Etude photoelectronique de la separation du plomb et du cadmium par echange ionique sur le phosphate de hafnium: X-ray photoelectronic study of the separation of lead and cadmium ions on crystalline hafnium phosphate used as a cation exchanger

X-ray photoelectronic study of the separation of lead and cadmium ions on crystalline hafnium phosphate used as a cation exchanger.Crystalline hafnium monohydrogenphosphate monohydrate [Hf(HPO₄)₂·H₂O] is a useful cationic exchanger for separating lead(II) and cadmium(II) ions. Studies have been carried out at various pH and in the presence of various ligands. X-ray photoelectron spectroscopy has shown that lead diffuses into the deeper layers of the exchanger while cadmium remains near the surface. This property can be used to improve the selectivity of the method by masking cadmium with a large ligand (1,10-phenanthroline), which prevents the metal from adsorbing without any effect on lead fixation.     

The Crystal Structure of 5,5′,7,7′-tetramethyl-3,3′,9-triethyl thiacarbocyanine perchlorate

The crystal structure of the title compound has been determined by X-ray crystallographic analysis from diffractometer data. The compound is found to exist in the crystalline state as the mono-cis isomer (a). The conjugated chain is in a folded configuration and the two sulfur atoms are on opposing sides. It is the first time such a mono-cis isomer has been analysed by X-ray crystallography.     

[η<Superscript>5</Superscript>-C<Subscript>9</Subscript>H<Subscript>5</Subscript>(1,3-SiMe<Subscript>3</Subscript>)<Subscript>2</Subscript>]HfCl<Subscript>3</Subscript>: A monomeric 12-electron half-sandwich complex

The half-sandwich hafnium complex [gh⁵-C₉H₅(1,3-SiMe₃)₂]HfCl₃ (II) has been synthesized for the first time. The molecular structures of II and its synthetic precursor C₉H₅(1,1,3-SiMe₃)₃ (I) have been determined by X-ray crystallography. Compound II in the crystalline state, is a rare example of a monomeric 12-electron half-sandwich complex.     

Concentration, separation and determination of scandium, zirconium, hafnium and thorium with a silica-based sulphonic acid cation-exchanger

A study has been made of the dependence of the sorption of scandium, zirconium, hafnium and thorium from aqueous solutions with a silica-based sulphonic cation-exchanger (SCE-SiO(2)) on the concentration and nature of the acid medium, time of contact, concentration of the element, and the ionic strength. The selectivity decreases in the order Zr approximately Hf > Th > Sc > Fe(III). The sorption characteristics of silica gel and SCE-SiO(2) have been compared, and the sorption mechanism is discussed. The SCE-SiO(2) exchanger has been used for 100-fold concentration of scandium, zirconium, hafnium and thorium from their 10(-8)-10(-7) M solutions, and a spectrophotometric method has been developed for their determination with a detection limit of 0.5 ng/ml for Zr and Sc and 0.1 ng/ml for Hf and Th. Zirconium and hafnium have been determined in the solvent phase by X-ray fluorescence and atomic-emission methods.     

Thermal Decomposition of Hafnium Phosphate and Related Materials

The thermal decomposition of hafnium phosphate (both in amorphous and crystalline forms), molybdate and tungstate was investigated. Hafnium phosphate has a layered structure, that of molybdate and of tungstate are tetragonal one. On investigating these materials two main endothermic processes with mass loss were observed in the temperature range of 298–1023 K. These processes were identified as crystal and structural water loss of the materials. The total mass loss of hafnium phosphate, molybdate and tungstate was 11,35 and 6.0%, respectively. In the case of mixed hafnium-titanium salts various crystal water quantities were found, depending on the titanium content of the sample. This revised version was published online in July 2006 with corrections to the Cover Date.     

Sels d'aziridinium stables C-fonctionnalisés III: Synthèse et caractérisation d'aziridines protonées épimères à l'azote

Aziridinium ions were prepared from aziridines bearing a functionality on a ring carbon and as isolated crystalline fluorosulfate salts either by protonation in fluorosulfuric acid solution or by alkylation with methyl fluorosulfate. The structural assignement of these ions is based on nmr spectra and on quenching experiments with sodium carbonate. The configurations of the epimeric ions have been assigned by the nuclear Qverhauser effect and the stereoselectivity in protonation is disucussed.     

Hafnium Trialkyls Stabilized by Bulky,Electron‐Rich Aminopyridinates

A series of hafnium aminopyridinates were synthesized and spectroscopically analyzed. In addition, selected examples of these hafnium complexes were characterized by X‐ray single crystal structure analysis. The aminopyridinato ligands used here carry an additional dialkylamine substituent to enhance the electron donating ability of the ligands. Structural data and low temperature NMR spectroscopic investigations are indicative of the increased donating ability of the ligands. Ethylene polymerization studies revealed a rather low catalytic activity most likely due to catalyst instability. Details of the deactivation reaction were investigated by NMR spectroscopy.     

