Sorption of the peroxocomplex of titanium on silica gel and its analytical use

Summary Sorption of the titanium peroxocomplex on silica gel was studied in dependence on the pH and on the presence of various complexing substances, especially tartaric and citric acids. The distribution coefficients for the titanium peroxocomplex and for some other components were determined. Optimum conditions were established for the separation of small amounts of titanium from a number of accompanying cations and anions on a column and under static conditions.     

Determination of small amounts of titanium in pure molybdenum,tungsten, vanadium and their oxides after separation on silica gel

A new method for the separation of titanium from molybdenum, tungsten and vanadium is described, based on sorption of the titanium complex with hydrogen peroxide on silica gel under dynamic conditions. The eluted titanium is determined spectrophotometrically with diantipyrylmethane. The method can be applied to the determination of small amounts of titanium in tungsten, molybdenum and vanadium metals and in their oxides.     

Determination of microamounts of zirconium(IV) and titanium(IV) with preliminary TLC separation

By the application of thin-layer chromatography on silica gel H and the solvent system consisting of 6 M HCl:acetylacetone: 9 M H₂SO₄ (60:2:1, v/v/v), zirconium and titanium have been quantitatively separated from each other, as well as from numerous other interfering ions. The efficiency of the chromatographic separation was evaluated by semiquantitative determination of zirconium and titanium by visual colorimetry of spots in situ, as well as by spectrophotometric determination of zirconium with rutin after its elution from silica gel H thin-layer.     

Colorimetric and gravimetric determination of silicon in titanium and titanium alloys

Improved colorimetric and gravimetric methods are proposed for the determination of silicon in titanium and titanium alloys. In the colorimetric method the sample is dissolved in hydrofluoric acid. boric acid added and the; titanium oxidized with hydrogen peroxide and permanganate. The bulk of the titanium is precipitated as a crystalline precipitate by heating in boiling water, and the molybdenum color developed. A portion of the solution is filtered and the transmittance measured. In the gravimetric method the sample is fumed with milfuric acid. the silica ignited and fused with aodium carbonate, The silica is then dehydrated with perchloric acid. Thecolorimetric method is recommended for 0.003 to 1.5% silicon, and the gravimetric method for 0.3 to 5% silicon.     

Synthesis of silica–titania composite oxide via “green” aqueous peroxo-route

The preparation procedure of silica–titania composite oxide using novel solution/sol single precursor containing titanium peroxocomplex and silicic acid has been described. Pechini-type sol–gel process has been used to prepare oxides from the aqueous precursor. Some structural, morphological and textural characteristics of the prepared material have been presented. Composite SiO₂/TiO₂ has high surface area (c.a. 300 m²/g), and it is composed of anatase nanoparticles with the mean diameter of 5 nm embedded in amorphous silica, then TiO₂ prepared via similar method is presented as a mixture of anatase and rutile phases. The proposed synthetic procedure meets the requirements of “green chemistry”.     

Precise determination of boron in titanium by inductively coupled plasma mass spectrometry

A method was developed for the determination of boron in titanium by inductively coupled plasma mass spectrometry (ICP-MS). A commercially available PTFE sample introduction system, leading to the desired low detection limits for boron, was used. The method is suitable for the determination of boron concentrations down to about 1 μg g^?1 in the solid material. The influence of the internal standard on the precision was studied and beryllium was selected as the internal standard. For the titanium analysed (BCR reference material 090), the ICP-MS result agreed with those obtained using other techniques. Several bars of titanium reference material were supplied and a study of the homogeneity of boron in this material was made. Using analysis of variance on the results obtained for the different bars, the homogeneity of boron in the reference material could be estimated to be better than 2.1%.     

Analytical control of silica glass production. Voltammetric determination of titanium and iron in raw materials and silica glass samples

Adsorptive stripping voltammetric (AdSV) methods are presented for the determination of titanium and iron in quartz and silica glass samples obtained after pressure decomposition. Mandelic acid and catechol were used as complexing agents for titanium and iron, respectively. The method for titanium determination is based on the catalytic effect of chlorate ions. An insoluble residue remaining after decomposition of quartz and silica glass samples in HF+H2SO4 mixture was checked by energy-dispersive X-ray analyses. ET-AAS was applied as a reference method to AdSV measurements.     

Analytical control of silica glass production. Voltammetric determination of titanium and iron in raw materials and silica glass samples

Adsorptive stripping voltammetric (AdSV) methods are presented for the determination of titanium and iron in quartz and silica glass samples obtained after pressure decomposition. Mandelic acid and catechol were used as complexing agents for titanium and iron, respectively. The method for titanium determination is based on the catalytic effect of chlorate ions. An insoluble residue remaining after decomposition of quartz and silica glass samples in HF+H₂SO₄ mixture was checked by energy-dispersive X-ray analyses. ET-AAS was applied as a reference method to AdSV measurements.     

