Influence of Light Scattering by Residual Alumina Nanoparticles on the Analysis of Surfactants Adsorption Using Spectroscopy

The adsorption of a surfactant mixture, based on an anionic surfactant, sodium dodecyl benzenesulfonate (SDBS) and a nonionic surfactant (Triton X-100, or TX100), on alumina nanoparticles was determined by solution depletion method combined with spectrometric measurement. It is shown that the light scattering, originated from the residual adsorbent alumina particles in the supernatant after centrifugation separation, interferes with the measurements of absorbance of the surfactant molecules, and therefore constitutes an error source for determination of the surfactant concentration in the supernatant by spectrometric means. The intensity of this light scattering, namely the influence of the residual alumina nanoparticles upon the surfactant adsorption, was related to the surfactant adsorption and its equilibrium concentration and varied among a batch. In this paper we report a Kalman filter method in order to eliminate the variational scattering background caused by non-separated residual alumina nanoparticles in each supernatant. This method is of interest as it is simple, easy to carry out and of high precision.     

Creeping motion of an assemblage of composite spheres relative to a fluid

The sedimentation of a homogeneous distribution of spherical composite particles and the fluid flow through a bed of these particles are investigated theoretically. Each composite particle is composed of a spherical solid core and a surrounding porous shell. In the fluid-permeable porous shell, idealized hydrodynamic frictional segments are assumed to distribute uniformly. The effect of interactions among the particles is taken into explicit account by employing a fundamental cell-model representation which is known to provide good predictions for the motion of a swarm of nonporous spheres within a fluid. In the limit of a small Reynolds number, the Stokes and Brinkman equations are solved for the flow field in a unit cell, and the drag force exerted by the fluid on the particle is obtained in a closed form. For a distribution of composite spheres, the normalized mobility of the particles decreases or the particle interactions increase monotonically with a decrease in the permeability of their porous shells. The effect of particle interactions on the creeping motion of composite spheres relative to a fluid can be quite significant in some situations. In the limiting cases, the analytical solutions describing the drag force or mobility for a suspension of composite spheres reduce to those for suspensions of solid spheres and of porous spheres. The hydrodynamic behavior for composite spheres may be approximated by that for permeable spheres when the porous layer is sufficiently thick, depending on the permeability.     

Application of algebraic method to the high overtones of C6H6 and C6D6

Both the spectra and infrared transition strengths of C₆H₆ and C₆D₆ for the C? H stretching overtones up to as high as v = 10 are described in high precision with few parameters (six for the spectra and four for the transition strengths) by the Iachello–Oss algebraic model. The Hamiltonian model is solved in the symmetry adapted bases, which are constructed by the symmetrized boson representation (SBR) technique. The results show that the combination of the algebraic method and SBR technique is a powerful method for describing vibrations of large molecules and high overtones. © 2004 Wiley Periodicals, Inc. Int J Quantum Chem, 2005     

Surface properties of the binary mixed systems of alkylpyridinium halides and sodium alkylsulfonates

Surface properties of the binary mixed systems of decyl- and dodecylpyridinium chloride or bromide and sodium pentyl- and heptylsulfonate have been investigated. The surface tension of solutions of equimolar mixtures of surfactants and individual surfactants was measured, and the composition of mixed monolayers and surface interaction parameter β were calculated with the regular solution theory. Our results indicate that the properties of mixed films depend on both ionic strength and the kind of added inorganic electrolyte. With the increase of inorganic electrolyte concentration, the content of more surface active ions in the adsorption films enhances and is the highest in the presence of NaI and the smallest when solutions contain NaCl. Mutual interactions in mixed adsorbed films were found to be attractive. However, the strength of interaction weakens with the increase of ionic strength and depends on the kind of inorganic ions in the order: Cl⁻>Br⁻>I⁻.     

Freezing of Lennard-Jones fluid in cylindrical nanopores under tensile conditions

We have shown the Lennard-Jones (LJ) phase diagram for a slit-shaped nanopore by molecular simulations and thermodynamically predicted the results with no adjustable parameter. With this success, LJ phase diagrams are predictable. In this study, the freezing of an LJ CH₄ capillary condensate under a tensile condition in a nonstructural carbon nanopore with a cylindrical geometry was examined using molecular dynamics (MD) simulation. We employ a unit cell in contact with a bulk vapor phase, which is useful for the determination of the bulk vapor pressure in equilibrium with the molecules in a pore. The MD simulation results show liquid-solid (amorphous) phase transitions with a variation in the bulk vapor pressure. The frozen particles are arranged in concentric circular regions along the wall similar to those reported by Maddox and Gubbins. The freezing points are determined from the variations in density, enthalpy, arrangement, and structural functions. The obtained liquid-solid coexistence points are found to exhibit a significant dependence of the freezing point on the equilibrium bulk vapor pressure, forming an extraordinarily skewed curve on the p-T diagram, in contrast to the bulk phase coexistence that is represented by an almost vertical line. The origin of the significant dependence is considered to be the Laplace effect on the capillary condensate similar to the case with a slit-shaped pore. A simple model, which the authors earlier presented for slit-shaped nanopores, successfully predicted the p-T relation of the freezing point for cylindrical nanopores as well.     

