Solubilizing constant, effective

It seems likely that the cationic CPC micelles, which have a large positive charge at or near the micellar surface, interact attractively with the n-molecular orbital system of benzene, and that this interaction contributes to the fact that the solubilization constant for benzene in CPC is approximately twice as large as that in SDS micelles. A preferential interaction between cationic surfactants and aromatic solutes has been reported by several groups of investigators (25-27), and recent work in our laboratory shows that 1-hexadecyltrimethylammonium bromide micelles also solubilize benzene more effectively than do the anionic alkylsulfate surfactant micelles (28). Thus, the tendency of benzene molecules to solubilize near the surface of the cationic micelles, at low XB values, may lead to a partial saturation of surface "sites" by benzene, diminishing the ability of additional benzene molecules to bind near the surface. Such an effect could be responsible for the initial increase in activity coefficient that occurs, particularly in the CPC solutions, as Xg increases. 

Inspection of Table II reveals several trends for the values of the solubilization constants. For DDIEN at pH = 7.0, the values of Kl increase dramatically as the surfactant is changed from CTAB to DDAO to SDS. At the pH specified, DDIEN most likely exists in the diprotonated form (H2L " ") in all three surfactants (32-34). Thus, electrostatic interactions appear to have a major effect on the observed value of Kl for... 

One may then determine the effective solubilizing constant Ksoi of the chelating agent, which is the ratio of bound soluble... 

The product is equal to the equilibrium constant X for the reaction shown in equation 30. It is generally considered that a salt is soluble if > 1. Thus sequestration or solubilization of moderate amounts of metal ion usually becomes practical as X. approaches or exceeds one. For smaller values of X the cost of the requited amount of chelating agent may be prohibitive. However, the dilution effect may allow economical sequestration, or solubilization of small amounts of deposits, at X values considerably less than one. In practical appHcations, calculations based on concentration equihbrium constants can be used as a guide for experimental studies that are usually necessary to determine the actual behavior of particular systems. 

It was noted early by Smid and his coworkers that open-chained polyethylene glycol type compounds bind alkali metals much as the crowns do, but with considerably lower binding constants. This suggested that such materials could be substituted for crown ethers in phase transfer catalytic reactions where a larger amount of the more economical material could effect the transformation just as effectively as more expensive cyclic ethers. Knbchel and coworkers demonstrated the application of open-chained crown ether equivalents in 1975 . Recently, a number of applications have been published in which simple polyethylene glycols are substituted for crowns . These include nucleophilic substitution reactions, as well as solubilization of arenediazonium cations . Glymes have also been bound into polymer backbones for use as catalysts " " . 

The effect of chain length on the pseudo rate constant is shown in Fig. 18. Clearly, the optimum chain length for AOS is 16 carbon atoms. However, at this optimum the rate of oil solubilization for AOS is still below that observed for the reference compound DOBS 103, a sodium alkylbenzenesulfonate with 10-13 carbon atoms in the alkyl chain. Increasing the chain length of IOS subjected to an aging step before hydrolysis with NaOH (IOSa in Fig. 18) leads to a continuously increasing rate of oil solubilization. The highest rate was... 

FIG. 18 The effect of chain length on the pseudo rate constants (Km (100 90)) of n-hexadecane solubilization by olefinsulfonates/dobanol 45-3 solutions at 40°C. AOS, a-olefinsulfonate IOS a, aged I-olefinsulfonate IOS d, directly hydrolyzed I-olefin-sulfonate. 

Solubilization increases almost linearly with hydrogen pressure, at constant temperature and methanol charge. There is a strong effect of temperature, leading to complete solubility at 275°C in less than 30 minutes. Incorporation is best limited by using lower methanol ratios and higher hydrogen pressures. 

What characterizes surfactants is their ability to adsorb onto surfaces and to modify the surface properties. At the gas/liquid interface this leads to a reduction in surface tension. Fig. 4.1 shows the dependence of surface tension on the concentration for different surfactant types [39]. It is obvious from this figure that the nonionic surfactants have a lower surface tension for the same alkyl chain length and concentration than the ionic surfactants. The second effect which can be seen from Fig. 4.1 is the discontinuity of the surface tension-concentration curves with a constant value for the surface tension above this point. The breakpoint of the curves can be correlated to the critical micelle concentration (cmc) above which the formation of micellar aggregates can be observed in the bulk phase. These micelles are characteristic for the ability of surfactants to solubilize hydrophobic substances in aqueous solution. So the concentration of surfactant in the washing liquor has at least to be right above the cmc. 

The extent of solubilization of the substrate to the micelle can be related with the association constant or the binding constant. Some of the important models developed to explain the micellar effect are described briefly as follows ... 

The behavior of metal ions in reversed micelles may be more interesting, since the reversed micelle provides less solvated metal ions in its core (Sunamoto and Hamada, 1978). Through kinetic studies on the hydrolysis of the p-nitrophenyl ester of norleucine in reversed micelles of Aerosol OT and CC14 which solubilize aqueous cupric nitrate, Sunamoto et al. (1978) observed the formation of naked copper(II) ion this easily formed a complex with the substrate ester (formation constant kc = 108—109). The complexed substrate was rapidly hydrolyzed by free water molecules acting as effective nucleophiles. 

Zhong et al. (2003) studied the apparent solubility of trichloroethylene in aqueous solutions, where the experimental variables were surfactant type and cosolvent concentration. The surfactants used in the experiment were sodium dihexyl sulfo-succinte (MA-80), sodium dodecyl sulfate (SDS), polyoxyethylene 20 (POE 20), sorbitan monooleate (Tween 80), and a mixture of Surfonic- PE2597 and Witconol-NPIOO. Isopropanol was used as the alcohol cosolvent. Eigure 8.20 shows the results of a batch experiment studying the effects of type and concentration of surfactant on solubilization of trichloroethylene in aqueous solutions. A correlation between surfactant chain length and solubilization rate may explain this behavior. However, the solubilization rate constants decrease with surfactant concentration. Addition of the cosolvent isopropanol to MA-80 increased the solubility of isopropanol at each surfactant concentration but did not demonstrate any particular trend in solubilization rate of isopropanol for the other surfactants tested. In the case of anionic surfactants (MA-80 and SDS), the solubility and solubilization rate increase with increasing electrolyte concentration for all surfactant concentrations. 

The kinetics and mechanism for oxygen transfer between 4-cyano-V,V,-dimethylaniline V-oxide and a C2-capped mexo-tetraphenylporphyrinatoiron(III) and mc5 o-tetrakis(pentafiuorophenyl)-porphyrinatoiron(III) have been established. Addition of a copper(II) porphyrin cap to an iron(II)-porphyrin complex has the expected effect of reducing both the affinities and rate constants for addition of dioxygen or carbon monoxide. These systems were studied for tetradecyl-substituted derivatives solubilized by surfactants such as poly(ethylene oxide) octaphenyl ether. ... 

Equilibrium constants for the binding between substrates and micelles — Reaction (G) — generally range from 103 to 106 for hydrophobic organic substrates. Furthermore, they are expected to increase as the hydrophobic character of the substrate increases. Figure 8.10b shows that this effect sometimes overshoots optimum solubilization. The figure shows, on a... 

Estimate the effective dielectric constant at the surface of the micelle from the fact that max occurs at 286 nm for dodecyl pyridinium iodide micelles in water. In light of the value estimated in Section 8.3 for the dielectric constant in the vicinity of solubilized benzene, does it seem likely that the value of er for bulk water applies in the Stern layer ... 

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