CHEMISTRY 12

Chapter 9

Aqueous Solutions and Solubility Equilibria

Solutions for Practice Problems
Student Textbook page 424
1. Problem (a) (b) (c) (d)

Predict whether an aqueous solution of each salt is neutral, acidic, or basic. NaCN LiF Mg(NO3)2 NH4I

What Is Required? Predict whether each aqueous solution is acidic, basic, or neutral. What Is Given? The formula of each salt is given. Plan Your Strategy Determine whether the cation is from a strong or weak base, and whether the anion is from a strong or weak acid. Ions derived from weak bases or weak acids react with water and affect the pH of the solution. Act on Your Strategy
(a) Sodium cyanide, NaCN, is the salt of a strong base (NaOH) and a weak acid

(HCN). Only the cyanide ions react with water. The solution is basic. (b) Lithium uoride, LiF, is the salt of a strong base (LiOH) and a weak acid (HF). Only the uoride ions react with water. The solution is basic. (c) Magnesium nitrate, Mg(NO3)2, is the salt of a strong base (Mg(OH)2) and a strong acid (HNO3(aq)). Neither ion reacts with water, so the solution is neutral. (d) Ammonium iodide, NH4I, is the salt of a weak base (NH3(aq)) and a strong acid (HI(aq)). Only the ammonium ions react with water. The solution is acidic. Check Your Solution Check that you have correctly identified whether the cation is from a strong or weak base, and whether the anion is from a strong or weak acid.
2. Problem

Is the solution of each salt acidic, basic, or neutral? For solutions that are not neutral, write equations that support your predictions. (a) NH4BrO4 (b) NaBrO4 (c) NaOBr (d) NH4Br What Is Required? Predict whether each aqueous solution is acidic, basic, or neutral. Write equations that represent the solutions that are acidic or basic.

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What Is Given? The formula of each salt is given. Plan Your Strategy Determine whether the cation is from a strong or weak base, and whether the anion is from a strong or weak acid. Ions derived from weak bases or weak acids react with water and affect the pH of the solution. Act on Your Strategy (a) Ammonium perbromate, NH4BrO4 , is the salt of a weak base (NH3(aq)) and a strong acid (HBrO4). Only the ammonium ions react with water. NH4+(aq) + H2O( ) NH3(aq) + H3O+(aq) The solution is acidic. (b) Sodium perbromate, NaBrO4 , is the salt of a strong base (NaOH) and a strong acid (HBrO4). Neither ion reacts with water, so the solution is neutral. (c) Sodium hypobromite, NaOBr, is the salt of a strong base (NaOH) and a weak acid (HOBr(aq)). Only the hypobromite ions react with water. OBr(aq) + H2O( ) HOBr(aq) + OH(aq) The solution is basic. (d) Ammonium bromide, NH4Br, is the salt of a weak base (NH3(aq)) and a strong acid (HBr(aq)) . Only the ammonium ions react with water. NH4+(aq) + H2O( ) NH3(aq) + H3O+(aq) The solution is acidic. Check Your Solution The equations that represent the reactions with water support the prediction that NH4BrO4 and NH4Br dissolve to form an acidic solution and NaOBr dissolves to form a basic solution. Sodium hypobromite is the salt of a strong base-strong acid, so neither ion reacts with water and the solution is neutral.
3. Problem

Ka for benzoic acid, C6H5COOH, is 6.3 105 . Ka for phenol, C6H5OH, is 1.3 1010. Which is the stronger base, C6H5COO(aq) or C6H5O(aq)? Explain your answer. What Is Required? You must determine which ion, C6H5COO(aq) or C6H5O(aq), is the stronger base. What Is Given? The Ka of each conjugate acid is given. Plan Your Strategy For a conjugate acid-base pair, KaKb = 1.0 1014 . Therefore, a small value of Ka for an acid results in a large value of Kb for the conjugate base.

Act on Your Strategy Because Ka for phenol is smaller than Ka for benzoic acid, Kb for the phenolate ion must be larger than Kb for the benzoate ion. Consequently, C6H5O(aq), is the stronger base. Check Your Solution Using the equation KaKb = 1.0 1014 , you can calculate the Kb for each conjugate base. Kb for C6H5COO(aq) is 1.6 1010 . Kb for C6H5O(aq) is 7.7 105 . This supports the reasoning that C6H5O(aq) is the stronger base.

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4. Problem

Sodium hydrogen sulte, NaHSO3 , is a preservative that is used to prevent the discolouration of dried fruit. In aqueous solution, the hydrogen sulte ion can act as either an acid or a base. Predict whether NaHSO3 dissolves to form an acidic solution or a basic solution. (Refer to Appendix E for ionization data.) What Is Required? You must decide whether NaHSO3 dissolves to form an acidic solution or a basic solution. What Is Given? Ka for H2SO3(aq) = 1.4 102 Ka for HSO3(aq) = 6.3 108 Plan Your Strategy The hydrogen sulte ion is amphoteric. Compare the equilibrium constants Ka and Kb for HSO3(aq) acting as an acid and a base, to determine which reaction goes farthest to completion. Act on Your Strategy The ion reactions with water are HSO3(aq) + H2O( ) SO32(aq) + H3O+(aq) Ka = 6.3 108 HSO3 (aq) + H2O( ) H2SO3(aq) + OH(aq) Kb = ? Kb can be calculated using the value for Ka of H2SO3(aq) . Kb = Kw Ka 14 = 1.0 10 2 1.4 10 = 7.1 1013 The equilibrium constant (Ka) for the hydrogen sulte ion acting as an acid is greater than the equilibrium constant (Kb) for the ion acting as a base. Therefore, the solution is acidic. Check Your Solution It is a common difculty in this type of problem to identify correctly the base reaction and the corresponding value for Kb . Kb must be calculated using the Ka value for H2SO3(aq) , because HSO3(aq) is the conjugate base of H2SO3(aq) .

Solutions for Practice Problems

Student Textbook page 428
5. Problem

After titrating sodium hydroxide with hydrouoric acid, a chemist determined that the reaction had formed an aqueous solution of 0.020 mol/L sodium uoride. Determine the pH of the solution. What Is Required? You need to calculate the pH of the solution. What Is Given? [NaF] = 0.020 mol/L From Appendix E, Ka for HF(aq) = 6.3 104 Plan Your Strategy Step 1 Decide which ion reacts with water. Write the equation that represents the hydrolysis reaction.

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Step 2 Step 3 Step 4 Step 5 Step 6

Determine the equilibrium constant for the ion involved in the hydrolysis reaction. Divide the ion concentration by the appropriate equilibrium constant to determine whether the change in concentration of the ion can be ignored. Set up an ICE table for the ion that is involved in the reaction with water. Let x represent the change in the concentration of the ion that reacts. Write the equilibrium expression. Substitute the equilibrium concentrations into the expression, and solve for x. Use the value of x to determine [H3O+]. Then calculate the pH of the solution.

Act on Your Strategy Sodium uoride is the salt of a strong base (NaOH) and a weak acid (HF). Thus, only the uoride ion reacts with water. HF(aq) + OH(aq) F(aq) + H2O( ) Step 2 Kb for the uoride ion can be calculated using Ka for HF(aq) . Kb = Kw Ka 14 = 1.0 10 4 6.3 10 = 1.6 1011 Na+(aq) + F(aq) Step 3 NaF(aq) [F] = 0.020 mol/L 0.020 F = Kb 1.6 1011 = 1.2 109 Because this value is much greater than 500, the change in concentration of F(aq) can be ignored compared with its initial concentration.
Step 1 Step 4 Concentration (mol/L) Initial Change Equilibrium Step 5 F (aq) 0.020 x 0.020 x 0.020 + H2O(
)

2HF(aq) 0 +x x

OH(aq) ~0 +x x

Kb = [HF][OH ] [F ] 1.6 1011 = (x)(x) 0.020

x =

3.2 1013

= 5.6 107 mol/L Step 6 x = [OH] = 5.6 107 mol/L pOH = log[OH] = log(5.6 107) = 6.25 pH = 14.00 pOH = 14.00 6.25 = 7.75 Check Your Solution The pH of the solution is weakly basic. This is consistent with a dilute aqueous solution of the salt of a strong base and a weak acid.

