Monte Carlo simulations of Lennard-Jones nonionic surfactant adsorption at the liquid/vapor interface

We present Monte Carlo simulations of nonionic surfactant adsorption at the liquid/vapor interface of a monatomic solvent. All molecules in the system, solvent and surfactant, are characterized by the Lennard-Jones (LJ) potential using differing interaction parameters. Surfactant molecules consist of an amphiphilic chain with a solvophilic head and a solvophobic tail. Adjacent atoms along the surfactant chain are connected by finitely extensible harmonic springs. Solvent molecules move via the Metropolis random-walk algorithm, whereas surfactant molecules move according to the continuum configurational bias Monte Carlo (CBMC) method. We generate quantitative thermodynamic adsorption and surface tension isotherms in addition to surfactant radius of gyration, tilt angles, and potentials of mean force. Surface tension simulations compared to those calculated from the simulated adsorbed amounts and the Gibbs adsorption isotherm agree confirming equilibrium in our simulations. We find that the classical Langmuir isotherm is obeyed for our LJ surfactants over the range of head and tail lengths studied. Although simulated surfactant chains in the bulk solution exhibit random orientations, surfactant chains at the interface orient roughly perpendicular and the tails elongate compared to bulk chains even in the submonolayer adsorption regime. At a critical surfactant concentration, designated as the critical aggregation concentration (CAC), we find aggregates in the solution away from the interface. At higher concentrations, simulated surface tensions remain practically constant. Using the simulated potential of mean force in the submonolayer regime and an estimate of the surfactant footprint at the CAC, we predict a priori the Langmuir adsorption constant, KL, and the maximum monolayer adsorption, Gammam. Adsorption is driven not by proclivity of the surfactant for the interface, but by the dislike of the surfactant tails for the solvent, that is by a "solvophobic" effect. Accordingly, we establish that a coarse-grained LJ surfactant system mimics well the expected equilibrium behavior of aqueous nonionic surfactants adsorbing at the air/water interface.     

Percolation transition in supercritical water: a Monte Carlo simulation study

Computer simulations of water have been performed on the canonical ensemble at 15 different molecular number densities, ranging from 0.006 to 0.018 A-3, along the supercritical isotherm of 700 K, in order to characterize the percolation transition in the system. It is found that the percolation transition occurs at a somewhat higher density than what is corresponding to the supercritical extension of the boiling line. We have shown that the fractal dimension of the largest cluster and the probability of finding a spanning cluster are the most appropriate properties for the location of the true percolation threshold. Thus, percolation transition occurs when the fractal dimension of the largest cluster reaches 2.53, and the probability of finding a cluster that spans the system in at least one dimension and in all the three dimensions reaches 0.97 and 0.65, respectively. On the other hand, the percolation threshold cannot be accurately located through the cluster size distribution, as it is distorted by appearance of clusters crossing the finite simulated system even far below the percolation threshold. The structure of the largest water cluster is dominated by a linear, chainlike arrangement, which does not change noticeably until the largest cluster becomes infinite.     

Monte Carlo simulation of mixed lennard-jones nonionic surfactant adsorption at the liquid/vapor interface

New Monte Carlo simulations are presented for nonionic surfactant adsorption at the liquid/vapor interface of a monatomic solvent specifically investigating the roles of tail attraction and binary mixtures of different tail lengths. Surfactant molecules consist of an amphiphilic chain with a solvophilic head and a solvophobic tail. All molecules in the system, solvent and surfactant, are characterized by the Lennard-Jones (LJ) potential. Adjacent atoms along the surfactant chain are connected by finitely extensible harmonic springs. Solvent molecules move via the Metropolis random-walk algorithm, whereas surfactant molecules move according to the continuum configurational bias Monte Carlo (CBMC) method. We generate thermodynamic adsorption and surface-tension isotherms and compare results quantitatively to single-surfactant adsorption (Langmuir, 2007, 23, 1835). Surfactant tail groups with attractive interaction lead to cooperative adsorption at high surface coverage and higher maximum adsorption at the interface than those without. Moreover, adsorption and surface-tension isotherms with and without tail attraction are identical at low concentrations, deviating only near maximum coverage. Simulated binary mixtures of surfactants with differing lengths give intermediate behavior between that of the corresponding single-surfactant adsorption and surface-tension isotherms both with and without tail attraction. We successfully predict simulated mixture results with the thermodynamically consistent ideal adsorbed solution (IAS) theory for binary mixtures of unequal-sized surfactants using only the simulations from the single surfactants. Ultimately, we establish that a coarse-grained LJ surfactant system is useful for understanding actual surfactant systems when tail attraction is important and for unequal-sized mixtures of amphiphiles.     

