Metal- hydroxide surfaces

Huang, C. Stone, A.T. Hydrolysis of naptalam and structurally related amides inhibition by dissolved metal ions and metal hydroxide surfaces. J. Agric. Food Chem. 1999, 47, 4425. 

The mechanism for the formation of metal hydroxide surface precipitates is not clearly understood. It is clear that the type of metal ion determines whether metal hydroxide surface precipitates form, and the type of surface precipitate formed (i.e., metal hydroxide or mixed metal hydroxide) is dependent on the sorbent type. The precipitation could be explained by the combination of several processes (Yamaguchi et al., 2001). First, the electric field of the mineral surface attracts metal ions (e.g., Ni) through adsorption, leading to a local supersaturation... 

The formation of metal hydroxide surface precipitates and subsequent residence time effects on natural sorbents can greatly affect metal release and hysteresis. It has generally been thought that the kinetics of formation of surface precipitates was slow. However, recent studies have shown that metal hydroxide precipitates can form on time scales of minutes. In Figure 3.7 one can see that mixed Ni-Al hydroxide precipitates formed on pyrophyllite within 15 minutes, and they grew in intensity as time increased. Similar results have been observed with other soil components and with soils (Scheidegger et ak, 1998 Roberts et ak, 1999 Sparks, 2002, 2005). 

The formation and subsequent aging of the metal hydroxide surface precipitate can have a significant effect on metal release. In Figure 3.8 one sees that as residence time (aging) increased from 1 hour to 2 years, Ni release from pyrophyllite, as a percentage of total Ni sorption, decreased from 23 to 0% when HNO3 (at pH 6.0) was employed as a dissolution agent for 14 days. This... 

A1 as the carboxylate anion, but this interaction results in a weakly bound, easily displaced adsorbate [296, 297]. Schwartz and Bernasek [468-470] developed a method to increase the binding of SAMs of carboxylic acids on a hydroxide terminated AI2O3 /A1 surface by first priming the metal hydroxide surface vyith Zr alkoxide. This study... 

Electrical properties of filled resin systems are also improved by filler treatment. Filler particles are naturally hydrophilic via their metal hydroxide surfaces, and the particles naturally seek to agglomerate with each other, and so transport electrical charges through resin composite. Treatment with silane-coupling agent alters the chemistry of the filler surface, allow better dispersion of the filler throughout the resin matrix, and imparts improved electrical properties to the composite. Table 15.13 indicates the improved electrical properties of a quartz-fiUed epoxy resin system with 0.3% silane admixed into the formulation. Improved insulation values, including reduced dielectric constant and reduced dissipation factor, are also denoted. 

Thermal Quenching. Endothermic degradation of the flame retardant results in thermal quenching. The polymer surface temperature is lowered and the rate of pyrolysis is decreased. Metal hydroxides and carbonates act in this way. 

Figure 18-82 illustrates the relationship between solids concentration, iuterparticle cohesiveuess, and the type of sedimentation that may exist. Totally discrete particles include many mineral particles (usually greater in diameter than 20 Im), salt crystals, and similar substances that have httle tendency to cohere. Floccnleut particles generally will include those smaller than 20 [Lm (unless present in a dispersed state owing to surface charges), metal hydroxides, many chemical precipitates, and most organic substances other than true colloids. 

When ethoxylated nonylphenol and polyethylene glycol is treated with a mixture of H2S04 and H3P04 and neutralized with an alkali metal hydroxide or amine, surfactants containing sulfate esters and phosphate esters are obtained which cause little corrosion of metals such as surfaces of laundering equipments and automobiles [55]. 

Thus, it was established that adsorption of metal hydroxide species on the surface of the substrate provides a nucleation layer which is chemically converted to the metal chalcogenide. The forming metal chalcogenide layer acts then as a catalytic surface for subsequent anion and cation adsorption. 

