TERNARY NaCl+LiCl+H2O MIXED ELECTROLYTE SYSTEM: DETERMINATION OF ACTIVITY COEFFICIENTS BASED ON POTENTIOMETRIC METHOD

The mean activity coefficients for NaCl in a ternary electrolyte system were determined by the potentiometric method, at 25°C, using a solvent polymeric (PVC) sodium-selective membrane electrode (Na⁺ ISE), containing N,N′-dibenzyl-N,N′-diphenyl-1,2-phenylenedioxydiacetamide as ionophore, and combined with an Ag/AgCl electrode. The potentiometric measurements were performed at the same ionic strengths in different series of mixed salt solutions, each characterized by a fixed salt molal ratio r (where r = m₁/m₂ = 1, 10, 50, 100). The nonideal behavior of the ternary NaCl(m₁) + LiCl(m₂) + H₂O electrolyte system was described based on the Pitzer ion-interaction model for mixed salts over the ionic strength ranging from 0.01 up to about 4 mol/kg. Two- and three-particle Pitzer interaction parameters for a mixed electrolyte system were determined based on potentiometric data, and the critical role of potentiometric selectivity coefficient (K ₁₂) of ISE as limiting factor in the potentiometric measurements was analyzed.     

MEASUREMENT AND CORRELATION OF LIQUID-LIQUID EQUILIBRIA FOR TERNARY SYSTEMS OF WATER+RUBIDIUM CHLORIDE+PROPANOL

Liquid-liquid equilibria for ternary systems of water + rubidium chloride + 1-propanol and water + rubidium chloride + 2-propanol were measured at T = 298.15, 308.15, and 318.15 K. The experimental data were correlated using Othmer-Tobias and Bancroft correlations. The salting-out effect of 1-propanol in the two-liquid region was greater than that for 2-propanol, but the effect of temperature on the equilibrium was not significant.     

五元体系HCl-NaCl-CaCl2-H3BO3-H2O在298.15K的Pitzer模型及其应用研究

采用等温溶解法测定了三元体系CaCl₂-H₃BO₃-H₂O在298.15 K的溶解度和液相的折射率,该三元体系为简单共饱型,有1个共饱点,2条溶解度曲线和2个单盐结晶区,分别为CaCl₂·6H₂O和H₃BO₃。结合本文测定和文献中的溶解度数据,拟合了五元体系HCl-NaCl-CaCl₂-H₃BO₃-H₂O中含H₃BO₃的Pitzer参数,结合固相的溶解平衡常数,构建了该五元体系的Pitzer模型,并计算了该五元体系及其子体系的溶解度。根据Pitzer模型和计算相图,对氯化钠、氯化钙共存卤水中硼酸的分离进行了计算,获得了分离过程中的析盐顺序和卤水组成的变化规律。计算结果表明酸性条件下更容易实现H₃BO₃的分离。     

用电势法测定混合电解质溶液中各个组分的活度系数

本文用无液接电势电池：Ｎａ－ＩＳＥ（或Ｋ－ＩＳＥ）｜（ＮａＣｌ（ｍＡ），ＫＣｌ（ｍＢ），Ｈ２Ｏ｜Ｃｌ－ＩＳＥ同时测定了２９８．１５Ｋ，溶液离子强度Ｉ：０．１、０．５、１．０、１．５、２．０和２．５ｍｏｌ／ｋｇ时，钠电极与氯电极组成的电池和钾电极与氯电极组成的电池的可逆电势值，根据Ｎｅｒｎｓｔ方程分别求出ＮａＣｌ－ＫＣｌ－Ｈ２Ｏ体系中，ＮａＣｌ和ＫＣｌ的平均活度系数。用Ｐｉｔｚｅｒ方程拟合两套实验数据，求出两套基本一致的Ｐｉｔｚｅｒ混合参数θＮａ－Ｋ和。将混合参数代回Ｐｉｔｚｅｒ方程，分别求出另一组分的平均活度系数，计算值与实验值比较，标准偏差分别为：０．００８１（ＮａＣｌ）和０．００７３（ＫＣｌ）。     

THERMODYNAMICS OF ALKANOLAMINE+WATER SYSTEM

Design of gas treating processes requires knowledge of the vapor-liquid equilibrium behavior of the (acid gas + aqueous alkanolamine) system. The present study is focused on thermodynamics and associated nonideal behavior of binary MEA + H₂O, DEA + H₂O, and MDEA + H₂O systems, which is required to predict the vapor-liquid equilibrium of acid gases such as CO₂ and H₂S over aqueous alkanolamine solutions. Determination of binary interaction parameters and analytical prediction of infinite dilution activity coefficient, heats of solution at infinite dilution, the excess Gibbs free energy, and excess enthalpy for nonideal alkanolamine-water systems are the objectives of this study.     

