Slightly soluble solute precipitation

Suppose we have a solution that contains lead(II), mercury(I), silver, copper(II), and zinc ions. The method is outlined in Fig. 11.20, which includes additional cations, and is illustrated in Fig. 11.21. Most chlorides are soluble so, when hydrochloric acid is added to a mixture of salts, only certain chlorides precipitate (see Table 11.4). Silver and mercury(I) chlorides have such small values of Ksp that, even with low concentrations of Cl ions, the chlorides precipitate. Lead(II) chloride, which is slightly soluble, will precipitate if the chloride ion concentration is... 

Where the compound is listed in Table 6.2 as slightly soluble, the precipitate may appear only as a milkiness in the solution. 

The complex ions A1(H20)5(0H) and A1(H20)4(0H)2" remain in solution, whereas the hydroxide AKOH) , is very slightly soluble and precipitates if more than a very small amount is formed precipitation occurs when the pH is greater than 3. 

EXAMPLE 18-5 Applying the Criteria for Precipitation of a Slightly Soluble Solute... 

Criteria for Precipitation and Its Completeness—To determine whether a slightly soluble solute will precipitate from a solution, the ion product, Qsp, is compared with the solubility product constant, K p. Q p is based on the initial ion concentrations in a solution. K p, on the other hand, is based on the equilibrium ion concentrations in a saturated solution. If Qgp > K p, precipitation will... 

Lead(Il) chromate VI) is precipitated when a soluble chromate(VI) or dichromatelVl) is added to a solution of a lead salt in neutral or slightly acid solution ... 

Arsenic(III) oxide is slightly soluble in water, giving a solution with a sweetish taste—but as little as 0.1 g can be a fatal dose (The antidote is freshly-precipitated iron(III) hydroxide.) The solution has an acid reaction to litmus, due to the formation of arsenic(III) acid ... 

Dissolve 0 5 ml. of glycerol in 20 ml. of w ater, and add 20 ml. of the above 5% aqueous sodium periodate solution. After 15-20 minutes add 12 ml. of the above 10% ethanolic dimedone solution, and stir well at intervals for another 15 minutes. The addition of the dimedone solution may cause a rapid precipitation of some of the dimedone itself, which is only slightly soluble in water, whereas the formaldehyde-dimedone compound separates more slowly from the solution. 

Tl>e base is only slightly soluble in ether, thus rendering its use uneconomical. It may be extracted with chloroform and precipitated from the dried chloroform solution with carbon tetrachloride. 

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. 

Monofluorophosphates. Monofluorophosphates are probably the best characterized series of fluoroxy salts. The PO F ion is stable ia neutral or slightly alkaline solution. The alkaU metal and ammonium monofluorophosphates are soluble ia water but the alkaline-earth salts are only slightly soluble, eg, CaPO F is not water-soluble and precipitates as the dihydrate. 

Iodine is only slightly soluble in water and no hydrates form upon dissolution. The solubiHty increases with temperature, as shown in Table 2 (36). Iodine is soluble in aqueous iodide solutions owing to the formation of polyiodide ions. For example, an equiHbrium solution of soHd iodine and KI H2O at 25°C is highly concentrated and contains 67.8% iodine, 25.6% potassium iodide, and 6.6% water. However, if large cations such as cesium, substituted ammonium, and iodonium are present, the increased solubiHty may be limited, owing to precipitation of sparingly soluble polyiodides. Iodine is also more... 

Lead Chloride. Lead dichloride, PbCl2, forms white, orthorhombic needles some physical properties are given in Table 1. Lead chloride is slightly soluble in dilute hydrochloric acid and ammonia and insoluble in alcohol. It is prepared by the reaction of lead monoxide or basic lead carbonate with hydrochloric acid, or by treating a solution of lead acetate with hydrochloric acid and allowing the precipitate to settle. It easily forms basic chlorides, such as PbCl Pb(OH)2 [15887-88 ] which is known as Pattinson s lead white, an artist s pigment. 

Mercurous Sulfate. Mercurous s Ai2LX.e[7783-36-0] Hg2S04, is a colodess-to-shghfly-yellowish compound, sensitive to light and slightly soluble ia water (0.05 g/100 g H2O). It is more soluble ia dilute acids. The compound is prepared by precipitation from acidified mercurous nitrate solution and dilute sulfuric acid. The precipitate is washed with dilute sulfuric acid until nitrate-free. Its most important use is as a component of Clark and Weston types of standard cells. 

