Chapter 15

AP*
Chapter 15
Acid-Base Equilibria
AP Learning Objectives
 LO 1.20 The student can design, and/or interpret data from an experiment that
uses titration to determine the concentration of an analyte in a solution. (Sec
15.4-15.5)
 LO 3.3 The student is able to use stoichiometric calculations to predict the
results of performing a reaction in the laboratory and/or to analyze deviations
from the expected results. (Sec 15.4)
 LO 6.1 The student is able to, given a set of experimental observations regarding
physical, chemical, biological, or environmental processes that are reversible,
construct an explanation that connects the observations to the reversibility of
the underlying chemical reactions or processes. (Sec 15.1-15.5)
 LO 6.12 The student can reason about the distinction between strong and weak
acid solutions with similar values of pH, including the percent ionization of the
acids, the concentrations needed to achieve the same pH, and the amount of
base needed to reach the equivalence point in a titration. (Sec 15.4)
 LO 6.13 The student can interpret titration data for monoprotic or polyprotic
acids involving titration of a weak or strong acid by a strong base (or a weak or
strong base by a strong acid) to determine the concentration of the titrant and
the pKa for a weak acid, or the pKb for a weak base. (Sec 15.4)
 LO 6.15 The student can identify a given solution as containing a mixture of
strong acids and/or bases and calculate or estimate the pH (and concentrations
of all chemical species) in the resulting solution. (Sec 15.4)
 LO 6.16 The student can identify a given solution as being the solution of a
monoprotic weak acid or base (including salts in which one ion is a weak acid or
base), calculate the pH and concentration of all species in the solution, and/or
infer the relative strengths of the weak acids or bases from given equilibrium
concentrations. (Sec 15.1-15.2)
 LO 6.17 The student can, given an arbitrary mixture of weak and strong acids
and bases (including polyprotic systems), determine which species will react
strongly with one another (i.e. with K >1) and what species will be present in
large concentration at equilibrium. (Sec 15.1-15.2)
 LO 6.18 The student can design a buffer solution with a target pH and buffer
capacity by selecting an appropriate conjugate acid-base pair and estimating the
concentrations needed to achieve the desired capacity. (Sec 15.2)
 LO 6.19 The student can relate the predominant form of a chemical species
involving a labile proton (i.e. protonated/deprotonated form of a weak acid) to
the pH of a solution and the pKa associated with the labile proton. (Sec 15.2)
 LO 6.20 The student can identify a solution as being a buffer solution and
explain the buffer mechanism in terms of the reactions that would occur on
addition of acid or base. (Sec 15.2-15.3)
Section 15.1
Solutions of Acids or Bases Containing a
Common Ion
AP Learning Objectives, Margin Notes and References
 Learning Objectives
 LO 6.1 The student is able to, given a set of experimental observations regarding physical, chemical, biological, or
environmental processes that are reversible, construct an explanation that connects the observations to the
reversibility of the underlying chemical reactions or processes.
 LO 6.16 The student can identify a given solution as being the solution of a monoprotic weak acid or base
(including salts in which one ion is a weak acid or base), calculate the pH and concentration of all species in the
solution, and/or infer the relative strengths of the weak acids or bases from given equilibrium concentrations.
 LO 6.17 The student can, given an arbitrary mixture of weak and strong acids and bases (including polyprotic
systems), determine which species will react strongly with one another (i.e. with K >1) and what species will be
present in large concentration at equilibrium.
Section 15.1
Common Ion
Common Ion Effect
 Shift in equilibrium position that occurs because of
the addition of an ion already involved in the
equilibrium reaction.
 An application of Le Châtelier’s principle.
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Section 15.1
Common Ion
Example
HCN(aq) + H2O(l) H3O+(aq) + CN-(aq)
 Addition of NaCN will shift the equilibrium to the left

because of the addition of CN-, which is already
involved in the equilibrium reaction.
 A solution of HCN and NaCN is less acidic than a
solution of HCN alone.
Section 15.2
Buffered Solutions

