Phase Equilibria and Critical Curves of Binary Ammonia–Hydrocarbon Mixtures

Liquid or dense supercritical ammonia has been suggested as an extraction fluid. It is indeed good solvent for very different classes of compounds, as can be seen from phase diagrams. Such diagrams for binary systems of ammonia and hydrocarbons are presented and discussed on the basis of their critical curves. Apparatus and methods for the measurement of phase equilibria and equation of state data of fluid mixtures at high pressure are described.     

硫氰酸甲基三烷基季铵盐萃取Co（Ⅱ）的动力学

有关Co(Ⅱ)、Ni(Ⅱ)萃取分离的研究一直受到人们的重视。Preston报导了硫氰酸季铵盐(Q~ SCN-)萃取Co(Ⅱ)、Ni(Ⅱ)的平衡研究,认为Co(Ⅱ)的萃合物组成为Q_2Co(SCN)_4.本文用上升液滴法技术考察了Co(Ⅱ)/0.10mol·L~(-1)SO_4~(2-)/QSCN-煤油体系在298±1K条件下萃取速率R与CoSO_4、SO_4~(2-)和QSCN浓度的关系,确定了正向初始萃取速率方程,拟定了速控步骤。     

Shape analysis based critical Eotvos numbers for buoyancy induced partial detachment of oil drops from hydrophilic surfaces

Removal of oil drops from solid surfaces immersed in an aqueous medium is of interest in many applications. It has been shown that drop shape analysis can be used to predict conditions at which the stability limit of a lighter than water oil drop on a solid surface immersed in an aqueous bath is reached (Adv. Colloid Interface Sci. 98 (2002) 265). However the above analysis is restricted to cases where the contact angle made by the drop is below 90degrees and when the surface conditions result in a 'pinned' contact line. In this paper, it is shown that drop shape analysis can be used to predict the critical conditions at which drop stability limit is reached for drop contact angles of 90degrees and above, which is encountered with 'hydrophilic' surfaces. This critical condition can predict the occurrence of partial oil drop detachment, before complete removal due to 'roll-up', which occurs when the hydrophilic surface is adequately smooth which prevents 'pinning' of the contact line. The critical conditions at which partial drop detachment occurs can also be approximately predicted from simple force balances. It has been shown (Adv. Colloid Interface Sci. 98 (2002) 265) that for contact angles less than 90degrees, the critical limit based on shape analysis appears to resolve the differences that arise due to alternate expressions for capillary retention force. This paper shows that even for contact angles above 90degrees, the critical conditions predicted from the shape analysis resolves the differences in the predictions from the alternate force balances. Drop shape analysis used in this paper is based on the 'Arc-length' form of Young-Laplace or 'drop shape' equation, which is different from the 'Y vs X' form of the above equation that is used in Adv. Colloid Interface Sci. 98 (2002) 265. The above drop shape equation is solved by a fourth order Runge-Kutta technique and it is shown that for angles less than 90degrees, the two forms of the drop shape equation, predict almost identical values of the critical Eotvos number. This paper highlights the competing effects of interfacial tension lowering induced drop instability and 'roll-up', a term that is used to describe the retraction of the contact line of an oil drop on a surface, in being the primary c ause for drop detachment.     

Applications of ethylammonium and propylammonium nitrate solvents in liquid-liquid extraction and chromatography

Ethyl- and propylammonium nitrate are novel ionic solvents, liquid at room temperature, suitable for use as selective solvents for the isolation of analytes containing proton donor functional groups (alcohols, amines, phenols, carboxylic acids, etc.) by liquid-liquid distribution. These solvents form immiscible solvent pairs with non-polar aliphatic and aromatic hydrocarbons, ethers and alkyl halide solvents (e.g., methylene chloride, chloroform). Analytes can be recovered from the ionic solvents by back-extraction into ah organic solvent after dilution with water or pH buffer or, preferably, by extractive derivatization when gas chromatography is used for the analyses, avoiding the accumulation of salt on the column that results in poor baseline stability. Alkylation, acylation and particularly silylation are suitable methods for extractive derivatization using standard reaction conditions. Applications are presented for the isolation of polar analytes from an urban dust, shale oil and urine samples and for the determination of low-molecular-weight alcohols in gasahol and glycerol in soap. Liquid-liquid chromatographic systems with the liquid organic salt as stationary phase can be used to predict distribution constants for a particular separation and for the separation of polar solutes, particularly isomeric compounds possessing a proton donor functional group.     

Determination of butyl- and phenyltin compounds in biological material by gas chromatography-flame photometric detection after ethylation with sodium tetraethylborate

A reliable and rapid speciation method for the simultaneous determination of butyl- and phenyltin species in biological samples has been developed. Three extraction procedures are compared: enzymatic hydrolysis and solubilization by ethanoic and hydrochloric acids. Derivatization is performed by the one-step ethylation/extraction procedure using the sodium tetraethylborate reagent directly in the aqueous phase in the presence of an isooctane layer. Analysis is performed using capillary gas chromatography coupled to flame photometric detection. The detection limits are in the range of a few ng(Sn)/g. Analysis of the environmental samples and the certified reference material demonstrates the accuracy of the analytical method.     