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6. Problem

Part way through a titration, 2.0 101 mL of 0.10 mol/L sodium hydroxide has been added to 3.0 101 mL of 0.10 mol/L hydrochloric acid. What is the pH of the solution? What Is Required? You need to calculate the pH of the solution. What Is Given? 20 mL of 0.10 mol/L NaOH(aq) has been added to 30 mL of 0.10 mol/L HCl(aq) . Plan Your Strategy Step 1 Calculate the amount of each reagent using the following equation: Amount (mol) = concentration (mol/L) volume (L) Step 2 Write the chemical equation for the reaction and determine the excess reagent. Step 3 Calculate the concentration of the excess reagent using the following equation: Concentration (mol/L) = amount in excess (mol) total volume (L) Step 4 Calculate the pH of the solution. Act on Your Strategy Step 1 Amount NaOH(aq) = (0.10 mol/L) (2.0 102 L) = 2.0 103 mol Amount HCl(aq) = (0.10 mol/L) (3.0 102 L) = 3.0 103 mol Step 2 NaOH(aq) + HCl(aq) NaCl(aq) + H2O( ) Because the acid and base react in a 1:1 ratio, the HCl(aq) is in excess. Step 3 Amount of excess HCl(aq) = (3.0 103 mol) (2.0 103 mol) = 1.0 103 mol Total volume = (2.0 102 L) + (3.0 102 L) = 5.0 102 L 3 mol [HCl] = 10 10 2 5.0 10 L = 2.0 102 mol/L Step 4 HCl(aq) is a strong acid. Therefore, [H3O+] = 2.0 102 mol/L . pH = log[H3O+] = log(2.0 102) = 1.70

Check Your Solution The solutions have the same molar concentration. Because the volume of hydrochloric acid is greater, the solution should be acidic and the pH less than 7.
7. Problem

0.025 mol/L benzoic acid, C6H5COOH, is titrated with 0.025 mol/L sodium hydroxide solution. Calculate the pH at equivalence. What Is Required? You need to calculate the pH at equivalence. What Is Given? You know that 0.025 mol/L C6H5COOH(aq) reacts with 0.025 mol/L NaOH(aq) . Tables of Ka and Kb values are in Appendix E.
Step 1 Step 2

Plan Your Strategy Write the balanced chemical equation for the reaction. Calculate the concentration of the salt formed, based on the amount (in mol) and the total volume of the solution.
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Step 3 Step 4 Step 5

Step 6 Step 7 Step 8

Decide which ion reacts with water. Write the equation that represents the reaction. Determine the equilibrium constant for the ion that is involved in the hydrolysis reaction. Divide the concentration of the ion identied in Step 3 by the appropriate ionization constant to determine whether the change in concentration of the ion can be ignored. Set up an ICE table for the ion that is involved in the reaction with water. Let x represent the change in the concentration of the ion that reacts. Write the equilibrium expression. Substitute the equilibrium concentrations into the expression, and solve for x. Use the value of x to determine [H3O+]. Then calculate the pH of the solution.

Act on Your Strategy The following chemical equation represents the reaction. C6H5COOH(aq) + NaOH(aq) NaC6H5COO(aq) + H2O( ) Step 2 The acid and base react in a 1:1 ratio, and the concentrations are the same. Therefore, the volume of each reagent must be the same and the total volume will be double the initial volume. Therefore, [NaC6H5COO] = 0.025 mol/L 2 = 0.0125 mol/L Step 3 The salt forms Na+(aq) and C6H5COO(aq) in solution. Na+(aq) is the cation of a strong base, so it does not react with water. C6H5COO(aq) is the conjugate base of a weak acid, so it does react with water. The pH of the solution is therefore determined by the extent of the following reaction. C6H5COO(aq) + H2O( ) C6H5COOH(aq) + OH(aq) Step 4 Therefore, Kb for C6H5COO(aq) = Kw Ka 14 = 1.0 10 5 6.3 10 = 1.6 1010
Step 1 Step 5

[C6H5COO] = 0.012510 Kb 1.6 10 = 7.8 107 This is well above 500, so the change in [C6H5COO] can be ignored.
+ H2O(
)

Step 6 Concentration (mol/L) C6H5COOH(aq) Initial Change Equilibrium 0.0125 x 0.0125 x 0.0125 C6H5COOH(aq) 0 +x x + OH(aq) ~0 +x x

Step 7

[C6H5COOH][OH] [C6H5COO] 1.6 1010 = (x)(x) 0.0125 x = 2.0 1012 Kb = = 1.4 106 mol/L
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Step 8

x = [OH] = 1.4 106 mol/L pOH = log[OH] = log(1.4 106) = 5.85 pH = 14.00 5.85 = 8.15

Check Your Solution The titration forms an aqueous solution of a salt derived from a strong base and a weak acid. The solution should be basic, which is supported by the calculation of the pH.
8. Problem

50.0 mL of 0.10 mol/L hydrobromic acid is titrated with 0.10 mol/L aqueous ammonia. Determine the pH at equivalence. What Is Required? You need to calculate the pH at equivalence. What Is Given? You know that 50 mL of 0.10 mol/L HBr(aq) reacts with 0.10 mol/L NH3(aq) . Tables of Ka and Kb values are in Appendix E. Plan Your Strategy Step 1 Write the balanced chemical equation for the reaction. Step 2 Find the volume of NH3(aq) added to neutralize the hydrobromic acid based on the amount and concentration of HBr(aq) . Step 3 Calculate the concentration of the salt formed, based on the amount (in mol) and the total volume of the solution. Step 4 Decide which ion reacts with water. Write the equation that represents the reaction. Step 5 Determine the equilibrium constant for the ion that is involved in the hydrolysis reaction. Step 6 Divide the concentration of the ion identified in Step 4 by the appropriate ionization constant to determine whether the change in concentration of the ion can be ignored. Step 7 Set up an ICE table for the ion that is involved in the reaction with water. Let x represent the change in the concentration of the ion that reacts. Step 8 Write the equilibrium expression. Substitute the equilibrium concentrations into the expression, and solve for x. Step 9 Use the value of x to determine [H3O+]. Then calculate the pH of the solution. Act on Your Strategy Step 1 The following chemical equation represents the reaction. NH3(aq) + HBr(aq) NH4Br(aq) Step 2 Amount (in mol) of NH3(aq) = 0.20 mol/L 0.020 L = 4.0 103 mol Step 3 NH3(aq) and HBr(aq) react in a 1:1 ratio. Because [NH3] = [HBr], the volume of aqueous ammonia added must be the same as the volume of hydrobromic acid. Therefore, the volume of NH3(aq) is 50 mL, and the total volume of the solution is twice the volume of HBr(aq) used. Thus, the [NH4Br] must be half the initial [HBr]. Therefore, [NH4Br] = 0.050 mol/L

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The titration results in an aqueous solution of ammonium bromide, NH4Br(aq) . NH4+(aq) is the conjugate acid of a weak base, so it reacts with water. Br(aq) is the conjugate base of a strong acid, so it does not react with water. The solution will be acidic, and the pH is determined by the extent of the following reaction. NH4+(aq) + H2O( ) NH3(aq) + H3O+(aq) Step 5 From Appendix E, Kb for NH3(aq) is 1.8 105 . Ka for the conjugate base, NH4(aq) , can be calculated using the relationship KaKb = Kw. Ka = Kw Kb 14 = 1.0 10 5 1.8 10 = 5.6 1010
Step 4 Step 6

0.050 [NH4+] = Ka 5.6 1010 = 8.9 107 This is well above 500, so the change in [NH+] can be ignored. 4
Concentration (mol/L) Initial Change Equilibrium NH4+(aq) + 0.050 x 0.050 x 0.050 H2O(
)

Step 7

NH3(aq) 0 +x x

H3O+(aq) ~0 +x x

Step 8

[NH3][H3O+] [NH4+] 5.6 1010 = (x)(x) 0.050 x = 2.8 1011 Ka =

= 5.3 106 mol/L Step 9 x = [H3O+] = 5.3 106 mol/L pH = log[H3O+] = log(5.3 106) = 5.28 Check Your Solution The titration forms an aqueous solution of a salt derived from a weak base and a strong acid. The solution should be acidic, which is supported by the calculation of the pH.

