纳滤膜对电解质溶液分离特性的理论研究(Ⅰ):单一电解质溶液

电解质溶液在纳滤膜中的截留率对于膜法海水淡化和重金属离子的脱除非常重要.本文假定膜具有狭缝状孔,采用扩展Nernst-Planck方程、Donnan平衡模型和Gouy-Chapman理论来描述电解质溶液中离子在膜孔内的传递现象.使用纯水透过系数、膜孔径及膜表面电势来表征纳滤膜的分离特征,这三个参数可通过Levenberg-Marquardt方法由实验数据关联得到.本文使用该模型计算了两种商用纳滤膜(NF45和SU200)对1-1型(NaCl,KCl,LiCl),2-1型(K2SO4)和2-2型(MgSO4)单一电解质溶液的截留率,并与实验数据进行了比较,两者吻合较好.计算结果表明电解质溶液中离子在纳滤膜孔内传递的主要机理是离子的扩散和电迁移,纳滤膜对电解质溶液中离子的分离效果主要由空间位阻和静电效应决定.该模型在低浓度时对电解质溶液通过纳滤膜的截留率计算结果较准确,但对高浓度电解质溶液则偏差较大.     

纳滤膜对电解质溶液分离特性的理论研究(I): 单一电解质溶液

电解质溶液在纳滤膜中的截留率对于膜法海水淡化和重金属离子的脱除非常重要. 本文假定膜具有狭缝状孔, 采用扩展Nernst-Planck方程、Donnan平衡模型和Gouy-Chapman理论来描述电解质溶液中离子在膜孔内的传递现象. 使用纯水透过系数、膜孔径及膜表面电势来表征纳滤膜的分离特征, 这三个参数可通过Levenberg-Marquardt方法由实验数据关联得到. 本文使用该模型计算了两种商用纳滤膜(NF45和SU200)对1-1型(NaCl, KCl, LiCl), 2-1型(K₂SO₄)和2-2型(MgSO₄)单一电解质溶液的截留率, 并与实验数据进行了比较, 两者吻合较好. 计算结果表明电解质溶液中离子在纳滤膜孔内传递的主要机理是离子的扩散和电迁移, 纳滤膜对电解质溶液中离子的分离效果主要由空间位阻和静电效应决定. 该模型在低浓度时对电解质溶液通过纳滤膜的截留率计算结果较准确, 但对高浓度电解质溶液则偏差较大.     

纳滤膜对电解质溶液分离特性的理论研究(II): 混合电解质溶液

假定纳滤膜具有狭缝状孔, 使用纯水透过系数、膜孔径及膜表面电势来表征纳滤膜的分离特征, 用流体力学半径和无限稀释扩散系数表征了离子特性. 采用扩展Nernst-Planck方程、Donnan平衡模型和Poisson-Boltzmann理论描述了混合电解质溶液中离子在膜孔内的传递现象, 计算了三种商用纳滤膜(ESNA1-LF, ESNA1和LES90)对同阴离子、同阳离子和含四种离子的混合电解质体系中离子的截留率, 并与实验数据进行了比较. 计算结果表明, 电解质溶液中离子在纳滤膜孔内传递的主要机理是离子的扩散和电迁移, 纳滤膜对混合电解质溶液中离子的分离效果主要由空间位阻和静电效应决定. 该模型在低浓度时对含一价离子的混合电解质溶液通过纳滤膜的截留率计算结果比较准确, 但对高浓度或含高价离子的混合电解质溶液则偏差较大.     

计算离子液体溶液汽液相平衡的分子热力学模型

用平均球近似理论、微扰理论和UNIFAC基团贡献方法分别考虑离子之间的长程静电作用、离子与溶剂之间的中程静电作用以及所有粒子之间的短程作用,本文提出了一种新的分子热力学模型,可用于离子液体溶液中溶剂活度系数的计算.通过对含烷基咪唑磷酸酯类离子液体与水、甲醇或乙醇组成的9个二元体系的饱和蒸汽压数据进行关联,获得了相关的模型参数,即溶剂的分子直径和基团之间的交互作用能参数.溶剂活度系数及饱和蒸汽压的计算结果与实验值的平均偏差为1.40%,符合良好,因此本模型可望用于含离子液体体系汽液相平衡的预测.     

