Solubility Product Principle 23 23:4 Solubility Product Constant Most insoluble ionic solids are actually soluble in water to a limited extent, These solids dissociate slightly in water. The compound silver chloride dissociates slightly in water to give silver ions, Ag*, and chloride ions, CI. An equilibrium is established in the saturated solution between the solid and the ions in the solution. The equation. for this equilibrium is AgCl == Agt + Clr The above equation can be represented mathematically by a con- stant, K, called the equilibrium constant. By definition, this constant is equal to the concentration of the products in moles per liter divided by the concentration of the reactants in moles per liter. The concentration of each ion is raised to a power which is equal to the coefficient of the ion in the balanced equation. This constant can be expressed as follows: a [products] ea ~ [reactants] From the balanced equation: _ taetItcr] Kea = TagCl] The concentration of a pure solid such as AgClis a constant. Since both terms, [AgCI] and K,, are constants, they can be multiplied together to form a new constant which is termed the solubility product con- stant, Ky. 203204 — Solubility Product Principle [Ag*][Cl-] = K,,{AsCl] = K,, ‘The expression, [Ag*][CI-], is called the solubility product. The equation generally used in calculations is fAg*][cl-] = Ky, ion product — solubility product constant The concentration of the ions in moles per liter (the solubility product) is equal to the K,, when an equilibrium is established between the satu- rated solution and the solid particles. Note that there is no limit on the concentrations of the Ag* and Cl- ions. In a solution containing only AgCl, the concentrations of Ag* and Cl- are the same. However, if the solution contains AgCl and AgNO,, the concentration of the Ag* is greater than the concentration of the CI-. Similarly, the Cl~ concentra- tion can be larger than the Ag* concentration if the solution contains NaCl and AgCl. The only restriction is that the concentration of the Ag* multiplied by the concentration of the Cl” must be equal to the K,,. The solubility product constant, K,,, is the product of the concen- trations of the ions in a saturated solution raised to the power of their coefficients in the balanced equation. For example, the expression of the solubility product for PbCl, would be PbCl, <== Pb + 2Cl- K,, = [Pb*][Cl-? Using the equation for K,,, it is possible to calculate the solubility of a salt if its K,, is known, or to calculate the K,, from the solubility. The K,, is an experimental value. Example 4 A 1 liter saturated solution of AgCl is evaporated to dryness and the residue is equivalent to 1.34 x 10-5 mole. Whatis the experimental K,, of the silver chloride? Solving Process: The equation for the system is AgCl = Ag* + Cl. Therefore, in a saturated solution of AgCl, 1.34 x 10-$ mole AgCl gives 1.34 x 10-5 mole Agt and 1.34 x 10-5 moleCI-. The solubility product expression for AgCl is Ky = (AQ*IICI] Since the concentration in moles per liter is given, substitute directly into the equation:Solubility Product Principle _205 Kyp = 1.34 x 10°5][1.34 x 10°] = 1.80 x 40-19 Example 2_———————$—__$__$_$?