Ionic interactions in aqueous electrolyte-polyelectrolyte mixtures: Comparisons with mixtures of sodium chloride and the model electrolyte benzyltrimethyl-ammonium chloride at 25°C

Osmotic coefficients for aqueous mixtures of sodium chloride with benzyltrimethylammonium chloride, BzMe₃NCl, obtained by the gravimetric isopiestic vapor pressure comparison method are interpreted with the McKay-Perring transform, with the Scatchard neutral electrolyte treatment, and with the Pitzer ion-component equations. Molal ionic and mean ionic activity coefficients for Na⁺ and Cl^– ions and for NaCl, respectively, in these mixtures at unit total ionic strength also were determined with an electrochemical cell. The excess free energy chenges G^ex on mixing NaCl with BzMe₃NCl were estimated and employed to gain an insight into the relative importance of like and unlike cation-cation interactions.     

The chemical potential for dilute hard-sphere mixtures

Accurate Monte Carlo evaluation of the probability of inserting an additional particle of arbitrary size into a hard-sphere fluid at various densities allows a quantitative check on the scaled particle interpolation formula for this probability, which is rigorously known when the added particle is either very small or very large. The simple scaled particle formula is remarkably accurate due to a favorable choice of the functional dependence of the surface tension on curvature. The biggest deviation occurs at liquid-like densities where the insertion probability is about 20% larger for larger particles, indicating a larger probability of occurrence of larger density fluctuations, and resulting in a smaller (3%) excess chemical potential than the simple theory predicts. On the other hand, at lower densities the insertion probability for large particles is slightly smaller than the theory predicts.     

Thermodynamic properties of electrolyte solutions: An EMF study of the activity coefficients of KCl in the system KCl−KNO3−H2O at 25, 35 and 45°C

Electromotive force measurements were carried out on the system KCl–KNO₃–H₂O at constant total ionic strengths of 0.5, 1.0, 2.0 and 3.0 mol-kg^–1 and at 25, 35 and 45°C using a cell consisting of a potassium ionselective electrode and a Ag/AgCl electrode. The Harned coefficients and the Pitzer binary and ternary interaction parameters for the system have been evaluated at each temperature. The osmotic coefficients, excess free energies of mixing and heats of mixing of the system have been predicted at each of the experimental temperatures and ionic strengths. The solubility data at 25°C are also interpreted.     

Activity coefficients in binary electrolyte mixtures HCl + MgCl2 + H2O at 298.15°K

Activity coefficients of hydrochloric acid in aqueous mixed solutions with magnesium chloride have been determined at 298.15°K from electromotiveforce measurements of the cell Pt, H₂(g, 1 atm.)HCl(m_A), MgCl₂(m_B)AgClAg at constant total ionic strengths of 0.1, 0.5, 1.0, 2.0, and 3.0 moles-kg^–1. The data were interpreted in terms of Scatchard's and Pitzer's equations whereupon it was found that the former gave a better fit of the experimental data but the latter were reasonably adequate. Activity coefficients for magnesium chloride in the mixtures were derived using Pitzer's equations.     

Ionic interactions in aqueous electrolyte-polyelectrolyte mixtures: Comparisons with mixtures of sodium chloride with the model electrolyte sodiumpara-ethylbenzenesulfonate at 25°C

Osmotic coefficients for aqueous mixtures of sodium chloride with sodiumpara-ethylbenzenesulfonate NapEBS and lithiumpara-ethylbenzenesulfonate LipEBS with NapEBS obtained by the gravimetric isopiestic vapor pressure comparison method are interpreted with the Scatchard neutral-component and with the Pitzer ion-component equations. Ionic and mean ionic activity coefficients for Na⁺ and Cl^– ions and for NaCl, respectively, were also determined with an electrochemical cell. The ±(NaCl) values at constant unit ionic strength,I=1.00, were compared with those computed from osmotic-coefficient measurements. Strong anion-anion interactions were observed in the NaCl-NapEBS mixtures.     

