A simple derivation of Vonnegut's equation for the determination of interfacial tension by the spinning drop technique

A simple derivation of Vonnegut's equation for use in the determination of interfacial tension by the spinning drop technique is described. The derivation involves a cylindrical approximation and calculates the kinetic energy of rotation of the system from a consideration of its moment of inertia.     

Coalescence of droplets in viscoelastic matrix with diffuse interface under simple shear flow

The coalescence process of two droplets in simple shear flow was modeled and simulated by the diffuse interface method. The collision between two droplets was investigated. The systems with small Peclet number, which denotes highly diffuse ability of concentration, were found to coalesce faster and easier due to the overlap of interfacial layers. The effect of matrix elasticity on droplet coalescence was studied thoroughly. The matrix elasticity was found to decrease the hydrodynamic interactions between droplets, and delay the coalescence process. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1856–1869, 2007     

A simple apparatus for the determination of mercury by amalgamation with gold

The method of Eschka for the determination of mercury by amalgamating with gold has been modified by using a simple apparatus which eliminates errors caused by loss of mercury vapour. The method does not require a skilled operator and it is suitable for routine analysis. For a sample containing 3% mercury, the estimated standard deviation is 0.06.     

Phase behavior of a simple dipolar fluid under shear flow in an electric field

Nonequilibrium molecular dynamics simulations are performed on a dense simple dipolar fluid under a planar Couette shear flow. Shear generates heat, which is removed by thermostatting terms added to the equations of motion of the fluid particles. The spatial structure of simple fluids at high shear rates is known to depend strongly on the thermostatting mechanism chosen. Kinetic thermostats are either biased or unbiased: biased thermostats neglect the existence of secondary flows that appear at high shear rates superimposed upon the linear velocity profile of the fluid. Simulations that employ a biased thermostat produce a string phase where particles align in strings with hexagonal symmetry along the direction of the flow. This phase is known to be a simulation artifact of biased thermostatting, and has not been observed by experiments on colloidal suspensions under shear flow. In this paper, we investigate the possibility of using a suitably directed electric field, which is coupled to the dipole moments of the fluid particles, to stabilize the string phase. We explore several thermostatting mechanisms where either the kinetic or configurational fluid degrees of freedom are thermostated. Some of these mechanisms do not yield a string phase, but rather a shear-thickening phase; in this case, we find the influence of the dipolar interactions and external field on the packing structure, and in turn their influence on the shear viscosity at the onset of this shear-thickening regime.     

Precise and sensitive determination of nitrite by coulometric backtitration under flow conditions

A novel method performing for coulometric backtitrations in flow channels was developed, which was applied for the precise and sensitive determination of low concentrations of nitrite. Under acid conditions nitrite is reacting stoichiometrically with hydrazine, the remained excess of which is backtitrated with electrogenerated bromine. The titration course is recorded either amperometrically or chemiluminometrically. Hydrazine can be determined precisely and accurately in the range between 0.1 microM and 1 mM without calibration. Nitrite is reduced by hydrazine according to the reaction 2 NO2- + 2 H+ + NH2-NH2 --> N2O + N2 + 3 H2O. Applying the amperometric and the chemiluminometric end-point location nitrite was determined accurately and precisely in the ranges 0.25-65 microM and 0.10-50 microM, respectively. The method was applied to the determination of nitrite in tap and river water.     

Precise and sensitive determination of nitrite by coulometric backtitration under flow conditions

A novel method performing for coulometric backtitrations in flow channels was developed, which ¶was applied for the precise and sensitive determination of low concentrations of nitrite. Under acid conditions nitrite is reacting stoichiometrically with hydrazine, the remained excess of which is backtitrated with electrogenerated bromine. The titration course is recorded either amperometrically or chemiluminometrically. Hydrazine can be determined precisely and accurately in the range between 0.1 μM and 1 mM without calibration. Nitrite is reduced by hydrazine according to the reaction 2 NO₂ ^– + 2 H⁺ + NH₂-NH₂→N₂O + N₂ + 3 H₂O. Applying the amperometric and the chemiluminometric end-point location nitrite was determined accurately and precisely in the ranges 0.25–65 μM and 0.10–50 μM, respectively. The method was applied to the determination of nitrite in tap and river water.     

