Sorption properties of zirconogels

The effect of the pH of precipitation and the nature of the initial zirconium salt and the ionic medium on sorption properties (surface charge, kinetic parameters of sorption) of zirconogels formed due to alkaline hydrolysis of zirconium(iv) sulfate and zirconyl nitrate was studied. Zero point of charge methods, indicator reactions of heterogeneous hydrolysis, drop titration, and thermography were used in the study. The properties of the zirconogels are very close to those of Ferro- and titanogels obtained under similar conditions. The composition of zirconogels, the activation energies of the indicator reactions of heterogeneous hydrolysis, and the dependences of the rate constants of these reactions on the nature and concentration of the ionic medium were determined.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2653–2657, November, 1996,     

Sorption properties of hydrogels of transition and p-metal oxide hydroxides

The experimental data on the sorption properties of hydrogels of Fe^III, Ti^IV, Zr^IV, Sn^IV, In^III, Cr^III, Sm^III, Co^II, and Zn^II oxide hydroxides are summarized. The data were obtained by the point of zero-charge method and by measurin the rates of the indicator reaction,viz., heterogeneous hydrolysis of the chloro complexes of platinum group metals. The compositions of the oxide hydroxides, the pH of the point of zero charge in various ionic media, and the rate constants of the indicator reactions were determined. The values obtained were analyzed in terms of their correlation with the charge, the radius, and the electronic struture of the central ion and with the composition and the preparation conditions of the oxide hydroxide. A data base that allows one to choose an appropriate oxide hydroxide sorbent for extraction of particular complex-forming metals from complexing media is presented. The data obtained confirm the model of the mechanism of heterogeneous hydrolysis and extend its predicting ability. The model was tested experimentally in relation to tin(IV) oxide hydroxide. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 2, pp. 228–238, February, 1999.     

Comparison of the sorption properties of crystalline and amorphous samarium(III) oxohydroxides

The influence of the pH of precipitation (pH₁) and the ionic medium on the sorption properties of as-precipitated samarium(III) oxohydroxides,i.e., the pH of zero charge point and the rate of heterogeneous hydrolysis of the IrCl₆ ²⁻, RhCl₆ ³⁻, and PtCl₄ ²⁻ complexes, was studied. The composition of precipitates was studied by the drop titration of solutions of samarium nitrate and thermography. It was found that as-predipitated samarium oxohydroxides are amorphous and the substitution of NO₃ ⁻ ions by OH⁻ is not complete even at pH₁ 11. Heterogeneous hydrolysis occurs on the surface of samarium oxohydroxide, and its rate increases with increasing pH₁. The as-precipitated samarium oxohydroxides have much higher sorption activities than crystalline Sm₂O₃, and their activities are similar to those of ferrogels. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 583–588, April, 1998.     

The use of the pH at the point of zero charge for characterizing the properties of oxide hydroxides

The modern theoretical views on the point of zero charge of the oxide hydroxide surface are considered. Methods for determination of the pH of the point of zero charge and the use of this value to characterize the properties of oxide hydroxides are described. Examples of using the pH of the point of zero charge in studies of oxide anodes and amorphous oxide hydroxide sorbents are presented. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1029–1035, June, 1999.     

Changes in the acid-base properties of hydrogels of metal oxide hydroxides induced by aging in solutions of electrolytes

Changes in the acid-base properties of titanium(IV), zirconium(IV), iron(III), chromium(III), and indium(III) hydrogels of oxide hydroxides induced by aging in sodium chloride and sulfate solutions were studied by the point of zero charge method. On aging in a solution of the sulfate electrolyte the hydrogels loose their basic properties much more rapidly than in the chloride solution. The most changes were observed in the region of high pH of the point of zero charge of the hydrogels. The changes in the acid-base properties can be explained by a decrease in the content of surface OH groups with are displaced by the supporting electrolyte ions, and due to the oxolation of the hydrogels. Published inIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 8, pp. 1329–1332, August, 2000.     

纳米碳纤维负载钯催化剂在Heck反应中的应用——载体相互作用的影响

使用多元醇还原法制备了均匀分散的钯纳米颗粒.将钯纳米颗粒负载于板式、鱼骨式和管式纳米碳纤维,得到稳定、可重复使用的非均相催化剂.实验结果表明,钯纳米胶粒同载体之间的电位差对钯在载体上的负载量、粒子大小以及Heck反应中钯的溶失量有很大的影响.在制备过程中,增加钯纳米胶粒同纳米碳纤维表面的电位差能够大大降低钯在Heck反应中的流失.催化剂的反应活性随钯粒子的增大而降低.     

Sorption and diffusion of gases in a polyimide

Sorption and diffusion of gases (CO₂, N₂, and He) in a polyimide (PI2080) film were measured by using an apparatus which gives the sorption rate curves from the initial state to the equilibrium state. Nonlinear isotherms observed for CO₂ sorption were interpreted successfully in terms of the dual-mode model for sorption in glassy polymers. Linear isotherms observed for N₂ and He seemed to obey Henry's law. Two diffusion coefficients (D_I and D_E) were obtained using the short-time method and the long-time method for a Fickian diffusion model, together with the equilibrium solubility (C_e) from each experiment. The initial sorption rate curves agreed with the calculated curves using D_I, however near sorption equilibrium the curves are in accord with the calculated curves using D_E. These observations suggest that some relaxation process is superimposed on the diffusion process. The non-Fickian transport data were correlated successfully with a model that combines time-dependent diffusion and the Fickian model.     

