溶剂在交联硅橡胶中无限稀释扩散系数测定

气相色谱法测定溶剂与聚合物材料之间的相互关系是一个快速、准确、方便的方法，为此利用气相色谱法测定了小分子溶剂在不同交联剂含量的交联硅橡胶中的无限稀释扩散系数，并研究了交联剂用量对无限稀释扩散系数的影响，这为研究交联硅橡胶特性提供了新方法。     

Measurement of activity coefficients at infinite dilution for hydrocarbons in imidazolium-based ionic liquids and QSPR model

The separations of olefin/paraffin, aromatic/aliphatic hydrocarbons or olefin isomers using ionic liquids instead of volatile solvents have interested many researchers. Activity coefficients γ ^∞ at infinite dilution of a solute in ionic liquid are generally used in the selection of solvents for extraction or extractive distillation. In fact, the measurement of γ ⁻⁸ by gas-liquid chromatography is a speedy and cost-saving method. Activity coefficients at infinite dilution of hydrocarbon solutes, such as alkanes, hexenes, alkylbenzenes, styrene, in 1-allyl-3-methylimidazolium tetrafluoroborate ([AMIM][BF₄]) and 1-butyl-3-methyl imidazolium hexafluorophosphate ([BMIM][PF₆]), 1-isobutenyl-3-methylimidazolium tetrafluoroborate ([MPMIM][BF₄]) and [MPMIM][BF₄]-AgBF₄ have been determined by gas-liquid chromatography using ionic liquids as stationary phase. The measurements were carried out at different temperatures from 298 to 318 K. The separating effects of these ionic liquids for alkanes/hexane, aliphatic hydrocarbons/benzene and hexene isomers have been discussed. The hydrophobic parameter, dipole element, frontier molecular orbital energy gap and hydration energy of these hydrocarbons were calculated with the PM3 semi-empirical quantum chemistry method. The quantitative relations among the computed structure parameters and activity coefficients at infinite dilution were also developed. The experimental activity coefficient data are consistent with the correlated and predicted results using QSPR models.     

Studies on molecular transport of n‐alkanes through poly(tetrafluoroethylene‐co‐propylene) elastomeric membrane

Molecular transport of a series of n‐alkanes through commercial TFE elastomer (FA 150L) has been studied in the temperature range 30–50 °C using sorption‐gravimetric method. The Fickian diffusion equation was used to calculate the diffusion coefficients, which were dependent on the size of the alkanes and temperature. The diffusion coefficients at 30°C varied from 4.53 × 10^?8 cm²/s (n‐heptane) to 0.18 × 10^?8 cm²/s (n‐hexadecane). The liquid concentration profiles have also been computed using analytical solution of Fick's equation with the appropriate initial and boundary conditions and these were presented as a function of penetration depth of molecular migration and time of immersion. These results have been discussed in terms of molecular size of alkanes as well as temperature. In all the liquid penetrants, the transport phenomenon was found to follow the anomalous behavior. From the temperature dependence of diffusion and permeation coefficients, the Arrhenius activation parameters have been estimated. These parameters do not exhibit any systematic variation with the size of the penetrants. The resulting low diffusion coefficients, contribute to the superior barrier performance of the membrane, is due, in part, to the high glass transition temperature of Aflas? TFE elastomer. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2228–2235, 2006     

Cyclic voltammetry investigation of diffusion of ferrocene within propylene carbonate organogel formed by gelator

Propylene carbonate organogel containing LiClO₄ was formed in the presence of gelator bis-(4-stearoylaminophenyl) methane (BSAPM). The electrochemical behavior and diffusion of ferrocene (Fc) and ferricenium (Fc⁺) entrapped within the organogel was investigated by cyclic voltammetry. The Fc molecules still show redox activity within the organogels in comparison with corresponding solutions of propylene carbonate containing LiClO₄. The shape of the cyclic voltammograms of the Fc electrooxidation in organogel was similar to that in corresponding solutions. The results indicated that redox reactions of Fc/Fc⁺ were a quasi-reversible process of diffusion-controlled single electron transfer in organogels. The diffusion coefficients of Fc and Fc⁺ in organogels decreased with an increase of the concentration of gelator BSAPM, but increased with an increase of temperature. The temperature dependence of the diffusion coefficient in organogels followed classical Arrhenius equation. The activation energy in organogels was found of no difference from that in corresponding solutions.     

Prediction of mass diffusivity of CO2 into bitumen

The infinite dilution and mutual diffusion coefficients for the CO₂/bitumen system were predicted using existing correlations. Out of seven semi-empirical correlations tested, the Umesi-Danner correlation was found to be best suited for the prediction of gas-liquid infinite dilution diffusion coefficient. For the mutual diffusion coefficient, Teja's method based on the generalized corresponding states principle was successfully used. The predictions are compared with the limited CO₂/bitumen diffusivity data available in the literature.     