Determination of interfacial tension from crystallization and dissolution data: a comparison with other methods

Methods for the determination of interfacial tension between a solid and a liquid are reviewed including solubility/particle size, crystallization and dissolution kinetics. The use of solubility as a function of particle size, originally put forward by Ostwald and later corrected by Freundlich, may be unjustified for determining interfacial tension at solid-liquid interfaces. The interfacial tension values between solutions and sparingly soluble minerals such as hydroxyapatite, fluorapatite, brushite, octacalcium phosphate, calcium oxalate monohydrate, barium sulfate, calcium sulfate, calcite, and divalent metal fluorides are discussed. A comparison of these results is made with contact angle or wetting measurements. The interfacial tension values obtained from constant composition reaction kinetics are of the same order of magnitude as those determined using a contact angle method involving thin layer wicking techniques.     

Experimental and theoretical investigation of simple gas hydrate formation with or without presence of kinetic inhibitors in a flow mini-loop apparatus

Gas hydrates are ice-like crystalline compounds, which form through a combination of water and suitably sized guest molecules under low temperature and elevated pressure conditions. These solid compounds give rise to problems in the natural gas oil industry because they can plug pipelines and process equipment. Low dosage hydrate inhibitors are a recently developed hydrate control technology, which can be more cost-effective than traditional practices such as methanol and glycols. The kinetics of hydrate growth has been modeled by numerous authors who have measured the gas consumption rate during hydrate formation in batch agitator reactors.     

Anisotropic and enhanced self-diffusion of a macromolecular chain under simple shear flow as revealed by Monte Carlo simulation on lattices

Two-dimensional simple shear flow of a self-avoiding macromolecular chain is simulated by a lattice Monte Carlo (MC) method with a pseudo-potential describing the flow field. The simulated velocity profile satisfies the requirements of simple shear flow unless the shear rate is unreasonably high. Some diffusion problems for a free-draining bead-spring chain with excluded volume interaction are then investigated at low and relatively high shear rates. Three diffusion coefficients are defined and examined in this paper: the conventional self-diffusivity in zero field, D_self, the apparent self-diffusivity in flow field, D_app, and the flow diffusivity in simulation, D_flow reflecting actually the transport coefficient. It is found that these three diffusivities for a flexible chain are different from each other. What is more important is that self-diffusion exhibits a high anisotropy in the flow field. The apparent self-diffusion along the flow direction is enhanced to a large extent. It is increased monotonically with the increase of shear time or shear strain, whereas the chain configuration can achieve a stationary anisotropic distribution following an interesting overshoot of the coil shape and size. Besides a single self-avoiding chain, an isolated Brownian bead and a group of self-avoiding beads with a quasi-Gaussian spatial distribution are also simulated. According to the comparison, the effects of the connectivity of the chain on the diffusion behavior are revealed. Some scaling relations of D_app versus t are consistent with the theoretical analyses in the pertinent literature.     

Experimental study on dynamic interfacial tension with mixture of SDS-PEG as surfactants in a coflowing microfluidic device

In this work, a coflowing microfluidic device was used to determine the influence of different mixed sodium dodecyl sulfate (SDS)-poly(ethylene glycol) (PEG) compound systems on dynamic interfacial tension and, by extension, corresponding emulsion droplet sizes. The aqueous solutions were used as the continuous phase in the microfluidic device, while octane was used as the organic dispersed phase. Combined SDS-PEG systems lower the interfacial tension more than either component can alone up to the critical aggregation concentration (CAC) of SDS. Octane droplet sizes produced in the microfluidic device using combined SDS-PEG systems were smaller than those produced using SDS alone, and a reduction in dynamic interfacial tension as determined by drop size followed a pattern similar to that observed in the static case (PEG4000 > PEG600 > PEG400 > PEG200 > PEG8000) with the exception of PEG8000. Finally, a previously formulated model relating interfacial tension to droplet size was used to estimate the dynamic interfacial tensions in the microfluidic device.     

