Measurements of molecular and thermal diffusion coefficients in ternary mixtures

Thermal diffusion coefficients in three ternary mixtures are measured in a thermogravitational column. One of the mixtures consists of one normal alkane and two aromatics (dodecane-isobutylbenzene-tetrahydronaphthalene), and the other two consist of two normal alkanes and one aromatic (octane-decane-1-methylnaphthalene). This is the first report of measured thermal diffusion coefficients (for all species) of a ternary nonelectrolyte mixture in literature. The results in ternary mixtures of octane-decane-1-methylnaphthalene show a sign change of the thermal diffusion coefficient for decane as the composition changes, despite the fact that the two normal alkanes are similar. In addition to thermal diffusion coefficients, molecular diffusion coefficients are also measured for three binaries and one of the ternary mixtures. The open-end capillary-tube method was used in the measurement of molecular diffusion coefficients. The molecular and thermal diffusion coefficients allow the estimation of thermal diffusion factors in binary and ternary mixtures. However, in the ternaries one also has to calculate phenomenological coefficients from the molecular diffusion coefficients. A comparison of the binary and ternary thermal diffusion factors for the mixtures comprised of octane-decane-1-methylnaphthalene reveals a remarkable difference in the thermal diffusion behavior in binary and ternary mixtures.     

Combined Diffusion Coefficients in CO<Subscript>2</Subscript> Thermal Plasmas Contaminated with Cu,Fe or Al

Our work aims at the computation of combined diffusion coefficients in CO₂–metal (Cu, Fe, Al) mixtures at a temperature interval of 2000–30,000 K at 0.1 MPa and aims at the investigation of the impact of the concentration and nature of metal vapor (Cu, Fe, Al) on diffusion phenomena. The combined diffusion coefficients have four components, more specifically, combined ordinary diffusion coefficient, combined electric field diffusion coefficient, combined temperature diffusion coefficient and combined pressure diffusion coefficient due to the gradients of the species densities, applied electrical field temperature and pressure. The results indicate that, for Cu and Fe, the combined diffusion coefficients are quite identical under the condition of same metal concentrations (1 and 10% mass concentration). Compared with Cu and Fe under the same metal concentrations (1 and 10%), Al results in a larger enhancement of combined electric field and ordinary diffusion coefficients while smaller enhancement of combined temperature diffusion coefficients. All the combined diffusion coefficients exhibit an upward trend with metal concentrations except for combined electric field, temperature and pressure diffusion coefficients. These three mentioned coefficients are attenuated by the metal vapor above the certain concentration such as, in the case of combined temperature diffusion coefficients, 70% Cu, 70% Fe and 50% Al for CO₂–Cu, CO₂–Fe and CO₂–Al mixtures respectively. Namely, compared with Cu and Fe, less quantity of Al is required to achieve the maximum of combined diffusion coefficients. Maximum peaks for the combined coefficients are shifted to the higher temperature with increasing metal concentrations.     

Diffusion of polarizable colloids in electromagnetic fields

Diffusion of polarizable colloids in electromagnetic fields is considered. Extensive and intensive thermodynamic formulations of magnetic and electric polarization energy is used to establish driving forces that generate diffusion of colloids. Effects of concentration, activity coefficient, and interfacial and polarization energies are formulated in terms of corresponding concentration dependent diffusion coefficients. Magnetic and electric diffusion coefficients are defined and it is shown that the former can be made comparable and even larger than ordinary diffusion coefficients of polarizable colloids. Magnetic diffusion coefficients are derived for mono- and polydisperse colloid mixtures relative to the fluid and then are transformed to the dispersion frame of reference. It is shown that ordinary and magnetic diffusion coefficients of polydisperse colloids can be resolved into four and three basic coefficients, respectively.     

Calculation of diffusion coefficients for carbon dioxide + solute system near the critical conditions by non-equilibrium molecular dynamics simulation

A non-equilibrium molecular dynamics simulation was adopted to calculate the diffusion coefficients for a pseudo-binary system of carbon dioxide and for a carbon dioxide + solute system at 308.2 and 318.2 K. The calculated results were compared with the self- and tracer diffusion coefficients calculated by an equilibrium molecular dynamics simulation. The simulated results for the pseudo-binary system of carbon dioxide by the non-equilibrium molecular dynamics simulation are in good agreement with the results of self diffusion coefficients for pure carbon dioxide by the equilibrium molecular dynamics simulation. The simulated results of mutual diffusion coefficients for the carbon dioxide + solute system by the non-equilibrium molecular dynamics simulation are slightly lower than the results of the tracer diffusion coefficients by the equilibrium molecular dynamics simulation. The anomalous behavior of diffusion coefficients near the critical concentration was represented by the results of the non-equilibrium molecular dynamics simulation.     