_$__$ What is the experimental K,,, of CaCO, if the residue after evapo- ration of a 1.00 liter saturated solution is found to have a mass of 6.90 milligrams? Solving Process: Since the expression for K,, requires the concentration in moles per liter, convert the 6.90 mg/L to moles per liter: moles CaCO, _ 6.90. mg-GaGO; | 1.gGaeOz | 1 mol CaCO, liter = 4 | 1000.mg-Ga66z | 100.9 CaeOy The equation CaCO, = Ca** + CO,?- indicates that [Ca?*] = [CO,2-] = 6.90 x 10°§ mol CaCO;/L. Substituting into the K,, expres- sion: K,, = [Ca?+}[CO,?-] = [6.90 x 10°*][6.90 x 10-5] = 4.76 x 10° Example 3 A saturated solution of lead(II) chloride contains 4.50 grams of PbCl, per liter. What is the K,, of the compound? Solving Process: Convert to the solubility in moles per liter. 4.50.gPb€t; | 1 mol PbCl, iL 278.g- Peer, The equation PbCl, = Pb?* + 2CI- indicates that 1 mole PbCl, dissociates to give 1 mole Pb?* and 2 moles Cl-. Therefore, 1.62 x 10-2 mole PbCl, gives 1.62 x 10-? mole Pb?* and 3.24 x 10-? mole CI. By definition of the K,,, the concentration of ions is raised to a power which is equal to the coefficient of the ion. Thus the CIl- concen- tration is squared. K,y = (Pb? ICIP = [1.62 x 10°7I[3.24 x 102? = 1.70 x 10° 1.62 x 107? mol PbCl,/L Problems 1. From the solubilities, determine the experimental value of the K,, for cach compound: a. Agr 2.88 x 10-7 g/100 mL b. BaCO, —_7.00 x 10°$ mol/L c. CaF, 1.70 mg/100 mL206 = Solubility Product Principle d. Pb(OH), 4.20 x 10-6 mol/L. e. SrF, 1.22 x 10°? g/100 mL f Pb(O;), 2.30mg/100 mL Example 4 Ifthe K,, of AgClis 1.81 x 107", determine the solubility of AgCl in grams per liter. Solving Process: From the equation AgC! < Ag* + CI”, note that the concentration of Ag* is equal to the concentration of Cl-. Let the Ag* concentration be equal to x: [Ag*] = [Cr] = x Substitute into the K,, equation: [Ag*J[CI-] = bx] = K,, = 1.81 x 10-1? x? = 1.81 x 1071 x= VIB XK 10-% = 1.35 x 10-5 The x, which is termed the molar solubility, is 1.35 x 10- mole per liter. In grams per liter it is _ ' Alias os ae mg — AGC! _ 4.93 x 10-8 g AGCI/L Example 5. For a saturated silver chromate solution calculate the molar solu- bility, the molar concentration of Ag* and CrO,?-, and the solubility in grams per 100 mL of silver chromate. The K,, of Ag,CrO, is 1.12 x 10-1, Solving Process: From the equation Ag,CrO, = 2Ag* + CrO,?- note that the con- centration of the Ag* ion is twice the concentration of the CrO,?- ion. Let x equal the molar solubility: [Ag*] = 2x [CrO?-] = x Substitute into the K,, expression: [Ag*PICrO,?-] = Kyp [2x}?-[x] = 4x3 = 1.12 x 10-7? = 1.12 x 10-1? 4 x = 280 x 10-8 x = 280 x 107% = 1/280 x 10-5Solubility Product Principle 207 x = 6.54 x 10-8 = molar solubility The concentrations of the ions are [Agt] = 2x = 1.31 x 10 [CrO,2-] = x = 6.54 x 10° Solubility in grams per 10.0 mL is 6.54 x 10-S-molAgzere; | 332 g Ag,CrO, | te | 1000-mE ae | Tamar Agg6r@; | 1000 | 10(100 mL) = 2.17 x 10°3.g/100 mL Problems 2. Calculate the molar solubility of the following compounds from their K,, values: a. CuS 6.31 x 10% b. SrC,0, 158 x 10-7 c. ANOH), 1.26 x 10-3 d. PbI, 1.66 x 10-8 The following two Examples deal with the common ion effect. Example 6 ———_$_$_$_€?_/_+___ What is the molar solubility of BaSO, in a solution that contains 0.100M Na,SO,? The K,, of BaSO, is 1.15 x 10-1 Solving Process: This solution contains Na,SO, which is assumed to dissociate completely into Na* and SO,?