氟离子对TiO2/膨润土光催化降解酸性桃红的影响

研究了在紫外光照射下, 添加氟离子对P25(锐钛矿)和TiO2/膨润土光催化降解酸性桃红(SRB)的影响. 紫外可见光谱测定结果表明无氟的反应体系, pH值越小, 光降解速率越快; pH值固定, 添加氟离子越多, 反应速率越快, 在TiO2/膨润土催化剂上, 当氟离子浓度达到一定程度时, 反应速率不再变化. 在P25和TiO2/膨润土催化剂上, 添加氟离子对H2O2的产生量影响不同, 通过电子顺磁共振(EPR)技术探测到了超氧自由基和羟基自由基, 这两个体系添加氟离子对其产生强度影响不同, 这可能是因为TiO2/膨润土催化剂为层状结构, BET 比表面积较大, 经XRD和TEM测试表明其晶粒直径约为57.9 nm. TiO2/膨润土催化剂连续循环使用11次, 光催化活性基本不变, 这个现象说明TiO2/膨润土催化剂既易于从分散体系中分离出来, 而且其稳定性也好, 它是一个有应用前途的催化剂.     

钠基膨润土吸附亚甲基蓝热力学与动力学研究

利用钠基膨润土吸附亚甲基蓝水溶液,探讨了不同参数如接触时间、初始pH值、温度等对其吸附性能的影响。结果表明,室温下,pH10,钠基膨润土吸附60min,其吸附量达198.71mg/g,且吸附量随温度的升高而增大。通过计算不同温度下的热力学参数?G,?H和?S,证实该吸附为一自发的吸热过程。其等温吸附平衡更符合Langmuir模型;吸附动力学更适合准二级反应方程。     

Li2B4O7-MgCl2(B)-H2O体系热力学性质的等压研究及离子相互作用模型

采用等压法测定了298.15 K下Li-Mg-Cl-borate-H2O体系离子强度范围为0.0581～0.6320 mol*kg-1, MgCl2不同离子浓度分数的等压摩尔平衡浓度、水活度,计算了Li2B4O7和MgCl2混合溶液的饱和水蒸汽压、渗透系数等热力学性质.考虑了在不同的总硼浓度范围的硼酸(H3BO3)和硼氧配阴离子[B(OH)-4, B3O3(OH)-4, B4O5(OH)2-4]的不同生成反应平衡.由实验结果对修正的Pitzer渗透系数方程进行了参数化研究,提出了一简化的参数化模型,减少了模型的经验参数量,获得了锂、镁、氯离子与硼物种组合之间、及不同硼氧配阴离子之间的组合相互作用参数,用该模型计算的渗透系数值与实验结果取得合理的一致性,从而将离子作用模型扩展到对含硼、锂、镁的复杂体系的表述.对完善含锂、硼的盐湖卤水体系的热力学模型和盐湖资源的综合开发利用具有重要意义.     

钠基膨润土吸附亚甲基蓝的热力学与动力学研究

利用钠基膨润土吸附亚甲基蓝水溶液,探讨了不同参数如接触时间、初始pH值、温度等对其吸附性能的影响。结果表明,室温下,pH10,钠基膨润土吸附60min,其吸附量达198.71mg/g,且吸附量随温度的升高而增大。通过计算不同温度下的热力学参数?G,?H和?S,证实该吸附为一自发的吸热过程。其等温吸附平衡更符合Langmuir模型;吸附动力学更适合准二级反应方程。     