Extending reversed-flow chromatographic methods for the measurement of diffusion coefficients to higher temperatures

A reversed-flow gas-chromatography (RF-GC) apparatus for the measurement of binary diffusion coefficients is described and utilized to measure the binary diffusion coefficients for several systems at temperatures from (300 to 723)K. Hydrocarbons are detected using flame ionization detection, and inert species can be detected by thermal conductivity. The present apparatus has been utilized to measure diffusion coefficients at substantially higher temperatures than previous RF-GC work. Characterization of the new apparatus was accomplished by comparing measured binary diffusion coefficients of dilute argon in helium to established reference values. Further diffusion coefficient measurements for dilute helium in argon and dilute nitrogen in helium (using thermal conductivity detection) and dilute methane in helium (using flame ionization detection) were performed and found to be in excellent agreement with literature values. The measurement of these well-established diffusion coefficients has shown that specific experimental conditions are required for accurate diffusion measurements using this technique, particularly at higher temperatures. Numerical simulations of the diffusion experiments are presented to demonstrate that artifacts of the analysis procedure must be specifically identified to ensure accuracy, particularly at higher temperatures.     

Direct quantification of intraparticle protein diffusion in chromatographic media

Diffusion coefficients of proteins in chromatographic media are important parameters for the rational design of stationary phases and purification schemes. In contrast to free diffusion, intraparticle diffusion is hindered by the porous structure of the media. Direct intraparticle diffusion analysis (IDA) is a novel approach for the determination of intraparticle protein diffusion coefficients. IDA is based on the evaluation of spatially and temporally resolved intraparticle concentration profiles. To prevent adsorption and to study diffusion only, the chromatographic media are investigated in underivatized form. With IDA, intraparticle concentration profiles are measured in a microcolumn by confocal laser scanning microscopy (CLSM). From this dynamic data, the diffusion coefficients are determined by parameter estimation, using a spheric diffusion model. The boundary condition is given by the measured protein concentration in the bulk phase. IDA is applied to determine intraparticle diffusion coefficients of seven different proteins in Sepharose 6 FF. The results show excellent congruence of experimental data and simulation results. Moreover, the determined diffusion coefficients lie well within the range of data published in the literature. Given that the material in question allows optical analysis, IDA is a general approach for studying protein diffusion in porous particles and is easily adapted to different proteins, solution conditions and stationary phases.     

Molecular and thermal diffusion coefficients of alkane-alkane and alkane-aromatic binary mixtures: effect of shape and size of molecules

New molecular and thermal diffusion coefficients of binary mixtures of normal decane-normal alkanes and methylnaphthalene-normal alkanes are measured at atmospheric pressure and T = 25 degrees C. The normal alkanes used in this work include nC5-nC20. Thermal diffusion coefficients were measured in a thermogravitational column. Molecular diffusion coefficients were measured using an open-ended capillary tube technique. Results show a significant effect of molecular shape and size on thermal and molecular diffusion coefficients. Molecular diffusion coefficients show a monotonic behavior in both aromatic-normal alkane and normal decane-normal alkane mixtures. Thermal diffusion coefficients reveal a nonmonotonic trend with molecular size in the normal decane-normal alkane mixtures. This is the first report of the nonmonotonic behavior in the literature. The data presented in this paper provide an accurate self-molecular diffusion coefficient for nC10 from binary data.     

Measurement of effective Knudsen diffusion coefficients for powder beds used in heterogeneous uptake experiments

The effective Knudsen diffusion coefficients for characteristic oxide powder beds used in heterogeneous uptake experiments have been measured using countercurrent diffusion and transient pressure drop techniques. Room-temperature thermal-velocity-normalized effective Knudsen diffusion coefficients are found to lie in the 0.15 to 0.35 microm range for magnesium silicate, aluminum oxide, and iron oxide powder beds. Measured values are compared with theoretical estimates and are consistent with low bed tortuosities (below 3) expected for media with open porosity above 0.5. The impact of uncertainties in effective diffusion coefficients on corrections of measured uptake coefficients is discussed. The value of careful uptake measurements in both the low and high sample mass limits is reinforced, as this allows uptake corrections independent of explicitly measured or estimated diffusion coefficient values. It is suggested that correction procedures requiring tortuosity values greater than 3 are suspect.     