Diantipyrilmethane as complex-forming reagents in the thin-layer chromatographic determination of metals

Summary The efficiency of diantipyrilmethane used as a reagent for the chromatographic separation of metals, including titanium, zirconium and hafnium, rare earth elements, transition and platinum metals is shown. The peculiarities of the chromatographic behaviour of metal diantipyrilmethanates and the mechanism of their retention in TLC are discussed. Methods were developed for the determination of metals based on complex formation directly in the sorbent layer or by liquid extraction. The chromatographic separation takes place in silica gel thin layers with elution by organic solvent-mineral acid mixtures. The metals are determined by densitometric or spectrophotometric methods. After the complexes are isolated from the layer. The procedures are characterized by simplicity, efficiency, and a rather high selectivity. They were used to analyze steels, alloys, industrial solutions and other samples.     

聚丙烯接枝马来酸酐/SiO_2复合载体型钛催化剂制备及表征

可用于负载烯烃聚合催化剂的材料很多,目前无机载体以SiO2和MgCl2最为普遍.但SiO2和MgCl2容易出现团聚现象,特别是由于SiO2表面羟基分布不均匀,会造成载体局部区域的催化剂浓度过大,活性中心过于集中,对烯烃共聚合时共聚单体的分布不利[1].聚合物载体由于表面的官能团分布均匀及分布密度可调,负载后的催化体系对氧、水的稳定性增加.但聚合物载体制备较为复杂,且用研磨法得到的载体颗粒形态及分布不易控制,用于高温聚合时容易破裂.由于无机和有机载体各自具有某些特殊的优点,可以进行互补克服某些不利的因素,因而怎样利用不同类型载体的复配,得到性能优良的复合载体,已成为烯烃催化剂载体化研究的一个重要方向.本文制备了聚丙烯接枝马来酸酐(PMA)/SiO2复合载体,制备了负载化TiCl4烯烃聚合催化剂,其既可以避免由纯无机物为载体而引入过多的无机灰分,又可以避免仅用聚合物为载体而造成的负载率低的缺点,同时保持了无机载体的刚性和聚合物载体官能团的多分布性.     

Structure of products formed in chemisorption of titanium tetrachloride by porous silicas

IR and diffuse-reflectance spectroscopies were used to study the effect of the porous structures of the starting silica and temperature conditions of thermal pretreatment of the matrix and TiCl₄ chemisorption on the structure of titanium oxochloride complexes formed on the silica gel surface.     

Modification of silica gels with small admixtures of titanium ions

Microporous silica gels containing small amounts of titanium ions are synthesized. Addition of Ti ions to the silica gels during the sol-forming step is demonstrated to increase the specific surface area and decrease the volume of sorptive pores. Spectral results indicate that Ti ions uniformly distribute in the silica gel matrix and isomorphously replace Si.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2217–2222, October, 1991.     

Determination of titanium in sea water using catalytic cathodic stripping voltammetry

Titanium(IV) dissolved in sea water can be determined using adsorptive cathodic stripping voltammetry in the presence of mandelic acid. The method is improved by the addition of chlorate to the sample, which causes the peak current to increase by more than an order of magnitude owing to the reoxidation of the Ti(III) (mediated by the chlorate), which was produced at the electrode surface during the potential scan, to Ti(IV), where it again contributed to the reduction current. The sensitivity of the voltammetric technique was thus improved by a factor of 20, and the limit of detection was lowered to 7 pM with 60 s adsorption (ca. 1 pM with 600 s adsorption), sufficiently low to determine titanium in water of oceanic origin. The method was applied to the determination of titanium in the estuary of the River Mersey. The titanium concentration was found to vary between 0.2 and 0.3 nM (at salinities of 32–33) and 1.5 nM (at salinities of 1–4), revealing a conservative behaviour at salinities above 20 and some removal at low salinities.     

A spectrophotometric method for estimation of titanium alkoxide,a catalytically active form of titanium in oligomer/ polymers

A spectrophotometric method was developed for the selective estimation of titanium in alkoxide form in the presence of TiO₂. Polymers like polybutylene terephthalate have been synthesized by using homogeneous catalyst such as titanium tetra-isopropoxide (TTIP). These types of catalysts are susceptible to moisture and convert to inactive TiO_2. Hence, it is essential to have analytical method for selective estimation of alkoxide form of titanium. In this study, we have used O-cresol to convert TTIP to tetra O- cresyl titanate, a colored compound, which was quantitatively analyzed by spectrophotometric technique. Polymer matrix was used in standard solution to compensate the effect of matrix during UV-VIS measurements. Method validation was successfully carried out for linearity, reproducibility, recovery, specificity and the observed acceptable results as per ICH guidelines. 2-sample t-test was performed to check the variation observed between two analysts and the observed p-value indicated the results were statistically similar to each other. Mechanism of color formation was established by synthesis of colored complex called tetra O-cresyl titanate. The structure was supported by ICP, CHNS and NMR analysis. The method is simple and easy to implement at manufacturing plant for initial monitoring of active catalyst concentration in polymer/oligomer samples.     