Solutions for Practice Problems

Student Textbook page 432
9. Problem

Write the balanced chemical equation that represents the dissociation of each compound in water. Then write the corresponding solubility product expression. (a) copper(I) chloride (b) barium uoride (c) silver sulfate (d) calcium phosphate

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Solution First, write a balanced equation for the equilibrium between excess solid and dissolved ions in a saturated aqueous solution. Then use the balanced equation to write the expression for Ksp. Cu+(aq) + Cl(aq) (a) CuCl(s) Ksp = [Cu+][Cl] Ba2+(aq) + 2F(aq) (b) BaF2(s) 2+ Ksp = [Ba ][F]2 2Ag+(aq) + SO42(aq) (c) Ag2SO4(s) Ksp = [Ag+]2[SO42] 3Ca2+(aq) + 2PO43(aq) (d) Ca3(PO4)2(s) 2+ 3 Ksp = [Ca ] [PO43]2 Check Your Solution The Ksp expressions are based on balanced equations for saturated solutions of slightly soluble ionic compounds. The exponents in the Ksp expressions match the corresponding coefficients in the chemical equations. The coefficient 1 is not written, following chemistry conventions.
10. Problem

Write a balanced dissolution equation and solubility product expression for silver carbonate, Ag2CO3 . Solution First, write a balanced equation for the equilibrium between excess solid and dissolved ions in a saturated aqueous solution. Then use the balanced equation to write the expression for Ksp. Ag2CO3(s) 2Ag+(aq) + CO3(aq) Ksp = [Ag+]2[CO3] Check Your Solution The Ksp expression is based on the balanced equation between excess solid and dissolved ions. The exponents in the Ksp expression match the corresponding coefcients in the chemical equation.
11. Problem

Write a balanced dissolution equation and solubility product expression for magnesium ammonium phosphate, MgNH4PO4 . Solution First, write a balanced equation for the equilibrium between excess solid and dissolved ions in a saturated aqueous solution. Then use the balanced equation to write the expression for Ksp. MgNH4PO4(s) Mg2+(aq) + NH4+(aq) + PO43(aq) + 2+ Ksp = [Mg ][NH4 ][PO43] Check Your Solution The Ksp expression is based on the balanced equation between excess solid and dissolved ions. The exponents in the Ksp expression match the corresponding coefcients in the chemical equation.
12. Problem

Iron (III) nitrate has very low solubility.

(a) Write the solubility product expression for iron(III) nitrate. (b) Do you expect the value of Ksp of iron(III) nitrate to be larger or smaller than the

Ksp for aluminum hydroxide, which has a slightly higher solubility?

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Solution (a) Write a balanced equation for the equilibrium between excess solid iron(III) nitrate and dissolved ions in a saturated aqueous solution. Then use the balanced equation to write the expression for Ksp. Fe(NO3)3(s) Fe3+(aq) + 3NO3(aq) Ksp = [Fe3+][NO3]3 (b) Write a balanced equation for the equilibrium between excess solid aluminum hydroxide and dissolved ions in a saturated aqueous solution. Then use the balanced equation to write the expression for Ksp. Finally, compare the two equilibrium expressions and decide which expression is larger. Al3+(aq) + 3OH(aq) Al(OH)3(s) 3+ Ksp = [Al ][OH]3 The equilibrium expressions have the same form. In both cases, if x mol/L of salt dissolves, Ksp is given by x 4 . Therefore, the most soluble salt will have the larger value of Ksp. The value of Ksp for iron(III) nitrate is smaller than Ksp for aluminum hydroxide. Check Your Solution Each Ksp expression is based on the balanced equation between excess solid and dissolved ions. The exponents in the Ksp expressions match the corresponding coefcients in the chemical equations. The equilibrium expressions are of the same form, so the least soluble salt has the lower value for Ksp.

Solutions for Practice Problems

Student Textbook page 433
13. Problem

The maximum solubility of silver cyanide, AgCN, is 1.5 108 mol/L at 25C. Calculate Ksp for silver cyanide. What Is Required? You need to nd the value of Ksp for AgCN at 25C. What Is Given? You know the solubility of AgCN at 25C. Plan Your Strategy Step 1 Write an equation for the dissolution of AgCN. Step 2 Use the equation to write the solubility product expression. Step 3 Find the concentration (in mol/L) of each ion. Step 4 Substitute the concentrations into the solubility product expression, and calculate Ksp.

Act on Your Strategy Ag+(aq) + CN(aq) Step 1 AgCN(s) + Step 2 Ksp = [Ag ][CN] Step 3 [Ag+] = [CN] = [AgCN] = 1.5 108 mol/L Step 4 Ksp = [Ag+][CN] = (1.5 108)(1.5 108) = 2.2 1016 Ksp for silver cyanide is 2.2 1016 at 25C. Check Your Solution The value of Ksp is less than the concentration of the salt, as expected. It has the correct number of signicant digits.
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14. Problem

A saturated solution of copper(II) phosphate, Cu3(PO4)2 , has a concentration of 6.1 107g Cu3(PO4)2 per 1.00 102 mL of solution at 25C. What is Ksp for Cu3(PO4)2 at 25C ? What Is Required? You need to nd the value of Ksp for Cu3(PO4)2 at 25C. What Is Given? You know 6.1 107 g of Cu3(PO4)2 is dissolved in 1.00 102 mL of solution at 25C. Plan Your Strategy Step 1 Write an equation for the dissolution of Cu3(PO4)2 . Step 2 Use the equation to write the solubility product expression. Step 3 Find the concentration (in mol/L) of copper(II) phosphate. Next, nd the concentration (in mol/L) of each ion. Step 4 Substitute the concentrations into the solubility product expression, and calculate Ksp. Act on Your Strategy 3Cu2+(aq) + 2PO43(aq) Step 1 Cu3(PO4)2(s) 2+ 3 Step 2 Ksp = [Cu ] [PO43]2 Step 3 The molar mass of Cu3(PO4)2 is 380.6 g/mol. 6.1 107g Amount of Cu3(PO4)2 = 380.6 g/mol = 1.6 109 mol
9 [Cu3(PO4)2] = 1.6 10 mol 0.100 L = 1.6 108 mol/L 2+ [Cu ] = 3 [Cu3(PO4)2]

= 3 (1.6 108 mol/L) = 4.8 108 mol/L [PO43] = 2 [Cu3(PO4)2] = 3.2 108 mol/L Step 4 Ksp = [Cu2+]3[PO43]2 = (4.8 108)3(3.2 108)2 = 1.1 1037 Ksp for copper(II) phosphate is 1.1 1037 at 25C. Check Your Solution Check that you wrote the balanced chemical equation and the corresponding Ksp equation correctly. Pay attention to molar relationships and to the exponent of each term. Check the concentration calculations carefully.
15. Problem

A saturated solution of CaF2 contains 1.2 1020 formula units of calcium uoride per litre of solution. Calculate Ksp for CaF2 .

What Is Required? You need to nd the value of Ksp for CaF2 . What Is Given? You know one litre of solution contains 1.2 1020 formula units of CaF2 .

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Plan Your Strategy Step 1 Write an equation for the dissolution of CaF2 . Step 2 Use the equation to write the solubility product expression. Step 3 Find the concentration (in mol/L) of calcium uoride. Next, nd the concentration (in mol/L) of each ion. Step 4 Substitute the concentrations into the solubility product expression, and calculate Ksp. Act on Your Strategy Ca2+(aq) + 2F(aq) Step 1 CaF2(s) 2+ Step 2 Ksp = [Ca ][F]2 Step 3 The amount of CaF2 is given by the following formula: Amount = number of formula units Avogadros constant 1.2 1020 formula units 6.0 1023 formula units/mol = 2.0 104 mol [CaF2] = 2.0 104 mol/L [Ca2+] = [CaF2] = 2.0 104 mol/L [F] = 2 [CaF2] = 2 (2.0 104 mol/L) = 4.0 104 mol/L Step 4 Ksp = [Ca2+][F]2 = (2.0 104)(4.0 104)2 = 3.2 1011 Ksp for calcium uoride is 3.2 1011. = Check Your Solution Check that you wrote the balanced chemical equation and the corresponding Ksp equation correctly. Pay attention to molar relationships and to the exponent of each term. Check the concentration calculations carefully.
16. Problem

The concentration of mercury(I) iodide, Hg2I2 , in a saturated solution at 25C is 1.5 104 ppm. (a) Calculate Ksp for Hg2I2 . The solubility equilibrium is written as follows: Hg2I2 Hg22+ + 2I (b) State any assumptions that you made when you converted ppm to mol/L. What Is Required? You need to nd the value of Ksp for Hg2I2 at 25C. What Is Given? You know the concentration of Hg2I2 in a saturated solution at 25C is 1.5 104 ppm. You are given the dissolution equation. Plan Your Strategy Use the dissolution equation to write the solubility product expression. Find the concentration (in mol/L) of mercury(I) iodide. Then, nd the concentration (in mol/L) of each ion. Step 3 Substitute the concentrations into the solubility product expression, and calculate Ksp.
Step 1 Step 2

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Act on Your Strategy (a) Step 1 Ksp = [Hg22+][I]2 Step 2 1 ppm is equivalent to 1 mg of solute dissolved in 1 kg of solution. 1 kg of water at 4C has a volume of 1 L. Therefore, 1.5 104 mg of Hg2I2 is dissolved in 1.0 L of solution. 1.5 104 mg = 1.5 107g The molar mass of Hg2I2 is 655 g/mol. 1.5 107 g Amount of Hg2I2 = 655 g/mol = 2.3 1010 mol [Hg2I2] = 2.3 1010 mol/L [Hg22+] = [Hg2I2] = 2.3 1010 mol/L [I] = 2 [Hg2I2] = 2 (2.3 1010 mol/L) = 4.6 1010 mol/L Step 3 Ksp = [Hg22+][I]2 = (2.3 1010)(4.6 1010)2 = 4.9 1029 Ksp for mercury(I) iodide is 4.9 1029 at 25C.
(b) 1 ppm is equivalent to 1 mg of solute dissolved in 1 kg of solution. This leads to

two assumptions in this problem. Firstly, that the solution is so dilute it can be treated as 1 kg of water. Secondly, you assume that 1 kg of water has a volume of 1 L. This is only strictly true at 4C. Check Your Solution Check that you wrote the Ksp equation correctly. Pay attention to molar relationships and to the exponent of each term. Check the concentration calculations carefully.

