Phase behaviour and interfacial properties of ternary system CO2 + n-butane + n-decane: coarse-grained theoretical modelling and molecular simulations

ABSTRACT

This work illustrates the application of a three-party approach based on theoretical modelling, molecular dynamic (MD) simulations and available experimental data for describing the phase equilibrium and interfacial properties for the ternary system: carbon dioxide + n-butane + n-decane and its corresponding binary sub-systems at 344.3 K. Specifically, a coarse-grained force field is employed for both theoretical predictions and MD. The interfacial region is described by the square gradient theory where the homogenous Helmholtz energy density contribution is provided by the Statistical Associated Fluid Theory equation of state for potentials of variable range for molecules conformed of segments interacting through the Mie potential (SAFT-VR Mie) and MD simulations in the canonical ensemble where the molecules are represented by a coarse-grained Mie force field. The novelty here is that both the theory and the simulations uniquely share the same underlying intermolecular potentials; hence, the experimental data are employed to verify both the theory and simulations. In this schema, the ternary mixture is full predictive as its parameters are only based on pure fluids parameters and binary interactions. It is observed that the phase equilibria and the interfacial properties are equally well represented by the used approach.     

Test of the Gouy-Chapman theory for a charged lipid membrane against explicit-solvent molecular dynamics simulations

A wealth of experimental data has verified the applicability of the Gouy-Chapman (GC) theory to charged lipid membranes. Surprisingly, a validation of GC by molecular dynamics (MD) simulations has been elusive. Here, we report a test of GC against extensive MD simulations of an anionic lipid bilayer solvated by water at different concentrations of NaCl or KCl. We demonstrate that the ion distributions from the simulations agree remarkably well with GC predictions when information on the adsorption of counterions to the bilayer is incorporated.     

Molecular dynamic simulations and global equation of state of square-well fluids with the well-widths from λ = 1.1 to 2.1

We present the results of extensive new molecular dynamic (MD) simulations in the one-phase region for square well fluids with well widths λ?=?1.10, 1.15, 1.20, 1.25, 1.375, 1.50, 1.75, 1.90, 2.0, and 2.10. These data have been used in developing a crossover equation of state (CR EOS) for square-well fluids with well widths 1.1?≤?λ?≤?2.1. The CR EOS incorporates non-analytic scaling laws in the critical region, and in the limit of low densities yields the exact second and third virial coefficients. Also in the high-temperature region, it reproduces first-order perturbation theory results. The CR EOS was tested against our new MD simulations, and earlier MD and Monte-Carlo (MC) simulations reported by other authors as well. Excellent agreement between calculated values and simulation data for all SW fluids is observed. In combination with the density-functional theory, the CR EOS is also capable of reproducing surface tension simulations with high accuracy. Application of the CR EOS for solid–liquid equilibrium calculations in combination with the Lennard–Jones and Devonshire cell model for the solid phase, is also discussed.     

Computer simulations of critical phenomena and phase behaviour of fluids

Computer simulation techniques such as Monte Carlo (MC) and Molecular Dynamics (MD) methods yield numerically exact information (apart from statistical errors) on model systems of classical statistical mechanics. However, a systematic limitation is the restriction to a finite (and often rather small) particle number N (or box linear dimension L, respectively). This limitation is particularly restrictive near critical points (due to the divergence of the correlation length of the order parameter) and for the study of phase equilibria (possibly involving interfaces, droplets, etc.). Starting out with simple lattice gas (Ising) models, finite size scaling analyses have been developed to overcome this limitation. These techniques work for both simple Lennard-Jones fluids and their mixtures, including generalizations to approximate models for quadrupolar fluids such as carbon dioxide, benzene etc. and various mixtures, whose phase behaviour can be predicted. A combination of MC and MD allows the study of dynamic critical phenomena, and specialised techniques (umbrella sampling plus thermodynamic integration) yield the surface free energy of droplets as function of droplet size. Thus, computer simulation has become a versatile and widely applicable tool for the study of fluids.     

