Sulfide solubility products

An example is given in Figure 6.11, giving both complex stabilities and sulfide solubility products. 

Metal Sulfide Solubility Product Constant (Ksffi... 

Tall oil rosin is a by-product of paper manufacturing. Raw wood chips are digested under heat and pressure with a mixture of sodium hydroxide and sodium sulfide. Soluble sodium salts of lignin, rosin, and fatty acids are formed, which are removed from the wood pulp as a dark solution. The soaps of the rosin and fatty acids float to the top of the mixture, where they are skimmed off and treated with sulfuric acid to free the rosin and fatty acids. This mixture, known as cmde tall oil (CTO), is refined further to remove color and odor bodies fractional distillation separates the tall oil rosin acids from the fatty acids (see Tall oil). 

By contrast with the water-soluble sulfides of Groups 1 and 2, the corresponding heavy metal sulfides of Groups 11 and 12 are amongst the least-soluble compounds known. Literature values are often wildly discordant, and care should be taken in interpreting the data. Thus, for black HgS the most acceptable value of the solubility product [Hg +][S ] is 10- mol2l-2, i.e. 

Other useful solid-state electrodes are based on silver compounds (particularly silver sulfide). Silver sulfide is an ionic conductor, in which silver ions are the mobile ions. Mixed pellets containing Ag2S-AgX (where X = Cl, Br, I, SCN) have been successfiilly used for the determination of one of these particular anions. The behavior of these electrodes is determined primarily by the solubility products involved. The relative solubility products of various ions with Ag+ thus dictate the selectivity (i.e., kt] = KSp(Agf)/KSP(Aw)). Consequently, the iodide electrode (membrane of Ag2S/AgI) displays high selectivity over Br- and Cl-. In contrast, die chloride electrode suffers from severe interference from Br- and I-. Similarly, mixtures of silver sulfide with CdS, CuS, or PbS provide membranes that are responsive to Cd2+, Cu2+, or Pb2+, respectively. A limitation of these mixed-salt electrodes is tiiat the solubility of die second salt must be much larger than that of silver sulfide. A silver sulfide membrane by itself responds to either S2- or Ag+ ions, down to die 10-8M level. 

The equilibrium constant for the solubility equilibrium between an ionic solid and its dissolved ions is called the solubility product, Ksp, of the solute. For example, the solubility product for bismuth sulfide, Bi2S3, is defined as... 

Sulfides with widely different solubilities and solubility products can be selectively precipitated by adding S2 ions to the solution removed from the chlorides in the first step (see Fig. 11.20). Some metal sulfides (such as CuS, HgS, and Sb2S3) have extremely small solubility products and precipitate if there is the merest trace of S2" ions in the solution. Such a very low concentration of S2 ions is achieved by adding hydrogen sulfide, H2S, to an acidified solution. A higher hydronium ion concentration shifts the equilibrium... 

The commonly accepted underlying mechanism involves decomposition (hydrolysis) of thiourea in the alkaline solution to form sulfide ions (3.10), which react with Cd " ions released by the decomplexation reaction (3.11), with precipitation of cadmium sulfide (3.12) upon exceeding the solubility product of the compound... 

The solubility product (JCsp) for the precipitation of metal sulfide (MmSn) from a solution containing m Mz+ and n S2 ions is... 

Figure 12 clearly shows the effect of iron sulfide content of the coal on total conversion and liquid product yield during hydrogenation. The conversion increased from about 52 per cent to 70 per cent using the hot-rod reactor with no added catalyst. The yield of toluene soluble product (oil plus asphaltene) increased from about 30 to 44 per cent with total sulfur increase from 1 to 6.5 per cent. Thus it would appear that iron sulfide can act catalytically in the dry hydrogenation reaction as well as in slurried reactions (15). 

Fig. 1.8. The solubility products of hydroxides (----------) and sulfides (— ) which have been of...

In reviewing the basic solubility products for these systems, the sulfide system removes the most inorganics, with the exception of arsenic, because of the low solubility of sulfide compounds. This increased removal capability is offset by the difficulty in handling the chemicals and the fact that sulfide sludges are susceptible to oxidation to sulfate when exposed to air, resulting in resolubilization of the metals. The carbonate system is a method that relies on the use of soda ash (sodium carbonate) and pH adjustment between 8.2 and 8.5. The carbonate system, although... 

Stability constants (ethylendiamine, glycinate, oxalate), surface complex formation constants and solubility products (sulfides) of transition ions. The surface complex formation constant is for the binding of metal ions to hydrous ferric oxide =Fe-OH + Me2+ =FeOMe++ H+ K. ... 

The -pH relations for the important iron-water system at 25 °C are summarized in Fig. 15.3 with some simplifications. First, it is assumed that no elements other than Fe, O, and H are involved in a natural water system, the presence of C02 would oblige us to include FeCC>3 (siderite), and sulfur compounds could lead to precipitation of iron sulfides in certain Eh-pH regimes. As it is, the only Fe-O-H solids we have considered are Fe metal, Fe(OH)2, and Fe(OH)3, whereas in practice magnetite (Fe30,i), hematite (a-Fe2C>3), goethite [a-FeO(OH)], and other Fe-O-H phases could be present. Indeed, our choice of solubility products for Fe(OH)2 and... 

In the presence of hydrogen sulfide produced by anaerobic bacterial activity, particularly sulfate reducers, conditions are created whereby sulfides of copper and zinc could be formed. The partition of these metals between the sulfide phase and the organic phase depends on the relation between the stability constants of the complexes and the solubility product of the sulfides of these metals. Elements with small solubility products of their sulfides and low stability constants of their chelates would be expected to go into the sulfide phase when hydrogen sulfide is present. Copper is typical of such elements. Chalcocite has a solubility product of about 10" ° and covellite about 10"44, whereas the most stable chelates of copper have stability constants of about 10" Consequently, copper could be expected to be accumulated as the sulfide. Zinc sulfide has a much larger solubility product however, the stability of its chelates is lower. From the fact that zinc appears to be completely associated with the inorganic fraction of coal, it can be assumed that the relation between the solubility product of any of its sulfides and its chelates favors formation of the sulfide. Iron could be expected to follow a similar pattern. 

Solubility Products in Acid (/Cspa) at 25°C for Metal Sulfides... 

The solubility product for CuS is very low ( sp = 10 19 as written) so that the presence of sulfide in water acts to immobilize Cu (and many other metals) and reduce effective exposure. The formation of metal sulfides is important in anaerobic soil and sediment, stagnant ponds and basins, and many industrial and domestic sewage treatment plants and discharges. Co-precipitation of metals also can be a very important removal process in natural waters. In aerobic systems, the precipitation of hydrous... 

Tin in ambient waters may exist as divalent cationic (positively charged) ions (Sn ) or as quadrivalent ions (Sn +). Stannous tin (Sn ) dominates in reduced (oxygen-poor) water, and will readily precipitate as a sulfide (SnS) or as a hydroxide (Sn(OH)2) in alkaline water. Stannic tin (Sn ) readily hydrolyzes, and can precipitate as a hydroxide (Wedepohl et al. 1978). The solubility product of Sn(OH)4 has been measured as approximately 10 g/L at 25°C (Wedepohl et al. 1978). 

In an attempted determination of the solubility product of TI2S, the solubility of this compound in pure C02-free water was determined as 3.6 x 10-5 mol/L. What is the Ksp for TI2S Assume that the dissolved sulfide hydrolyzes practically completely to HS, and that there is no further hydrolysis to H2S. ... 

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