四元体系LiB5O8+NaB5O8+KB5O8+H2O在298.15K实验与理论预测相平衡研究

采用等温溶解平衡法研究了四元体系LiB₅O₈ + NaB₅O₈ + KB₅O₈ + H₂O在298.15 K下的相平衡。实验测定了该体系在298.15 K下的固液相平衡溶解度和物理性质（密度和折射率）,基于实验溶解度绘制了四元体系的干盐相图、水图和物理性质组成图。在该四元体系的干基图中,有一个共饱点（LiB₅O₈·5H₂O + NaB₅O₈·5H₂O + KB₅O₈·4H₂O）、3条单变量溶解度曲线和3个单盐结晶区（LiB₅O₈·5H₂O、NaB₅O₈·5H₂O和KB₅O₈·4H₂O）。该体系在298.15 K下没有复盐和固溶体生成,属于简单四元水溶液体系。结合三元体系溶解度,拟合获得了3种碱金属五硼酸盐的单盐参数和三离子混合作用参数;应用Pitzer及其扩展的HW模型对溶解度进行预测,预测值与实验值吻合较好,表明获得的Pitzer参数可靠。研究结果可为碱金属五硼酸盐分离纯化提供理论基础。     

四元体系NaCl+NaBO2+Na2CO3+H2O 298.15 K 相平衡研究

柴达木盐湖中具有丰富的盐湖离子,对其中的一个四元体系水盐相图开展研究,采用等温溶解平衡法开展了298.15 K时四元体系NaCl+NaBO₂+Na₂CO₃+H₂O相平衡研究,测定了体系平衡液相组成及密度和折光率,绘制了四元体系NaCl+NaBO₂+Na₂CO₃+H₂O 298.15 K的相图及相应的物化性质图。研究发现NaCl+NaBO₂+Na₂CO₃+H₂O四元体系298.15 K 时包含2个共饱点（E₁、E₂）、5条溶解度曲线（AE₁、BE₁、CE₂、DE₂、E₁E₂）、4个结晶区（NaCl、NaBO₂·4H₂O、Na₂CO₃·7H₂O、NaCl·NaBO₂·2H₂O）。其中三元体系NaCl+NaBO₂+H₂O在298.15 K下产生了复盐NaCl·NaBO₂·2H₂O,通过研究发现该四元体系NaCl+NaBO₂+Na₂CO₃+H₂O在298.15 K下也具有NaCl·NaBO₂·2H₂O复盐区。     

IN-SITU FT-IR SPECTROSCOPIC STUDIES OF FUEL CELL ELECTRO-CATALYSIS: FROM SINGLE-CRYSTAL TO NANOPARTICLE SURFACES

The work presented in this article shows the power of the variable temperature, in-situ FT-IR spectroscopy system developed in Newcastle with respect to the investigation of fuel cell electro-catalysis. On the Ru(0001) electrode surface, CO co-adsorbs with the oxygen-containing adlayers to form mixed [CO + (2 × 2)-O(H)] domains. The electro-oxidation of the Ru(0001) surface leads to the formation of active (1 × 1)-O(H) domains, and the oxidation of adsorbed CO then takes place at the perimeter of these domains. At 20°C, the adsorbed CO is present as rather compact islands. In contrast, at 60°C, the CO_ads is present as a relatively looser and weaker adlayer. Higher temperature was also found to facilitate the surface diffusion and oxidation of CO_ads. No dissociation or electro-oxidation of methanol was observed at potentials below approximately 950 mV; however, the Ru(0001) surface at high anodic potentials was observed to be very active. On both Pt and PtRu nanoparticle surfaces, only one linear bond CO adsorbate was formed from methanol adsorption, and the PtRu surface significantly promoted both methanol dissociative adsorption to CO and its further oxidation to CO₂. Increasing temperature from 20° to 60°C significantly facilitates the methanol turnover to CO₂.     

