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ZIRCONIUM (IV) CHLORIDE

ZIRCONIUM (IV) CHLORIDE


IUPAC names: Zirconium tetrachloride, Zirconium(IV) chloride
CAS Number: 10026-11-6
EC Number: 233-058-2
Chemical formula: ZrCl4
Molar mass: 233.04 g

Zirconium(IV) chloride, also known as zirconium tetrachloride, (ZrCl4) is an inorganic compound frequently used as a precursor to other compounds of zirconium.
This white high-melting solid hydrolyzes rapidly in humid air.

Structure
Unlike molecular TiCl4, solid ZrCl4 adopts a polymeric structure wherein each Zr is octahedrally coordinated.
This difference in structures is responsible for the disparity in their properties: TiCl
4 is distillable, but ZrCl
4 is a solid.
In the solid state, ZrCl4 adopts a tape-like linear polymeric structure—the same structure adopted by HfCl4.
This polymer degrades readily upon treatment with Lewis bases, which cleave the Zr-Cl-Zr linkages.

Synthesis
This conversion entails treatment of the oxide with carbon as the oxide "getter" and chlorine.
ZrO2 + 2 C + 2 Cl2 → ZrCl4 + 2 CO

A laboratory scale process uses carbon tetrachloride in place of carbon and chlorine:[5]
ZrO2 + 2 CCl4 → ZrCl4 + 2 COCl2

Applications:
Precursor to Zr metal:
ZrCl4 is an intermediate in the conversion of zirconium minerals to metallic zirconium by the Kroll process.
In nature, zirconium minerals invariably exist as oxides (reflected also by the tendency of all zirconium chlorides to hydrolyze).

For their conversion to bulk metal, these refractory oxides are first converted to the tetrachloride, which can be distilled at high temperatures.
The purified ZrCl4 can be reduced with Zr metal to produce zirconium(III) chloride.

Other uses:
ZrCl4 is the most common precursor for chemical vapor deposition of zirconium dioxide and zirconium diboride.

In organic synthesis Zirconium (IV) Chloride is used as a weak Lewis acid for the Friedel-Crafts reaction, the Diels-Alder reaction and intramolecular cyclisation reactions.
Zirconium (IV) Chloride is also used to make water-repellent treatment of textiles and other fibrous materials.

Properties and reactions:
Hydrolysis of ZrCl4 gives the hydrated hydroxy chloride cluster called zirconyl chloride.
This reaction is rapid and virtually irreversible, consistent with the high oxophilicity of zirconium(IV).
For this reason, manipulations of ZrCl4 typically require air-free techniques.

ZrCl4 is the principal starting compound for the synthesis of many organometallic complexes of zirconium.
Because of its polymeric structure, ZrCl4 is usually converted to a molecular complex before use.
Zirconium (IV) Chloride forms a 1:2 complex with tetrahydrofuran: CAS [21959-01-3], mp 175–177 °C.
NaC5H5 reacts with ZrCl4(THF)2 to give zirconocene dichloride, ZrCl2(C5H5)2, a versatile organozirconium complex.

One of the most curious properties of ZrCl4 is its high solubility in the presence of methylated benzenes, such as durene.
This solubilization arises through the formation of π-complexes.

The log (base 10) of the vapor pressure of Zirconium (IV) Chloride (from 480 to 689 K) is given by the equation: log10(P) = −5400/T + 11.766, where the pressure is measured in torrs and temperature in kelvins.
The log (base 10) of the vapor pressure of solid Zirconium (IV) Chloride (from 710 to 741 K) is given by the equation log10(P) = −3427/T + 9.088.
The pressure at the melting point is 14,500 torrs.

Appearance: white crystals
Density: 2.80 g/cm3
Melting point: 437 °C
Solubility: Decomposed by water to form ZrOCl2 and HCl

Boiling point: 331 °C 
Hydrogen Bond Donor Count: 0
Hydrogen Bond Acceptor Count: 0
Rotatable Bond Count: 0

Exact Mass: 231.777159
Monoisotopic Mass: 229.780110
Topological Polar Surface Area: 0 Ų
Heavy Atom Count: 5

Complexity: 19.1
Isotope Atom Count: 0
Defined Atom Stereocenter Count: 0
Undefined Atom Stereocenter Count: 0

Defined Bond Stereocenter Count: 0
Undefined Bond Stereocenter Count: 0
Covalently-Bonded Unit Count: 1
Compound Is Canonicalized: Yes

Zirconium (IV) Chloride is a white lustrous crystalline solid.
Used as a source of pure zirconium, as a tanning agent, in analytical chemistry and in treating textiles.
Zirconium (IV) Chloride is decomposed by water.
Corrosive to metals in the presence of moisture and to tissue.

