Stabilization, ionic steric

The stability of the concentrated emulsions has a kinetic origin. Repulsive double layer forces together with hydration forces are responsible for stability when the surfactant which is adsorbed upon the surface of the thin films is ionic steric repulsion as well as hydration forces are involved in stability when the adsorbed surfactant is non-ionic. 

This chapter will concentrate on the chemistry of metal-14-centered anions (Ge, Sn, Pb). These compounds and their silyl analogues are ionic or polarized alkaline and alkaline earth metal-14 compounds, as well as delocalized molecules such as metalloles. Ammonium metallates Mi4 R4N+ or metal-14-centered anion radicals are also considered. The subject was explored during the 1960s and 1970s and thoroughly reviewed in 1982 and 1995 in Comprehensive Organometallic Chemistry, Vols. I and and for silicon species in a previous volume of this series . By that time the main routes to metal-14 anions were known. Since then, the subject has been developed in the topics of particular syntheses, stabilization using steric hindrance, electronic effects and complexation, spectroscopic and structural analyses "... 

Salad dressings and mayonnaise can be stabilized by ionic surfactants, which provide some electrostatic stabilization as described by DLVO theory, or by nonionic surfactants which provide a viscoelastic surface coating. The protein-covered oil (fat) droplets tend to be mostly stabilized by steric stabilization (rather than electrostatic stabilization) [34,126,129], particularly at very high levels of surface protein adsorption, in which case the adsorption layer can include not just protein molecules but structured protein globules (aggregates). In some cases, lipid liquid crystal layers surround and stabilize the oil droplets, such as the stabilization of O/W droplets by egg-yolk lecithins in salad dressing [34,135]. 

An analysis presented of the forces contributing to the attraction and repulsion interactions between macromolecules in acrylate latices. The electrostatic repulsion forces, enthalpy and entropy effects, and the attraction forces from the expanded Hamaker equation are analysed. The influence of the structure of copolymers consisting of monomeric units of alkyl acrylate or methacrylate (methyl to n-butyl) and acryhc or methacryhc acid on the physico-chemical properties of the latices and their stabihty were determined. On the basis of experiments and calculations it was established that the stability of latices is decided by two mechanisms. The first (ionic stabilisation) consists in adsorption of anionic emulsifier particles, and the second (ionic-steric stabilisation) involves adsorption of such an emulsifier on an adsorption layer formed by the polymer macromolecules forming the latex. 25 refs. Articles from this journal can be requested for translation by subscribers to the Rapra produced International Polymer Science and Technology. 

In media of low dielectric constant, electrostatic stabilization is of little importance. Colloidal dispersions in non-aqueous media are thus more likely to be stabilized by steric barriers formed by adsorbed surfactants and polymers. Relatively little work has been done on the adsorption of surfactants on to solids from non-aqueous solvents, a limiting factor of course being the insolubility of many surfactants in solvents other than water. Non-ionic surfactants tend to be soluble in both aqueous and non-polar solvent systems. Rupprecht [6] has made a series of investigations of adsorption of non-ionic alkyl polyethers on to silica in various organic solvents. Fig. 9.20 shows some of the adsorption isotherms for nonylphenol Eg. 5 from dichloromethane, n-butanol, n-propanol, ethanol, 1,4-dioxan and DMSO. As might be expected, adsorption is greatest from the dichloromethane and the effect of increasing polarity is clearly seen with the three alcohols. 

Solvation effects may change the interaction between reacting molecules. A polar medium will stabilize ionic or polar states. Reactions occurring in the micropores of solids may also experience steric constraints. 

An important factor that is not taken into account in the DLVO theory is adsorption, on the particle s surface, of long polymeric chains. The adsorption of a non-ionic polymer or a polyelectrolyte on the solid surface can cause, not only a modification of the zeta potential, but also a critical difference between the value of the zeta potential and the state of dispersion. Steric repulsion is associated with the obstmction effect of these polymers that are capable to form a sufficiently thick layer to prevent the particles from approaching one another in the distanee of influence of the Van der Waals attractive forces. Steric stabihzation will therefore depend on the adsorption of the polymeric dispersant and the thickness of the layer developed. Several interpretation models for stabilization by steric effect have been put forward. They rely either on a statistical approach, or on the thermodynamics of solutions. Steric stabilization is particularly useful in organic, fairly non-polar or non-polar environments, as in the case of tape casting (see section 5.4.3). 

