Nonaqueous phase

Solids present in oil and synthetic muds must be kept wet with the nonaqueous phase to prevent coagulation and settling and mud instabiUty. Oil-wetting agents are normally incorporated in the basic mud package. These materials are typically amines or quaternary ammonium salts having hydrocarbon chains of 10 or more carbon atoms. They also render clays or lignites oil-wet for use in viscosity and filtration control (128). 

Surface activity is not limited to aqueous systems, however. AH of the combiaations of aqueous and nonaqueous phases are known to occur, but because water is present as the solvent phase in the overwhelming proportion of commercially important surfactant systems, its presence is assumed in much of the common terminology of industry. Thus, the water-soluble amphipathic groups are often referred to as solubilizing groups. 

Nonaqueous phase Hquids (NAPLs) present special problems for soil and ground water cleanup. Contaminant transport through ground water depends in part on the water solubiHty of the compound. Because NAPLs cling to subsurface particles and are slow to dissolve in ground water, they hinder cleanups and prolong cleanup times. Dense nonaqueous phase Hquids (DNAPLs) migrate downward in the aquifer and can coUect in pools or pockets of the substmcture. Examples of DNAPLs are the common solvents tetrachloroethylene (PCE) and trichloroethylene (TCE) which were used extensively at many faciHties before the extent of subsurface contamination problems was realized. 

There are many cases of contamination by dense nonaqueous phase Hquids (DNAPLs) that have fmstrated pump and treat efforts. The general consensus is that pump and treat can reduce contamination or keep it from spreading, but it has failed ia many cases to remediate aquifers to stringent cleanup goals. 

In addition to maintaining the circulation of the reaction Hquid, the inert gas is important in temperature control, and it prevents the formation of a separate nonaqueous phase by carrying off substantial quantities of dichloropropane in the effluent. 

An extensive survey has been carried out by McKervey and coworkers [7], who prepared the carbo-alkoxymethyl ethers of p-tert-h x y calix[4]arene, p-/< r/-butyl calix[6]arene, p-tert-bu y calix[8]arene, ca-lix[4]arene, calix[6Jarene, and calix[8]arene, and measured their abilities to extract cations from the aqueous phase into the nonaqueous phase. They concluded the following general aspects for the phase-transfer experiments (1) the calix[4]arene compounds show the greatest selectivity for Na (2) phase-transfer of Li is inefficient with all of the compounds (3) the calix[6]arene compounds show less affinity for Na than for K, with plateau selectivity for Rb" and Cs (4) the calix[8]ar-ene compounds are the least efficient of the cyclic oligomers, showing low levels of transport and low discrimination for all five cations (5) the calix[6]arene... 

Ny lon-6 (108 g) carpet backed with calcium-carbonate-filled latex and polypropylene was charged to a 1000-mL three-neck round-bottom flask (equipped with a condenser) with 6 mL of 85% phosphoric acid. Superheated steam was injected continuously during a 45-min period. The vapor temperature of the reaction medium was 250-300°C. The volume of distillate collected was 1065 mL. The distillate contained 1.9% e-caprolactam (as determined by GC), which corresponded to a crude yield of 37.5%. The distillate was fractionated in a distillation column and the nonaqueous phase removed. The remaining aqueous phase was treated with 2% potassium permanganate at 40-50°C for 2 h. Evaporation of... 

The majority of trichloroethylene present on soil surfaces will volatilize to the atmosphere or leach into the subsurface. Once trichloroethylene leaches into the soil, it appears not to become chemically transformed or undergo covalent bonding with soil components. When trichloroethylene was absorbed onto kaolinite and bentonite, the nuclear magnetic resonance (NMR) spectra showed no evidence of chemical reactions (Jurkiewicz and Maciel 1995). Because trichloroethylene is a dense nonaqueous phase liquid, it can move through the imsaturated zone into the saturated zone where it can displace soil pore water (Wershaw et al. 1994). 

This approach allowed us also to determine the difference in the surface potentials between mutually saturated water and an organic solvent namely, nitrobenzene, nitroethane and 1,2-dichloroethane, and isobutyl methyl ketone (IBMK). The qualitative data show a very strong influence of the added organic solvent on the surface potential of water, while the presence of water in the nonaqueous phase has practically no... 

Ghoshal S, RG Luthy (1996) Bioavailability of hydrophobic organic compounds from nonaqueous-phase liquids the biodegradation of naphthalene from coal tar. Environ Toxicol Chem 15 1894-1900. 

Today, lipophilicity can be determined in many systems that are classified by the characteristics of the nonaqueous phase. When the second phase is an organic solvent (e.g. n-octanol), the system is isotropic, when the second phase is a suspension (e.g. liposomes), it is anisotropic, and when the second phase is a stationary phase in liquid chromatography, it is an anisotropic chromatographic system [6]. Here, we discuss the main aspects of isotropic and anisotropic lipophilicity and their biological relevance the chromatographic approaches are investigated in the following chapter by Martel et al. 

The I term is of particular relevance since, in anisotropic media such as liposomes and artiflcial membranes in chromatographic processes, ionic charges are located on the polar head of phospholipids (see Section 12.1.2) and thus able to form ionic bonds with ionized solutes, which are therefore forced to remain in the nonaqueous phase in certain preferred orientations. Conversely, in isotropic systems, the charges fluctuate in the organic phase and, in general, there are no preferred orientations for the solute. Given this difference in the I term (but also the variation in polar contributions, less evident but nevertheless present), it becomes clear that log P in anisotropic systems could be very different from the value obtained in isotropic systems. 

This dependence is fundamental for electrochemistry, but its key role for liquid-liquid interfaces was first recognized by Koryta [1-5,35]. The standard transfer energy of an ion from the aqueous phase to the nonaqueous phase, AGf J, denoted in abbreviated form by the symbol A"G is the difference of standard chemical potential of standard chemical potentials of the ions, i.e., of the standard Gibbs energies of solvation in both phases. 

As an immiscible organic liquid retained by capillary forces in the pore space between the soil particles. This free organic phase is often referred to with the abbreviation NAPL (nonaqueous phase liquid). 

The formation of semirigid films around nonaqueous-phase liquids (NAPL) with a high resistance to NAPL-water mass transfer... 

Besides petroleum products, other hazardous substances (see Tables 18.7-18.9) are also stored in USTs. Among them, a common and important group is the dense nonaqueous phase liquids (DNAPLs). This group has some different physical properties from petroleum (especially gasoline) that make them behave differently in the way they move underground. This section presents the important factors associated with the cleanup of DNAPLs. 

An insoluble liquid or gas will separate from water, resulting in immiscible-phase separation. The behavior of nonaqueous-phase liquids (NAPLs) that may be lighter (LNAPLs) or denser (DNAPLs)... 

Palmer, C.D. and Johnson, R.L., Physical processes controlling the transport of nonaqueous phase liquids in the subsurface, in Transport and Fate of Contaminants in the Subsurface, EPA 625/4-89/019, U.S. EPA, Washington, 1989. 

Greater tendency to partition into the vapor phase from the nonaqueous phase (vapor pressure) (with the exception of TBA, ethanol, and TAME). 

High airflow rates may result in unintended fracturing leading to nonuniform flow or short-circuiting of injected air in the subsurface, or may result in unintended mobilization of contaminants as nonaqueous phase liquids (NAPL), dissolved in groundwater, or in soil gas. 

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