Zirconium (IV) Chloride is a zirconium coordination entity comprising four chlorine atoms bound to a central zirconium atom.
Zirconium (IV) Chloride has a role as a catalyst.
Zirconium (IV) Chloride is a zirconium coordination entity and an inorganic chloride.

About Zirconium (IV) Chloride:
Helpful information
Zirconium (IV) Chloride is registered under the REACH Regulation and is manufactured in and / or imported to the European Economic Area, at ≥ 1 000 to < 10 000 tonnes per annum.

Uses at industrial sites:
Zirconium (IV) Chloride is used in the following products: metals.
Zirconium (IV) Chloride has an industrial use resulting in manufacture of another substance (use of intermediates).
Zirconium (IV) Chloride is used for the manufacture of: chemicals and metals.
Release to the environment of Zirconium (IV) Chloride can occur from industrial use: as an intermediate step in further manufacturing of another substance (use of intermediates).

Manufacture:
Release to the environment of Zirconium (IV) Chloride can occur from industrial use: manufacturing of the substance.

Zirconium(IV) Chloride (Zirconium Tetrachloride) is an excellent water soluble crystalline Zirconium source for uses compatible with chlorides.
Chloride compounds can conduct electricity when fused or dissolved in water.
Chloride materials can be decomposed by electrolysis to chlorine gas and the metal.

They are formed through various chlorination processes whereby at least one chlorine anion (Cl-) is covalently bonded to the relevant metal or cation.
Ultra high purity and proprietary formulations can be prepared.
The chloride ion controls fluid equilibrium and pH levels in metabolic systems.

They can form either inorganic or organic compounds.
Zirconium Chloride is generally immediately available in most volumes.
High purity, submicron and nanopowder forms may be considered.
We also produce Zirconium Chloride Solution.

American Elements produces to many standard grades when applicable, including Mil Spec (military grade); ACS, Reagent and Technical Grade; Food, Agricultural and Pharmaceutical Grade; Optical Grade, USP and EP/BP (European Pharmacopoeia/British Pharmacopoeia) and follows applicable ASTM testing standards. Typical and custom packaging is available, as is additional research, technical and safety (MSDS) data.
Please contact us above for information on specifications, lead time and pricing.

Zirconium (IV) Chloride is commonly utilized as a Lewis acid catalyst in many organic synthesis reactions.
Zirconium (IV) Chloride is an important source for organometallic complexes of zirconium.
Zirconium (IV) Chloride is practiced in many areas like nuclear industry, metal industry, photography, glass, and ceramic industry.

Zirconium (IV) chloride, also known as Zirconium (IV) Chloride, is the inorganic compound with the formula ZrCl4.
This white high-melting solid hydrolyzes rapidly in humid air.
Zirconium (IV) Chloride is a key reagent in the chemistry of zirconium.
In organic synthesis Zirconium (IV) Chloride is used as a weak Lewis acid for the Friedel-Crafts reaction, the Diels-Alder reaction and intramolecular cyclisation reactions.
Zirconium (IV) Chloride is also used to make waterrepellent textiles.

Zirconium (IV) chloride is found to be an efficient catalyst for the electrophilic addition reaction of indole with aldehydes/ketones to afford the corresponding bis(indolyl methanes in good yields.
The remarkable features of this new procedure are high conversions, shorter reaction times, cleaner reaction profiles and simple experimental and work-up procedures.

Zirconium (IV) Chloride (Zirconium Tetrachloride) is an excellent water-soluble crystalline Zirconium source for uses compatible with chlorides.
Chloride compounds can conduct electricity when fused or dissolved in water.
Chloride materials can be decomposed by electrolysis to chlorine gas and the metal.

They are formed through various chlorination processes whereby at least one chlorine anion (Cl-) is covalently bonded to the relevant metal or cation.
Ultra-high purity and proprietary formulations can be prepared.
The chloride ion controls fluid equilibrium and pH levels in metabolic systems.
They can form either inorganic or organic compounds.

Zirconium (IV) Chloride Applications:
Used for making zirconium metal, pigment, textile waterproofing agent, leather tanning agent, etc.
Used for the preparation of zirconium compounds and organometallic organic compounds, can be used as a solvent and the purification agent of remelting magnesium, with the effect of removing iron and silicon

Chemical Properties:
Zirconium (IV) Chloride forms lustrous, white, monoclinic crystals that melt at 437 ℃.
Zirconium (IV) Chloride is a corrosive powder.
Zirconium (IV) Chloride is hygroscopic, and thus soluble in cold water, alcohol, ether, and concentrated hydrochloric acid.
Zirconium (IV) Chloride reacts vigorously with water forming hydrogen chloride (irritating vapor) and zirconium oxychloride.

