Adsorbable solutes, organic

Fe electrodes with electrochemically polished (cathodically pretreated for 1 hr) and renewed surfaces have been investigated in H20 + KF and H20 + Na2S04 by Rybalka et al.721,m by impedance. A diffuse-layer minimum was observed at E = -0.94 V (SCE) in a dilute solution of Na2S04 (Table 19). In dilute KC1 solutions E,njn was shifted 40 to 60 mV toward more negative potentials. The adsorbability of organic compounds (1-pentanol, 1-hexanol, cyclohexanol, diphenylamine) at the Fe electrode was very small, which has been explained in terms of the higher hydro-philicity of Fe compared with Hg and Hg-like metals. 

Fig. 4.20b shows how, in addition to adsorption, biodegradation can affect the movement of organic compounds (note that the abscissa in Fig. 20b is different from that in Fig. 20a). While a conservative contaminant would behave just as the water in which it is contained, an adsorbable solute (as in Fig. 20a) is retarded and arrives at the observation well later than the conservative contaminant. Biodegradation would act to destroy the organic contaminant, so it s concentration at the observation well would never reach Co its concentration would initially be governed by dispersion alone, until sufficient time had passed to establish an acclimated bacterial population with sufficient mass to change the organic concentration (McCarty et al 1981).

In any study of electrosorption of neutral molecules on metallic electrodes, the ions of supporting electrolytes should not be specifically adsorbed. Nevertheless, the interaction of the electrolyte ions with the electrode surface may depend on the interaction of the ions with the solvent. Usually, the stronger the ion-solvent interaction, the weaker the adsorption of the ion. Since the ions are more weakly solvated in nonaqueous solvents than in water, the ions that are not adsorbed from aqueous solutions may still be adsorbed from organic solvents. However, even in the absence of... 

Before analysis of semi- or nonvolatile components can proceed, it is necessary that the hydrocarbon components be brought into solution. In a sample from a contaminated site, semi- and nonvolatile molecules may exist in the soil pores in the free form within the pore spaces, but are far more likely to be adsorbed by organic matter attached to the soil. Indeed, the probability of such adsorption increases with increasing hydrophobicity of the molecules. 

The XAD-4 quaternary resin used in these studies was prepared by the Ames Laboratory in Ames, Iowa. This resin had been used in studies by the Ames group for the adsorption and selective separation of acidic material in waste waters. For this study, the resin was chosen for its effectiveness in concentrating anionic material from solution. At the same time, it was thought that sufficient sites would be available to effectively adsorb neutral organic compounds from water. The resin was basically an XAD-4 macroreticular cross-linked polystyrene into which a trimethylamine group was introduced. The resin was stored in the chloride form but was converted to the hydroxide form before use in the resin sorption experiments. 

Reduced Surface Tension. Just as surfactants self-organize in the bulk solution as a result of their hydrophilic and hydrophobic segments, they also preferentially adsorb and organize at the solution—vapor interface. In the case of aqueous surfactant solutions, the hydrophobic tails protrude into the vapor and leave only (he hydrophilic head groups in contact with the solution. The favorable energetics of the arrangement can be seen by the reduction in Ihe interracial free energy per unit area, nr surface tension, it. 

The surface of the sample container may interact with the analyte. The surfaces can provide catalysts (e.g., metals) for reactions or just sites for irreversible adsorption. For example, metals can adsorb irreversibly on glass surfaces, so plastic containers are chosen for holding water samples to be analyzed for their metal content. These samples are also acidified with HNO3 to help keep the metal ions in solution. Organic molecules may also interact with polymeric container materials. Plasticizers such as phthalate esters can diffuse from the plastic into the sample, and the plastic can serve as a sorbent (or a membrane) for the organic molecules. Consequently, glass containers are suitable for organic analytes. Bottle caps should have Teflon liners to preclude contamination from the plastic caps. 

Erosion-corrosion. Generally, all types of corrosive media can cause erosion-corrosion, including aqueous solutions, organic media, gases, and liquid metals. The corrodent can be a bulk fluid, a film, droplets or a substance adsorbed on or absorbed on another substance. For example, hot gases may oxidize a metal at high velocity and blow off an otherwise protective scale. Solid suspensions in liquids (slurries) are particularly destructive from the standpoint of erosion corrosion.16 31... 

Adsorbed films of ethykriethoxysilane and vinyltriethoxy-silane were formed on silica and alumina by retraction from hydrocarbon solution and their wettabilities and water-stabilities determined. The vinyltriethoxysilane films were generally more oleophobic, more hydrophobic and more resistant to contact with water than the films formed by the ethyl analog. Neither adsorbate formed stable films on a-alumina. The addition of low molecular weight organic acids or bases to the adsorbate solution resulted in both the ethyl and vinyl compound forming hydrophobic and water-stable films on silica and ot-alumina. Films of p-chloro-phenyl-ft-ethyltrichloro, -trimethoxy, and -triethoxysilane were also studied and found to be water-stable and to have wettabilities characteristic of a surface comprised of closely-spaced p-chlorophenyl groups. 

Acid-Base Catalyzed Adsorption. It was found that the addition of low molecular weight organic acids and bases to the adsorbate solutions produced ETES and VTES films that were much more hydrophobic and resistant to the water desorption test than the films formed by the tri-ethoxysilanes alone. Tables I and II list the values of yc and 0H2o for the films produced in the presence of various acids and bases. Also included are the data for the films formed by ETES and VTES alone. In all cases the adsorption time was 20-24 hours, the solvent was a-chloro-naphthalene and the triethoxysilane concentration was 1% by weight. 

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