Solutions for Practice Problems

Student Textbook page 436
17. Problem

Ksp for silver chloride, AgCl, is 1.8 1010 at 25C. (a) Calculate the molar solubility of AgCl in a saturated solution at 25C. (b) How many formula units of AgCl are dissolved in 1.0 L of saturated silver chloride solution? (c) What is the percent (m/v) of AgCl in a saturated solution at 25C? What Is Required? You need to determine the solubility (in mol/L, in formula units, and expressed as a mass/volume percent) of AgCl at 25C. What Is Given? At 25C, Ksp for AgCl is 1.8 1010. Plan Your Strategy Write the dissolution equilibrium equation. Use the equilibrium equation to write an expression for Ksp. Set up an ICE table. Let x represent molar solubility. Use the stoichiometry of the equilibrium equation to write expressions for the equilibrium concentrations of the ions. Step 4 Substitute your expressions into the expression for Ksp, and solve for x. (b) Convert the molar solubility to formula units per litre. (c) Convert the molar solubility to a percent (m/v).
(a) Step 1 Step 2 Step 3
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Act on Your Strategy Ag2+(aq) + Cl(aq) (a) Step 1 AgCl(s) + Step 2 Ksp = [Ag ][Cl]
Step 3 Concentration (mol/L) Initial Change Equilibrium Step 4 AgCl(s) Ag+(aq) 0 +x x + Cl(aq) 0 +x x

Ksp = [Ag+][Cl] = (x)(x) Therefore, 1.8 1010 = x 2 x = 1.8 1010 = 1.3 105 mol/L The molar solubility of AgCl in water is 1.3 105 mol/L. (b) 1.3 105 mol = (1.3 105) (6.0 1023 formula units/mol) = 7.8 1018 formula units The solubility of AgCl in water is 7.8 1018 formula units/L mass of solute (g) 100% (c) Mass/volume percent = volume of solution (mL) Molar mass of AgCl = 143.3 g/mol Mass in 1 L of solution = (1.3 105 mol/L) (143.3 g/mol) = 1.9 103 g/L 1.9 103 g Mass/volume percent = 100% 1000 mL The solubility of AgCl at 25C is 1.9 104% (m/v). Check Your Solution Substitute the values of [Ag+] and [Cl] into the Ksp equation. You should get the given Ksp. Check the number of signicant digits given in the question, and the number of digits in the answers.
18. Problem

Iron(III) hydroxide, Fe(OH)3 , is an extremely insoluble compound. Ksp for Fe(OH)3 is 2.8 1039 at 25C. Calculate the molar solubility of Fe(OH)3 at 25C. What Is Required? You need to determine the solubility (in mol/L) of Fe(OH)3 at 25C. What Is Given? At 25C, Ksp for Fe(OH)3 is 2.8 1039. Plan Your Strategy Step 1 Write the dissolution equilibrium equation. Step 2 Use the equilibrium equation to write an expression for Ksp. Step 3 Set up an ICE table. Let x represent molar solubility. Use the stoichiometry of the equilibrium equation to write expressions for the equilibrium concentrations of the ions. Step 4 Substitute your expressions into the expression for Ksp, and solve for x.

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Act on Your Strategy Fe3+(aq) + 3OH(aq) Step 1 Fe(OH)3(s) 3+ Step 2 Ksp = [Fe ][OH]3
Step 3 Concentration (mol/L) Initial Change Equilibrium Step 4 Fe(OH)3(s) Fe3+(aq) 0 +x x + 3OH(aq) 0 +3x 3x

Ksp = = = 39 2.8 10 = x =
4

[Fe3+][OH]3 (x) (3x)3 27x 4 27x 4

2.8 1039 27 = 1.0 1010 mol/L The molar solubility of Fe(OH)3 in water is 1.0 1010 mol/L. Check Your Solution Recall that x = [Fe3+]eq and 3x = [OH]eq . Substitute these values into the Ksp equation. You should get the given Ksp.
19. Problem

Ksp for zinc iodate, Zn(IO3)2 , is 3.9 106 at 25C. Calculate the solubility (in mol and in g/L) of Zn(IO3)2 in a saturated solution.

What Is Required? You need to determine the solubility (in mol/L and in g/L) of Zn(IO3)2 at 25C. What Is Given? At 25C, Ksp for Zn(IO3)2 is 3.9 106 . Plan Your Strategy Step 1 Write the dissolution equilibrium equation. Step 2 Use the equilibrium equation to write an expression for Ksp. Step 3 Set up an ICE table. Let x represent molar solubility. Use the stoichiometry of the equilibrium equation to write expressions for the equilibrium concentrations of the ions. Step 4 Substitute your expressions into the expression for Ksp, and solve for x. Step 5 Determine the solubility in g/L.
Step 1 Step 2 Step 3

Act on Your Strategy Zn(IO3)2(s) Zn2+(aq) + 2IO3(aq) 2+ Ksp = [Zn ][IO3]2

Concentration (mol/L) Initial Change Equilibrium Zn(IO3)2(s) Zn2+(aq) 0 +x x + 2IO3(aq) 0 +2x 2x

Step 4

Ksp = = = 3.9

[Zn2+][IO3]2 (x) (2x)2 4x 3 106 = 4x 3

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3.9 106 4 = 9.9 103 mol/L The molar solubility of Zn(IO3)2 in water is 9.9 103 mol/L. Step 5 Molar mass of Zn(IO3)2 = 415.2 g/mol 9.9 103 mol/L = (9.9 103mol/L) (415.2 g/mol) = 4.1 g/L The solubility of Zn(IO3)2 in water is 4.1 g/L. x =
3

Check Your Solution Recall that x = [Zn2+]eq and 2x = [IO3]eq . Substitute these values into the Ksp equation. You should get the given Ksp. The answers have the correct number of signicant digits.
20. Problem

What is the maximum number of formula units of zinc sulde, ZnS, that can dissolve in 1.0 L of solution at 25C? Ksp for ZnS is 2.0 1022. What Is Required? You need to determine the solubility (in formula units) of ZnS at 25C. What Is Given? At 25C, Ksp for ZnS is 2.0 1022. Plan Your Strategy Write the dissolution equilibrium equation. Use the equilibrium equation to write an expression for Ksp. Set up an ICE table. Let x represent molar solubility. Use the stoichiometry of the equilibrium equation to write expressions for the equilibrium concentrations of the ions. Step 4 Substitute your expressions into the expression for Ksp, and solve for x. Step 5 Determine the number of formula units dissolved in 1.0 L.
Step 1 Step 2 Step 3 Step 1 Step 2 Step 3

Act on Your Strategy ZnS(s) Zn2+(aq) + S2(aq) Ksp = [Zn2+][S2]

Concentration (mol/L) Initial Change Equilibrium ZnS(s) Zn2+(aq) 0 +x x + S2(aq) 0 x x

Ksp = [Zn2+][S2] = x 2 Therefore, 2.0 1022 = x 2 x = 2.0 1022 = 1.4 1011 mol/L The molar solubility of ZnS in water is 1.4 1011 mol/L. Step 5 1.4 1011 mol = (1.4 1011 mol) (6.0 1023 formula units/mol) = 8.4 1012 formula units The solubility of ZnS in water is 8.4 1012 formula units/L.
Step 4

Check Your Solution Recall that x = [Zn2+]eq = [S2]eq . Substitute these values into the Ksp equation. You should get the given Ksp.