-. There are two sources of SO,2- from the barium sulfate and from the sodium sulfate. Na,SO, —> 2Na* + SO?- BaSO, == Ba*t + SO,- Let x equal the moles of BaSO, that dissolve per liter of 0.100M Na,SO,. The equation BaSO, = Ba** + SO,?- indicates that the concentra- tion of Ba* is equal to the concentration of SO,2-, for these two ions come from the barium sulfate. However, the solution already con- tains 0.100M SO,2-. The concentration of the ions in the solution is therefore [Ba+] =x [S0,2-] = x + 0.100 Substitute into the K,, expression: [Ba?*][SO,2-] = (x(x + 0.100) = K,, = 1.15 x 107°208 — Solubility Product Principle Ifthe K,, is small, very little BaSO, will dissolve. Some of the BaSO, will ionize but according to Le Chatelier’s principle, a reaction shifts equilibrium in such a way as to relieve a stress. The additional so?- ions are removed from solution by uniting with Ba?+ to form BaSO,. Then, assume that x + 0.100 = 0.100. (The symbol =means approxi- mately equal to.) Thus: = a Sto 1020 : 0.100x = 1.15 x 10 xe = 11S x 108M Example 7 Determine the molar solubility of iron(II) hydroxide in 0.0500M NaOH. The K,, of Fe(OH), is 7.94 x 10°18. Solving Process: Assume that the NaOH is completely dissociated and gives 0.0500M OH" ions. There are two sources of OH~ ions — the NaOH and the Fe(OH),. NaOH —> Nat + OH™ Fe(OH), == Fe** + 20H- Let x equal the molar solubility or concentration in moles/liter. Using the equation Fe(OH), = Fe*+ + 2OH™ we get the following: [Fe] =x [OH] = 2x + 0.0500 Substitute into the K,, expression: [Fe®*]]OH-? = (x(2x + 0.0500)? = K,, = 7.94 x 10-18 Assume that 2x + 0.0500 = 0.0500. (0.0500)*x = 7.94 x 10-76 7.94 X 10-18 _ os Beoecos = 218 x 107M Note that the OH- concentration is squared without regard to the source of the OH-. Since the x is small compared to the 0.0500, the assumption is valid. Thus, 3.18 x 10-'3 mole Fe(OH), can be dissolved in 1 liter of 0.0500M NaOH to give a saturated solution containing 3.18 x 10-13 mole Fe** and 0.0500 mole OH". x= Problems 3. Determine the molar solubility or concentration of silver chloride when the compound is dissolved in: a. pure water b. 0.1000M NaCl c. 0.0100M NaCl The K,, of AgCl is 1.81 x 107!Solubility Product Principle _ 209 4. Determine the molar solubility or concentration of calcium hy- droxide when the compound is dissolved in: a. pure water c. 0.01M NaOH b. 010M NaOH d. 0.10M Ca(NO,)2 The K,, of Ca(OH), is 5.50 x 10-¢ 5, Find the molar solubility or concentration of silver chromate when the compound is dissolved in: a. pure water b. 0.04MAgNO, ¢._ 0.25MK,CrO, The K,, of Ag,CrO, is 1.12 x 107! 23:2 Predicting Precipitation A useful application of the K,, data is to determine if precipitation will occur when a salt and a solution or two solutions are mixed. Precip- itation takes place only when the ion product exceeds the Kjy. If it exceeds the K,,, precipitation will occur. ion product < K,, no precipitate will f ion product > K,, precipitate will form Remember, that if the final solution is formed by mixing two solutions it is necessary to consider dilution. Each solute is diluted when the other solution is added. Example 8 Will precipitation occur in a solution containing a concentration of 2.00 x 10-4M Pb?