Surfactant solubilization rate

Flocculation values achieved from turbidity measurements using the light scattering technique showed improvement with nonylphenol ether carboxylic acid (4 mol EO) in particular. The oil solubilization rate has been found to be proportional to the surfactant micellar size [190]. 

This paper presents a new finding that the oil solubilization rate is a function of the surfactant aggregate size. This idea originated from Chiu s observation on solubilization phenomena in tertiary oil recovery. 

Although the proposed theory has been used effectively in several practical applications, no experimental proof has been given that the oil solubilization rate is a function of surfactant aggregate size. In view of the importance of solubilization and the existence of practical methods of measuring and controlling surfactant aggregate size, we decided to correlate the solubilization rate with micellar properties for some anionic and nonionic surfactants. 

Light scattering technique was used in determining the oil solubilization rate. Debye s equation ( ) was used in the interpretation. The basic principle involves the measurement of the surfactant aggregate size during the solubilization. As the oil goes into the surfactant micelle, the increased size will be reflected by the turbidity of the solution. 

A Proposed Theory. In earlier publications (1-3), a theory was proposed to correlate solubilization rate, interfacial tension and size of the surfactant aggregate (1) the interfacial tension lowering between the oil-surfactant solution interface is a function of the rate of solubilization of oil, and (2) the rate of solubilization (AS/At) is a function of the effective volume for solubilization ... 

Up to this moment we have studied the solubilization rate of several oily materials in some nonionic and anionic surfactants. 

This paper presents a very basic principle in surfactant solubilization. More quantitative measurement in correlating solubilization rate with micellar properties and more applications of this principle to improve performance of various solubilization processes remain the subject of our investigation. 

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. 

Fig. 8.20 Solubilization rate of trichloroethylene as affected by surfactant type and concentration Cs and C denote surfactant concentration and initial surfactant concentration, respectively. Reprinted from Zhong L, Mayer AS, Pope GA (2003) The effects of surfactant formulation on nonequUibrium NAPL solubilization. J Contam Hydrol 60 55-75. Copyright 2003 with permission of Elsevier.

Proteins and enzymes have been successfully entrapped in surfactant-solubilized water pools in organic solvents [268-278]. Furthermore, many reversed-micelle-entrapped enzymes retained their activity and could be used for peptide synthesis [273,274]. That the water pools corresponding to very small w-values exhibited freezing points Mow — 50°C enabled both the enzyme structures and the rates of enzyme-catalyzed reactions to be investigated at low temperatures. These studies much aided the development of cryoenzymology [279, 180],... 

In previous studies, the solubilization of hydrophobic organic contaminants using surfactants has been shown to increase the rate of contaminant desorption from soil to water (Deitsch and Smith 1995 Yeom et al. 1995 Tiehm et al. 1997). A 3,000 mg/L solution of Triton X-100 (CMC = 140 mg/L) increased the rate of desorption of laboratory-contaminated TCE from a peat soil (Deitsch and Smith 1995). However, the solubilization effect was secondary compared to the surfactant s effect on the desorption rate coefficient. Yeom et al (1995) developed a model that satisfactorily predicted the extent of polycyclic aromatic hydrocarbon solubilization from a coal tar-contaminated soil. Only at high surfactant dosages did the model fail to accurately predict the ability of different surfactants to solubilize polycyclic aromatic hydrocarbons. It was hypothesized that mass-transfer limitations encountered by the polycyclic aromatic hydrocarbons in the soil caused the observed differences between the data and the model simulations. In another study (Tiehm et al. 1997), two nonionic surfactants, Arkopal N-300 and Saogenat T-300, increased the rate of polycyclic aromatic hydrocarbon desorption from a field-contaminated soil. The primary mechanism for the enhanced desorption of polycyclic aromatic hydrocarbons was attributed to surfactant solubilization of the polycyclic aromatic hydrocarbons. 

The overall objective of this research was to evaluate the effects of cosolvent addition on the ability of an ethoxylated nonionic surfactant to recover PCE from a heterogeneous, 2-D system. The specific tasks of this work were to (a) quantify the PCE solubilization rate and capacity in the presence and absence of a representative cosolvent (EtOH) and (b) investigate the effects of EtOH addition on surfactant delivery, plume migration and PCE recovery in a 2-D, layered sand tank. A representative nonionic surfactant, polyoxyethylated (POE) (20) sorbitan monooleate (Tween 80), was selected for study because of its capacity to solubilize PCE ( 0.7 g PCE/g surf at 20°C) and relatively high interfacial tension with PCE (5 dynes/cm). EtOH was chosen as the representative cosolvent because of its relatively low density (p = 0.79 g/cm1) and regulatory acceptance. 

Enhanced bacterial growth rate and increased rate of n-alkane consumption Surfactant solubilization increases aqueous solubility of hydrocarbon 24... 

In the next section a simple model is described that provides some understanding of the essentials of solubilization. Then some measurement techniques, experimental results, and theories of equilibrium solubilization are presented for micelles and microemulsions. Finally, dynamic phenomena such as solubilization rates and solubilization by intermediate phases formed after the solute contacts a surfactant solution are discussed. 

FIGURE 9.6 Schematic illustration of contacting experiment in which a small oil drop is injected into an aqueous surfactant solution to measure solubilization rate. 

For solutions of typical ionic surfactants with no added salts the studies of Carroll and Ward showed that solubihzation rates were much smaller than those for nonionic surfactants, presumably because the surfactant ions adsorbed at the oil-water interface repelled the micelles of like charge in the solution. Indeed, Bolsman et al. found no measurable solubilization of n-hexadecane into solutions of a pure benzene sulfonate and a commercial xylene sulfonate. They injected small oil drops into the surfactant solutions and observed whether the resulting turbidity disappeared over time due to solubilization. Similarly, Kabalnov found from Ostwald ripening experiments that the rate of solubilization of undecane into solutions of pure SDS was independent of surfactant concentration and about the same as the rate in the absence of surfactant. That is, the hydrocarbon presumably left the bulk oil phase in this system by dissolving in virtually miceUe-free water near the interface. In similar experiments TayloC and Soma and Papadopoulos observed a small increase in the solubilization rate of decane with increasing SDS concentration. De Smet et al., who used sodium dodecyl benzene sulfonate, which does not hydrolyze, found, like Kabalnov, a minimal effect of surfactant concentration. 

Here a is the drop radius, k a specific solubilization rate determined experimentally, c, the concentration of surfactant in micelles, and 0g and 9 the ratios of concentrations of the soluble species in the bulk and at the interface to the equilibrium solubilization capacity at c,. This equation for interfacially controlled transport is the counterpart to the well-known von Smoluchowski equation for diffusion-controlled transport ... 

Selective solubilization can also occur in mixtures of polar and nonpolar oils. Using their oil drop method described previously, Chen et al. measured solubilization rates of mixtures of triolein and oleic acid in solutions of pure nonionic surfactants. As Figure 9.9 shows for a drop initially containing 85/15 triolein/oleic acid by weight injected into 2 wt% Tergitol 15-S-7 at 35°C, they observed that the solubilization process consisted of two stages. In the first stage, the drop radius... 

Wen and Papadopoulos used videomicroscopy to measure the rate of shrinkage of a single drop of pure water immersed in a surfactant-containing oil phase, which itself was in contact with an aqueous solution of NaCl. They found that the solubilization rate of water was controlled by phenomena at the drop interface, suggesting that transport in multiple emulsions is limited by interfacial effects, not diffusion. 

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