Kinetic sonication effects in light of molecular dynamics simulation of the reaction medium

Molecular dynamics (MD) simulation of the structure of ethyl acetate solutions in two water–ethanol mixtures was performed at 280 and 330 K. The MD simulations revealed that ethyl acetate was preferentially solvated by ethanol, water being mainly located in the next solvation layer. With increasing temperature ethanol was gradually replaced by water in the first solvation shell. These findings explain the decrease in the rate of ester hydrolysis with increasing molar ratio of ethanol in the solution as the reaction rate was linearly dependent on the relative ethanol content in the first solvation shell of the ester. Predominance of ethanol results in decreased polarity and water activity in the shell and accordingly in a decreased reaction rate. Based on the results of the MD simulations, the principal conclusion of this work is that ultrasound enhances the kinetic energy (the effective temperature) of species in the solution and, in this way, evokes shifts in the solvation equilibria thus affecting the reaction rate. It appears that ultrasound does not completely break down the solvent shells or clusters in the solution as previously believed. Phenomena of thermo-solvatochromism and reaction rate levelling by ultrasound in binary solvents are described.     

Heat and mass transfer at adiabatic evaporation of binary zeotropic solutions

Results of numerical simulation of heat and mass transfer in a laminar flow of three-component gas at adiabatic evaporation of binary solutions from a flat plate are presented. The studies were carried out for the perfect solution of ethanol/methanol and zeotrope solutions of water/acetone, benzene/acetone, and ethanol/acetone. The liquid-vapor equilibrium is described by the Raoult law for the ideal solution and Carlson–Colburn model for real solutions. The effect of gas temperature and liquid composition on the heat and diffusion flows, and temperature of vapor-gas mixture at the interface is analyzed. The formula for calculating the temperature of the evaporation surface for the binary liquid mixtures using the similarity of heat and mass transfer was proposed. Data of numerical simulations are in a good agreement with the results of calculations based on the proposed dependence for all examined liquid mixtures in the considered range of temperatures and pressures.     

一种危险液体混合物的拉曼光谱定性定量识别方法

危险液体混合物的拉曼光谱定性定量分析一直是现场应用难点,为解决该问题,分析了多种物质混合后拉曼光谱的峰位、峰值、峰型变化情况,选取拉曼光谱关键特征峰进行数学简化,构建了从混合物物质成分到混合物拉曼光谱的映射关系,该映射关系描述多种物质成分混合的混合物拉曼特征峰响应只和混合物中各成分本身拉曼特征峰响应以及各物质成分混合比例有关,各物质成分按混合比例贡献拉曼特征谱峰,共同形成最终的混合物拉曼光谱。由该映射关系求逆,可实现从采集到的混合物拉曼光谱计算出各物质成分的混合比例。基于此,设计了危险液体混合物成分定性定量识别方法,主要方法步骤包括,首先进行拉曼光谱数据采集,然后进行拉曼光谱数据处理并获得拉曼特征峰,再进行测试样品与数据谱库标准品的正反向特征峰匹配,如果正反向特征峰匹配系数都比较高,在满足一定阈值条件下,可认定测试样品是某种纯净物,如果不是纯净物,则进入混合物分析,通过拉曼光谱特征峰反向匹配系数筛选,确定混合物成分构成,混合物成分确定后再进行混合物成分比例计算,最终实现危险液体混合物定性定量分析。实验部分,选定丙酮、甲苯、三氯甲烷、乙醇及其混合物进行实验验证,当混合物样品是丙酮、乙醇两种成分按3∶7比例混合时,经拉曼光谱识别方法计算,混合成分计算值是丙酮占比0.245 7,乙醇占比0.706 0;当混合物样品是甲苯、三氯甲烷两种成分按3∶7比例混合时,经拉曼光谱识别方法计算,混合成分计算值是甲苯占比0.323 4,三氯甲烷占比0.763 0;当混合物样品是丙酮、甲苯、乙醇三种成分按4∶3∶3比例混合时,经拉曼光谱识别方法计算,混合成分计算值是丙酮占比0.795 9、甲苯占比0.303 5、乙醇占比0.287 5,实验结果表明,当危险液体混合物成分是两种或三种成分混合时,混合成分计算值基本和实际值吻合,应用危险液体混合物的拉曼光谱定性定量识别方法,可较准确的从拉曼混合光谱中解析出各混合物成分以及各成分在混合物中的比例,可以判断混合物每个拉曼特征谱峰都来自于哪个成分或哪些成分拉曼特征谱峰的混合,谱图解析结果良好,对危险液体混合物现场分析鉴别有较大应用价值。     

