Solubility of Triethylamine in Tetraethylammonium Chloride Aqueous Solutions from 20 to 35°C

Solubilities of triethylamine in aqueous tetraethylammonium chloride solutions were measured at 20, 25, and 35°C. The molalities in Et₄NCl of the aqueous solvents ranged from 0.03 to 1 mol-kg^–1. The data were evaluated from density measurements using a vibrating-tube densimeter. At each temperature, least-squares method was used to fit experimental density data points to double polynomial equations of various degrees. Triethylamine molalities of the saturated aqueous phases were estimated by extrapolation from those equations. Experimental data were interpreted in terms of hydrophobic and electrostatic perturbed domains in the hydration shells of the noneleceory and of the cation of the salt, as a function of temperature and salt concentration. The conclusions obtained are consistent with previous volumetric studies.     

Influence of silica gel pretreatment and bonding technique on PAH selectivity of octadecyl bonded phases

Summary The effect of silica gel pretreatment and of different bonding techniques, on the chromatographic properties of octadecyl bonded phases is described. The experiments show that a monomeric octadecyl bonded phase, prepared from silica gel that has not been treated before bonding, has a poor selectivity towards polycyclic aromatic hydrocarbons (PAHs) and shows high adsorption of basic components. Silica gel treatment before the bonding of the monofunctional silane does not give a substantial improvement. Polymeric phases on the other hand show a much better PAH selectivity and a lower adsorptivity towards basic components. Further improvement can be achieved with the polymeric modification if silica gel treatment is carried out before bonding.     

含氧空位的氟掺杂二氧化锰助力稳定锌离子电池

将无机盐NH₄F加入到MnO₂的前驱体溶液中,通过高效、简单的一步水热法制备了具有氧缺陷的F掺杂α-MnO₂纳米棒(记为F-MnO₂)。氧空位和F掺杂对提高F-MnO₂的导电性、促进离子扩散、提高倍率性能起着至关重要的作用。另外,由于F掺杂,形成了F—Mn键,这可以有效地抑制放电产物中Mn³⁺的Jahn-Teller畸变,从而提高结构的稳定性。得益于这些协同效应,组装的Zn||F-MnO₂全电池在0.5 A·g^-1下,首圈放电比容量高达274 mAh·g^-1,且具有较长的循环寿命和优异的倍率性能。同时,通过循环伏安(CV)和恒流充放电(GCD)曲线证明了F-MnO₂的储能机制为H⁺和Zn²⁺的共嵌入/脱出过程。     

Copper‐catalyzed Clauson–Kass pyrroles synthesis in aqueous media

An efficient and convenient copper‐catalyzed Clauson–Kass reaction of 2,5‐dimethoxytetrahydrofuran with amines in aqueous media has been developed, providing a wide range of N‐substituted pyrroles in good yields. It is noteworthy that the Clauson–Kass reaction of 2,5‐dimethoxytetrahydrofuran with p‐phenylenediamine or m‐phenylenediamine proceeds smoothly to afford the corresponding monopyrroles and bispyrroles with high selectivity in impressive yields. A plausible mechanism for the formation of N‐substituted pyrroles has been proposed. Copyright © 2012 John Wiley & Sons, Ltd.     

拉曼光谱及其检测时样品前处理的研究进展

拉曼光谱具有操作简单,所需样本量小,检测灵敏度高等特点,可进行现场快速筛查、检测及鉴别。样品前处理直接影响分析结果的准确度和精密度,而且操作繁琐费时。发展快速、高效的样品前处理技术进而结合拉曼光谱检测技术具有重要的研究意义,特别是与增强拉曼光谱相结合进行食品、农产品中等残留物的衡量检测已成为研究热点。本文阐述了拉曼光谱产生的原理,介绍了拉曼光谱的起源和发展,讨论了表面增强拉曼光谱技术、针尖增强拉曼光谱技术和壳层隔绝纳米粒子增强拉曼光谱技术,并对拉曼检测之前的样品预处理进行了讨论。     

Combining ultrasound,vacuum and/or ethanol as pretreatments to the convective drying of celery slices

This work studied three emerging approaches to improve the convective drying (50 °C, 0.8 m/s) of celery. Celery slices of 2 mm thick were pretreated for 5 min using ultrasound (32 W/L, 40 kHz), vacuum (75 kPa vacuum pressure) and ethanol (99.8% v/v, as drying accelerator) applied individually or in combination. To evaluate individual effects of ultrasound and vacuum, the treatments were also performed with distilled water or air medium, respectively. Moreover, the cavitational level was characterized in each condition. Drying kinetics was evaluated tending into account the drying time required by each treatment and the Page’s model parameters. In addition, microstructural effects and shrinkage were evaluated. As results, ethanol combined with ultrasound significantly improved drying kinetics reducing drying time by around 38%. However, vacuum pretreatment did not affect drying kinetics even in combination with ethanol and/or ultrasound. Microstructural evaluation did not evidence cell disruption, suggesting changes in intercellular spaces, pores and/or cell wall permeability. The use of ethanol and vacuum showed a greater effect on shrinkage after pretreatment and after drying, respectively. In conclusion, at the studied conditions, the drying acceleration by vacuum and ultrasound is lower compared to the effect produced using ethanol.     

