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Chapter 17- Aqueous Equilibria
Section 17.1 The Common Ion Effect
The Common-Ion Effect

Consider a solution of acetic acid:
HC2H3O2(aq) + H2O(l) H3O+(aq) + C2H3O2(aq)

Consider a solution of acetic acid:
HC2H3O2(aq) + H2O(l) H3O+(aq) + C2H3O2(aq)
If acetate ion is added to the solution, Le Chtelier says the equilibrium will shift to the left.

The extent of ionization of a weak electrolyte is decreased by adding to the solution a strong electrolyte that has an ion in common with the weak electrolyte.

Calculate the fluoride ion concentration and pH of a solution that is 0.20 M in HF and 0.10 M in HCl. Ka for HF is 6.8 104.

Calculate the fluoride ion concentration and pH of a solution that is 0.20 M in HF and 0.10 M in HCl. Ka for HF is 6.8 104.
Ka= [H3O+] [F] [HF] = 6.8 10-4

HF(aq) + H2O(l) H3O+(aq) + F(aq) Because HCl, a strong acid, is also present, the initial [H3O+] is not 0, but rather 0.10 M.
[HF], M Initially Change At Equilibrium 0.20 x 0.20 x 0.20 [H3O+], M 0.10 +x 0.10 + x 0.10 [F], M 0 +x x

6.8 104 (0.10) (x) = (0.20)
(0.20) (6.8 104) =x (0.10) 1.4 103 = x

Therefore, [F] = x = 1.4 103 [H3O+] = 0.10 + x = 0.10 + 1.4 103 = 0.10 M

Therefore, [F] = x = 1.4 103 [H3O+] = 0.10 + x = 1.01 + 1.4 103 = 0.10 M So, pH = log (0.10) pH = 1.00

Section 17.2 Buffers
Bellwork
Bellwork
a) [NH4+] = 0.10 M [Cl] = 0.10 M [NH3] = 0.12 M
Bellwork
a) [NH4+] = 0.10 M [Cl] = 0.10 M [NH3] = 0.12 M b) Cl
Bellwork
a) [NH4+] = 0.10 M [Cl] = 0.10 M [NH3] = 0.12 M b) Cl c)NH3(aq) + H2O(l) NH4+(aq) + OH(aq)
Buffers:
Buffers:
Solutions of a weak conjugate acid-base pair.
Buffers:
Solutions of a weak conjugate acid-base pair. They are particularly resistant to pH changes, even when strong acid or base is added.
HNO3 and NO3 will not work as a buffer because NO3 is a spectator ion.
Buffers
If a small amount of hydroxide is added to an equimolar solution of HF in NaF, for example, the HF reacts with the OH to make F and water.
Buffers
If acid is added, the F reacts to form HF and water.
The NaOH reacts with HC2H3O2 converting some of it into C2H3O2 .
Buffer Calculations
Consider the equilibrium constant expression for the dissociation of a generic acid, HA: HA + H2O H3O+ + A
Buffer Calculations
Consider the equilibrium constant expression for the dissociation of a generic acid, HA: HA + H2O
Ka =
H3O+ + A
[H3O+] [A] [HA]
Buffer Calculations
Rearranging slightly, this becomes
Ka = [H3O+] [A] [HA]
Buffer Calculations
Ka = [H3O+] [A] [HA]
Taking the negative log of both sides, we get
Buffer Calculations
Ka = [H3O+] [A] [HA]
Taking the negative log of both sides, we get

log Ka = log [H3O+] + log
pKa pH
[A] [HA]
base
acid
Buffer Calculations
So [base] pKa = pH log [acid]
Buffer Calculations
So [base] pKa = pH log [acid] [base] pH = pKa + log [acid]
Rearranging, this becomes
Buffer Calculations
So [base] pKa = pH log [acid] [base] pH = pKa + log [acid] This is the HendersonHasselbalch equation.
Rearranging, this becomes
HendersonHasselbalch Equation
What is the pH of a buffer that is 0.12 M in lactic acid, HC3H5O3, and 0.10 M in sodium lactate? Ka for lactic acid is 1.4 104.
HendersonHasselbalch Equation
[base] pH = pKa + log [acid] pH = log (1.4 104) (0.10) + log (0.12)
pH = 3.85 + (0.08) pH = 3.77
PRACTICE EXERCISE
Calculate the pH of a buffer composed of 0.12 M benzoic acid and 0.20 M sodium benzoate. (Refer to Appendix D.)
PRACTICE EXERCISE
Calculate the pH of a buffer composed of 0.12 M benzoic acid and 0.20 M sodium benzoate. (Refer to Appendix D.)
Answer: 4.42
How many moles of NH4Cl must be added to 2.0 L of 0.10 M NH3 to form a buffer whose pH is 9.00? (Assume that the addition of NH4Cl does not change the volume)
The major species in the solution will be NH4+, Cl, and NH3. Of these, the Cl ion is a spectator (it is the conjugate base of a strong acid).
and so
and so
Because Kb is small and the common ion NH4+ is present, the equilibrium concentration of NH3 will essentially equal its initial concentration:
Comment: Because NH4+ and NH3 are a conjugate acidbase pair, we could use the HendersonHasselbalch equation to solve this problem. To do so requires first using Equation 16.41 to calculate pKa for NH4+ from the value of pKb for NH3. Try this approach to convince yourself that you can use the HendersonHasselbalch equation for buffers for which you are given Kb for the conjugate base rather than Ka for the conjugate acid.
PRACTICE EXERCISE
Calculate the concentration of sodium benzoate that must be present in a 0.20 M solution of benzoic acid (HC7H5O2) to produce a pH of 4.00.
PRACTICE EXERCISE
Calculate the concentration of sodium benzoate that must be present in a 0.20 M solution of benzoic acid (HC7H5O2) to produce a pH of 4.00.
Answer: 0.13 M
pH Range
The pH range is the range of pH values over which a buffer system works effectively.
pH Range
The pH range is the range of pH values over which a buffer system works effectively. It is best to choose an acid with a pKa close to the desired pH.
pH = 4.74, this is pKa of acetic acid
When Strong Acids or Bases Are Added to a Buffer
When Strong Acids or Bases Are Added to a Buffer

