Metal-hydroxide surface precipitates

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... 

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). 

Co-precipitation. - The preparation of supported catalysts by the coprecipitation of metal ions with the support ions usually produces an intimate mixing of catalysts and support. An example of this technique is the coprecipitation of metal ions with aluminium ions to produce a precipitated alumina gel containing the metal hydroxide. This precipitate when calcined produces a refractory support with active component dispersed throughout the bulk as well as at the surface. However, in the preparation of multi-component catalysts, it is possible under improper conditions to obtain a heterogeneous product because of the different solubility products of the constituents. Care should be taken therefore to avoid this undesirable situation by appropriate forethought. 

Mixed Co-Al and Zn-Al hydroxide surface precipitates can also form on aluminum-bearing metal oxides and phyllosilicates (Towle et al., 1997 Thompson et al., 1999a,b Ford and Sparks, 2000). This is not surprising, as Co " ", Zir+, and NP+ all have radii similar to AP+, enhancing substitution in the mineral structure and formation of a coprecipitate. However, surface precipitates have not been observed with Pb2+, as Pb-+ is too large to substitute for AP+ in mineral structures (Sparks, 2002, 2005). 

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. 

The carbon dioxide produced can contribute to the corrosion of metal. The deposits of ferric hydroxide that precipitate on the metal surface may produce oxygen concentration cells, causing corrosion under the deposits. Gallionalla and Crenothrix are two examples of iron-oxidizing bacteria. 

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. 

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. 

Several other explanations have been put advanced to explain retention hysteresis, including (1) surface precipitation of metallic cations whose hydroxides, phosphates, or carbonates are sparingly soluble (2) chemical reactions with solid surfaces, including organic surfaces, which form complexes with metallic cations and (3) incorporation into the subsurface organic matter through chemical reactions and biochemical transformation. For the case described by Fig. 5.9 or explanations (1) and (2), the contaminant release always exhibits a hysteresis... 

Metal removal from surface water, groundwater or wastewater streams is more straightforward than that from soils. Typically, removal is achieved by concentration of the metal within the wastestream using flocculation, complexation, and/or precipitation. For example, the use of lime or caustic soda will cause the precipitation and flocculation of metals as metal hydroxides. Alternatively, ion exchange, reverse osmosis, and electrochemical recovery of metals can be used for metal removal (Chalkley et al., 1989 Moore, 1994). Unfortunately, these techniques can be expensive, time-consuming and sometimes ineffective, depending on the metal contaminant present. 

Smectite-type materials were synthesized with a hydrothermal method [5]. The aqueous solution of sodium silicate (Si02 / NajO= 3.22) and sodium hydroxide was mixed with the aqueous solution of metal chloride to precipitate Si-M (M divalent metal cation, Si M = 8 6) hydroxides. The precipitation pH of Si-M hydroxide was controlled by changing the molar ratio of sodium hydroxide to sodium silicate. After separating and washing of Si-M hydroxide, slurries were prepared from Si-M hydroxide and water. The Si-M slurries were treated hydrothermally in an autoclave at 473 K under autogaseous water vapor pressure for 2 h. The resultant samples were dried at 353 K then we obtained smectite samples. The smectite-type materials are denoted by the divalent species in octahedral sheets and BET surface area, e.g., Ni-481 for the Ni2+ substituted smectite-type material with a surface area of 481 m2g. ... 

It is well known that hydrolyzed polyvalent metal ions are more efficient than unhydrolyzed ions in the destabilization of colloidal dispersions. Monomeric hydrolysis species undergo condensation reactions under certain conditions, which lead to the formation of multi- or polynuclear hydroxo complexes. These reactions take place especially in solutions that are oversaturated with respect to the solubility limit of the metal hydroxide. The observed multimeric hydroxo complexes or isopolycations are assumed to be soluble kinetic intermediates in the transition that oversaturated solutions undergo in the course of precipitation of hydrous metal oxides. Previous work by Matijevic, Janauer, and Kerker (7) Fuerstenau, Somasundaran, and Fuerstenau (I) and O Melia and Stumm (12) has shown that isopolycations adsorb at interfaces. Furthermore, it has been observed that species, adsorbed at the surface, destabilize colloidal suspensions at much lower concentrations than ions that are not specifically adsorbed. Ottewill and Watanabe (13) and Somasundaran, Healy, and Fuerstenau (16) have shown that the theory of the diffuse double layer explains the destabilization of dispersions by small concentrations of surfactant ions that have a charge opposite to... 

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