* ions when enough solid NaF is added to bring the fluoride ion concentration to 3.00 x 10-M? The K,, of PbF, is 2.69 x 10-8. (Ignore volume changes.) Solving Process: For precipitation to take place, the K,, value must be exceeded. The value of the ion product must be calculated and then compared to the K,, value. Since the dissociation equation is PbF, = Pb?* + 2F-, the ion product is [Pb**][F~P. [Pb2*][F-]? = [2.00 x 10°4}[3.00 x 107 = (2.00 x 10-4)(9.00 x 1074) 80 x 107 Since 1.80 x 1077 is larger than the K,, value (2.69 x 10°), pre- cipitation will occur.240 — Solubility Product Principle Example 9. Will precipitation occur when 50.0 mL of a3.00 x 10-?M Pb(NOs3), solution is added to 50.0 mL of 2.00 x 10-$M KCI? The K,, of PbCl, is 1.62 x 10-5. Solving Process: Assume that no change in volume occurs when the two solutions are mixed and that the final volume will be 100.0 mL. First calculate the concentration of ions in the mixture as if they do not react. The Pb?* concentration, because of a twofold dilution, is 1.50 x 10-?M. The CI- concentration, because of a twofold dilution, is 1.00 x 10-°M. Use these new concentrations of Pb?* and Cl" to calculate the ion product and determine if it exceeds the K,,. The equation for a saturated ‘solution is PbCl, = Pb** + 2Cr-. Therefore, on substitution the ion product becomes: [Pb2*][CI-P = [1.50 x 10-2][1.00 x 10-3]? = 1.50 x 10% Since 1.50 x 10-8 is smaller than the K,, of PbCI, (1.62 x 10-5), pre- cipitation does not occur. The 100 mL solution is unsaturated. Example 10 What concentration of carbonate should be added to a silver solution to reduce the concentration of Ag* ion to 2.00 x 10-® mole? The K,, of AgCOz is 7.07 x 10-2, Solving Process: From the equation Ag,CO, = 2Ag* + CO,?-, obtain the K,, expression. K,, = [Ag*P[CO7] Solve for CO,?- concentration. K, 7.07 x 10-72 7.07 x 10712 2] = — 2 = ee ee (001 = Fagte = Ta00 x 10F = 4.00 x 10% = 7 MONE Example 14 Calculate the [OH] from iron(II) hydroxide in a water solution saturated with Fe(OH). The K,, of Fe(OH), is 3.98 x 10-**. Determine the pH of the solution. Solving Process: From the equation, write the K,, expression. Fe(OH); <= Fe + 30H- Let x = [Fe*+] and 3x = [OH").Solubility Product Principle 244 K,, = [Fe*]JOH-P = 3.98 x 10° [xP = 3.98 x 10-% _ 3.98 x 10-8 a 87 x = 1.96 x 10°1°M [OH-] from Fe(OH), = 3(1.96 x 10-19) = 5.88 x A0et. x4 Because of the small quantity of [OH™] from Fe(OH), the pH = 7 since the water will provide [OH~] = 10-7 mol/L. Chapter Review Problems 6. % 10. Given the following solubilities, determine the K,, for each com- pound: a. Ag,S 1.60 x 10-! g/100 mL b. As,S; 5.17 x 10-5 g/100 mL c. AgPO, 8.50 x 10-g/100 mL d. Bi,S; 1.70 x 10-!5 mol/L e. Mn(OH), 2.10 x 10-4 g/100 mL £ Ca,(PO,), 3.92 X 10-¢ mol/L Calculate the molar solubility for each using the following K,, values: a. Ag,S 6.31 x 10-8 b. BaCrO, 1.17 x 10-19 c. Fe(OH), 7.94 x 10-16 d. Pb,(PO,), 7.94 x 10-3 Determine the molar concentration of the metallic ions from the K,, values of the following compounds: a. BaSO; 7.94 x 10-7 e. Ba(OH), 4.01 x 10-3 b. MgF, 646x109 fs Hg, Cl, 1.32 x 10718 ApcO, 14x08 |g AgPO, | 145 x 108 d. Ca,PO,), 2.00 x 10°? From the K,, values, calculate the solubility in milligrams per 100 milliliters for the following compounds: a. CdCO, 5.25 x 10-2 d. CaSO, 9.12 x 10-¢ b. CuOH), 219x107 e. AgCl 1.81 x 10-1 c. Fe(OH); 3.98 10% —f_ Ag,CO3 7.07 x 10-? Ifa solution contains 1.00 x 10°2M chloride ions and 1.00 x 10-°M iodide ions, which will precipitate first, AgClor Agl, if a solution of ‘AgNO; is added one drop at a time? The K,, of AgClis 1.81 x 10-1 K,, of Agl is 8.32 x 10-7,212 11, 12, 13. 14. 15, 16. 17. 18. 19, 20. 21 Solubility Product Principle If a solution contains 2.00 x 10~3M lead ions and 1.00 x 10-7M silver ions, which will precipitate first, PbSO, or Ag,SO,, when a solution of Na,SO, is added one drop at a time? The K,, of PbSO, is 1.62 x 10-8; the K,, of Ag,SO, is 1.45 x 10-5. Would it be possible to separate a solution containing 0.00200M Pb?+ and 0.0300M Ag* by adding drops of Na,CO, solu- tion? If so, which compound, PbCO, or Ag,CO,, would precipitate first? The Ky, of PbCO, is 7.41 x 10-4; the K,, of Ag,CO, is 7.07 x 10713, What concentration of hydroxide ion would be required to bring about precipitation of the following metallic ions? a ABt 2.00 x 105M K,, A(OH); = 1.26 x 10-33 b. Ba?+ 400x 104M _—K,, Ba(OH), = 5.01 x 10-3 ce Cou 1.50 x 103M _—_K,, Co(OH), = 1.58 x 107!5 Determine if precipitation would occur in the following cases: a. 100.0mL of a 5.00 x 10-3M Ba(NO,), is mixed with 100.0L of 2.00 x 10-?M NaF. K,, of BaF, is 1.05 x 10-6. b. 50.0mL of 6.0 x 10-*MAgNO, is mixed with 50.0mL of 5.0 x 104M K,CrO,. K,, of Ag,CrO, is 1.12 x 107! c. 25.0mL of 6.0 x 10-°M Sr(NO,), is mixed with 25.0mL of 4.0 x 10-7M H,PO,. K,, of Sr,(PO,), is 4.07 x 10-8, The solubility product of barium sulfate is 1.15 x 10-1°. Find the solubility of BaSO, in 0.0100M BaCl,. Determine the mass of calcium fluoride, CaF,, that will dissolve in 200.0 mL of water. Assume that there is no volume change. K,, of CaF, is 2.69 x 107". Determine if a precipitate of silver chromate, Ag,CrO,, will form when 100.0mL of 0.100MAgNO, are added to 100.0mL of 0.350M K,CrO,. K,, of Ag,CrO, is 1.12 x 107, Pure silver sulfate, Ag,SO,, is dissolved in enough water to make 800.0 mL of a saturated solution. Determine the grams of Ag,SO, that dissolve if the K,, is 1.45 x 107. Determine the mass in grams of Fe3* in exactly 1.000 mL of a saturated solution of iron(II) hydroxide. The K,, is 3.98 x 10-38, A solution containing 0.100M HF also contains 0.0100M Ca(NO;),. Hydrochloric acid is added slowly till the solution has a pH of 2.00. Will a precipitate of calcium fluoride, CaF,, occur? For the HF, K, = 6.46 X 10-4; and for the CaF, K,, = 2.69 x 10-4. Iron(II) hydroxide, Fe(OH),, has a K,, of 7.94 x 10-'*. If a solution has a pH of 10.00, what is the solubility of the metallic hydroxide?22. 23. Solubility Product Principle 243 Solid silver nitrate, AgNO, is slowly added to a solution containing 0.100M chloride ion and 0.100M chromate ion. Assume that the addition of the solid causes no volume change. Which will precipi- tate first, the silver chloride or the silver chromate? For AgCl, Kp = 1.81 X 107%; for Ag,CrO,, K,y = 1-12 x 107. Using the information in problem 22, determine the chloride ion concentration when the red silver chromate just begins to precipi- tate. What percent of the chloride ion originally present (0.100!) remains in solution when precipitation begins?