Zirconium pivalate: Synthesis and volatility

Zirconium pivalate is synthesized using an original procedure starting from hydrous zirconium oxochloride. The volatility of zirconium pivalate is characterized for the first time in the range from 130 to 210°C using mass spectrometry: the enthalpies of sublimation and the vapor pressure are determined as functions of temperature. Experiments are carried out to compare the thermal stabilities of zirconium pivalate and zirconium acetylacetonate. The property of zirconium pivalate to serve as the precursor for MOCVD of zirconia films is shown.     

A rapid procedure for the simultaneous determination of zirconium and hafnium in high-temperature alloys by means of a spectrophotometric masking approach

Data are presented for a refined spectrophotometric procedure for the simultaneous determination of zirconium and hafnium based on the combined effects of hydrogen peroxide, sodium sulphate, and excess of zirconium ion on the hafnium and zirconium complexes with Xylenol Orange in 0.2M perchloric acid. Isolation procedures for the hafnium/zirconium content of complex high-temperature alloys which result in an ionic substrate compatible with the spectrophotometric masking method were devised.     

Changes in the zirconium local surrounding on ligand substitution in solutions

EXAFS and SAXS methods have been used to examine zirconium hydroxide and oxychloride aqueous solutions in the presence of sulfuric acid in a wide range of concentrations, as well as a zirconium sulfate aqueous solution. The structure of the complexes and their transformation regularities were determined. Structures of the given complexes and structures of zirconium hydroxide and zirconium oxychloride and hydroxide complexes in aqueous solutions were compared. Complexes in zirconium hydroxide and oxychloride aqueous solutions have identical structures in the presence of sulfuric acid. When the concentration ratio of sulfuric acid and the initial compound is low (20–30), the complex is an open trimer with zirconium atoms bonded by sulfate groups. Bridge sulfate groups form Zr-O-S-O-Zr bonds. Apart from the bridge sulfate groups, there are three terminal sulfate groups and three terminal hydroxyl groups for each zirconium atom. When the concentration of sulfuric acid is increased (up to a ratio of 40–100), closed trimers are observed in the solution.     

Gravimetric determination of barium in zirconium metal and in certain zirconium salts

Barium may be determined gravimetrically in quantities ranging from 0.2 to 2.0 mg (± o.1 mg) in hydrated zirconyl chloride and in zirconium metal after complete separation of the zirconium. As much as 10 g of zirconium may be removed by a double precipitation in a (3 to 1) hydrochloric acid medium followed by a cupferron precipitation-chloroform extraction of the residual zirconium. The barium is then determined gravimetrically as barium sulfate in the iron-free, zirconium-free filtrate by precipitation with an excess of ammonium sulfate. As much as 0.015% barium has been found in impure zirconyl chloride, 0.004% in commercial “purified” zirconyl chloride, 0.000% barium in crystal bar zirconium metal and 0.003% barium in zirconium metal sheet. Reproducibility is 0.001%.     

Synthesis of a zirconium sandwich complex and crystallographic characterization of its adduct with tetrahydrofuran

Reductive elimination of alkane from a silylated bis-indenyl zirconium isobutyl hydride affords a zirconium sandwich complex with an unusual eta6 indenyl ligand. Crystallographic characterization of its adduct with tetrahydrofuran has been achieved and reveals significant localization in the six-membered ring. Complexation of more potent ligands such as carbon monoxide and diphenylacetylene are effective in promoting haptotropic rearrangement of the eta6 indenyl ligand and provides familiar bent zirconocene derivatives. The zirconium sandwich compound also undergoes oxidative addition of carbon-hydrogen bonds of pyridyl ligands, resulting in a crystallographically characterized dimethylamino pyridyl hydride complex of zirconium.     

Sol-Gel Technique for Production of Spherically Granulated Zirconium(IV) Phosphate

A sol-gel technique for production of spherically granulated zirconium(IV) phosphate of Termoksid-3A brand is described. The method includes the following main stages: electrolysis of a zirconium(IV) chloride solution to give a sol of zirconium(IV) hydroxide, drop dispersion of the sol into an ammonia solution, conversion of gel-spheres of zirconium(IV) hydroxide into zirconium(IV) phosphate, and washing and drying of gel-spheres. The physicochemical and ion-exchange properties of the product obtained were studied.__________Translated from Zhurnal Prikladnoi Khimii, Vol. 78, No. 2, 2005, pp. 229–234.Original Russian Text Copyright © 2005 by Sharygin, Kalyagina, Borovkov.     

