Dynamic viscosity estimation of hydrogen sulfide using a predictive scheme based on molecular dynamics

An approach based on molecular dynamics results on Lennard–Jones spheres is proposed to model the viscosity of hydrogen sulfide, H₂S. The molecular parameters, that have a strong physical meaning, are the depth of the potential, and the length at which the potential is null (the “molecular diameter”), which take into account the dipolar moment of the hydrogen sulfide through an isotropic dipolar approximation. The interest of the method is that the adjustment does not involve any viscosity data because only density values have been used in order to estimate the molecular parameters. Consequently, the model is entirely predictive. A comparison between the data generated by our model, REFPROP7 and REFPROP8 database and the few available experimental viscosity data (dilute gas and saturated liquid) is performed and it clearly demonstrates the performance of this predictive model. It is even shown that this model is, without fitting, slightly better than REFPROP7 and REFPROP8 which uses viscosity experimental database to adjust their parameters. In addition, in typical petroleum reservoirs conditions, it is shown that non-negligible deviations appear when comparing results predicted by REFPROP7, REFPROP8 and the model proposed. Due to its predictive nature, we believe that the values evaluated by the proposed model make sense in such reservoir conditions, at least for industrial purposes. Moreover, the scheme proposed is shown to be very easily extended to deal with mixtures involving H₂S with the limit that the Lennard–Jones fluid model is appropriate for the other species of the mixtures.     

Zero electric field gradient mixtures for the elucidation of orientational mechanisms

A novel zero electric field gradient nematic liquid crystal made up from two nematic liquid crystal components is employed as a solvent for a series of molecules ranging from small molecules to mesogens themselves. Nuclear magnetic resonance is used to determine the degree of order of the solute and solvent molecules. Results are compared to those obtained for two completely different zero electric field gradient nematic mixtures. The comparison strongly indicates that for a variety of molecules largely differing in size, shape and flexibility their degree of order can be described by a single orientation mechanism. This mechanism can be adequately modelled by a simple phenomenological mean field model based on the size and shape anisotropy of the dissolved species. The use of zero electric field gradient mixtures in combination with this mean field model allows the prediction of solute order parameters at approximately the 10 per cent level.     

Apparent viscosity characteristics and prediction model of an unstable oil-in-water or water-in-oil dispersion system

A series of theoretical analysis and experimental measurements were done to analyze the characteristic of the apparent viscosity of oil-water unstable mixtures which display the similar distributions as the mixtures in pipeline flow. Based on the experimental results, it can be concluded that the unstable oil-water dispersed mixtures are always show the characteristic of non-Newtonian fluid. The shear rate has a great influence on the apparent viscosity, particular for the water-in-oil mixtures. The effect of dispersed phase volume fraction on the apparent viscosity of the unstable mixtures displays the similar rules as the stable emulsions. Also, the influences of the dispersed phase distribution and viscosity on the apparent viscosity were studied through the corresponded experiments systematically. Furthermore, a new kind of prediction model was obtained in the present study. The unstable and non-Newtonian fluid characteristics of oil-water two-phase dispersed mixtures were considered in this model to improve their range of application and the prediction accuracy. Moreover, this kind of apparent viscosity prediction model was validated by using the experimental data from some other literatures including different kinds of oils such as white oil and crude oil, and the average deviation was always less than 9% which was a great accuracy of apparent viscosity prediction.     

Solid-liquid equilibrium using the SAFT-VR equation of state: Solubility of naphthalene and acetic acid in binary mixtures and calculation of phase diagrams

A solid-liquid equilibrium (SLE) thermodynamic model based on the SAFT-VR equation of state (EOS) is presented. The model allows for the calculation of solid-liquid phase equilibria in binary mixtures at atmospheric pressure. The fluid (liquid) phase is treated with the SAFT-VR approach, where molecules are modelled as associating chains of tangentially bonded spherical segments interacting via square-well potentials of variable range. The equilibrium between the liquid and solid phase is treated following a standard thermodynamic method that requires the experimental temperature and enthalpy of fusion of the solute. The model is used to calculate the solubilities of naphthalene and acetic acid in common associating and non-associating organic solvents and to determine the solid-liquid phase behaviour of binary mixtures with simple eutectics. The SAFT-VR pure component model parameters are determined by comparison to experimental vapour pressure and saturated liquid density data with the choice of association models according to the nature of the molecule; in addition, an unlike adjustable parameter (k_ij) is used to model the solutions. The solubility data of naphthalene and acetic acid in both associating and non-associating solvents are reproduced essentially within the accuracy of the experimental measurements. The phase boundaries and the position of the eutectic points in the binary mixtures considered are, in most cases, reproduced with the accuracy commensurate with the industrial applications. Overall, the results presented show that the SAFT-VR EOS can be used with confidence for the prediction of the SLE of binary systems at atmospheric pressure.     

