In the air, it is easily subject to deliquescence, being soluble in water, alcohol and acid. In acid solution, it can be gradually oxidized in the air by O2, can also be oxidized by Fe3 +, Cr2O72-and VO3-and other oxidants; at high temperature, it can react with HCl to generate TiCl4; it can react with Fe2O3, TiO2 and SiO2 at 600 ℃ to generate TiOCl; Under heating, it can be reduced by alkali metal or alkaline earth metal to generate metal Ti. It is unstable chloride with dissociation at high temperatures and disproportionation reaction generating TiCl2 and TiCl4. For anhydrous titanium trichloride (TiCl3), we can use H2, Na, Mg, Al, and Ti as the reducing agent to make it through reducing TiCl4 under appropriate conditions. The aqueous solution of titanium trichloride can be prepared by dissolving the metal Ti in hydrochloric acid under the protection of an H2 atmosphere or an inert gas.
This information was edited by Xiao Nan from lookchem (2015-08-22).
Four crystal forms of titanium trichloride
Titanium trichloride has four crystal forms and one hexahydrate:
?(1) Under high temperature, what obtained through reduction of TiCl4 is alpha type of TiCl3, exhibiting purple sheet structure, belonging to hexagonal system, lattice constant a = 6.122 × 10-8cm, c = 17.52 × 10-8cm. It has a relative density of 2.64. It will undergo decomposition under 440 ° C and has a boiling point of 660 ° C (14.132 × 103Pa).
(2) Reduction of TiCl4 with AlCl3 can give β-TiCl3, a brown powder with fibrous structure. In an inert gas stream and at 250 to 300 ° C, it will be converted to α-type.
(3) Aluminum reduction of TiCl4 will get γ-type TiCl3, a kind of red purple layered crystal.
(4) Grindγ-TiCl3 to obtain δ-type TiCl3, δ-type is purple powder with unknown structure, and has higher catalytic performance than other crystalline TiCl3. It has a melting point of 730 ℃-920 ℃, the relative density of 2.69 and the boiling point of 660 °C (106 × 133.322 Pa). It exhibits purple color after being dissolved in water and slightly dissolved in ethanol with heating leading to blue solution color. The color will go back to become purple after cooling. It will be faded after being stored for a long time under the air, and undergo precipitation of metatitanic acid (H2TiO3) precipitate. It is insoluble in ether. Titanium trichloride is a catalyst for many organic chemical reactions, widely used as the main catalyst for the production of polypropylene. Used as azo dye analysis titration solution, and for colorimetric determination of Cu, Fe and V.
In addition to four different crystal forms, the titanium trichloride also has a hexahydrate (TiCl3 ? 6H2O), being further divided into purple stable type and green unstable type due to ligand coordination. It will undergo disproportionation reaction at a temperature of 450 ° C or more to produce titanium dichloride and titanium tetrachloride. It is insoluble benzene, slightly soluble in chloroform and soluble in ethanol. The hexahydrate is a pale purple crystal. It is easy to absorb moisture, being soluble in water. In dry air, it can undergo slow oxidation and decolorization. In wet air, it will be quickly transformed into titanium dichloride hydrate.
Preparation
Aluminum reduction process: apply an excess of titanium tetrachloride to react with aluminum powder at 136 °C with aluminum chloride being taken as the initiator to produce titanium trichloride and aluminum trichloride. Heat and steam out excess amount titanium tetrachloride for recycling usage. Meanwhile, the aluminum trichloride undergoes sublimation to get finished product of titanium trichloride. Its reaction equation is:
3TiCl4 + Al → 3TiCl3 + A1C13
Preparation
Titanium trichloride may be prepared by reducing titanium tetrachloride with hydrogen at 600°C. The tetrachloride may alternatively be reduced with aluminum, zinc, magnesium, tin, or by electrolysis.
Explosive properties
it is corrosive
Flammable and Hazardous characteristics
In the case of oxidants, H Hole agent is flammable; in case of cyanide, it will release toxic hydrogen cyanide gas with thermal decomposition generating toxic chloride smoke
Storage and transportation characteristics
Treasury should be ventilated, low-temperature and dry; store it separately from oxidants, cyanide, H Hole agent and alkali.
