On the derivation of the incompressible Mavier-Stokes equation for Hamiltonian particle systems

We consider a Hamiltonian paticle system interacting by means of a pair potetial. We look at the behavior of the system on a space scale of order ^-1, times of order ^-2 and mean velocities of order , with a scale parameter. Assuming that the phase space density of the particles is give by a series in (the analog of the Chapman-Enskog expansion), the behavior of the system under this rescaling is described, to the lowest order in , by the incompressible Navier-Stokes equations. The viscosity is given in terms of microscopic correlations, and its expression agrees with the Green-Kubo formula.     

Classical fluids of negative heat capacity

It is shown that new parametersX can be defined such that the heat capacity C_xT(S/T)_x is negative, even when the canonical ensemble [i.e., at fixed T=(U/S)_Y and YX] is stable. This implies an extension of the classical theory of polytropes from ideal gases to general fluids. As examples of negative heat capacity systems we treat blackbody radiation and general gas systems with nonsingular _T. For the case of a simple ideal gas we even exhibit an apparatus which enforces a constraint X(p, V)=const that makes C_x<0. We then show that it is possible to infer the statistical mechanics of canonicallyunstable systems-for which even the traditional heat capacities are negative-by imposing constraints that stabilize the associated noncanonical ensembles. Two explicit models are discussed.     

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.     

Surface chemistry of nanoscale Fe_3O_4 dispersed in magnetic fluids

The interaction between stabilizers and nanoparticles is one of the important factors to prepare stable magnetic fluids. The magnetic nano-size Fe3O4 core with single domain and the average grain size around 8-12 nm were prepared by chemical precipitation method. The O/Fe molar ratio of the particle surface was measured by X-ray photoelectron spectroscopy (XPS). The heat effects of stabilizers ad- sorption on nanoparticles were measured by solution calorimetry. The excess amount of oxygen was possibly the result of the hydroxygen formed on the surface of the nanoparticles. The heat effects showed that compounds containing carboxyl groups can be adsorbed chemically on magnetite by forming chemical bonds. The other stabilizers involving NH-groups, such as polyethylene-imine, can be adsorbed physically. The exothermic value is about half of the former case.     

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.     

Oxidation of Styrene with Molecular Oxygen in Supercritical CO2

The oxidation of styrene with molecular oxygen catalyzed by PdCl2 CuCl2 has been investigated in supercritical CO2 with a batch reactor. The oxidative system of styrene contains four components at the beginning and seven components during the reaction. The critical temperature, critical pressure, and critical density at different conversions are determined by using a high-pressure view cell. The effect of phase behavior on the conversion and selectivity were studied. Experimental results showed that the critical parameters of the reaction mixture at fixed initial molar ratio changed with the conversion of reactant. The conversion of styrene reached maximum near the critical density of the reaction mixture. Product selectivity also varied with density of reaction mixture and could be tuned to some degree.     

Carbon Paste Electrode for the Potentiometric Flow Injection Analysis of Drotaverine Hydrochloride in Serum and Urine

A carbon paste electrode for drotaverine hydrochloride (DvCl) was prepared and fully characterized in terms of composition, life span, usable pH range, response time and temperature. The electrode was applied to the potentiometric determination of drotaverinium ions in pharmaceutical preparations and biological fluids in steady state and flow injection conditions (FIA). The electrode is based on a mixture of two ion exchangers, namely, drotaverinium-silicotungestate and drotaverinium-tetraphenylborate dissolved in tricresyl phosphate as pasting liquid. The modified electrode showed a near-Nernstian slope of 59.34±2mV over the concentration range of 5.0×10^–7–1.0 × 10^–2M. The electrode exhibits good selectivity for DvCl with respect to a large number of inorganic cations, organic cations, sugars and amino acids. Potentiometric titrations of DvCl with several titrants have been monitored using this modified carbon paste electrode as an end-point indicator electrode. The proposed electrode offers the advantages of simplicity, accuracy, automation feasibility and applicability to turbid and colored samples.     

Multicommuted flow-through fluorescence optosensor for determination of furosemide and triamterene

Multicommutation implemented with flow-through optosensors is a very promising area of research. This recent approach benefits from the advantages of both methods and results in high sensitivity, selectivity, and speed, and little waste generation. This paper reports the simultaneous determination of furosemide and triamterene, two widely used diuretics, by measurement of their native fluorescence. The system has been proved to be useful for determination of both analytes in pharmaceutical preparations and for determination of triamterene in human urine and serum. A minicolumn filled with Sephadex SPC-25 microbeads was used to achieve separation of both analytes before detection in a flow-through cell filled with the same resin. The sensor is linear in the range 50–1200 and 0.4–8 ng mL⁻¹ with detection limits of 15 and 0.1 ng mL⁻¹ for furosemide and triamterene, respectively.     

Comments on the mean spherical approximation for hard-core and soft potentials and an application to the one-component plasma

The thermodynamic properties of the mean spherical (MSA), Percus-Yevick (PY), and hypernetted-chain (HNC) approximations are derived by a simple and unified approach by considering the RPA free-energy functionalF and employing an Ewald-type identity. It is demonstrated that with decreasing relative contribution of the hard-core insertion to the thermodynamic functions, the MSA changes its nature from PY-like to HNC-like, withF changing its role from excess pressure to excess free energy, respectively. It is found that the condition of continuity of the MSA pair functions is equivalent to a stationarity condition forF and leads to thermodynamic consistency between the virial and energy equations of state for the (thus defined) soft-MSA (SMSA), withF playing the role of the excess free energy. It is shown that the PY-compressibility and virial equations of state forD-dimensional hard spheres may be simply obtained one from the other without knowing any details of the solution of the model. Using this relation we find an indication that the PY approximation for hard spheres becomes less accurate with increasing dimensionality. A general variational formulation is presented for the application of the MSA for soft potentials, and results for the one-component plasma are discussed and extended.On sabbatical leave from the Nuclear Research Center-Negev, P.O. Box 9001, Beer Sheva, Israel.     

Simultaneous Determination of Aluminum and Iron in High Salt Content Matrices by Adsorptive Stripping Voltammetry. Application to Dialysis Fluids

A new analytical procedure for the simultaneous determination of aluminum(III) and iron(II) in two kinds of dialysis fluids (peritoneal and hemodialysis fluids) by differential pulse adsorptive stripping voltammetry (DPAdSV) is described. The voltammetric measurements were performed using, as working electrode, a stationary mercury electrode, and a platinum electrode and a Ag|AgCl|KCl_(sat.) electrode as auxiliary and reference electrodes, respectively, employing acetate buffer solutions at different pH as supporting electrolyte. As complexing agents, Solochrome Violet RS, Palatine Chrome Black 6BN, Chromazurol S and Eriochrome Black T were employed. For both elements, the accuracy, expressed as relative recovery R%, was very satisfactory being in the range 94–105%, the precision as repeatability, expressed as relative standard deviation s_r%, was lower than 6%, while the limits of detection were of the order of a few units of μg/L. The analytical voltammetric procedure has been validated by comparison with spectroscopic (graphite furnace atomic absorption spectroscopy, GFAAS) measurements.