Coprecipitates, formation

O Day et al., 1994). When the precipitate consists of chemical species derived from both the aqueous solution and dissolution of the mineral, it is referred to as a coprecipitate. The composition of the coprecipitate varies between that of the original solid and a pure precipitate of the sorbing metal. The ionic radius of the sorbing metal and sorbent ions must be similar for coprecipitates to form. Thus, Co(II), Mn(II), Ni(II), and Zn(ll) form coprecipitates on sorbents containing Al(III) and Si(lV) but not Pb(ll), which is considerably larger (1.20 A). Coprecipitate formation is most limited by the rate of mineral dissolution ratlier than by the lack of thermodynamic favorability (McBride, 1994 Scheidegger et al., 1998). If the formation of a precipitate occurs under solution conditions that would in the absence of a sorbent be undersaturated with respect to any known solid phase, this is referred to as surface-induced precipitation (Towle et al., 1997 Sparks, 2002). 

Denecke MA, Reich T, Pompe S, Bubner M, Heise KH, Nitsche H, Allen PG Bucher JJ, Edelstein NM, Shuh DK, Czerwinski KR (1998b) EXAFS investigations of the interaction of humic acids and model compounds with uranyl cations in sohd complexes. Radiochim Acta 82 103-108 Dent AJ, Ramsay JDF, Swanton SW (1992) An EXAFS study of uranyl ions in solutions and sorbed onto sihca and montmorillonite clay colloids. J Colloid Interface Sci 150 45-60 d Espinose de la Caillerie J-B, Kermarec M, Clause (1995a) Impregnation of y-alumina with ( ) and ( ) ions at neutral pH Hydrotalcite-type coprecipitate formation and characterization J Am Chem Soc 117 11471-11481... 

In short, EXAFS can be used as a fingerprint of the coprecipitate formation onto alumina, providing the hydrotalcite structures are not too poorly crystallized. Furthermore, the M(II)/A1(III) atomic ratio in the coprecipitates can be roughly estimated. Thus, the influence of preparation parameters such as the M(II) concentration in the impregnating solution, can also be evaluated. 

The stoichiometry must be exact. Coprecipitation by solid-solution formation, foreign ion entrapment, and adsorption are possible sources of error. 

Inclusions, occlusions, and surface adsorbates are called coprecipitates because they represent soluble species that are brought into solid form along with the desired precipitate. Another source of impurities occurs when other species in solution precipitate under the conditions of the analysis. Solution conditions necessary to minimize the solubility of a desired precipitate may lead to the formation of an additional precipitate that interferes in the analysis. For example, the precipitation of nickel dimethylgloxime requires a plT that is slightly basic. Under these conditions, however, any Fe + that might be present precipitates as Fe(01T)3. Finally, since most precipitants are not selective toward a single analyte, there is always a risk that the precipitant will react, sequentially, with more than one species. 

Another important class of titanates that can be produced by hydrothermal synthesis processes are those in the lead zirconate—lead titanate (PZT) family. These piezoelectric materials are widely used in manufacture of ultrasonic transducers, sensors, and minia ture actuators. The electrical properties of these materials are derived from the formation of a homogeneous soHd solution of the oxide end members. The process consists of preparing a coprecipitated titanium—zirconium hydroxide gel. The gel reacts with lead oxide in water to form crystalline PZT particles having an average size of about 1 ]lni (Eig. 3b). A process has been developed at BatteUe (Columbus, Ohio) to the pilot-scale level (5-kg/h). 

The toxic nature of mercury and its compounds has caused concern over environmental pollution, and governmental agencies have imposed severe restrictions on release of mercury compounds to waterways and the air (see Mercury). Methods of precipitation and agglomeration of mercurial wastes from process water have been developed. These methods generally depend on the formation of relatively insoluble compounds such as mercury sulfides, oxides, and thiocarbamates. MetaUic mercury is invariably formed as a by-product. The use of coprecipitants, which adsorb mercury on their surfaces facihtating removal, is frequent. 

Fig. 15-5 Comparative adsorption of several metals onto amorphous iron oxyhydroxide systems containing 10 M Fej and 0.1 m NaNOs. (a) Effect of solution pH on sorption of uncomplexed metals, (b) Comparison of binding constants for formation of soluble Me-OH complexes and formation of surface Me-O-Si complexes i.e. sorption onto Si02 particles, (c) Effect of solution pH on sorption of oxyanionic metals. (Figures (a), (c) reprinted with permission from Manzione, M. A. and Merrill, D. T. (1989). "Trace Metal Removal by Iron Coprecipitation Field Evaluation," EPRI report GS-6438, Electric Power Research Institute, California. Figure (b) reprinted with permission from Balistrieri, L. et al. (1981). Scavenging residence times of trace metals and surface chemistry of sinking particles in the deep ocean, Deep-Sea Res. 28A 101-121, Pergamon Press.)...

