Reductive precipitation

The first equation is an example of hydrolysis and is commonly referred to as chemical precipitation. The separation is effective because of the differences in solubiUty products of the copper(II) and iron(III) hydroxides. The second equation is known as reductive precipitation and is an example of an electrochemical reaction. The use of more electropositive metals to effect reductive precipitation is known as cementation. Precipitation is used to separate impurities from a metal in solution such as iron from copper (eq. 1), or it can be used to remove the primary metal, copper, from solution (eq. 2). Precipitation is commonly practiced for the separation of small quantities of metals from large volumes of water, such as from industrial waste processes. 

Cementation, the removal of a metal ion from solution by reduction of the metal with a more electropositive material, is also known as reductive precipitation. For a simple case the following can be used ... 

Alternative wet routes to hydrolytically stable halides are metathetical precipitation and reductive precipitation reactions, e.g. ... 

The last definition has widespread use in the volumetric analysis of solutions. If a fixed amount of reagent is present in a solution, it can be diluted to any desired normality by application of the general dilution formula V,N, = V N. Here, subscripts 1 and 2 refer to the initial solution and the final (diluted) solution, respectively V denotes the solution volume (in milliliters) and N the solution normality. The product VjN, expresses the amount of the reagent in gram-milliequivalents present in a volume V, ml of a solution of normality N,. Numerically, it represents the volume of a one normal (IN) solution chemically equivalent to the original solution of volume V, and of normality N,. The same equation V N, = V N is also applicable in a different context, in problems involving acid-base neutralization, oxidation-reduction, precipitation, or other types of titration reactions. The justification for this formula relies on the fact that substances always react in titrations, in chemically equivalent amounts. 

Because of their multiple oxidation states, the chalcogens, particularly sulfur, can engage in numerous redox couples participating in acid-base, oxidation-reduction, precipitation, and complexation equilibria. 

The penultimate categorization of the chemical precipitation processes detailed in this chapter is reduction. The process basically involves electron transfer from different ions. The reductive precipitation may be either homogeneous (which may be ionic or non-ionic), or heterogeneous (which may be electrochemical or electrolytic). Electrolytic processes are described in Chapter 6, and no account of these need be given here. 

Polarisation titrations are often referred to as amper-ometric or biamperometric titrations. It is necessary that one of the substances involved in the titration reaction be oxidisable or reducible at the working electrode surface. In general, the polarisation titration method is applicable to oxidation-reduction, precipitation and complex-ation titrations. Relatively few applications involving acid/base titration are found. Amperometric titrations can be applied in the determination of analyte solutions as low as ICE5 M to 10-6 M in concentration. 

Figure 6.4 shows an example of an existing plating facility and its conventional reduction-precipitation wastewater treatment system in New Britain, TN.15... 

FIGURE 6.4 Conventional reduction-precipitation wastewater treatment system. 

A modified reduction-flotation system (Figure 6.5) is very similar to the existing conventional reduction-precipitation system (Figure 6.4), except that a DAF clarifier [T-101F] is used for clarification15-57 instead of using a conventional sedimentation clarifier (Tank T-101, Figure 6.4). 

It should be noted that the chemical reactions of the conventional reduction-precipitation system (Figure 6.4) and the modified reduction-flotation system are identical. 

The first system, shown in Figure 6.6, is identical to the conventional reduction-precipitation in chemistry (i.e., neutralization, chromium reduction, pH adjustment, metal hydroxide precipitation, and so on). However, a flotation-filtration clarifier (Tank T101SF, as shown in Figure 6.6) is used. The unit consists of rapid mixing, flocculation, high-rate DAF, and sand filtration.1557... 

The treatment efficiency of this system (Figure 6.6) is much higher than that of the conventional reduction-precipitation wastewater treatment system (Figure 6.4).15... 

It is seen from Figure 6.7 that this system is much simpler, more cost-effective, and easier to operate in comparison with all other process systems discussed earlier. The treatment efficiency of the new flotation-filtration system is expected to be higher than that of the conventional reduction-precipitation system. The new flotation-filtration system also requires much less land space.15... 

Characteristics of Typical Wastewater Discharge of Conventional Reduction-Precipitation System3... 

Table 6.3 shows the characteristics of a typical effluent discharge from a conventional reduction-precipitation system. The effluent quality meets industrial pretreatment requirements. 