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Solutions for Practice Problems

Student Textbook page 439
21. Problem

Determine the molar solubility of AgCl

(a) in pure water (b) in 0.15 mol/L NaCl

What Is Required? You need determine the solubility of AgCl (in mol/L) in water, and then in a solution of NaCl. What Is Given? From Appendix E, Ksp for AgCl = 1.77 1010 . You know the concentration of the solution of NaCl. Plan Your Strategy Write the dissolution equilibrium equation. Use the equilibrium equation to write an expression for Ksp. Set up an ICE table. Let x represent molar solubility. Use the stoichiometry of the equilibrium equation to write expressions for the equilibrium concentrations of the ions. Step 4 Substitute your expressions into the expression for Ksp, and solve for x. (b) Step 1 Set up an ICE table. The initial concentrations are based on the solution of NaCl. Let x represent the concentration of chloride (the common ion) that is contributed by AgCl. Step 2 Solve for x.
(a) Step 1 Step 2 Step 3 (a) Step 1 Step 2 Step 3

Act on Your Strategy AgCl(s) Ag+(aq) + Cl(aq) + Ksp = [Ag ][Cl] = 1.77 1010
Concentration (mol/L) Initial Change Equilibrium Step 4 AgCl(s) Ag+(aq) 0 +x x + Cl(aq) 0 +x x

Ksp = [Ag+][Cl] 1.77 1010 = x 2 x = 1.77 1010 x = 1.33 105 The negative root has no physical meaning. The solubility of AgCl is 1.33 105 mol/L.

(b) Step 1

Concentration (mol/L) Initial Change Equilibrium

AgCl(s)

Ag+(aq) 0 +x x

Cl(aq) 0.15 +x 0.15 + x

Step 2

Since Ksp is very small, you can assume that x is much smaller than 0.15. To check the validity of this assumption, determine whether or not 0.15 is more than 500 times greater than Ksp, as shown on the next page.

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0.15 0.15 = Ksp 1.77 1010 = 8.5 108 > 500 Therefore, in the (0.15 + x) term, x can be ignored. In other words, (0.15 + x) is approximately equal to 0.15. As a result, you can simplify the equation as follows: Ksp = [Ag+][Cl] 1.77 1010 = (x)(0.15 + x) (x)(0.15) Therefore, 0.15x 1.77 1010 x 1.18 109 mol/L The solubility of AgCl in a solution of 0.15 mol/L NaCl is 1.18 109 mol/L. Check Your Solution Your approximation in Step 6 was reasonable. The solubility x is much smaller than 0.15. Le Chteliers principle predicts a smaller solubility in a solution containing a common ion, and this is conrmed by the calculations.
22. Problem

Determine the molar solubility of lead(II) iodide, PbI2 , in 0.050 mol/L NaI. What Is Required? You need to determine the solubility of PbI2 (in mol/L) in a solution of NaI. What Is Given? From Appendix E, Ksp for PbI2 = 9.8 109 . You know the concentration of the solution of NaI. Plan Your Strategy Write the dissolution equilibrium equation. Use the equilibrium equation to write an expression for Ksp. Set up an ICE table. The initial concentrations are based on the solution of NaI. Let x represent the concentration of iodide (the common ion) that is contributed by NaI. Step 4 Substitute your expressions into the expression for Ksp, and solve for x.
Step 1 Step 2 Step 3

Act on Your Strategy Pb2+(aq) + 2I(aq) Step 1 PbI2(s) 2+ 2 Step 2 Ksp = [Pb ][I ]
Step 3 Concentration (mol/L) Initial Change Equilibrium Step 4 PbI2(s) Pb2+(aq) 0 +x x + 2I(aq) 0.050 +2x 0.050 + 2x

Since Ksp is very small, you can assume that 2x is much smaller than 0.050. To check the validity of this assumption, determine whether or not 0.050 is more than 500 times greater than Ksp, as shown. 0.050 = 0.050 Ksp 9.8 109 = 5.1 106 > 500

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Therefore, in the (0.050 + 2x) term, 2x can be ignored. In other words, (0.050 + 2x) is approximately equal to 0.050. As a result, you can simplify the equation as follows: Ksp = [Pb2+][I]2 9.8 109 = (x)(0.050 + 2x)2 (x)(0.050)2 Therefore, (2.5 103)(x) 9.8 109 x 3.9 106 mol/L The solubility of PbI2 in a solution of 0.050 mol/L NaI is 3.9 106 mol/L. Check Your Solution Your approximation in Step 4 was reasonable. The solubility 2x is much smaller than 0.050. You can substitute your calculated values of equilibrium concentrations into the expression you wrote for Ksp. The calculated value should equal the given value for Ksp, within the errors introduced by mathematical rounding.
23. Problem

Calculate the solubility of calcium sulfate, CaSO4 , (a) in pure water (b) in 0.25 mol/L Na2SO4 What Is Required? You need determine the solubility of CaSO4 (in mol/L) in water, and then in a solution of Na2SO4. What Is Given? From Appendix E, Ksp for CaSO4 = 4.93 105 . You know the concentration of the solution of Na2SO4 . Plan Your Strategy (a) Step 1 Write the dissolution equilibrium equation. Step 2 Use the equilibrium equation to write an expression for Ksp. Step 3 Set up an ICE table. Let x represent molar solubility. Use the stoichiometry of the equilibrium equation to write expressions for the equilibrium concentrations of the ions. Step 4 Substitute your expressions into the expression for Ksp, and solve for x.
(b) Step 1

Set up an ICE table. The initial concentrations are based on the solution of Na2SO4 . Let x represent the concentration of sulfate (the common ion) that is contributed by Na2SO4 . Step 2 Solve for x.

Act on Your Strategy Ca2+(aq) + SO42(aq) (a) Step 1 CaSO4(s) 2+ Step 2 Ksp = [Ca ][SO42] = 4.93 105
Step 3 Concentration (mol/L) Initial Change Equilibrium Step 4 CaSO4(s) Ca2+(aq) 0 +x x + SO42(aq) 0 +x x

Ksp = [Ca+][SO42] = x 2 4.93 105 = x 2 x = 4.93 105 x = 7.02 103

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The negative root has no physical meaning. The solubility of CaSO4 is 7.02 103 mol/L.
(b) Step 1 Concentration (mol/L) Initial Change Equilibrium Step 2 CaSO4(s) Ca2+(aq) 0 +x x + SO42(aq) 0.25 +x 0.25 + x

Since Ksp is very small, you can assume that x is much smaller than 0.25. To check the validity of this assumption, determine whether or not 0.25 is more than 500 times greater than Ksp, as shown below. 0.25 0.25 = Ksp 4.93 105 = 5.1 103 > 500 Therefore, in the (0.25 + x) term, x can be ignored. In other words, (0.25 + x) is approximately equal to 0.25. As a result, you can simplify the equation as follows: Ksp = [Ca2+][SO42] 4.93 105 = (x)(0.25 + x) (x)(0.25) Therefore, 0.25x 4.93 105 x 1.97 104 mol/L The solubility of AgCl in a solution of 0.15 mol/L NaCl is 1.97 104 mol/L.

Check Your Solution Your approximation in Step 6 was reasonable. The solubility x is a much smaller than 0.25. Le Chteliers principle predicts a smaller solubility in a solution containing a common ion, and this is conrmed by the calculations.
24. Problem

Ksp for lead(II) chloride, PbCl2 , is 1.6 105 . Calculate the molar solubility of PbCl2. (a) in pure water (b) in 0.10 mol/L CaCl2 What Is Required? You need to determine the solubility of PbCl2 (in mol/L) in water, and then in a solution of CaCl2 . What Is Given? You know that Ksp for PbCl2 is 1.6 105 , and you know the concentration of the solution of CaCl2 . Plan Your Strategy (a) Step 1 Write the dissolution equilibrium equation. Step 2 Use the equilibrium equation to write an expression for Ksp. Step 3 Set up an ICE table. Let x represent molar solubility. Use the stoichiometry of the equilibrium equation to write expressions for the equilibrium concentrations of the ions. Step 4 Substitute your expressions into the expression for Ksp, and solve for x. (b) Step 1 Set up an ICE table. The initial concentrations are based on the solution of CaCl2 . Let x represent the concentration of chloride (the common ion) that is contributed by CaCl2 . Step 2 Solve for x.