Micellisation behaviour of mixtures of sodium dodecylsulphate and sodium lauroylsarcosinate in water

The critical micelle concentrations of binary mixtures of sodium dodecylsulphate (SDS) and sodium lauroylsarcosinate (SLAS) have been determined in water by conductivity measurements at different mole fractions for each of the components. The critical micelle concentrations were slightly lower than that predicted from ideal mixing theory indicating positive synergistic interactions in mixed micelle formation. The results of the mixed systems were analysed using the Regular Solution Theory and the approach based on the Gibbs–Duhem equation which allowed for the determination of the composition of the mixed micelle, the activity coefficients and the pair-wise molecular interaction parameter β. The β values were all negative at all mole fractions investigated, showing a slight deviation from ideality, with an average value of –0.27. The excess free energy of the mixed systems was also calculated and the values were all negative for the mixed systems studied, an indication that the mixed micelles are thermodynamically stable relative to the individual component. This thermodynamic parameter also exhibits symmetrical behaviour with respect to micellar composition suggestive of a regular solution behaviour of the mixed surfactant system.     

Measurement and modeling of osmotic coefficients of aqueous solution of ionic liquids using vapor pressure osmometry method

Osmotic coefficients of binary mixtures containing an ionic liquid, (1-butyl-3-methylimidazolium tetrafluoroborate, [BMIm]BF₄, 1-ethyl-3-methylimidazolium ethyl sulfate, [EMIm]ES, and 1-butyl-3-methylimidazolium methyl sulfate, [BMIm]MS) with water were measured until about 3 molal concentrations using vapor pressure osmometry method (VPO) at temperature ranges 298.15–328.15 K and modeled using different electrolyte excess Gibbs free energy models including electrolyte non-random two liquids (NRTL), modified NRTL (MNRTL), mean spherical approximation NRTL (MSA-NRTL), non random factor (NRF), and extended Wilson models. The results show that osmotic coefficient data increase with increasing temperature. The calculated standard deviations of the studied systems show that the applicability of these models for the correlation of VLE properties of ionic liquid solutions. The average standard deviations for the models have the order σ(?) MNRTL < σ(?) Wilson < σ(?) NRTL < σ(?) MSA-NRTL < σ(?)NRF. The results show MNRTL model is able to reproduce experimental osmotic coefficients of aqueous solution of studied ionic liquids with good precision.     

Solute activity coefficients in dilute aqueous electrolyte mixtures. III. The ternary system HClO4+UO2(ClO4)2+H2O at 25°C

Isopiestic vapor pressure comparison measurements were conducted with the three-component system HClO₄+UO₂(ClO₄)₂+H₂O in the concentration range between I=0.05 and 1.9m. Analysis of the mixture composition and concentration dependence of the osmotic coefficients with the Scatchard neutral-electrolyte and ion-component methods and with the Pitzer ioncomponent methods gave equally satisfactory results. Prediction of the observed osmotic coefficients by two-component approximations was satisfactory, and the data agreed well with values estimated with a model based on the osmolal fraction. A fair concordance was also found between predicted solute activity coefficients from simple models and values derived from complete treatments which included interaction terms.     

Thermodynamic properties of alkali halides. V. Temperature and pressure dependence of excess free energies in water

A simple equation has been derived relating the temperature dependence of activity functions with excess enthalpies and excess heat capacities. Using experimentally determined parameters at 298.15°K, it is possible to predict osmotic coefficients and mean activity coefficients of alkali halides in water up to 1 m from 273°K to about 350°K. In general, the predicted functions agree with the measured values within the uncertainty of the activity data. An equation is also given for the pressure dependence of the excess free energies, but it was not possible to check the limitation of this equation due to lack of activity data at various pressures.To whom correspondence should be addressed.     