Bis(2‐but­yl‐N,N′‐diisopropyl­amidinato)dichloro­hafnium(IV)

The title compound, [Hf(C₁₁H₂₃N₂)₂Cl₂], is a monomeric hafnium(IV) complex containing two bidentate amidinate ligands and two cis Cl atoms. The crystals are triclinic (space group ) and there is one independent six‐coordinate monomer with a highly distorted octa­hedral geometry in the asymmetric unit. The reported structure is the first hafnium–amidinate complex to be characterized successfully by single‐crystal X‐ray diffraction.     

水热法合成钛硅酸盐新型无机离子交换剂

用水热法合成出一种新型的结晶水合钛硅酸盐（ＣＳＴ）,并用ＸＲＤ、ＳＥＭ、ＤＴＡ－ＴＧＡ、Ｘ－荧光方法对它进行了表征。在１ｍｏｌ／Ｌ ＨＮＯ３的水溶液中,ＣＳＴ对Ｃｓ交换量为０．６３ｍｍｏｌ／ｇ,在ｐＨ＝３时,ＣＳＴ对Ｃｓ的交换量达最大为１．６ｍｍｏｌ／ｇ,表明ＣＳＴ可以在酸性水溶液中作为Ｃｓ的离子交换剂使用。     

Aminopyridinate–FI Hybrids,Their Hafnium and Titanium Complexes,and Their Application in the Living Polymerization of 1‐Hexene

Based on two well‐established ligand systems, the aminopyridinato (Ap) and the phenoxyimine (FI) ligand systems, new Ap‐FI hybrid ligands were developed. Four different Ap‐FI hybrid ligands were synthesized through a simple condensation reaction and fully characterized. The reaction of hafnium tetrabenzyl with all four Ap‐FI hybrid ligands exclusively led to mono(Ap‐FI) complexes of the type [(Ap‐FI)HfBn₂]. The ligands acted as tetradentate dianionic chelates. Upon activation with tris(pentafluorophenyl)borane, the hafnium‐dibenzyl complexes led to highly active catalysts for the polymerization of 1‐hexene. Ultrahigh molecular weights and extremely narrow polydispersities support the living nature of this polymerization process. A possible deactivation product of the hafnium catalysts was characterized by single‐crystal X‐ray analysis and is discussed. The coordination modes of these new ligands were studied with the help of model titanium complexes. The reaction of titanium(IV) isopropoxide with ligand 1 led to a mono(Ap‐FI) complex, which showed the desired fac‐mer coordination mode. Titanium (IV) isopropoxide reacted with ligand 4 to give a complex of the type [(ApH‐FI)₂Ti(OiPr)₂], which featured the ligand in its monoanionic form. The two titanium complexes were characterized by X‐ray crystal‐structure analysis.     

Possibilities of using hafnium neutron filters for reactor NAA with fast neutrons

The possibilities of using hafnium irradiation filters for reactor fast neutron activation analysis have been evaluated. The filter characteristics of hafnium for this application are discussed and compared with some traditional filter materials. The main advantage for hafnium is its ability to remove a great portion of the slowing down neutrons, which may enhance the sensitivity of determination via threshold reactions.     

Nature of ThF bonding in crystalline and glassy states using EXAFS and XANES

A binary glass of thorium and hafnium tetrafluorides (with dopant concentrations of LaF₃) has been investigated using EXAFS and XANES analysis of the L_Ill edge spectra of thorium. Results of EXAFS analysis indicate that there is no change in the number of nearest neighbors of thorium ions. However, the intensity of the white line in XANES is significantly higher in the glass. This increase in intensity has been explained semiquantitatively in terms of enhanced covalency of ThF bonding. Since the coordination number of Th⁴⁺ remains constant in both crystalline and glassy states, covalency enhancement seems to be a general characteristic of glassy state of ionic materials.     

Synthèse du méthanesulfonate de (pyrimidyl-2)-1-(méthylène)-(dioxy-3, 4-benzyl)-4-pipérazinium (Piribedil) marqué au 14C

The synthesis of crystalline 1-(2-pyrimidyl)-4-(3, 4-methylenedioxybenzyl)-piperazin methanesulfonate (ET 495) labelled with ¹⁴C fixed on the piperazine nitrogen N(4) has been realized in five steps from barium carbonate ¹⁴C; Specific activity of the final product: 32,8 mCi/mmol (110 m?Ci/mg); radiochemical purity: around 99%. The mass spectrum of the labelled compound is in agreement with the chemical structure and the labelling position expected.     

A simple method for the preparation of pure hafnium

The separation of zirconium and hafnium by fractional precipitation as pyrophosphate¹ has been extended for the preparation of pure hafnium. The favourable uptake of hafnium, in spite of the decreasing tendency of partition factor when hafnium concentration is high, is maintained for all concentration of hafnium (relative to zirconium). Particularly significant is the fact that at very high concentrations of hafnium (at≈84%) the uptake of zirconium sharply falls. So pure hafnium can be prepared from natural zirconium by a simple process of eight or nine stages of fractional precipitations as pyrophosphate. This process yields reactor grade zirconium on the one side and pure hafnium on the other side.     