Vapor–liquid and liquid–liquid equilibrium for binary systems ester + a new protic ionic liquid

This study reports the synthesis of a new protic ionic liquid, bis(2-hydroxyethyl)ammonium butyrate (2-HE₂AB), performed by a Brønsted acid–base reaction between butanoic acid and bis(2-hydroxyethyl)ammonia. The new ionic liquid was characterized by 1D hydrogen NMR spectrum. The ionic liquid shows complete solubility in water, methanol, and ethanol, and is partially soluble in methyl acetate, ethyl acetate, and propyl acetate, while it is not soluble in some alkanes. Density, refractive index, and vapor–liquid equilibrium were measured for the binary system 2-HE₂AB + methyl acetate at atmospheric pressure. Furthermore, density, refractive index, and liquid–liquid equilibrium were measured for the binary systems 2-HE₂AB + ester (methyl acetate, ethyl acetate, or propyl acetate) at 293.2 K. The Peng-Robinson equation of state, coupled with the Wong-Sandler mixing rule, was used in the thermodynamic modeling of density, vapor–liquid, and liquid–liquid equilibrium data. The COSMO-SAC activity coefficient model was used to calculate the activity coefficient within the Wong-Sandler mixing rule. The calculations show deviations for density, for the vapor–liquid equilibrium, and for the non-polar and polar phases of the liquid–liquid equilibrium within 13.0, 0.1, 132.5, and 23.8 %, respectively.     

Multivariate optimization and comparison between conventional extraction (CE) and ultrasonic-assisted extraction (UAE) of carotenoid extraction from cashew apple

Carotenoids are an essential component of cashew and can be used in pharmaceuticals, cosmetics, natural pigment, food additives, among other applications. The present work focuses on optimizing and comparing conventional and ultrasound-assisted extraction methods. Every optimization step took place with a 1:1 (w:w) mixture of yellow and red cashew apples lyophilized and ground in a cryogenic mill. A Simplex-centroid design was applied for both methods, and the solvents acetone, methanol, ethanol, and petroleum ether were evaluated. After choosing the extractor solvent, a central composite design was applied to optimize the sample mass (59–201 mg) and extraction time (6–34 min). The optimum conditions for the extractor solvent were 38% acetone, 30% ethanol, and 32% petroleum ether for CE and a mixture of 44% acetone and 56% methanol for UAE. The best experimental conditions for UAE were a sonication time of 19 min and a sample mass of 153 mg, while the CE was 23 min and 136 mg. Comparing red and yellow cashews, red cashews showed a higher carotenoid content in both methodologies. The UAE methodology was ca. 21% faster, presented a more straightforward composition of extracting solution, showed an average yield of superior carotenoid content in all samples compared to CE. Therefore, UAE has demonstrated a simple, efficient, fast, low-cost adjustment methodology and a reliable alternative for other applications involving these bioactive compounds in the studied or similar matrix.     

气相色谱法同时测定乙酸乙酯、乙酸丁酯、环己酮和苯系物

采用活性碳吸附,二硫化碳解吸进样,利用DB-1毛细管色谱柱采用恒温条件分离,以FID为检测器,同时测定空气或废气中乙酸乙酯、乙酸丁酯、环己酮、苯系物。结果表明,该方法分离效果好,精密度高,准确度高,分析时间短,适合空气或废气环境分析的要求,结果令人满意。     