Reactions of terminal acetylenes with aryl iodides catalyzed by palladium complexes under interfacial conditions

Conclusions It was shown that in reactions of aryl iodides with terminal acetylenes catalyzed by palladium complexes, potash or alkali can be used as a base in the interfacial system.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 604–606, March, 1988.     

On the behavior of an oblate spheroidal hematite particle in a simple shear flow under a uniform magnetic field applied in the flow direction

We discuss the orientational properties of an oblate spheroidal hematite particle and also its influence on the rheological characteristics of a dilute suspension of these magnetic particles, by means of an analytical approach based on the orientational distribution function. A hematite particle with oblate spheroidal shape has an important characteristic; that is, it is magnetized in a direction normal to the particle axis. From the balance of the torques acting on a particle, we have developed the basic equation of the orientational distribution function. This basic equation has been numerically solved in order to investigate the dependence of the orientational distribution on the various factors. If both the magnetic field and the shear flow are weak, the particle does not exhibit specific directional characteristics. If the magnetic field is more dominant, the particle inclines such that the oblate surface is parallel to the magnetic field direction. If the shear flow becomes more dominant, the particle shows a sharper peak of the orientational distribution in the shear flow direction. The viscosity due to the magnetic torque increases and finally converges to a constant value as the magnetic field increases. In a sedimentation process under the gravitational field, the translational diffusion coefficient decreases with increasing magnetic field strength in the present case of the magnetic field direction.     

Chemorheological analysis of a gelled resol resin curing under non-isothermal conditions by shear strain

The chemorheological behavior of curing of a resol resin was analyzed under non-isothermal conditions beyond the gelation point. Two heating ramps (0.5 and 1 °C/min) from 0 to 100 °C were performed. The rheological measurements of the resin were performed using oscillatory shear strain. The obtained profiles for the resin’s complex viscosity were applied, after treatment by two calculation methods, to the four- and six-parameter Arrhenius models. These models allow one to establish the viscous flow region of the resin and the kinetic parameters of the material’s curing process. The six-parameter Arrhenius model was selected as the best method for modeling of the resin’s rheological behavior during its curing process. The viscous-flow activation energies determined for the gelled resol resin curing were 67.1 and 58.3 kJ/mol for the 0.5 and 1 °C/min heating rates, respectively. The activation energies of the resin curing process were 41.7 and 67.0 kJ/mol for each temperature ramp.     

Transport coefficients and orientational distributions of rodlike particles with magnetic moment normal to the particle axis under circumstances of a simple shear flow

We have investigated the influences of the magnetic field strength, shear rate, and random forces on transport coefficients such as viscosity and diffusion coefficient, and also on the orientational distributions of rodlike particles of a dilute colloidal dispersion. This dispersion is composed of ferromagnetic spheroidal particles with a magnetic moment normal to the particle axis. In the present analysis, these spheroidal particles are assumed to conduct the rotational Brownian motion in a simple shear flow as well as an external magnetic field. The basic equation of the orientational distribution function has been derived from the balance of the torques and solved numerically. The results obtained here are summarized as follows. For a very strong magnetic field, the rodlike particle is significantly restricted in the field direction, so that the particle points to a direction normal to the flow direction (and also to the magnetic field direction). However, the present particle does not exhibit a strong directional characteristic, which is one of the typical properties for the previous particle with a magnetic moment parallel to the particle axis. That is, the particle can rotate around the axis of the magnetic moment, although the magnetic moment nearly points to the field direction. The viscosity significantly increases with the field strength, as in the previous particle model. The particle of a larger aspect ratio leads to the larger increase in the viscosity, since such elongated particles induce larger resistance in a flow field. The diffusion coefficient under circumstances of an applied magnetic field is in reasonable agreement between theoretical and experimental results.     

