Experimental analysis and thermodynamic modelling of Nitroxynil solubility in pure solvent and binary solvent

Nitroxynil(NIT) is a commonly used anti-liver fluke drug for cattle and sheep, Its solubility is closely related to its preparation. In this work, the molar solubility of NIT in nine pure solvents (methanol, ethanol, 1,2-propanediolethyl, isopropanol, ethyl acetate, acetonitrile, n-butanol, phemethylol) and two kinds of binary mixtures with different ratio(ethanol + phemethylol; ethanol + acetonitrile) was determined by shake flask method over the temperature from 278.15 ～ 323.15 K at atmosphere pressure. Results show that the solubility of NIT in all tested solvents was increased with raised temperature. In mono-solvents, the mole fraction solubility of NIT was highest in phemethylol and the solubility order is: phemethylol > acetonitrile > ethyl acetate > methanol > n-butanol > ethanol > 1,2-propanediolethyl > isopropanol > water. In binary solvents, the mole fraction solubility increased with increasing ratio of phemethylol/acetonitrile. In mono-solvents, the modified Apelblat equation, λh equation, Van't Hoff model were applied to correlate the solubility data. In binary solvents, the modified Apelblat equation, λh equation, GSM model and Jouyban-Acree model were to correlate the solubility data. Solubility order of NIT in nine pure solvent and two binary solvent systems were analysed by using the Hansen solubility parameter (HSP). Activity coefficient was to access the solute–solvent molecular interactions. In addition, the dissolution of NIT is an endothermic and entropy-friendly process, since thermodynamic parameters such as enthalpy, entropy, and apparent standard Gibbs free energy are all greater than zero. The results will supply some essential data on recrystallization process, purification and formulation development of NIT in pharmaceutical applications.     

利用基于Gouy-Chapman模型的离子有效电荷定量表征离子特异性效应

离子特异性效应在固-液界面反应中是普遍存在的. 近期研究指出, 在较低电解质浓度的某些体系中, 离子特异性效应可能并非来源于色散力、经典诱导力、离子半径或水合半径的大小等, 而是界面附近强电场中的离子极化作用. 这种作用可使界面附近的吸附态反号离子被强烈极化(高达经典极化的10⁴倍). 强烈极化的结果将导致离子在界面附近受到的库仑力远远超过离子电荷所能产生的库仑力, 这体现在离子的有效电荷将远大于离子的实际电荷. 因此胶体体系中基于这种强极化的离子有效电荷可以用来定量表征离子特异性效应的强度. 本研究在蒙脱石-胡敏酸混合悬液凝聚过程中发现了Na⁺、K⁺、Ca²⁺、Cu²⁺四种离子的离子特异性效应, 提出了基于激光散射技术测定离子有效电荷的方法, 并成功获得了被强烈极化后的离子有效电荷数值. 实验测得的Na⁺、K⁺、Ca²⁺、Cu²⁺四种离子的有效电荷值分别为: Z_{Na(effective)}=1.46, Z_K(effective)=1.86, Z_{Ca(effective)}=3.92, Z_{Cu(effective)}=6.48.该结果表明: (1) 离子在强电场中的极化将大大提高离子的有效电荷, 从而极大地增强离子所受的库仑作用力;(2) 离子的电子层数越多, 离子极化越强烈, 离子的有效电荷增加越多.     

一元强碱滴定一元弱酸溶液的林邦滴定曲线方程及其应用

以林邦副反应思想为基础,用质子条件式PBE、物料平衡式MBE、滴定分数和条件稳定常数等知识推导出一元强碱滴定一元弱酸溶液的林邦滴定曲线方程,并用滴定曲线方程讨论了滴定开始至化学计量点时任意一点p H的计算。     

气体节流膨胀过程的热力学分析

探讨气体节流膨胀过程中的熵(S)的变化,指出任何气体的节流膨胀都是熵增过程,并且是不可逆的。在此基础上,讨论和总结了节流膨胀过程的全部热力学特征。     

Prediction and simulation of wear response of Linz–Donawitz (LD) slag filled glass–epoxy composites using neural computation

This article reports on the implementation of a soft computing technique based on artificial neural networks (ANNs) in analyzing the wear performance of a new class of hybrid composites filled with Linz–Donawitz slag (LDS). LDS is a major solid waste generated in huge quantities during steel making. It comes from slag formers such as burned lime/dolomite and from oxidizing of silica, iron etc. while refining the iron into steel in the LD furnace. In this work, hybrid composites consisting of short glass fiber (SGF) reinforced epoxy filled with different LDS content (0, 7.5, 15 and 22.5 wt%) are prepared by simple hand lay‐up technique. Solid particle erosion trials, as per ASTM G 76 test standards, are conducted on the composite samples following a well‐planned experimental schedule based on Taguchi design of experiments. Significant process parameters predominantly influencing the rate of erosion are identified. The study reveals that the LDS content is the most significant among various factors influencing the wear rate of these composites. Further, a model based on ANN for the prediction of erosion performance of these composites is implemented. The ANN prediction profiles for the characteristic wear properties exhibit very good agreement with the measured results demonstrating that a well‐trained network has been created. The simulated results explaining the effect of significant process variables on the wear rate indicate that the trained neural network possesses enough generalization capability of predicting wear rate even beyond the experimental range. Copyright © 2014 John Wiley & Sons, Ltd.     

