Coalescence studies

Coalescence studies on the equilibrium 114/115 by recording the NMR spectra at different temperatures revealed that the coalescence temperature for the NH protons was found to be 65°C, and 70°C for the CH3 protons. Based on these coalescence temperatures and the chemical shift differences of the two separate peaks in the slow exchange region (82MI2), the free energy of activation AG was calculated as 20.8 kcal/mol. 

In the present work, we summarize recent observations on the coalescence behavior of several oil-water-surfactant systems. We are particularly interested in the behavior exhibited by low tension systems and the role of bulk phase viscous effects and dynamic interfacial properties such as interfacial shear and dilatational viscosities. Also, a new experimental approach for conducting coalescence studies is described which involves tests in an inclined spinning drop device. This approach allows for coalescence tests under controlled conditions and provides an efficient method for quickly screening and evaluating different surfactant systems. 

Most studies of the behavior of block copolymers as compatibilizing agents consider two opposing effects during deformation a reduction in critical droplet size due to a reduction in the interfhcial tension (droplet breakup) proposed by Taylor, and an increase in droplet size due to increased collision frequency between droplets (droplet coalescence) studied by Smoluchowski. The problem of droplet breakup in a... 

It was pointed out in Section XIII-4A that if the contact angle between a solid particle and two liquid phases is finite, a stable position for the particle is at the liquid-liquid interface. Coalescence is inhibited because it takes work to displace the particle from the interface. In addition, one can account for the type of emulsion that is formed, 0/W or W/O, simply in terms of the contact angle value. As illustrated in Fig. XIV-7, the bulk of the particle will lie in that liquid that most nearly wets it, and by what seems to be a correct application of the early oriented wedge" principle (see Ref. 48), this liquid should then constitute the outer phase. Furthermore, the action of surfactants should be predictable in terms of their effect on the contact angle. This was, indeed, found to be the case in a study by Schulman and Leja [49] on the stabilization of emulsions by barium sulfate. 

External and internal loop air-lifts and bubble column reactors containing a range of coalescing and non-Newtonian fluids, have been studied (52,53). It was shown that there are distinct differences in the characteristics of external and internal loop reactors (54). Overall, in this type of equipment... 

Although the thermodynamic aspects of acylotropy are well documented, there have been few kinetic studies of the process. The activation barrier is much higher than for prototropy and only Castells et al. (72CC709) have succeeded in observing a coalescence phenomenon in H NMR spectra. At 215 °C in 1-chloronaphthalene the methyl groups of N-phenyl-3,5-dimethylpyrazole-l-carboxamide coalesce. The mechanism of dissociation-combination explains the reversible evolution of the spectra (Scheme 9). 

As mentioned earlier, surfactants and ionic solutions significantly affect mass transfer. Normally, surface affects act to retard coalescence and thus increase the mass transfer. For example, Hikata et al. [Chem. Eng. J., 22, 61-69 (1981)] have studied the effect of KCl on mass transfer in water. As KCI concentration increased, the mass transfer increased up to about 35 percent at an ionic strength of 6 gi7i/l. Other investigators have found similar increases for hquid mixtures. 

The prediction of drop sizes in liquid-liquid systems is difficult. Most of the studies have used very pure fluids as two of the immiscible liquids, and in industrial practice there almost always are other chemicals that are surface-active to some degree and make the pre-dic tion of absolute drop sizes veiy difficult. In addition, techniques to measure drop sizes in experimental studies have all types of experimental and interpretation variations and difficulties so that many of the equations and correlations in the literature give contradictoiy results under similar conditions. Experimental difficulties include dispersion and coalescence effects, difficulty of measuring ac tual drop size, the effect of visual or photographic studies on where in the tank you can make these obseiwations, and the difficulty of using probes that measure bubble size or bubble area by hght or other sample transmission techniques which are veiy sensitive to the concentration of the dispersed phase and often are used in veiy dilute solutions. 

This is most readily studied with cyclohexane- /n in which 11 of the 12 protons are replaced with deuterium. The spectrum of cyclohexane- /n resembles the behavior shown in Fig. 4-8 at about — 100°C (the slow exchange regime) two sharp lines are seen these broaden as the temperature is increased, reaching coalescence at — 61.4°C, and becoming a single sharp line at higher temperatures. (The deuterium nuclei must be decoupled by rf irradiation.) Rate constants t for the conversion were measured over the temperature range — 116.7°C to — 24.0°C by Anet and Bourne. It is probable that the chair-chair inversion takes place via a boat intermediate. 

The transition from non-protective internal oxidation to the formation of a protective external alumina layer on nickel aluminium alloys at 1 000-1 300°C was studied by Hindam and Smeltzer . Addition of 2% A1 led to an increase in the oxidation rate compared with pure nickel, and the development of a duplex scale of aluminium-doped nickel oxide and the nickel aluminate spinel with rod-like internal oxide of alumina. During the early stages of oxidation of a 6% A1 alloy somewhat irreproducible behaviour was observed while the a-alumina layer developed by the coalescence of the rodlike internal precipitates and lateral diffusion of aluminium. At a lower temperature (800°C) Stott and Wood observed that the rate of oxidation was reduced by the addition of 0-5-4% A1 which they attributed to the blocking action of internal precipitates accumulating at the scale/alloy interface. At higher temperatures up to 1 200°C, however, an increase in the oxidation rate was observed due to aluminium doping of the nickel oxide and the inability to establish a healing layer of alumina. 

Ring inversions of 1H- and 4//-azepines between their two stable boat forms have been studied extensively by HNMR spectroscopy.37,38-40-76 82,85 A coalescence temperature of — 55 7 C and a AG value for ring inversion of 42.7 kJ mol have been determined for the two conformers 10 A and 10 B of A-phenyl-3//-azepin-2-amine.82... 

Numerous studies of the formation and flow of gas bubbles in liquids have appeared in the literature, and a complete review will not be attempted. Attention is drawn to two recently published reviews, that of Jackson (Jl) on the formation and coalescence of drops and bubbles in liquids, and that of Govier (G6) on developments in the understanding of the vertical flow of two phases. 

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