The treatment efficiencies of the two innovative flotation-filtration wastewater treatment systems (Figures 6.6 and 6.7) are expected to be higher than those of the conventional reduction-precipitation system. 

In addition to the heavy metals stated in Table 22.10, ferro- and ferricyanide are also part of the pollutants in the wastewater generated in a chrome pigment plant. These wastes are generally combined and treated through reduction, precipitation, equalization, and neutralization to be followed by clarification and filtration processes. Most of the heavy metals are precipitated using lime or caustic soda at specific pH. Chromium is reduced by S02 to a trivalent form, wherein it is precipitated as chromium hydroxide at specific pH. Sodium bisulfide is also employed to precipitate some of the metals at a low pH. The treated water is recycled for plant use while the sludge is sent to landfills (Figure 22.7). 

Nakashima et al. [719] detail a procedure for preliminary concentration of 16 elements from coastal waters and deep seawater, based on their reductive precipitation by sodium tetrahydroborate, prior to determination by graphite-furnace AAS. Results obtained on two reference materials are tabulated. This was a simple, rapid, and accurate technique for determination of a wide range of trace elements, including hydride-forming elements such as arsenic, selenium, tin, bismuth, antimony, and tellurium. The advantages of this procedure over other methods are indicated. 

Three methods for trace metal preconcentration were examined liquid-liquid extraction aided by a chelating agent, concentration on a synthetic chelating resin and reductive precipitation with NaBTLt. The latter method gave 1000-fold preconcentration factors with total recovery of Pb and other elements17. Preconcentration of nanogram amounts of lead can be carried out with a resin incorporating quinolin-8-ol (3)18. Enhancement factors of 50-100 can be achieved by such preconcentration procedures followed by determination in a FLA (flow injection analysis) system limits of detection are a few pg Pb/L19. 

The fate of the bipyridinium radical cation in the mercaptan monolayer is not clear. The second reduction wave (Figure 3) possesses structure suggesting a precipitated phase similar sharp peaks are seen during the reductive precipitation of Cu.bpyMe2 ... 

Common chemical titrations include acid-base, oxidation-reduction, precipitation, and complexometric analysis. The basic concepts underlying all titration are illustrated by classic acid-base titrations. A known amount of acid is placed in a flask and an indicator added. The indicator is a compound whose color depends on the pH of its environment. A solution of base of precisely known concentration (referred to as the titrant) is then added to the acid until all of the acid has just been reacted, causing the pH of the solution to increase and the color of the indicator to change. The volume of the base required to get to this point in the titration is known as the end point of the titration. The concentration of the acid present in the original solution can be calculated from the volume of base needed to reach the end point and the known concentration of the base. 

Cementation is the process of recovery of metals from dilute aqueous solution by reductive precipitation using another metal with a more negative electrode potential, e.g., Cu + Fe° Cu° + Fe. The product, in this case cement copper, is relatively impure because of iron contamination. However, cementation can be used in conjunction with a solvent extraction flow sheet to remove small amounts of a metallic impurity, for example, removal of copper from a nickel solution by cementation with nickel powder. Here the dissolved nickel conveniently augments the nickel already in solution. 

It is state of the art to deposit the platinum catalyst on the membrane surface by a diffusion process in which platinum salt solutions (from the cathode side of the membrane) and a reductant, like hydrazine, are counter-diffusing causing reductive precipitation of dispersed platinum close to and on the surface of the membrane. The BBC Membrel cell is reported to contain a catalyst load of only 0.2 mg Pt per square centimeter (97). The cathode is reported to exhibit only from 50 to 70 mV overpotential at current densities of 1 A/cm2 and 80°C. 

Chemical reactions in preparation of nano copper by reduction-precipitation... 

The experimental equipment system for the preparation of nano copper powder by reduction-precipitation is shown in Fig. I4.l, where the submerged circulative impinging stream reactor (SCISR) has the same structure as was used in the investigations described in the previous chapters in Part II of this book, with the same effective volume of 3.6x10 3 m it is also operated without the top cover but is made of titanium for anti-corrosion of Cl-. 

The make-up of the reactant solutions is an important link in the preparation of nano copper by reduction-precipitation affecting the efficiency of the process. The procedures for the two solutions are as follows ... 

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