 LO 6.16 The student can identify a given solution as being the solution of a monoprotic weak acid or base (including
salts in which one ion is a weak acid or base), calculate the pH and concentration of all species in the solution,
and/or infer the relative strengths of the weak acids or bases from given equilibrium concentrations.
 LO 6.17 The student can, given an arbitrary mixture of weak and strong acids and bases (including polyprotic
systems), determine which species will react strongly with one another (i.e. with K >1) and what species will be
present in large concentration at equilibrium.
 LO 6.18 The student can design a buffer solution with a target pH and buffer capacity by selecting an appropriate
conjugate acid-base pair and estimating the concentrations needed to achieve the desired capacity.
 LO 6.19 The student can relate the predominant form of a chemical species involving a labile proton (i.e.
protonated/deprotonated form of a weak acid) to the pH of a solution and the pK a associated with the labile proton.
 LO 6.20 The student can identify a solution as being a buffer solution and explain the buffer mechanism in terms of
the reactions that would occur on addition of acid or base.
 Additional AP References
 LO 6.18 (see APEC 15, “Buffers and Buffered Systems”)
Section 15.2
Buffered Solutions
Key Points about Buffered Solutions

 Buffered Solution – resists a change in pH.
 They are weak acids or bases containing a common ion.
 After addition of strong acid or base, deal with
stoichiometry first, then the equilibrium.

Section 15.2
Buffered Solutions
Adding an Acid to a Buffer
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Section 15.2
Buffered Solutions
Buffers

Section 15.2
Buffered Solutions
Solving Problems with Buffered Solutions

Section 15.2
Buffered Solutions
Buffering: How Does It Work?

Section 15.2
Buffered Solutions
Buffering: How Does It Work?

Section 15.2
Buffered Solutions
Henderson–Hasselbalch Equation
 A  
pH = pK a + log
 HA 
 For a particular buffering system (conjugate acid–base
pair), all solutions that have the same ratio [A–] / [HA]
will have the same pH.

Section 15.2
Buffered Solutions
EXERCISE!
What is the pH of a buffer solution that is 0.45 M acetic

acid (HC2H3O2) and 0.85 M sodium acetate (NaC2H3O2)?
The Ka for acetic acid is 1.8 × 10–5.
pH = 5.02

Section 15.2
Buffered Solutions

Section 15.2
Buffered Solutions
Buffered Solution Characteristics

 Buffers contain relatively large concentrations of a weak
acid and corresponding conjugate base.
 Added H+ reacts to completion with the weak base.
 Added OH- reacts to completion with the weak acid.

Section 15.2
Buffered Solutions
Buffered Solution Characteristics

 The pH in the buffered solution is determined by the
ratio of the concentrations of the weak acid and weak
base. As long as this ratio remains virtually constant, the
pH will remain virtually constant. This will be the case as
long as the concentrations of the buffering materials (HA
and A– or B and BH+) are large compared with amounts
of H+ or OH– added.

Section 15.3
Buffering Capacity

 LO 6.20 The student can identify a solution as being a buffer solution and explain the buffer mechanism in terms of
the reactions that would occur on addition of acid or base.
 LO 6.20 (see APEC 16, “Acids, Bases and Buffers”)
Section 15.3
Buffering Capacity
 The amount of protons or hydroxide ions the buffer can

absorb without a significant change in pH.
 Determined by the magnitudes of [HA] and [A–].
 A buffer with large capacity contains large
concentrations of the buffering components.

Section 15.3
Buffering Capacity
 Optimal buffering occurs when [HA] is equal to [A–].

 It is for this condition that the ratio [A–] / [HA] is most
resistant to change when H+ or OH– is added to the
buffered solution.

Section 15.3
Buffering Capacity
Choosing a Buffer
 pKa of the weak acid to be used in the buffer should be
as close as possible to the desired pH.

