Influence of the mobility of the medium on the dynamics of metallotropy in tin-containing 2-(R-oxy)phenoxyls 3. Dynamics of nondegenerate tautomerism in viscous media

The influence of the mobility of the medium on the dynamics of the stannotropy of 3,5-di-tert-butyl-6-chloro-2-(chlorodimethylstannyloxy)phenoxyl, which is a nondegenerate tautomeric transformation, has been investigated. It has been shown that the rate of the forward and reverse reactions involving the intramolecular migration of the SnClMe₂ group in the radical decreases as the mobility of the medium is lowered, but the equilibrium constant does not vary in the range of accuracy of the measurements.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 368–370, February, 1991.     

Effect of the mobility of the medium on the metallotropy dynamics in tin 2-R-oxyphenoxyls. 2. Rotational mobility and the stannotropy dynamics of 3,6-di-tert-butyl-2-(chlorodimethylstannyl)oxyphenoxyl in viscous media

EPR spectroscopy was used to study the rotational mobility and stannotropy dynamics of 3,6-di-tert-butyl-2-(chlorodimethylstannyl)oxyphenoxyl in viscous media. The correlation times for rotational motion of 3,6-di-tert-butyl-2-(triphenylstannyl)- and 3,6-di-tert-butyl-2-(chlorodimethylstannyl)oxyphenoxyls upon variation of the viscosity of the medium and temperature in a broad range. These times are related to each by a constant. A relationship was shown between the mobility of the medium and the stannotropy dynamics. A linear relationship was found between the time for intramolecular migration of the SnClMe₂ fragment and rotational motion correlation time.For previous communication see [1].Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1535–1539, July, 1990.     

Correlation between solvent-reorganization dynamics and the kinetics of metallotropy in polar media

The kinetics of metallotropy of the 3,6-di-tert-butyl-2-(triphenylstannyl)oxyphenoxyl radical has been studied by ESR. The correlation between chemical exchange time _ex, solvent polarity, and longitudinal relaxation time of the solvent corresponds to the model of a process controlled by molecular dynamics. A linear relation between _ex and correlation time _c for reorientation movements of the radical is found: _ex = · _c. The coefficient depends on the dielectric properties of the solvent.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 410–413, March, 1994.This work was supported by the Russian Foundation for Basic Research, project No. 93-03-4372.     

Influence of nonwetting on the aggregation dynamics of micronic solid particles in a turbulent medium

The aim of this work was to determine and to interpret the influence of nonwetting on the aggregation dynamics of micronic solid particles in a turbulent medium. Two silica granular samples were studied: one was naturally hydrophilic; the other was made hydrophobic. Aggregation in an aqueous ethanol solution was followed by in situ turbidimetry. The influence of stirring rate and deaeration was determined. Aggregates of hydrophilic particles were small and fragile, whereas aggregates of hydrophobic particles were large and solid. Moreover, they differred greatly in optical properties. Within the proposed approach, different features of the aggregate morphology were identified: fractal dimension, maximum size, and gas content of the hydrophobic clusters. These elements are taken into account in the models of aggregation dynamics proposed here.     

Influence of ultraviolet light on some copper chelates of β-dicarbonyl compounds : Spectral evidence for a photoactivated metallotropy

The influence of ultraviolet light on heptane solutions of the copper chelates of several β-dicarbonyl compounds has been followed by spectroscopy. Reversible transformations are apparent, leading us to assume the presence of a photoactivated metalotropy.     

Effects of interface mobility on the dynamics of colliding bubbles

At its core, the outcome of the collision between air bubbles is determined by the hydrodynamic interaction forces, which in turn are strongly dependent on the tangential mobility of the gas–liquid interfaces. A clean gas–liquid interface is tangentially mobile, whereas the presence of surfactant contaminants can immobilise the interface. Bubbles with mobile surfaces coalescence much easier because of the low hydrodynamic resistance to drainage of the thin liquid film separating the colliding bubbles. In this opinion, we highlight recent experimental and numerical simulations demonstrating that in addition to the expected faster coalescence, mobile-surface bubbles can produce a much stronger rebound from a mobile liquid interface compared to an immobile one. The stronger rebound is explained by the lower viscous dissipation during collisions involving mobile surfaces. The role of the surface mobility in controlling the stability of gas or liquid emulsion should be reassessed in the light of these new findings.     

Electrophoretic mobility of a soft particle in a salt-free medium

A theory is presented for the electrophoretic mobility mu of dilute spherical soft particles (i.e., polyelectrolyte-coated particles) in salt-free media containing only counterions. As in the case of other types of particles (rigid particles and liquid drops) in salt-free media, there is a certain critical value of the particle charge separating two cases, the low-surface-charge case and the high-surface-charge case. For the low-charge case, the mobility is proportional to the particle charge and coincides with that of a soft particle in an electrolyte solution in the limit of very low electrolyte concentrations kappa-->0 (Hückel's limit), where kappa is the Debye-Hückel parameter. For the high-charge case, however, mu becomes essentially constant, independent of the particle charge, due to the counterion condensation effect.     