it is safe to assume that all of the strong acid or base is consumed in the reaction.
Addition of Strong Acid or Base to a Buffer

1. Determine how the neutralization reaction affects the amounts of the weak acid and its conjugate base in solution.
Addition of Strong Acid or Base to a Buffer

1. Determine how the neutralization reaction affects the amounts of the weak acid and its conjugate base in solution. 2. Use the HendersonHasselbalch equation to determine the new pH of the solution.
Calculating pH Changes in Buffers

A buffer is made by adding 0.300 mol HC2H3O2 and 0.300 mol NaC2H3O2 to enough water to make 1.00 L of solution. The pH of the buffer is 4.74. Calculate the pH of this solution after 0.020 mol of NaOH is added.

Before the reaction, since mol HC2H3O2 = mol C2H3O2 pH = pKa = log (1.8 105) = 4.74

The 0.020 mol NaOH will react with 0.020 mol of the acetic acid:
HC2H3O2(aq) + OH(aq) C2H3O2(aq) + H2O(l) HC2H3O2 Before reaction After reaction 0.300 mol 0.280 mol C2H3O2 OH
0.300 mol 0.020 mol 0.320 mol 0.000 mol

Now use the HendersonHasselbalch equation to calculate the new pH:
(0.320) pH = 4.74 + log (0. 280) pH = 4.74 + 0.06 pH = 4.80
PRACTICE EXERCISE
Determine (a) the pH of the original buffer described in Sample Exercise 17.5 after the addition of 0.020 mol HCl, and (b) the pH of the solution that would result from the addition of 0.020 mol HCl to 1.00 L of pure water.
PRACTICE EXERCISE
Determine (a) the pH of the original buffer described in Sample Exercise 17.5 after the addition of 0.020 mol HCl, and (b) the pH of the solution that would result from the addition of 0.020 mol HCl to 1.00 L of pure water.
Answers: (a) 4.68, (b) 1.70

Section 17.3 Titrations
Titration
A known concentration of base (or acid) is slowly added to a solution of acid (or base).
Titration
A pH meter or indicators are used to determine when the solution has reached the equivalence point, at which the stoichiometric amount of acid equals that of base.
Titration of a Strong Acid with a Strong Base

From the start of the titration to near the equivalence point, the pH goes up slowly.

Just before and after the equivalence point, the pH increases rapidly.

At the equivalence point, moles acid = moles base, and the solution contains only water and the salt from the cation of the base and the anion of the acid.

As more base is added, the increase in pH again levels off.
SAMPLE EXERCISE 17.6 Calculating pH for a Strong AcidStrong Base Titration
Calculate the pH when the following quantities of 0.100 M NaOH have been added to 50.0 mL of 0.100 M HCl: (a) 49.0 mL, (b) 51.0 mL.
Solve: The number of moles of H+ in the original HCl solution is given by the product of the volume of the solution (50.0 mL = 0.0500 L) and its molarity (0.100 M):
Solve: The number of moles of H+ in the original HCl solution is given by the product of the volume of the solution (50.0 mL = 0.0500 L) and its molarity (0.100 M):
The number of moles of OH in 49.0 mL of 0.100 M NaOH is
There are more moles of H+ present than OH. Each mole of OH will react with one mole of H+.
The volume of the reaction mixture increases as the NaOH solution is added to the HCl solution. At this point in the titration, the solution has a volume of 50.0 mL + 49.0 mL = 99.0 mL. Thus, the concentration of H+(aq) is
The volume of the reaction mixture increases as the NaOH solution is added to the HCl solution. At this point in the titration, the solution has a volume of 50.0 mL + 49.0 mL = 99.0 mL. Thus, the concentration of H+(aq) is
The corresponding pH equals
Plan: We are now past the equivalence point and have more OH in the solution than H+. The initial number of moles of each reactant is determined from their volumes and concentrations. The reactant present in smaller stoichiometric amount (the limiting reactant) is consumed completely, leaving an excess this time of hydroxide ion.
In this case the total volume of the solution is
In this case the total volume of the solution is Hence, the concentration of OH(aq) in the solution is
Thus, the pOH of the solution equals
Thus, the pOH of the solution equals and the pH equals
PRACTICE EXERCISE Calculate the pH
when the following quantities of 0.100 M HNO3 have been added to 25.0 mL of 0.100 M KOH: (a) 24.9 mL, (b) 25.1 mL.
PRACTICE EXERCISE Calculate the pH
when the following quantities of 0.100 M HNO3 have been added to 25.0 mL of 0.100 M KOH: (a) 24.9 mL, (b) 25.1 mL.
Answers: (a) 10.30, (b) 3.70
Titration of a Weak Acid with a Strong Base

