Iron silicate adsorption

Silicates. For many years, siUcates have been used to inhibit aqueous corrosion, particularly in potable water systems. Probably due to the complexity of siUcate chemistry, their mechanism of inhibition has not yet been firmly estabUshed. They are nonoxidizing and require oxygen to inhibit corrosion, so they are not passivators in the classical sense. Yet they do not form visible precipitates on the metal surface. They appear to inhibit by an adsorption mechanism. It is thought that siUca and iron corrosion products interact. However, recent work indicates that this interaction may not be necessary. SiUcates are slow-acting inhibitors in some cases, 2 or 3 weeks may be required to estabUsh protection fully. It is beheved that the polysiUcate ions or coUoidal siUca are the active species and these are formed slowly from monosilicic acid, which is the predorninant species in water at the pH levels maintained in cooling systems. 

Yoshimura et al. [193] carried out microdeterminations of phosphate by gel-phase colorimetry with molybdenum blue. In this method phosphate reacted with molybdate in acidic conditions to produce 12-phosphomolybdate. The blue species of phosphomolybdate were reduced by ascorbic acid in the presence of antimonyl ions and adsorbed on to Sephadex G-25 gel beads. Attenuation at 836 and 416 nm (adsorption maximum and minimum wavelengths) was measured, and the difference was used to determine trace levels of phosphate. The effect of nitrate, sulfate, silicic acid, arsenate, aluminium, titanium, iron, manganese, copper, and humic acid on the determination were examined. 

Brewer and Spencer [428] have described a method for the determination of manganese in anoxic seawaters based on the formulation of a chromophor with formaldoxine to produce a complex with an adsorption maximum at 450 nm. Sulfide (50 xg/l), iron, phosphate (8 ig/l), and silicate (100pg/l) do not interfere in this procedure. The detection limit is 10 pg/1 manganese. 

As pointed out by Sposito (1984) this equation initiated the surface chemistry of naturally occurring solids. Maarten van Bemmelen published this equation (now referred to as the Freundlich isotherm) more than 100 years ago and distilled from his results, that the adsorptive power of ordinary soils depends on the colloidal silicates, humus, silica, and iron oxides they contain. 

The large specific surface areas of the Fe solid phases (Fe(II,III)(hydr)oxides, FeS2, FeS, Fe-silicates) and their surface chemical reactivities facilitate specific adsorption of various solutes. This is one of the causes for the interdependence of the iron cycle with that of many other elements, above all with heavy metals, some metalloids, and oxyanions such as phosphate. 

Ghromate adsorption by iron oxides is suppressed by a large excess of carbonate or silicate species. Gompetition between silicate and borate adsorption on ferrihydrite was reported by McPhail et ak (1972). Low levels of sulphate suppress uptake of phthalic and chelidimic acids by goethite (Ali Dzombak, 1996 a). 

Anion adsorption and then the exchange of anions mainly takes place on the protonated surface sites of silicates and other oxides (e.g., iron, manganese oxides) and hydroxides, as well as on the positive functional group (e.g., protonated amino groups) of humic substances. It is directed by electrostatic forces. The degree of anion exchange of rocks and soils is usually much less than that of cation exchange. 

There has been recent interest in a somewhat different aspect of adsorption and reaction on metal oxides photocatalysis. The interest stems partially from that role that some transition-metal oxides can play in photochemical reactions in the atmosphere. Atmospheric aerosol particles can act as substrates to catalyze heterogeneous photochemical reactions in the troposphere. Most tropospheric aerosols are silicates, aluminosilicates and salts whose bandgaps are larger than the cutoff of solar radiation in the troposphere (about 4.3 eV) they are thus unable to participate directly in photoexcited reactions. However, transition-metal oxides that have much smaller bandgaps also occur as aerosols — the most prevalent ones are the oxides of iron and manganese — and these materials may thus undergo charge-transfer excitations (discussed above) in the pres-... 

Siliceous oozes are accumulations of opaline silica (opal-A, an amorphous phase of high water content and porosity) in the tests of diatoms, radiolarians, and/or silicoflagellates. Opal-A solubility at 25 °C is 60-130 ppm Si02(aq) (e.g., Williams etal., 1985), and solubility increases with increasing temperature and pressure (Walther and Helgeson, 1977). Adsorption of aluminum and iron on the surfaces of siliceous tests decreases their solubility (Her, 1955 Lewin, 1961). Opal-A is a metastable phase that with burial eventually recrystallizes to quartz, often with another metastable intermediary phase, opal-CT (e.g., Hein et ai, 1978 Williams et ah, 1985 Williams and Crerar, 1985). Opal-CT structurally resembles an inter-layering of the two silica phases, cristobalite... 

Toxic trace elements were isolated from water samples by extraction with di-ethyldithiocarbamate (Table 2.1.2). Following this pre-concentration step the metal ions were adsorbed on a cation-exchange resin using a mixture of tetrahydro-furan-methylglycol-6 M HCl as sorption solution. The succesive elution was treated with 6 M HCl, 1 M HCl and 2 M HNO3 for fractional separation. In another application hexane-isopropanol-HCl mixture was used as the adsorption medium An analytical scheme which provides quantitative results, is described for ion-exchange separation of fifteen major, minor and trace elements in silicates For concentration and separation of copper, chromium, lead and iron an ion-exchanger in phosphate or OH -form was used in various combinations ... 

