Metal surface precipitates, formation

As the amount of metal cation or anion sorbed on a surface (surface coverage or loading, which is affected by the pH at which sorption occurs) increases, sorption can proceed from mononuclear adsorption to surface precipitation (a three-dimensional phase). There are several thermodynamic reasons for surface precipitate formation (1) the solid surface may lower the energy of nucleation by providing sterically similar sites (McBride, 1991) (2) the activity of the surface precipitate is less than 1 (Sposito, 1986) and (3) the solubility of the surface precipitate is lowered because the dielectric constant of the solution near the surface is less than that of the bulk solution (O Day et al., 1994). There are... 

Thus, witli time, one can see that metal sorption on soil minerals can often result in a continuum of processes from adsorption to precipitation to solid-phase transformation (Figure 3.10), particularly in the case of metals such as Co, Ni, and Zn. The formation of metal surface precipitates could be an important mechanism... 

Ni Sorption on Clay Minerals A Case Study. Initial research with Co/clay mineral systems demonstrated the formation of nucleation products using XAFS spectroscopy, but the stmcture was not strictly identified and was referred to as a Co hydroxide-like stmcture (11,12). Thus, the exact mechanism for surface precipitate formation remained unknown. Recent research in our laboratory and elsewhere suggests that during sorption of Ni and Co metal ions, dissolution of the clay mineral or aluminum oxide surface can lead to precipitation of mixed Ni/Al and Co/Al hydroxide phases at the mineral/water interface (14,16,17,67,71). This process could act as a significant sink for metals in soils. The following discussion focuses on some of the recent research of our group on the formation kinetics of mixed cation hydroxide phases, using a combination of macroscopic and molecular approaches (14-17). 

Precipitate formation can occur upon contact of iajection water ions and counterions ia formation fluids. Soflds initially preseat ia the iajectioa fluid, bacterial corrosioa products, and corrosion products from metal surfaces ia the iajectioa system can all reduce near-weUbore permeability. Injectivity may also be reduced by bacterial slime that can grow on polymer deposits left ia the wellbore and adjacent rock. Strong oxidising agents such as hydrogen peroxide, sodium perborate, and occasionally sodium hypochlorite can be used to remove these bacterial deposits (16—18). 

Reduced injectivity due to formation damage can be a significant problem in injection wells. Precipitate formation due to ions present in the injection water contacting counterions in formation fluids, solids initially present in the injection fluid (scaling), bacterial corrosion products, and corrosion products from metal surfaces in the injection system can all reduce permeability near the wellbore (153). The consequent reduced injection rate can result in a lower rate of oil production at offset wells. Dealing with corrosion and bacterial problems, compatibility of ions in the injection water and formation fluids, and filtration can all alleviate formation damage. 

Adsorption influences the reactivity of surfaces. It has been shown that the rates of processes such as precipitation (heterogeneous nucleation and surface precipitation), dissolution of minerals (of importance in the weathering of rocks, in the formation of soils and sediments, and in the corrosion of structures and metals), and in the catalysis and photocatalysis of redox processes, are critically dependent on the properties of the surfaces (surface species and their strucutral identity). 

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). 

Fe(III)(hydr)oxides introduced into the lake and formed within the lake - Strong affinity (surface complex formation) for heavy metals, phosphates, silicates and oxyanions of As, Se Fe(III) oxides even if present in small proportions can exert significant removal of trace elements. - At the oxic-anoxic boundary of a lake (see Chapter 9.6) Fe(III) oxides may represent a large part of settling particles. Internal cycling of Fe by reductive dissolution and by oxidation-precipitation is coupled to the cycling of metal ions as discussed in Chapter 9. 

Filer JM, Mojzsis SJ, Arrhenius G (1997) Carbon isotope evidence for early life discussion. Nature 386 665 Emerson D (2000) Microbial oxidation of Ee(II) and Mn(II) at circumneutral pH. In Environmental metal-microbe interactions. Lovley DR (ed) ASM Press, Washington DC, p 31-52 Ewers WE (1983) Chemical factors in the deposition and diagenesis of banded iron-formation. In Iron formations facts and problems. Trendall AF, Morris RC (eds) Elsevier, Amsterdam, p 491-512 Farley KJ, Dzombak DA, Morel FMM (1985) A surface precipitation model for the sorption of cations on metal oxides. J Colloid Interface Sci 106 226-242... 