Unlike in the previous case, the conjugate base of the acid affects the pH when it is formed.

Unlike in the previous case, the conjugate base of the acid affects the pH when it is formed. The pH at the equivalence point will be >7.

Unlike in the previous case, the conjugate base of the acid affects the pH when it is formed. The pH at the equivalence point will be >7. Phenolphthalein is commonly used as an indicator in these titrations.
At each point below the equivalence point, the pH of the solution during titration is determined from the amounts of the acid and its conjugate base present at that particular time.

With weaker acids, the initial pH is higher and pH changes near the equivalence point are more subtle.
The nearly vertical equivalence point portion of the titration curve is smaller for a weak acid-strong base titration, and fewer indicators undergo their color change within this narrow range.
Titration of a Weak Base with a Strong Acid

The pH at the equivalence point in these titrations is < 7.

The pH at the equivalence point in these titrations is < 7. Methyl red is the indicator of choice.
Titrations of Polyprotic Acids

In these cases there is an equivalence point for each dissociation.
SAMPLE EXERCISE 17.7 Calculating pH for a Weak AcidStrong Base Titration
Calculate the pH of the solution formed when 45.0 mL of 0.100 M NaOH is added to 50.0 mL of 0.100 M HC2H3O2 (Ka = 1.8 105).
Plan: We first must determine the number of moles of weak acid and strong base that have been combined. This will tell us how much of the weak acids conjugate base has been produced, and we can solve for pH using the equilibrium-constant expression.
Solve: Stoichiometry Calculation:
Plan: We first must determine the number of moles of weak acid and strong base that have been combined. This will tell us how much of the weak acids conjugate base has been produced, and we can solve for pH using the equilibrium-constant expression.
Solve: Stoichiometry Calculation:
The 4.5 103 mol of NaOH consumes 4.5 103 mol of HC2H3O2:
The total volume of the solution is
The resulting molarities of HC2H3O2 and C2H3O2 after the reaction are therefore
The resulting molarities of HC2H3O2 and C2H3O2 after the reaction are therefore Equilibrium Calculation: The equilibrium between HC2H3O2 and C2H3O2 must obey the equilibrium-constant expression for HC2H3O2:
The resulting molarities of HC2H3O2 and C2H3O2 after the reaction are therefore Equilibrium Calculation: The equilibrium between HC2H3O2 and C2H3O2 must obey the equilibrium-constant expression for HC2H3O2: Solving for [H+] gives
The resulting molarities of HC2H3O2 and C2H3O2 after the reaction are therefore Equilibrium Calculation: The equilibrium between HC2H3O2 and C2H3O2 must obey the equilibrium-constant expression for HC2H3O2: Solving for [H+] gives
We could have solved for pH using the HendersonHasselbalch equation.
PRACTICE EXERCISE
(a) Calculate the pH in the solution formed by adding 10.0 mL of 0.050 M NaOH to 40.0 mL of 0.0250 M benzoic acid (HC7H5O2, Ka = 6.3 105). (b) Calculate the pH in the solution formed by adding 10.0 mL of 0.100 M HCl to 20.0 mL of 0.100 M NH3.
PRACTICE EXERCISE
(a) Calculate the pH in the solution formed by adding 10.0 mL of 0.050 M NaOH to 40.0 mL of 0.0250 M benzoic acid (HC7H5O2, Ka = 6.3 105). (b) Calculate the pH in the solution formed by adding 10.0 mL of 0.100 M HCl to 20.0 mL of 0.100 M NH3.
Answers: (a) 4.20, (b) 9.26
SAMPLE EXERCISE 17.8 Calculating the pH at the Equivalence Point
Calculate the pH at the equivalence point in the titration of 50.0 mL of 0.100 M HC2H3O2 with 0.100 M NaOH.
Analyze: Because the neutralization of a weak acid produces its anion, which is a weak base, we expect the pH at the equivalence point to be greater than 7. Plan: Determine how many moles of acetic acid there are initially. This will tell us how many moles of acetate ion there will be at the equivalence point. Determine the volume of the solution at the equivalence point and the resultant concentration of acetate ion. Because the acetate ion is a weak base, we can calculate the pH using Kb and the concentration of acetate .
Solve:
Solve: Hence 5.00 103 mol of C2H3O2 is formed. It will take 50.0 mL of NaOH to reach the equivalence point . 50 mL + 50 mL = 100mL = 0.1000 L.
Solve: Hence 5.00 103 mol of C2H3O2 is formed. It will take 50.0 mL of NaOH to reach the equivalence point . 50 mL + 50 mL = 100mL = 0.1000 L. The C2H3O2 ion is a weak base.
The Kb for C2H3O2 can be calculated from the Ka value of its conjugate acid, Kb = Kw/Ka = (1.0 1014)/(1.8 105) = 5.6 1010.
Approximating that and then solving for x, we have x = [OH] = 5.3 106 M, which gives pOH = 5.28 and pH = 8.72. Check: The pH is above 7, as expected for the salt of a weak acid and strong base.
PRACTICE EXERCISE
Calculate the pH at the equivalence point when (a) 40.0 mL of 0.025 M benzoic acid (HC7H5O2, Ka = 6.3 105) is titrated with 0.050 M NaOH; (b) 40.0 mL of 0.100 M NH3 is titrated with 0.100 M HCl.
PRACTICE EXERCISE
Calculate the pH at the equivalence point when (a) 40.0 mL of 0.025 M benzoic acid (HC7H5O2, Ka = 6.3 105) is titrated with 0.050 M NaOH; (b) 40.0 mL of 0.100 M NH3 is titrated with 0.100 M HCl.
Answers: (a) 8.21, (b) 5.28