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Act on Your Strategy Pb2+(aq) + 2Cl(aq) (a) Step 1 PbCl2(s) 2+ Step 2 Ksp = [Pb ][Cl]2 = 1.6 105
Step 3 Concentration (mol/L) Initial Change Equilibrium Step 4 PbCl2(s) Pb2+(aq) 0 +x x +

2Cl(aq) 0 +2x 2x

Ksp = [Pb2+][Cl]2 1.6 105 = x(2x)2 1.6 105 = 4x 3 3 x = 4.0 106 x = 1.6 102 The solubility of PbCl2 is 1.6 102 mol/L. (b) Step 1 Each formula unit of calcium chloride dissociates to form two chloride ions. Therefore, 0.10 mol/L CaCl2 dissociates to give [Cl] = 0.20 mol/L .
Concentration (mol/L) Initial Change Equilibrium Step 2 PbCl2(s) Pb2+(aq) 0 +x x + 2Cl(aq) 0.20 +2x 0.20 + 2x

Since Ksp is very small, you can assume that x is much smaller than 0.20. To check the validity of this assumption, determine whether or not 0.20 is more than 500 times greater than Ksp, as shown below. 0.20 0.20 = Ksp 1.6 105 = 1.2 104 > 500 Therefore, in the (0.20 + 2x) term, 2x can be ignored. In other words, (0.20 + 2x) is approximately equal to 0.20. As a result, you can simplify the equation as follows: Ksp = [Pb2+][Cl]2 1.6 105 = (x)(0.20 + 2x)2 (x)(0.20)2 Therefore, (4.0 102)(x) 1.6 105 x 4.0 104 mol/L The solubility of PbCl2 in a solution of 0.10 mol/L CaCl2 is 4.0 104 mol/L.

Check Your Solution Your approximation in Step 6 was reasonable. The solubility 2x is a much smaller than 0.20. Le Chteliers principle predicts a smaller solubility in a solution containing a common ion, and this is confirmed by the calculations.

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Solutions for Practice Problems

Student Textbook Page 441
25. Problem

A buffer solution is made by mixing 250 mL of 0.200 mol/L aqueous ammonia and 400 mL of 0.150 mol/L ammonium chloride. Calculate the pH of the buffer solution. What Is Required? You need to determine the pH of the buffer solution. What Is Given? 250 mL of 0.200 mol/L aqueous ammonia and 400 mL of 0.150 mol/L ammonium chloride are mixed. From Appendix E, Kb for NH3(aq) is 1.8 105 . Plan Your Strategy Step 1 Determine the initial concentrations of NH3(aq) and NH4+(aq) in the buffer solution. Step 2 Write the reaction for the dissociation of NH3(aq) . Set up an ICE table, including the initial concentration of NH4+(aq) in the buffer. Step 3 Write the equation for Kb , and substitute equilibrium terms into the equation. Step 4 Solve the equation for x. Assume that x is small compared with the initial concentrations. Check the validity of this assumption when you nd the value of x. Step 5 Use the following equations: pOH = log[OH] pH = 14.00 = pOH Act on Your Strategy Step 1 When the solutions are mixed, the total volume is: (250 mL + 400 mL) = 650 mL [NH3] = 0.250 L 0.200 mol/L 0.650 L = 7.69 102 mol/L [NH4+] = 0.400 L 0.150 mol/L 0.650 L = 9.23 102 mol/L
Step 2 Concentration (mol/L) Initial Change Equilibrium
2

NH3(aq)

H2O(

NH4+(aq) + 9.23 102 +x

OH(aq) ~0 +x x

7.69 102 x 7.69 10 x

9.23 10 + x

+ Kb = [NH4 ][OH ] [NH3] 2 + = (9.23 10 2 x)(x) (7.69 10 x) Step 4 Assume that (7.69 102 x) 7.69 102 and (9.23 102 + x) 9.23 102 . 2 )(x) Kb = (9.23 10 2 = 1.8 105 (7.69 10 ) Therefore, x = 1.5 105 mol/L = [OH]

Step 3

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Step 5

pOH = log(1.5 105) = 4.82 pH = 14.00 4.82 = 9.18 The pH of the buffer solution is 9.18.

Check Your Solution The value of x (1.5 105) is negligible compared with the initial concentration of each component. A buffer that is made using a weak base and its conjugate acid should have a pH that is greater than 7.
26. Problem

A buffer solution is made by mixing 200 mL of 0.200 mol/L aqueous ammonia and 450 mL of 0.150 mol/L ammonium chloride. Calculate the pH of the buffer solution. What Is Required? You need to determine the pH of the buffer solution. What Is Given? 200 mL of 0.200 mol/L aqueous ammonia and 450 mL of 0.150 mol/L ammonium chloride are mixed. From Appendix E, Kb for NH3(aq) is 1.8 105 . Plan Your Strategy Step 1 Determine the initial concentrations of NH3(aq) and NH4+(aq) in the buffer solution. Step 2 Write the reaction for the dissociation of NH3(aq) . Set up an ICE table, including the initial concentration of NH4+(aq) in the buffer. Step 3 Write the equation for Kb , and substitute equilibrium terms into the equation. Step 4 Solve the equation for x. Assume that x is small compared with the initial concentrations. Check the validity of this assumption when you nd the value of x. Step 5 Use the following equations: pOH = log[OH] pH = 14.00 pOH Act on Your Strategy Step 1 When the solutions are mixed, the total volume is (250 + 400) = 650 mL . [NH3] = 0.200 L 0.0200 mol/L 0.650 L = 6.15 102 mol/L [NH4+] = 0.450 L 0.150 mol/L 0.650 L = 1.04 101 mol/L
Step 2 Concentration (mol/L) Initial Change Equilibrium Step 3
2

NH3(aq)

H2O(

NH4+(aq) + 1.04 101 +x

OH(aq) ~0 +x x

6.15 102 x 6.15 10 x

1.04 10 + x

+ Kb = [NH4 ][OH ] [NH3] 1 + = (1.04 10 2 x)(x) (6.15 10 x)

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Assume that (6.15 102 x) 6.15 102 and (1.04 101 + x) 1.04 101 . 1 x)(x) = 1.8 105 Kb = (1.04 10 +2 (6.15 10 ) Therefore, x = 1.1 105 mol/L = [OH] Step 5 pOH = log(1.1 105) = 4.96 pH = 14.00 4.96 = 9.04 The pH of the buffer solution is 9.04.
Step 4

Check Your Solution The value of x (1.1 105) is negligible compared with the initial concentration of each component. A buffer that is made using a weak base and its conjugate acid should have a pH that is greater than 7.
27. Problem

A buffer solution contains 0.200 mol/L nitrous acid, HNO2(aq), and 0.140 mol/L potassium nitrite, KNO2(aq) . What is the pH of the buffer solution? What Is Required? You need to determine the pH of the buffer solution. What Is Given? 0.200 mol/L HNO2(aq) is mixed with 0.140 mol/L potassium nitrite, KNO2(aq) . From Appendix E, Ka for HNO2 is 5.6 104 . Plan Your Strategy Step 1 Write the reaction for the dissociation of HNO2 . Set up an ICE table, including the initial concentration of NO2 in the buffer. Step 2 Write the equation for Ka, and substitute equilibrium terms into the equation. Step 3 Solve the equation for x. Assume that x is small compared with the initial concentrations. Check the validity of this assumption when you nd the value of x. Step 4 Use the equation pH = log[H3O+].
Step 1

Act on Your Strategy HNO2 + H2O(

H3O+(aq) + NO2(aq)
HNO2(aq) + 0.200 x 0.200 x H2O(
)

Concentration (mol/L) Initial Change Equilibrium Step 2

NO2(aq) + H3O+(aq) 0.140 +x 0.140 + x ~0 +x x

[NO][H3O+] 2 [HNO2] = (0.140 + x)(x) (0.200 x) Step 3 Assume that (0.140 + x) 0.140 and (0.200 x) 0.200. Ka = (1.40)(x) = 5.6 104 (0.200) Ka = x = 8.0 104 mol/L Step 4 pH = log(8.00 104) = 3.10 The pH of the buffer solution is 3.10.
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Check Your Solution The value of x (8.0 104) is negligible compared with the initial concentration of each component. A buffer that is made using a weak acid and its conjugate base should have a pH that is less than 7.
28. Problem

A buffer solution is prepared by dissolving 1.80 g of benzoic acid, C6H5COOH, and 1.95 g of sodium benzoate, NaC6H5COO, in 800 mL of water. Calculate the pH of the buffer solution. What Is Required? You need to determine the pH of the buffer solution. What Is Given? 1.8 g of C6H5COOH and 1.95 g of NaC6H5COO are dissolved in 800 mL of water. From Appendix E, Ka for C6H5COOH is 6.3 105 . Plan Your Strategy Step 1 Determine the initial concentrations of C6H5COOH and C6H5COO in the buffer solution. Step 2 Write the reaction for the dissociation of C6H5COOH. Set up an ICE table, including the initial concentration of C6H5COO in the buffer. Step 3 Write the equation for Ka, and substitute equilibrium terms into the equation. Step 4 Solve the equation for x. Assume that x is small compared with the initial concentrations. Check the validity of this assumption when you nd the value of x. Step 5 Use the following equation: pH = log[H3O+] Act on Your Strategy Step 1 The molar mass of C6H5COOH is 122.1 g/mol. 1.80 g [C6H5COOH] = 122.1 g/mol = 1.47 102 mol The molar mass of NaC6H5COO is 144.1 g/mol. 1.95 g [NaC6H5COO] = 144.1 g/mol = 1.35 102 mol
Step 2 Concentration (mol/L) C6H5COOH(aq) + Initial Change Equilibrium Step 3 1.47 102 x 1.47 102 x H2O(
)

C6H5COOH(aq) + 1.35 102 +x 1.35 102 + x

H3O+(aq) ~0 +x x

[C6H5COO][H3O3] [C6H5COOH] 2 + = (1.35 10 2 x)(x) (1.47 10 x) Step 4 Assume that (1.35 102 + x) 1.35 102 and (1.47 102 x) 1.47 102 . 2 x)(x) = 6.3 105 Ka = (1.35 10 +2 (1.47 10 ) x = 6.9 105mol/L Ka =
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Step 5

pH = log(6.9 105) = 4.16 The pH of the buffer solution is 4.16.