Viscosity Arrhenius parameters correlation: extension from pure to binary fluid mixtures

Knowledge of fluids’ physicochemical properties is mandatory for the design and optimisation of industrial processes and products. A data quantity of most importance, in this regard, turns out to be the value of fluid viscosity. Many empirical and semi-empirical formulas have been proposed in the literature to describe the viscosity of pure liquids and binary liquid mixtures. Recently, an interesting equation is proposed for pure solvents correlating the two parameters in the viscosity Arrhenius-type equation, namely the activation energy (E_a) and the pre-exponential factor (A_s). This paper aims to extend the said correlation to binary liquid mixtures. To achieve this purpose, statistical methods are applied using data sets from the literature of some solvent binary mixtures at different compositions and temperatures. The validation of the extended proposed equation for binary liquid mixtures is important since it simplifies the estimation of viscous behaviour and the ensuing calculations.     

On the unsteady-state species separation of a binary liquid mixture in a rectangular thermogravitational column

This paper investigates the unsteady-state species segregation of binary liquid mixtures in rectangular thermogravitational columns. The analysis leads to a procedure to obtain both molecular and thermal diffusion coefficients from transient separation measurements. Two models are presented: first, an ideal model where buoyancy only depends on temperature and second, a general model where buoyancy also varies with composition. Steady-state measurements are not required regardless of which model is chosen. As a result, the new procedure is faster than steady-state procedures. When either the molecular or thermal diffusion coefficient is known a priori, the other can be obtained without knowledge of fluid properties such as density, viscosity, thermal expansion, and compositional coefficients.     

Temperature dependence of viscosity and density of viscous liquids determined from thermal noise spectra of uncalibrated atomic force microscope cantilevers

We demonstrate that the thermal response of uncalibrated atomic force microscope cantilevers can be used to extract the density and the viscosity of viscous liquids with good accuracy. Temperature dependent thermal noise spectra were measured in water/poly(ethylene glycol) mixtures. Empirical parameters characteristic of the resonance behavior of the system were extracted from data recorded for one of the solutions at room temperature. These parameters were then employed to determine both viscosity and density values of the solutions simultaneously at different temperatures. In addition, activation energies for viscous flow were determined from the viscosity values obtained. The method presented is both fast and reliable and has the potential to be applied in connection with microfluidic systems, making macroscopic amounts of liquid and separate measurements with a viscometer and a densimeter redundant.     

Dynamics of fluid mixtures in nanospaces

A multicomponent extension of our recent theory of simple fluids [U. M. B. Marconi and S. Melchionna, J. Chem. Phys. 131, 014105 (2009)] is proposed to describe miscible and immiscible liquid mixtures under inhomogeneous, nonsteady conditions typical of confined fluid flows. We first derive from a microscopic level the evolution equations of the phase space distribution function of each component in terms of a set of self-consistent fields, representing both body forces and viscous forces (forces dependent on the density distributions in the fluid and on the velocity distributions). Second, we numerically solve the resulting governing equations by means of the lattice Boltzmann method, whose implementation contains novel features with respect to existing approaches. Our model incorporates hydrodynamic flow, diffusion, surface tension, and the possibility for global and local viscosity variations. We validate our model by studying the bulk viscosity dependence of the mixture on concentration, packing fraction, and size ratio. Finally, we consider inhomogeneous systems and study the dynamics of mixtures in slits of molecular thickness and relate structural and flow properties.     

传递性质的自由体积模型对方阱流体的应用

对简单分子构成的稀薄气体的传递性质已有较严格的分子动力学理论，但对稠密流体，尤其是液体，严格的理论方法尚难以解决实际问题词．实用中仍以经验或半经验模型为主．半经验模型以Eyring的绝对反应速率理论[1，2]和自由体积理论[3-11]为典型代表．由于自由体积模型可以同时反映温度和压力的影响，其应用潜力更大，值得进一步研究．对理论模型的检验一般用实际物系的测定数据．这种检验虽然直接可靠，但往往受到实验条件的限制，例如高温高压；近年来迅速发展的计算机分子模拟为建立和验证理论模型提供了一个有效手段．由于计算机模拟数…     

Revealing the influence of the strength of coulomb interactions on the viscosity and interfacial tension of ionic liquid cosolvent mixtures