SORPTION EQUILIBRIUM OF COPPER BY PARTIALLY-COAGULATED CALCIUM ALGINATE GEL

The sorption equilibrium of dissolved copper by spherical partially-coagulated gels of calcium alginate was investigated in this work. The gels were formed by dispensing a viscous algin (food grade sodium alginate from kelp) solution with a multi-tip dispenser into 0.05 M CaCl₂ solution in a loop fluidized bed reactor. The resultant semi-rigid spherical gels were then transferred to another reactor operated batch wise to absorb dissolved copper at low concentrations (10-40 ppm). When the concentration of the inert neutral salt NaNO₃, added to the reactor fluid was 0.01 M, the amount of copper absorbed was found to be substantially higher than that at 0.1 MNaN0₃. The conventional Langmuir's model based on the concentration of copper in solution yielded different values of conditional stability constant at different ionic strengths in the reactor fluid. However, by defining the copper-binding stability constant on the basis of copper activity in the gel phase with the competition from calcium for metal binding sites taken into account, a unique copper-binding stability constant and a unique calcium-binding stability constant were obtained. The numerical procedure for estimating the activity of copper in the gel fluid was modified from Jang et al. Water Research, 1990, in press).     

Back-extraction Of Pu4 From 20% Tributyl Phosphate - 20% Mixed Trialkyl Phosphine Oxides/kerosene In The Presence Of

Back-extraction of Pu^4 +  from a mixture of 20% tributyl phosphate (TBP) and 20% mixed trialkyl phosphine oxides (TRPO) in kerosene in the presence of UO²⁺₂was studied. The back-extractants investigated may be divided into three groups: carboxylic acids and salts, amino polycarboxylates, and phosphonic acid. The distribution coefficients of both Pu^4 +  and UO²⁺₂using a number of different back-extractants were measured and compared. The results obtained suggest that the only practical back-extractants are carboxylic acids. Among the carboxylic acids tested, oxalic acid is suitable when the UO²⁺₂ concentration in the organic phase is less than 2 g/L. For UO²⁺₂concentrations between 2 and 10 g/L, oxalic acid-nitric acid mixtures may be used. For UO²⁺₂concentrations greater than 10 g/L, the only practical back-extractant is glycolic acid. The results obtained here may be used to further develop a new process for separation of Pu^4 +  and UO²⁺₂ from TBP-TRPO/kerosene mixture.     

SEPARATION OF AROMATIC AND ALIPHATIC HYDROCARBONS WITH IONIC LIQUIDS

Naphtha cracker feeds may contain 10-25 wt% aromatic compounds. Removal of these aromatic compounds from the feed to the cracker would offer several advantages: higher capacity, higher thermal efficiency, and less coke formation. In this work, we investigated the separation of toluene from heptane by extraction with ionic liquids.

Several ionic liquids are suitable for extraction of toluene from toluene/heptane mixtures. The selectivities for the aromatic/aliphatic hydrocarbon separation with all ionic liquids tested increase with decreasing aromatic content in the feed. The toluene/heptane selectivities at 10% toluene in the feed at T = 40°C and 75°C with several ionic liquids ([emim]HSO₄, [mmim] methylsulfate, [emim] ethylsulfate, [bmim]BF₄, [emim] tosylate, [mebupy]BF₄, and [mebupy] methylsulfate) are a factor of 1.5-2.5 higher than those obtained with sulfolane, which is a conventional solvent for the extraction of aromatic hydrocarbons from a mixed aromatic/aliphatic hydrocarbon stream. The three most suitable ionic liquids from the ionic liquids tested for the separation of aromatic and aliphatic hydrocarbons are [mebupy]BF₄, [mebupy]CH₃SO₄, and [bmim]BF₄ and at 75°C also [emim] tosylate. The ionic liquid [mebupy]BF₄ is selected for further testing in our extraction pilot plant.

Because ionic liquids have a negligible vapor pressure, evaporating the extracted hydrocarbons from the ionic liquid phase could achieve the recovery of the ionic liquid. A conceptual process scheme for the extraction has been set up. Preliminary calculations show that both the investment costs and the energy costs will be considerably lower with ionic liquids than with sulfolane as the solvent.     

Thermodynamic modeling of CO2 solubility in aqueous solutions of NaCl and Na2SO4

A thermodynamic model based on the electrolyte NRTL activity coefficient equation and PC-SAFT equation-of-state is developed for CO₂ solubility in aqueous solutions of NaCl and Na₂SO₄ with temperature up to 473.15 K, pressure up to 150 MPa, and salt concentrations up to saturation. The Henry's constant parameters of CO₂ in H₂O and the characteristic volume parameters for CO₂ required for pressure correction of Henry's constant are identified from fitting the experimental gas solubility of CO₂ in pure water with temperature up to 473.15 K and pressure up to 150 MPa. The NRTL binary parameters for the CO₂-(Na⁺, Cl⁻) pair and the CO₂-(Na⁺, SO₄²⁻) pair are regressed against the experimental VLE data for the CO₂-NaCl-H₂O ternary system up to 373.15 K and 20 MPa and the CO₂-Na₂SO₄-H₂O ternary system up to 433.15 K and 13 MPa, respectively. Model calculations on solubility and heat of solution of CO₂ in pure water and aqueous solutions of NaCl and Na₂SO₄ are compared to the available experimental data of the CO₂-H₂O binary, CO₂-NaCl-H₂O ternary and CO₂-Na₂SO₄-H₂O ternary systems with excellent results.     

Understanding Hydrolysis and Condensation Kinetics of γ-Glycidoxypropyltrimethoxysilane

Monitoring the kinetics of hydrolysis and condensation of γ-glycidoxypropyltrimethoxy-silane (γ-GPS) was carried out by NMR spectroscopy (²⁹Si-, ¹³C-, and ¹H-). The course of these reactions was followed in 2 wt% aqueous dilution conditions (26% D₂O/74% H₂O), pH 5.4, and temperatures of 26, 50, and 70°C. At ambient temperature, hydrolysis and condensation proceed at very different time scales: a few hours for the hydrolysis versus several weeks for the condensation. Distortionless Enhancement by Polarization Transfer (DEPT) sequences by ²⁹Si- and ¹³C-NMR spectroscopy were optimized for determining the complete spectral assignment for each hydrolysis step, i.e., RSi(OMe)_3-n(OH)_n (with R = (CH₂OCH)CH₂OCH₂CH₂CH₂-;andn = 1, 2, 3). A pseudo-first order rate constant for the first hydrolysis step, T0^(OMe)3 + H₂O → T0^(OMe)2OH + MeOH, was calculated to be 0.026 min^-1. Simultaneously to the condensation reactions, we have observed epoxy ring opening of the glycidyl- group. All three processes (hydrolysis, condensation, and epoxy ring opening) are dramatically accelerated with temperature increases from 26 to 70°C. The activation energy of the epoxy ring opening leading to the formation of a diol structure at the extremity of the glycidoxypropyl- chain was estimated to be 68.4 kJ/mol.     

Densities,conductivities, and viscosities of aqueous solutions of N-hexyl,methylpyrrolidinium bromide and N-butyl,methylpyrrolidinium bromide at different temperatures

The densities, conductivities, and viscosities were measured for ternary solutions of N-hexyl, methylpyrrolidinium bromide ([PP1,6]Br)-N-butyl,methylpyrrolidinium bromide ([PP1,4]Br)-H2O and its binary...     

THE INFLUENCE OF PROCESS PARAMETERS ON STRUVITE CONTINUOUS CRYSTALLIZATION KINETICS

Experimental data concerning the kinetics of mass crystallization of struvite during the process of magnesium ion removal from water with the use of ammonium dihydrogenphosphate, NH₄H₂PO₄, addition under alkaline conditions are presented. The tests were carried out in a continuous laboratory DTM MSMPR crystallizer with internal circulation of suspension (T = 298 K). The influence of concentration of Mg^2 +  ions in the raw material, pH of the process environment, and residence time of suspension on the nucleation and growth rates of struvite crystals was established. Kinetic parameters were evaluated from the crystal size distributions using selected size-dependent growth (SDG) models.     

三元体系AlCl3+CaCl2+H2O，AlCl3+FeCl3+H2O和CaCl2+FeCl3+H2O在35℃时的相平衡

缺少含AlCl₃、CaCl₂和FeCl₃的溶液相平衡,使通过蒸发结晶从粉煤灰盐酸浸取液中制备纯净的AlCl₃·6H₂O变得比较困难。采用等温溶解法研究了三元体系AlCl₃+CaCl₂+H₂O,AlCl₃+FeCl₃+H₂O和CaCl₂+FeCl₃+H₂O在35℃时的相平衡关系,测定了相应的溶解度及密度,并绘制了相应相图及密度-组成图。实验结果表明：三元体系AlCl₃+CaCl₂+H₂O和AlCl₃+FeCl₃+H₂O分别有两条溶解度曲线,两个单盐结晶区,无复盐和共溶体产生,同离子效应导致增加溶液中CaCl₂和FeCl₃浓度会有效降低AlCl₃的溶解度;CaCl₂+FeCl₃+H₂O体系会形成复盐CaCl₂·2FeCl₃·7H₂O;所得35℃相图与25℃相图相比,三元体系AlCl₃+CaCl₂+H₂O和AlCl₃+FeCl₃+H₂O中AlCl₃·6H₂O结晶区增大,CaCl₂·6H₂O结晶区转变成CaCl₂·4H₂O结晶区,CaCl₂+FeCl₃+H₂O体系中CaCl₂·2FeCl₃·8H₂O结晶区转变为CaCl₂·2FeCl₃·7H₂O结晶区。     