苯基二氯化膦一三氯化磷体系汽液平衡的研究

用静态法测定了苯基二氯化膦的饱和蒸汽压曲线，回归得到了它们的Antoine方程参数。用标准的Swietoslawski型沸点计测定了三氯化磷一苯基二氯化膦二元体系的常压沸点数据，从而推算出两端的无限稀释活度系数，采用Wilson活度系数方程回归出其中的Wilson参数，并对该体系的等温气液平衡数据进行了推算。     

Observations of the diffusion coefficient of the hydroxyl ion in lithium hydroxide solutions

The diffusion coefficient of OH^? in LiOH solution was found to be 6.8 × 10^?5 cm²/s at 298 K at infinite dilution. The experimental technique utilized a rde at which the limiting current for O₂ evolution was measured. Because the O₂ gas bubbles impact on convection at the electrode, the Levich equation was modified to account for this effect. Mean diffusion coefficients of LiOH were determined. At infinite dilution, it is 2.19 × 10^?5 cm²/s at 298 K. Values are given for the concentration range from 0.5 to 5 M LiOH.     

3种芳香烃在聚乙烯膜中的无限稀释扩散系数

基于Hadj-Romdhane和Danner色谱过程的数学模型 ,采用反相气相色谱法在 348.2～ 36 3.2K温度范围内测定了苯、甲苯和乙苯 3种芳香烃溶剂在聚乙烯膜中的无限稀释扩散系数 .实测数据的关联结果表明 ,采用空穴自由体积替代Vrentas-Duda自由体积理论方程中自由体积项的修正方程 ,能很好地描述溶剂分子的无限稀释扩散系数随温度的变化关系 .同时在修正方程的基础上建立了一般化自由体积方程 ,并对该方程的预测能力进行了探讨     

Flow injection analysis estimation of diffusion coefficients of pauci- and polydisperse polymers such as polystyrene sulfonates

Flow injection analysis, often used for determination of diffusion coefficients of nonpolymeric substances, has now been applied to the characterization of pauci- and polydisperse polymers in solution. A relative method was found useful for obtaining moderate quality evaluations of diffusion coefficients and related parameters of polymers. The width at half-height W_1/2 of the trace peak is found to be proportional to the number average molecular weight M?_n of pauci- and polydisperse polymers, allowing estimation of M?_r and diffusion coefficients. For sodium polystyrene sulfonates at substantially infinite dilution in 1.0 g L^?1 Na₂SO₄, a linear relation has been observed between the logarithms of the molecular weight M?_n and the mean diffusion coefficient D in the M?_n range of 1000–90,000 g mol^?1 or the D range of 30 × 10^?7 to 2 × 10^?7 cm² s^?1.     

Experimental study of diffusivity of hexane in bitumen-saturated porous media under high temperature/pressure conditions

Solvent mass transfer plays a key role in a thermal gravity drainage process involving solvent. The diffusion coefficients of solvent in such a process are not well studied. This article presents the effective diffusion coefficients of solvent in bitumen-saturated sands under high temperature/pressure conditions measured using a CT scanning technique. Experimental results show that the effective diffusion coefficient of n-hexane in bitumen-saturated sands varied with the solvent concentration or with the viscosity of solvent–bitumen mixture (i.e., D_e ∝ c^0.4 or D_e ∝ μ_m^−0.46). The solvent concentration weighted diffusion coefficient of n-hexane in the bitumen under the condition 160–170°C/1,900 kPa had an order of magnitude of about 10⁻⁵ cm²/s for solvent volume concentration less than 0.2. The penetration distance of n-hexane in bitumen-saturated sands depended on the nonlinearity of diffusion and had a value of −2 cm after 1-day diffusion. The stronger the nonlinearity of diffusion, the shorter the penetration distance.     

Extending the UNIFAC model for ionic liquid–solute systems by combining experimental and computational databases

Considering that the predictive UNIFAC model is highly valuable for the solvent selection, process design and optimization of separation tasks, a large extension of this model to ionic liquid (IL)–solute systems is presented by combining experimental and COSMO-RS derived databases. The experimental infinite dilution activity coefficient (γ^∞) data of different solutes in ILs are first collected exhaustively to extend UNIFAC-IL to cover all involved IL and conventional functional groups. Afterwards, the experimental and COSMO-RS calculated γ^∞ are compared for different types of solutes to evaluate the potential of using COSMO-RS predictions as quasi-experimental data for further UNIFAC-IL extension. In the cases where COSMO-RS can provide quantitatively accurate predictions after calibration, additional γ^∞ database is specifically generated to regress more group interaction parameters in the UNIFAC-IL model. Finally, a large experimental liquid–liquid and vapor–liquid equilibria database is collected and employed to evaluate the predictive performance of the obtained γ^∞-based UNIFAC-IL model.     