Monte Carlo study of surfactant adsorption on heterogeneous solid surfaces

The equilibrium between free surfactant molecules in aqueous solution and adsorbed layers on structured solid surfaces is investigated by lattice Monte Carlo simulation. The solid surfaces are composed of hydrophilic and hydrophobic surface regions. The structures of the surfactant adsorbate above isolated surface domains and domains arranged in a checkerboard-like pattern are characterized. At the domain boundary, the adsorption layers display a different behavior for hydrophilic and hydrophobic surface domains. For the checkerboard-like surfaces, additional adsorption takes place at the boundaries between surface domains.     

A Monte Carlo study of water clusters

The free energy, internal energy and entropy for water clusters of 8 and 64 molecules have been calculated using the Monte Carlo method and both the Lie-Clementi (C-XII) and Stillinger (ST2) potential functions. Detailed structural data for a cluster of 64 water molecules was also obtained by averaging over a large number of configurations. Average dipole orientations and radial density distributions indicated that individual water molecules were not particularly restricted to fixed orientations and that general ordering tendencies were small.     

Coagulation of nanoparticles in reverse micellar systems: a Monte Carlo model

The process of formation of nanoparticles obtained by mixing two micellized, aqueous solutions has been simulated using the Monte Carlo technique. The model includes the phenomena of finite nucleation, growth via intermicellar exchange, and coagulation of nanoparticles after their formation. Using the model, an exploratory study has been conducted to analyze whether the coagulation of nanoparticles is the reason for the formation of nanoparticles whose sizes are comparable to the size of the reverse micelles. The model explains the possible mechanism of coagulation of semiconductor nanoparticles formed within reverse micelles and its effect on the evolution of their size with time. The model is predictive in nature, and the simulation results compare well with those observed experimentally.     

Structure of the nonionic surfactant triethoxy monooctylether C8E3 adsorbed at the free water surface, as seen from surface tension measurements and Monte Carlo simulations

The adsorption layer of the nonionic surfactant triethoxy monooctylether C8E3 has been investigated at the free water surface by means of both experimental and computer simulation methods. The surface tension of the aqueous solution of C8E3 has been measured by pendant drop shape analysis in the entire concentration range in which C8E3 is soluble in water. The data obtained from these measurements are used to derive the adsorption isotherm. The critical micellar concentration and the surface excess concentration of the saturated adsorption layer are found to be 7.48 mM and 4.03 micromol/m2, respectively, the latter value corresponding to the average area per molecule of 41 A2. In order to analyze the molecular level structure of the unsaturated adsorption layer, Monte Carlo simulations have been performed at four different surface concentration values, i.e., 0.68, 1.36, 2.04, and 2.72 micromol/m2, respectively. It has been found that the water surface is already almost fully covered at the lowest surface density value investigated, and the adsorbed molecules show a strong preference for lying parallel with the interface in elongated conformations. No sign of the penetration of the hydrophilic triethoxy headgroups into the aqueous phase to any extent has been observed. With increasing surface densities the preferential orientation of the apolar octyl tails gradually turns from lying parallel with the interface to pointing toward the vapor phase by their CH3 end, whereas the conformation of the adsorbed molecules becomes gradually less elongated. Both of these changes lead to the increase of the number of C8E3 molecules being in a direct contact (i.e., forming hydrogen bonds) with water. However, the increasing number of the C8E3 molecules hydrogen bonded to water is found to be accompanied by the weakening of this binding, i.e., the decrease of both the number of hydrogen bonds a bound C8E3 molecule forms with water and the magnitude of the average binding energy of the adsorbed C8E3 molecules.     

Mixed micellization of gemini surfactant with nonionic surfactant in aqueous media: a fluorometric study

Herein we report on the study of the interactions between alkanediyl-α,ω-type cationic dimeric (gemini) surfactant and the nonionic Triton X-100 in aqueous medium. The critical micelle concentrations of binary mixtures were determined by fluorometric study. Using the regular solution theory for the analysis of the experimental data, the attractive nature of interactions and synergistic behavior of gemini surfactant and Triton X-100 mixture were demonstrated. The micelle aggregation number was measured using steady state fluorescence quenching method. The micropolarity, binding constant and dielectric constant of mixed systems were determined from the ratio of peak’s intensity (I ₁/I ₃) in the pyrene fluorescence emission spectrum.     

Modeling the structure of amorphous MoS3: a neutron diffraction and reverse Monte Carlo study

A model for the structure of amorphous molybdenum trisulfide, a-MoS3, has been created using reverse Monte Carlo methods. This model, which consists of chains of MoS6 units sharing three sulfurs with each of its two neighbors and forming alternate long, nonbonded, and short, bonded, Mo-Mo separations, is a good fit to the neutron diffraction data and is chemically and physically realistic. The paper identifies the limitations of previous models based on Mo3 triangular clusters in accounting for the available experimental data.     

