Association of Formaldehyde in Aqueous-Alcoholic Systems

In the neutral systems formaldehyde-water-alcohol (methanol, ethanol, ethylene glycol) at 25°C, formaldehyde is preferentially present as hemiacetals. The mean equilibrium constants of step polycondensation of formaldehyde are calculated.     

Kinetic Aspects of Dimethylamine Hydroxyethylation in the Presence of Water

The kinetics of dimethylamine hydroxyethylation at an ethylene oxide : dimethylamine : water molar ratio of 1 : 3 : (0.1–0.5) was studied in the temperature range 20–50°C. A kinetic model of the reaction, which adequately describes the experimental data, was suggested.__________Translated from Zhurnal Prikladnoi Khimii, Vol. 78, No. 4, 2005, pp. 687–689.Original Russian Text Copyright © 2005 by Danov, Kolesnikov, Efremov, Mezhenin.     

Formation of Cyclic Oligomers in Concentrated Aqueous Solutions of Formaldehyde

An MNDO calculation gave the formation enthalpies of the components of equilibrium mixtures in concentrated aqueous acid solutions of formaldehyde. The results of this study suggest that intramolecular cyclization of linear oligomers with 5 and 9 CH₂O units, respectively, is the most plausible mechanism of formation of cyclic oligomers of formaldehyde — trioxane and tetraoxane. Ring protonation by the hydroxonium ion with ring opening is the most energetically favorable route of cyclic acetal decomposition.     

Kinetic relationships in synthesis of dimethoxymethane

The kinetics of formation of dimethoxymethane by acetalization of formaldehyde with methanol, catalyzed by silicotungstic heteropoly acid, were studied.Translated from Zhurnal Prikladnoi Khimii, Vol. 77, No. 12, 2004, pp. 2018–2020.Original Russian Text Copyright © 2004 by Danov, Kolesnikov, Logutov.     

Interactions between particles with an undulated contact line at a fluid interface: capillary multipoles of arbitrary order

A colloidal particle adsorbed at a fluid interface could have an undulated, or irregular contact line in the presence of surface roughness and/or chemical inhomogeneity. The contact-line undulations produce distortions in the surrounding liquid interface, whose overlap engenders capillary interaction between the particles. The convex and concave local deviations of the meniscus shape from planarity can be formally treated as positive and negative "capillary charges," which form "capillary multipoles." Here, we derive theoretical expressions for the interaction between two capillary multipoles of arbitrary order. Depending on the angle of mutual orientation, the interaction energy could exhibit a minimum, or it could represent a monotonic attraction. For undulation amplitudes larger than 5 nm, the interaction energy is typically much greater than the thermal energy kT. As a consequence, a monolayer from capillary multipoles exhibits considerable shear elasticity, and such monolayer is expected to behave as a two-dimensional elastic solid. These theoretical results could be helpful for the understanding of phenomena related to aggregation and ordering of particles adsorbed at a fluid interface, and for the interpretation of rheological properties of particulate monolayers. Related research fields are the particle-stabilized (Pickering) emulsions and the two-dimensional self-assembly of microscopic particles.     

On the Viscosity of Dilute Emulsions

The slow motion of a liquid droplet in a shear flow in the presence of surfactants is studied. The effects of the interfacial viscosity, Gibbs elasticity, surface diffusion and bulk diffusion of surfactants in both phases are taken into account. The analytical solution of the problem for small Reynolds and Peclet numbers gives a simple criterion for estimation of the tangential mobility of the droplet interface. By applying the standard procedure for averaging of the stress tensor flux at an arbitrary surface of the dilute emulsion, an analytical formula for the viscosity of emulsions in the presence of surfactants is derived. The result is a natural generalization of the well-known formula of Einstein for the viscosity of monodisperse dilute suspensions and of the expressions derived by Taylor and Oldroyd for the viscosity of monodisperse dilute emulsions taking into account the Marangoni effect. Copyright 2001 Academic Press.     

A Kinetic Model for the Epoxidation of Allyl Alcohol with Hydrogen Peroxide on Titanium Silicate TS-1

The kinetic regularities of the oxidation of allyl alcohol into glycidol in the presence of titanium silicate are studied at varied initial concentrations of the reagents, products, and temperature. The probable mechanism is used as the basis to develop a substantial kinetic model, which adequately describes the obtained experimental data.     

Slow motions of a solid spherical particle close to a viscous interface

In order to investigate the hydrodynamic interaction between an interface and a spherical particle and its dependence on the type of interface, it is essential to compute the drag and torque exerted on the sphere in the vicinity of the interface. In this paper, the problem of all slow elementary motions (relative translation and rotation) and stationary movement of a spherical particle next to a solid, viscous or free interface is considered. For low capillary numbers and different values of surface dilatational and shear viscosities in a curvilinear co-ordinate system of revolution with bicylindrical co-ordinates in meridian planes, the problem reduces from three to two dimensions. The model equations and boundary conditions, which contain second-order derivatives of the velocities, transform to an equivalent well-defined system of second-order partial differential equations which is solved numerically for medium and small values of the dimensionless distance to the interface. Very good agreement with the asymptotic equation for a translating sphere close to a solid interface could be achieved. The numerical results reveal in all cases the strong influence of the surface viscosity on the motion of the solid sphere. For small distances from the interface, the drag and torque coefficients change significantly depending on the surface viscosity.     

Kinetics of butanol-2 oxidation on titanium silicalite

Kinetics of butanol-2 oxidation by hydrogen peroxide on titanium silicalite was studied. The experimental data obtained were used to calculate parameters of the kinetic model suggested.     

Nonlinear waves on shallow water in the presence of a horizontal magnetic field

Benjamin [1] and Davis and Acrivos [2] derived an equation for long steady nonlinear internal waves in an infinitely deep stratified fluid when the density varies only in a layer whose thickness is small compared with the characteristic perturbation length. Ono [3] generalized this equation to the unsteady case. The resulting equation was subsequently called the Benjamin—Ono equation. Steady solutions of this equation were found by Benjamin and Ono in the form of solitons and periodic waves. In the present paper it is shown that long nonlinear waves on shallow water in the presence of a horizontal magnetic field can also be described by the Benjamin—Ono equation, and not the Korteweg—de Vries equation [4], as in the case when there is no field. Moreover, in contrast to a soliton in a stratified fluid a soliton on shallow water in a horizontal magnetic field moves with a velocity less than the velocity of infinitely long perturbations of small amplitude. The dependence of the parameters of a soliton and a periodic wave on the intensity and direction of the unperturbed magnetic field is investigated.