多孔磺化树脂分离柱及其高效离子排斥色谱性能

近年来,由于高效分离柱和高灵敏检测器的研究与应用,使离子色谱技术的发展十分显著。在环境保护、工业生产和科学研究中得到广泛的应用。离子排斥色谱是离子色谱技术中的一个分支,其分离原理建立在Donnan排斥效应的基础上,即分离柱填料上的官能团趋向于在填料颗粒间空体积内的淋洗液和颗粒孔隙内吸留的淋洗液之间形成一种称为Donnan膜的半透膜。这种膜对于离子化程度不同的溶质具有不同的排斥能力而使之得以分离。离子排斥色谱不仅可使有机酸快速分离,也可以从有机酸中分     

脂肪酸离子排斥分配色谱分离中的吸附作用

酸在氢型阳离子交换树脂柱上的分离机理已有研究,Glod等根据离子排斥色谱中的Donnan膜平衡,推导出分配系数K_d与酸离解常数K_a的关系,能大致预测酸的流出顺序,但不能说明为什么pK_a极为相近的有机酸却有较大的保留时间差别.Bafna等从分子吸附的角度考察了某些有机酸在阳离子交换树脂上的吸附平衡和洗脱行为.本文从有机酸离子排     

Modeling of the Ion Exchange in Pulp Suspensions by Gibbs Energy Minimization

The ion exchange processes, which occur when two compartments of aqueous solutions separated by a semipermeable interface are placed in aqueous electrolyte solutions, were modeled using the multiphase Gibbs energy-minimization method. The Gibbs energy-minimization technique was applied for the ion-exchange system consisting of pulp fibers and the surrounding aqueous bulk solution. In such a system, the anionic acid groups inside the fibers cause an uneven distribution of ionic species between the solution within the fiber walls and the solution external to the fibers. The method was tested with four cation concentrations, which are naturally present in the fibers and whose partitioning between the fiber phase and the external solution phase has been described earlier. Although the Donnan distribution constant is not explicitly calculated in the Gibbs energy-minimization model, the results are consistent with the Donnan equilibrium theory. With the Gibbs energy-minimization multiphase model, the formation of solid precipitates can also be calculated.     

Sorption kinetics of strontium in porous hydrous ferric oxide aggregates I. The Donnan diffusion model

Sorption of ions by hydrous ferric oxide (HFO) often shows a fast initial sorption reaction followed by a much slower sorption process. The second step is diffusion-controlled and can continue for days or months before equilibrium is reached. In this paper, we demonstrate that the diffusion rate may be explained by electrostatic interactions. The internal and external surfaces of HFO are generally positively charged and therefore repel cations. This can result in extremely low cation concentrations in pores, and therefore a significant reduction in pore diffusion rate. The theory is demonstrated here for sorption of Sr(2+) in HFO aggregates. The ion concentrations in the pore space are calculated using a Donnan model and diffusion is calculated from the Donnan concentration and potential gradients. This diffusion model is compared with nonelectrostatic pore diffusion, which does not take electrostatic interactions into account. The Donnan model predicts very low concentrations of Sr(2+) in the pores and diffusion rates that are up to 8000 times lower than predicted with a nonelectrostatic model.     

Density functional study on the structural and thermodynamic properties of aqueous DNA-electrolyte solution in the framework of cell model

A density functional theory (DFT) in the framework of cell model is proposed to calculate the structural and thermodynamic properties of aqueous DNA-electrolyte solution with finite DNA concentrations. The hard-sphere contribution to the excess Helmholtz energy functional is derived from the modified fundamental measure theory, and the electrostatic interaction is evaluated through a quadratic functional Taylor expansion around a uniform fluid. The electroneutrality in the cell leads to a variational equation with a constraint. Since the reference fluid is selected to be a bulk phase, the Lagrange multiplier proves to be the potential drop across the cell boundary (Donnan potential). The ion profiles and electrostatic potential profiles in the cell are calculated from the present DFT-cell model. Our DFT-cell model gives better prediction of ion profiles than the Poisson-Boltzmann (PB)- or modified PB-cell models when compared to the molecular simulation data. The effects of polyelectrolyte concentration, ion size, and added-salt concentration on the electrostatic potential difference between the DNA surface and the cell boundary are investigated. The expression of osmotic coefficient is derived from the general formula of grand potential. The osmotic coefficients predicted by the DFT are lower than the PB results and are closer to the simulation results and experimental data.     