For most vinyl polymers, head-to-tail addition is the dominant mode of addition. Variations from this generalization become more common for polymerizations which are carried out at higher temperatures. Head-to-head addition is also somewhat more abundant in the case of halogenated monomers such as vinyl chloride. The preponderance of head-to-tail additions is understood to arise from a combination of resonance and steric effects. In many cases the ionic or free-radical reaction center occurs at the substituted carbon due to the possibility of resonance stabilization or electron delocalization through the substituent group. Head-to-tail attachment is also sterically favored, since the substituent groups on successive repeat units are separated by a methylene... 

There are two general theories of the stabUity of lyophobic coUoids, or, more precisely, two general mechanisms controlling the dispersion and flocculation of these coUoids. Both theories regard adsorption of dissolved species as a key process in stabilization. However, one theory is based on a consideration of ionic forces near the interface, whereas the other is based on steric forces. The two theories complement each other and are in no sense contradictory. In some systems, one mechanism may be predominant, and in others both mechanisms may operate simultaneously. The fundamental kinetic considerations common to both theories are based on Smoluchowski s classical theory of the coagulation of coUoids. 

One of the most important parameters that defines the structure and stability of inorganic crystals is their stoichiometry - the quantitative relationship between the anions and the cations [134]. Oxygen and fluorine ions, O2 and F, have very similar ionic radii of 1.36 and 1.33 A, respectively. The steric similarity enables isomorphic substitution of oxygen and fluorine ions in the anionic sub-lattice as well as the combination of complex fluoride, oxyfluoride and some oxide compounds in the same system. On the other hand, tantalum or niobium, which are the central atoms in the fluoride and oxyfluoride complexes, have identical ionic radii equal to 0.66 A. Several other cations of transition metals are also sterically similar or even identical to tantalum and niobium, which allows for certain isomorphic substitutions in the cation sublattice. 

To sum up, in addition to the electronic stabilization and solvation, classical steric congestion caused by either the cation or anion moieties effectively controls the ease of ionic dissociation of the carbon-carbon a bond in hydrocarbons. 

As the cation becomes progressively more reluctant to be reduced than [53 ], covalent bond formation is observed instead of electron transfer. Further stabilization of the cation causes formation of an ionic bond, i.e. salt formation. Thus, the course of the reaction is controlled by the electron affinity of the carbocation. However, the change from single-electron transfer to salt formation is not straightforward. As has been discussed in previous sections, steric effects are another important factor in controlling the formation of hydrocarbon salts. The significant difference in the reduction potential at which a covalent bond is switched to an ionic one -around -0.8 V for tropylium ion series and —1.6 V in the case of l-aryl-2,3-dicyclopropylcyclopropenylium ion series - may be attributed to steric factors. 

Stability may be inherent or induced. In the latter case, the original system is in a condition of metastable or neutral eouilibrium. External influences which induce instability in a dispersion on standing are changes in temperature, volume, concentration, chemical composition, and sediment volume. Applied external influences consist of shear, introduction of a third component, and compaction of the sediment. Interfacial energy between solid and liquid must be minimized, if a dispersion is to be truly stable. Two complementary stabilizing techniques are ionic and steric protection of the dispersed phase. The most fruitful approach to the prediction of physical stability is by electrical methods. Sediment volumes bear a close relation to repulsion of particles for each other. 

Best approach toward a general solution of all problems of induced stability appears to be a two-pronged surface treatment involving electrostatic and steric protection. In order to increase repulsion energy, zeta should be increased and to enable the particles to resist compression to a distance of separation less than that at E, a bulky molecule should be attached firmly to the surface. Some systems do not accept both steric and ionic protection but for those that do, the combination shows most promise. Er should not be increased without some assurance that the particles will not be subjected to drastic compressive forces. 

When supported complexes are the catalysts, two types of ionic solid were used zeolites and clays. The structures of these solids (microporous and lamellar respectively) help to improve the stability of the complex catalyst under the reaction conditions by preventing the catalytic species from undergoing dimerization or aggregation, both phenomena which are known to be deactivating. In some cases, the pore walls can tune the selectivity of the reaction by steric effects. The strong similarities of zeolites with the protein portion of natural enzymes was emphasized by Herron.20 The protein protects the active site from side reactions, sieves the substrate molecules, and provides a stereochemically demanding void. Metal complexes have been encapsulated in zeolites, successfully mimicking metalloenzymes for oxidation reactions. Two methods of synthesis of such encapsulated/intercalated complexes have been tested, as follows. 

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