Spectrophotometric determination of cloud point of Brij 35 nonionic surfactant

The cloud point of nonionic surfactant polyoxyethylene (23) lauryl ether (Brij-35) was determined in the presence of various inorganic electrolytes. The measurements of cloud point (CP) were carried out with UV-vis spectrophotometer instead of visual observation. CP of Brij-35 could not be measured directly because its CP is more than 100 °C. Therefore, CP values of Brij-35 were lowered by the addition of electrolytes. In this study, NaF, NaCl, NaBr, KNO₃, K₂CO₃, K₃PO₄, Li₂SO₄, Na₂SO₄, K₂SO₄, (NH₄)₂SO₄, CuSO₄, ZnSO₄, CoSO₄ were used as electrolytes. Linear lines which were drawn with CP values were extrapolated to zero electrolyte concentration. The real CP value of Brij-35 which is merely listed as >100 °C in the literature was found as 118.5 ± 0.5 °C for all samples. Furthermore, the effects of the nature of the cation and the anion and the valencies of the cations on CP were reported and the rate of decrease in CP with concentration is discussed.     

Effect of surfactant conformation on the structures of small size nonionic reverse micelles: a molecular dynamics simulation study

We used constant pressure (P=0.1 MPa) and temperature (T=298 K) molecular dynamics simulations to study the structures and dynamics of small size reverse micelles (RMs) with poly(ethylene glycol) alkyl ether (CmEn) surfactants. The water-to-surfactant molar ratio was 3, with decane as the apolar solvent. We focused on the effect of the two possible imposed conformations (trans vs gauche) for the surfactant headgroups on RMs structures and water dynamics. For this purpose, we built up two RMs, which only differ by their surfactant headgroup conformations. The results obtained for the two RMs were compared to what is known in the literature. Here, we show that the surfactant headgroup conformation affects mainly the water-related properties such as the water core size, the area per surfactant headgroup, the headgroup hydration, and the water core translational diffusion. The properties computed for the RM with the surfactant in trans conformation fit better with the experimental data than the gauche conformation. We further show that the surfactant hydrophilic headgroup plays a crucial role in the micellar structures, favors the entrapment of the micellar water, and reduces strongly their diffusion compared to the bulk water.     

Condensation phenomena in nanopores: a Monte Carlo study

The nonequilibrium dynamics of condensation phenomena in nanopores is studied via Monte Carlo simulations of a lattice-gas model. Hysteretic behavior of the particle density as a function of the density of a reservoir is obtained for various pore geometries in two and three dimensions. The shape of the hysteresis loops depend on the characteristics of the pore geometry. The evaporation of particles from a pore can be fitted to a stretched exponential decay of the particle density. Phase-separation dynamics inside the pore is effectively described by a random walk of the non-wetting phases. Domain evolution is significantly slowed down in the presence of a random wall-particle potential and gives rise to a temperature-dependent growth exponent. A geometric roughness of the pore wall only delays the onset of a pure domain growth.     

Structure and dynamics of water in nonionic reverse micelles: A combined time-resolved infrared and small angle x-ray scattering study

We study the structure and reorientation dynamics of nanometer-sized water droplets inside nonionic reverse micelles (water/Igepal-CO-520/cyclohexane) with time-resolved mid-infrared pump-probe spectroscopy and small angle x-ray scattering. In the time-resolved experiments, we probe the vibrational and orientational dynamics of the O-D bonds of dilute HDO:H(2)O mixtures in Igepal reverse micelles as a function of temperature and micelle size. We find that even small micelles contain a large fraction of water that reorients at the same rate as water in the bulk, which indicates that the polyethylene oxide chains of the surfactant do not penetrate into the water volume. We also observe that the confinement affects the reorientation dynamics of only the first hydration layer. From the temperature dependent surface-water dynamics, we estimate an activation enthalpy for reorientation of 45 ± 9 kJ mol(-1) (11?±?2 kcal mol(-1)), which is close to the activation energy of the reorientation of water molecules in ice.     

Hexagonal close packing of nonionic surfactant micelles in water

The knowledge of the exact shapes of micelles in various micellar phases found in both lyotropic and thermotropic liquid crystals is very important to our understanding of the underlying principles of molecular self-assembly. In the current paper we present a detailed structural study of the hexagonal close packed (hcp, space group P63/mmc) micellar phase, observed in the binary mixtures of nonionic surfactant C12EO8 and water. The reconstructed electron density map of the phase shows perfectly spherical micelles. A spherical core/shell model of micelles, which fits the observed X-ray diffraction pattern satisfactorily, is subsequently constructed. The results confirm the previous assumption that the hcp phase consists of spherical close contacting micelles, each of which contains a low-density core of aliphatic parts and a high-density shell of hydrated ethylene oxide segments, with the gaps between the micelles filled by pure water.     

Hydrogen storage in sH hydrates: a Monte Carlo study

Grand canonical Monte Carlo simulations are performed to evaluate the hydrogen-storage capacity of the recently discovered hydrogen hydrates of the sH type, at 274 K and up to 500 MPa. First, the pure H2 hydrate is investigated in order to determine the upper limit of H 2 content in sH hydrates. It is found that the storage capacity of the hypothetical pure H2 hydrate could reach 3.6 wt % at 500 MPa. Depending on pressure, the large cavity of this hydrate can accommodate up to eight H2 molecules, while the small and medium ones are singly occupied even at pressures as high as 500 MPa. Next, the binary H2-methylcyclohexane sH hydrate is examined. In this case, the small and medium cavities are again singly occupied, resulting in a maximum H2 uptake of 1.4 wt %. Finally, the results from simulations on pure H2 and binary hydrates are utilized to investigate the potential of H2 storage in sH hydrates where the promoter molecules occupy the medium instead of the large cavities.     

Pressure-induced ordering in adamantane: a Monte Carlo simulation study

Isothermal-isobaric ensemble Monte Carlo simulation of adamantane has been carried out with a variable shape simulation cell. The low-temperature crystalline phase and the room-temperature plastic crystalline phases have been studied employing the modified Williams potential. We show that at room temperature, the plastic crystalline phase transforms to the crystalline phase on increase in pressure. Further, we show that this is the same phase as the low-temperature ordered tetragonal phase of adamantane. The high-pressure ordered phase appears to be characterized by a slightly larger shift of the first peak toward a lower value of r in C-C, C-H, and H-H radial distribution functions as compared to the low-temperature tetragonal phase. The coexistence curve between the crystalline and plastic crystalline phase has been obtained approximately up to a pressure of 4 GPa.     

Polymer chains in a soft nanotube: a Monte Carlo study

We study the equilibrium properties of flexible polymer chains confined in a soft tube by means of extensive Monte Carlo simulations. The tube wall is that of a single sheet six-coordinated self-avoiding tethered membrane. Our study assumes that there is no adsorption of the chain on the wall. By varying the length N of the polymer and the tube diameter D we examine the variation of the polymer gyration radius Rg and diffusion coefficient Ddiff in soft and rigid tubes of identical diameter and compare them to scaling theory predictions. We find that the swollen region of the soft tube surrounding the chain exhibits a cigarlike cylindrical shape for sufficiently narrow tubes with D相似文献   

Activity coefficient of monomer in different aggregates of a surfactant solution: a Lattice Monte Carlo Study

In this paper, canonical lattice Monte Carlo simulation technique is used to derive cluster size distribution of a surfactant solution, by which activity coefficient of a monomer in solution and in the micellar phase is estimated. To do this, correlation of cluster concentration with the aggregation number is needed. The multiple equilibrium method is used to relate cluster size distribution to the activity coefficient. The introduced idea is not only applicable to the lattice model techniques, but also to any method that can produce cluster size distribution. The method can be used as a reference to test activity coefficient data of lattice-based equations of state. Results show that the activity coefficients of monomers in micellar aggregates are much greater than unity, in accordance with the experimental results.     

Aminolysis ofO-alkylO-4-nitropyenyl chloromethylphosphonates in reverse micellar solutions of the nonionic surfactant

The reaction ofn-hexylamine withO-alkylO-4-nitrophenyl chloromethylphosphonates in toluene solutions of poly(ethylene glycol)-600 monolaurate (PM) has been studied by spectrophotometry. The reverse micelles of the nonionic surfactant increase more than tenfold the observed rate constant of aminolysis. The catalytic activity of the surfactant is practically independent of the alkyl radical length of phosphonate. An increase in the concentration of amine results in a decrease in the catalytic efficiency. The character of the dependence of the rate constant on the concentration of PM is affected by the alkyl chain length of the substrate. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1735–1738, September, 1998.     

Interfacial properties of cyclic hydrocarbons: a Monte Carlo study

The Monte Carlo technique is used to study the vapor-liquid interface of cyclopentane, cyclohexane, and benzene. The OPLS and TraPPE potential fields are compared in the temperature range from 298.15 to 348.15 K (273.15-298.15 K for C5H10). A new method for the treatment of the long-range interactions in inhomogeneous simulations is used. When this new method is employed, the obtained values of saturated liquid density and of enthalpy of vaporization are equal to those obtained using the bulk isothermal-isobaric Monte Carlo technique. The values of surface tension become independent of the cutoff distance and they are significantly larger than those when only simple spherical truncation of intermolecular interactions is used.