Adiabatic compressibility and solvation of drag reducing polymers in aqueous solutions

Adiabatic compressibilities of aqueous solutions of some drag reducing polymers have been evaluated from ultrasonic velocity and density measurements. The solvation numbers of the repeat units of the polymers have been further evaluated by using Passynsky equation. It is observed that the solvation number increases with the shear stability of drag reducing polymers in turbulent flow.     

Relative viscosity and the solvation number in solutions

It has been shown that part of the free volume of a solvent attaching to the solvation shell must be excluded from the total free volume in the Bachinskii equation. This determines the increase of viscosities of solutions with positive solvation. An equation has been obtained for the inverse relative viscosity of solutions ₀/ = 1-zN₂/(1-N₂), where no and are the dynamic viscosities respectively of the solvent and the solution; z is the solvation number, N₂ is the mole fraction of dissolved material. A method is proposed for determining the solvation number (hydration) from solution viscosity data. Solvation numbers obtained by this method are in good agreement with values of z obtained from the literature and determined by other methods.Translated from Teoreticheskaya i Experimental'naya Khimiya, Vol. 21, No. 5, pp. 627–631, September–October, 1985.The author wish to express their gratitude to professors Yu. Ya. Fialkov and M. A. kvadrigin for fruitful discussions of the result of the current work.     

Solvation of lithium chloride in aqueous and mixed solutions of an aprotic solvent

The dynamic hydration and solvation numbers of lithium chloride are estimated on the basis of experimental data on the limiting electrodialysis concentration of an electrolyte from aqueous and aqueousorganic solutions containing aprotic solvent N,N-dimethylacetamide. It is established that the dependence of the hydration numbers of the salt on the volume fraction of the aprotic solvent is of an extreme character, and its solvation number on N,N-dimethylacetamide does not depend on the composition of the mixed solution.     

Solvation of amides of formic and acetic acids in water-glycerol mixture. Additivity of thermochemical characteristics of solutions

Values of the solution enthalpy of are measured and values of solvation enthalpy are calculated for formamide and N,N-two-substituted methyl-and ethylamides of formic and acetic acids in the mixed solvent: water-glycerol. Enthalpy coefficients of pair interactions between amides and glycerol in aqueous solutions are calculated. The influence of mixture composition and also of a structure and properties of the dissolved compounds on enthalpy characteristics is considered. Within the frames of the offered additive scheme the contributions from the structural fragments of molecules of amides to enthalpy characteristics of solutions are established. It has allowed us to analyze quantitatively the role of nonspecific and specific solvation of amides in solution, to predict the enthalpy of evaporation, solution, solvation, the enthalpy coefficients of pair interactions of experimentally unstudied N-methylformamide, N-ethylformamide, N-methyl-N-ethylformamide, N-methylacetamide, N-ethylacetamide, and N-methyl-N-ethylacetamide in the mixtures of water-glycerol, and also to evaluate the donor numbers of these specified amides.     

Microcalorimetric study of thermal unfolding of lysozyme in water/glycerol mixtures: an analysis by solvent exchange model

Folded protein stabilization or destabilization induced by cosolvent in mixed aqueous solutions has been studied by differential scanning microcalorimetry and related to difference in preferential solvation of native and denatured states. In particular, the thermal denaturation of a model system formed by lysozyme dissolved in water in the presence of the stabilizing cosolvent glycerol has been considered. Transition temperatures and enthalpies, heat capacity, and standard free energy changes have been determined when applying a two-state denaturation model to microcalorimetric data. Thermodynamic parameters show an unexpected, not linear, trend as a function of solvent composition; in particular, the lysozyme thermodynamic stability shows a maximum centered at water molar fraction of about 0.6. Using a thermodynamic hydration model based on the exchange equilibrium between glycerol and water molecules from the protein solvation layer to the bulk, the contribution of protein-solvent interactions to the unfolding free energy and the changes of this contribution with solvent composition have been derived. The preferential solvation data indicate that lysozyme unfolding involves an increase in the solvation surface, with a small reduction of the protein-preferential hydration. Moreover, the derived changes in the excess solvation numbers at denaturation show that only few solvent molecules are responsible for the variation of lysozyme stability in relation to the solvent composition.     

Development of Abraham model correlations for predicting enthalpies of solvation of nonionic solutes dissolved in formamide

Experimental enthalpy of solution data for 81 solutes dissolved in formamide have been compiled from the published literature and converted to enthalpies of solvation data using standard thermodynamic relationships. Abraham model correlations were derived from the compiled enthalpy of solvation data. The derived mathematical equations describe the observed experimental to within overall standard deviations of 2.3 kJ mol^?1. A principal component analysis based on the calculated equation coefficients, and the coefficients for water and 23 organic solvents previously determined, shows that formamide is both a hydrogen-bond acid and a hydrogen-bond base. Of the solvents that we have studied thus far, formamide is the closest to water in terms of enthalpies of solvation of dissolved solutes.     

