Strontium and cesium sorption of some Anatolian zeolites

Zeolite samples of Tertiary age obtained from different areas of Anatolia (Turkey) are classified as Clinoptilolite, Analcime or Heulandite and we have investigated their sorption capacity for Cs⁺ and Sr²⁺ ions from aqueous solutions. Quantitative analysis of the zeolite samples untreated and treated with chloride salts of Cs⁺ or Sr²⁺ in aqueous solutions, for Na, Mg, Al, Si, P, K, Ca, Ti, Mn and Fe were performed using EDXRF. Chemical analysis indicated that the Clinoptilolite type zeolite from the deposits of Cankiri-Corum Basin of Anatolia is the best sorber for Sr and Cs ions.Presented at the Sixth International Seminar on Inclusion Compounds, Istanbul, Turkey, 27–31 August, 1995.     

Physicochemical properties of alkali-metal exchanged type X zeolites

The changes in the physicochemical properties of a series of faujasite type X zeolites cation exchanged with K⁺, Rb⁺ and Cs⁺ have been studied by XRD, IR, thermoanalytical methods and sorption measurements. As a consequence of the enhanced scattering of X-rays by larger alkali metal cations, the percent relative intensity of the XRD peaks of cation exchanged zeolites was found to have decreased considerably. The framework IR spectra also showed analogous changes. The alkali metal exchange was found to enhance the thermal stability of the parent zeolite. The available void volume and specific surface area (obtained by low temperature nitrogen sorption) also decreased with the increase in the degree of exchange and cationic size. Equilibrium sorption capacities (298 K andP/P ₀=0.5) for water,n-hexane, cyclohexane and 1,3,5-trimethylbenzene also exhibited the same trend.NCL communication no. 6056.     

Adsorption equilibrium studies for O‐xylene vapour and modified clays system

Tunisian bentonites were used to prepare three modified clays: two organoclays by intercalating respectively didodecyldimethylammoniumbromide (DDMAC) and hexadecyltrimethylammoniumbromide (HDTMAC), and synthesis of NaX zeolite. The X‐ray diffraction, infrared and thermogravimetric analyses enabled us to differentiate between the structures obtained. Clay materials systems were used as adsorbent for the investigation of the adsorption isotherms and saturation capacity of O‐xylene, a toxic volatile organic compound, by gravimetric method at three different temperatures 20, 30, and 40 °C. The absolute values of the volatile organic compound adsorbed amounts in the intercalated clays (604 mg g^?1) were higher than for the zeolite (296 mg g^?1). The adsorption isotherms were analysed by the Freundlich and Langmuir equations. The latter was found to describe better the equilibrium adsorption data. Mass transfer coefficient of O‐xylene is evaluated using uptake curve method, and all values are in the order of 10^?2 s^?1. Copyright © 2014 John Wiley & Sons, Ltd.     

Thermochemical Properties of Chemically Modified Zeolite

Zeolites chemically modified with 1, 4 or 6 M aqueous solutions of NaOH were studied by DTA, TG and ETA (emanation thermal analysis) in the temperature range 201–200°C. The structural changes in the modified zeolites at room temperature and in the modified zeolites annealed at 1000°C were studied by XRD analysis. Thermal analysis demonstrated dehydration, dehydroxylation, structural changes and a glass transition. A gradual loss in crystallinity of the chemically modified zeolites was also observed. XRD analysis revealed structural changes caused by chemical treatment and also by annealing.This revised version was published online in November 2005 with corrections to the Cover Date.     

Synthesis and adsorption investigations of zeolites MCM-22 and MCM-49 modified by alkali metal cations

Ion exchange was made on MCM-22 and MCM-49 zeolites with different Si/Al molar ratios, with Li⁺, Na⁺, K⁺, and Cs⁺ ions and the study of the influence of alkali metal cations on CO₂ adsorption properties was performed. The degree of ion-exchange decreased for larger cations (Cs⁺) apparently due to steric hindrances. The exchange with different cations led to a decrease in the surface area and the micropore volume. Our study shows that the adsorption capacity of the tested zeolites depends significantly on the nature and the concentration of the charge-compensating cations. The highest CO₂ adsorption capacity was obtained on the MWW zeolites with the lowest Si/Al molar ratio and the Li⁺ or K⁺ cations.     

Selective catalytic reduction of nitric oxide with ammonia over Fe-Cu modified highly silicated zeolites

In the present study, the solid-state ion exchange method (SSIE) was applied to introduce iron and copper into highly silicate zeolites: beta (BEA, Si/Al = 12.5), ferrierite (FER, Si/Al = 10) and mordenite (MOR, Si/Al = 10). The activity of the prepared samples in the selective catalytic reduction of NO with ammonia (NH₃-SCR) was measured. The highest performance was recorded for Cu-Fe-BEA followed by Cu-Fe-MOR while Cu-Fe-FER showed a low catalytic activity over the entire reaction temperature range. It is shown in this study that the zeolite framework is one of the parameters controlling the amount, environment and distribution of metal species formed during the ion exchange process in Cu-Fe-zeolite catalysts.     

Gas sorption and transport properties of bisphenol-I-polycarbonate

Gas sorption and transport characterization of a new polymer in the polycarbonate family, based on the bisphenol of 3,3,5-trimethylcyclohexane-1-one (BPI) is reported at 35°C. By comparison with properties of other known polycarbonates, the effects of inhibition of both packing and segmental motion due to the introduction of the bulky substituent in the backbone are elucidated. The T_g of the material was measured with differential scanning calorimeter (DSC) and was found to be unusually high for a polycarbonate (233°C). This indicates a successful inhibition of the large-scale segmental mobility of the polymer. Variable ¹³C NMR analysis indicated that rotation of one phenylene ring has an unusually high (ca. 10 kcal) energy barrier, whereas the other phenylene ring has a more typical rotation profile (barrier < 3 kcal). The density was measured and found to be low (1.107 g/cm³), indicating a high fractional free volume (FFV) for the polymer. Consistent with expectations, the introduction of the bulky-substituted cyclohexane group gave high permeabilities for the various gases tested (N₂, O₂, He, CH₄, CO₂) compared to most standard polycarbonates. On the other hand, the permselectivities were typical for standard polycarbonates. The solubility coefficients of all gases were rather high, as expected for a polymer with such an open structure. © 1994 John Wiley & Sons, Inc.     

Study of benzene sorption in H-ZSM-5 zeolite under catalytic conditions

The equilibrium of the sorption of benzene in an H-ZSM-5 zeolite has been investigated in the temperature range of 100-400°С and at partial pressures 0.11÷0.57 аtm. The data on the sorption under these conditions could be fitted with the Langmuir isotherms taking into account a linear decrease in heats of sorption with the increase in the sorbate loading. The equilibrium constants and heat of the sorption have been determined. This revised version was published online in June 2006 with corrections to the Cover Date.     

Design of modified plastic surfaces for antimicrobial applications: Impact of ionizing radiation on the physical and mechanical properties of polypropylene

Surface modification of polypropylene (PP) sheets was carried out by radiation induced graft polymerization of hydrophilic functional molecules such as N,N-dimethylacrylamide (DMA) and [2-methacryloyloxy)ethyl] trimethylammonium chloride, which is a quaternary ammonium salt (QAS).Polypropylene sheets were activated prior to the grafting reaction by using electron beam radiation. The changes in morphology, crystallinity and tensile parameters like deformation and stress at yield and deformation at break of PP after irradiation were investigated. The results showed that a minor crystalline reorganization takes place during the irradiation of PP at 100 kGy.The grafting has been observed to be strongly dependent on the monomer dilution in the reaction medium. After grafting of QAS (40%) and DMA (20%) it was possible to develop highly hydrophilic surfaces (water contact angle comprised between 30 and 41°). The surfaces of virgin, irradiated and grafted PP were studied using polarized optical microscopy (POM) and scanning electron microscopy (SEM). Spherical particles (i.e. polystyrene or silica beads) adhering to the modified samples were studied according to the surface parameters. Adhesion tests confirmed the strong influence of substrate type (mainly hydrophilicity and roughness) and to a lesser extent underlined the role of electrostatic interactions for the design of plastic surfaces for antimicrobial applications.     

催化裂化条件下噻吩与改性Y分子筛的作用机制

以HY、NiY和稀土离子改性的Y分子筛(REY)为研究对象,采用固定床装置评价噻吩模拟油催化裂化性能;运用气相色谱-氢火焰离子发光检测器(GC-FID)、气相色谱-硫化学发光检测器(GC-SCD)和原位红外光谱技术分析产物,关联分子筛的酸性,研究催化裂化条件下噻吩与改性Y分子筛的作用机制。实验结果表明,催化裂化条件下,噻吩与分子筛的作用机制差异主要取决于与B酸或L酸相关的非骨架铝物种或金属离子物种的存在形式。其中,NiY分子筛中,噻吩主要是吸附在与NiOH⁺物种相关的L酸中心,而Ni₄AlO₄³⁺等物种减弱B酸性中心从而降低其裂化性能。对HY来说,噻吩易在与AlO⁺等物种相邻的B酸中心上聚合形成三联噻吩,并发生一定的氢转移和裂化反应;而对REY而言,分子筛中与RE物种相关的L酸位会促进噻吩在与非骨架铝羟基等物种(如Al(OH)₂⁺、Al(OH)²⁺等)相邻的B酸中心形成的二联噻吩发生氢转移和裂化反应。     

Ideal gas thermochemical properties of silicon containing inorganic,organic compounds,radicals, and ions

The ideal gas thermochemical properties such as standard heat of formation, entropy, and heat capacities of 112 inorganic and 35 organic neutral compounds, radicals, and ions containing silicon were calculated using molecular properties obtained with the G3B3 (or G3//B3LYP) method. Among them were linear and cyclic silanes, silenes, hydrocarbonsilanes, fluorine, and oxygen containing compounds. Many of their molecular and thermodynamic properties were calculated for the first time and 16 of them had no CAS number. Additionally the thermochemical properties were presented in the NASA 7 term polynomial format for the temperature range of 200‐6000 K commonly used in chemical kinetic modeling and simulation programs. The polynomials are available in the Supporting Information supplement to this article free of charge.     

A new thermochemical splitting cycle of sodium chloride for chlorine and sodium hydroxide production

A new thermochemical closed cycle of sodium chloride for the preparation of chlorine and sodium hydroxide is presented in this paper. The optimum conditions of the main reactions in the cycle were obtained from a series of experimental results. The heat flow of the cycle system was calculated based on the related thermodynamic equations and data. The kinetic study of the heterogeneous reaction in the cycle was carried out by means of a thermogravimetric method. The result shows that the proposed cycle demonstrates an obviously energy-saving advantage over all the other methods of chlorine and sodium hydroxide productions. It may become economically competitive with the current electrolytic method in the future.     

The thermochemical reactivity of silicate minerals in hydrogen and methane

The thermochemical reduction of transition metal silicates, i.e. garnierite (Ni,Mg)₆[(OH)₈(Si₂O₇)], chrysocolla (Cu,Al)₂H₂Si₂O₅(OH₄)·nH₂O, dioptase CuSiO₃·H₂O, willemite Zn₂SiO₄, and hemimorphite Zn₄Si₂O₇(OH)₂·H₂O has been studied. By means of combined thermogravimetric/mass spectrometric measurements, X-ray diffraction and analytical scanning electron microscopy it is shown that in a 5% H₂/95% N₂ or in a methane atmosphere the transition metals are selectively reduced at temperatures qualitatively corresponding to their electrochemical potential. Mixtures of elemental transition metals and quartz, SiO₂, are obtained as solid products. Depending on the nature of the parent mineral, different mixtures of volatile products are obtained. Principal volatile product, however, is water vapour. The reduction in methane leads to the formation of syngas.The authors acknowledge the financial support of the Schweizerisches Bundesamt für Energiewirtschaft as well as the Fonds der Chemischen Industrie.     

Determination of enthalpies of formation of organic free radicals from bond dissociation energies 2. Halosubstituted radicals

The enthalpies of formation (ΔH _f ^o) for 23 halosubstituted radicals were determined from the published data on bond dissociation energies. The ΔH _f ^o values of the corresponding molecules necessary for the calculation of ΔH _f ^o of the radicals were taken from handbooks or calculated by the additive-group method. The conjugation energies of the radicals are calculated, and the effect of substituents at the π-system on these values was shown. Errors of determination of the ΔH _f ^o values of the radicals were estimated. For Part 1, see Ref. 1. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 643–646, April, 1998.     

Synthesis of HZSM-5 zeolites with excellent DME aromatization properties by orthogonal test

Abstract

The synthesis conditions of HZSM-5 zeolite, including crystallization temperature, crystallization time and raw material ratio, were investigated by L₃₂ (4⁸) orthogonal test to specifically optimize its performance in dimethyl ether (DME) aromatization for the first time. Based on the total yield of aromatic products, the synthesis conditions of HZSM-5 zeolite with the best DME aromatization properties were obtained by comprehensive analysis and validation experiments. The relationship between the aromatization performance, crystalline structure, pore structure, and acidity of HZSM-5 zeolite were analyzed. The results showed that the HZSM-5 zeolite accompanied by hierarchical structure, an appropriate Brønsted and Lewis acid content and uniform crystal morphology, was successfully synthesized under optimized conditions. Over this unmodified and un-doped catalyst, the conversion of DME approached to 99.3% and the total yield of aromatics reached was 53.5%.     

Study of structural aspects of thermochemical conversions of compounds modeling oligophenylenes containing acenaphthylenyl and acenaphthenyl groups

With the aim of elucidating the mechanism of the thermochemical conversion of oligophenylenes containing acenaphthylenyl groups, the thermolysis of model compounds: l,3,5-tris(5-acenaphthylenyl)benzene (1), 1,3,5-tris(5-acenaphthenyl)benzene (2), acenaphthylene, and acenaphthene, was studied by differential thermal analysis (DTA), dynamic thermogravimetric analysis (TGA), and mass spectrometry. Compounds1 and2 were studied by X-ray structural analysis. A scheme for the formation of secondary structures was suggested. Optimum temperature conditions were found for preparing thermostable, heat-resistant, and stable to thermooxidation polymers based on compounds containing the acenaphthylenyl groups.Deceased in 1993.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 846–854, May, 1994.We thank V. M. Laktionov for performing the differential scanning calorimetric analysis.     

A molecular-dynamics study of thermal and physical properties of platinum nanoclusters

Metallic nanoclusters are interesting because of their utility in catalysis and sensors. The thermal and physical characteristics of metallic Pt nanoclusters with different sizes were investigated via molecular-dynamics simulations using Quantum Sutton-Chen (QSC) potential. This force field accurately predicts solid and liquid states properties as well as melting of the bulk platinum. Molecular dynamic simulations of Pt nanoclusters with 256, 456, 500, 864, 1372, 2048, 2916, 4000, 5324, 6912, 8788 atoms have been carried out at various temperatures. The Pt-Pt radial distribution function, internal energy, heat capacity, enthalpy, entropy of the nanoclusters were calculated at some temperatures. These properties are used to characterize the physical phase and also to determine the melting transition of each nanocluster. The melting point predicted by the various properties is consistent with each other and shows that the melting temperature increases with the particle size, approaching to the bulk limit for the largest one. The size dependence of the melting point has been reported, both experimentally and theoretically for the atomic nanoclusters. We have found that the melting of the platinum nanoclusters commences at the surface and the relation T_m,N=T_m,bulk−αN^−1/3 between the melting point of nanocluster (T_m,N) and that of the bulk (T_m,bulk) holds. The extrapolation of T_m,N versus N^−1/3 gives T_m,bulk = 2058.1 K which is in a good agreement with the experimental value of 2041 K.     

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,     

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.     

医用聚丙烯酰胺水凝胶理化性能测试

测试了医用聚丙烯酰胺水凝胶产品的pH值、折射率、重金属含量、红外光谱、化学热稳定性和丙烯酰胺单体残留量等主要理化性能，重点研究了样品中残留单体丙烯酰胺的高效液相色谱分析法。