Base-insoluble sulfides and

Group 3. Base-insoluble sulfides and hydroxides After the solution is filtered to remove any acid-insoluble sulfides, it is made slightly basic, and (NH4)2S is added. In basic solutions the concentration of is higher than in acidic solutions. Thus, the ion products for many of the more soluble sulfides are made to exceed their K p values and precipitation occurs. The metal ions precipitated at this stage are Al +, Cr Fe +, Zn +, Ni +, Co +, and Mn + (The Al +, and Cr ions do not form insoluble sulfides instead they precipitate as insoluble hydroxides, as Figure 17.23 shows.)... 

In contrast, B-type metal ions coordinate preferentially with bases containing I, S, or N as donor atoms. Thus metal ions in this class may bind ammonia more strongly than water, CN in preference to OH , and form more stable P or Cl complexes than F complexes. These metal cations, as well as transition-metal cations, form insoluble sulfides and soluble complexes with and HS . 

The analyses for individual ions in fhe acid-insoluble and base-insoluble sulfides are a bit more complex, but the same general principles are involved. The detailed procedures for carrpng out such analyses are given in many laboratory manuals. 

It is good practice to keep concentrations of airborne nickel in any chemical form as low as possible and certainly below the relevant standard. Local exhaust ventilation is the preferred method, particularly for powders, but personal respirator protection may be employed where necessary. In the United States, the Occupational Safety and Health Administration (OSHA) personal exposure limit (PEL) for all forms of nickel except nickel carbonyl is 1 mg/m. The ACGIH TLVs are respectively 1 mg/m for Ni metal, insoluble compounds, and fume and dust from nickel sulfide roasting, and 0.1 mg/m for soluble nickel compounds. The ACGIH is considering whether to lower the TLVs for all forms of nickel to 0.05 mg/m, based on nonmalignant respiratory effects in experimental animals. 

Thiosulfates. The ammonium, alkaU metal, and aLkaline-earth thiosulfates are soluble in water. Neutral or slightly alkaline solutions containing excess base or the corresponding sulfite are more stable than acid solutions. Thiosulfate solutions of other metal ions can be prepared, but their stabiUty depends on the presence of excess thiosulfate, the formation of complexes, and the prevention of insoluble sulfide precipitates. 

Cu may be reduced to Cu", especially if soft bases such as halides and S are present to stabilize the Cu" " ion. All are chalcophiles and tend to form insoluble sulfides in anaerobic conditions (pKs = 21.3-25.6, 19.4-26.6 and 36.1, respectively). They therefore tend to have low mobilities in submerged soils, especially Cu +, and accumulate. 

Most base-metal sulfides are very insoluble compounds and, in principle, processes based on the differences in their solubilities can be used in the selective precipitation of sulfides. For example, the strong affinity of copper ions for sulfide ion is used to good effect in the removal of traces of copper from leach liquors in the recovery of nickel,406 cobalt407 and manganese.408 For manganese, other impurity metal ions such as cobalt, nickel and zinc are also selectively precipitated by the use of sulfide ions. 

Ray et al. [77] used an indirect method based on AAS for the determination of sulfide in flooded acid sulfate soils. Hydrogen sulfide, evolved during the anaerobic metabolism of sulfate, is readily converted into insoluble metal sulfides, chiefly iron sulfide, in flooded acid sulfate soils. A method for determining sulfide is based on the precipitation of the sulfide as zinc sulfide and subsequent determination by methylene blue formation or iodine titrimetry. 