槲皮素在溶液中的化学交换和自扩散运动

通过对溶于氘代二甲亚砜（DMSO d6）中的槲皮素的自扩散系数和槲皮素羟基质子与溶剂中水质子之间的交换速率常数的NMR测量,研究了交换速率常数与扩散系数随温度和含水量的变化情况.结果表明,化学交换与扩散系数是相互独立的两种运动,活泼质子的化学交换并不需要通过槲皮素分子的扩散而进行.但是活泼质子的表观扩散系数却显著地受化学交换的影响.当以活泼质子为对象时,这种影响需要引起足够的重视.     

Complications in the Use of the Taylor Dispersion Method for Ternary Diffusion Measurements: Methanol + Acetone + Water Mixtures

The Taylor dispersion technique is used to measure the ternary mutual diffusion coefficients of aqueous nonelectrolyte solutions at 25°C. The dispersion of the injected solutes is recorded by a differential refractometer and an ultraviolet-visible detector. The diffusion coefficients are calculated directly by fitting the theoretical dispersion equations to about six experimental curves simultaneously. If the ternary diffusion effects in the measured dispersion profiles are not confused by the inaccuracy of the experimental method or an unfavorable relative detector sensitivity, the diffusion coefficients are precise. For the system methanol + acetone + water, it is shown that the Taylor dispersion method is unsuitable for the determination of all the diffusion coefficients if the methanol mole fraction is less than 0.45 or the acetone mole fraction if more than 0.001.     

Relation between hydraulic permeability and diffusion in homogeneous swollen membranes

The question of viscous flow versus molecular diffusion mechanisms for pressure-induced liquid transport through membranes is critically examined for the specific case of homogeneous swollen membranes. It is shown that previous attempts to compute diffusion coefficients from hydraulic permeabilities for such systems have used an equation which is grossly in error. It estimates diffusion coefficients which are orders of magnitude too high and often exceed self-diffusion coefficients. This has frequently led to the conclusion that viscous flow predominates. The origins of the errors in this equation are indicated, and a substitute equation is developed which gives diffusion coefficients well below that for self-diffusion when applied to literature data. As a result it is concluded that molecular diffusion is the dominant mechanism in homogeneous systems.     

Molecular dynamics simulation of self- and mutual diffusion coefficients for confined mixtures

The self- and mutual diffusion coefficients for binary mixtures of Ar-Kr both in the bulk and in the nanopores were studied by molecular dynamics simulations. The composition dependences and the relationships between the self- and the mutual diffusion coefficients both in the bulk and in the nanopores were further discussed. It was found that the simulation results (D(c.m.)) are close to the calculated ones (D(s)) for the Ar-Kr system. Both self- and mutual diffusion coefficients in nanopores are much lower than that of the bulk, and they ever decrease as the pore width decreases. Nevertheless, the self- and mutual diffusion coefficients increase as the mole fraction of Ar increases, and as expected, increase as the temperature increases. The self-diffusion coefficients of mixtures both in the bulk and in the nanopores are predicted by the Carman model and by the molecular cluster model.     

New thermal diffusion coefficient measurements for hydrocarbon binary mixtures: viscosity and composition dependency

New thermal diffusion coefficients of binary mixtures are measured for n-decane-n-alkanes and 1-methylnaphthalene-n-alkanes with 25 and 75 wt % at 25 degrees C and 1 atm using the thermogravitational column technique. The alkanes range from n-pentane to n-eicosane. The new results confirm the recently observed nonmonotonic behavior of thermal diffusion coefficients with molecular weight for binary mixtures of n-decane- n-alkanes at the compositions studied. In this work, the mobility and disparity effects on thermal diffusion coefficients are quantified for binary mixtures. We also show for the binary mixtures studied that the thermal diffusion coefficients and mixture viscosity, both nonequilibrium properties, are closely related.     

铁、钴、镍在汞中扩散系数的测定

用恒电位球形汞齐电极伏安法可测定金属在汞中的扩散系数^[1,2].本文报导了用这个方法测定的铁、钴、镍在汞中的扩散系数值.     

Study of diffusion of alkali metals and ammonium chlorides through nanofiltration membrane with selective layer

The diffusion of alkali metals and ammonium chlorides through an OPMN-KM3 composite nanofiltration membrane is studied as a function of the electrolyte concentration on both sides of the membrane. A model is proposed for calculating diffusion coefficients that takes into account changes in the electrolyte concentration in selective pores of membrane. The diffusion coefficients are calculated both using the proposed model and by Fick’s equation. The effect of the orientation of the membrane with respect to the diffusion flux on the diffusion coefficients of salts is analyzed.     