Understanding length dependences of effective thermal conductivity of nanowires

We have studied the length dependence of effective thermal conductivity of silicon nanowires by a thermon gas model and MD simulations. After modifications of the force term by considering the resistance enhancements from thermon gas interactions with the confined surfaces and the ends (inlet and outlet), the theoretical predictions of effective thermal conductivity agree well with the results of MD simulations in the length range of 4 to 550 nm. The result suggests that the resistance enhancement effect by thermon–boundary interactions, instead of the heat inertia, plays the dominating role in the non-Fourier heat conduction in silicon nanowires.     

The origins of multifractality in financial time series and the effect of extreme events

In this paper, we study the impacts of noise and time delay in the monomer-dimer (MD) surface reaction model by using theoretical analysis. The MD models for various dimer adsorption mechanisms (namely, local and random adsorption models), which exhibit the first- and second-order phase transitions (PTs), are analyzed. By comparison with two various dimer adsorption, it is found that the qualitative predictions of the well-known first- and second-order PTs are better for the random adsorption model than that for the local adsorption model. The validity of approximate analytic results is checked by numerical simulations.     

Statistical fluid theory for associating fluids containing alternating heteronuclear chain molecules

Statistical associating fluid theory of homonuclear dimerized chain fluids and homonuclear monomer-dimer mixture chain fluids are extended to fluids containing alternating heteronuclear chain molecules separately. The proposed models account for the appropriate site-site correlation functions at contact. The modified equations of state show a good agreement with generalized Flory dimer theory and MD simulation data for small and medium size ratio of hard sphere diameters.     

Predicting XAFS scattering path cumulants and XAFS spectra for metals (Cu,Ni, Fe,Ti, Au) using molecular dynamics simulations

The ability of molecular dynamics (MD) simulations to support the analysis of X‐ray absorption fine‐structure (XAFS) data for metals is evaluated. The low‐order cumulants (ΔR, σ², C₃) for XAFS scattering paths are calculated for the metals Cu, Ni, Fe, Ti and Au at 300 K using 28 interatomic potentials of the embedded‐atom method type. The MD cumulant predictions were evaluated within a cumulant expansion XAFS fitting model, using global (path‐independent) scaling factors. Direct simulations of the corresponding XAFS spectra, χ(R), are also performed using MD configurational data in combination with the FEFFab initio code. The cumulant scaling parameters compensate for differences between the real and effective scattering path distributions, and for any errors that might exist in the MD predictions and in the experimental data. The fitted value of ΔR is susceptible to experimental errors and inadvertent lattice thermal expansion in the simulation crystallites. The unadjusted predictions of σ² vary in accuracy, but do not show a consistent bias for any metal except Au, for which all potentials overestimate σ². The unadjusted C₃ predictions produced by different potentials display only order‐of‐magnitude consistency. The accuracy of direct simulations of χ(R) for a given metal varies among the different potentials. For each of the metals Cu, Ni, Fe and Ti, one or more of the tested potentials was found to provide a reasonable simulation of χ(R). However, none of the potentials tested for Au was sufficiently accurate for this purpose.     

Distribution of light alkanes in the reaction of graphite hydrogenation at pressure of 0.1–7.8 GPa and temperatures of 1000–1350°C

ABSTRACT

We studied the effect of pressure and temperature on the hydrocarbon (HC) chain length distribution and total amount of HCs in the reaction of direct graphite hydrogenation at pressures of 0.1–7.8?GPa and temperatures of 1000–1350°C. An increase in pressure was found to lead both to an increase in the absolute yield of HCs due to direct graphite hydrogenation and to chain elongation of HC products. Light alkanes predominate among HCs in the entire studied range of P–T parameters. However, their concentration in quenched fluids increases as pressure is elevated, from less than 10?rel.% at 0.1?GPa to more than 40–50?rel.% at P?≥?3.8?GPa. Methane is actually the only light alkane among reaction products at 0.1?GPa and 1000°C, while it is a minor component at 7.8?GPa and 1350°C. The most stable alkane at pressures above 3.8?GPa is ethane (C₂H₆).     