Determination of zirconium and hafnium with xylenol orange and methylthymol blue

Both Xylenol Orange and Methylthymol Blue are highly selective and sensitive reagents for zirconium and hafnium forming intensely red complexes in an acidic medium. The factors affecting the color formation have been studied. The properties of the complexes have been determined and compared. In general, zirconium forms a more stable complex with the two dyes than hafnium, and Xylenol Orange forms a stronger complex with either zirconium or hafnium than Methylthymol Blue. Hydrogen peroxide can completely mask the zirconium complexes of either dye but only slightly affects the hafnium complex of Xylenol Orange. Zirconium and hafnium can both be determined without separation using peroxide as a masking agent and sulfate as a demasking agent. A bleaching reaction was observed when small amounts of hafnium were added to the red zirconium complex of Methylthymol Blue in 2.4 N perchloric acid or a small amount of zirconium was added to the red hafnium complex of Methylthymol Blue solution at pH 2 to 3.     

Properties of zirconium compounds likely to be of interest to the analytical chemist

A review of zirconium chemistry, with emphasis on the features underlying the chemical methods of determining this element, and an application of zirconium compounds in the analytical chemistry of other species.     

Anion-exchange properties of composite ceramic membranes containing hydrated zirconium dioxide

Composite membranes consisting of an inert ceramic matrix based on aluminum and zirconium oxides and of an ion-exchange component, hydrated zirconium dioxide, were prepared. The selectivity of these membranes to Cl^? ions was studied.     

Synthesis of ordered mesoporous zirconium phosphate films by spin coating and vapor treatments

Ordered mesoporous zirconium phosphate films were prepared on a silicon substrate by spin coating using a mixture of zirconium isopropoxide, triethyl phosphate, Pluronic P123 triblock copolymer, nitric acid, ethanol, and water. The spin-on film was consecutively treated with vapors of phosphoric acid and ammonia. The post-vapor treatments effectively enhanced the thermal stability of an ordered mesostructure when heated to 500 degrees C. XRD and TEM analyses show that the calcined zirconium phosphate film has a hexagonal structure with straight channels parallel to the film surface. The zirconium phosphate film exhibited high proton conductivity of 0.02 S/cm parallel to the film surface at 80% RH and 25 degrees C.     

Mandelic acid and halogen-substituted mandelic acids as reagents for the determination of zirconium

o-, m-, and p-Fluoro- and -trifluoromethylmandelic acids have been prepared and an assessment made of their value as précipitants for zirconium. Though the p-derivatives are satisfactory there are no obvious advantages in their use. Direct weighings of zirconium mandelate and p-bromomandelate, about which there have been conflicting reports in the literature, have been investigated also. P-Bromomandelic acid has been used successfully for the determination of amounts of zirconium oxide between 3 and 50 mg per 100 ml but ignition of the precipitate to zirconium oxide is necessary. Of the acids examined, mandelic itself gives the only precipitate which is almost constant and stoichiometric in composition. The composition of this compound, however, varies slightly with the amount of zirconium present in the solution under test, and though an overall empirical factor can be applied its use is recommended only if a high order of accuracy is not required. If a series of determinations in a narrow range is to be carried out by direct weighing of zirconium mandelate, more accurate results might be obtained by determination of the appropriate factor for that range.     

Zirconocene‐Mediated Carbonylative Coupling of Grignard Reagents

Organozirconocenes are versatile synthetic intermediates that can undergo carbonylation to yield acyl anion equivalents. Zirconocene hydrochloride ([Cp₂ZrHCl]) is often the reagent of choice for accessing these intermediates but generates organozirconocenes only from alkenes and alkynes. This requirement eliminates a broad range of substrates. For example, organozirconocenes in which the zirconium center is bonded to an aromatic ring, a benzylic group, or an alkyl group that possesses a tertiary or quaternary carbon atom α to the carbon–zirconium bond can not be formed in this way. To provide more generalized access to acyl zirconium reagents, we explored the transmetalation of Grignard reagents with zirconocene dichloride under a CO atmosphere. This protocol generates acyl zirconium(IV) complexes that are inaccessible with the Schwartz reagent, including those derived from secondary and tertiary alkyl and aryl Grignard reagents.     

Lipid bilayer templated gold nanoparticles nanoring formation using zirconium ion coordination chemistry

We used positively charged lipids to prepare lipid bilayer assemblies (LBAs) upon which we assembled negatively charged gold nanoparticles (AuNPs). Treatment of the assembly with zirconium chloride resulted in the formation of nanorings of the diameters inversely related to the zirconium ion concentration. The nanorings were attributed to the zirconium ion coordinated AuNPs formed during the lipid bilayer budding process promoted by the acid effect of zirconium chloride. Nanoring organization was also dependent on the fluidity of lipid bilayers, an indication of LBA-assisted nanomaterials organization. We suggest that such bioorganic-inorganic hybrid assemblies coupled to unique topological and morphological variations might be useful as stimuli-responsive sensors or storage compartments for proteins or drugs.     

X-ray determination of traces of hafnium in zirconium metal or traces of zirconium in hafnium metal after separation by ion exchange

A method is proposed for the determination of traces of hafnium in zirconium metal or zirconium in hafnium metal. The trace metals are first separated from the matrix metals on an ion-exchange column and then determined by X-ray analysis.     