Within this work, viscosity and interfacial tension of selected ionic liquid cosolvent mixtures, [EMIM][EtOSO3] (1-ethyl-3-methyl-immidazolium ethyl sulfate) with water and ethanol, were studied as a function of composition by surface light scattering (SLS) and the pendant drop method in a consistent manner, allowing a close insight into the nature of interactions. Here, we show that the viscosity behavior clearly reflects the bulk structure of the ionic liquid cosolvent mixtures and correlates to the fluid structure at the phase boundary. In contrast to former work, we found the viscosity of ionic liquid [EMIM][EtOSO3] to be decreasing the stronger by small amounts of the cosolvents and the lower their dielectric constant. Furthermore, two distinct trends for the dependence of the viscosity on the cosolvent concentration were resolved. These were assigned to ion-dipole interactions dominating in the salt-rich region and to dipole-dipole interactions in the diluted one. A crossover between both regions is reflected by the interfacial tension data, where it seems that up to a "critical" concentration almost no cosolvent is present at the phase boundary.     

Rotational viscosity of fluids composed of linear molecules: an equilibrium molecular dynamics study

In this paper, we investigate the rotational viscosity for a chlorine fluid and for a fluid composed of small linear molecules by using equilibrium molecular dynamics simulations. The rotational viscosity is calculated over a large range of state points. It is found that the rotational viscosity is almost independent of temperature in the range studied here but exhibits a power-law dependency on density. The rotational viscosity also shows a power-law relationship with the molecular length, and the ratio between the shear and rotational viscosities approaches 0.5 for the longest molecule studied here. By changing the number of atoms or united atomic units per molecule and by keeping the molecule length fixed, we show that fluids composed of molecules which have a rodlike shape have a lower rotational viscosity. We argue that this phenomenon is due to the reduction in intermolecular connectivity, which leads to larger fluctuations around the values possessed by the fluid on average. The conclusions here can be extended to fluids composed of uniaxial molecules of arbitrary length.     

Correlation of viscosity of binary liquid mixtures

A new two-parameter model presented in the previous work for correlating the viscosity of pure liquids is extended to correlate the viscosity of binary liquid mixtures. The correlation relates this non-equilibrium property to some equilibrium properties, the volume, the internal energy of vaporization and their excess properties. The viscosities of 47 binary liquid mixtures, including different kinds, which having no maximum or minimum viscosity, which having one maximum or one minimum viscosity, and which having both of one maximum and one minimum viscosities in the whole composition range, are correlated using the model and compared with data reported in the literature with the overall average absolute deviation of 1.05%. Further comparison with a good correlation, a free-volume type correlation, is also discussed. The results show that the new method is satisfactory.     

Orientational order in binary mixtures of hard Gaussian overlap molecules

Based on a standard constant-pressure Monte Carlo molecular simulation, we have studied liquid crystal phases of binary mixtures of nonspherical molecules. The components of the mixtures are two types of hard Gaussian overlap (HGO) molecules. The first type of molecule has a small molecularelongation parameter (short HGO molecules) and cannot form stable liquid crystal phase in the bulk by themselves. The second type of molecule has a large elongation parameter (long HGO molecules) and can form a liquid crystal phase easily. In the mixtures, the short HGO molecules can form an orientationally ordered phase because the long HGO molecules form confining surfaces to induce the alignment of the short molecules. We also study the isotropic-nematic phase transition in different mixtures composed of short and long HGO molecules with different elongations and concentrations. The obtained result implies that small anisotropic molecules can show liquid crystal behavior.     

A modified square well model in obtaining the surface tension of pure and binary mixtures of hydrocarbons

A model based on the perturbation theory of fluids was proposed to correlate the experimental data for surface tension of pure hydrocarbons in a wide range of temperature. The results obtained for the pure hydrocarbons were directly used to predict the surface tension for binary hydrocarbon mixtures at various temperatures. In the proposed model, a modified form of the square well potential energy between the molecules of the reference fluid was taken into account while the Lennard–Jones dispersion energy was considered to be dominant amongst the molecules as the perturbed term to the reference part of the model. In general, the proposed model has three adjustable parameters which are chain length, m, size, σ, and energy, ε/κ, parameters, but in some cases the number of parameters was reduced to two, thereby setting the chain length to be unity for pure hydrocarbons. The regressed values of these parameters were obtained using the experimental data for pure hydrocarbons at different temperatures. The results showed that these parameters can be related to the molar mass of hydrocarbons. The model was also extended to predict the surface tension of binary hydrocarbon mixtures using the parameters obtained for the pure compounds. It is worth noting that no additional parameter has been introduced into the model in the extension of the model to the mixtures studied in this work. The results showed that the proposed model can accurately correlate the surface tension of pure hydrocarbons. Also the results showed that the surface tension for binary mixture of hydrocarbons can be accurately predicted using the proposed model over a wide temperature range.     