Extinguishing agent water
water, carbon dioxide, foam
Air & Water Reactions
Pyrophoric, very reactive with water and moisture in air produces hydrochloric acid, [Merck 11th ed. 1989]. Ignites spontaneously on contact with air; decomposed by water and water vapor forming HCl. [Handling Chemcials Safely 1980. p. 905].
Reactivity Profile
Acidic salts, such as TITANIUM TRICHLORIDE, are generally soluble in water. The resulting solutions contain moderate concentrations of hydrogen ions and have pH's of less than 7.0. They react as acids to neutralize bases. These neutralizations generate heat, but less or far less than is generated by neutralization of inorganic acids, inorganic oxoacids, and carboxylic acid. They usually do not react as either oxidizing agents or reducing agents but such behavior is not impossible. Many of these compounds catalyze organic reactions. 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.)
Hazard
Fire risk in the presence of oxidizing materials.
Irritant to skin and tissue; open container only
in oxygen-free or inert atmosphere.
Health Hazard
Fire will produce irritating, corrosive and/or toxic gases. Inhalation of decomposition products may cause severe injury or death. Contact with substance may cause severe burns to skin and eyes. Runoff from fire control may cause pollution.
Fire Hazard
Flammable/combustible material. May ignite on contact with moist air or moisture. May burn rapidly with flare-burning effect. Some react vigorously or explosively on contact with water. Some may decompose explosively when heated or involved in a fire. May re-ignite after fire is extinguished. Runoff may create fire or explosion hazard. Containers may explode when heated.
Flammability and Explosibility
Pyrophoric
Safety Profile
A corrosive irritant to
skin, eyes, and mucous membranes. A
severe corrosive because it liberates heat and
hydrochloric acid upon contact with
moisture. If spilled on slun, wipe off with
dry cloth before applying water. May ignite
spontaneously in air. Flammable when
exposed to heat or flame. Reacts violently
with K, HF. Experimental reproductive
effects. When heated to decomposition it
emits toxic fumes of Cl-. See also
TITANIUM COMPOUNDS.
Purification Methods
It is a brown purple powder that is very reactive to H2O and pyrophoric when dry. It should be manipulated in a dry box. It is soluble in CH2Cl2 and tetrahydrofuran, and is used as a M solution in these solvents in the ratio of 2:1, and stored under N2. It is a powerful reducing agent. [Ingraham et al. Inorg Synth VI 52 1960.]
Check Digit Verification of cas no
The CAS Registry Mumber 7705-07-9 includes 7 digits separated into 3 groups by hyphens. The first part of the number,starting from the left, has 4 digits, 7,7,0 and 5 respectively; the second part has 2 digits, 0 and 7 respectively.
Calculate Digit Verification of CAS Registry Number 7705-07:
(6*7)+(5*7)+(4*0)+(3*5)+(2*0)+(1*7)=99
99 % 10 = 9
So 7705-07-9 is a valid CAS Registry Number.
InChI:InChI=1/3ClH.Ti/h3*1H;/q;;;+2/p-3
7705-07-9Relevant academic research and scientific papers
Mahanthappa, Mahesh K.,Huang, Kuo-Wei,Cole, Adam P.,Waymouth, Robert M.
, p. 502 - 503 (2002)
Two titanium compounds containing monoanionic ligands derived from TEMPO were synthesized and structurally characterized, demonstrating the flexibility of the coordination modes adopted by the ligand.
Pollini
, p. 403 - 408 (1983)
The reflectance spectrum of alpha -TiCl//3 has been investigated in the range of photon energy between 1. 8 and 10. 4 ev. The optical constants have been obtained by a Kramers-Kronig analysis of the near normal incidence reflectance. The absorption spectrum of beta -TiCl//3 crystalline films in the same energy region is presented. The results are interpreted by means of a model containing both localized and one-electron band states. The low energy peaks of alpha - and beta -TiCl//3 (between 2 and 4 ev) are assigned to localized interionic transitions between d states of neighboring Ti ions. The strong bands beyond 4 ev are ascribed to charge transfer and band-to-band transitions. It is suggested that the interband gap between the anion 3p and the cation 4s bands is around 7. 5 ev in alpha -TiCl//3 and 6. 9 ev in beta -TiCl//3.