Scaling laws for diffusion coefficients in mixtures of alkanes

Natural fluids, such as crude oils, are often mixtures of a broad range of different molecules, and in situ measurement of their composition is highly desirable. Furthermore, the relationship between their composition and their physical properties has always been a challenge for such mixtures. We have analyzed diffusion in alkane mixtures to find a power law for the self-diffusion coefficient in terms of molecular sizes. We demonstrate that this power law can be used to obtain the molecular size distribution of crude oils using noninvasive measurements of diffusion distributions.     

Dynamical structure functions,collective modes,and energy gap in charged-particle bilayers

The dynamical properties of strongly coupled charged-particle bilayers are investigated by molecular dynamics (MD) simulation and theoretical analysis. The spectra of the current correlation functions show the existence of two (in-phase and out-of-phase) longitudinal and two (in-phase and out-of-phase) transverse collective modes. The out-of-phase modes possess finite frequencies at wave numbers k-->0, confirming the existence of the predicted long-wavelength energy gap in the bilayer system. A theoretical model based on an extended Feynman ansatz for the dynamical structure functions provides predictions on the strength of the collective modes that are verified by the MD experiment.     

Ostwald Ripening of Concentrated Alkane Emulsions: A preliminary report

Fiber optic dynamic light scattering (FODLS) was used to study the kinetics of aging processes in emulsions of n-alkanes stabilized by a surfactant. The method is particularly useful for this purpose because it permits measurements in concentrated emulsions. Complications that may occur in traditional DLS due to the extreme dilution, such as solubilization of the particles in the medium, can be easily avoided in this way. The experimental results show that the main aging process is Ostwald ripening. The results are in agreement with theoretical predictions based on the Lifshitz-Slyozov-Wagner (LSW) theory as far as it concerns the relation between the molecular solubility of the n-alkanes (in the aqueous phase) and the Ostwald ripening rate. This illustrates that the main rate-determining factor is the molecular diffusion of the alkane molecules through the continuous (aqueous) phase. The Ostwald ripening rate is affected by the concentration of surfactant but in all situations is higher than expected from LSW theory.     

Surface tension of the restrictive primitive model for ionic liquids

Hybrid molecular dynamics and Monte Carlo simulations are performed to study the liquid-vapor interface of the restricted primitive model (RPM) of ionic fluids. We report for the first time simulation results of the surface tension associated to this interface. The RPM accurately predicts experimental surface tensions of ionic salts and good agreement with theoretical predictions that include the idea of ion association is found. The simulation results indicate that the structure of an ionic liquid-vapor interface is rather rough. This is reflected in the interfacial thickness, larger than that observed in simple fluids and water.     

Molecular dynamic studies on materials under laser shocks

Molecular dynamic (MD) simulations offer a powerful means of understanding the microscopic characteristics of shock-propagation through solids and fluids, especially for the short spatial and temporal scales relevant to laser-driven shocks. First-principles molecular dynamics can be directly compared with time-resolved experimental measurements, and methods based on empirical (embedded-atom) potentials fitted to first-principles quantum-mechanical calculations are effective for MD simulations of shock propagation through many millions of atoms. In comparison, thermodynamic approaches based on free-energy considerations do not provide detailed information about mechanical-relaxation or phase-transformation processes within the shock front. We illustrate these ideas by way of embedded-atom simulations of shock-wave propagation through copper crystals of different orientation.     