Section 15.4
Titrations and pH Curves

 LO 1.20 The student can design, and/or interpret data from an experiment that uses titration to determine the
concentration of an analyte in a solution.
 LO 3.3 The student is able to use stoichiometric calculations to predict the results of performing a reaction in the
laboratory and/or to analyze deviations from the expected results.
 LO 6.12 The student can reason about the distinction between strong and weak acid solutions with similar values of
pH, including the percent ionization of the acids, the concentrations needed to achieve the same pH, and the
amount of base needed to reach the equivalence point in a titration.
 LO 6.13 The student can interpret titration data for monoprotic or polyprotic acids involving titration of a weak or
strong acid by a strong base (or a weak or strong base by a strong acid) to determine the concentration of the
titrant and the pKa for a weak acid, or the pKb for a weak base.
 LO 6.15 The student can identify a given solution as containing a mixture of strong acids and/or bases and calculate
or estimate the pH (and concentrations of all chemical species) in the resulting solution.
Section 15.4

 LO 1.20 (see APEC 4, “Analysis of Vinegar”)
 LO 6.13 (see APEC 14, “Titration Curves”)
 LO 6.13 (see Appendix 7.10, “Polyprotic Acid Titrations”)
Section 15.4
Titration Curve
 Plotting the pH of the solution being analyzed as a
function of the amount of titrant added.
 Equivalence (Stoichiometric) Point – point in the titration
when enough titrant has been added to react exactly
with the substance in solution being titrated.

Section 15.4
Neutralization of a Strong Acid with a Strong Base

Section 15.4
The pH Curve for the Titration of 50.0 mL of 0.200 M HNO3
with 0.100 M NaOH

Section 15.4
The pH Curve for the Titration of 100.0 mL of 0.50 M NaOH
with 1.0 M HCI

Section 15.4
Weak Acid–Strong Base Titration

Step 1: A stoichiometry problem (reaction is
assumed to run to completion) then
determine concentration of acid
remaining and conjugate base formed.
Step 2: An equilibrium problem (determine
position of weak acid equilibrium and
calculate pH).

Section 15.4
CONCEPT CHECK!
Consider a solution made by mixing 0.10 mol of HCN

(Ka = 6.2 × 10–10) with 0.040 mol NaOH in 1.0 L of
aqueous solution.
What are the major species immediately upon mixing

(that is, before a reaction)?
HCN, Na+, OH–, H2O

Section 15.4
Let’s Think About It…

 Why isn’t NaOH a major species?
 Why aren’t H+ and CN– major species?
 List all possibilities for the dominant reaction.

Section 15.4

The possibilities for the dominant reaction are:
1. H2O(l) + H2O(l) H3O+(aq) + OH–(aq)

2. HCN(aq) + H2O(l) H3O+(aq) + CN–(aq)
3. HCN(aq) + OH–(aq) CN–(aq) + H2O(l)
4. Na+(aq) + OH–(aq) NaOH
5. Na+(aq) + H2O(l) NaOH + H+(aq)

Section 15.4

 How do we decide which reaction controls the pH?
H2O(l) + H2O(l) H3O+(aq) + OH–(aq)

HCN(aq) + H2O(l) H3O+(aq) + CN–(aq)
HCN(aq) + OH–(aq) CN–(aq) + H2O(l)
Section 15.4

HCN(aq) + OH–(aq) CN–(aq) + H2O(l)
 What are the major species after this reaction occurs?
HCN, CN–, H2O, Na+

Section 15.4

 Now you can treat this situation as before.
 List the possibilities for the dominant reaction.
 Determine which controls the pH.

Section 15.4
CONCEPT CHECK!
Calculate the pH of a solution made by mixing 0.20

mol HC2H3O2 (Ka = 1.8 × 10–5) with 0.030 mol NaOH in
1.0 L of aqueous solution.

Section 15.4

 What are the major species in solution?
Na+, OH–, HC2H3O2, H2O
 Why isn’t NaOH a major species?
 Why aren’t H+ and C2H3O2– major species?

Section 15.4

 What are the possibilities for the dominant reaction?
1. H2O(l) + H2O(l) H3O+(aq) + OH–(aq)

2. HC2H3O2(aq) + H2O(l) H3O+(aq) + C2H3O2–(aq)
3. HC2H3O2(aq) + OH–(aq) C2H3O2–(aq) + H2O(l)
4. Na+(aq) + OH–(aq) NaOH(aq)
5. Na+(aq) + H2O(l) NaOH + H+(aq)
 Which of these reactions really occur?

Section 15.4

 Which reaction controls the pH?
H2O(l) + H2O(l) H3O+(aq) + OH–(aq)

HC2H3O2(aq) + H2O(l) H3O+(aq) + C2H3O2–(aq)
HC2H3O2(aq) + OH–(aq) C2H3O2–(aq) + H2O(l)
 How do you know?