Mamaeva, G. I.,Romanov, G. V.,Spiridonov, V. P.,Troyanov, S. I.
, p. 846 - 849 (1987)
A method for the electron-diffraction investigation of unstable halides of transition elements with lower valences is described.The relative pressures of TiCl4, TiCl3, TiCl2, and TiCl vapors in the TiCl4 + Ti system at 400-2000 deg K were calculated.Electron-diffraction patterns of gaseous TiCl3 at 1100 deg K were obtained.The effective geometrical and vibrational parameters of the TiCl3 molecule were determined.The equilibrium structure with D3h symmetry was found within the harmonic approximation, and the vibrational frequencies and force constants were evaluated.
Reduction of dinitrobenzenes by electron-carrying catalysts in the electrosynthesis of diaminobenzenes
Abakumov, M. V.,Leonova, M. Yu.,Mikhalchenko, L. V.,Novikov, V. T.,Zaplavin, A. P.
, p. 1927 - 1933 (2021/11/05)
The interaction of isomeric dinitrobenzenes (DNBs) with titanium(III), tin(II), and vanadium(II) chlorides, which are reducing agents used as electron carriers in the electrosynthesis of diaminobenzenes, has been studied. Rate constants of the reduction of isomeric DNBs and nitrophenylhydroxylamines by SnCl2 and TiCl3 in a 2 M water-alcohol solution (10 vol.% C2H5OH) of HCl were measured, and activation energies of the reduction of isomeric DNBs were determined. The rates of interaction of DNBs with the listed mediators increase in the series SnCl2 3 2. It is shown that the electrolysis of DNBs in the presence of an excess of these mediators makes it possible to obtain the corresponding diaminobenzenes with a yield of 60–90%.
Fundamental study on synthesis and enrichment of titanium subchloride
Takeda, Osamu,Okabe, Toru H.
, p. 376 - 383 (2009/02/01)
In order to establish a new high-speed/(semi-)continuous titanium production process based on the magnesiothermic reduction of titanium subchlorides (subhalide reduction process), a novel synthetic process for obtaining titanium subchlorides (TiClx, x = 2, 3) by the reaction of titanium tetrachloride (TiCl4) with titanium metal at 1273 K was investigated. It was demonstrated that the efficiency of the TiClx formation improved drastically when molten salts were used as the reaction medium as compared with that of the synthesis by employing the direct reaction of TiCl4 gas with solid titanium. The feasibility of the enrichment process of TiClx in molten salt was also demonstrated. The method for producing the titanium subchlorides investigated in this study can be applied to the new high-speed production process of titanium.
Redox reactions with bis(η6-arene) derivatives of early transition metals
Calderazzo, Fausto,Englert, Ulli,Pampaloni, Guido,Volpe, Manuel
, p. 3321 - 3332 (2007/10/03)
The reactivity of M(η6-arene)2 derivatives of early transition metals (M = Ti, Cr, Mo, arene = MeC6H5; M = V, Nb, arene = 1,3,5-Me3C6H3) has been investigated and the syntheses of new and known compounds are described. The derivatives M(CH3COO)3, M = Ti, V, Nb, Cr; M(CF 3COO)3, M = Ti, Nb, Cr; M(acac)3, M = Ti, V, Mo, acac = acetylacetonato, and M(F6acac)3, F 6acac = hexafluoroacetylacetonato, M = V, Nb have been prepared by reaction of the metal bis(arene) derivatives with the appropriate Lewis acid. The crystal and molecular structure of V(F6acac)3 has been determined. Hydrogen halides or halogens react with M(η6-arene) 2 with formation of metal halides, a highly reactive form of VCl 3 being obtained from V(η6-1,3,5-Me3C 6H3)2 and hydrogen chloride in heptane. TiCl4 oxidizes Ti(η6-arene)2 with complete loss of the arene ligands. An electron transfer process affording ionic derivatives of formula [M(η6-MeC6H5) 2][TiCl4(THF)2], M = Cr (structurally characterized), Mo, has been observed between the THF-adduct of TiCl4 and the appropriate metal-arene derivative of Group 6.