Electrical properties of (Bi2O3)0.75(RE2O3)0.25 ceramics (RE=Dy, Y, Ho, Er and Yb)

Five kinds of rare earth stabilized bismuth oxide ceramics, (Bi₂O₃)_0.75(RE₂O₃)_0.25 (RE=Dy, Y, Ho, Er and Yb), were synthesized by sintering a mixture of Bi₂O₃ and RE₂O₃ at 900–1100 °C and their electrical properties were investigated. The bulk density and the lattice constant linearly increased with an increase in the atomic weight of RE and the ionic radius of RE³⁺, respectively. The electrical conductivity at 300 °C slightly increased with the increasing ionic radius of RE³⁺, while at 500 and 700 °C, it was constant regardless of the ionic radius of RE³⁺. The migration activation energy and the association activation energy showed a maximum value and a minimum value at RE=Er, respectively.     

TUNGSTEN TRIOXIDE HYDRATE INCORPORATED NAFION COMPOSITE MEMBRANE FOR PROTON EXCHANGE MEMBRANE FUEL CELLS OPERATED ABOVE 100°C

A new composite membrane is fabricated by incorporating tungsten trioxide hydrate into Nafion to be employed as a candidate electrolyte for proton exchange membrane fuel cells (PEMFCs) operated above 100°C. Thermal behavior and proton conductivity of the composite membrane are studied by means of thermogravimetric/differential thermal analyis (TG/DTA) and AC impedance measurements, respectively. These results demonstrate that the thermal stability of the composite membrane has no appreciable change when compared with the native Nafion membrane. The proton conductivity of the composite membrane is found to be better than that of the native Nafion membrane at high temperature and lower relative humidity. When the composite membrane is used as an electrolyte in H₂/O₂ PEMFC under the operating conditions of 110°C, 1.36 atm gas pressure, and 70% relative humidity, the observed current density value at 0.4 V is 1.5 times higher than that of the cell employing native Nafion membrane as an electrolyte.     

NaBr-CaBr2-H2O和KBr-CaBr2-H2O三元体系273.15 K相平衡实验及计算

采用等温溶解平衡法对两个三元体系NaBr-CaBr₂-H₂O和KBr-CaBr₂-H₂O在273.15 K下的固液相平衡关系进行了研究,测定了相关盐在水溶液中的溶解度,绘制其等温相图。结果表明,两个三元体系均为水合物型,即平衡固相中未发现任何复盐及固溶体。两个三元体系在273.15 K下的等温相图均由一个共饱点、两条等温溶解度曲线、两个平衡固相结晶区组成。三元体系NaBr-CaBr₂-H₂O在273.15 K的两个结晶区的平衡固相分别为NaBr·2H₂O和CaBr₂·6H₂O,NaBr·2H₂O的结晶区远大于CaBr₂·6H₂O。三元体系KBr-CaBr₂-H₂O在273.15 K的两个结晶区的平衡固相分别为KBr和CaBr₂·6H₂O,KBr的结晶区远大于CaBr₂·6H₂O。基于Pitzer模型,运用已报道的Pitzer参数对所研究的两个三元体系在273.15 K下的等温溶解度进行模拟计算,其计算结果与实验结果基本吻合。     

PHASE EQUILIBRIUM FOR TERNARY LIQUID SYSTEMS OF WATER CARBOXYLIC ACID CHLORINATED HYDROCARBON: THERMODYNAMIC MODELING THROUGH SERLAS

Liquid-liquid equilibrium data of the solubility (binodal) curves and tie-line end compositions are presented for mixtures of [water (1) + formic acid, or acetic acid, or propanoic acid (2) + chlorobenzene, or 1,2-dichloroethane (3)] at T = 293.2 K and P = 101.3 ± 0.7 kPa. A log-basis approach, SERLAS (solvation energy relation for liquid-associated system), has been proposed to estimate the properties and liquid-liquid equilibrium (LLE) of associated systems containing proton-donating and -accepting and polar components capable of a physical interaction through hydrogen bonding or dipole-dipole interaction. The tie lines were also correlated using the UNIFAC-original model. The reliability of the models has been analyzed against the LLE data with respect to the distribution coefficient and separation factor. The proposed model appears to be an improvement in data fit for the ternary systems, yielding a mean relative error of 10.1% for all the systems considered.