Electrophoretic mobility of a liquid drop in a salt-free medium

A theory is proposed for the electrophoretic mobility mu of dilute spherical liquid drops of radius a in salt-free media containing only counterions (e.g., nonaqueous media). As in the case of the electrophoretic mobility of rigid particle in salt-free media, there is a certain critical value of the drop surface charge separating two cases, that is, the low-surface-charge case and the high-surface-charge case. For the low-surface-charge case, mu coincides with that of a drop in an electrolyte solution in the limit of very low electrolyte concentrations kappaa-->0 (Hückel's limit), where kappa is the Debye-Hückel parameter. For the high-surface-charge case, however, mu becomes constant independent of the drop surface charge, since the counterion condensation takes place near the drop surface.     

Influence of formation path on the CH2BrCl2+ dissociation dynamics

To get further insight into the CH2BrCl site-selective fragmentation previously observed upon inner-shell ionization, we have performed high-resolution Br 3d and Cl 2p Auger and spin-orbit resolved Br 3d Auger spectra, and studied the dissociation properties of the CH2BrCl2+ dication formed at threshold by means of threshold electron pair-ion coincidence measurements. The key point is that the origin of site-specific bond breaking is found in the Auger decay itself, as it preferentially populates selected dication states. Whereas the predominance of the C-Br bond breaking is observed in both threshold and inner-shell studies, no signature of selective C-Cl rupture is reported for the dication formed at threshold.     

Electrophoretic mobility of a spherical colloidal particle in a salt-free medium

A general expression as well as approximate expressions are derived for the electrophoretic mobility of dilute spherical colloidal particles in a salt-free medium containing only counter ions. It is shown that there is a certain critical value of the particle surface charge. When the particle surface charge is lower than the critical value, the electrophoretic mobility is proportional to the particle surface charge or the particle zeta potential, following Hückel's formula. When the particle surface charge is higher than the critical value, the electrophoretic mobility becomes independent of the particle surface charge. This is due to the effect of counter ion condensation in the vicinity of the particle surface.     

Electrophoretic mobility of a cylindrical colloidal particle in a salt-free medium

Approximate expressions are derived for the electrophoretic mobility of dilute cylindrical colloidal particles in a salt-free medium containing only counterions. The cylinder is assumed to be infinitely long. It is shown that as in the case of a spherical particle, there is a certain critical value of the particle surface charge separating two cases. When the particle surface charge is lower than the critical value (case 1), the electrophoretic mobility increases with increasing particle surface charge per unit length. When the particle surface charge is higher than the critical value (case 2), the mobility becomes constant (for a cylinder in a transverse field) or the increase in the electrophoretic mobility with the particle surface charge becomes suppressed (for a cylinder in a tangential field). These phenomena are caused by the effect of counterion condensation in the vicinity of the particle surface. The critical value of the particle charge is essentially independent of the particle volume fraction phi for the dilute case, unlike the case of a sphere, in which case the critical charge value is proportional to ln(1/phi).     

Dynamic electrophoretic mobility of spherical colloidal particles in a salt-free medium

A theory is proposed for the dynamic electrophoretic mobility mu(omega) of spherical colloidal particles in a salt-free medium containing only counterions in an oscillating electric field of frequency omega. The dynamic mobility depends on the frequency omega of the applied electric field and on the particle volume fraction as well as on the particle surface charge. It is found that as in the case of the static electrophoretic mobility mu(0) in salt-free media, there is a certain critical value of the particle surface charge separating two cases, that is, the low-surface-charge case and the high-surface-charge case (in the latter case the counterion condensation takes place near the particle surface). For the low-surface-charge case, the dynamic mobility agrees with that of a sphere in an electrolyte solution in the limit of very low electrolyte concentrations kappaa-->0 (Hückel's limit), where kappa is the Debye-Hückel parameter and a is the particle radius. For the high-surface-charge case, however, the dynamic mobility becomes constant independent of the particle surface charge, because of the counterion condensation effects. A simple expression for the ratio mu(omega)/mu(0) applicable for all cases is given.     

Influence of crosslinking on charge carrier mobility in crosslinkable polyfluorene derivatives

Carrier mobility is a key parameter for the application of conjugated polymers. In this work, a series of polyfluorenes (PF2/6) with different fractions of crosslinkable acrylate groups is investigated. Mobility measurements are carried out to assess the influence of crosslinking with different photoinitiators on the performance of the material. For the regime of low to medium charge carrier density, relevant for OLEDs and OPVs, we used a novel technique based on the injection of charge carriers from the electrodes of an optoelectronic device: MIS‐CELIV (MIS: metal‐insulator‐semiconductor). For large charge carrier densities we performed OFET measurements. We find that using optimized conditions crosslinking does not influence the hole mobility in the investigated system. Furthermore, we demonstrate that the crosslinking process may be triggered solely by thermal activation and UV‐illumination without the need of any initiator. Thus, densely crosslinked networks are obtained without the formation of undesired decomposition products from added photoinitiator. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 112–120     

Influence of a reduced mobility layer on the structural relaxation dynamics of aluminum capped ultrathin films of poly(ethylene terephthalate)

