Sparingly soluble salts and solubility products

If the solubility of an ionic salt is extremely small (i.e. a saturated solution contains very few ions), the salt is said to be sparingly soluble. Such salts may include some that we might loosely refer to as being insoluble , for example AgCl and BaS04. Equation 6.44 shows the equilibrium that is established in aqueous solution when CaF2 dissolves. 

An expression for the equilibrium constant should strictly be given in terms of the activities (see Section 6.3) of the species involved, but since we are dealing with very dilute solutions, we may express K in terms of concentrations (equation 6.45). 

The activity of any solid is, by convention, unity. The equilibrium constant is thereby given in terms of the equilibrium concentrations of the dissolved ions and is referred to as the solubility product, or solubility constant, K p (equation 6.46). 

Values of K p for a range of sparingly soluble salts are listed in Table 6.4. 

One mole of Pbl2 dissolves to give one mole of Pb + and two moles of I , and the solubility of Pbl2 (in moldm ) equals the concentration of aqueous Pb. Since [1 ] = 2[Pb +], we can rewrite the expression for and thus find [Pb +]  

The solubility product for Pbl2 is 8.49 x 10 (298 K). Calculate the solubility of Pbl2. 

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The solution will then contain the free acid and the hydrochloride of the base either of these may separate if sparingly soluble. If a sohd crystallises from the cold solution, filter, test with sodium bicarbonate solution compare Section 111,85, (i) and compare the m.p. with that of the original compound. If it is a hydrolysis product, examine it separately. Otherwise, render the filtrate alkahne with sodium hydroxide solution and extract the base with ether if the presence of the unchanged acyl canpound is suspected, extract the base with weak acid. Identify the base in the usual manner (see Section IV, 100). The acid will be present as the sodium salt in the alkaline extract and may be identified as described in Section IV,175. 

Hydrocotarnine, C12HJ5O3N. HjO. This basic hydrolytic product of narcotine occurs in opium. It crystallises from light petroleum in colourless plates, m.p. 55-5-56-5°, and yields well-crystallised salts of which the hydrobromide, B. HBr, m.p. 236-7°, is sparingly soluble in water. On oxidation, hydrocotarnine is converted into cotarnine, and on reduction by sodium in alcohol it yields hydrohydrastinine (p. 164) by loss of a mcthoxyl group. 

Chelerythrine crystallises from alcohol in colourless, prismatic leaflets, m.p. 207°, containing one molecule of alcohol. The alkaloid absorbs carbon dioxide from the air, becoming yellow. The solutions fluoresce blue when the alkaloid is contaminated with its oxidation product, which is formed by mere exposure of solutions to air. The salts, which are quaternary, are intensely yellow. The hydrochloride, B. HCl. HjO, forms citron-yellow needles, and the sulphate, B. H2SO4.2HjO, golden-yellow needles, sparingly soluble in water the platinichloride, B2. HaPtCl. ... 

It is important to note that the solubility product relation applies with sufficient accuracy for purposes of quantitative analysis only to saturated solutions of slightly soluble electrolytes and with small additions of other salts. In the presence of moderate concentrations of salts, the ionic concentration, and therefore the ionic strength of the solution, will increase. This will, in general, lower the activity coefficients of both ions, and consequently the ionic concentrations (and therefore the solubility) must increase in order to maintain the solubility product constant. This effect, which is most marked when the added electrolyte does not possess an ion in common with the sparingly soluble salt, is termed the salt effect. 

If the dissociation constant of the acid HA is very small, the anion A- will be removed from the solution to form the undissociated acid HA. Consequently more of the salt will pass into solution to replace the anions removed in this way, and this process will continue until equilibrium is established (i.e. until [M + ] x [A-] has become equal to the solubility product of MA) or, if sufficient hydrochloric acid is present, until the sparingly soluble salt has dissolved completely. Similar reasoning may be applied to salts of acids, such as phosphoric(V) acid (K1 = 7.5 x 10-3 mol L-1 K2 = 6.2 x 10-8 mol L-1 K3 = 5 x 10 13 mol L-1), oxalic acid (Kx = 5.9 x 10-2 mol L-K2 = 6.4 x 10-5molL-1), and arsenic)V) acid. Thus the solubility of, say, silver phosphate)V) in dilute nitric acid is due to the removal of the PO ion as... 

Solid Bi2S3 does not appear in the expression for K,p, because it is a pure solid and its activity is 1 (Section 9.2). A solubility product is used in the same way as any other equilibrium constant. However, because ion-ion interactions in even dilute electrolyte solutions can complicate its interpretation, a solubility product is generally meaningful only for sparingly soluble salts. Another complication that arises when dealing with nearly insoluble compounds is that dissociation of the ions is rarely complete, and a saturated solution of Pbl2, for instance, contains substantial... 

Upon heating anthraquinone with fuming sulphuric acid at 160° for about 1 hour, the main product Is anthraquinone-p-sulphonic acid, which is isolated as the sparingly soluble sodium salt. The latter when heated imder pressure with sodium hydroxide solution and an oxidising agent (sodium or potassium chlorate) yields first the corresponding hydroxy compound further hydroxy-lation occurs in the a-position through oxidation by the chlorate and 1 2-di-hydroxyanthraquinone (alizarin) is formed. 

In general, if S is the solubility (in g-moles liter-1) of a sparingly soluble salt having the formulae B in pure water, one has [B+] = % S and [A-] = y S, assuming complete dissociation. Therefore, Ksp = [B+]x A F= (x S)x (y S)y = xx yY Sx+r. This is the general expression showing the relationship between solubility and the solubility product. It is known that solubility varies with temperature, and so does the solubility product. 