Multi-Component Diffusion Coefficients in Nitrogen Plasma Under Thermal Equilibrium and Non-equilibrium Conditions

Multi-component diffusion coefficients are calculated for a seven species model of nitrogen plasma under thermal non-equilibrium following the first order perturbation technique of Chapman and Enskog. Binary, thermal, thermal ambipolar, general and general ambipolar diffusion coefficients are presented over electron temperatures ranging from 300 to 50,000 K and thermal non-equilibrium parameter (Te/Th) ranging from 1 to 5. Considering large volume of data, binary, general and general ambipolar diffusion coefficients are presented only for atmospheric pressure. Thermal and thermal ambipolar diffusion coefficients are presented for pressures ranging from 0.1 to 2 atm. The results are compared with published experimental and theoretical data. Necessary electronic levels, associated transition data and collision integrals are collected from recent literature. Details of behaviour of each of the coefficients are presented.     

Determination of diffusion coefficients by gas chromatography

Gas chromatography (GC), apart from the qualitative and quantitative analysis of gaseous mixtures, offers many possibilities for physicochemical measurements, among which the most important is the determination of diffusion coefficients of gases in gases and liquids and on solids. The gas chromatographic techniques used for the measurement of diffusion coefficients, namely the methods based on the broadening of the chromatographic elution peaks, and those based on the perturbation of the carrier gas flow-rate, are reviewed from the GC viewpoint, considering their running though the history, the experimental arrangement and procedure, the appropriate mathematical analysis and the main results with brief discussions. The experimental data on diffusion coefficients, determined by the various gas chromatographic techniques, are compared with those quoted in the literature or estimated by the known empirical equations predicting diffusion coefficients. This comparison permits the calculation of the precision and accuracy of the techniques applied to the measurement of diffusion coefficients.     

Interactions between n-octyl and n-nonyl beta-D-glucosides and alpha- and beta-cyclodextrins as seen by self-diffusion NMR

In this work (1)H NMR self-diffusion experiments have been performed to determine the self-diffusion coefficients of n-octyl beta-d-glucoside and n-nonyl beta-d-glucoside in alpha-cyclodextrin and beta-cyclodextrin solutions at 25 degrees C. Two questions are addressed. The first concerns the general influence on nonionic surfactant transport properties when cyclodextrins are present in solution. The second question concerns the influence of surfactant-chain length and cyclodextrin cavity volume on the association constant. The self-diffusion coefficients of the alkyl glucosides, in cyclodextrin-containing solutions, depend on the cyclodextrin concentration on account of the formation of complexes. The cyclodextrin diffusion is only mildly influenced, since the complex has similar diffusion coefficients as the free cyclodextrin. There are some obstruction effects at the highest surfactant concentrations which decrease the cyclodextrin diffusion. A set of equations to model the self-diffusion coefficients of the surfactant and cyclodextrin was developed and is presented. On the basis of such equations, properties such as association constants, and micelle and complex diffusion coefficients can be estimated.     

Diffusion Coefficients of Three Organic Solutes in Aqueous Sodium Dodecyl Sulfate Solutions

Tracer diffusion coefficients of phenol, toluene, and benzoic acid in aqueous solutions of sodium dodecyl sulfate (SDS) were measured by the Taylor dispersion technique. In addition, the viscosities and densities of the SDS solutions were measured. For phenol and toluene, the effect of micelle formation on the diffusion coefficient is pronounced. When the SDS concentration is below the critical micelle concentration (cmc), the diffusion coefficients are almost independent of the SDS concentration. However, above the cmc there is a rapid decrease in the diffusion coefficients, and the apparent diffusion coefficients of the two solutes are the weighted average of free solute diffusion and the micelle diffusion. A model is presented to describe the diffusion behavior of the two solutes in aqueous micellar solutions of SDS. The interaction between the two solutes and the micelles has been investigated and the fraction of each solute that is solubilized by the micelles is estimated from the measured apparent diffusion coefficient. For benzoic acid, the diffusion coefficient is dependent on the joint contribution of the benzoic acid molecules that are solubilized by the micelles as well as the corresponding benzoate ions. The effect of micelle formation on the diffusion coefficient of benzoic acid is not as pronounced as for phenol and toluene. Copyright 2000 Academic Press.     

Tracer diffusion of Co2+ ions in agar gel containing multi-electrolyte systems

Tracer diffusion coefficients of cobalt ions have been measured in the supporting medium containing multi-electrolyte systems of alkali bromides. The electrolyte concentration was varied between 10^–6-0.1M at 25°C and the diffusion coefficients were determined by zone-diffusion technique using agar gel medium. The trend in the theoretical values of diffusion coefficients is accounted for by considering the relative contribution of mobility function, ionic strength as well as ion size parameter to the theoretical value in different systems. While the deviations between theoretical and experimental values of diffusion coefficients are explained on the basis of various co-occurring effects in ion-gel-water system.