High-temperature liquid chromatography. Part II: Determination of the viscosities of binary solvent mixtures—Implications for liquid chromatographic separations

This paper is the second in a series of consecutive publications, explaining the concept of high temperature liquid chromatography under various important aspects. The second publication deals with the determination of the viscosity of binary solvent mixtures used in reversed phase liquid chromatography in a temperature range between 25 and 250 °C. In literature, only limited data of the temperature dependent viscosities of liquid solvents or binary solvent mixtures can be found. Therefore, the viscosities of the pure solvents as well as the binary mixtures had to be determined experimentally up to 250 °C. The viscosity data were used to estimate the pressure drop in a capillary connecting a high-temperature HPLC system with a mass spectrometer. The solvent perturbation could be avoided by adjusting the diameter of the transfer capillary to the viscosity and vapour pressure of the mobile phase. The viscosity data were also used to show that a significant gain in analysis speed is theoretically feasible. This factor clearly depends on the nature of the solvent system, because for mixtures with a large viscosity maximum at ambient temperature, this effect is most pronounced.     

Model for Plateau border drainage of power-law fluid with mobile interface and its application to foam drainage

A model for drainage of a power-law fluid through a Plateau border is proposed which accounts for the actual Plateau border geometry and interfacial mobility. The non-dimensionalized Navier-Stokes equations have been solved using finite element method to obtain the contours of velocity within the Plateau border cross section and average Plateau border velocity in terms of dimensionless inverse surface viscosity and power-law rheological parameters. The velocity coefficient, the correction for the average velocity through a Plateau border of actual geometry compared to that for a simplified circular geometry of the same area of cross section, was expressed as a function of dimensionless inverse surface viscosity and flow behavior index of the power-law fluid. The results of this improved model for Plateau border drainage were then incorporated in a previously developed foam drainage model [G. Narsimhan, J. Food Eng. 14 (1991) 139] to predict the evolution of liquid holdup profiles in a standing foam. Foam drainage was found to be slower for actual Plateau border cross section compared to circular geometry and faster for higher interfacial mobility and larger bubble size. Evolution of liquid holdup profiles in a standing foam formed by whipping and stabilized by 0.1% beta-lactoglobulin in the presence of xanthan gum when subjected to 16g and 45g centrifugal force fields was measured using magnetic resonance imaging for different xanthan gum concentrations. Drainage resulted in the formation of a separate liquid layer at the bottom at longer times. Measured bubble size, surface shear viscosity of beta-lactoglobulin solutions and literature values of power-law parameters of xanthan gum solution were employed in the current model to predict the evolution of liquid holdup profile which compared well with the experimental data. Newtonian model for foam drainage for zero shear viscosity underpredicted drainage rates and did not agree with the experimental data.     

Rheological Properties and Crosslinking Rheo-Kinetics of CMHEC/CTAB Synergistic Systems

Aiming at synergistic interaction between carboxymethyl hydroxyethyl cellulose (CMHEC) and cetyltrimethyl ammonium bromide (CTAB), mixtures of CMHEC and CTAB solutions were investigated, employing relative viscosity and rheological measurements. The effects of mass ratio of CMHEC and CTAB solutions, temperature, and polysaccharide concentration on relative viscosities of CMHEC/CTAB systems were studied. Rheological method was used to study rheo-kinetics of the isothermal crosslinking process for CMHEC/CTAB synergistic fracturing fluid, and the novel crosslinking rheo-kinetics equation was established. The results showed the strong synergism between CMHEC and CTAB, resulting in a higher relative viscosity, storage modulus G′, and loss modulus G″ than that of separate ones. CMHEC/CTAB systems behave as pseudoplastic fluids with considerable thixotropy and viscoelasticity, and the flow behavior can be well described by Carreau?Williamson model. The crosslinking rheo-kinetics equation can well describe the isothermal crosslinking process at different shear rates. The model parameters are well-defined and reasonable.     

Damping by bulk and shear viscosity of confined acoustic phonons for nanostructures in aqueous solution

A nanoparticle in aqueous solution is modeled as a homogeneous elastic isotropic continuum sphere in contact with an infinite viscous compressible Newtonian fluid. The frequencies and damping of the confined vibrational modes of the sphere are calculated for the material parameters of a CdSe nanoparticle in water and a poly(methyl methacrylate) nanosphere in water. Although the effects of viscosity are found to be negligible for macroscopic objects, for nanoscale objects, both the frequency and damping of the vibrational modes are significantly affected by the viscosity of the liquid. Furthermore, both shear viscosity and bulk viscosity play an important role. A model of the spherical satellite tobacco mosaic virus consisting of outer solid layers with a water core is also investigated, and the viscosity of the water core is found to significantly damp the free vibrational modes. The same approach can be applied for nonspherical geometries and also to viscoelastic nanoparticles.