Anisotropic inertial term of the solvation energy in binary solutions

An expression based on the Fröhlich theorem is given for the anisotropic inertial solvation potential of solutions. The principle of the additivity of the anisotropic inertial solvation potentials of solution components is put forward and substantiated. A model thermodynamic function of the anisotropic inertial solvation potential of a binary solution is suggested. The effect of formation of 1:1 complexes and bimolecular associates on the anisotropic inertial solvation potential of a binary solution is analyzed. The composition dependences of the anisotropic inertial solvation potentials of binary solutions of nitrobenzene, acetonitrile, nitromethane, and tetrachloromethane in associated and nonassociated polar and nonpolar solvents and in water are determined. The dependences obtained are compared to the corresponding model functions. Changes in the contribution of specific intermolecular interactions to the anisotropic inertial term of the Helmholtz energy of solvation of binary solutions are revealed by this method. Previously unknown anisotropic inertial solvation potentials are obtained for associated and polar nonassociated liquids in relation to their content in hexane. Conclusions on the magnitude and character of changes in the microstructure of solutions are made. The transformation of the anisotropic inertial to isotropic noninertial term of the Helmholtz energy of solvation is noted by the example of a solution with the ethanol volume fraction in hexane of 0.13.     

Thermodynamic properties of ternary systems: Calculation of standard enthalpies of solvation of triols, diols, and a series of their ethers in water-methanol mixed solvent

An equation for the standard enthalpy of solvation of a compound in a binary solvent is derived. The enthalpies of solvation in water-methanol mixtures are estimated for 1,3-propane-and 1,6-hexanediols, 1,2,4-butane-and 1,3,5-pentanetriols, 2-methoxy-and 2-propoxyethanols, and diethylene glycol. The enthalpy of solvation of 1,2-dimethoxyethane in the water-methanol mixed solvent is determined experimentally.     

Association of ionic liquids in solution: a combined dielectric and conductivity study of [bmim][Cl] in water and in acetonitrile

Ion association of the ionic liquid [bmim][Cl] in acetonitrile and in water was studied by dielectric spectroscopy for salt concentrations c ≤ 1.3 M at 298.15 K and by measurement of molar electrical conductivities, Λ, of dilute solutions (c ≤ 0.006 M) in the temperature range 273.15 ? T/K ≤ 313.15. Whilst acetonitrile solutions of [bmim][Cl] exhibit moderate ion pairing, with an association constant of K°(A) ≈ 60 M(-1) and increasing with temperature, [bmim][Cl] is only weakly associated in water (K°(A) ≈ 6 M(-1)) and ion pairing decreases with rising temperature. Only contact ion pairs were detected in both solvents. Standard-state enthalpy, entropy and heat capacity changes of ion association were derived, as well as the activation enthalpy of charge transport and the limiting conductivity of the cation, λ(∞)?([bmim](+)). These data, in conjunction with effective solvation numbers obtained from the dielectric spectra, suggest that the solvation of [bmim](+) is much weaker in water than in acetonitrile.     

聚乙烯醇水溶液反复冷冻过程中的溶剂化效应

采用示差扫描量热技术(DSC)对聚乙烯醇(PVA)水溶液反复冰冻过程中的溶剂化效应进行研究.引入水化数的概念来表征溶剂化效应的大小.结果表明不同浓度区间的PVA水溶液其在反复冰冻过程中溶剂化效应显著不同,主要归因于高分子链分子内和分子间缠结程度对溶剂分子"参与"溶剂化的程度和方式的不同.作者把极稀高分子溶液的研究结果拓展到高分子稀溶液或亚浓溶液区间,阐述了高分子溶液中高分子链的物理图像.冷冻次数的增加导致链间缠结增加,部分溶剂则被包裹在由链间缠结点所形成的网圈内成为分子链的一部分.溶液溶剂化程度的变化受到包裹溶剂与高分子链脱溶剂化的综合影响.     

Development of the theory of strong electrolytes considering the concentration dependence of hydration numbers

An expression for the Gibbs free energy is obtained that takes into account the contribution of interactions in the hydrate shells of ions and is compared with experimental data on the concentration dependence of hydration numbers. The activity coefficient derived from this expression is consistent with experiment up to the concentrations corresponding to the total solvation boundary (TSB). The relations describing the thermodynamics of solutions in the region of concentrations exceeding TSB are proposed. The analysis of the obtained expressions confirms their adequacy to experiments.     

Surface properties of diluted solutions of cyclohexanol and cyclopentanol in ethylene glycol

The surface tension, sigma, of dilute solutions of cyclohexanol and cyclopentanol in ethylene glycol was measured in the temperature range between 293.15 and 323.15 K by means of the ring detachment method. The surface entropies and enthalpies were calculated. The surface excess values were obtained using the Gibbs equation. The surface tension data were analyzed using the extended Langmuir (EL) model and the surface composition were obtained from this model. It was shown that clathrate-like solvates (hydrophobic-like solvation) are forming in the dilute solution of cyclohexanol in ethylene glycol.     