When moist, Zirconium (IV) Chloride reacts with common materials to form hydrochloric acid that is corrosive to many metals.
Through hydrolysis to HCl, Zirconium (IV) Chloride can irritate the respiratory tract and other superficial surfaces of the body on exposure.
Zirconium (IV) Chloride readily forms coordinate bonds with oxygen and nitrogen in organic molecules.

Physical properties:
White monoclinic crystals; hygroscopic; density 2.80 g/cm3; sublimes at 331°C; triple point 437°C; vapor pressure 1 torr at 190°C; critical temperature 504.85°C; critical pressure 56.95 atm; critical volume 319 cm3/mol; decomposed by water; soluble in alcohol, ether, and concentrated hydrochloric acid.

Uses
Friedel-Crafts catalyst.
Component of Ziegler-type catalysts in the condensation of ethylene.
Starting material in the synthesis of a number of organic derivatives of zirconium, such as alkoxides and zircocene.
The alkoxides have been shown to be of value in the curing of silicone plastic films.
The alkoxyzirconium carboxylates are said to be useful in the water-repellent treatment of textiles and other fibrous materials.

Uses:
Zirconium(IV) chloride (ZrCl4) is a Lewis acid catalyst, which has low toxicity.
Zirconium (IV) Chloride is a moisture resistant material that is used as a catalyst in organic transformations.
ZrCl4 can be used as a catalyst for a variety of organic syntheses, such as Friedel-Crafts reaction, condensation reaction and other reduction reactions.

For applications in organozirconium chemistry.
Activates pyrrolidines for improved conversion, via a modified Bouveault reaction, to the corresponding α,α-dimethylamines.
Zirconium (IV) chloride is used as an efficient catalyst in the Pechmann condensation reaction of phenols with β‐keto esters leading to the formation of coumarin derivatives in good yields under solvent‐free conditions.

Zirconium (IV) Chloride is commonly utilized as a Lewis acid catalyst in many organic synthesis reactions. Zirconium (IV) Chloride is an important source for organometallic complexes of zirconium.
Zirconium (IV) Chloride is practiced in many areas like nuclear industry, metal industry, photography, glass, and ceramic industry.

Preparation:
Zirconium (IV) chloride is obtained as an intermediate in recovering zirconium metal from zircon and other minerals.
The tetrachloride is obtained by heating a mixture of zirconium hydroxide and car 1004 bon with chlorine gas
Also, tetrachloride can be made by reacting zirconium hydroxide with hydrochloric acid: Zr(OH)4 + 4HCl → ZrCl4 + 4H2O.

Zirconium (IV) chloride hydrolyzes rapidly in humid air.
Zirconium (IV) Chloride is a key precursor to other compounds of zirconium.
Unlike molecular TiCl4, solid ZrCl4 adopts a polymeric structure wherein each Zr is octahedrally coordinated.
This difference in structures is responsible for the striking difference in their properties: TiCl4 is distillable, but ZrCl4 is a solid with a high melting point.
In the solid state, ZrCl4 adopts a tape-like linear polymeric structure—the same structure adopted by HfCl4.
This polymer degrades readily upon treatment with Lewis bases, which cleave the Zr-Cl-Zr linkages.

Zirconium(IV) chloride has been found to be a new, highly efficient, and reusable catalyst for acetylation of structurally diverse phenols, thiols, amines, and alcohols under solvent-free condtions.
Acetylation of sterically hindered and electron deficient phenols is achieved in excellent yields with stoichiometric amounts of Ac2O at room temperature.

Acid-sensitive alcohols undergo acetylation with excellent chemoselectivity without competitive side reactions such as dehydration or rearrangement.
The mild Lewis acid property of the catalyst enables the acetylation to be ­carried out with optically active substrates without any detrimental effect on the optical purity.

Zirconium(IV) chloride is used extensively in organic synthesis as an ideal Lewis acid since it is an efficient, stable, inexpensive, environmentally friendly and convenient catalyst for the preparation of useful synthetic intermediates and for use in key steps of natural products synthesis.

This review is broadly divided into four sections based on zirconium(IV) chloride mediated reactions carbon-carbon bond-formation reactions, protection and deprotection chemistry, reduction reactions, and other applications.
This review is an attempt to cover the important advances in the field of synthetic organic chemistry that have been carried out to date.

Applications:
Nano-materials & Thin Films
Catalysis & Synthesis
Optics & Glasses
Sensor
Atomic Layer Deposition

Zirconium (IV) Chloride is an important material with a variety of industrial applications.
Zirconium (IV) Chloride is used in the Kroll process as a precursor to metallic zirconium, as a catalyst in organic synthesis pathways, and for chemical vapor deposition.
Zirconium (IV) Chloride is also encountered in nuclear applications for the recycling of zirconium cladding using a chloride volatility process.