Distribution coefficients and diffusivities in three polymers for nineteen aqueous nonvolatile solutes

Experimental results at 25°C are reported for infinite‐dilution distribution coefficients for 19 nonvolatile solutes between aqueous solution and three kinds of polymer films, and for their diffusion coefficients in the polymer matrix. The experiments were performed by coupling UV spectroscopy and gravimetric measurements with mass balances. The solutes are aromatic nonvolatile compounds that are of interest in environmental technology and may serve as model compounds for drug‐delivery systems. The polymers are ethylene‐vinyl acetate copolymers with 33 (EVAc33) and 45 (EVAc45) weight percentage vinyl acetate, and poly(vinyl acetate) (PVAc) widely used in drug‐delivery devices. For PVAc, a long time is required to reach equilibrium. Because the required time is too long for reasonable experimental studies, equilibrium distribution coefficients were calculated from finite‐time data by using a diffusion model. The contribution of surface adsorption is shown to be negligible. Infinite‐dilution distribution coefficients K_s, defined as the volume fraction of solute in the polymer divided by that in water, tend to increase with vinyl acetate content; they range from near unity to several hundred. Diffusion coefficients, determined from time‐dependent sorption data, are significantly larger in EVAc copolymers (10^?10 to 10^?8 cm²/s) than in PVAc (10^?12 cm²/s). These data may be useful for design of membrane processes, for controlled delivery of drugs, and for application in packaging and storage of food, chemicals, and pharmaceuticals. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2041–2052, 2002     

Diffusion of methyl esters of higher fatty acid in polypropylene

Diffusion coefficients of several methyl esters of linear higher fatty acid (C₁₀?C₁₈) into polypropylene (PP) were determined, over the temperature range of 50 to 110°C, using a mass uptake technique. The relations between an amount of mass uptake and t^1/2 were linear within 10 min, indicating Fickian diffusion. The diffusion coefficients were in the range of 4.6×10^?8 to 6.2×10^?12 cm² sec^?1, increased with temperature, and decreased with increasing n-alkyl chain length of fatty acid. The plots of In D vs. the molecular weight of methyl esters were approximately linear. The temperature dependence of diffusion followed an Arrhenius relationship, and the activation energies were in the range of 133 ? 147 KJ mol^?1 and increased with an increase in n-alkyl chain length of corresponding fatty acid. The diffusion coefficients were discussed with the interaction between methyl esters of higher fatty acid and PP. The diffusion coefficients of methyl esters, at the simultaneous diffusion process, were always higher than that derived from the single diffusion process, except for methyl decanoate with lower molecular weight. The difference in diffusion coefficients in single and simultaneous diffusion was discussed thermodynamically. © 1994 John Wiley & Sons, Inc.     

反相气相色谱法测定小分子溶剂在聚乙烯粒子中的无限稀释扩散系数

基于经典线性非平衡色谱过程的矩分析理论,用反相气相色谱法测定了323.15～358.15 K温度范围内二氯甲烷、三氯甲烷、四氯甲烷3种不同相对分子量的同系物小分子及正己烷在聚乙烯粒子中的无限稀释扩散系数。采用聚合物粒子直接填充的色谱柱,考察了温度、同系物小分子分子量及聚乙烯结晶度对扩散系数的影响。实验结果表明,对同一种小分子溶剂/聚乙烯体系,扩散系数均随温度升高而增大。不同相对分子量的同系物小分子在同一种聚乙烯中扩散系数随分子量增加而减小,聚乙烯结晶度增加也会导致扩散系数减小。采用文献中所报道的Krevelen扩散系数预测模型的计算值与实验测量值较为吻合,表明本文所采用的以聚合物粒子直接填充色谱柱的反相气相色谱扩散分析具有一定的可靠性。     

Prediction of infinite-dilution activity coefficients with neural collaborative filtering

Accurate prediction of infinite dilution activity coefficient (γ^∞) for phase equilibria and process design is crucial. In this work, an experimental γ^∞ dataset containing 295 solutes and 407 solvents (21,048 points) is obtained through data integrating, cleaning, and filtering. The dataset is arranged as a sparse matrix with solutes and solvents as columns and rows, respectively. Neural collaborative filtering (NCF), a modern matrix completion technique based on deep learning, is proposed to fully fill in the γ^∞ matrix. Ten-fold cross-validation is performed on the collected dataset to test the effectiveness of the proposed NCF, proving that NCF outperforms the state-of-the-art physical model and previous machine learning model. The completed γ^∞ matrix makes solvent screening and extension of UNIFAC parameters possible. Taking two typical hard-to-separate systems (benzene/cyclohexane and methyl cyclopentane/n-hexane mixtures) as examples, the NCF-developed database provides high-throughput screening for separation systems in terms of solvent selectivity and capacity.     

