On the fluid phase behaviour of fluid binary mixtures using the Yukawa fluid molecular model

By expanding Ginoza’s mean spherical approximation (MSA) results in an inverse-temperature expansion, Henderson et al. obtained explicit results for the thermodynamic functions of a pure Yukawa fluid. We have recently published explicit results for the coefficients in an inverse-temperature expansion of the thermodynamic functions for the MSA for mixtures of Yukawa fluids. Attention is drawn to the fact that the MSA in the Ginoza formulation, does not always yield a convergent solution. The expansion used in this paper will always yield a result. In this work we present our investigations of the fluid phase diagram of Yukawa binary mixtures by considering an expansion of the MSA Helmholtz free energy up to the fifth order of the inverse-temperature expansion. The calculated fluid phase diagrams for Yukawa binary mixtures are similar to those of real mixtures.     

Multiscale Lagrangian fluid dynamics simulation for polymeric fluid

We have developed a simulation technique of multiscale Lagrangian fluid dynamics to tackle hierarchical problems relating to historical dependency of polymeric fluid. We investigate flow dynamics of dilute polymeric fluid by using the multiscale simulation approach incorporating Lagrangian particle fluid dynamics technique (the modified smoothed particle hydrodynamics) with stochastic coarse‐grained polymer simulators (the dumbbell model). We have confirmed that our approach is well in agreement with the macroscopic results obtained by a constitutive equation corresponding to the dumbbell model, and observed that microscopic thermal fluctuation appears in macroscopic fluid dynamics as dispersion phenomena. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 886–893, 2010     

Viscoelastic dilatation processes of fluid/fluid interfaces: time-domain representation

Dynamic interfacial phenomena are shown to be most satisfactorily interpreted within the general framework of the theory for system analysis. All time-dependent dilational behaviours of interfaces can be quantitatively predicted from knowledge of the dilational modulus, that is, of the transfer function of the interfacial system.The unifying mathematical formalism allows traditional experiments, known in the literature, to be connected one to another.The presented relationships are also the foundations of the transient techniques for the measurement of interfacial quantities.Problems involving diffusive surface relaxation in quiescent hydrodynamic conditions are easily analytically or numerically solved. Other complex relaxation mechanisms introduce no additional conceptual complication.     

Direct coupling of CO2 fluid extraction with capillary supercritical fluid chromatography

Summary An interface described in the literature was modified to accommodate small sample quantities. The simple and inexpensive method can be used to obtain rapid qualitative sample information of complex matrices by extraction in sub- or supercritical conditions (SFE) with a concurrent separation by capillary supercritical fluid chromatography (CSFC). Compared to traditional solvent extraction methods the potential for analyte degradation and contamination is minimized resulting in reduced sample amount necessary for extraction and separation, and also in faster extractions. Complex matrices of a plastic material, a natural product and a soil spiked with a substituted hydrocarbon test mixture were analyzed to show the usefulness of the interface.     

Analysis of sulphonamides using supercritical fluid chromatography and supercritical fluid chromatography-mass spectrometry

Packed-column supercritical fluid chromatography has been used for the separation of mixtures of sulphonamides on silica and amino-bonded stationary phases utilizing carbon dioxide with methanol modifier as the mobile phase. The effect of modifier concentration, column pressure and modifier identity on retention was also studied. Packed-column supercritical fluid chromatography-mass spectrometry (SFC-MS) of these mixtures utilizing both moving-belt and modified thermospray interfaces was also studied. The identification of sulphamethazine in a spiked porcine kidney extract was performed by SFC-MS using the moving-belt interface.     

Supercritical fluid extraction

Supercritical fluid extraction (SFE) provides for the first time a viable option to conventional and widely used Soxhlet extraction. The ability to change the solvating power of a single supercritical fluid by changing its density is an exceedingly attractive feature. An environmentally safe alternative such as supercritical carbon dioxide to organochlorine solvents which are widely used today in many government and industrial analytical laboratories for sample preparation is desirable. SFE may also constitute a viable alternative to other popular sample preparation techniques such as liquid-liquid extraction, solid phase extraction and purge/trap. Much research, however, must be done in order to understand, optimize and apply this technology. For example, (a) automation of extraction, (b) matrix effects, (c) new fluids/modifiers/additives, (d) trapping efficiency, (e) recovery of extracted analytes, and (f) extraction kinetics are some areas which need a greater understanding. This review is concerned with many of these topics as they relate to trace organic analysis wherein SFE is the primary sample preparation technique.     

Considerations for analytical supercritical fluid extraction of sulfonyl ureas employing a modified fluid

Important considerations are discussed for analytical SFE method development employing methanol–modified carbon dioxide and solid-phase trapping. The focus of this study was to break the method development procedure into distinct steps so that the origins of low recoveries could be determined conclusively. Sulfonyl urea herbicides were used as probe analytes. Analyte solubility, analyte trapping, analyte trap removal (solid-phase), and extract analysis were all shown to be equally important in achieving quantitative SFE recoveries.     

Supercritical fluid injection of high-molecular-weight polycyclic aromatic compounds in capillary supercritical fluid chromatography

A sample introduction system for capillary supercritical fluid chromatography, which allows the dissolution of the sample in the supercritical mobile phase before being introduced into the column, was constructed and evaluated. Supercritical n-pentane was shown to solvate high-molecular-weight polycyclic aromatic compounds that could not be solvated using typical liquid solvents. In addition, split injection of a supercritical fluid solution was found to be more reproducible than split injections of a liquid solution. The potential of such an injection system was demonstrated, although further developments are needed in order to make the technique of practically utility.     