Check Your Solution The value of x (6.9 105) is negligible compared with the initial concentration of each component. A buffer that is made using a weak acid and its conjugate base should have a pH that is less than 7.

Solutions for Practice Problems

Student Textbook page 446
29. Problem

A solution contains 0.15 mol/L of NaCl and 0.0034 mol/L Pb(NO3)2 . Does a precipitate form? Include a balanced chemical equation for the formation of the possible precipitate. Ksp for PbCl2 is 1.7 105 . Solution Write the ion product expression for lead(II) chloride. Then substitute the ion concentrations into the expression to determine Qsp . Compare Qsp with Ksp, and predict whether or not a precipitate will form. PbCl2(s) Pb2+(aq) + 2Cl(aq) Ion product expression = [Pb2+][Cl]2 Qsp = (0.0034) (0.15)2 = 7.6 105 Because Qsp is greater than Ksp, a precipitate will form. Check Your Solution It seems reasonable that a precipitate formed, since Ksp for lead(II) chloride is small compared with the concentration of chloride ions and lead ions.
30. Problem

One drop (0.050 mL) of 1.5 mol/L potassium chromate, K2CrO4 , is added to 250 mL of 0.10 mol/L AgNO3 . Does a precipitate form? Include a balanced chemical equation for the formation of the possible precipitate. Ksp for Ag2CrO4 is 2.6 1012. What Is Required? Will silver chromate precipitate under the given conditions? What Is Given? You know the concentration and volume of the potassium chromate and silver nitrate solutions. For K2CrO4 , c = 1.5 mol/L and V = 0.050 mL. For AgNO3 , c = 0.10 mol/L and V = 250 mL. You also know Ksp for silver chromate. Plan Your Strategy Step 1 Determine the concentrations of silver ions and chromate ions in the reaction mixture. Step 2 Substitute the ion concentrations into the ion product expression for silver chromate to determine Qsp . Step 3 Compare Qsp with Ksp, and predict whether or not a precipitate will form.

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Act on Your Strategy Step 1 Because the volume of the potassium chromate solution is much smaller than the volume of the silver nitrate solution, you can ignore it. In other words, assume that the nal volume of the reaction mixture is 0.250 L. AgNO3(aq) Ag+(aq) + NO3(aq) [Ag+] = [AgNO3] = 0.10 mol/L K2CrO4(aq) 2K+(aq) + CrO42(aq) [CrO42] = [K2CrO4] = c Vinitial Vnal 3 = (1.5 mol/L)(0.050 mL 1.0 10 L/mL) 0.250 L 4 = 3.0 10 mol/L Step 2 The possible precipitate is silver chromate. 2Ag+(aq) + CrO42 Ag2CrO4(s) Qsp = [Ag+]2[CrO42] = (0.10)2 (3.0 104) = 3.0 106 Step 3 Since Qsp > Ksp , Ag2CrO4 will precipitate until Qsp = 2.6 1012 . Check Your Solution The units are correct in the calculation of the concentration of silver ions. It seems reasonable that a precipitate formed, since Ksp for silver chromate is very small compared with the concentration of chromate ions and silver ions.
31. Problem

A chemist adds 0.010 g of CaCl2 to 5.0 102 mL of 0.0015 mol/L sodium carbonate, Na2CO3. Does a precipitate of calcium carbonate form? Include a balanced chemical equation for the formation of the possible precipitate. What Is Required? Will calcium carbonate precipitate under the given conditions? What Is Given? You know the concentration and volume of the sodium carbonate solution. For Na2CO3, c = 0.0015 mol/L and V = 5.0 102 mL. For CaCl2 , 0.010 g is added to the solution. From Appendix E, you also know that Ksp for calcium carbonate is 3.36 109 . Plan Your Strategy Step 1 Determine the concentrations of calcium ions and carbonate ions in the reaction mixture. Step 2 Substitute the ion concentrations into the ion product expression for calcium carbonate to determine Qsp . Step 3 Compare Qsp with Ksp, and predict whether or not a precipitate will form.

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Act on Your Strategy Step 1 Na2CO3(aq) 2Na+(aq) + CO32(aq) [CO32] = [Na2CO3] = 0.0015 mol/L The molar mass of CaCl2 is 111.0 g/mol. Therefore, 0.010 g Amount CaCl2 = 111.0 g/mol = 9.0 105 mol
5 [CaCl2] = 9.0 10 mol 0.50 L = 1.8 104 mol/L CaCl2(aq) Ca2+(aq) + 2Cl(aq) Therefore, [Ca2+] = [CaCl2] = 1.8 104 mol/L Step 2 The possible precipitate is calcium carbonate. Ca2+(aq) + CO32 CaCO3(s) Qsp = [Ca2+][CO32] = (1.8 104) (0.0015) = 2.7 107 Step 3 Since Qsp > Ksp , CaCO3 will precipitate until Qsp = 3.36 109 .

Check Your Solution The units are correct in the calculation of the concentration of silver ions. It seems reasonable that a precipitate formed, since Ksp for calcium carbonate is small compared with the concentration of calcium ions and carbonate ions.
32. Problem

0.10 mg of magnesium chloride, MgCl2 , is added to 2.5 102 mL of 0.0010 mol/L NaOH. Does a precipitate of magnesium hydroxide form? Include a balanced chemical equation for the formation of the possible precipitate. What Is Required? Will magnesium hydroxide precipitate under the given conditions? What Is Given? You know the concentration and volume of the sodium hydroxide solution. For NaOH, c = 0.0010 mol/L and V = 2.5 102 mL. For MgCl2 , 0.10 mg is added to the solution. From Appendix E, you also know that Ksp for magnesium hydroxide is 5.61 1012 . Plan Your Strategy Step 1 Determine the concentrations of magnesium ions and hydroxide ions in the reaction mixture. Step 2 Substitute the ion concentrations into the ion product expression for magnesium hydroxide to determine Qsp . Step 3 Compare Qsp with Ksp, and predict whether or not a precipitate will form.

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Act on Your Strategy Step 1 NaOH(aq) Na+(aq) + OH(aq) Therefore, [OH] = [NaOH] = 0.0010 mol/L The molar mass of MgCl2 is 95.2 g/mol. Therefore, 0.10 mg 103 g/mg Amount MgCl2 = 95.2 g/mol = 1.1 106 mol
6 [MgCl2] = 1.1 10 mol 0.25 L = 4.2 106 mol/L MgCl2(aq) Mg2+(aq) + 2Cl(aq) Therefore, [Mg2+] = [MgCl2] = 4.2 106 mol/L. Step 2 The possible precipitate is magnesium hydroxide. Mg2+(aq) + 2OH(aq) Mg(OH)2(s) Qsp = [Mg2+][OH]2 = (4.2 106) (0.0010)2 = 4.2 1012 Step 3 Since Qsp < Ksp , no precipitate forms.

Check Your Solution The units are correct in the calculation of the concentration of silver ions. It seems reasonable that no precipitate formed, since the concentration of magnesium ion is small.

Solutions for Practice Problems

Student Textbook page 447
33. Problem

1.0 102 mL of 1.0 103 mol/L Pb(NO3)2 is added to 40 mL of 0.040 mol/L NaCl. Does a precipitate form? Include a balanced chemical equation for the formation of the possible precipitate. What Is Required? Decide whether a precipitate will form under the given circumstances. Write a balanced chemical equation for the formation of the possible precipitate.

What Is Given? You know the initial concentration and volume of the lead(II) nitrate and sodium chloride solutions. For Pb(NO3)2 , c = 1.0 103 mol/L and V = 1.0 102 mL. For NaCl, c = 0.040 mol/L and V = 40 mL. As well, you have the solubility guidelines in Table 9.3. Plan Your Strategy Step 1 Decide whether a compound with low solubility forms when lead(II) nitrate and sodium chloride are mixed, using the solubility guidelines. Step 2 If an insoluble compound forms, write an equation that represents the reaction. Look up Ksp for the compound in Appendix E. Step 3 Determine the concentrations of the ions that make up the compound. Step 4 Substitute the concentrations of the ions into the ion product expression for the compound to determine Qsp . Step 5 Compare Qsp with Ksp, and predict whether or not a precipitate forms.