The effect of ionic strength on the diffusion of 125I in Gaomiaozi bentonite

The diffusion of ¹²⁵I^? in compacted Gaomiaozi (GMZ) bentonite was investigated by capillary in-diffusion method. Apparent and effective diffusion coefficients and accessible porosity of iodide in GMZ bentonite were obtained, and the effect of ionic strength on diffusion parameters was studied. The apparent diffusion coefficients of iodide in compacted GMZ bentonite are in the range of 1.0–6.0 × 10^?10 m² s^?1 under the conditions of dry bulk density 1,500 kg m^?3 and temperature 298 K, and increase with increasing ionic strength. This effect was explained through the analysis of microscopic structure of compacted bentonite. The iodide can only diffuse in unbound interparticle pore solution of compacted bentonite. The apparent diffusion coefficient is a function of accessible porosity which is decided by the thickness of diffusion double layer, and the thickness is in turn controlled by ionic strength.     

Membrane potential across anion-exchange membranes in acidic solution system

The membrane potential across anion-exchange membranes in H2SO4 and Na2SO4 solutions was measured, and the experimental results were fitted to the theory in the 2-1 electrolyte system based on the Donnan equilibrium and the Nernst-Planck flux equations. For the Na2SO4 solution, the Donnan potential makes a significant contribution to the membrane potential, but for the H2SO4 solution, the diffusion potential significantly contributes to the membrane potential. The diffusion potential has a greater contribution to the membrane potential across AEM-2 with a high water content than that across AEM-1. These results suggest that a proton with a high mobility can move without substantial influence of electrostatic interaction in a positively charged membrane.     

Sorption and diffusion of 90Sr2+in compacted bentonite investigated by a capillary method

Summary The effects of bentonite density and fulvic acid on the sorption and diffusion of ⁹⁰Sr²⁺in compacted bentonite were investigated by using a capillary method. The experiments were carried out at pH 7.0±0.1 in the presence of 0.01M NaClO₄. The results suggest that the sorption and diffusion of ⁹⁰Sr²⁺in compacted bentonite decreases with increasing the density of compacted bentonite. The presence of FA enhances the sorption of Sr²⁺, but reduces the diffusion of Sr²⁺in compacted bentonite. The porosity of the compacted bentonite plays an important role in the sorption and diffusion behavior of ⁹⁰Sr²⁺. Using the calculated effective diffusion coefficients the long-term relative concentration distribution of strontium was evaluated in compacted bentonite.     

Diffusion of ionic species in bentonite

We present a macroscopic model of ionic diffusion in bentonites including the effect of the hydraulic-electrical-chemical couplings expected in such charged porous medium. The anomalous concentrations of the ions in the pore water of the bentonite are modeled with a modified Donnan model in which we account for the partition of the counterions between the Stern and Gouy-Chapman layers. This is accomplished using an electric triple layer (TLM) model combined with an explicit complexation model at the mineral/water interface. The porosity entering into the determination of the formation factor of the medium is an effective porosity obtained by removing the fraction of hydration water covering the surface of the clay minerals. We investigate two different cases of diffusion. In the first case, we consider a salinity gradient between two reservoirs in contact with a cylindrical sample of bentonite. The model predicts an increase of the diffusivity of the salt with the salinity of the solution in contact with the bentonite in agreement with experimental data. In the second case, we analyze a self-diffusion experiment of an ionic tracer. The model predicts an increase of the diffusivity of anions with the effective porosity and with the ionic strength. This is also in good agreement with experimental data.     