Dining the last couple of years CdS-containing Nafion membranes have been apphed for the photocleavage of H2S . They are not comparable with the monograin membranes because the CdS particles are at randomly distributed in a rather thick Nafion membrane. This technique is attractive for some applications because the semiconductor particles are immobilized . On the other hand, problems may arise because of diffusion problems in the nafion membrane. Mainly the photoassistol Hj-formation at CdS was investigated in the presence of a Pt-catalyst and with coprecipitated ZnS CdS without a catalyst . 

Kahn, M., Coprecipitation, Deposition, and Radiocolloid Formation of Carrier-Free Tracers, Radioactivity applied to Chemistrv(A. C. Wahl, and N. A. Bonner, ed) pp. 403-433, John Wiley Sons, Inc., New York (1951). 

There are several chemical compounds found in the waste waters of a wide variety of industries that must be removed because of the danger they represent to human health. Among the major classes of contaminants, several aromatic molecules, including phenols and aromatic amines, have been reported. Enzymatic treatment has been proposed by many researchers as an alternative to conventional methods. In this respect, PX has the ability to coprecipitate certain difficult-to-remove contaminants by inducing the formation of mixed polymers that behave similarly to the polymeric products of easily removable contaminants. Thus, several types of PX, including HRP C, LiP, and a number of other PXs from different sources, have been used for treatment of aqueous aromatic contaminants and decolorization of dyes. Thus, LiP was shown to mineralize a variety of recalcitrant aromatic compounds and to oxidize a number of polycyclic aromatic and phenolic compounds. Furthermore, MnP and a microbial PX from Coprinus macrorhizus have also been observed to catalyze the oxidation of several monoaromatic phenols and aromatic dyes (Hamid and Khalil-ur-Rehman 2009). 

Steps are normally taken to prevent the simultaneous precipitation of materials other than the desired analyte species. Incorporation of impurities into the precipitate may however occur by coprecipitation or post-precipitation. The former arises during the formation of the precipitate, and the latter after it has been formed. The various modes of coprecipitation are summarized in Table 5.16. 

Figure 1.9 TG, DTG, and DTA profiles for an amorphous catalyst precursor obtained by coprecipitation of Fe(N03)3 and Mg(N03)2 in solution [65], This precursor is heated at high temperatures to produce a MgFe204 spinel, used for the selective oxidation of styrene. The thermal analysis reported here points to four stages in this transformation, namely, the losses of adsorbed and crystal water at 110 and 220°C, respectively, the decomposition and dehydroxylation of the precursor into a mixed oxide at 390°C, and the formation of the MgFe204 spinel at 640°C. Information such as this is central in the design of preparation procedures for catalysts. (Reproduced with permission from Elsevier.)...

We already touched on some aspects of carbonate surface chemistry e.g., in Chapter 3.4. We have already illustrated some of the factors that affect surface charge and the point of zero charge, pHpzc, in Chapter 3.5, and have discussed certain elementary aspects of CaC03 nucleation in Chapter 6.5 and of coprecipitation (and solid solution formation) in Chapter 6.7. 

The phenomena of surface precipitation and isomorphic substitutions described above and in Chapters 3.5, 6.5 and 6.6 are hampered because equilibrium is seldom established. The initial surface reaction, e.g., the surface complex formation on the surface of an oxide or carbonate fulfills many criteria of a reversible equilibrium. If we form on the outer layer of the solid phase a coprecipitate (isomorphic substitutions) we may still ideally have a metastable equilibrium. The extent of incipient adsorption, e.g., of HPOjj on FeOOH(s) or of Cd2+ on caicite is certainly dependent on the surface charge of the sorbing solid, and thus on pH of the solution etc. even the kinetics of the reaction will be influenced by the surface charge but the final solid solution, if it were in equilibrium, would not depend on the surface charge and the solution variables which influence the adsorption process i.e., the extent of isomorphic substitution for the ideal solid solution is given by the equilibrium that describes the formation of the solid solution (and not by the rates by which these compositions are formed). Many surface phenomena that are encountered in laboratory studies and in field observations are characterized by partial, or metastable equilibrium or by non-equilibrium relations. Reversibility of the apparent equilibrium or congruence in dissolution or precipitation can often not be assumed. 

Non-lattice sites may play an important role in the incorporation of large foreign ions in crystal structures during coprecipitation Pingitore (Chapter 27) discusses the importance of these sites in the formation of coprecipitates of calcium carbonate containing Srz+ or Ba. White and Yee (Chapter 28) discuss the diffusion of alkali ions into defect structures in the surfaces of glasses and crystalline feldspars. 

Nielson, A.E., Precipitates Formation, Coprecipitation, and Aging, In Treatise on Analytical Chemistry,... 

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