Structures de deux β-énaminoesters cycliques: l'α-(tétrahydropyrrolidinylidéne-2) acétate d'éthyle et l'α-(hexahydroazepinylidéne-2) acétate d'éthyle

The structure of ethyl α-(tetrahydro-2-pyrrolidinylidene) and α-(hexahydro-2-azepinylidene) acetates has been determined from the X-ray crystallographic analysis. The results show that, in a solid state, these compounds exist as β-enaminoesters which have a Z configuration. They also show the presence of intra and intermolecular hydrogen bonding.     

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.     

Extractive separation of group IVB elements: analysis of alloy samples

A method is proposed for the extraction and mutual separation of quadrivalent titanium, zirconium and hafnium from hydrochloric acid using triphenylphosphine oxide dissolved in toluene as an extractant. The optimum conditions for the extraction and separation have been evaluated from critical study of acid concentration, extractant concentration, period of equilibration and effect of diluent. The effect of foreign ions on the extraction and determination is also discussed. The probable composition of the extracted species has been deduced from logD-logC plots. The method affords mutual separation of titanium, zirconium and hafnium and is applicable to the analysis of alloy samples.     

Tautoméric entre structures α-aleoxy énaminocétone et β-céto iminoéther présentée par les pipéridéines résultant de la semihydrogénation d'alcoxy-2 acyl-3 pyridines

The palladium or platinium-catalyzed partial hydrogenation of some 2-alkoxy-3-acylpyridines has been performed in order to study the tautomerism of the resulting tetrahydropyridines. Reduction of the pyridine ring to tetrahydropyridine occurs selectively for the bicyclic compounds 2 and 3, while predominant reduction of the keto group takes place in the case of the derivative 1 carrying the acyl group in an open chain; this different behaviour towards partial hydrogenation is tentatively explained as a consequence of “I-strain” effect. Whereas the bicyclotetrahydropyridine 6 and 7 present exclusively an α-alkoxy enaminoketone structure, the open chain substituted tetrahydro-pyridine 5 exists only as a β-keto iminoether as shown by ir and proton nmr studies. Total displacement of tautomerism towards one of these two structures is interpreted as the result of the unfavourable interaction of nitrogen and oxygen lone pairs which would occur in a bicyclic iminoether, as compared to the stabilizing interaction of an oxygen lone pair and the N-H bond of the enaminoketone structure, which can be realized without increase of steric crowding in the bicyclic case.     

Synthesis of mono and diesters using eco-friendly solid acid catalyst – zirconium titanium phosphate

Abstract

Amorphous zirconium titanium phosphate (ZTPA), an advanced inorganic ion exchanger of the class of tetravalent bimetallic acid (TBMA) salt, has been synthesized by sol gel route. ZTPA has been characterized by inductively coupled plasma atomic emission spectrometer (ICP-AES), Thermal analysis, Fourier transform infrared spectrometer (FTIR), and X-ray diffraction (XRD). The acid sites present in ZTPA indicate good potential to be explored as solid acid catalyst. The catalytic characteristics of ZTPA have been evaluated by determining surface area and surface acidity. The catalytic performance of ZTPA as a solid acid catalyst has been explored by studying esterification as a model reaction wherein mono and diesters have been synthesized. Crystalline zirconium titanium phosphate as well as amorphous and crystalline phases of zirconium phosphate and titanium phosphate have also been synthesized, characterized, and their catalytic performance investigated for comparative studies. TBMA salt exhibits enhanced catalytic activity compared to its single salt counterparts and amorphous phases exhibit higher catalytic activity compared to their crystalline phases.     

Radiothermoluminescence of <Emphasis Type="Italic">n</Emphasis>-eicosane mixtures with <Emphasis Type="Italic">n</Emphasis>-tetracosane: Effect of mixture composition

Radiothermoluminescence (RTL) curves of mixtures of C20 and C24 n-alkanes have been deconvoluted into the curves of crystalline and disordered regions, and their change depending on the mixture composition has been analyzed. The shape of the total RTL curve of the mixture regardless of the its composition is fundamentally different from that shape of the sum of the curves of the individual components taken in the relevant ratios. The difference becomes noticeable at as low a C20 amount in the mixture as 2% and is manifested in the disappearance of the intense RTL peaks of the individual components and appearance of new intense peaks in temperature intervals other than those of the RTL peaks of the components. It has been shown that these changes correlate with changes of the crystalline structure of the mixture: a new crystalline structure other than the structure of any of the individual components emerges and the mixture becomes amorphous. High selectivity of charge trapping in disordered regions of the mixture has been revealed: the contribution of RTL of the disordered regions to the total curve is many times higher than their volume fraction in the mixture. This selectivity might be due to an increase in concentration of defects in the unordered regions of the mixture in comparison with their concentration in the pure alkanes. These defects are traps for electrons that are accessible to acceptors introduced into the mixture.