Removal of zinc metal ion (Zn) from its aqueous solution by kaolin clay mineral: A kinetic and equilibrium study

A laboratory batch study has been performed to study the effect of various physic-chemical factors such as initial metal ion concentration, solution pH, and amount of adsorbent, contact time and temperature on the adsorption characteristics of zinc (Zn²⁺) metal ions onto kaolin. It has been found that the amount of adsorption of zinc metal ion increases with initial metal ion concentration, contact time, solution pH but decreases with the amount of adsorbent and temperature of the system. Kinetic experiments clearly indicate that adsorption of zinc metal ion (Zn²⁺) on kaolin is a two steps process: a very rapid adsorption of zinc metal ion to the external surface is followed by possible slow decreasing intra-particle diffusion in the interior of the adsorbent which has also been confirmed by intra-particle diffusion model. The equilibrium time is found to be in the order of 60 min. Overall the kinetic studies showed that the zinc adsorption process followed pseudo-second-order kinetics among pseudo-first-order and intra-particle diffusion model. The different kinetic parameters including rate constant are determined at different initial metal ion concentration, solution pH, amount of adsorbent and temperature respectively. The equilibrium adsorption results are analyzed by both Langmuir and Freundlich models to determine the mechanistic parameters associated with the adsorption process. The value of separation factor, R_L from Langmuir equation also gives an indication of favorable adsorption. Finally thermodynamic parameters are determined at three different temperatures and it has been found that the adsorption process is exothermic due to negative ΔH° accompanied by decrease in entropy change and Gibbs free energy change (ΔG°).     

Adsorption of acid dyes from aqueous solutions onto acid-activated bentonite

The adsorption of two dyes, namely, Acid Red 57 (AR57) and Acid Blue 294 (AB294), onto acid-activated bentonite in aqueous solution was studied in a batch system with respect to contact time, pH, and temperature. Acidic pH was favorable for the adsorption of these dyes. The surface characterization of acid-activated bentonite was performed using the FTIR technique. The pseudo-first-order and pseudo-second-order kinetic models and the intraparticle diffusion model were used to describe the kinetic data and the rate constants were evaluated. The dynamic data fitted the pseudo-second-order kinetic model well and also followed the intraparticle diffusion model up to 90 min, but diffusion is not the only rate controlling step. The Langmuir and Freundlich adsorption models were applied to describe the equilibrium isotherms and the isotherm constants were determined. The Freundlich model agrees very well with experimental data. The activation energies of adsorption were also evaluated for the adsorption of AR57 and AB294 onto activated bentonite.     

99TcO4 − diffusion and sorption in compacted GMZ bentonite studied by capillary method

Sorption and diffusion of ⁹⁹TcO₄ ^? in compacted bentonite from Gaomiaozi county (Inner Mongolia, China) (denoted as GMZ bentonite) was studied by capillary method. The distribution coefficient (K _d) and diffusion coefficient (D _a) were calculated from diffusion curves of ⁹⁹TcO₄ ^? in compacted GMZ bentonite. The D _a and K _d values decreased with the increasing of the bulk dry density of the compacted bentonite. With increasing pH values, the D _a values increased whereas the K _d values decreased, which is attributed to the ion exchange and electrostatic repulsion between the negative surface charged bentonite and negative charged ⁹⁹TcO₄ ^? ions at high pH values. The diffusion and relative concentration distributions of ⁹⁹TcO₄ ^? in compacted bentonite after long aging time were simulated from the distribution and diffusion coefficients. Effect of aging time on the diffusion of ⁹⁹TcO₄ ^? in compacted bentonite was also calculated using the theoretical equation. The results indicated that ⁹⁹TcO₄ ^? was an easily mobile radionuclide in environment and the release of ⁹⁹TcO₄ ^? from the radioactive waste repository was dangerous to the environmental pollution.