运用系统动力学模型预测稀土战略储备规模

基于全球稀土资源的供需形势和中国稀土资源减少的趋势,运用系统动力学的模型来预测未来17年我国稀土资源储备量。选取了2000~2013的生产和消费数据,通过定量模拟计算中国稀土供需差波动系数,设计了稀土资源供需差波动范围分别为0%,20%的两个方案,模拟计算了两个方案的年储备量、累计储备量和储备量绝对值。方案一范围是(-0%,+0%),仿真预测出稀土未来17年累积储备量为720551 t,即战略储备规模达到720551 t,该方案下不论供需差发生如何波动,国家都会进行储备或释放调节;方案二范围是(-20%,+20%),预测出未来17年战略储备规模为461331 t,国家只需在这个范围外进行收储释放调节,从而调节市场供求,降低价格波动幅度。本文从不同供需差的波动系数来模拟计算储备量,目的是为国家相关部门在进行稀土储备决策时提供参考,可以根据我国经济景气状况和供需形势,以及稀土产业发展状况,进行不同规模的稀土储备。     

Modeling hydrate formation conditions in the presence of electrolytes and polar inhibitor solutions

In this paper, a new predictive model is proposed for prediction of gas hydrate formation conditions in the presence of single and mixed electrolytes and solutions containing both electrolyte and a polar inhibitor such as monoethylene glycol (MEG), diethylene glycol (DEG) and triethylene glycol (TEG). The proposed model is based on the γ–φ approach, which uses modified Patel–Teja equation of state (VPT EOS) for characterizing the vapor phase, the solid solution theory by van der Waals and Platteeuw for modeling the hydrate phase, the non-electrolyte NRTL-NRF local composition model and Pitzer–Debye–Huckel equation as short-range and long-range contributions to calculate water activity in single electrolyte solutions. Also, the Margules equation was used to determine the activity of water in solutions containing polar inhibitor (glycols). The model predictions are in acceptable agreement with experimental data. For single electrolyte solutions, the model predictions are similar to available models, while for mixtures of electrolytes and mixtures of electrolytes and inhibitors, the proposed model gives significantly better predictions. In addition, the absolute average deviation of hydrate formation pressures (AADP) for 144 experimental data in solutions containing single electrolyte is 5.86% and for 190 experimental data in mixed electrolytes solutions is 5.23%. Furthermore, the proposed model has an AADP of 14.13%, 5.82% and 5.28% in solutions containing (Electrolyte + MEG), (Electrolyte + DEG) and (Electrolyte + TEG), respectively.     

Ternary mutual diffusion coefficients of aqueous {l-dopa (1) + β-CD (2)} solutions at T = 298.15 K

Ternary mutual diffusion coefficients (D₁₁, D₂₂, D₁₂ and D₂₁) measured by the Taylor dispersion method are reported for aqueous solutions of {levodopa (l-dopa) + β-cyclodextrin (β-CD)} solutions at T = 298.15 K and concentrations up to 0.007 mol · dm⁻³. Significant effects on the diffusion were observed, suggesting interactions between this carbohydrate and l-dopa. Support for this came from ¹H NMR spectroscopy, which shows that these effects are due to formation of 1:1 (β-CD:l-dopa) complexes.     

Effect of Y2O3 on microstructural characteristics and wear resistance of cobalt‐based composite coatings produced on TA15 titanium alloy surface by laser cladding

The effects of Y₂O₃ on the microstructure, phase composition of the coatings, microhardness and wear resistance of cobalt‐based composite coatings prepared by laser cladding were investigated. The TA15 titanium alloy was selected as substrate which the cobalt‐based composite powder with different content of Y₂O₃ was cladded on. The microstructure of the coatings was observed by scanning electron microscope (SEM) and metallurgical microscope. The phase structure of the coatings was determined by X‐ray diffraction (XRD), and the microhardness and wear resistance of the coatings were measured by hardness tester and wear testing machine. The results show that the rare earth oxide Y₂O₃ can refine and purify the microstructure of the coatings, reduce the porosities and cracks and improve compactness of the coatings. Moreover the addition of Y₂O₃ improves the microhardness of the coatings and reduces the friction coefficient, thus improving the wear property of the coatings. And the wear resistance of the coating with Y₂O₃ has improved about 50 times; the highest value of microhardness in the coating is HV1181.1. And 0.8 wt% content of Y₂O₃ in the coating is the best choice for improving the microhardness and wear resistance of the coating. It is feasible to improve the microstructure and tribological properties of laser cladding coatings by adding of Y₂O₃. Copyright © 2014 John Wiley & Sons, Ltd.