番茄红素可见吸收光谱和荧光光谱的测量与分析

采用ICCD光谱探测系统对不同浓度番茄红素的二硫化碳溶液吸收谱的相对吸收强度进行了测量,结果显示在一定浓度范围内,番茄红素稀溶液的吸收规律满足朗伯-比尔定律;分别用丙酮、正己烷、石油醚、苯、乙酸乙酯和二硫化碳作为溶剂对番茄红素可见吸收光谱进行了测量,对结果进行分析后发现苯、乙酸乙酯和二硫化碳的番茄红素溶液的特征吸收峰的波长位置与以丙酮作为溶剂相比有不同程度的红移效应;番茄红素-丙酮溶液中加入水后溶液颜色随着加水量的增加逐渐变浅,溶液吸光度降低,当丙酮与水的体积比为4∶1时吸收光谱在紫外出现一新的吸收峰。产生这些现象的原因是番茄红素溶于不同溶剂时,溶剂分子对番茄红素分子作用不同。用荧光光度计采集不同浓度的番茄红素丙酮溶液的荧光光谱,结果表明番茄红素溶液的荧光光谱主要集中在500～680 nm波段,浓度低于50 μg·mL^-1时,番茄红素的荧光强度随着浓度的增加而呈线性增加。当浓度高于60 μg·mL^-1时,荧光强度因为番茄红素分子间的相互作用而下降。     

Capacitive technique for measuring the component concentration in drops of binary solutions

A capacitive technique for measuring the component concentration in drops of binary mixtures consisting of liquids with different permittivities is described. Test results for the technique are presented, and the component concentration in drops of ethanol, methanol, and acetone aqueous solutions vaporizing in an air flow is measured.     

Effect of ultrasound on ester hydrolysis in aqueous ethanol.

Kinetics of the acid-catalyzed hydrolysis of ethyl acetate in ethanol-water binary solutions were investigated without sonication and under ultrasound at 22 kHz. Rate enhancements by 1.03-2.4 times were found with a minimum at 18 wt.% and a maximum at 45 wt.% of ethanol. The results suggest that ultrasonic acceleration of the reaction may be interrelated to the perturbation of the molecular structure of the binary solvent.     

Adiabatic evaporation of binary liquid mixtures on the porous ball surface

Measured data for the temperature of a porous spherical surface to which an evaporating binary liquid mixture was supplied are reported. In the experiments, solutions of ethyl and methyl alcohols in water, and also solutions of acetone in water, were used. The concentration of mixture components was varied throughout the widest possible range of X _L = 0–1, and the temperature of dry air flow past the sphere was in the range t ₀ = 15–300 °C. In the present study, a strong influence of the composition of the mixtures on their adiabatic evaporation temperature was established. In the heat- and mass-transfer process, the air temperature is also of paramount importance. An experimental correlation is obtained which generalizes data on adiabatic evaporation temperature in a broad range of component concentrations and temperatures for the experimentally examined binary liquid mixtures. This work was supported by the Russian Foundation for Basic Research (Grant No. 06-08-39002—GFEN).     

Kinetics of the thermal decomposition reaction of diethylketone cyclic triperoxide in acetone–toluene and acetone–1‐propanol binary solvent mixtures

The thermal decomposition reaction of diethylketone triperoxide (DEKT) ca. 0.02 M was studied in binary mixtures of acetone–toluene and acetone–1‐propanol at 150 °C. Products of DEKT thermolysis in solution, detected by GC analysis, were diethylketone, bibenzyl and butane. The reactions were explored by GC at different solvent compositions and in each case the reactions followed a pseudo first order kinetic law, up to at least 90% peroxide conversion. The rate coefficient value of the reaction is affected by the solvent properties, showing an increase in the k_obs values with increases in the polarity of the solvent mixture in acetone–toluene systems. Changes in the rate coefficient values are probably caused by the presence of the apolar toluene solvent, which dominates the preferential solvation around the DEKT molecule through non‐specific interactions. In acetone–1‐propanol mixtures the solvation effect is slightly dominated by the specific interactions between the 1‐propanol and a polar intermediate specie represented by the biradical, initially formed. The rate coefficient value increases ca. 6% in the mixture with 0.1 mole fraction of 1‐propanol in comparison with the value in pure acetone; but no more changes in rate coefficient values are observed when the amount of the alcohol increases. The critical state of the reaction (intermediate biradical) is preferentially solvated by the 1‐propanol instead of acetone, but in mixtures of different composition, it is not possible to detect any effect on the reactivity for homolytic rupture of the O? O bond. Copyright © 2008 John Wiley & Sons, Ltd.     