The structural dynamics of ultrathin polymer films of poly(ethylene terephthalate) capped between aluminum electrodes have been investigated by dielectric relaxation spectroscopy. A deviation from bulk behavior, appearing as an increase of the relaxation time at a fixed temperature, is observed for films of thickness below 35 nm. The slowing down acts as a constant shift factor independent from the temperature, and the fragility is constant. The interfacial energy between aluminum and poly(ethylene terephthalate) is calculated to be 3 mJ/m2, confirming a strong interaction between polymer and substrate, which leads to the presence of a layer characterized by a reduced mobility at their interfaces. We proposed a mathematical schematization of a multylayer model that allowed qualitative reproduction of the observed thickness dependences of the static and dynamic properties. In terms of such a model, the upper limit for the thickness of the reduced mobility layer was estimated as 20 nm. The conditions to extend the proposed model to different observables are finally suggested.     

Effect of a porous medium on the phase transitions and mobility of cyclohexane molecules

The effect of a porous medium on the phase transitions and molecular mobility of cyclohexane at a liquid content corresponding to a monolayer is studied by pulsed NMR. The times of longitudinal T ₁ and transverse T ₂ magnetic relaxation of protons of cyclohexane introduced into granulated porous glasses of the Vycor type with average pore diameters of 4, 11, and 32 nm are measured in the temperature range of 128–293 K. In spite of a relatively low liquid content, two phase transitions are observed for all porous glass samples at temperatures lower than those inherent in pure cyclohexane. At low temperatures, nonfreezing cyclohexane volumes with characteristic times of T ₂ ～ 100–200 μs and relative populations of 5–10% remain preserved due to the presence of a small number of micropores commensurable with molecular sizes. The appearance of an additional component with T ₂ ～ 200 μs upon temperature elevation to 148 K attests to thawing out of some cyclohexane volumes, which begins long before the crystal-plastic crystal phase transition. The nonexponential character of the transverse magnetization decay of cyclohexane above the temperature of the plastic crystal-liquid phase transition in the porous glass with a pore diameter of 4 nm suggests the existence of barriers for rapid molecular exchange. The obtained experimental results are indicative of the cluster mechanism of cyclohexane adsorption in the studied porous glasses.     

Influence of aminodiester on steel hydrogenation in a hydrosulfuric medium

The influence of N-(2-carboethoxyethene)-N-(2-carbobuthoxyethyl)methylamine on the process of hydrogen penetration in steel (St.3) in a hydrosulfuric medium was studied.     

Influence of the crystalline phase on the molecular mobility of PVDF

Dielectric relaxation and pyrocurrent of PVDF were studied by thermostimulated current spectroscopy. The transition spectrum of the material was investigated by differential scanning calorimetry. Two well-resolved relaxation peaks have been observed in the temperature range [?100–100°C]. The molecular mechanisms of these phenomena have been discussed, based on a comparative study of α-PVDF. and β-PVDF. The β relaxation mode is located at ?41°C in α-PVDF and is slightly shifted toward higher temperatures in the stretched material. This mode has been ascribed to the dielectric manifestation of the glass transition (T_g) of PVDF. It is comprised of two components corresponding to the free and constrained amorphous phases, respectively, in the order of increasing temperatures. The α_c transition/relaxation has been associated with molecular motions in the crystalline/amorphous interphase. At higher temperatures, a compensation phenomenon corresponding to cooperative movements liberated at the Curie transition has been observed in β-PVDF. © 1993 John Wiley & Sons, Inc.     

Correlation between the rotational mobility and the kinetics of the intramolecular exchange of the unpaired electron and bond in a tin-containing free radical with two pyrocatechol ligands

EPR spectroscopy was used to study the effect of the mobility of the medium on the dynamics of the interligand exchange of the unpaired electron and bond in the free radical formed upon the reaction of stannous bis-3,6-di-tert-butyl-o-semiquinolate with 3,6-di-tert-butyl-2-hydroxyphenoxyl in the presence of triphenylphosphine. A dependence exists between the characteristic exchange time _ex and the correlation time for the rotational mobility of the radical _c; _ex= _c. A temperature dependence was found for coefficient .Translated from Izvestiya Akademii Nauk SSSR. Seriya Khimicheskaya, No. 7, pp. 1663–1666, July, 1990.     

Influence of the reaction medium on platinum surface formation

The effect of an organic reaction medium on the Pt-black surface formation has been studied. It has been shown that under the action of the reaction medium an irreversible change of the catalyst surface occurs.

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Numerical calculation of the electrophoretic mobility of a spherical particle in a salt-free medium

By extending an approximate theory of the electrophoretic mobility of dilute spherical colloidal particles in a salt-free medium containing only counterions (H. Ohshima, J. Colloid Interface Sci. 248 (2002) 499--503), a systematic numerical method is given for the calculation of the electrophoretic mobility, which is based on an iteration method. We assume that each sphere is surrounded by a spherical free volume, within which counterions are distributed so that electro-neutrality is satisfied. The electrophoretic mobility is found to be determined mainly by the pressure due to the counterions at the outer surface of the free volume. It is shown how the mobility values deviate from those expected from Hückel's formula for high particle charges or zeta potentials because of the counterion condensation effect.