Examples solubility product

Aqueous ammonia can also behave as a weak base giving hydroxide ions in solution. However, addition of aqueous ammonia to a solution of a cation which normally forms an insoluble hydroxide may not always precipitate the latter, because (a) the ammonia may form a complex ammine with the cation and (b) because the concentration of hydroxide ions available in aqueous ammonia may be insufficient to exceed the solubility product of the cation hydroxide. Effects (a) and (b) may operate simultaneously. The hydroxyl ion concentration of aqueous ammonia can be further reduced by the addition of ammonium chloride hence this mixture can be used to precipitate the hydroxides of, for example, aluminium and chrom-ium(III) but not nickel(II) or cobalt(II). 

These are practically insoluble in water, are not hydrolysed and so may be prepared by addition of a sufficient concentration of sulphide ion to exceed the solubility product of the particular sulphide. Some sulphides, for example those of lead(II), copper(II) and silver(I), have low solubility products and are precipitated by the small concentration of sulphide ions produced by passing hydrogen sulphide through an acid solution of the metal salts others for example those of zincfll), iron(II), nickel(II) and cobalt(II) are only precipitated when sulphide ions are available in reasonable concentrations, as they are when hydrogen sulphide is passed into an alkaline solution. 

Solubility can often be decreased by using a nonaqueous solvent. A precipitate s solubility is generally greater in aqueous solutions because of the ability of water molecules to stabilize ions through solvation. The poorer solvating ability of nonaqueous solvents, even those that are polar, leads to a smaller solubility product. For example, PbS04 has a Ks of 1.6 X 10 in H2O, whereas in a 50 50 mixture of H20/ethanol the Ks at 2.6 X 10 is four orders of magnitude smaller. 

Potentiometric electrodes are divided into two classes metallic electrodes and membrane electrodes. The smaller of these classes are the metallic electrodes. Electrodes of the first kind respond to the concentration of their cation in solution thus the potential of an Ag wire is determined by the concentration of Ag+ in solution. When another species is present in solution and in equilibrium with the metal ion, then the electrode s potential will respond to the concentration of that ion. Eor example, an Ag wire in contact with a solution of Ck will respond to the concentration of Ck since the relative concentrations of Ag+ and Ck are fixed by the solubility product for AgCl. Such electrodes are called electrodes of the second kind. 

Solubility Product — The solubility product constant commonly referred to as the solubility product provides a convenient method of predicting the solubility of a material in water at equilibrium. Copper hydroxide, for example, dissolves according to the following equilibrium ... 

Note that the brackets, [ ], refer to the concentration of the species. K,p is the solubility product constant hence [Cu " ] and [OH] are equal to the molar concentrations of copper and hydroxyl ions, respectively. The K p is commonly used in determining suitable precipitation reactions for removal of ionic species from solution. In the same example, the pH for removal of copper to any specified concentration can be determined by substituting the molar concentration into the following equation ... 

Obviously, there are many good reasons to study ionic liquids as alternative solvents in transition metal-catalyzed reactions. Besides the engineering advantage of their nonvolatile natures, the investigation of new biphasic reactions with an ionic catalyst phase is of special interest. The possibility of adjusting solubility properties by different cation/anion combinations permits systematic optimization of the biphasic reaction (with regard, for example, to product selectivity). Attractive options to improve selectivity in multiphase reactions derive from the preferential solubility of only one reactant in the catalyst solvent or from the in situ extraction of reaction intermediates from the catalyst layer. Moreover, the application of an ionic liquid catalyst layer permits a biphasic reaction mode in many cases where this would not be possible with water or polar organic solvents (due to incompatibility with the catalyst or problems with substrate solubility, for example). 

In this example of the corrosion of zinc in a reducing acid of pH = 4, the corrosion product is Zn (aq.), but at higher pHs the thermodynamically stable phase will be Zn(OH)j and the equilibrium activity of Zn will be governed by the solubility product of Zn(OH)j and the pH of the solution at still higher pHs ZnOj-anions will become the stable phase and both Zn and Zn(OH)2 will become unstable. However, a similar thermodynamic approach may be adopted to that shown in this example. 

The general approach illustrated by Example 18.7 is widely used to determine equilibrium constants for solution reactions. The pH meter in particular can be used to determine acid or base equilibrium constants by measuring the pH of solutions containing known concentrations of weak acids or bases. Specific ion electrodes are readily adapted to the determination of solubility product constants. For example, a chloride ion electrode can be used to find [Cl-] in equilibrium with AgCl(s) and a known [Ag+]. From that information, Ksp of AgCl can be calculated. 

When two solutions are mixed, a precipitate may form. For example, suppose solutions of calcium chloride, CaCl2, and sodium sulfate, Na2S04, are mixed. The mixture contains both calcium ions, Ca+1, and sulfate ions, S04-2, so solid calcium sulfate may form. The solubility product permits us to predict with confidence whether it will or not. 