Modeling infinite dilution activity coefficients of organic-aqueous systems using a modified regular solution equation and cubic equations-of-state

Expressions derived from the regular solution equation and the generalized cubic equations-of-state (EOS) were employed to model the infinite dilute activity coefficient (γ^∞) of organic-aqueous systems. A database of 119 organic species in aqueous systems, divided into six classes, was gathered for models evaluations. The use of the molar density, the first order molecular connectivity, and the dipole moment appear to be adequate correlating variables for describing the structural dependence of the residual part in the modified regular solution equation (MRS). The Soave-Redlich-Kwong (SRK) and Peng-Robinson (PR) were specified and employed in the generalized cubic EOS form. The excess activity coefficient concept was used in the SRK and PR EOS models to account for the deficiency of EOS in dealing with highly non-ideal or polar systems. The abilities of two existing correlation models along with two modified versions of the UNIFAC model were also assessed. The proposed models provide creditable equations for correlating γ^∞ of organic-aqueous systems.     

Bias Correction Estimation for a Continuous‐Time Asset Return Model with Jumps

In this article, local linear estimators are adapted for the unknown infinitesimal coefficients associated with continuous‐time asset return models with jumps, which can correct the bias automatically due to their simple bias representation. The integrated diffusion models with jumps, especially infinite activity jumps, are mainly investigated. In addition, under mild conditions, the weak consistency and asymptotic normality are provided through the conditional Lindeberg theorem as the time span T→∞ and the sample interval Δ _n →0. Furthermore, our method presents advantages in bias correction through simulation whether jumps belong to the finite activity case or infinite activity case. Finally, the estimators are illustrated empirically through the returns of stock index under 5‐minute high sampling frequency for real application.     

Adsorption and Diffusion of VO2+ and VO2 + across Cation Membrane for All‐Vanadium Redox Flow Battery

A method based on a selectivity coefficient and the Nernst‐Planck equation is proposed to determine diffusion coefficients of vanadium ions across a cation exchange membrane in VO²⁺/H⁺ and VO₂ ⁺/H⁺ systems. This simplified method can be applied to high concentrations of vanadium ions. Three cation exchange membranes were studied. The logarithmic value of the selectivity coefficient was linearly dependent on the molar fraction of vanadium ions in solution. The diffusion coefficient of vanadium ions decreased with decreasing water content. The membrane with the lowest diffusion coefficient was selected as a battery separator and showed the lowest capacity loss of the studied membranes.     

Correlations for prediction of molecular diffusivities in liquids at infinite dilution

Diffusivities measured at 278.2 K to 323.2 K are reported for propene in acetic acid, acetone, n-butanol, chloroben-zene, N, N dimethyl formamide, ethyl acetate and n-octane. Measurements were made utilizing the steady-state capil-lary cell method. It was found that the diffusivities were reduced in the associating solvents when compared with those obtained in non-polar solvents at the same temperature. Three new empirical correlations have been developed for the prediction of diffusivities in liquids at infinite dilution and these are: for n-alkane solutions, for dissolved gases in organic solvents, and for dissolved gases in water.     

Sorption and diffusion of water into melamine–formaldehyde‐incorporated poly(vinyl acetate)–polyester nonwoven fabric composites

A series of composites were fabricated by impregnating a polyester nonwoven fabric with melamine–formol (MF)‐incorporated poly(vinyl acetate) (PVAc) latex. The effect of different weight ratios of MF/PVAc, i.e. 0/100, 5/100, 10, 100, 15/100 and 20/100 (dry, wt/wt), on the water sorption and diffusion into the composites was evaluated. Water sorption studies were carried out at different temperatures, i.e. 30, 50 and 70 °C, based on the immersion weight gain method. From the sorption results, the diffusion (D) and permeation (P) coefficients of water penetrant were calculated. A significant increase in the diffusion and permeation coefficients was observed with an increase in the temperature of sorption. Drastic reductions in diffusion and permeation coefficients were noticed with increasing MF content in the composites. Attempts were made to estimate the empirical parameters like n, which suggests the mode of transport, and K, a constant which depends on the structural characteristics of the composite in addition to its interaction with water. The temperature dependence of the transport coefficients was used to estimate the activation energy parameters for diffusion (E_D) and permeation (E_p) processes from Arrhenius plots. Copyright © 2006 Society of Chemical Industry