Synthesis of some new bis-3,4-dihydropyrimidin-2(1H)-ones by using silica-supported tin chloride and titanium tetrachloride

<正>Silica-supported tin chloride and titanium tetrachloride were prepared by the reaction of tin chloride and titanium tetrachloride with activated silica gel in refluxing toluene.These solid acids have been employed as the catalysts for the synthesis of bisdihydropyrimidin -2(1H)-ones from aromatic dialdehydes,1,3-dicarbonyl compounds and urea at 90℃under solvent-free conditions.     

Determination of tin and titanium in soils, sediments and sludges using electrothermal atomic absorption spectrometry with slurry sample introduction

Fast-heating programmes for determining titanium and tin in soils, sediments and sludges using electrothermal atomic absorption spectrometry (ETAAS) with slurry sampling are developed. For titanium determination, suspensions are prepared by weighing 5-40 mg of sample and adding 25 ml of a solution containing 50% (v/v) concentrated hydrofluoric acid. For tin determination, suspensions are prepared by weighing up to 300 mg of sample and then adding 1 ml of a solution containing 25% (v/v) concentrated hydrofluoric acid. Palladium (30 μg) and ammonium dihydrogen phosphate (7% w/v) are used as matrix modifiers for titanium and tin, respectively. Prior mild heating in a microwave oven is recommended for titanium determination. Calibration is carried out using aqueous standards. The tin and titanium contents of a number of samples obtained by using the slurry approach agree with those obtained by means of a procedure based on the total dissolution of the samples using microwave oven digestion. The reliability of the procedures is also confirmed by analysing several certified reference materials.     

Synthesis, characterization, and sorption properties of amorphous titanium phosphate and silica-modified titanium phosphates

Amorphous titanium hydroxyphosphate with formula Ti(OH)(1.36)(HPO(4))(1.32).2.3H(2)O and a new silica-modified titanium hydroxyphosphate with a general formula Ti(OH)(2x)(HPO(4))(2-x).ySiO(2).nH(2)O are synthesized and characterized using IR, TG, XRD, SEM, solid-state NMR, and BET techniques. It is concluded that SiO(2) is evenly distributed within the titanium phosphate (TiP) agglomerates and that neither the separate silica phase nor the titanium silicates are formed during the synthesis of silica-modified titanium hydroxyphosphate. Correlations between the texture, ion-exchange properties of the amorphous titanium hydroxyphosphate, and the amount of SiO(2) present within the TiP matrix are established. Sorption properties of silica-modified titanium hydroxyphosphate toward Cs(+) and Sr(2+) are studied in a series of samples with an increasing amount of silica, at different pH, and in NaCl solutions with a varying ionic strength. It is found that sorption of Cs(+) does not depend practically on the amount of SiO(2) present, whereas the Sr(2+) uptake drastically decreases with an increase of silica amount. The effects of pH and of the electrolyte concentration on the sorption behavior of titanium phosphate are discussed in terms of ionic hydration shell and titanium phosphate structural specificity. The kinetics of sorption processes is also investigated, and the diffusion coefficients for cesium and strontium are obtained.     

共沉淀法制备氧化硅改性的纳米二氧化钛及其性质

采用共沉淀法合成了氧化硅改性的具有高比表面积的纳米二氧化钛.氧化硅的添加提高了二氧化钛纳米颗粒的热稳定性能,有效地抑制了纳米二氧化钛的颗粒增长、团聚和锐钛向金红石的晶型转换.光催化降解亚甲基蓝证明,样品具有较高的光催化活性,而且随着氧化硅添加量的增加,光催化活性提高.     

TiO2光催化氧化-分光光度法测定总磷的研究

借助自行设计并制作的微型高效光催化氧化反应器,采用超细TiO2光催化氧化法对有机磷样品进行氧化处理,测定了有机磷水处理剂及循环冷却水中总磷量。以2-磷酸基丁烷-1,2,4-三羧酸(PBTC)为样本,研究了多种催化反应条件对降解率的影响。本法加标回收率为95.4%~99.1%,相对标准偏差(RSD)0.93%。将测定结果与国标法进行比较,证明此法是一种适宜的总磷分析方法。     

Selective response of dopamine in the presence of ascorbic acid on carbon paste electrode modified with titanium phosphated silica gel

Titanium phosphate grafted on the surface of silica gel (devoted briefly as Si-TiPH) was synthesized and used as bulk modifier to fabricate a renewable three-dimensional chemically modified electrode. The Si-TiPH bulk modified carbon paste electrode was used for the selective determination of dopamine (DA) in the presence of ascorbic acid (AA). The modified electrode offers an excellent and stable response for the determination of DA in the presence of AA. The differential pulse voltammetry peak current was found to be linear with the DA concentration in the range 2 × 10⁻⁷ to 1 × 10⁻⁶ and 2 × 10⁻⁶ to 6 × 10⁻⁵ mol L⁻¹. The detection limit of the proposed method in the presence of 2.0 × 10⁻⁵ M of AA was found to be 4.3 × 10⁻⁸ mol L⁻¹ for DA determination. The proposed method was successfully applied for the determination of DA in injections.