Section 17.4 Solubility Equilibria Section 17.5 Solubility Factors
Solubility rules predict that AgCl is insoluble.

The term slightly soluble is more accurate because with very low concentrations of Ag+ and Cl- there is no AgCl(s) formed.

The term slightly soluble is more accurate because with very low concentrations of Ag+ and Cl- there is no AgCl(s) formed. Equilibrium calculations allow us to determine the solubility of these compounds.

The term slightly soluble is more accurate because with very low concentrations of Ag+ and Cl- there is no AgCl(s) formed. Equilibrium calculations allow us to determine the solubility of these compounds.
How much can be in solution before a solid is formed or the maximum solute that can be dissolved in a given amount of solvent.
Solubility Products
Consider the equilibrium that exists in a saturated solution of BaSO4 in water:
BaSO4(s)
Ba2+(aq) + SO42(aq)
Solubility Products
The equilibrium constant expression for this equilibrium is Ksp = [Ba2+] [SO42] where the equilibrium constant, Ksp, is called the solubility product.
SAMPLE EXERCISE 17.9 Writing Solubility-Product (Ksp) Expressions
Write the expression for the solubility-product constant for CaF2, and look up the Ksp value in Appendix D.
From Appendix D- this Ksp has a value of 3.9 1011.
PRACTICE EXERCISE
Give the solubility-product-constant expressions and the values of the solubilityproduct constants (from Appendix D) for the following compounds: (a) barium carbonate, (b) silver sulfate.
(a) Ksp = [Ba2+][CO32] = 5.0 109; (b) Ksp = [Ag+]2[SO42] = 1.5 105
PRACTICE EXERCISE
Give the solubility-product-constant expressions and the values of the solubilityproduct constants (from Appendix D) for the following compounds: (a) barium carbonate, (b) silver sulfate.
(a) Ksp = [Ba2+][CO32] = 5.0 109; (b) Ksp = [Ag+]2[SO42] = 1.5 105
Solubility Products
Solubility Products
Ksp is not the same as solubility.
Solubility Products
Ksp is not the same as solubility. Solubility is generally expressed as the mass of solute dissolved in 1 L (g/L) or 100 mL (g/mL) of solution, or in mol/L (M).
AgCl is most soluble with the highest Ksp
SAMPLE EXERCISE 17.10 Calculating Ksp from Solubility
Solid silver chromate is added to pure water at 25C. Some of the solid remains undissolved at the bottom of the flask. The mixture is stirred for several days to ensure that equilibrium is achieved.
Analysis of the equilibrated solution shows that its Ag+ concentration is 1.3 104 M.
Assuming that Ag2CrO4 dissociates completely in water and that there are no other important equilibria involving the Ag+ or CrO42 ions in the solution, calculate Ksp
for this compound.
Analysis of the equilibrated solution shows that its Ag+ concentration is 1.3 104 M,
calculate Ksp for this compound.

Solve: There are 2 Ag+ ions for each CrO42 ion in solution.
[CrO42] is half of [Ag+]. [CrO42] = 1/2 [Ag+]


Check: We obtain a small value, as expected for a slightly soluble salt.
PRACTICE EXERCISE A saturated solution of Mg(OH)2 in contact with undissolved solid is prepared at 25C. The pH of the solution is found to be 10.17. Assuming that Mg(OH)2 dissociates completely in water and that there are no other simultaneous equilibria involving the Mg2+ or OH ions in the solution, calculate Ksp for this compound.
PRACTICE EXERCISE A saturated solution of Mg(OH)2 in contact with undissolved solid is prepared at 25C. The pH of the solution is found to be 10.17. Assuming that Mg(OH)2 dissociates completely in water and that there are no other simultaneous equilibria involving the Mg2+ or OH ions in the solution, calculate Ksp for this compound.
Answer: 1.6 1012
SAMPLE EXERCISE 17.11 Calculating Solubility from Ksp
The Ksp for CaF2 is 3.9 1011 at 25C. Assuming

that CaF2 dissociates completely upon dissolving and that there are no other important equilibria affecting its solubility,
calculate the solubility of CaF2 in grams per liter.