东北草甸棕壤的零电荷点和界面酸-碱反应特征平衡常数

分别采用电势滴定(Potentiometric titration)法, 质量滴定(Mass titration)法和惰性电解质滴定(Inert electrolyte titration)法测定了荷结构负电荷的东北草甸棕壤的零净电荷点(PZNC), 研究表明荷结构负电荷的土壤依然存在与电解质浓度无关的零净电荷点, 三种方法的实验结果分别为2.9, 5.0和3.3. 相比较而言, 电势滴定法和惰性电解质滴定法的结果相近, 而质量滴定法的结果偏高. 对文献中推算表面质子活性位密度(N_s)的方法进行了改进, 得到东北草甸棕壤样品的N_s为2.5 mmol•g^－1. 根据实验测定的pH_PZNC, N_s和结构电荷密度(σ_st)值直接计算得出东北草甸棕壤样品的界面反应特征平衡常数即1-pK模型中的pK, 2-pK模型中pK_a1^int和pK_a2^int, 分别为3.37, 2.42和4.32, 与文献报道的沉积物和蒙脱土的值相吻合.     

Proton adsorption and acid-base properties of Tunisian illites in aqueous solution

Suspensions of illite clay minerals samples of three different origins (American illite from Montana, It(Mo), Tunisian glauconite from Gafsa, It(Ga), and Tunisian illite — chlorite mixed layer from El Hamma, It(Ha)) were prepared. The Fourier Transform Infrared (FTIR) spectroscopy, X-ray Diffractometry (XRD), Electron Scanning Microscopy (SEM) and surface area measurements were used to characterize the three illite samples having different extent of isomorphic substitution. The layers have a permanent negative charge due to isomorphic substitutions and pH dependent charges on the surface hydroxyls on the edges. Surface speciation of these samples was investigated using continuous potentiometric titration and mass titration curves between pH 4 and 11 at 0.001 M, 0.01 M, and 0.1 M NaCl solutions at ambient temperature. The two methods revealed point of zero charge (PZC) of the amphoteric edges sites approximately similar to the purified samples, in the range ～7.5–8.5, ～8.2–8.7, and ～ 9.0–9.3 for It(Mo), It(Ha) and It(Ga), respectively. The PZCs of freshly prepared dispersions are higher than those reported in the literature indicating basic character of these samples (pH of equilibrium suspensions in distilled water were ～7.9–9). In the present study, the focus was on the surface charge characteristics. A simple SCM model approach is presented to explain the illite H⁺ adsorption data. Surface weak acidic sites and surface ionization constants were calculated from titration data using regression methods. Sites with pKa ₁ ^int values of 6–6.7; 5.4–5.8; 6.1–6.6 and sites at pKa ₂ ^int values of 9.2–9.9; 10.2–10.4; 9.3–10 for It(Mo), It(Ga) and It(Ha), respectively, were assigned to amphoteric Al-OH and/or Fe-OH and Si-OH groups on the edges of illite samples.     

Sorption properties of heterocyclic compounds differing by heteroatom in capillary gas chromatography

The dependence of sorption properties on the nature of heteroatoms in substituted five- and six-membered heterocyclic compounds with two heteroatoms (sulfur and oxygen), thiophenes and furans bearing alkyl, formyl, acetyl, and sulfide substituents have been investigated. Equations for calculating the retention indices of analogs have been proposed, and the indices of 35 previously non-investigated substances of these classes have been predicted.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1224–1227, July, 1993.     

Sorption properties of natural clinoptilolite modified by Fe-containing solutions

Sorption properties of clinoptilolite tuff modified by Fe-containing solutions were studied. The absence of sorption of monocharged anions at any pH of the solution and a high sorption capacity (up to 2.0 to 2.5 mg-eq g^–1) for phosphate ions at pH 10 to 11.5 were shown. Desorption of phosphates by solutions of salts and mineral acids was studied.     

Mg-Al-NO_3层状双金属氢氧化物电性质研究

采用电泳法和电势滴定法测定出不同电解质（LiCl,NaCl和KCl）溶液中Mg-Al- NO_3层状双金属氢氧化物（Mg-Al-NO_3LDH）颗粒的ξ电位、等电点、永久电荷密 度以及零电荷点等电化学物理量，探讨了电解质、pH和样品化学组成对Mg-Al- NO_3LDH电性质的影响，研究发现一价阳离子Li~+,Na~+,K~+对Mg-Al-NO_3LDH颗粒 的等电点有影响，电荷点依次增大，而等电点依次降低。     

Study on electric property at interface of positive sol of magnesium aluminum hydroxide

The isoelectric point (IEP) and zero point of charge (ZPC) of magnesium aluminumhydroxide were studied by electrophoresis method,potentiometric titration method,and elemental analysis.Results showed that the charge of magnesium aluminum hydroxide was composed of variable charge and permanent positive charge.Because of the permanent positive charge,the IEP and ZPC obtained were higher than calculated.The IEP decreased and ZPC increased as X increased.     