吸收峰混叠的太赫兹光谱区间组合特征提取算法

太赫兹光谱是物质识别的前沿方法之一。由于不同物质的分子组成或结构各异,许多物质的太赫兹吸收谱会在特定频率上出现吸收峰,可以作为混合物成分检测的重要特征。有效准确地提取这些吸收峰的参数,是提高识别率的关键。多峰拟合算法将光谱曲线拟合成若干个标准峰函数之和,能够同时提取到吸收峰的频率、峰高、峰宽等信息。但是该算法以寻峰算法结果为基础确定吸收峰的大致位置和数量,寻峰结果不一定是最优的拟合结果,而且很难准确识别定位混叠状态的吸收峰。为了提高混叠光谱中吸收峰的识别定位精度,提出以大幅度平滑后的曲线波谷为分界点,将预处理后的光谱分成若干个子区间。然后将子区间组合起来进行多峰拟合,通过遗传算法得到最优的拟合子区间组合和吸收峰频率近似值,拟合时每个子区间中通过峰数递增最优化方法确定拟合的吸收峰数,最后微调优化得到最优的吸收峰频率、峰高值。为了实现物质的识别,通过密度聚类算法得到同一类纯净物在多次测量中的共同吸收峰,以此作为标准数据,通过提出的基于吸收峰特征的光谱匹配算法实现了纯净物和不同含量混合物的快速识别。对10类纯净物的实际光谱数据进行拟合聚类,得到其吸收峰参数,结果与太赫兹光谱数据库一致。通过识别算法对纯净物测试集进行识别的识别率为100%,证明了特征提取和物质识别算法的有效性。对于含有混叠峰的混合物光谱,二阶导数法对葡萄糖-乳糖混合物光谱中被掩盖吸收峰(1.280 THz)的识别率仅为70%,提取到的频率平均值为1.316 THz;而该算法提高识别率至95%,频率平均值为1.281 THz,该算法提高了对混叠峰的分辨能力,能够精确定位混叠峰。对10类纯净物构成的6类不同程度混叠的二元混合物前二、三识别率分别达到90.8%和98.3%,提取到的特征能够有效应用于混合物的成分检测。该算法能够以纯净物数据为标准数据实现成分各异的混合物成分检测,对于太赫兹光谱混合物成分检测有重要意义。     

光谱法分析塑料抛光膏的组分

分别采用硅胶柱色谱法和溶剂抽提,分离优质塑料抛光膏中的油脂和磨料部分。油脂部分依次以石油醚、苯、氯仿、乙酸乙酯、丙酮、乙醇为淋洗剂进行洗脱,利用红外光谱、核磁共振光谱法对所分离组分进行了结构鉴定。磨料部分通过原子发射光谱和X射线衍射法进行金属元素及形态分析。通过上述光谱法确定了该塑料抛光膏的化学组成和结构。     

Characterization and adsorptive application of ordered mesoporous silicas

The adsorption behaviour of the n-octane/ethanol binary liquid mixture has been studied on ordered mesoporous silica materials. Adsorption excesses on SBA-15, SBA-16 and MCM-48 solids are measured and described by mathematical functions. The experimental adsorption excess isotherms are presented and discussed. The mesoporous silicas used for liquid-adsorption experiments are characterized by nitrogen adsorption before and after liquid adsorption by the powder X-ray diffraction (XRD) and by the sample controlled thermal analysis (SCTA).     

兰索拉唑中有机溶剂残留量的测定

文章建立了采用直接进样毛细管气相色谱法测定兰索拉唑中甲醇、乙醇、乙酸乙酯残留量的方法.色谱柱为HP-FFAP石英毛细管柱,采用程序升温,载气为氮气,检测器为FID,以二氧六环为溶剂.在上述色谱条件下,甲醇的线性范围为6-54mg/L,乙醇和乙酸乙酯的线性范围为10-90mg/L;平均加样回收率分别为99.36、101.26%和101.57%.本方法简便、专属性强、准确度高,可用于测定原料药中甲醇、乙醇、乙酸乙酯的残留量.     

