Non-miscible

The capillary effect is apparent whenever two non-miscible fluids are in contact, and is a result of the interaction of attractive forces between molecules in the two liquids (surface tension effects), and between the fluids and the solid surface (wettability effects). 

Since no special ligand design is usually required to dissolve transition metal complexes in ionic liquids, the application of ionic ligands can be an extremely useful tool with which to immobilize the catalyst in the ionic medium. In applications in which the ionic catalyst layer is intensively extracted with a non-miscible solvent (i.e., under the conditions of biphasic catalysis or during product recovery by extraction) it is important to ensure that the amount of catalyst washed from the ionic liquid is extremely low. Full immobilization of the (often quite expensive) transition metal catalyst, combined with the possibility of recycling it, is usually a crucial criterion for the large-scale use of homogeneous catalysis (for more details see Section 5.3.5). 

Separation layer mixers use either a miscible or non-miscible layer between the reacting solutions, in the first case most often identical with the solvent used [48]. By this measure, mixing is postponed to a further stage of process equipment. Accordingly, reactants are only fed to the reaction device, but in a defined, e.g. multi-lamination-pattem like, fluid-compartment architecture. A separation layer technique inevitably demands micro mixers, as it is only feasible in a laminar flow regime, otherwise turbulent convective flow will result in plugging close to the entrance of the mixer chamber. 

Kcurentjes et al. (1996) have also reported the separation of racemic mixtures. Two liquids are made oppositely chiral by the addition of R- or S-enantiomers of a chiral selector, respectively. These liquids are miscible, but are kept separated by a non-miscible liquid contained in a porous membrane. These authors have used different types of hollow-fibre modules and optimization of shell-side flow distribution was carried out. The liquid membrane should be permeable to the enantiomers to be separated but non-permeable to the chiral selector molecules. Separation of racemic mixtures like norephedrine, ephedrine, phenyl glycine, salbutanol, etc. was attempted and both enantiomers of 99.3 to 99.8% purity were realized. 

Nielsen LP, Besenbacher F, Stensgaard 1, Laegsgaard E, Engdahl C, Stoltze P, Jacobsen KW, Nprskov JK. 1995. Initial growth of Au on Ni(llO) Surface alloying of non-miscible metals. Phys Rev Lett 71 754. 

Over the past 20 years no new commodity polymer has been developed. This is because of the advances in fabrication, blends (both miscible and non-miscible), fibre reinforcement, etc. Thus films with up to 11 different polymer layers have been developed. 

According to Figure 5.2 and to chemical experience, the selection of other pairs of non-miscible organic liquids is difficult and yields mainly unusual (not to say, exotic) solvents or pairs of solvents [68] such as fluorous liquids (cf. Chapter 6). This is the reason why no other organic-organic biphasic catalytic processes have yet been commercialised. 

For many years, prior to the development of current phase-transfer catalytic techniques, tetraalkylammonium borohydrides have been used in non-hydroxylic solvents [see, e.g. I, 2], Originally, the quaternary ammonium borohydrides were obtained by metathesis in water or an alcohol [3, 4], However, with greater knowledge of the phase-transfer phenomenon, an improved procedure has been developed in which the ammonium salt is transferred into, and subsequently isolated from, dichloromethane [5, 6], In principle, it should be possible to transfer the quaternary ammonium borohydride for use in any non-miscible organic solvent. It should be noted, however, that quaternary ammonium cations are susceptible to hydrogeno-lysis by sodium borohydride in dipolar aprotic solvents to yield tertiary amines [4]. 

Another approach to isolate the catalyst from the products is the application of perfluorinated catalytic systems, dissolved in fluorinated media [63], which are not non-miscible with the products and some commonly used solvents for catalysis like THE or toluene at ambient temperature. Typical fluorinated media include perfluorinated alkanes, trialkylamines and dialkylethers. These systems are able to switch their solubility properties for organic and organometallic compounds based on changes of the solvation ability of the solvent by moving to higher temperatures. This behavior is similar to the above-mentioned thermomorphic multiphasic PEG-modified systems [65-67]. 

Lipophilicity is a molecular property experimentally determined as the logarithm of the partition coefficient (log P) of a solute between two non-miscible solvent phases, typically n-octanol and water. An experimental log P is valid for only a single chemical species, while a mixture of chemical species is defined by a distribution, log D. Because log P is a ratio of two concentrations at saturation, it is essentially the net result of all intermolecular forces between a solute and the two phases into which it partitions (1) and is generally pH-dependent. According to Testa et al. (1) lipophilicity can be represented (Fig. 1) as the difference between the hydrophobicity, which accounts for hydrophobic interactions, and dispersion forces and polarity, which account for hydrogen bonds, orientation, and induction forces ... 

Several liquid phases coexist in a system when the solvents are not completely miscible. Liquid-liquid equilibrium properties are very useful in solvent extraction and in biotransformation or enzymatic syntheses in two-solvent systems. One speaks about liquid-liquid equilibrium in two cases (1) if the two solvents are not completely miscible, it is said that there is partial miscibility of the two solvents (2) if there is distribution of a compound in the two non-miscible solvents. 