In operationally defined speciation the physical or chemical fractionation procedure applied to the sample defines the fraction isolated for measurement. For example, selective sequential extraction procedures are used to isolate metals associated with the water/acid soluble , exchangeable , reducible , oxidisable and residual fractions in a sediment. The reducible, oxidisable and residual fractions, for example, are often equated with the metals associated, bound or adsorbed in the iron/manganese oxyhydroxide, organic matter/sulfide and silicate phases, respectively. While this is often a convenient concept it must be emphasised that these associations are nominal and can be misleading. It is, therefore, sounder to regard the isolated fractions as defined by the operational procedure. Physical procedures such as the division of a solid sample into particle-size fractions or the isolation of a soil solution by filtration, centrifugation or dialysis are also examples of operational speciation. Indeed even the distinction between soluble and insoluble species in aquatic systems can be considered as operational speciation as it is based on the somewhat arbitrary definition of soluble as the ability to pass a 0.45/Am filter. 

Zinc oxide (ZnO), which is produced by burning zinc vapor in atmospheric oxygen, is by far the most important compound of zinc. Under the name of zinc white, the oxide is used as a paint pigment. It is also used as a base in the manufacture of enamels and glass, and as a ruler in the fabrication of automobile tires and other kinds of rubber goods. Zinc sulfide (ZnS) is also an important white paint pigment which is used either as such or in the form of lithopone, which is a mixture of zinc sulfide and barium sulfate. This widely used pigment is prepared by the metathetical reaction between zinc sulfate and barium sulfide, a reaction in which both of the products are insoluble ... 

In the section entitled Cleaning Up at the end of each experiment the goal is to reduce the volume of hazardous waste, to convert hazardous waste to less hazardous waste, or to convert it to nonhazardous waste. The simplest example is concentrated sulfuric acid. As a by-product from a reaction, it is obviously hazardous. But after careful dilution with water and neutralization with sodium carbonate, the sulfuric acid becomes a dilute solution of sodium sulfate, which in almost every locale can be flushed down the drain with a large excess of water. Anything flushed down the drain must be accompanied by a large excess of water. Similarly, concentrated base can be neutralized, oxidants such as Cr " can be reduced, and reductants such as hydrosulfite can be oxidized (by hypochlorite— household bleach). Dilute solutions of heavy metal ions can be precipitated as their insoluble sulfides or hydroxides. The precipitate may still be a hazardous waste, but it will have a much smaller volume. 

Not all of the elements selected for study are expected to behave in the same way, based on general chemical properties, when buried in a reducing, sulfide-rich, marine environment. As a first approximation, the expected concentrations of dissolved metals can be estimated from published solubility-product constants, by assuming a free-sulfide concentration and neglecting complex formation, as has been done in Table XII. The calculated equilibrium concentrations are extremely low, except for Mn and possibly Fe, which suggests that Cu, Zn, and Pb should be fixed as their insoluble sulfides, whereas Mn might be chemically mobile. 

The separation of atropine, Z-hyoscyamine and Z-scopolamine has been effected by the fractional crystallization of their aurichlorides. It has been pointed out, however, that the solubility relations of these derivatives are dependent upon impurities and the relative amoimts of each present in the mixture (50). The bases may be recovered by decomposing an aqueous solution of the aurichloride with hydrogen sulfide and filtering to remove the gold sulfide. The base is liberated by addition of potassium carbonate to the filtrate and extraction with chloroform. An alternate method for the separation of atropine and Z-hyoscyamine (25) is by fractional crystallization of their oxalates from acetone and ether in which the Z-hyoscyamine derivative has the greater solubility. Z-Scopolamine and dioscorine on the other hand are purified through their insoluble hydrobromides. 

Another class of compounds whose cations may not be precipitated by the addition of hydroxide ions are the most stable complexes of metal cations with Lewis bases, such as ammonia, amines, and tertiary phosphines. Because of the large number of these compounds and their wide range of properties, it is not possible to give a general procedure for separating the cations. In many cases, metal sulfides can be precipitated directly from aqueous solutions of the complexes by the addition of aqueous sodium sulfide. If a test-tube experiment shows that other measures are needed, the addition of hydrochloric acid to produce a slightly acidic solution will often decompose the complex by protonation of the basic ligand. Metal ions that form insoluble sulfides under acid conditions can then be precipitated by drop wise addition of aqueous sodium sulfide. 

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