The solubility of a substance is the quantity that can dissolve in solvent, whereas the solubilityproduct constant, Ksp, is an equilibrium constant.


The solubility of a substance is the quantity that can dissolve in solvent, whereas the solubilityproduct constant, Ksp, is an equilibrium constant.
2x moles/liter of F are produced for each x moles/liter of CaF2 that dissolve.
The Ksp for CaF2 is 3.9 1011 at 25C. Calculate the solubility of CaF2 in grams per liter.
(Remember that to calculate the cube root of a number, you can use the yx function on your calculator, with )
Solubilities are measured per mole or gram of formula unit (ionic formula). The solubility is x.
Solubilities are measured per mole or gram of formula unit (ionic formula). The solubility is x. [F-] = 4.2 x 10-4mol/L [Ca2+] = 2.1 x 10-4mol/L The molar solubility of CaF2 is 2.1 104 mol/L.
Solubilities are measured per mole or gram of formula unit (ionic formula). The solubility is x. [F-] = 4.2 x 10-4mol/L [Ca2+] = 2.1 x 10-4mol/L The molar solubility of CaF2 is 2.1 104 mol/L.
[F-] = 4.2 x 10-4mol [Ca2+] = 2.1 x 10-4mol/L The molar solubility of CaF2 is 2.1 104 mol/L.
Check: We expect a small number for the solubility of a slightly soluble salt.
If we reverse the calculation, we should be able to recalculate Ksp: Ksp = (2.1 104)(4.2 104)2 = 3.7 1011, close to the Ksp, 3.9 1011 .
Comment: Because
F is the anion of a weak acid, you might expect that the hydrolysis of the ion would affect the solubility of CaF2.
Comment: Because
F is the anion of a weak acid, you might expect that the hydrolysis of the ion would affect the solubility of CaF2. The basicity of F is so small (Kb = 1.5 1011), however, that the hydrolysis occurs to only a slight extent and does not significantly influence the solubility.
Comment: Because
F is the anion of a weak acid, you might expect that the hydrolysis of the ion would affect the solubility of CaF2. The basicity of F is so small (Kb = 1.5 1011), however, that the hydrolysis occurs to only a slight extent and does not significantly influence the solubility. The reported solubility is 0.017 g/L at 25C.
PRACTICE EXERCISE The Ksp for LaF3 is 2 1019 . What is the solubility of LaF3 in water in moles per liter? Answer: 9.28 106 mol/L
PRACTICE EXERCISE The Ksp for LaF3 is 2 1019 . What is the solubility of LaF3 in water in moles per liter? Answer: 9.28 106 mol/L
Factors Affecting Solubility

If one of the ions in a solution equilibrium is already dissolved in the solution, the equilibrium will shift to the left and the solubility of the salt will decrease.
BaSO4(s) Ba2+(aq) + SO42(aq)
SAMPLE EXERCISE 17.12 Calculating the Effect of a Common Ion on Solubility
Calculate the molar solubility of CaF2 at 25C in a solution that is (a) 0.010 M in Ca(NO3)2, (b) 0.010 M in NaF.
In (a) the common ion is Ca2+ and NO3 is a spectator ion. In (b) the common ion is F and Na+ is a spectator ion.
Because the slightly soluble compound is CaF2, we need to use the Ksp for this compound, which is available in Appendix D:
Because the slightly soluble compound is CaF2, we need to use the Ksp for this compound, which is available in Appendix D:
The value of Ksp is unchanged by the presence of additional solutes, but the solubility of the salt will decrease in the presence of common ions.
Calculate the molar solubility of CaF2 at 25C in a solution that is (a) 0.010 M in Ca(NO3)2, (b) 0.010 M in NaF. Solve: (a) The initial concentration of Ca2+ is 0.010 M
because of the dissolved Ca(NO3)2:
Calculate the molar solubility of CaF2 at 25C in a solution that is (a) 0.010 M in Ca(NO3)2, (b) 0.010 M in NaF. Solve: (a) The initial concentration of Ca2+ is 0.010 M
because of the dissolved Ca(NO3)2:
Even without the common-ion effect, the solubility of CaF2 is very small. Assume
Substituting into the solubility-product expression gives
The very small value for x validates the simplifying assumption we have made. Our calculation indicates that 3.1 105 mol of solid CaF2 dissolves per liter of the 0.010 M Ca(NO3)2 solution.
(b) In this case the common ion is F, and at equilibrium we have
(b) In this case the common ion is F, and at equilibrium we have
Assuming that
Thus, 3.9 107 mol of solid CaF2 should dissolve per liter of 0.010 M NaF solution.
the molar solubility of CaF2 in pure water 2.1 104 M in 0.010 M Ca2+ 3.1 105 M in 0.010 M F 3.9 107 M.
More effect because [F-] is squared
Much less with common ion!!
PRACTICE EXERCISE
The value for Ksp for manganese(II) hydroxide, Mn(OH)2 , is 1.6 1013. Calculate the molar solubility of Mn(OH)2 in a solution that contains 0.020 M NaOH.
Answer: 4.0 1010 M
PRACTICE EXERCISE
The value for Ksp for manganese(II) hydroxide, Mn(OH)2 , is 1.6 1013. Calculate the molar solubility of Mn(OH)2 in a solution that contains 0.020 M NaOH.