Optimization of Pretreatment Method for Alkylmercuries Speciation in Coal by High‐Performance Liquid Chromatography Coupled with UV‐Digestion Cold Vapor Atomic Fluorescence Spectrometry

Abstract

Exhaustive extraction of analytes in their original chemical forms from samples with complex matrices is a pivotal step for speciation analysis. Herein we propose a pretreatment method for extracting and preconcentrating methylmercury and ethylmercury from coal samples by using KBr–H₂SO₄/CuSO₄–C₆H₅CH₃–Na₂S₂O₃ system. The extraction conditions, including the volume of the organic phase and the extraction time, were optimized in detail. Speciation analysis of alkylmercuries was carried out by high‐performance liquid chromatography online coupled with UV‐digestion and cold vapor atomic fluorescence spectrometry. The detection limits were 0.6 ng mL^?1 for methylmercury and 1 ng mL^?1 for ethylmercury, respectively. The recoveries of methylmercury and ethylmercury spiked in a sample were 84% and 82%, respectively. The method was applied successfully to analysis of alkylmercuries in four coal samples collected from northeast China.     

Phase diagram of aqueous solution at high pressure and low temperature

Abstract

This paper presents a constant mass high pressure isothermal calorimeter and describes the range of applications that this type of equipment can deal with. As an example, the thermophysical properties of an aqueous solution of MgSO₄ at low temperature and at high pressure have been investigated. The main results showed that the phase change heat of the solution decreased with increasing pressure and the phase change temperature of the eutectic concentration was depressed under high pressure. Those changes could be related to the MgSO₄ solubility and to water latent heat changes.     

氯化钠水溶液结构的研究

利用上海光源(SSRF)的第三代同步辐射光源测定室温下摩尔浓度分别为0.172 mol/L、0.343 mol/L、0.699 mol/L、1.064 mol/L、2.832 mol/L、3.910 mol/L、5.289 mol/L的NaCl水溶液的X射线散射数据。由X射线散射数据可知,随着NaCl水溶液浓度的增大,X射线散射曲线的特征峰由12.6°到13.4°发生偏移。运用Pair Distribution Function(PDF)理论对X射线散射数据进行处理,得到了不同浓度NaCl水溶液及纯水的差值对分布函数,其中的O-O峰随着浓度的增大逐渐分裂为两峰,O-O峰位在0.282 nm处。利用分子动力学模拟研究不同浓度的NaCl水溶液,表明Na+、Cl-的引入对水分子的氢键结构有一定的破坏,当浓度大于15%时,这种效果尤其明显。Na+、Cl-均存在两层水化层,各离子间配位数随浓度的增大而减少。H2O分子的自扩散系数远大于Na+和Cl-的自扩散系数,后两者的值随浓度的增大逐渐减少,Na+和Cl-的水化半径均随浓度增大而降低。     

A three-parameter model describing the experimental relation between shear stress and shear rate for laminar flow of aqueous polymer solutions

Summary A three-parameter model is introduced to describe the shear rate — shear stress relation for dilute aqueous solutions of polyacrylamide (Separan AP-30) or polyethylenoxide (Polyox WSR-301) in the concentration range 50 wppm – 10,000 wppm. Solutions of both polymers show for a similar rheological behaviour. This behaviour can be described by an equation having three parameters i.e. zero-shear viscosity ₀, infinite-shear viscosity , and yield stress ₀, each depending on the polymer concentration. A good agreement is found between the values calculated with this three-parameter model and the experimental results obtained with a cone-and-plate rheogoniometer and those determined with a capillary-tube rheometer.

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Zusammenfassung Der Zusammenhang zwischen Schubspannung und Schergeschwindigkeit von strukturviskosen Flüssigkeiten wird durch ein Modell mit drei Parametern beschrieben. Mit verdünnten wäßrigen Polyacrylamid-(Separan AP-30) sowie Polyäthylenoxidlösungen (Polyox WSR-301) wird das Modell experimentell geprüft. Beide Polymerlösungen zeigen im untersuchten Schergeschwindigkeitsbereich von ein ähnliches rheologisches Verhalten. Dieses Verhalten kann mit drei konzentrationsabhängigen Größen, nämlich einer Null-Viskosität ₀, einer Grenz-Viskosität und einer Fließgrenze ₀ beschrieben werden. Die Ergebnisse von Experimenten mit einem Kegel-Platte-Rheogoniometer sowie einem Kapillarviskosimeter sind in guter Übereinstimmung mit den Werten, die mit dem Drei-Parameter-Modell berechnet worden sind.

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a Pa^–1 physical quantity defined by:a = {1 – ( / ₀)}/ ₀ - c l concentration (wppm) - D m capillary diameter - L m length of capillary tube - P Pa pressure drop - R m radius of capillary tube - u m s^–1 average velocity - v _r m s^–1 local axial velocity at a distancer from the axis of the tube - shear rate (–dv _r /dr) - local shear rate in capillary flow - s^–1 wall shear rate in capillary flow - Pa s dynamic viscosity - _a Pa s apparent viscosity defined by eq. [2] - ( _a ) Pa s apparent viscosity in capillary tube at a distanceR from the axis - ₀ Pa s zero-shear viscosity defined by eq. [4] - Pa s infinite-shear viscosity defined by eq. [5] - l ratior/R - kg m^– density - Pa shear stress - ₀ Pa yield stress - _r Pa local shear stress in capillary flow - _R Pa wall shear stress in capillary flow _R = (PR/2L) - _v m³ s^–1 volume rate of flow With 8 figures and 1 table