Although many soil scientists had considered the possible mechanisms which soils employ for the retention [fixation] of phosphorus, it remained for Haseman et al. (1950) to demonstrate that phosphorus could — and in experimental situations did — replace the silicon of micas and clay minerals in order to form crystalline hydrous aluminium phosphates of sodium, ammonium and potassium. Prior to experimentation by this group, associated with the laboratories of the Tennessee Valley Authority (TVA), most authors attributed the retention of phosphorus by soils to combination with calcium to produce fairly insoluble minerals to adsorptive, exchangeable combination with silicate minerals and to formation of phosphates of iron... 

Other publications postulate specific adsorption between the surface and the /3-plane. For example Barrow and Bowden [69] interpreted adsorption of anions on goethite in terms of the mentioned above four layer model. The four layers are (in order of increasing distance from the surface) surface layer (H" and OH ions), the layer of specifically adsorbed anions, the first layer of inert electrolyte counterions (analogous to the /3-layer in TLM). and diffuse layer. This model requires an additional adjustable parameter, namely, the capacitance between the surface and the layer of specifically adsorbed anions. Barrow and Bowden report 2.99 F m for phosphate and 60,000 F m ( ) for silicate. The fit in the four layer model was substantially better than with simpler models for fluoride adsorption, but for other anions equally good fit could be obtained without introducing the additional electrostatic plane. In another paper of this series the capacitance of 3-5 F was used in model calculations of phosphate adsorption on aluminum and iron oxides [92]. Similar approach was used by Venema et al. [93] who applied the 1-pK model to interpret the Cd binding by goethite. The ions were assumed to... 

Noncrystalline aluminosilicates (allophanes), oxides, and hydroxides of Fe, Al, and Mn, and even the edges of layer silicate clays to a lesser extent, provide surface sites for the chemisorption of transition and heavy metals. All of these minerals present a similar type of adsorptive site to the soil solution a valence-unsatisfied OH or H2O ligand bound to a metal ion (usually Fe ", AF, or Mn ). For example, on iron oxides, a trace metal, M, may bind according to the reaction... 

In dishwashing, one must consider soil and surfactant adsorption to both polar and nonpolar surfaces. Metals (aluminum, stainless steel, carbon steel, cast iron, silver, and tin), siliceous surfaces (china, glass, and pottery), and organics (polyethylene, polypropylene, polyethylene terephthalate (PET), polytetrafluoroethylene (PTFE), and wood) present a wide variety of surface characteristics. They span the range of high interfacial free energy (metals and many ceramics) to low interfacial free energy (hydrocarbon polymers) surfaces [27,28],... 

For the study of adsorption to general oxide surfaces, the ideal ionic force-field would be consistent with a molecular mechanics model for dissociable water. Such a forcefield has indeed been developed and has been applied to the study of silicate (Rustad Hay, 1995) and iron(III) (Rustad et al., 1995) hydrolysis in solution, to bulk iron oxyhydroxide structures (Rustad et al., 1996a) and to the protonation of goethite surfaces (Rustad et al., 1996b). 

A conceptual and mechanistic model of particle interactions in silica-iron binary oxide suspensions is described. The model is consistent with a process involving partial Si02 dissolution and sorption of silicate onto Fe(OH)3. The constant capacitance model is used to test the mechanistic model and estimate the effect of particle interactions on adsorbate distribution. The model results, in agreement with experimental results, indicate that the presence of soluble silica interferes with the adsorption of anionic adsorbates but has little effect on cationic adsorbates. 

Type 1 isotherms exhibit prominent adsorption at low relative pressures p/po (the relative pressure p/po is defined as the equilibrium v or pressure divided by the saturation vapor pressure) and then level off. Type 1 isotherm is usually considered to be indicative of adsorption in micropores (e.g., adsorption of benzene on microporous active carbon) or monolayer adsorption due to the stror adsorbent-adsorbate interactions (which may be the case for chemisorption, which involves chemical bonding between adsorbate and the adsorbent surface, e.g., adsorption of hydrogen on iron). In the case of nonpolar gases commonly used for charactmzation of porous solids (nitrogen, argon) [10, 12, 13, 17, 56], chemisorption is unlikely and therefore e I reflects usually adsorption on microporous solids. However, type I isotherms may also be observed for mesoporous materials with pore size close to the micropore range. In particular, in the case of adsorption of N2 at 77 K or Ar at both 77 K and 87 K in cylindrical pores, a type I isotherm would have to level off below the relative pressure of about 0.1 for the material to be exclusively microporous, as inferred fi-om tile results of recent studies of siliceous and carbonaceous ordered mesoporous materials (OMM) [57-59]. Consequently, when a type 1 isotherm does not level off below the relative... 

T-H Hsia, S-L Lo, C-F Lin, D-Y Lee. Characterization of arsenate adsorption on hydrous iron oxide using chemical and physical methods. CoU Surf 85 1-7, 1994. RB Robinson, GD Reed, B Frazier. Iron and manganese sequestration facilities using sodium silicate. J Am Water Works Assoc 84 77-82, 1992. 

Silicate can potentially also affect the surface charge of iron hydroxide (Goldberg, 1985). Silicate is not a primary constituent of the artificial water but it may be dissolved from the quartz sand. The concentration of silicate in equilibrium with Si02 (amorphous) calculated by PHREEQC2 is about 1 mmol/L H4Si04 in case of the artificial water at pH 6. Experimentally determined surface complexation constants for the adsorption of silicate on iron hydroxide were not available. Instead estimates made by linear free-energy relationships from Dzombak and Morel (1990) were implemented in... 

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