pH
If a substance has a basic anion, it will be more soluble in an acidic solution. Substances with acidic cations are more soluble in basic solutions.
SAMPLE EXERCISE 17.13 Predicting the Effect of Acid on Solubility
Which of the following substances will be more soluble in acidic solution than in basic solution:
(a) Ni(OH)2(s), (c) BaF2(s), (b) CaCO3(s), (d) AgCl(s)?
Ionic compounds that dissociate to produce a basic anion will be more soluble in acid solution.
(a) Ni(OH)2(s) will be more soluble in acidic solution because of the basicity of OH ; the H+ ion reacts with the OH ion, forming water.
(b) Similarly, CaCO3(s) dissolves in acid solutions because CO32 is a basic anion.
The reaction between CO32 and H+ occurs in a stepwise fashion, first forming HCO3. H2CO3 forms in appreciable amounts only when the concentration of H+ is sufficiently high.
(c) The solubility of BaF2 is also enhanced by lowering the pH, because F is a basic anion.
(d) The solubility of AgCl is unaffected by changes in pH because Cl is the anion of a strong acid and therefore has negligible basicity.
PRACTICE EXERCISE
Write the net ionic equation for the reaction of the following compounds with acid: (a) CuS, (b) Cu(N3)2.
PRACTICE EXERCISE
Write the net ionic equation for the reaction of the following compounds with acid: (a) CuS, (b) Cu(N3)2.

Complex Ions Metal ions can act as Lewis acids and form complex ions with Lewis bases in the solvent.

Complex Ions The formation of these complex ions increases the solubility of these salts.
SAMPLE EXERCISE 17.14 Evaluating an Equilibrium Involving a Complex Ion
Calculate the concentration of Ag+ present in solution at equilibrium when concentrated NH3 is added to 0.010M AgNO3 to give an equilibrium concentration of [NH3] = 0.20M.
Neglect the small volume change that occurs when NH3 is added.
When NH3(aq) is added to Ag+(aq) a reaction occurs forming Ag(NH3)2+. Because Kf for the formation of Ag(NH3)2+ is quite large, we assume that essentially all the Ag+ is converted to Ag(NH3)2+ and approach the problem as though we are concerned with the dissociation of Ag(NH3)2+ rather than its formation.
When NH3(aq) is added to Ag+(aq) a reaction occurs forming Ag(NH3)2+. Because Kf for the formation of Ag(NH3)2+ is quite large, we assume that essentially all the Ag+ is converted to Ag(NH3)2+ and approach the problem as though we are concerned with the dissociation of Ag(NH3)2+ rather than its formation. We need to reverse the formation equation to represent the formation of Ag+ and NH3 from Ag(NH3)2+ and also make the corresponding change to the equilibrium constant.
If [Ag+] is 0.010 M initially, then [Ag(NH3)2+] will be 0.010 M following addition of the NH3.
If [Ag+] is 0.010 M initially, then [Ag(NH3)2+] will be 0.010 M following addition of the NH3. Note that the NH3 concentration given in the problem is an equilibrium concentration rather than an initial concentration.
If [Ag+] is 0.010 M initially, then [Ag(NH3)2+] will be 0.010 M following addition of the NH3. Note that the NH3 concentration given in the problem is an equilibrium concentration rather than an initial concentration.
Solving for x, we obtain x = 1.5 108 M = [Ag+]. Formation of the Ag(NH3)2+ complex drastically reduces the concentration of free Ag+ ion in solution.
PRACTICE EXERCISE Calculate [Cr3+] in equilibrium with Cr(OH)4 when 0.010 mol of Cr(NO3)3 is dissolved in a liter of solution buffered at pH 10.0.
PRACTICE EXERCISE Calculate [Cr3+] in equilibrium with Cr(OH)4 when 0.010 mol of Cr(NO3)3 is dissolved in a liter of solution buffered at pH 10.0.
Answer: 1 1016 M

Amphoterism
Amphoteric metal oxides and hydroxides are soluble in strong acid or base, because they can act either as acids or bases.

Amphoterism
Amphoteric metal oxides and hydroxides are soluble in strong acid or base, because they can act either as acids or bases.
Examples of such cations are Al3+, Zn2+, and Sn2+.
They are insoluble in water but dissolve readily in the presence of an acid or base.
They are insoluble in water but dissolve readily in the presence of an acid or base.

