Secondary hydration force

Beyond this, the inclusion of the competition for surface sites of different competing species (e.g. H vs. Na" ") gives rise to the further problem of surface charge regulation [22, 27-30], with a concomitant appearance of a so-called "secondary hydration force". Surface localised dipole-dipole correlations give rise to a further force [31, 32], and much of what was confused falls into place. These developments represent a first conceptual step forward on the way to a more complete and necessary stage of... 

It is well-known that free films of water stabilized by surfactants can exist as somewhat thicker primary films, or common black films, and thinner secondary films, or Newton black films. The thickness of the former decreases sharply upon addition of electrolyte, and for this reason its stability was attributed to the balance between the electrostatic double-layer repulsion and the van der Waals attraction. A decrease in its stability leads either to film rupture or to an abrupt thinning to a Newton black film, which consists of two surfactant monolayers separated by a very thin layer ofwater. The thickness of the Newton black film is almost independent of the concentration of electrolyte this suggests that another repulsive force than the double layer is involved in its stability. This repulsion is the result of the structuring of water in the vicinity of the surface. Extensive experimental measurements of the separation distance between neutral lipid bilayers in water as a function of applied pressure1 indicated that the hydration force has an exponential behavior, with a decay length between 1.5 and 3 A, and a preexponential factor that varies in a rather large range. 

The DLVO theory does not explain either the stability of water-in-oil emulsions or the stability of oil-in-water emulsions stabilized by adsorbed non-ionic surfactants and polymers where the electrical contributions are often of secondary importance. In these, steric and hydrational forces, which arise from the loss of entropy when adsorbed polymer layers or hydrated chains of non-ionic polyether surfactant intermingle on close approach of two similar droplets, are more important (Fig. 4B). In emulsions stabilized by polyether surfactants, these interactions assume importance at very close distances of approach and are influenced markedly by temperature and degree of hydration of the polyoxyethylene chains. With block copolymers of the ethylene oxide-propylene oxide... 

Further thinning can cause an additional transformation into a thinner stable region (a stepwise transformation). This usually occurs at high electrolyte concentrations, which in turn leads to a second, very stable, thin black film that usually is referred to as Newton secondary black film, with a thickness in the region of 4nm. Under these conditions the short-range steric or hydration forces control the stability, and this provided the third contribution to the disjoining press, as described in Equation (16.9). 

Electrostatic forces hold a small number of H2O molecules around a Li ion in a primary hydration sphere. These molecules, in turn, hold other molecules, but more weakly, in a secondary hydration sphere. 

While the system conforms to coagulation in a secondary minimum, the redispersion region is best accounted for in terms of gel formation originating from the rod-like shape of the particles and hydrated surface. During the final coagulation process additional attractive forces such as dipolar and hydrogen bonding form floes which are irreversible and denser than those formed at a lower salt concentration. 

Bonding Forces Between Dye and Fiber. Dye anions can participate in ionic interactions with fibers that possess cationic groups. However, the formation of ionic bonds is not sufficient to explain dye binding, because compounds that can dissociate are cleaved in the presence of water. Secondary bonds (dispersion, polar bonds, and hydrogen bonds) are additionally formed between dye and fiber [47], Close proximity between the two is a prerequisite for bond formation. However, this is counteracted by the hydration spheres of the dye and of wool keratin. On approach, these spheres are disturbed, especially at higher temperature, and common hydration spheres are formed. The entropy of the water molecules involved is increased in this process (hydrophobic bonding). In addition, coordinate and covalent bonds can be superimposed on secondary and ionic bonds. 

Hydrated ruthenium dioxide will act as a catalyst for the oxidation of primary allylic alcohols (equations 8 and 9) in an oxygen atmosphere (a trace of the antioxidant 2,6-di-r-butyl-4-methylphenol is required to prevent autoxidation of the aldehyde to the acid). The oxidation is not accompanied by any loss in double bond stereochemistry, secondary allylic alcohols are oxidized but at a decreased rate, and saturated alcohols are scarcely oxidized at all. However, a-hydroxy ketones and a-hydroxylactones will oxidize under forcing conditions, so there is clearly likely to some degree of substrate dependence. ... 

Of course, Van der Waals and other secondary forces can be included in more sophisticated computations. Thus, as the water content drops below a level at which completely populated hydration shells can exist, the electrostatic shielding effect of the... 

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