Section 15.4
HC2H3O2(aq) + OH– C2H3O2–(aq) + H2O
Before 0.20 mol 0.030 mol 0

Change –0.030 mol –0.030 mol +0.030 mol
After 0.17 mol 0 0.030 mol
K = 1.8 × 109

Section 15.4
Steps Toward Solving for pH
HC2H3O2(aq) + H2O H3O+ + C2H3O2-(aq)
Initial 0.170 M ~0 0.030 M

Change –x +x +x
Equilibrium 0.170 – x x 0.030 + x
Ka = 1.8 × 10–5
pH = 3.99
Section 15.4
EXERCISE!
Calculate the pH of a 100.0 mL solution of 0.100 M

acetic acid (HC2H3O2), which has a Ka value of 1.8 × 10–5.
pH = 2.87

Section 15.4
CONCEPT CHECK!
Calculate the pH of a solution made by mixing 100.0

mL of a 0.100 M solution of acetic acid (HC2H3O2),
which has a Ka value of 1.8 × 10–5, and 50.0 mL of a
0.10 M NaOH solution.
pH = 4.74

Section 15.4
CONCEPT CHECK!
Calculate the pH of a solution at the equivalence point

when 100.0 mL of a 0.100 M solution of acetic acid
(HC2H3O2), which has a Ka value of 1.8 × 10–5, is titrated
with a 0.10 M NaOH solution.
pH = 8.72

Section 15.4
The pH Curve for the Titration of 50.0 mL of 0.100 M
HC2H3O2 with 0.100 M NaOH

Section 15.4
The pH Curves for the Titrations of 50.0-mL Samples of 0.10 M Acids
with Various Ka Values with 0.10 M NaOH

Section 15.4
The pH Curve for the Titration of 100.0 mL of 0.050 M NH3
with 0.10 M HCl

Section 15.5
Acid-Base Indicators

 LO 1.20 The student can design, and/or interpret data from an experiment that uses titration to determine the
concentration of an analyte in a solution.
 LO 1.20 (see APEC 4, “Analysis of Vinegar”)
Section 15.5
 Marks the end point of a titration by changing color.

 The equivalence point is not necessarily the same as the
end point (but they are ideally as close as possible).

Section 15.5
The Acid and Base

Forms of the Indicator
Phenolphthalein

Section 15.5
The Methyl Orange Indicator is Yellow in Basic Solution and
Red in Acidic Solution

Section 15.5
Useful pH Ranges for Several Common Indicators

Chapter 15

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 Addition of NaCN will shift the equilibrium to the left

AP Learning Objectives, Margin Notes and References

Key Points about Buffered Solutions

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Adding an Acid to a Buffer

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Solving Problems with Buffered Solutions

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Buffering: How Does It Work?

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Buffering: How Does It Work?

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What is the pH of a buffer solution that is 0.45 M acetic

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Buffered Solution Characteristics

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Buffered Solution Characteristics

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AP Learning Objectives, Margin Notes and References

 The amount of protons or hydroxide ions the buffer can

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 Optimal buffering occurs when [HA] is equal to [A–].

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AP Learning Objectives, Margin Notes and References

AP Learning Objectives, Margin Notes and References

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Neutralization of a Strong Acid with a Strong Base

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Weak Acid–Strong Base Titration

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Consider a solution made by mixing 0.10 mol of HCN

What are the major species immediately upon mixing

HCN, Na+, OH–, H2O

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Let’s Think About It…

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Let’s Think About It…

1. H2O(l) + H2O(l) H3O+(aq) + OH–(aq)

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Let’s Think About It…

H2O(l) + H2O(l) H3O+(aq) + OH–(aq)

Let’s Think About It…

 What are the major species after this reaction occurs?

HCN, CN–, H2O, Na+

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Let’s Think About It…

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Calculate the pH of a solution made by mixing 0.20

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Let’s Think About It…

Na+, OH–, HC2H3O2, H2O

 Why isn’t NaOH a major species?

 Why aren’t H+ and C2H3O2– major species?

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Let’s Think About It…

1. H2O(l) + H2O(l) H3O+(aq) + OH–(aq)