Section 17.6 & 17.7 Selective Precipitation/ Qualitative Analysis
Will a Precipitate Form?

In a solution,
If Q = Ksp, the system is at equilibrium and the solution is saturated.

In a solution,
If Q = Ksp, the system is at equilibrium and the solution is saturated. If Q < Ksp, more solid will dissolve until Q = Ksp.

In a solution,
If Q = Ksp, the system is at equilibrium and the solution is saturated. If Q < Ksp, more solid will dissolve until Q = Ksp. If Q > Ksp, the salt will precipitate until Q = Ksp.
SAMPLE EXERCISE 17.15 Predicting Whether a Precipitate Will Form
Will a precipitate form when 0.10 L of 8.0 103 M Pb(NO3)2 is added to 0.40 L of 5.0 103 M Na2SO4?
Plan: Determine the concentrations of all ions immediately upon mixing of the solutions and compare the value of the reaction quotient, Q, to the solubility-product constant, Ksp, for any potentially insoluble product.
Plan: Determine the concentrations of all ions immediately upon mixing of the solutions and compare the value of the reaction quotient, Q, to the solubility-product constant, Ksp, for any potentially insoluble product. The possible metathesis products are PbSO4 and NaNO3.
Plan: Determine the concentrations of all ions immediately upon mixing of the solutions and compare the value of the reaction quotient, Q, to the solubility-product constant, Ksp, for any potentially insoluble product. The possible metathesis products are PbSO4 and NaNO3. Sodium salts are quite soluble;
Plan: Determine the concentrations of all ions immediately upon mixing of the solutions and compare the value of the reaction quotient, Q, to the solubility-product constant, Ksp, for any potentially insoluble product. The possible metathesis products are PbSO4 and NaNO3. Sodium salts are quite soluble; PbSO4 has a Ksp of 6.3 107 (Appendix D), however, and will precipitate if the Pb2+ and SO42 ion concentrations are high enough for Q to exceed Ksp for the salt.
When the two solutions are mixed, the total volume is 0.10 L + 0.40 L = 0.50 L.
When the two solutions are mixed, the total volume is 0.10 L + 0.40 L = 0.50 L. The number of moles of Pb2+ is
When the two solutions are mixed, the total volume is 0.10 L + 0.40 L = 0.50 L. The number of moles of Pb2+ is
The concentration of Pb2+ in the 0.50-L mixture is therefore
The number of moles of SO42 is
The number of moles of SO42 is
Therefore, [SO42] in the 0.50-L mixture is
Because Q > Ksp, PbSO4 will precipitate.
PRACTICE EXERCISE
Will a precipitate form when 0.050 L of 2.0 102 M NaF is mixed with 0.010 L of 1.0 102 M Ca(NO3)2?
PRACTICE EXERCISE
Will a precipitate form when 0.050 L of 2.0 102 M NaF is mixed with 0.010 L of 1.0 102 M Ca(NO3)2?
yes, CaF2 precipitates because Q = 4.6 108 is larger than Ksp = 3.9 1011
SAMPLE EXERCISE 17.16 Calculating Ion Concentrations for Precipitation
A solution contains 1.0 102 M Ag+ and 2.0 102M Pb2+. When Cl is added to the solution, both AgCl (Ksp = 1.8 1010) and PbCl2 (Ksp = 1.7 105) precipitate from the solution. What concentration of Cl is necessary to begin the precipitation of each salt? Which salt precipitates first?
Plan: We can calculate what concentration of Cl ion would be necessary to begin precipitation of each. The salt requiring the lower Cl ion concentration will precipitate first.
[Ag+] = 1.0 102 M
[Ag+] = 1.0 102 M
Any Cl in excess of 1.8 x 10-10 will cause AgCl to precipitate.
A solution contains 1.0 102 M Ag+ and 2.0 102M Pb2+. When Cl is added to the solution, both AgCl (Ksp = 1.8 1010) and PbCl2 (Ksp = 1.7 105) precipitate from the solution. What concentration of Cl is necessary to begin the precipitation of each salt? Any Cl in excess of 1.8 x 10-10 Which salt precipitates first? will cause AgCl to precipitate.
A solution contains 1.0 102 M Ag+ and 2.0 102M Pb2+. When Cl is added to the solution, both AgCl (Ksp = 1.8 1010) and PbCl2 (Ksp = 1.7 105) precipitate from the solution. What concentration of Cl is necessary to begin the precipitation of each salt? Any Cl in excess of 1.8 x 10-10 Which salt precipitates first? will cause AgCl to precipitate.
[Cl] in excess of 2.9 102 M will cause PbCl2 to precipitate.
[Cl] in excess of 1.8 x 10-10 will cause AgCl to precipitate. [Cl] in excess of 2.9 102 M will cause PbCl2 to precipitate.
[Cl] in excess of 1.8 x 10-10 will cause AgCl to precipitate. [Cl] in excess of 2.9 102 M will cause PbCl2 to precipitate. AgCl will precipitate first because it requires a much smaller concentration of Cl.
[Cl] in excess of 1.8 x 10-10 will cause AgCl to precipitate. [Cl] in excess of 2.9 102 M will cause PbCl2 to precipitate. AgCl will precipitate first because it requires a much smaller concentration of Cl.
Ag+ can be separated from Pb2+ by slowly adding Cl so [Cl] is between 1.8 108 M and 2.9 102 M.
PRACTICE EXERCISE
A solution consists of 0.050 M Mg2+ and 0.020 M Cu2+. Which ion will precipitate first as OH is added to the solution? What concentration of OH is necessary to begin the precipitation of each cation? Ksp = 1.8 1011 for Mg(OH)2 Ksp = 2.2 1020 for Cu(OH)2.
PRACTICE EXERCISE
A solution consists of 0.050 M Mg2+ and 0.020 M Cu2+. Which ion will precipitate first as OH is added to the solution? What concentration of OH is necessary to begin the precipitation of each cation? Ksp = 1.8 1011 for Mg(OH)2 Ksp = 2.2 1020 for Cu(OH)2.
Answer: Cu(OH)2 precipitates first. Cu(OH)2 begins to precipitate when [OH] exceeds 1.0 109 M; Mg(OH)2 begins to precipitate when [OH] exceeds 1.9 105 M.
Cu2+(aq) + H2S(aq) CuS(s) + 2 H+(aq)
Cu2+(aq) + H2S(aq) CuS(s) + 2 H+(aq)
A high concentration of H2S and a low concentration of H+ (high pH) will reduce [Cu2+].
Selective Precipitation of Ions

