Chapter 17.

1 The Common-Ion Effect

 The common-ion effect

→ Common-ion Effect
Comment In Section 16.6 we calculated that a 0.30 M solution of CH3COOH has a
pH of 2.64
Comment Notice that for all practical purposes, the hydrogen ion concentration is due
entirely to the HCl; the HF makes a negligible contribution by comparison.
 Chapter 17.2 Buffered Solutions

 Buffered solutions
 Buffers are solutions of
a weak conjugate acid-
base pair.
 They are particularly
resistant to pH
changes, even when
strong acid or base is
added.

 Human blood pH 7.4, seawater pH 8.2.

 Many important applications in the lab and in medicine.
 Chapter 17.2 Buffered Solutions
 Buffered solutions
HF ⇄ H+ + F-
 Chapter 17.2 Buffered Solutions
 The HH Equation
Could we have used the HH equation?
 Chapter 17.2 Buffered Solutions
 Buffer Capacity and pH Range
 Buffer capacity is the amount of acid or base the buffer can
neutralize without a significant pH change.
 Consider
1 L solution of 1 M CH3COOH and 1 M CH3COONa
0.1 M CH3COOH and 0.1 M CH3COONa
pH? Buffer capacity?
 When the concentrations of weak acid and conjugate base
are equal, pH = pKa.
 Buffers usually have a usable range within ±1 pH unit of
pKa.
 An optimal buffer has a pKa close to the desired pH.
 Chapter 17.2 Buffered Solutions
 Addition of Strong Acid/Base
 pH in human blood is in the range of 7.35 ~ 7.45.
 <7.35, acidosis; >7.45, alkalosis
 Carbonic acid-bicarbonate buffer system

 CO2 provides a mechanism for the body to adjust pH.

exothermic
 The equilibrium shifts to the left with:
O2 consumption
decreasing pH
increasing CO2 by metabolism
increasing temperature
Red blood cells in an artery
 Chapter 17.3 Acid-Base Titrations

 Titrations

Methyl red indicator.

Figure 17.6 Measuring pH during a

titration.
 Chapter 17.3 Acid-Base Titrations
 Strong Acid-Strong Base Titrations

50 mL of 0.10 M HCl
is titrated with
0.1 M NaOH.
Sample Exercise 17.6 Calculating pH for a Strong Acid-Strong Base Titration
Calculate the pH when (a) 49.0 mL and (b) 51.0 mL of 0.100 M NaOH solution
have been added to 50.0 mL of 0.100 M HCl solution.

Solution
(a) 1. Calculate the mol difference after mixing

2. Calculate the concentration from the mol difference and the total volume
Sample Exercise 17.6 Calculating pH for a Strong Acid-Strong Base Titration
Calculate the pH when (a) 49.0 mL and (b) 51.0 mL of 0.100 M NaOH solution
have been added to 50.0 mL of 0.100 M HCl solution.

Solution
(b) 1. Calculate the mol difference after mixing

2. Calculate the concentration from the mol difference and the total volume
 Chapter 17.3 Acid-Base Titrations
 Strong Acid-Strong Base Titrations
 Chapter 17.3 Acid-Base Titrations
 Weak Acid-
Strong Base
Titrations
50 mL of
0.10 M CH3COOH
is titrated with
0.10 M NaOH.
Sample Exercise 17.7 Calculating pH for a Weak Acid-Strong 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 CH3COOH (Ka = 1.8 ×10-5).
Solution
1. Calculate the mol difference after mixing

2. Calculate the concentration of each component from the mol difference

and the total volume

= 5.70
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 CH3COOH with 0.100 M NaOH.

Solution
 Chapter 17.3 Acid-Base Titrations
 Weak Acid-Strong Base Titrations

Compared with strong acid-

strong base titration,
 Higher initial pH
 Smaller rapid-rise portion
of the curve

 Higher equivalent point pH

 Chapter 17.3 Acid-Base Titrations
 Weak Base-Strong Acid Titrations
 Chapter 17.3 Acid-Base Titrations

 Titrations of Polyprotic Acids

When one titrates a

polyprotic acid with
a base there is an
equivalence point
for each
dissociation.

© 2009, Prentice-Hall, Inc.

 Chapter 17.3 Acid-Base Titrations
 Acid-base indicators
 Chapter 17.3 Acid-Base Titrations
 Acid-base indicators
 Chapter 17.4 Solubility Equilibria

 Solubility Equilibria

Tooth decay
Tooth enamel dissolves in acidic
solutions causing tooth decay

Kidney stone (calcium oxalate)

The precipitation of certain salts in
our kidneys produces kidney
stones
 Chapter 17.4 Solubility Equilibria

 Solubility products
 Consider the equilibrium that exists in a saturated solution of
BaSO4 in water:

where the equilibrium constant (Ksp) is called the solubility

product.