Solid-phase mechanochemical synthesis of zirconium tetracarboxylates

The solid-phase synthesis of zirconium carboxylates Zr(OOCR)₄ (R = Alk) by reactions of zirconium tetrachloride with metal carboxylates (isobutyrate, pivalate, and palmitate) (the molar ratio ZrCl₄: RCOOM is 1: (4–5)) under mechanical activation is developed. Further thermal treatment of the reaction mixture and extraction with an organic solvent afford zirconium carboxylates.     

Carbon-oxygen bond cleavage with eta9,eta5-bis(indenyl)zirconium sandwich complexes

Treatment of the eta9,eta5-bis(indenyl)zirconium sandwich complex, (eta9-C9H5-1,3-(SiMe3)2)(eta5-C9H5-1,3-(SiMe3)2)Zr, with dialkyl ethers such as diethyl ether, CH3OR (R=Et, nBu, tBu), nBu2O, or iPr2O resulted in facile C-O bond scission furnishing an eta5,eta5-bis(indenyl)zirconium alkoxy hydride complex and free olefin. In cases where ethylene is formed, trapping by the zirconocene sandwich yields a rare example of a crystallographically characterized, base-free eta5,eta5-bis(indenyl)zirconium ethylene complex. Observation of normal, primary kinetic isotope effects in combination with rate studies and the stability of various model compounds support a mechanism involving rate-determining C-H activation to yield an eta5,eta5-bis(indenyl)zirconium alkyl hydride intermediate followed by rapid beta-alkoxide elimination. For isolable eta6,eta5-bis(indenyl)zirconium THF compounds, thermolysis at 85 degrees C also resulted in C-O bond cleavage to yield the corresponding zirconacycle. Both mechanistic and computational studies again support a pathway involving haptotropic rearrangement to eta5,eta5-bis(indenyl)zirconium intermediates that promote rate-determining C-H activation and ultimately C-O bond scission.     

Voltammetric determination of zirconium using azo compounds

The Optimum oconditions for zirconium complexation with azo compounds are found. The applicability of Eriochrome Red B, Calcon, and Calcion to the voltammetric determination of zirconium, total Zr(IV) and Hf(IV), and Zr(IV) in the presence of Zn(II), Cu(II), Cd(II), Ni(II), or Ti(IV) is demonstrated. The developed procedures are used to determine zirconium in a terbium alloy and in an alloy for airplane wheel drums.     

Sensitive spectrophotometric determination of traces of zirconium with 2-(6-bromo-2-benzothiazolylazo)-5-diethylaminophenol in the presence of sodium lauryl sulphate

A simple and highly sensitive procedure for spectrophotometric determination of zirconium has been developed. At pH 4.6, zirconium reacts with 2-(6-bromo-2-benzothiazolylazo)-5-diethylaminophenol in the presence of sodium lauryl sulphate to form a red-violet complex, which has an absorption maximum at 520 nm. The molar absorptivity at 520 nm is 4.4 × 10⁵ 1.mole⁻¹ .cm⁻¹. Beer's law is obeyed for 0.25–1.50 μg of zirconium in 25 ml of solution. The method has been used in the determination of zirconium in aluminium alloy and steel samples.     

Use of ultrasonic nebulizer with desolvator membrane for the determination of titanium and zirconium in human serum by means of inductively coupled plasma--mass spectroscopy

A technique for the determination of titanium and zirconium in human blood serum, after pressurized digestion utilizing ICP-MS coupled to an ultrasonic nebulizer (USN) and desolvating membrane is described. As no CRM for titanium is available, zirconium has been determined in order to demonstrate the accuracy of the technique, as the limits in blood are well known. Bone cement consists basically of a polymer, namely polymethylmethacrylate (PMMA). For better X-ray contrast some manufacturers use incorporated ZrO2 with a volume fraction of 10 to 15%. Thus, the zirconium present in the PMMA matrix can be used as an indicator for the PMMA particulate debris.     

Solid phase extraction of zirconium as arsenazo(III) complex on agar and spectrophotometric determination

A new solid phase extraction method for the separation and determination of zirconium using agar as an adsorbent is described. The method is based on the adsorption of zirconium as arsenazo(III) complex on agar in a mini-column, elution with sulfuric acid-acetone mixture and determination by spectrophotometry. The effect of different parameters such as pH, concentration of the reagent, eluting reagent, and volume of the sample, amount of the adsorbent and interfering ions was investigated. The calibration graph was linear in the range of 5?C300 ng ml^?1 of zirconium under optimum conditions. The limit of detection based on 3S_b was 1.3 ng ml^?1 and the relative standard deviation (R.S.D) for ten replicate measurements of 15 and 200 ng ml^?1 of zirconium was 3.7 and 1.8%, respectively. The method was applied to the determination of zirconium in water and soil samples.