Zirconium (IV) Chloride can be synthesized from the direct reaction between Zr metal and Cl2 gas at high temperatures (>350°C), or from the treatment of ZrO2 with CCl4 or Cl2 gas in the presence of carbon.
Zirconium (IV) Chloride is a very reactive material, it is hygroscopic and reacts rapidly with air to form zirconium oxychloride hydrates; therefore, special care is needed to prepare and handle this material.

Due to its air sensitivity, solid-state chemistry studies on ZrCl4 are sparse and the preparation and handling of ZrCl4 single-crystals suitable for X-ray diffraction is a challenging task.
In the solid-state, ZrCl4 has been characterized by vibrational spectroscopy and singlecrystal X-ray diffraction (SCXRD).

There has been only one SCXRD study on ZrCl4 which dates from the seventies.
Zirconium (IV) Chloride was shown that ZrCl4 crystallizes in the monoclinic space group P2/c and adopts a zigzag chain structure consisting of edge-sharing ZrCl6 octahedra.
The method used to prepare ZrCl4 involved the reaction of ZrO2 with Cl2 + CCl4 in the temperature range 500-700 °C; but the synthetic procedure (mass, reaction time, ramping temperature rate, annealing time,....) was not detailed; it was mentioned that the SCXRD measurement was performed at 20 °C, but the uncertainty on the temperature was not reported.

Because ZrCl4 will be produced from the reaction of Zr metal and Cl2 in zirconium cladding reprocessing, the investigation of the structure of ZrCl4 prepared from Zr metal is of importance; it will be of interest to compare the structure of ZrCl4 obtained from ZrO2 and from Zr metal.
Considering the strategic importance of ZrCl4, the re-determination of its crystallographic structure at various temperatures is also needed; obtaining accurate structural data on ZrCl4 in various ranges of temperature will help theoreticians prove the
accuracy of their theoretical model.

Zirconium chloride is of crucial importance in numerous research fields and industrial applications such as unconventional catalysis, refining of Zr-containing ores by Kroll reduction, chemical vapor deposition, and nuclear engineering.
Chlorination has been proposed for large-scale separation and selective recovery of Zr as ZrCl4 from U–Zr alloys or used nuclear fuel cladding.
Due to the presence of impurities (e.g., Sn, Cr, Fe, etc.) in the recovered ZrCl4, further efforts are necessary to improve the purification process.

This requires fundamental understanding of the materials during each stage of the process. Starting materials consist of Zr cladding such as Zircaloy-4, Zircaloy-2 and Zr–Nb alloys (Zirlo™ and Zr-2.5Nb) while the final product should be Zr metal.
In the chlorination process, the intermediate material is ZrCl4. Our previous efforts have been devoted on fundamental studies of the starting materials described above, followed by ZrCl4.

Therefore, an accurate knowledge of zirconium chlorides is crucial for efficient separation and selective recovery of Zr from cladding materials. While much attention has been given to the theoretical and experimental investigations of crystalline ZrCl4, accurate structural and thermomechanical information of ZrClx (x = 1, 2, 3, 4) molecular species remains scarce.
Due to their chemical similarities and the importance of the refinement process in the nuclear industry, studies on gaseous ZrCl4 are typically performed in conjunction with HfCl4.

The first electronographic approximations calculated the theoretical intensity curves based on the intermolecular distances in ZrCl4 (i.e. Zr–Cl = 2.32 Å and Cl···Cl = 3.79 Å) and in HfCl4 (i.e. Hf–Cl = 2.33 Å and Cl···Cl = 3.80 Å).
Recently, Barnes et al. reported that the vapor pressure of ZrCl4, FeCl3, CrCl4, NbCl5, and NbOCl3 are very similar at temperatures near 330 °C .
The vapor pressure of ZrCl4 has also been measured under vacuum and under argon atmospheres.

In addition, DFT models have been used to predict the volatility and adsorption enthalpies of ZrCl4, ZrOCl2, and ZrCl62− salts in comparison to the other Group IV metal chlorides. These models are for the most part in disagreement with experimental data, demonstrating the complexity of these gas phase interactions.
As for gaseous ZrCl2, the structure, vibrational frequencies, and heat of formation have been predicted, and they are in close agreement with experimental data.

Synonyms:
Tetrachlorozirconium
10026-11-6
ZrCl4
zirconium(4+) tetrachloride
MFCD00011306
Zirconium chloride (ZrCl4)
Zirconium chloride, tetra-
Zirconium chloride, (T-4)-
HSDB 2531
Zirconium(IV) chloride (1:4)
Cl4Zr
EINECS 233-058-2
UN2503
Zirconium chloride (ZrCl4), (T-4)-
DTXSID1044142
CHEBI:77566
8392AF
FT-0656506
EC 233-058-2
Zirconium tetrachloride [UN2503]
Q205630
12331-30-5 [RN]
231-717-9 [EINECS]
MFCD00011309
UNII:Z88176T871
UNII-Z88176T871
Z88176T871

 
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