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Act on Your Strategy Step 1 When you mix the solutions, lead(II) chloride, PbCl2 , and sodium nitrate, NaNO3 , can also form. Sodium nitrate is soluble, but lead(II) chloride is not, according to guideline 2. PbCl2(s) + NaNO3(aq) Step 2 Pb(NO3)2(aq) + NaCl(aq) From Table 9.2, Ksp for PbCl2 is 1.7 105 . Step 3 When calculating the volume of the reaction mixture, assume that it is equal to the sum of the volumes of the solutions. This is a reasonable assumption, because both solutions are dilute. [Pb2+] = [Pb(NO3)2] = c Vinitial Vnal 3 = (1.0 10 mol/L)(100 mL) (100 mL + 40 mL) = 7.1 104 mol/L [Cl] = [NaCl] = c Vinitial Vnal (0.040 mol/L)(40 mL) = (100 mL + 40 mL) = 1.1 102 mol Qsp = [Pb2+][Cl]2 = (7.1 104)(1.1 102)2 = 8.6 108 Step 5 Since Qsp < Ksp , no precipitate forms.
Step 4

Check Your Solution The units in the calculation of the concentrations of the ions are correct. It seems reasonable that no precipitate forms, since the concentrations of ions are relatively small.
34. Problem

2.3 102 mL of 0.0015 mol/L AgNO3 is added to 1.3 102 mL of 0.010 mol/L calcium acetate, Ca(CH3COO)2 . Does a precipitate form? Include a balanced chemical equation for the formation of the possible precipitate. Ksp for AgCH3COO is 2.0 103 . What Is Required? Decide whether a precipitate will form under the given circumstances. Write a balanced chemical equation for the formation of the possible precipitate. What Is Given? You know the initial concentration and volume of the silver nitrate and calcium acetate solutions. For AgNO3 , c = 0.0015 mol/L and V = 230 mL. For Ca(CH3COO)2 , c = 0.010 mol/L and V = 130 mL. As well, you have the solubility guidelines in Table 9.3. Plan Your Strategy The Ksp value for silver acetate indicates that it is not very soluble in water. Write an equation that represents the reaction to form silver acetate. Step 2 Determine the concentrations of the ions that make up the compound. Step 3 Substitute the concentrations of the ions into the ion product expression for the compound to determine Qsp . Step 4 Compare Ksp with Qsp , and predict whether or not a precipitate forms.
Step 1

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Act on Your Strategy 2AgCH3COO(s) + Ca(NO3)2(aq) Step 1 2AgNO3(aq) + Ca(CH3COO)2(aq) Step 2 When calculating the volume of the reaction mixture, assume that it is equal to the sum of the volumes of the solutions. This is a reasonable assumption, because both solutions are dilute. [Ag+] = [AgNO3] = c Vinitial Vnal (0.0015 mol/L)(230 mL) = (230 mL + 130 mL) = 9.6 104 mol/L [CH3COO] = 2 [Ca(CH3COO)2] = 2 c Vinitial Vnal (0.010 mol/L)(130 mL) =2 (130 mL + 230 mL) = 7.2 103 mol/L Qsp = [Ag+][CH3COO] = (9.6 104)(7.2 103) = 6.9 106 Step 4 Since Qsp < Ksp , no precipitate is formed.
Step 3

Check Your Solution The units in the calculation of the concentrations of the ions are correct. It seems reasonable that no precipitate formed, since Ksp for silver acetate is a relatively large value compared with the concentrations of the silver ions and acetate ions.
35. Problem

25 mL of 0.10 mol/L NaOH is added to 5.0 102 mL of 0.00010 mol/L cobalt(II) chloride, CoCl2 . Does a precipitate form? Include a balanced chemical equation for the formation of the possible precipitate. What Is Given? You know the initial concentration and volume of the sodium hydroxide and cobalt(II) chloride solutions. For NaOH, c = 0.10 mol/L and V = 25 mL. For CoCl2 , c = 0.00010 mol/L and V = 500 mL. As well, you have the solubility guidelines in Table 9.3. Plan Your Strategy Decide whether a compound with low solubility forms when sodium hydroxide and cobalt(II) chloride are mixed, using the solubility guidelines. Step 2 If an insoluble compound forms, write an equation that represents the reaction. Look up Ksp for the compound in Appendix E. Step 3 Determine the concentrations of the ions that make up the compound. Step 4 Substitute the concentrations of the ions into the ion product expression for the compound to determine Qsp . Step 5 Compare Qsp with Ksp, and predict whether or not a precipitate forms.
Step 1

Act on Your Strategy Step 1 When you mix the sodium hydroxide and cobalt(II) chloride solutions, sodium chloride, NaCl, and cobalt(II) hydroxide, Co(OH)2 , can also form. Sodium chloride is soluble, but cobalt(II) hydroxide is probably not, according to guideline 2. Step 2 NaOH(aq) + CoCl2(aq) NaCl(aq) + Co(OH)2(s) From Appendix E, Ksp for Co(OH)2 is 5.92 1015 .

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Step 3

When calculating the volume of the reaction mixture, assume that it is equal to the sum of the volumes of the solutions. This is a reasonable assumption, because both solutions are dilute. [Co2+] = [CoCl2] = c Vinitial Vnal = (0.00010 mol/L)(500 mL) (500 mL + 25 mL) = 9.5 105 mol/L [OH] = [NaOH] = c Vinitial Vnal = (0.10 mol/L)(25 mL) (25 mL + 500 mL) = 4.8 103 mol/L

Qsp = [Co2+][Cl]2 = (9.5 105)(4.8 103)2 = 2.2 109 Step 5 Since Qsp > Ksp , Co(OH)2 precipitates until Qsp = 5.92 1015 .
Step 4

Check Your Solution The units in the calculation of the concentrations of the ions are correct. It seems reasonable that a precipitate formed, since Ksp for cobalt hydroxide is very small compared with the concentrations of the cobalt ions and hydroxide ions.
36. Problem

250 mL of 0.0011 mol/L Al2(SO4)3 is added to 50 mL of 0.022 mol/L BaCl2 . Does a precipitate form? Include a balanced chemical equation for the formation of the possible precipitate. What Is Given? You know the initial concentration and volume of the aluminum sulfate and barium chloride solutions. For Al2(SO4)3 , c = 0.0011 mol/L and V = 250 mL. For BaCl2 , c = 0.022 mol/L and V = 50 mL. As well, you have the solubility guidelines in Table 9.3. Plan Your Strategy Step 1 Decide whether a compound with low solubility forms when calcium nitrate and sodium uoride are mixed, using the solubility guidelines. Step 2 If an insoluble compound forms, write an equation that represents the reaction. Look up Ksp for the compound in Appendix E. Step 3 Determine the concentrations of the ions that make up the compound. Step 4 Substitute the concentrations of the ions into the ion product expression for the compound to determine Qsp . Step 5 Compare Qsp with Ksp, and predict whether or not a precipitate forms. Act on Your Strategy Step 1 When you mix the aluminum sulfate and barium chloride solutions, aluminum chloride, AlCl3 , and barium sulfate, BaSO4 , can also form. Aluminum chloride is soluble, but barium sulfate is not, according to guideline 4. Step 2 Al2(SO4)3(aq) + 3BaCl2(aq) 2AlCl3(aq) + 3BaSO4(s) From Appendix E, Ksp for BaSO4 is 1.08 1010 .

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Step 3

When calculating the volume of the reaction mixture, assume that it is equal to the sum of the volumes of the solutions. This is a reasonable assumption, because both solutions are dilute. [Ba2+] = [BaCl2] = c Vinitial Vnal = (0.022 mol/L)(50 mL) (50 mL + 250 mL) = 3.7 103 mol/L [SO42] = 3 [Al2(SO4)3] = 3 c Vinitial Vnal = 3 (0.0011 mol/L)(250 mL) (250 mL + 50 mL) = 2.8 103 mol/L

Qsp = [Ba2+][SO42] = (3.7 103)(2.8 103) = 1.0 105 Step 5 Since Qsp > Ksp , BaSO4 precipitates until Qsp = 1.08 1010 .
Step 4

Check Your Solution The units in the calculation of the concentrations of the ions are correct. It seems reasonable that a precipitate formed, since Ksp for barium sulfate is very small compared with the concentrations of the barium ions and sulfate ions.

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