Nickel Carbonate. Nickel carbonate [3333-67-3], NiCO, is a light-green, rhombic crystalline salt, density 2.6 g/cm, that is very slightly soluble in water. The addition of sodium carbonate to a solution of a nickel salt precipitates an impure basic nickel carbonate. The commercial material is the basic salt 2NiCo2 3Ni(OH)2 4H20 [29863-10-3]. Nickel carbonate is prepared best by the oxidation of nickel powder in ammonia and CO2. Boiling away the ammonia causes precipitation of pure nickel carbonate (32). 

Silver Iodide. Silver iodide, Agl, precipitates as a yellow soHd when iodide ion is added to a solution of silver nitrate. It dissolves in the presence of excess iodide ion, forming an Agl2 complex however, silver iodide is only slightly soluble in ammonia and dissolves slowly in thiosulfate and cyanide solutions. 

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. 

Zinc forms salts with acids but since it is amphoteric, it also forms zincates, eg, [Zn(OH)2 H20] and Z.n([7) ). The tendency of zinc to form stable hydroxy complexes is also important because some basic zinc salts are only slightly soluble in water. Examples are 3Zn(OH)2 ZnSO [12027-98-4] and 4Zn(OH)2 ZnCl2 [11073-22-6] which may precipitate upon neutralization of acidic solutions of the salts. 

Antimony trioxide is insoluble in organic solvents and only very slightly soluble in water. The compound does form a number of hydrates of indefinite composition which are related to the hypothetical antimonic(III) acid (antimonous acid). In acidic solution antimony trioxide dissolves to form a complex series of polyantimonic(III) acids freshly precipitated antimony trioxide dissolves in strongly basic solutions with the formation of the antimonate ion [29872-00-2] Sb(OH) , as well as more complex species. Addition of suitable metal ions to these solutions permits formation of salts. Other derivatives are made by heating antimony trioxide with appropriate metal oxides or carbonates. 

Precipitated or synthetic barium carbonate is the most commercially important of all the barium chemicals except for barite. Barium carbonate is an unusually dense material, that is almost kisoluble ki water and only slightly soluble ki carbonated water. It does dissolve ki dilute hydrochloric, nitric, and acetic acids and is also soluble ki ammonium nitrate and ammonium chloride solutions. 

In general, hydrated borates of heavy metals ate prepared by mixing aqueous solutions or suspensions of the metal oxides, sulfates, or halides and boric acid or alkali metal borates such as borax. The precipitates formed from basic solutions are often sparingly-soluble amorphous soHds having variable compositions. Crystalline products are generally obtained from slightly acidic solutions. 

Citrazinic acid (2,6-dihydroxyisonicotinic acid) [99-11-6] M 155.1, m >300°, pK] 3.0, pK2 4.76. Yellow powder with a greenish shade, but is white when ultra pure and turns blue on long standing. It is insoluble in H2O but slightly soluble in hot HCl and soluble in alkali or carbonate solutions. Purified by precipitation from alkaline solutions with dilute HCl, and dry in a vacuum over P2O5. The ethyl ester has m 232° (evacuated tube) and a pKa of 4.81 in MeOCH2CH20H [IR Pitha Coll Czech Chem Comm 28 1408 1963]. 

The hydrolysis (which in the case of Fe produces acidic solutions) is virtually absent, and in aqueous solution the addition of C03 does not result in the evolution of CO2 but simply in the precipitation of white FeC03. The moist precipitate oxidizes rapidly on exposure to air but in the presence of excess CO2 the slightly soluble Fe(HC03)2 is formed. It is the presence of this in natural underground water systems, leading to the production of FeC03 on exposure to air, followed by oxidation to iron(III) oxide, which leads to the characteristic brown deposits found in many streams. 

Though both silver nitrate and sodium chloride have high solubility in water, silver chloride is very slightly soluble. What will happen if we mix a solution of silver nitrate and sodium chloride Then, we will have a solution that includes the species present in a solution of silver chloride, Ag+(aq) and Cl (ag), but now they are present at high concentration The Ag+(agJ came from reaction (8) and the Cl (aq) came from reaction (6) and their concentrations far exceed the solubility of silver chloride. The result is that solid will be formed. The formation of solid from a solution is called precipitation ... 

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