Most lanthanide compounds are sparingly soluble. Among those that are analytically important are the hydroxides, oxides, fluorides, oxalates, phosphates, complex cyanides, 8-hydroxyquinolates, and cup-ferrates. The solubility of the lanthanide hydroxides, their solubility products, and the pH at which they precipitate, are given in Table 2. As the atomic number increases (and ionic radius decreases), the lanthanide hydroxides become progressively less soluble and precipitate from more acidic solutions. The most common water-soluble salts are the lanthanide chlorides, nitrates, acetates, and sulfates. The solubilities of some of the chlorides and sulfates are also given in Table 2. 

An alternative way of expressing the partition constant of a sparingly soluble salt is to define its solubility product Rsp (also called the solubility constant Rs). Ks is defined as the product of the ion activities of an ionic solute in its saturated solution, each raised to its stoichiometric number v . Ks is expressed with due reference to the dissociation equilibria involved and the ions present. 

In 1904 Bally obtained a bluish violet solid by alkali fusion of benzanthrone at approximately 220 °C. Two isomeric compounds were isolated by vatting the reaction mixture and filtering off a sparingly soluble sodium salt. Oxidation of the filtrate gave a blue vat dye, violanthrone (6.75 Cl Vat Blue 20), as the main component. The less soluble residue similarly afforded a violet product, isoviolanthrone (6.76 Cl Vat Violet 10). The formation of isoviolanthrone can be suppressed by carrying out the fusion in a solvent such as naphthalene or a polyethylene glycol in the presence of sodium acetate and sodium nitrite. Dyes of this type are often referred to as dibenzanthrones. 

Sigma (a) bonds Sigma bonds have the orbital overlap on a line drawn between the two nuclei, simple cubic unit cell The simple cubic unit cell has particles located at the corners of a simple cube, single displacement (replacement) reactions Single displacement reactions are reactions in which atoms of an element replace the atoms of another element in a compound, solid A solid is a state of matter that has both a definite shape and a definite volume, solubility product constant (/ p) The solubility product constant is the equilibrium constant associated with sparingly soluble salts and is the product of the ionic concentrations, each one raised to the power of the coefficient in the balanced chemical equation, solute The solute is the component of the solution that is there in smallest amount, solution A solution is defined as a homogeneous mixture composed of solvent and one or more solutes. 

To learn that the solubility constants (products), of sparingly soluble salts can be obtained from a potentiometric titration the activity of one constituent ion is determined directly from the emf at the end point, and the salt stoichiometry then allows to be calculated. 

A solution of penicillin is not stable beyond two weeks even at refrigerator temperatures. However, the use of suspensions of sparingly soluble amine salts (procaine and hydrabamine salts) in aqueous vehicles allowed marketing of a ready-made penicillin product. 

Solubility data are presented for practically all entries. Quantitative data are also given for some compounds at different temperatures. In general, ionic substances are soluble in water and other polar solvents while the non-polar, covalent compounds are more soluble in the non-polar solvents. In sparingly soluble, slightly soluble or practically insoluble salts, degree of solubility in water and occurrence of any precipitation process may be determined from the solubility product, Ksp, of the salt. The smaller the Ksp value, the less its solubility in water. 

The presence of cyanamides of Cd and Pb in films of (Cd,Pb)S was confirmed by thermal desorption mass spectrometry [23]. Cyanamide (H2CN2) is a product of the decomposition of thiourea and forms sparingly soluble metal salts. The metal cyanamide content of the film varied from ca. 5% up to ca. 20% (by weight). The presence of the cyanamides decreased the intensity of the XRD reflections, presumably due to poorer crystallization of the sulphides. Interestingly, the photosensitivity of the films increased with higher metal cyanamide content, although whether this was due specifically to the presence of the cyanamide or to its effect on the crystal growth was not known. 

The salts of the series are bright red crystalline bodies. They are soluble in water, neutral in reaction, and dilute mineral acids do not transform them into aquo-salts. The least soluble member of the series is the sulphate [(NH3)4Co (OH)2 Co(NH3)4](S04)a.2H30, which is prepared by heating hydroxo-aquo-tetrammino-cobaltic sulphate at 100° C. till it is constant in weight. The mass is extracted with water and the sparingly soluble sulphate collected and dried. The crude product so obtained is converted into the chloride and an aqueous solution of this then treated with a solution of sodium sulphate, when a crystalline precipitate of the diol-sulphate is obtained. It is collected, washed with water, alcohol, and finally with ether. It forms small red needle-shaped crystals which contain two molecules of water of hydration. 

The stabilizing effect of buffers that have multiple charged species in solution should also be investigated to determine the potential reaction between excipients and API. For example, buffers that use carbonates, citrate, tartrate, and various phosphate salts may precipitate with calcium ions by forming sparingly soluble salts. However, this precipitation is dependent upon the solution pH. Because phosphate can exist in mono-, di-, and tribasic forms, each calcium salt has its own solubility product, and precipitation will only occur when one of the solubility product is exceeded. Calcium ions may also interact or chelate with various amino acids, and other excipients, which may also lower the effective concentration of calcium that is capable of interacting with phosphate ions. Finally, the activity of phosphate ions may be lowered due to interactions with other solution components. 

Complexes 123-131 were obtained by the direct reaction of the corresponding triazine and different silver salts according to Eq. (13). These products are sparingly soluble in acetone and insoluble in other conventional organic solvents. 

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