Sorption of light gases in glassy poly(ethyl methacrylate)

Although gas sorption in glassy polymers is a well‐studied phenomenon, no general microscopical model is developed which is able to describe the gas sorption in a wide temperature range using only characteristics of polymer and gas molecule. In this work, sorption isotherms and desorption kinetics of O₂, Ar, and N₂ for glassy poly(ethyl methacrylate) have been measured in the temperature range from 160 to 308 K. To describe both the phenomena, the model is developed which postulates that, in the frozen structure of glassy polymer, any cavities between macromolecules are the sorption sites for small molecules. The cavities of small size can expand elastically to accommodate a gas molecule. The sorption sites are considered to be the potential wells and their depths are distributed according to Gaussian law. The concentration of sorption sites, their mean depth and depths dispersion, and the frequency of molecules oscillations in the sorption sites are the only parameters which determine both the gas transport and sorption. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 288–296     

A Microcalorimetric Study of Water Vapor Sorption on Morphine Sulphate

Water vapor sorption on morphine sulphate was studied in a twin double sorption microcalorimeter at 25°C. The vapor sorption isotherm and the differential heats of sorption were determined simultaneously from dry condition to a water activity of 0.99. Two well resolved hydration steps were obtained on the sorption isotherm at water activities of 0.01 and 0.22 corresponding to the formation of dihydrate and pentahydrate of morphine sulphate. They were accompanied by constant values of the differential heats of sorption: –24 kJ mol^–1(H₂O) for the dihydrate formation and –10 kJ mol^–1(H₂O) for the pentahydrate formation.The calorimetrically obtained sorption isotherms were compared with the results of Karl Fisher titrations of morphine sulphate samples equilibrated at different water activities. The appearance of a liquid phase in the morphine sulphate at high water activities is discussed on the basis of the obtained differential heats of sorption and measured heat capacities of morphine sulphate at different water activities.This revised version was published online in November 2005 with corrections to the Cover Date.     

Sorption of Water Vapour on Exinite Concentrates

Maceral concentrates of the exinite group, isolated from the hard coals from the Janina and Brzeszcze Mines were studied. Sorption studies in the coal-water vapour system and the concentrates maceral-water vapour system were carried out using the volumetric method (under isothermal-isobaric conditions) at 298 K, at the following relative sorbate pressures: 0.19; 0.34; 0.52; 0.70 and 0.88.The presented sorption isotherms show that the exinites isolated from coals have higher water vapour sorption capacities than the coals from which they were isolated. Their sorption capacity is closely related to the accessibility of their porous structure during the interfacial-volumetric process of water vapour interaction in the coal substance.     

Temperature effects on the point of zero charge and isoelectric point of a red soil rich in kaolinite and iron minerals

The effects of temperature (373–1373 K) on the point of zero charge (PZC) and isoelectric point (IEP) of a red soil rich in kaolinite and iron minerals were studied. PZC values of the soil treated at 373 and 573 K indicated the presence of iron oxide. The soil calcined between 773 and 1173 K shows a PZC almost coincident with the respective values of kaolinite. At 1373 K, the PZC of the soil is nearer to the value of iron oxide. In the entire temperature range studied the PZC values were lower than the IEP values. An approach of PZC and IEP values was observed after a partial removal of iron oxide by the dithionite-citrate-bicarbonate (DCB) method. The analyses of the PZC and IEP values, of electron probe micro analysis (EPMA) data and of specific surface areas evidence a specific adsorption of iron oxide on kaolinite. Finally, the dissolution sequence of iron and aluminium contained in soil was determined using hydrochloric acid.     

多孔有机骨架:基于傅氏烷基化反应的合成与气体吸附性质

通过傅氏烷基化反应成功地合成了基于四苯锗烷构筑单元的多孔有机骨架材料PAF-9。用红外光谱,粉末射X线衍射,固体核磁共振,热重分析和低温氮气吸附-脱附表征了PAF-9材料的微结构与孔道性质。表征数据表明PAF-9具有非常高的热稳定性和化学稳定性,同时具有较高的比表面积。该PAF材料的BET比表面积为334m²·g^-1。此外,得到的PAF材料对二氧化碳具有较好的吸附能力。     

多孔有机骨架:基于傅氏烷基化反应的合成与气体吸附性质

通过傅氏烷基化反应成功地合成了基于四苯锗烷构筑单元的多孔有机骨架材料PAF-9。用红外光谱,粉末X射线衍射,固体核磁共振,热重分析和低温氮气吸附-脱附表征了PAF-9材料的微结构与孔道性质。表征数据表明PAF-9具有非常高的热稳定性和化学稳定性,同时具有较高的比表面积。该PAF材料的BET比表面积为334 m²·g^-1。此外,得到的PAF材料对二氧化碳具有较好的吸附能力。