Multiple steady states in a CSTR with total condenser: Comparison of equilibrium and nonequilibrium models

Comparison of equilibrium and nonequilibrium models of a CSTR with total condenser focused on the multiple steady states and dynamic behaviour was carried out. The steady-state behaviour of the model system, MTBE synthesis from methanol and isobutene in a reactive distillation column, was studied in terms of the input parameters, i. e. feed flow rate of methanol or butenes, reflux ratio, and mass of catalyst. The dynamic behaviour of the system during the start-up was investigated and perturbations of manipulated variables were found to cause transitions between the parallel steady states. Presented at the 33rd International Conference of the Slovak Society of Chemical Engineering, Tatranské Matliare, 22–26 May 2006.     

Indirect detection in reversed-phase liquid chromatography: Ion-pair retention models for cations on polystyrene polymers

Summary The distribution equilibria of cationic compounds in reversed-phase chromatographic systems (ion-pair chromatography) have been studied on the basis of their effect on a detectable mobile phase component. The solid phase was a polystyrene-divinylbenzene copolymer and the detectable component, a quaternary ammonium ion, 1-methylpyridine. The solutes were mono- and divalent amines and quaternary ammonium ions. The cations can be retained by ion-pair adsorption and ion exchange. Expressions for the ion-pair retention of the solutes and the mobile phase cation (system peak) have been developed assuming Langmuir distribution of ion pairs to a solid phase with one kind of binding site. The validity of the expressions has been tested by evaluation of ion-pair distribution constants using non-linear curve fitting techniques. Good agreement for the constants of common ion pairs was obtained from different kinds of capacity ratio expressions. Ion exchange retention can appear beside ion-pair retention, and it has been observed in the pH range 1.6–6.1. The effect depends not only on cations in the mobile phase, but also on the nature of the buffering systems.     

The thermorheological complexity of photoelastic behaviour of 2-hydroxyethyl methacrylate — dodecyl methacrylate copolymers

The viscoelastic photoelastic behaviour of networks of 2-hydroxyethyl methacrylate — dodecyl methacrylate (DMA) copolymers in the main transition and rubberlike region was investigated. With increasing DMA content, photoelastic functions are quickly shifted to lower temperatures or shorter times; a detailed course of the functions suggests heterogeneity of the copolymers. Due to the existence of long side chains, optical function of all samples change the sign from positive to negative with increasing temperature. While the temperature dependences of the moduli of copolymers can be described by the two-phase Takayanagi model, the temperature dependences of optical functions cannot be described by using this model. It has been found, however, that the tempeature and time dependences of photoelastic functions can be described semiquantitatively by a three-phase model with a hypothetical statistical copolymer as the third component. The high values of the volume fraction of the hypothetical statistical copolymer found for the individual samples, suggest a considerable miscibility and a strong influence of the interphase boundary on the photoelastic behaviour of the copolymers.     

Hydrogen-induced metal-oxide interaction studied on noble metal model catalysts

Summary The effect of hydrogen reduction on the structure and catalytic properties of “thin film”and “inverse”model systems for supported metal catalysts is discussed. Thin film model catalysts were obtained by epitaxial growth of Pt and Rh nanoparticles on NaCl(001), which were coated with amorphous or crystalline supports of alumina, silica, titania, ceria and vanadia. Structural and morphological changes upon hydrogen reduction between 473 and 973 K were examined by high resolution electron microscopy. Metal-oxide interaction sets in at a specific reduction temperature and is characterized by an initial “wetting”stage, followed by alloy formation at increasing temperature, in the order VO_x< TiO_x< SiO₂< CeO_x< Al₂O₃. “Inverse”model systems were prepared by deposition of oxides on a metal substrate, e.g. VO_x/Rh and VO_x/Pd. Reduction of inverse systems at elevated temperature induces subsurface alloy formation. In contrast to common bimetallic surfaces, the stable subsurface alloys of V/Rh and V/Pd have a purely noble metal-terminated surface, with V positioned in near-surface layers. The uniform composition of the metallic surface layer excludes catalytic ensemble effects in favor of ligand effects. Activity and selectivity, e.g. for CO and CO₂methanation and for partial oxidation of ethene, are mainly controlled by the temperature of annealing or reduction. Reduction above 573 K turned out to be beneficial for the catalytic activity of the subsurface alloys, but not for the corresponding thin film systems which tend to deactivate viaparticle encapsulation.</o:p>