Simultaneous determination of ethanol and glycerol in wines by a flow injection-pervaporation approach with in parallel photometric and fluorimetric detection

A simultaneous method for the determination of ethanol and glycerol in wines based on the coupling of pervaporation-chemical derivatisation-photometric detection for ethanol and biochemical derivatisation-fluorimetric detection for glycerol is proposed. After separation by pervaporation the ethanol is collected in a K(2)Cr(2)O(7) acceptor stream and the Cr(3+) formed is driven to the spectrophotometer and monitored at 600 nm. The determination of glycerol is based on its oxidation by oxidised beta-nicotinamide adenine dinucleotide (beta-NAD(+)) catalysed by glycerol dehydrogenase immobilised on controlled-pore glass, the reduced form of the coenzyme (NADH) being spectrofluorimetrically monitored (lambda(ex)=340 nm, lambda(em)=460 nm). The linear determination range is between 1-20% for ethanol and 2-8 g l(-1) for glycerol, with RSDs 3 and 2%, respectively. The method applied to red and white Spanish wines, compares well with the official methods for these analytes.     

Matrix effects on the determination of manganese in geological materials by atomic-absorption spectrophotometry under different flame conditions

Suppression caused by five of the seven matrix elements studied (Si, Al, Fe, Ca and Mg) was observed in the atomic-absorption determination of manganese in geological materials, when synthetic solutions and the recommended oxidizing air-acetylene flame were used. The magnitude of the suppression effects depends on (1) the kind and concentration of the interfering elements, (2) the type of acid medium, and (3) the concentration of manganese to be determined. All interferences noted are removed or alleviated by using a reducing nitrous oxide-acetylene flame. The atomic-absorption method using this flame can be applied to the determination of total and extractable manganese in a wide range of geological materials without interferences. Analyses of six U.S. Geological Survey rock standards for manganese gave results in agreement with the reported values.     

Occurrence of spontaneous resolution of ketoprofen with a racemic crystal structure by simple crystallization under nonequilibrium preferential enrichment conditions

Nearly racemic ketoprofen, which satisfies the requirements for the occurrence of preferential enrichment, was spontaneously resolved into the two enantiomers by simple crystallization under nonequilibrium conditions using high concentrations.     

Experimental analysis of floc size distributions in a 1-L jar under different hydrodynamics and physicochemical conditions

This study focuses on the relation among hydrodynamics, physicochemical conditions, and floc size. During ortho-kinetic flocculation, the floc size is controlled by a balance between hydrodynamic stress and aggregate strength. Special attention was paid to the influence of a hydrodynamic sequencing on both the aggregate strength and the flocculation processes. Experimental research was conducted in a 1-L jar for two different pH values. The hydrodynamic sequencing was made up of successive slow and rapid mixing periods, and different slow mixing intensities were studied. First, the large floc size was shown to decrease with increasing velocity gradient (G), with an expected trend (d proportional variant epsilon(-1/4)). Then, the aggregate strength was shown to depend on two main factors: the flocculation history and the physicochemical conditions, which control the cohesion forces between primary particles. Finally, flocculation processes are discussed in terms of aggregation and breakup phenomena, with relation to local hydrodynamics and physicochemical conditions.     

Epoxidation of olefins with a silica-supported peracid in supercritical carbon dioxide under flow conditions

Anhydrous 2-percarboxyethyl-functionalized silica (2b), a recyclable supported peracid, is a suitable reagent to perform the epoxidation of alkenes 1 in supercritical carbon dioxide at 250 bar and 40 °C under flow conditions. This procedure simplifies the isolation of the reaction products and uses only carbon dioxide as a solvent under mild conditions. The solid reagent 2b can be easily recycled by a reaction with 30% hydrogen peroxide in an acid medium.