Solubility counterion effects

It is important to point out that our investigation of counterion effects in carboxylate soaps has so far been concerned almost exclusively with laurate soaps. Laurate soaps were chosen partly because they are generally convenient to handle in that many of them are readily soluble in water to give solutions of low viscosity, and partly because, as has been shown above, laurate soaps are very effective in enhancing the mechanical and chemical stability of natural rubber latex. It must therefore be borne in mind that the conclusions which have been drawn from this investigation concerning effects attributable to counterion variation in laurate soaps may not be generally valid for carboxylate soaps as a family. 

Bouchet A, Brotin T, Cavagnat D, Buffeteau T (2010) Induced chiroptical changes of a water-soluble cryptophane by encapsulation of guest molecules and counterion effects. Chem Eur J 16 4507 518... 

Figure 20 shows the plot of the surface tension vs. the logarithm of the concentration (or-lg c-isotherms) of sodium alkanesulfonates C,0-C15 at 45°C. In accordance with the general behavior of surfactants, the interfacial activity increases with growing chain length. The critical micelle concentration (cM) is shifted to lower concentration values. The typical surface tension at cM is between 38 and 33 mN/m. The ammonium alkanesulfonates show similar behavior, though their solubility is much better. The impact of the counterions is twofold First, a more polarizable counterion lowers the cM value (Fig. 21), while the aggregation number of the micelles rises. Second, polarizable and hydrophobic counterions, such as n-propyl- or isopropylammonium and n-butylammonium ions, enhance the interfacial activity as well (Fig. 22). Hydrophilic counterions such as 2-hydroxyethylammonium have the opposite effect. Table 14 summarizes some data for the dodecane 1-sulfonates.

Solutions of polyelectrolytes contain polyions and the free (individual) counterions. The dissociation of a polyacid or its salt yields polyanions, and that of a polybase or its salt yields polycations, in addition to the simple counterions. The polyampholytes are amphoteric their dissociation yields polyions that have anionic and cationic functions in the same ion and often are called zwitterions (as in the case of amino acids having HjN and COO groups in the same molecule). Such an amphoter will behave as a base toward a stronger acid and as an acid toward a stronger base its solution properties (particularly its effective charge) will be pH dependent, and an isoelectric point (pH value) exists where anionic and cationic dissociation is balanced so that the polyion s charges add up to zero net charge (and solubility is minimal). 

In principle, all the curves in Figs. 6.1a, 6.2a, and 6.3a would be expected to have solubility limits imposed by the salt formation. Under conditions of a constant counterion concentration, the effect would be indicated as a point of discontinuity (pA flbbs), followed by a horizontal line of constant solubility. S, -. 

We studied the feasibility of phosphate determination in a low water-soluble API hydrochloride salt. The aim of the work was quantification of phosphate below 0.1% and evaluation of the effect of the high chloride counterion on the determination of phosphate. 

The solubility product is the equilibrium constant for the dissolution of a solid salt into its constituent ions in aqueous solution. The common ion effect is the observation that, if one of the ions of that salt is already present in the solution, the solubility of a salt is decreased. Sometimes, we can selectively precipitate one ion from a solution containing other ions by adding a suitable counterion. At high concentration of ligand, a precipitated metal ion may redissolve by forming soluble complex ions. In a metal-ion complex, the metal is a Lewis acid (electron pair acceptor) and the ligand is a Lewis base (electron pair donor). 

One of the first significant advances in the chemistry of TT-allylpalladium complexes was the discovery that alkenes could be directly converted into the corresponding allyl complex by substitution into the allylic C—H bond. A variety of recipes have now been reported that can accomplish this transformation. Initially, palladium chloride17-23 or its more soluble forms, sodium or lithium tetrachloropalladate24-27 and bisacetonitrile palladium dichloride,28-30 in alcohol or aqueous acetic acid solvent were employed. The use of palladium trifluoroacetate, followed by counterion exchange with chloride, represents the mildest and most effective means available to accomplish this reaction.31... 

The theoretical bases for interaction with counterions have been discussed in Sect. 5.1. However, these theories do not take into account the special nature of the ions and only the valency was considered [102-108,114-117]. The solubility caused by the variation in the counterions cannot, for example, be predicted. According to [35] the solubility of poly(diallyldimethylammonium halides) decreases in the order Cl" >Br" >1". The homopolymer precipitates in the iodide form. This is in contrast to ammonium halides where the iodide has the highest solubility [153]. Comparing the effects of Cl", S042", and P043" a very similar in-... 

High concentration, however, is not the only means to obtain LC phases of DNA in aqueous solutions. DNA has been found to collapse upon adding in the solutions various condensing agents, which introduce effective attractive interhelical interactions. This is what happens with alcohols and other solvents, which reduce DNA solubility [40], or with multivalent cations like spermidine, spermine, and cobalt hexamine, which are thought to establish correlated counterion fluctuations with... 

Exploration of the reactivity of cyclohexene silacyclopropane led Woerpel and coworkers to discover that the inclusion of metal salts enabled silylene transfer to monosubstituted olefins at reduced temperatures (Table 7.1).11,74 A dramatic reduction in the temperature of transfer was observed when cyclohexene silacyclopropane was exposed to copper, silver, or gold salts. Silver salts were particularly effective at decomposing 58 (entries 6-11). The use of substoichiometric quantities of silver triflate enabled ra-hexene silacyclopropane 61 to be formed quantitatively at —27°C (entry 6). The identity of the counterion did affect the reactivity of the silver salt. In general, better conversions were observed when noncoordinating anions were employed. While the reactivity differences could be attributed to the solubility of the silver salt in toluene, spectroscopic experiments suggested that the anion played a larger role in stabilizing the silylenoid intermediate. 

Generally speaking, for a stable emulsion a densely packed surfactant film is necessary at the interfaces of the water and the oil phase in order to reduce the interfacial tension to a minimum. To this end, the solubility of the surfactant must not be too high in both phases since, if it is increased, the interfacial activity is reduced and the stability of an emulsion breaks down. This process either can be undesirable or can be used specifically to separate an emulsion. The removal of surfactant from the interface can, for example, be achieved by raising the temperature. By this measure, the water solubility of ionic surfactants is increased, the water solubility of non-ionic emulsifiers is decreased whereas its solubility in oil increases. Thus, the packing density of the interfacial film is changed and this can result in a destabilisation of the emulsion. The same effect can happen in the presence of electrolyte which decreases the water solubility mainly of ionic surfactants due to the compression of the electric double layer the emulsion is salted out. Also, other processes can remove surfactant from the water-oil interface - for instance a precipitation of anionic surfactant by cationic surfactant or condensing counterions. 

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