Although the hydroxides of the alkaline earth elements become more soluble in water as we go down the column, the opposite trend is observed in the solubilities of the sulfates and carbonates. For example, Table 21-VII shows the solubility products of the alkaline earth sulfates. 

The following examples illustrate the method of calculating solubility products from solubility data and also the reverse procedure. 

Example 1. The solubility of silver chloride is 0.0015 g per L. Calculate the solubility product. 

Example 2. Calculate the solubility product of silver chromate, given that its solubility is 2.5 x 10-2gL-1. 

Example 3. The solubility product of magnesium hydroxide is 3.4 x 10-11 mol3 L 3. Calculate its solubility in grams per L. 

The great importance of the solubility product concept lies in its bearing upon precipitation from solution, which is, of course, one of the important operations of quantitative analysis. The solubility product is the ultimate value which is attained by the ionic concentration product when equilibrium has been established between the solid phase of a difficultly soluble salt and the solution. If the experimental conditions are such that the ionic concentration product is different from the solubility product, then the system will attempt to adjust itself in such a manner that the ionic and solubility products are equal in value. Thus if, for a given electrolyte, the product of the concentrations of the ions in solution is arbitrarily made to exceed the solubility product, as for example by the addition of a salt with a common ion, the adjustment of the system to equilibrium results in precipitation of the solid salt, provided supersaturation conditions are excluded. If the ionic concentration product is less than the solubility product or can arbitrarily be made so, as (for example) by complex salt formation or by the formation of weak electrolytes, then a further quantity of solute can pass into solution until the solubility product is attained, or, if this is not possible, until all the solute has dissolved. 

As an example, consider the precipitation of copper(II) sulphide (jKSCuS = 8.5 x 10 45) and iron( II) sulphide KSFeS— 1.5 x 10 19)from0.01Msolutionsofthe metallic ions in the presence of 0.25M hydrochloric acid. For copper(II) sulphide, the solubility product is readily exceeded ... 

Subsequent kinetic work has amply confirmed the mechanistic picture described above. For example, the reaction of diphenylmercury with Ph(COOEt).CH.HgBr gives an almost instantaneous reaction with precipitation of phenylmercuric bromide, whereas reaction of the soluble product with a second molar equivalent of mercuric bromide gave a very slow (ca. 2 weeks) precipitation of phenylmercuric bromide722, i.e. reaction involves (287) and (288)... 

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... 

EXAMPLE u.8 Sample Exercise Estimating the molar solubility from the solubility product... 

Sometimes it is important to know under what conditions a precipitate will form. For example, if we are analyzing a mixture of ions, we may want to precipitate only one type of ion to separate it from the mixture. In Section 9.5, we saw how to predict the direction in which a reaction will take place by comparing the values of J, the reaction quotient, and K, the equilibrium constant. Exactly the same techniques can be used to decide whether a precipitate is likely to form when two electrolyte solutions are mixed. In this case, the equilibrium constant is the solubility product, Ksp, and the reaction quotient is denoted Qsp. Precipitation occurs when Qsp is greater than Ksp (Fig. 11.17). 

LI 9 Estimate a solubility product from molar solubility and vice versa (Examples 11.7 and 11.8). 

The trivalent [P04] and [As04] ions react similarly. Examples of anions that give insoluble Hg(I) compounds in this way include halides, pseudohalides, halates, carboxylates and sulfate. A trace of HNO3 or HCIO4 is often added to the solution of the Hg(I) nitrate or perchlorate to prevent disproportionation induced by alkali. Table 1 lists common Hg(I) derivatives prepared in this way and includes values of the solubility products of the sparingly soluble Hg(I) compounds where these are measured. A similar reaction is used to prepare HgjCO, from a soluble bicarbonate ... 

By convention, a solubility equilibrium is written in the direction of a solid dissolving to give aqueous ions, and the equilibrium constant for this reaction is called the solubility product ( sp). Here, for example, is the reaction... 

Example deals with the second type of calculation, determining a concentration at equilibrium when the value of the solubility product is known. 

The solubility product (. sp) describes the equilibrium of a salt dissolving in water. In the laboratory and in industry, solubility equilibria are often exploited in the opposite direction. Two solutions are mixed to form a new solution in which the solubility product of one substance is exceeded. This salt precipitates and can be collected by filtration. Example illustrates how precipitation techniques can be used to remove toxic heavy metals from aqueous solutions. 

Having introduced matters pertaining to the electrochemical series earlier, it is only relevant that an appraisal is given on some of its applications. The coverage hereunder describes different examples which include aspects of spontaneity of a galvanic cell reaction, feasibility of different species for reaction, criterion of choice of electrodes to form galvanic cells, sacrificial protection, cementation, concentration and tempera lure effects on emf of electrochemical cells, clues on chemical reaction, caution notes on the use of electrochemical series, and finally determination of equilibrium constants and solubility products. 

Examples of solubility products are listed in Table 1.9. Similarly to the dissociation constants, the solubility products are also dimensionless quantities. However, because of the choice of the standard state, their values numerically correspond to units of moles per cubic decimetre. 

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