 The solubility product of a compound equals the product of

the concentration of the ions involved in the equilibrium
Ksp for BaSO4 at 25 ˚C is 1.1 X 10-10
 Chapter 17.4 Solubility Equilibria

 Solubility products
 Ksp is not the same as solubility.
 Solubility is generally expressed as the mass of
solute dissolved in 1 L (g/L) of solution, or in mol/L
(molar solubility).
Sample Exercise 17.10 Calculating Ksp from Solubility
Solid silver chromate is added to pure water at 25 ºC. 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 between the undissolved
Ag2CrO4(s) and the solution. Analysis of the equilibrated solution shows that
its silver ion concentration is 1.3 × 10-4 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.

Solution
Sample Exercise 17.11 Calculating Solubility from Ksp
The Ksp for CaF2 (MW 78.1 g/mol) is 3.9 ×10-11 at 25 ºC. 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.
(CaF2, 78.1 g/mol)
Solution
 Chapter 17.5 Factors Affecting Solubility

 Common-ion effect
 If one of the ions of a salt in a
solution is already dissolved in the
solution, the equilibrium will shift to
the left and the solubility of the salt
will decrease.
(a)

(b)
 Chapter 17.5 Factors Affecting Solubility

 Solubility and pH
 If a substance has a basic anion, it will be more
soluble in an acidic solution.
 The more basic the anion, the more solubility is
influenced by pH.

pH = 10.52

Suppose that the pH of the solution is buffered at pH = 9.0

© 2009, Prentice-Hall, Inc.

 Chapter 17.5 Factors Affecting Solubility
 Solubility and pH
 The solubility of PbF2 increases as the solution
becomes more acidic, too, because F- is a weak base
PbF (s) ← → Pb2+ (aq) + 2F- (aq)
2

F- (aq) + H+ (aq) →
← HF (aq)
PbF2 (s) + 2H+ (aq) →
← Pb2+ (aq) + 2HF (aq)
Sample Exercise 17.13 Predicting the Effect of Acid on Solubility
Which of these substances are more soluble in acidic solution than in basic solution: (a) Ni(OH)2(s),
(b) CaCO3(s), (c) BaF2(s), (d) AgCl(s)?

Solution
Analyze The problem lists four sparingly soluble salts, and we are asked to determine which are more soluble at
low pH than at high pH.
Plan Ionic compounds that dissociate to produce a basic anion are more soluble in acid solution.
Solve
(a) Ni(OH)2(s) is more soluble in acidic solution because of the basicity of OH–; the H+ 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 steps, with HCO3– forming first and H2CO3 forming in
appreciable amounts only when [H+] is sufficiently high.
Sample Exercise 17.13 Predicting the Effect of Acid on Solubility
Continued

(c) The solubility of BaF2 is 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 between an acid and (a) CuS, (b) Cu(N3)2.
 Chapter 17.5 Factors Affecting Solubility
 Formation of complex ions
 Lewis bases can interact with metal ions, particularly with transition-metal
ions, which can dramatically affect the solubility of a metal salt.
 Chapter 17.5 Factors Affecting Solubility
 Formation of complex ions
 Complex Ions
• An assembly of a metal ion and the Lewis bases
bonded to it, such as Ag(NH3)2+.
 Chapter 17.5 Factors Affecting Solubility
 Formation of complex ions
 Tooth enamel consists of mainly of a
mineral called hydroxyapatite,
Ca10(PO4)6(OH)2.
 Tooth cavities are caused when acids
dissolve tooth enamel

 Fluoride ion can react with hydroxyapatite to form fluoroapatite,

Ca10(PO4)6F2, which is less soluble in acidic condition.

 The fluoride ion is added to the public water supply in the form of
NaF or Na2SiF6.
 Chapter 17.5 Factors Affecting Solubility
 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+.

© 2009, Prentice-Hall, Inc.

 Chapter 17.6 Precipitation and Separation of Ions

 The reaction quotient, Q, and Ksp

BaCl2(s) + Na2SO4(s)
⇄ Ba2+(aq) + SO42- (aq) + 2Na+ (aq) + 2Cl- (aq)
Sample Exercise 17.15 Predicting Whether a Precipitate Forms
Does a precipitate form when 0.10 L of 8.0 × 10−3 M Pb(NO3)2 is added to 0.40 L
of 5.0 × 10−3 M Na2SO4?
Sample Exercise 17.16 Calculating Ion Concentrations for Precipitation
A solution contains 1.0 × 10-2 M Ag+ and 2.0 ×10-2 M Pb2+. When Cl– is
added to the solution, both AgCl (Ksp = 1.8× 10-10) and PbCl2 (Ksp = 1.7×10-5)
precipitate from the solution. What concentration of Cl– is necessary to begin
the precipitation of each salt? Which salt precipitates first?

Solution
Solve: For AgCl, we have
Because [Ag+] = 1.0 × 10-2 M, the
Proceeding similarly for PbCl2,
greatest concentration of Cl– that can
we have
be present without causing
precipitation of AgCl can be calculated
from the Ksp expression.

Any Cl– in excess of this very small

concentration will cause AgCl to
precipitate from solution.
Chapter 17.6 Precipitation and Separation of Ions
 Chapter 17.7 Qualitative Analysis of Metallic Elements
 Selective Precipitation of Ions
One can use differences in
solubilities of salts to
separate ions in a mixture.