短瓣金莲花不同提取部位的红外光谱分析

利用红外光谱的宏观指纹特性,对短瓣金莲花不同溶剂提取部位的红外光谱图和二阶导数红外光谱图进行了整体分析.综合分析可知,短瓣金莲花石油醚提取部位主含长链烷烃、脂肪酸或酯类成分,乙酸乙酯提取部位主含长链脂肪酸（酯）及黄酮类化合物,95％乙醇提取部位主含黄酮及黄酮苷类化合物,60％乙醇提取部位主含黄酮苷及多糖类成分,30％乙醇和去离子水提取部位主含多糖类成分.因此,利用红外光谱法可从整体上对中药不同提取部位的主体成分进行直接、快速的分析,为中药提取物的工艺优化及其分析研究提供有价值的参考和方向性指导.     

Inversion temperature for adiabatic evaporation of liquid into an air-steam mixture

This paper deals with adiabatic evaporation of various liquids into an air-steam mixture and pure superheated steam. The focus is made on the inversion temperature, which means that the rate of liquid evaporation into an air-steam mixture (superheated steam) becomes equal to the rate of evaporation into dry air. A simple analytical solution for finding of inversion temperature was derived, and the required conditions of existence of the given phenomenon are found. The influence of parameters of the main flow (vapor quantity, pressure, and flow regime) on the value of inversion temperature is analysed. It is shown that consideration of the influence of injection flow on relative function of heat transfer for inversion temperature definition of ethanol, acetone, and benzene is necessary. A comparison with numerical modelling was made to estimate the analytical solution accuracy. The work was financially supported by the Russian Foundation for Basic Research (Grants Nos. 05-02-16478 and 05-08-17981), and by President of the Russian Federation (Grant NSh-6965.2006.8).     

沸石类咪唑骨架材料吸附分离天然气的分子模拟

采用巨正则蒙特卡洛方法研究C₂H₆, CO₂和CH₄三种气体在两种沸石类咪唑骨架材料 (ZIF)-ZIF-2和ZIF-71中的吸附与分离性能. 考察了C₂H₆, CO₂和CH₄三种气体在ZIF-2和ZIF-71中的单组分吸附等温线、吸附热; C₂H₆-CH₄, CO₂-CH₄ 与C₂H₆-CO₂等摩尔二元混合物的分离; 以及C₂H₆-CO₂-CH₄三元体系的分离性能. 研究结果表明: 低压下不同气体的吸附量大小与其吸附热关系紧密; 而高压下因有限的孔空间, 尺寸较小的气体分子吸附量增长趋向更快; 多组分吸附分离中, 低压下能量效应通常占据主导, ZIF优先吸附作用力较强的组分; 高压下堆积效应影响显著, ZIF会优先吸附尺寸较小的组分. ZIF-2和ZIF-71对这3种二元体系的分离性能良好. 对于三元混合物吸附分离, 在常温下3000-4000kPa范围内, ZIF-2具有良好的天然气净化性能, 可有效地分离出天然气中的C₂H₆和CO₂. 关键词： 巨正则蒙特卡洛模拟 天然气分离 沸石类咪唑骨架     

Effect of pure and mixed solvents on the solubility, crystal growth and morphology of ethyl p-dimethylamino benzoate (EDMAB): An organic nonlinear optical material

The effects of pure and mixed solvents of ethanol and acetone on solubility, nucleation and growth of ethyl p-dimethylamino benzoate (EDMAB) were investigated. It was found that solubility of EDMAB increased as the volume ratio of acetone increased in the mixed solvent. Growth experiments were performed at 32 °C using pure and mixed solvents with different volume ratios of ethanol and acetone. Bulk single crystals of EDMAB were grown-in the experiment conducted using mixed solvent of 25% acetone and 75% of ethanol, whereas thin platelet crystal of EDMAB was obtained in the experiment conducted using pure ethanol. The acetone rich system resulted in uncontrolled nucleation with large number of tiny crystals, possibly due to high vapor pressure of acetone. The grown crystals were subjected to various analytical studies such as powder X-ray diffraction, Vickers microhardness, dielectric studies as a function of frequency and optical transmission and the powder Kurtz method.     

Growth and optical characterization of organic nonlinear optical crystal: indole-3-aldehyde

The metastable zone width for the solution of organic nonlinear material: indole-3-aldehyde (IA) has been determined for the various solvents of acetone, methanol and ethyl acetate and the corresponding IA crystals have been grown by temperature lowering technique. The surface analysis on different planes of the grown crystals has been carried out. The range of transmission and powder second harmonic generation efficiency of IA have been reported.