Selective spectrophotometric determination of TNT in soil and water with dicyclohexylamine extraction

Contaminated land and groundwater remediation in military waste dumping sites often necessitates the use of simple, cost-effective, and rapid tests for detecting trinitrotoluene (TNT) residues in the field along with their dinitro-analogues. A simple, rapid, low-cost, and field-adaptable (on-site) colorimetric method was developed for quantifying TNT in the presence of RDX, PETN, picric acid, 2,4-DNT (dinitrotoluene), dinitrophenol, and dinitroaniline. Most commercialized methods for TNT assay-with the exception of Cold Regions Research and Engineering Laboratory of the U.S. Army (CRREL) method-use proprietary chemicals, and the color stability and intensity are highly dependent on the composition of the organic solution comprised of acetone or methanol. The developed colorimetric method is based on the extraction of TNT from water-acetone solution into an organic solvent mixture of dicyclohexylamine (DCHA)-isobutyl methyl ketone (IBMK) (10:1, v/v), filtration through a filter paper into a stoppered optical cell containing anhydrous sodium sulfate, and measurement of the absorbance of the organic extract at 531 nm after 5 min. The red-violet color of the extract was due to intermolecular charge-transfer (CT) between the electron attracting TNT and electron-donating DCHA, and the molar absorptivity for TNT in final organic solution was (1.16 ± 0.02) × 10⁴ L mol⁻¹ cm⁻¹.The R.S.D. of the slope of calibration line was 0.7%. The LOD of the method in the final organic phase was 0.38 μM TNT, and LOD values expressed on the basis of original soil TNT content were 0.5, 1.3, and 1.5 ppm (μg g⁻¹) for clay, loamy clay, and sandy soils, respectively. Unlike other spectrophotometric methods, the developed assay was basically tolerant to common cations and anions found in soil and water at 100-fold weight ratios, and to soil humic acids. Among a number of compounds that may be encountered in polynitro-explosive storage and waste reclaimation sites such as picric acid, dinitrophenol, 2,4-dinitrotoluene, dinitroaniline, RDX, PETN, and tetryl, only tetryl interfered with the developed TNT assay. Water tolerance and exploitability over a wide pH range were other superiorities over the CRREL method. The CT-complex was relatively stable, as the absorbance of the organic extract was not significantly influenced from the dilution of the water-acetone phase. Aside from the extractive-photometric procedure established for aqueous solutions, a simulated field colorimetric assay for TNT directly applicable to soil was also devised, based on direct color development in a 4:1 (v/v) acetone-dicyclohexylamine organic extract of soil at a liquid-to-solid ratio of 5 mL g⁻¹.     

Physicochemical Principles of Extraction with Supercritical Gases

The present review considers some physicochemical properties of fluid mixtures that are of importance for fluid extraction and supercitical fluid chromatography (SFC). Firstly, the important types of phase diagrams are treated, the occurrence of solid phases also being considered in some simple cases. Specific examples are given of mixtures of a highly volatile component I (e.g. CO₂, C₂H₆) with a relatively involatile component II (e.g. squalane) of very different molecular size, shape, structure, and/or polarity, and it is shown how the rather complicated types of phase diagrams can be calculated and correlated. The importance of fluid mixtures extends far beyond the fields of science and technology reviewed.     

两相滴定法研究2-乙基己基膦酸单2-乙基己基酯从盐酸介质中萃取钕(Ⅲ)的动力学

本文利用两相滴定法作为分析手段,用恒界面池搅拌法考察了多种因素对2-乙基己基膦酸单2-乙基己基酯(HEHEHP,HA)从盐酸介质中萃取Nd(Ⅲ)动力学的影响,从实验结果推论出萃取过程为界面化学反应控制型机理。     

Sample preparation for organic acids in biological fluids

A review of sample preparation methods for organic acids in biological fluids, in particular serum and urine, is presented. It covers techniques on organic acid determination without sample preparation, release of organic acids from binding locations, removal of proteins by protein precipitation and ultrafiltration, isolation of the organic acids by liquid-liquid and liquid-solid extraction, purification of the extract, derivatization and pre-fractionation. The various alternative sample preparation steps are compared and critically discussed. Examples of applications including profile analysis of organic acids by gas chromatography (GC), determination of particular organic acids by GC or liquid chromatography and determination of fatty acids as a distinct chemical class of acids demonstrate that the kind of sample preparation chosen depends strongly on the analytical aims.     

三正辛胺(TOA)分离贵金属的系统研究 Ⅰ.反相萃取色层法分离七个贵金属

本文系统详细地研究了七种贵金属彼此分离以及与贱金属分离的可能条件。此种工作尚未见报道。用三正辛胺作固定相。分别用1mol/L HCl、6mol/LHCl、2mol/L HNO_3—2mol/L HCl、3mol/L HNO_3-2mol/L HCl、4mol/L HNO_3-2mo1/L HCl和5％硫脲-1mol/L HCl为淋洗液,可以将Rh、Ru、Pd、Pt、Ir、Os、Au分步淋洗下来,达到彼此完全分离。为了使Rh(Ⅱ)与贱金属分离,必须将RhC1_6~(3-)转化为RhBrb_6~(3-),然后在另一色层柱上使它与贱金属分离。合成矿样的分析结果符合分析要求。