Triple-decker: Interfacing atomistic–mesoscopic–continuum flow regimes

Multiscale flow phenomena in microfluidic and biomedical applications require the use of heterogeneous modeling approaches. In this paper we present a hybrid method based on coupling the Molecular Dynamics (MD) method, the Dissipative Particle Dynamics (DPD) method, and the incompressible Navier–Stokes (NS) equations. MD, DPD, and NS are formulated in separate subdomains and are coupled via an overlapping region by communicating state information at the subdomain boundaries. Imposition of boundary conditions in the MD and DPD systems involves particle insertion and deletion, specular wall reflection and body force terms. The latter includes a boundary pressure force in order to minimize near-boundary density fluctuations, and an adaptive shear force which enforces the tangential velocity component of boundary conditions. The triple-decker algorithm is verified for prototype flows, including simple and multi-layer fluids (Couette, Poiseuille, and lid-driven cavity), using highly accurate reference solutions. A zero-thickness interface is also possible if it is aligned with the flow streamlines.     

Scale-bridging phase-field simulations of microstructure responses on nucleation in metals and colloids

In the present studies we investigate the connection between atomistic simulation methods, i.e. molecular dynamics (MD) and phase-field crystal (PFC), to the mesoscopic phase-field methods (PFM). While the first describes the evolution of a system on the basis of motion equations of particles the second uses a Cahn–Hilliard type equation to described an atomic density field and the third grounds on the evolution of continuous local order parameter field. The first aim is to point out the ability of the mesoscopic phase-field method to make predictions of growth velocity at the nanoscopic length scale. Therefore the isothermal growth of a spherical crystalline cluster embedded in a melt is considered. We also show simulation techniques that enable to computationally bridge from the atomistic up to the mesoscopic scale. We use a PFM to simulate symmetric thermal dendrites started at an early stage of solidification related to nucleation. These techniques allow to simulate three dimensional dendrites from the state of nuclei (≈50?Å) converted from MD up to a size of some μm where ternary side-arms start to grow.     

Fractal Analysis of Power-Law Fluid in a Single Capillary

The fractai expressions for flow rate and hydraulic conductivity for power-law fluids in a single capillary are derived based on the fractai nature of tortuous capillaries. Every parameter in the proposed expressions has clear physical meaning. The flow rate and hydraulic conductivity for power-law fluids are found to be related to the tortuosity fractal dimension and the power-law index. The flow rate for power-law fluids increases with the increasing power-law index but decreases with the increasing tortuosity fractal dimension. Good agreement between the model predictions for flow in a fractai capillary and in a converging-diverging duct is obtained. The results suggest that the fractal capillary model can be used to model the power-law fluids with different rheologicai properties.     

Photoionization mass spectrometry and modeling studies of the chemistry of fuel-rich dimethyl ether flames

Reaction paths are identified for dimethyl ether (DME) combustion using modeling of new data from fuel-rich DME flat flames. A molecular-beam flame-sampling photoionization mass spectrometer, employing VUV synchrotron radiation, is applied to the measurement of mole fractions for 21 flame species in low-pressure premixed fuel-rich (Φ = 1.2, 1.68) DME/oxygen/argon flat flames. This approach is capable of resolving and identifying isomers and other flame species of near equal masses with ionization thresholds that differ by as little as 0.1 eV. The measurements agree well with flame modeling predictions, using a recently revised high-temperature DME kinetic mechanism, which identify reaction paths quite analogous to alkane combustion. They further reveal the presence of ethyl methyl ether, a molecule previously unobserved in flames and not included in present flame models.     

Localized vibrations in perfect anharmonic lattices: Trapping on phonons

A theory is developed, which allows one to calculate intrinsic local modes (ILMs) in infinite lattices and to find the effect of an ILM on phonons. One prediction is the appearance of linear local modes in the lattice nearby an ILM. To check these results, high-precision MD calculations of the vibrations of diatomic chains have been carried through. The results fully confirm the predictions.     

Equation of state of a supercritical fluid based on the Ornstein-Zernike equation

A numerical modeling of the thermodynamic properties of a fluid is performed using the method of integral equations. The predictions are compared with the results of MC and MD simulations. The problem of stability of the numerical solution is examined. The methods for correcting the correlation functions and for estimating their uncertainties are proposed.