Liquid/liquid emulsions consist of two or more non-miscible liquids. Classic examples of oil-in-water (O/W) emulsions are/milk, mayonnaise, lotions. 

For liquid or solid samples more complex than water, a combination of techniques is commonly required. Certainly a first step involves a need to obtain the components of interest in a solution phase. This may either involve leaching of a solid or extraction of a liquid sample with or without concurrent concentration. If the components of interest are then obtained in a water system, the techniques applicable to water analyses are immediately available. Conversely, if the extraction is into a non-miscible organic solvent and the components sought can be reextracted into water by appropriate choice of pH, then again the techniques of water sample processing can be used. 

Non-miscible liquids A mixture of non-miscible liquids forms as many number of liquid phases as that of liquids, because on standing they form separate layers, e.g., a mixture of water and chloroform forms two liquid phases. 

The concept of interpenetrating the polymer network was introduced in the early 1960s [108]. The basic idea is the formation of blends with two different independent polymer networks on the nano scale. The non-miscibility between two polymers is the general rule and an important question is to know if the gelation takes place before or after the phase separation, because the timing for these two phenomena will govern the size of each network domain [109,110]. 

The first question to be discussed is the polymer miscibility which governs the blend morphology. The solubility parameters of BMIs is 12-135 (cal cm 3)0,5 vs. 11-12 (cal cm"3)0,5 for the high-performance thermoplastics [112]. We can expect an important non-miscibility however, the morphology will also depend on some other factors (conversion at the gel point, viscosity...) and as a result different types of morphologies were identified. 

As shown in a previous section, fluorinated nadimides exhibit the best thermo-oxidative behavior. NR 150 linear polymers are prepared by reaction of HFDE and a mixture of para- and raefa-phenylenediamine. A semi-IPN was prepared by addition of a 150 °C staged PMR-15 to a solution of the NR 150 precursor. The solution was used for the composite manufacture. After curing at 250 °C, the DSC diagram showed two peaks in agreement with a non-miscible system. After curing, the Glc of the blend is higher than that of pure PMR-15 (Table 8) [119]. 

The role of the miscibility of semi-IPN components on the mechanical properties has been discussed. The linear bisnadimide was a benzhydrol bisnadimide (Fig. 33). Three polyimides prepared from the same diamine and three different dianhydrides (Fig. 37) were used as linear components. The blends were cured up to 300 °C in a similar fashion to the bisnadimide alone. The results for the blend containing 20% by weight of linear polymers are summarized in Table 9. The non-miscible character of the components gives a phase segregation leading to the best toughness [121]. 

Liquid/liquid emulsions consist of two (or more) non-miscible liquids. Classical examples for this are oil in water (O/W) emulsions, for example milk, mayonnaise, lotions, creams, water soluble paints, photo emulsions, and so on. As appliances, teeth-rimed rotor-stator emulsifiers and colloid mills, as well as high-pressure homogenizers are used. 

Equilibrium-restricted reactions (Section A9.3.3.1) have until now been the main field of research on CMRs. Other types of application, such as the controlled addition of reactants (Section A9.3.3.2) or the use of CMRs as active contactors (Section A9.3.3.3), seem however very promising, as they do not require permselective membranes and often operate at moderate temperatures. Especially attractive is the concept of active contactors where the membrane being the catalyst support becomes an active interface between two non-miscible reactants. Indeed this concept, initially developed for gas-liquid reaction [79] has been recently extended to aqueous-organic reactants [82], In both cases the contact between catalyst and limiting reactant which restricts the performance of conventional reactors is favored by the membrane. 

Emulsions are understood as dispersed systems with liquid droplets (dispersed phase) in another, non-miscible liquid (continuous phase). Either molecular diffusion degradation (Ostwald ripening) or coalescence may lead to destabilization and breaking of emulsions. In order to create a stable emulsion of very small droplets, which is, for historical reasons, called a miniemulsion (as proposed by Chou et al. [2]), the droplets must be stabilized against molecular diffusion degradation (Ostwald ripening, a unimolecular process or r, mechanism) and... 

Some liquids when put together form mixtures, just as some solids do. Neither one of them changes chemically or physically. This is what happened to the water and the juice. When liquids behave this way, they are said to diffuse, and they are called miscible. Liquids that will not diffuse with one another, like oil and water, are called non-miscible. 

This stochastic model of the flow with multiple velocity states cannot be solved with a parabolic model where the diffusion of species cannot depend on the species concentration as has been frequently reported in experimental studies. Indeed, for these more complicated situations, we need a much more complete model for which the evolution of flow inside of system accepts a dependency not only on the actual process state. So we must have a stochastic process with more complex relationships between the elementary states of the investigated process. This is the stochastic model of motion with complete connections. This stochastic model can be explained through the following example we need to design some flowing liquid trajectories inside a regular porous structure as is shown in Fig. 4.33. The porous structure is initially filled with a fluid, which is non-miscible with a second fluid, itself in contact with one surface of the porous body. At the... 

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