Physical chemistry of fluid metals

Ohne Zusammenfassung

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Physical chemistry of fluid metals

     

Small solid particles and liquid lenses at fluid/fluid interfaces

The behaviour of small solid particles and liquid droplets at fluid interfaces is of wide interest, in part because of the roles they play in the stability of foams and emulsions. Here we focus on solid particles at liquid interfaces, both singly and in highly structured monolayers. We briefly mention small oil lenses on water in connection with the determination of line tension, τ. Particles are surface-active in the sense that they often adhere quite strongly to liquid surfaces, although of course they are not usually amphiphilic. The three-phase contact line around a particle at an interface is associated with an excess free energy resulting in a tendency of the line to contract (positive τ, which is a 1D analogue of surface tension) or to expand (negative τ). Positive line tension acts so as to push the contact angle of a particle with the fluid interface further away from 90°, i.e. to force the particle towards the more “wetting” of the two bulk phases. It also leads to activation barriers to entry and departure of particles from an interface. The behaviour of particle monolayers at octane/water interfaces is also discussed . It is found that, for monodisperse spherical polystyrene particles containing ionisable sulphate groups at the surface, highly ordered monolayers are formed. This appears to result from very long range electrostatic repulsion mediated through the oil phase. Surface pressure–surface area isotherms are discussed for particle monolayers and it is shown, using light microscopy, that at monolayer “collapse” particles are not expelled from the monolayers but rather the monolayer folds, remaining intact. This has an important bearing on methods, involving the use of the Langmuir trough, for the experimental determination of contact angles and line tensions in particulate systems. Received: 18 July 1999/Accepted: 30 August 1999     

Supercritical fluid chromatography of carbohydrates

Supercritical fluid chromatography (SFC) is a relatively new technique applied to polar solutes such as carbohydrates about 10 years ago. The developments in the SFC of carbohydrates are summarized and a comparison between capillary and packed column SFC is presented. High-efficiency capillary columns are suitable only for derivatized carbohydrates since various packed columns are well adapted for non derivatized mono-, di- and trisaccharides and provide complementary selectivities.     

Coalescence of particle-laden fluid interfaces

Colloidal particles are capable of stabilizing emulsions and, thus, slowing or preventing their complete breakdown into phase-separated systems. Direct observations of the dynamics of such particles on both water and oil droplets are reported as two colloid-laden interfaces are brought into contact with each other. As coalescence proceeds, the complementary systems, representing oil-in-water and water-in-oil emulsions, exhibit contrasting mechanisms for the formation of ring and disk structures by the particles as they serve to temporarily stabilize the approaching surfaces. An explanation of such behavior leads to a better understanding of the stabilization and breaking mechanisms of so-called Pickering emulsions.     

Hydrodynamics of dielectric fluid films

We introduce a general hydrodynamic model to study the stability of lipid films against thermal fluctuations. As one novel aspect the model accounts before all for a complete intrinsic surface rheology of the film interfaces. Thus the rheological behaviour of the surface adsorbed lipids is modelled which screen the hydrophobic film interior against the aqueous exterior. For coloured films we demonstrate first the influence of electrical forces on the dynamics and film stability. For that we perform a linear stability analysis on a simplified mechanically symmetric film with i) symmetric surface charge distribution and ii) linear electric potential drop across the film. Based on the complete film model we then categorize the complete set of solutions of the linearized equations of motion and we study the growth rates of unstable film modes. Finally we discuss the stability properties of a black film after introducing a repulsive mechanism due to the steric hindrance of the interfacial lipids.     

Supercritical fluid extraction of pesticides

Summary The extraction behaviour of 10 g samples of five pesticides and some related compounds from glass wool with supercritical CO₂ has been investigated under several conditions (10 MPa, 20 MPa extraction pressure, 313 K, dry and water saturated CO₂). The extraction fluid was decompressed over a line of little columns, filled with 3 Si₆0 or RP18, and the amount of deposited material was analyzed by HPLC for each of these columns. Due to the progressive pressure/density reduction along the line, the solubility diminishes and hence the compounds are deposited according to their polarity/vapor pressure earlier or later on the line. Thus extraction and prefractionation of compounds of different polarity take place in one sample preparation step.

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Extraktion von Pesticiden mit überkritischen fluiden PhasenI. Extraktionseigenschaften von ausgewählten Pesticiden in CO₂

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Herrn Prof. Dr. R. Neeb zum 60. Geburtstag gewidmet     

Physicochemical aspects of fluid extraction

The present review considers some physicochemical properties of fluid mixtures that are important for fluid extraction, supercritical fluid chromatography (SFC) and other applications.

Firstly, the most important types of phase diagrams involving liquid-gas, liquid-liquid and gas-gas equilibria are treated. Specific examples are given of binary mixtures of a highly volatile component I (e.g. CO₂, C₂H₆, N₂) with a relatively involatile component II of very different molecular size, shape, structure and/ or polarity (e.g. long-chained hydrocarbons, alcohols). It is also shown how the rather complicated types of phase diagrams can be calculated and correlated.

Some important thermodynamic and transport properties of such fluid mixtures are shortly discussed e.g. density, viscosity, diffusion coefficient etc. Here it is of interest for many effects (e.g. mass transfer) that unusually low viscosities and large diffusion coefficients are found.

Finally some important applications are shortly reviewed. Most of these applications will be treated in detail in the following papers of this Meeting.