The approach comprises deposition-precipitation (DP) of Au(OH)3 onto the hydroxide surfaces of metal oxide supports from an alkaline solution of HAUCI4 [26] and grafting of organo gold complexes such as dimethyl gold (Ill)acetylacetonate (hereafter denoted as Au acac complex) [27] and Au(PPh3)(N03) [28] either in gas and liquid phase are advantageous in that a variety of metal oxides commercially available in the forms of powder, sphere, honeycomb can be used as supports. 

Proposed intermediates in the above reaction include atomic hydrogen [27, 28], hydride ions [29, 30], metal hydroxides [31], metaphosphites [32, 33], and excitons [34]. In general, the postulated mechanisms are not supported by direct independent evidence for these intermediates. Some authors [35] maintain that the mechanism is entirely electrochemical (i.e. it is controlled by electron transfer across the metal-electrolyte interface), but others [26] advocate a process involving a surface-catalyzed redox reaction without interfacial electron transfer. 

Two basic methods have been used to grow metal oxide thin films by the SILAR technique (see Table 8.1). The more common of these methods consists of the adsorption of metal hydroxide ions on the substrate surface followed by thermal treatment to convert hydroxide to an oxide. Another way to produce metal oxide films is to use hydrogen peroxide as the anion precursor and then to convert the formed metal peroxide film to an oxide film. Several examples of each approach are discussed in more detail below. 

The distribution of metals between solution and the ferric hydroxide surface varies strongly with pH (Fig. 31.5). As discussed in Sections 10.4 and 14.3, pH exerts an important control over the sorption of metal ions for two reasons. First, the electrical charge on the sorbing surface tends to decrease as pH increases, lessening the electrical repulsion between surface and ions. More importantly, because hydrogen ions are involved in the sorption reactions, pH affects ion sorption by mass action. The sorption of bivalent cations such as Cu++,... 

As a result, the metal ions are progressively partitioned onto the ferric hydroxide surface as pH increases. 

TETRA HDS [High density solids] A process for aiding the removal of heavy metals from wastewaters. It is a physical process which controls the characteristics of heavy metal hydroxide precipitates so that they settle quicker. The precipitates have a hydrophobic surface, so they are easy to de-water. Developed and licensed by Tetra Technologies, Houston, TX. Widely used by the iron and steel industry in the United States. Not to be confused with hydrodesulfurization, often abbreviated to HDS. 

In surface precipitation cations (or anions) which adsorb to the surface of a mineral may form at high surface coverage a precipitate of the cation (anion) with the constituent ions of the mineral. Fig. 6.9 shows schematically the surface precipitation of a cation M2+ to hydrous ferric oxide. This model, suggested by Farley et al. (1985), allows for a continuum between surface complex formation and bulk solution precipitation of the sorbing ion, i.e., as the cation is complexed at the surface, a new hydroxide surface is formed. In the model cations at the solid (oxide) water interface are treated as surface species, while those not in contact with the solution phase are treated as solid species forming a solid solution (see Appendix 6.2). The formation of a solid solution implies isomorphic substitution. At low sorbate cation concentrations, surface complexation is the dominant mechanism. As the sorbate concentration increases, the surface complex concentration and the mole fraction of the surface precipitate both increase until the surface sites become saturated. Surface precipitation then becomes the dominant "sorption" (= metal ion incorporation) mechanism. As bulk solution precipitation is approached, the mol fraction of the surface precipitate becomes large. 

Fig. 6.10 shows idealized isotherms (at constant pH) for cation binding to an oxide surface. In the case of cation binding, onto a solid hydrous oxide, a metal hydroxide may precipitate and may form at the surface prior to their formation in bulk solution and thus contribute to the total apparent "sorption". The contribution of surface precipitation to the overall sorption increases as the sorbate/sorbent ratio is increased. At very high ratios, surface precipitation may become the dominant "apparent" sorption mechanism. Isotherms showing reversals as shown by e have been observed in studies of phosphate sorption by calcite (Freeman and Rowell, 1981). 

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