The formation of carbon over Ni, Fe, and Co has been extensively studied, both for catalytic applications " and for dusting or dry corrosion, the problem of pitting when steels are exposed to hydrocarbons at high temperatures. Recently, the properties of Ni for forming carbon have even been proposed for use in the manufacture of carbon nanofibers. The mechanism on each of these metals, shown diagrammatically in Figure 8a, involves deposition of a carbon source onto the metal surface, dissolution of the carbon into the bulk of the metal, and finally precipitation of carbon as a fiber... 

Adsorption inhibitors act by forming a film on the metal surface. The action of traditional oil-based red lead paint formulations presumably involves the formation of soaps and the precipitation of complex ferric salts that reinforce the oxide film. There has been substantial interest in recent years in development of replacements for lead-based and chromate-based inhibitor systems. Adsorption inhibitors based on pol3rmers have been of particular interest. In this volume, Johnson et al. and Eng and Ishida discuss inhibitors for copper 2-undecylimidazole is shown to be effective in acid media, where it suppresses the oxygen reduction reaction almost completely. Polyvlnyllmidazoles are shown to be effective oxidation inhibitors for copper at elevated temperatures. Also in this volume, Chen discusses the use of N-(hydroxyalkyl)acrylamide copolymers in conjunction with phosphate-orthophosphate inhibitor systems for cooling systems. 

The corrosion process can be inhibited by the addition of phosphate or polyphosphate ions [344], inorganic inhibitors as, for example, chromate ions [336], adsorbed alcohols [345], adsorbed amines, competing with anions for adsorption sites [339,] as well as saturated linear aliphatic mono-carboxylate anions, CH3(CH2)n-2COO , n = 7 — 11, [24]. In the latter case, the formation of the passive layer requires Pb oxidation to Pb + by dissolved oxygen and then precipitation of hardly soluble lead carboxylate on the metal surface. The corrosion protection can also be related to the hydrophobic character of carboxylate anions, which reduce the wetting of the metal surface. 

The original parfait method rested on the use of vacuum distillation—lyophilization to concentrate the poorly volatile species in water. It might be expected that the removal of water under vacuum should be simple and straightforward. Vacuum distillation and lyophilization do indeed recover the poorly volatile contaminants from unfractionated surface waters. However, the compounds are often obtained in an intractable, insoluble form. These intractable precipitates are believed to form when bicarbonate dissociates under vacuum to form metal carbonate precipitates that trap organic polymers and lipids (4, 5). The parfait method prevents the formation of these precipitates by removing metal ions on an acidic cation-exchange bed. 

Redox Reactions. Aquatic organisms may alter the particular oxidation state of some elements in natural waters during activity. One of the most significant reactions of this type is sulfate reduction to sulfide in anoxic waters. The sulfide formed from this reaction can initiate several chemical reactions that can radically change the types and amounts of elements in solution. The classical example of this reaction is the reduction of ferric iron by sulfide. The resultant ferrous iron and other transition metals may precipitate with additional sulfide formed from further biochemically reduced sulfate. Iron reduction is often accompanied by a release of precipitated or sorbed phosphate. Gardner and Lee (21) and Lee (36) have shown that Lake Mendota surface sediments contain up to 20,000 p.p.m. of ferrous iron and a few thousand p.p.m. of sulfide. The biochemical formation of sulfide is undoubtedly important in determining the oxidation state and amounts of several elements in natural waters. 

We believe that these phenomena can be explained byassuminga skin of silica on the metal surface. The fact that such a skin develops is readily acceptable for the hydrosilicates, since actually the prereduction state shows this skin in the form of Si206 layers on top of the octahedral layers containing the Ni++ ions. That, however, even co-precipitation catalysts such as 5421 in which no hydrosilicate formation could be observed by thermal analysis show inaccessibility comes somewhat as a surprise (Fco/Fr = 0.8 46% Ni removable). 

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