Solvation of cations in the LiNO3-Ca(NO3)2-H2O system at 25°C. A molecular dynamics simulation study

A series of solutions of the ternary LiNO₃-Ca(NO₃)₂-H₂O system is simulated under standard conditions by means of classical molecular dynamics (MD). Several variants of the potentials of interparticle interactions predicting different structures and compositions of the lithium cation hydration shell are used in the calculations. The coordination numbers of ions, the mean residence times of water molecules and nitrate anions in the solvation shells of cations, and the self-diffusion coefficients of solution components are estimated for all of the investigated systems. The structural features of the solvation shells of cations in multicomponent aqueous solutions are described on the basis of the obtained data.     

镁离子作用下乙醇溶液的红外光谱研究

采用红外光谱法对MgCl2乙醇溶液进行了研究.乙醇分子的谱带变化表明,Mg<'2+>与乙醇分子中C-O发生强烈作用,同时,随着MgCl2的加入,原有氢键结构遭到破坏,形成新的结构,计算得到其溶剂化数为3.87～1.83.针对溶液中各聚体氢键峰面积的变化进行了定量分析,确定了在0.3406～1.6083mol/kg浓度范围内二聚体含量与MgCl2浓度呈线性关系,其线性方程为△A=0.24202+16.65859 C;,相关系数R=0.9922,二聚体和多聚体呈可逆平衡关系,进一步揭示了溶液溶剂化的微观过程.     

Drag reduction and solvation in polymer solutions

A model is described which explains drag reduction (DR) in dilute polymer solutions in terms of solvation of macromolecular chains and formation of relatively stable domains. The domains partly suppress the vortex formation, act as energy sinks, and also play a role in mechanical degradation in flow (MDF). We report ultrasonically determined solvation numbers for a series of copolymers with the same chemical structure but differing widely in their intrinsic viscosities. The solvation numbers confirm the model. Thus, we have a criterion for selection of DR agents with low MDF for: oil well operations; crude oil transport; fire fighting; high sewer throughput; irrigation; hydrotransport of solids; marine applications; and biomedical applications including the arteriosclerosis prevention.     

The importance of excluded solvent volume effects in computing hydration free energies

Continuum dielectric methods such as the Born equation have been widely used to compute the electrostatic component of the solvation free energy, DeltaG(solv)(elec), because they do not need to include solvent molecules explicitly and are thus far less costly compared to molecular simulations. All of these methods can be derived from Gauss Law of Maxwell's equations, which yields an analytical solution for the solvation free energy, DeltaG(Born), when the solute is spherical. However, in Maxwell's equations, the solvent is assumed to be a structureless continuum, whereas in reality, the near-solute solvent molecules are highly structured unlike far-solute bulk solvent. Since we have recently reformulated Gauss Law of Maxwell's equations to incorporate the near-solute solvent structure by considering excluded solvent volume effects, we have used it in this work to derive an analytical solution for the hydration free energy of an ion. In contrast to continuum solvent models, which assume that the normalized induced solvent electric dipole density P(n) is constant, P(n) mimics that observed from simulations. The analytical formula for the ionic hydration free energy shows that the Born radius, which has been used as an adjustable parameter to fit experimental hydration free energies, is no longer ill defined but is related to the radius and polarizability of the water molecule, the hydration number, and the first peak position of the solute-solvent radial distribution function. The resulting DeltaG(solv)(elec) values are shown to be close to the respective experimental numbers.     

Experimental and theoretical investigations of solvation dynamics of ionic fluids: appropriateness of dielectric theory and the role of DC conductivity

An analysis is provided of the subnanosecond dynamic solvation of ionic liquids in particular and ionic solutions in general. It is our hypothesis that solvation relaxation in ionic fluids, in the nonglassy and nonsupercooled regimes, can be understood rather simply in terms of the dielectric spectra of the solvent. This idea is suggested by the comparison of imidazolium ionic liquids with their pure organic counterpart, butylimidazole (J. Phys. Chem. B 2004, 108, 10245-10255). It is borne out by a calculation of the solvation correlation time from frequency dependent dielectric data for the ionic liquid, ethylammonium nitrate, and for the electrolyte solution of methanol and sodium perchlorate. Very good agreement is obtained between these theoretically calculated solvation relaxation functions and those obtained from fluorescence upconversion spectroscopy. Our comparisons suggest that translational motion of ions may not be the predominant factor in short-time solvation of ionic fluids and that many tools and ideas about solvation dynamics in polar solvents can be adapted to ionic fluids.     

Concentration dependence of NaCl in a wide range of temperatures and pressures

We use our own and literature data on density, ultrasound propagation velocity, and isobaric heat capacity to study the concentration, temperature, and pressure dependences of solvation numbers in aqueous NaCl solutions. We show that, in the parameter range: m = 0–6.0 mol·kg^?1, p = 1–1000 bar, and T = 283.15–323.15 K, the solvation numbers decrease with increasing concentration, pressure, and temperature.