桥函数在统计力学积分方程理论3d-RISM-HNC的应用和溶剂化自由能计算的改进

把氢-桥函数和氧-桥函数应用于统计力学积分方程理论的三维的参考作用点-超链模型(3d-RISM-HNC)中,用以改进极性和非极性溶质的水溶液的热力学性质的计算.用三维和二维图形考察了溶剂水分子的氢原子和氧原子的桥函数在改进溶剂作用点的平均密度分布函数〈ρ_H(r)〉和〈ρ_O(r)〉,和平均超额化学势〈Δμ(r)〉的计算的效果.计算结果表明,氢桥函数和氧桥函数极大地改进了3d-RISM-HNC 方法的精度,把这一方法提高到定量和半定量的水平.研究表明,溶质分子的作用点的超额化学势的径向分布函数〈Δμ(r)〉比平均密度分布函数〈ρ_s(r)〉能够更灵敏地反映桥函数的改进效果.研究表明,为提高3d-RISM-HNC 方法的精度,需要进一步改进桥函数的函数形式和优化其中的参数.     

Association studies of tetramethylguanidinium perchlorate and tetramethylguanidinium chloride in ethanol solutions at 25°C

Practical osmotic coefficients of ethanol solutions of tetramethylguanidinium perchlorate and tetramethylguanidinium chloride were determined by the isopiestic method at 25°C. The relations for the concentration dependences of practical osmotic coefficients, mean molal activity coefficients of solutes and for the excess Gibbs free energies of solutions and partial molal excess Gibbs free energies of solutes and solvents are given in analytical form. The results obtained are compared with those reported previously; in the case of tetramethylguanidinium perchlorate with its aqueous and methanol solutions, in the case of tetramethylguanidinium chloride with its aqueous solutions. The non-ideal behavior of the systems investigated is discussed on the basis of the structure of solute species, as well as on the nature of the solvent.     

Thermodynamics of multicomponent electrolyte solutions: Aqueous mixtures of two salts from among NaCl,KCl, NaH2PO4, and KH2PO4 at 25° C

Five of the six possible aqueous two-salt mixtures from among NaCl, KCl, NaH₂PO₄,and KH₂PO₄ have been studied by the isopiestic method at 25°C. The sixth mixture, NaCl–KCl, has been studied previously. The deviations from ideal mixing behavior are described by a series of coefficients which were found by regression analysis. The coefficients were used to calculate the excess Gibbs energies of mixing for equal ionic strength fractions of each salt and the trace activity coefficient of each salt at an ionic strength of 2 mode-kg^–1. The cross-square mixing rule is obeyed within experimental uncertainty for the excess Gibbs energies of mixing.     

Thermodynamics of mixed electrolyte solutions: The systems H2O−NaCl−CoCl2 and H2O−CaCl2−CoCl2 at 25°C

Osmotic coefficients for aqueous solutions of sodium chloride + cobalt chloride and calcium chloride + cobalt chloride obtained by the isopiestic method are interpreted in terms of the Scatchard neutral-electrolyte treatment to derive activity coefficients of the solutes. Excess Gibbs energy of mixing are calculated, and difficulties in the evaluation of this quantity are discussed. The mixture parameters of Pitzer's method are evaluated for the two systems.     

Infinite dilution activity coefficients and gas-to-liquid partition coefficients of organic solutes dissolved in 1-sec-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide and in 1-tert-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide

Inverse gas chromatography was used to measure infinite dilution activity coefficients and gas-to-liquid partition coefficients for 48 organic solute probes in either 1-sec-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide or 1-tert-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide in the temperature range from 323.15 to 373.15 K. Partial molar excess enthalpies of solution were calculated from the variation of the infinite dilution activity coefficients with temperature. Abraham model correlations were also derived from the experimental partition coefficient data. The derived Abraham model correlations describe the observed partition coefficients to within 0.11 log units.     