One can use differences in solubilities of salts to separate ions in a mixture.
The solution must contain one of the following cations: Ag+, Pb2+ or Hg22+.

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Chapter 17- Aqueous Equilibria

Section 17.1 The Common Ion Effect

The Common-Ion Effect

The Common-Ion Effect

The Common-Ion Effect

The Common-Ion Effect

The Common-Ion Effect

The Common-Ion Effect

The Common-Ion Effect

(0.20) (6.8 104) =x (0.10) 1.4 103 = x

The Common-Ion Effect

The Common-Ion Effect

Chapter 17- Aqueous Equilibria

a) [NH4+] = 0.10 M [Cl] = 0.10 M [NH3] = 0.12 M

a) [NH4+] = 0.10 M [Cl] = 0.10 M [NH3] = 0.12 M b) Cl

If acid is added, the F reacts to form HF and water.

The NaOH reacts with HC2H3O2 converting some of it into C2H3O2 .

Taking the negative log of both sides, we get

Taking the negative log of both sides, we get

Rearranging, this becomes

Rearranging, this becomes

pH = 3.85 + (0.08) pH = 3.77

pH = 4.74, this is pKa of acetic acid

When Strong Acids or Bases Are Added to a Buffer

When Strong Acids or Bases Are Added to a Buffer

Addition of Strong Acid or Base to a Buffer

Addition of Strong Acid or Base to a Buffer

Calculating pH Changes in Buffers

Calculating pH Changes in Buffers

Calculating pH Changes in Buffers

0.300 mol 0.020 mol 0.320 mol 0.000 mol

Calculating pH Changes in Buffers

(0.320) pH = 4.74 + log (0. 280) pH = 4.74 + 0.06 pH = 4.80

Chapter 17- Aqueous Equilibria

Titration of a Strong Acid with a Strong Base

Titration of a Strong Acid with a Strong Base

Titration of a Strong Acid with a Strong Base

Titration of a Strong Acid with a Strong Base

SAMPLE EXERCISE 17.6 Calculating pH for a Strong AcidStrong Base Titration

SAMPLE EXERCISE 17.6 Calculating pH for a Strong AcidStrong Base Titration

SAMPLE EXERCISE 17.6 Calculating pH for a Strong AcidStrong Base Titration

The number of moles of OH in 49.0 mL of 0.100 M NaOH is

The corresponding pH equals

In this case the total volume of the solution is

Thus, the pOH of the solution equals

Thus, the pOH of the solution equals and the pH equals

PRACTICE EXERCISE Calculate the pH

PRACTICE EXERCISE Calculate the pH

Titration of a Weak Acid with a Strong Base

Titration of a Weak Acid with a Strong Base

Titration of a Weak Acid with a Strong Base

Titration of a Weak Acid with a Strong Base

Titration of a Weak Acid with a Strong Base

Titration of a Weak Base with a Strong Acid

Titration of a Weak Base with a Strong Acid

Titration of a Weak Base with a Strong Acid

Titrations of Polyprotic Acids

SAMPLE EXERCISE 17.7 Calculating pH for a Weak AcidStrong Base Titration

SAMPLE EXERCISE 17.7 Calculating pH for a Weak AcidStrong Base Titration

Solve: Stoichiometry Calculation:

SAMPLE EXERCISE 17.7 Calculating pH for a Weak AcidStrong Base Titration

Solve: Stoichiometry Calculation: