洗涤剂用沸石的钙离子交换性能的研究

作为洗涤剂助剂,沸石的主要作用是通过离子交换降低水中的钙镁离子浓度、软化洗涤用水以提高洗涤剂中的表面活性剂的洗涤效率。因此,沸石对钙镁离子交换容量的大小和交换速率的快慢是评价洗涤用沸石的重要质量指标［１,２］。目前,使用最多的沸石类助剂为ＮａＡ沸石。为了弥补ＮａＡ型沸石镁离子交换能力的不足,先后又出现了Ａ、Ｘ型沸石混合使用［３］、高铝Ｘ型沸石(ＭＡＸ)［４～５］和高铝Ｐ型沸石(ＭＡＰ)等技术［１,２］。ＭＡＸ型和ＭＡＰ型沸石与ＮａＡ型沸石一样具有最小的硅铝比(ＳｉＯ２／Ａｌ２Ｏ３＝２)。因此,这三种沸石的…     

Sorption Behaviour of Molybdenum on Different Antimonates Ion Exchangers

Various antimonate compounds are well known as important inorganic ion exchangers, since they resist radiation and chemical degradation and also exhibit selectivities towards different cations. Ceric, silicon, titanium and ferric antimonates were prepared as inorganic ion exchangers. Characterization of these materials has been described using different techniques, including thermal analysis, surface area measurements, X-ray diffraction and IR-spectroscopy. In batch distribution experiments the influence of HNO₃ molarity and Mo concentration for Mo sorption on different matrices is described in terms of their retention capacities and distribution coefficients.The selectivities of these exchangers towards molybdenum are in the order: CeSb > SiSb > FeSb > TiSb.     

全氟磺酸型阳离子交换膜中氯离子和氢氧离子的扩散系数

在不同温度下,Nafion膜的氢氧离子扩散系数与氯离子的扩散系数之间具有相关性。在33种不同化学处理和物理处理的全氟磺酸型膜中,观察到氢氧离子和氯离子之间存在着D_(OH)~-=-7.82×10~(-10)+3.43D_(Cl)~-的关系。我们认为这种相关性,起因于离子的淌度之间的相关性。     

压力对带有pH值可调聚电解质刷的仿生纳米孔中离子选择性的影响

具有pH值可调聚电解质（Polyelectrolyte,PE）刷的合成纳米孔的仿生离子通道在纳米尺度下离子、流体和生物粒子的主动运输控制方面具有重大应用潜力. 离子选择性是纳流体设备中离子传输的重要现象,具有很大的现实意义和实用价值. 本文提出了施加压力控制纳米孔中离子选择度的方法,综合研究了溶液pH值、浓度、外加电压和压力对离子选择度的影响. 仿真结果表明,离子选择度对压力的刺激是敏感的,且不像电压对离子选择度的影响会受到溶液pH值和浓度的制约,且方向不定,速度不可控;压力对离子选择度的影响不受溶液性质制约,并且灵活可控. 该结果对设计带pH值可调聚电解质刷的纳米孔有重要的启发作用.     

Thermodynamics of exchange in clays: Ion exchange equilibria of transition metals and sodium ions on illite

Ion exchange equilibria of bivalent transition metal ions have been studied at 20, 30 and 45°C on illite surface. The exchange isotherms and free energy changes indicate a higher preference of the illite surface for the metal ions. Cd²⁺ and Mn²⁺ ions were preferred throughout the entire range while reversal of behaviour occurred during Cu²⁺, Zn²⁺ and Co²⁺ ions exchange on the illite surface. Enthalpy changes suggested a stronger preference of transition metal ions for the illite surface. Entropy changes indicated an increase in the order of system. The surface phase coefficients of the cations showed that with increasing metal ion saturationf _m continuously increases whilef _Na decreases. The excess thermodynamic functions snowed that the exchange reactions were non-ideal.     

磺酸型阳离子交换树脂催化合成肉桂酸甲酯

以磺酸型阳离子交换树脂为催化剂，由肉桂酸和甲醇合成了肉桂酸甲酯。考察了反应条件对酯化反应的影响和树脂的催化稳定性。结果表明，肉桂酸的转化率可达９５．５％，且催化剂的性能稳定。     

Simulation of ion mass transfer processes with allowance for the concentration dependence of diffusion coefficients

The system of equations describing ion transport in a binary electrolyte z _a-z _c with allowance for the linear dependence of the diffusion coefficients on the concentration was analyzed in the framework of the phenomenological Nernst-Planck approach. The expressions are obtained that define concentration profiles of ions and conditions favorable for the limiting current caused by the achievement of the concentration of a saturated solution (in the case of the anodic reaction) and depletion of the near-electrode region in electroactive cations (in the case of the cathodic reaction). The revealed theoretical dependence of the limiting current on the volume concentration of the salt agrees with published experimental data. The voltammetric characteristics of the corresponding systems were calculated. The role of the migrational component of the ion flow is discussed. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 638–642, April, 2006.     

高铝沸石的钙离子交换动力学研究

由于含磷洗涤剂的使用所带来的环境危害日益严重，高铝沸石作为洗涤剂助剂三聚磷酸钠的替代品已获得广泛的应用。作为洗涤剂助剂，沸石的Ca２＋、Mg２＋离子交换性能是影响其助洗效果的主要因素之一犤１，２犦。但目前对沸石的离子交换性质的研究多集中在离子交换平衡等温线的研究犤３～６犦，涉及沸石离子交换动力学的研究却鲜有报道。作为硬水的软化剂，洗涤剂用沸石对Ca２＋、Mg２＋离子的交换速率大小对洗涤效果的意义更为重要犤１犦。沸石的离子交换过程包括离子由溶液中扩散到沸石表面，再由沸石表面扩散到沸石孔道中的离子位等步骤…     

Kinetics Characterization of Ion Release under Dynamic and Batch Conditions. I. Weak Acid and Weak Base Ion Exchange Resins

The aim of the present work is concerned with a study of the kinetics of release of both Ca²⁺ and F⁻ from the corresponding loaded ion-exchange resins (weak acid and weak base character for Ca²⁺ for F⁻, respectively), using both dynamic and batch experimental conditions with an artificial saliva solution as the ion-exchange media at 293 and 310 K. The influence of resin particle size and the temperature were evaluated by the kinetics parameters for the effective rate of release (B) and diffusion coefficient (D). The rate of ion release increases with temperature and decreases with particle size. The experimental data were well fitted by models based on intraparticle diffusion-controlled processes. In dynamic studies, the linear dependence of −log ₁₀(B) with the diameter of the resin particles can be applied for the estimation of B values when resins of low particle size are considered. In batch processes, although resins of low particle size can be studied, a linear relationship was only attained for the case of slow ion-exchange kinetic systems.     

锂离子在石墨化碳纤维中的扩散系数

锂电子电池;嵌入电极;锂离子在石墨化碳纤维中的扩散系数     

Ion exchange and ion transport properties of sulfonated organically modified silica hydrogels

Sulfonated ormosil hydrogels (~80% water) were prepared using tetramethyl orthosilicate as a silica precursor and 2(4-chlorosulfonylphenyl)ethyltrichlorosilane to provide sulfonate functionality for ion-exchange and ion conductivity. Ruthenium(III) hexamine was used as a redox probe in electrochemical studies performed on porous carbon fibre paper electrodes impregnated with the gel. The gel-modified electrodes extracted Ru(NH₃)₆³⁺ from solutions in 0.1 M CF₃CO₂Na_(aq) with a partition coefficient of ~36, and with ~100% of the sulfonate sites being accessible for ion exchange. The Ru(NH₃)₆^3+/2+ couple exhibited reversible and facile electrochemistry in the gel, with a Ru(NH₃)₆²⁺ diffusion coefficient of 4.9×10^–8 cm² s^–1 determined by chronoamperometry. This is an order of magnitude higher than the mobility of this complex in Nafion. The hydrogel-modified electrodes were stable for days, and could be repeatedly loaded with Ru(NH₃)₆³⁺.Special Issue to celebrate the 70^th birthday of Professor Zbigniew Galus     

Synthesis and Electronic/ionic Transport Properties of MoO2/rGO Anode for Lithium Ion Batteries

MoO₂/rGO (reduced graphite oxide) composites have been synthesized by hydrothermal method followed by anneal and characterized by X‐ray diffraction (XRD) and scanning electron microscope (SEM). Galvanostatic charge/discharge testing and electrochemical impedance spectroscopy (EIS) techniques are employed to evaluate the kinetic behaviors of the MoO₂/rGO during lithiation/delithiation. The obtained MoO₂‐based materials have monoclinic crystal structure, and worm like shape with average dimensions of 100‐200 nm width and 500 nm‐1 μm length. There are two steps of lithium ion intercalation/de‐intercalation for the MoO₂/rGO anode at the potential ranging from 1.0 to 3.5 V, locating at E_Li/Li⁺ = 1.60/1.75 V, 1.25/1.40 V, and the first discharge and charge capacities are, respectively, 221.0 and 185.4 mAh g^?1. The resistances of R_SEI and R_CT for the MoO₂/rGO anode are 2‐4 Ω and below 5 Ω. Moreover, the lithium diffusion coefficient calculated from the EIS measurement is about 3.6×10^?9 cm² s^?1.     

Electrochemical determination of standard thermal diffusion characteristics for chlorides of hydrogen and potassium in water-ethanol solutions

Initial and steady-state temperature coefficients of the voltage generated by thermogalvanic cells comprising silver chloride and quinhydrone electrodes in the systems HCl-H₂O-C₂H₅OH and KCl-H₂O-C₂H₅OH are determined. Standard thermal diffusion Soret coefficients, the entropy of thermal diffusion transport of electrolytes, and the entropy of mobile ions H⁺, K⁺, and Cl^? are calculated for 298 K. The effect the nature of ions and the solvent composition exert on the obtained thermal diffusion transport characteristics is considered in terms of the De Bethune theory.     

Inorganic Salts Trapped in Neutral Carrier Ion-Selective Electrode Membranes form Ion-Exchange Sites

Abstract

Deliberately added hydrophilic salt contaminations behave as ion-exchange sites in the plasticized PVC membrane of a neutral carrier ion-selective electrode. The added salt does not influence the potenticmetric performance of the membrane. Since the membrane without added salt is itself an ion-exchanger, its ion-exchange capacity may be linked to ionizable hydrophilic impurities.     

Thermal Responsive Ion Selectivity of Uranyl Peroxide Nanocages: An Inorganic Mimic of K+ Ion Channels

An actinyl peroxide cage cluster, Li_48+mK₁₂(OH)_m[UO₂(O₂)(OH)]₆₀ (H₂O)_n (m≈20 and n≈310; U₆₀), discriminates precisely between Na⁺ and K⁺ ions when heated to certain temperatures, a most essential feature for K⁺ selective filters. The U₆₀ clusters demonstrate several other features in common with K⁺ ion channels, including passive transport of K⁺ ions, a high flux rate, and the dehydration of U₆₀ and K⁺ ions. These qualities make U₆₀ (a pure inorganic cluster) a promising ion channel mimic in an aqueous environment. Laser light scattering (LLS) and isothermal titration calorimetry (ITC) studies revealed that the tailorable ion selectivity of U₆₀ clusters is a result of the thermal responsiveness of the U₆₀ hydration shells.     

Permselectivity between two anions in anion exchange membranes crosslinked with various diamines in electrodialysis

A membranous copolymer crosslinked with divinylbenzene reacted with N,N,N′,N′-tetra-methylethylenediamine, N,N,N′,N′-tetramethyl-1,3-propanediamine, and N,N,N′,N′-tetramethyl-1,6-hexanediamine to prepare highly crosslinked anion exchange membranes. More than 80% of both tertiary amino groups of the diamines reacted with chloromethyl groups of the membrane to form crosslinkage. After formation of the high crosslinkage of the membrane was confirmed with dialysis of a neutral molecule, electrochemical properties of the obtained membranes (mainly, relative transport number between two anions in electrodialysis) were evaluated: nitrate ions to chloride ions, sulfate ions to chloride ions, fluoride ions to chloride ions, and bromide ions to chloride ions. Though larger anions, in general, were difficult to permeate through the membranes due to high crosslinkage, the number of methylene groups of the diamines (which means the increase in hydrophobicity of anion exchange groups) also affected the relative transport number between two anions. The lower the hydration of anions, the higher the relative transport number of the anions through the membranes with the hydrophobic anion exchange groups. © 1996 John Wiley & Sons, Inc.     

Ion exchange behaviour of polymeric zirconium cations

Summary Polymeric zirconium cations formed in weakly acid solution (pH2) are taken up strongly into macroporous cation exchange resins, while uptake into normal cation exchange resins (pore diameter about 1 nm) is low. Macroporous cation exchange resins loaded with polymeric Zr cations are shown to function as ligand exchange sorbents.

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Ionenaustauschverhalten polymerer Zirkonium-Kationen (Kurze Mitt.)

Zusammenfassung Polymere Zirkonium-Kationen, die in schwach sauren Lösungen (pH2) vorliegen, werden von makroporösen Kationenaustauschern stark aufgenommen, während bei den üblichen Kationenaustauschern (mit Porengrößen von etwa 1 nm) nur geringe Aufnahme stattfindet. Makroporöse Kationenaustauscher die mit polymeren Zr-Kationen beladen sind fungieren als Liganden-Austauschsorbentien.

     

全氟磺酸膜的离子选择性

研究了Ｎａｆｉｏｎ１１７膜（一种全氟磺酸膜）对阳离子的选择性,测定了含Ｋ＾＋,Ｎｉ＾２＋及Ｆｅ＾３＋的Ｎａｆｉｏｎ１１７膜的离子选择性系数,实验发现含Ｈ＾＋,Ｋ＾＋,Ｐｂ＾２＋,Ｎｉ＾２＋,Ｃｏ＾２＋,Ｆｅ＾３＋等离子的膜都能较好符合Ｎｅｒｎｓｔ响应。膜对一价离子的选择性优于二价及三价离子。     

Transport properties of plasticized polyvinyl chloride membranes based on alkylpyridinium alkylsulfates under conditions of diffusion mass transfer and constant current

Relationships are established for the permeability and flux of ionic surfactants with the concentration of electroactive compounds (EAC), the nature and concentration of solutions adjacent to the membrane, and membrane thickness. Values of permeability and ion fluxes decrease with decreasing EAC concentration and increasing membrane thickness. As the EAC concentration increases, i.e., as the number of charged centers in the membrane increases, permeabilities and ion fluxes also increase proportionally. The quantitative properties of membrane transport are an order of magnitude lower under conditions of diffusion mass transfer than with constant current.     

Oxygen-18 surface exchange and diffusion in Li2O-deficient single crystalline lithium niobate

¹⁸O/¹⁶O isotope exchange in combination with SIMS depth profiling was used to investigate oxygen transport in Li₂O-deficient single crystalline LiNbO₃ in the temperature range 983 ≤ T/K ≤ 1188 at 200 mbar oxygen. Within the limit of experimental error and for the investigated range of temperatures no significant differences between transport parallel and transport perpendicular to the c-axis were found. The following temperature dependencies were determined: for oxygen tracer diffusion D = 6.4 × 10⁻³exp[−333 kJ/mol/(RT)] m²/s; and for oxygen surface exchange k = 7.8 × 10²exp[−288 kJ mol⁻¹/(RT)] m/s. The activation enthalpy obtained for tracer diffusion can be interpreted as the enthalpy of migration of extrinsic oxygen vacancies induced by impurities with lower valency on niobium sites.