A simple statistical mechanical theory for the mutual solubility of fluid mixtures of water and organic solvents under high pressure

A simple statistical mechanical theory is presented to explain phase diagrams of fluid mixtures with both a lower critical solution temperature and an upper critical solution temperature under pressure. By postulating a temperature dependence for the interaction free energy parameter of the constituent molecules and a pressure dependence for the excess volume, phase diagrams with both lower critical solution temperature, and upper critical solution temperature and their pressure dependence can be reproduced by quadratic surfaces in temperature-concentration-pressure space. The topological aspects of the observed phase diagrams in this space have been related to our theoretical model, and the thermodynamical meaning of the topologies has been interpreted based on our model. Experimental data for the mutual solubility of water and 2-butanol under pressure and that of water and 3-methylpyridine with added salts have been analyzed quantitatively and theoretical parameters are determined.     

A note on electrolysis with forced convection at large peclet number in a channel and an excess of supporting electrolyte

Electrolysis of an aqueous solution of a metal salt with an excess of supporting electrolyte flowing in a two-dimensional channel is considered. The reaction kinetics is modeled by a Butler-Volmer law. The metal electrodes are symmetrically flush mounted in the channel walls, which are otherwise electrically insulating. Using the perturbation scheme originally proposed by Levich for electrolytes with an excess of supporting electrolyte, a solution in closed form, involving the root of a transcendental algebraic equation, is obtained for the polarization curve. For small and large values of the potential difference between the electrodes, explicit expressions for the polarization curve and the distributions of electric current and concentration on the electrodes are obtained. Particular attention is given to the conditions prevailing during the asymptotic approach to the limiting current. Published in Russian in Elektrokhimiya, 2008, Vol. 44, No. 4, pp. 508–517. The text was submitted by the authors in English.     

Structure,thermodynamics and diffusion in asymmetric binary mixtures: a molecular dynamics simulation study

Structural and thermodynamic properties as well as diffusion coefficients of binary fluid mixtures with asymmetry in mass, size, charge and their combinations have been studied using classical molecular dynamics simulations. The fluid mixture is modelled as spherical particles interacting via the Weeks–Chandler–Andersen and Coulomb potential. The diameter, charge and mass of the fluid particles are in the range 6–60 Å, 1–10e and 1—500 amu, respectively. Systematic variations in pair-correlation functions, thermodynamic properties as well as the self-diffusion coefficient are found with the size, charge and mass ratio of the particles. The self-diffusion coefficient for systems having more than one type of asymmetry is calculated and expressed in terms of diffusion coefficients of systems with only one type of asymmetry.     

Thermodynamics of mixed electrolyte solutions. VIII. An isopiestic study of the ternary system KCl−MgCl2−H2O at 25°C

The osmotic coefficients of aqueous solutions of mixtures of potassium and magnesium chlorides were derived from isopiestic measurements at 25°C. The isopiestic data were treated by the methods of both Scatchard and Friedman, and the results obtained agree very well over the ionic strength range of 1–5. Interaction coefficients were obtained from both formalisms. Excess free energies of mixing were calculated and compared with those of similar systems.     

电解质溶液的分子热力学模型研究进展

"本文从经典溶液理论及半经验模型、近代统计力学理论和分子模拟三大方面阐述了近年来国内外电解质溶液热力学的研究进展。指出电解质溶液的研究已逐渐从经典的溶液理论和半经验模型转向用统计力学理论进行研究, 从电解质的原始模型转向非原始模型。从分子和离子的微观参数出发建立高水平的热力学理论模型, 以预测电解质溶液体系的宏观热力学性质, 是发展的必然趋势。     

Thermodynamics of mixed electrolyte solutions. VI. An isopiestic study of a pseudo-ternary system: NaCl−KCl−MgCl2−H2O at 25°C

Activity coefficients for magnesium chloride in the aqueous pseudo-ternary system sodium chloride-potassium chloride-magnesium chloride were derived from isopiestic measurements at 25°C. The isopiestic data were treated by both McKay-Perring and Scatchard methods, and results obtained agree fairly well over the ionic strength range of 1–6. At constant ionic strength, the activity coefficient of MgCl₂ increased with addition of other salts. Interaction coefficients were obtained from Scatchard's and Friedman's formalisms. The excess free energy of mixing was calculated and compared with similar systems.