Change in regioselectivity in the monoreduction of 2,4,6-trinitrotoluene with titanium(III) and vanadium(II) ions in the presence of iron(II) and copper(II) salts
Leibzon,Michalchenko,Leonova,Gultyai
, p. 1203 - 1207 (2007/10/03)
Small additives of iron(II) or copper(II) salts change the regioselectivity of 2,4,6-trinitrotoluene monoreduction with titanium(III) chloride affording predominantly less accessible 2-amino-4,6-dinitrotoluene over 4-amino-2,6-dinitrotoluene (from 25% when the reduction occurs in the absence of the iron and copper salts to 70% in the presence of these salts). A possible mechanism of the process is discussed.
Solid state metathesis reactions in various applications
Gibson, Katharina,Stroebele, Markus,Blaschkowski, Bjoern,Glaser, Jochen,Weisser, Martina,Srinivasan, Radhakrishnan,Kolb, Heinz-Juergen,Meyer, Hans-Juergen
, p. 1863 - 1870 (2008/10/08)
Solid state metathesis reactions have been studied in fused silica tubes, by differential thermal analysis, and by X-ray powder diffraction. A selection of reactions between metal (La, Nb, and Ni) chlorides and lithium nitride or lithium acetylide were investigated to get more insight into reaction pathways and intermediate reaction stages that may be adopted on course of the formation of metal nitrides or carbides. Intermediate compounds are considered to be important because they can control the reactivity of a system. Such compounds were traced by changing the molar ratios of reaction partners away from the salt-balanced binary metal nitride or carbide target compositions. New preparative perspectives are discovered when metal chlorides were reacted with lithium nitridoborate or lithium cyanamide. Due to their reductive nature towards several d-block metal chlorides, (BN2)3- and (CN2)2- react to form metals or metal nitrides plus X-ray amorphous BN, and probably C3N4. With lanthanum chloride they can react to form nitridoborates and nitridocarbonates. The metathesis reaction between lithium cyanamide and cyanuric chloride (C3N 3Cl3) instead of metal chloride was studied for the synthesis of C3N4.
Synthesis and reactivity of cyclopentadienyl and indenyl ligands bearing ω-fluorinated pendant groups. Crystal structure of (ortho-F-C6H4)-CPh2-C5H 4SiMe3
Khvorost,Lemenovskii,Ustynyuk,Rufanov,Kipke
, p. 1207 - 1214 (2007/10/03)
A series of cyclopentadienes and indenes with ω-fluorinated pendant groups have been synthesised and their reactivity towards metallating agents n-BuLi, NaH, TIOEt, Me3SiCl, Me3SnCl, TiHal4, ZrX4 (X = Cl, NMe2) has been investigated. The crystal structure of 1-trimethylsilyl-3-(diphenyl-ortho-fluorophenyl-methyl)-cyclopentadiene (3) was determined.
Crystal Structures of Transition-Metal Halides TiCl4, α-TiCl3, WCl4, and TiI2
Troyanov,Snigireva
, p. 580 - 585 (2008/10/08)
The crystal structures of halides TiCl4, α-TiCl3 (low-temperature modification), WCl4, and TiI2 are determined. The crystals of TiCl4 are built of tetrahedral molecules with Ti-Cl distances of 2.156-2.172 A?. The phase transition in the three-layered modification α-TiCl3 below 220 K is accompanied by the distortion of the symmetry to triclinic and formation of the Ti?Ti pairs spaced by 3.43 A?. The structure of WCl4 contains linear chains of WCl6 octahedra that share opposite edges with the distances of 2.69 A? in the W-W pairs. In the layered structure of TiI2, the titanium atoms occupy the octahedral cavities in the two-layer packing of iodine atoms with a Ti-I distance of 2.903 A?.
