CHEMISTRY
The Central Science
9th Edition
Chapter 16
Acid-Base Equilibria
BrØnsted-Lowry Acids and
Bases
According to the Brønsted-Lowry theory,
• Acids donate a proton (H+).
• Bases accept a proton (H+).
NH3, A Brønsted-Lowry Base
In the reaction of ammonia and water,
• NH3 is the base that accept H+.
• H2O is the acid that donates H+.
Acid-Base Concepts: The
Brønsted-Lowry Theory
Acid-Dissociation Equilibrium
Hydronium ion = H3O1+
Acid-Base Concepts: The
Brønsted-Lowry Theory
Base-Dissociation Equilibrium
Conjugate Acid-Base Pairs
The conjugate acid-base pairs of HF/F− and
H2O/H3O+ are related by a loss or gain of H+.
A. Write the conjugate base of the following:
1. HBr
2. H2S
3. H2CO3
B. Write the conjugate acid of the following:
1. NO2-
2. NH3
3. OH-
Identify the sets of acid-base conjugate pairs.
1. HNO2, NO2-
2. H2CO3, CO32-
3. HCl, ClO4-
4. HS-, H2S
5. NH3, NH4+
Strengths of Acids
• A strong acid completely ionizes (100%) in aqueous
solutions.
HCl(g) + H2O(l) H3O+ (aq) + Cl- (aq)
• A weak acid dissociates only slightly in water to form
a few ions in aqueous solutions.
H2CO3(aq) + H2O(l) H3O+(aq) + HCO3− (aq)
Strong and Weak Acids
• In an HCl solution,
the strong acid HCl
dissociates 100%.
• A solution of the
weak acid
CH3COOH contains
mostly molecules
and a few ions.
Strong Acids
Strong acids
• Have weak conjugate bases.
• Are few in number compared to weak acids.
Weak Acids
Weak acids
• Have strong conjugate bases.
• Are typical of most acids.
Table 14.4
Strong Bases
Strong bases
• Form with metals of Groups 1A (1)
and 2A (2):
• Include LiOH, NaOH, KOH, and
Ca(OH)2
• Dissociate completely in water.
KOH(s) K+(aq) + OH−(aq)
Weak Bases
Weak bases
• Are most of the bases.
• Dissociate only slightly in water.
• Form only a few ions in water.
• Most contain nitrogen.
NH3(g) + H2O(l) NH4+(aq) + OH−(aq)
Acids and Bases
Dissociation Constants
Strong Acids
In water, a strong acid
• Dissociates into ions.
• Produces high
concentrations of H3O+
and an anion (A-).
Weak Acids
In weak acids,
• Equilibrium favors the undissociated
(molecular) form of the acid.
• The concentrations of H3O+ and anion (A-)
are low.
HA(aq) + H2O(l) H3O(aq) + A−(aq)
Equilibria in Solutions of Weak
Acids
HA(aq) + H2O(l) H3O1+(aq) + A1-(aq)
[H3O1+][A1-]
Acid-Dissociation Constant: Ka =
[HA]
Acid Characteristics and Ka
Table 14.6 Characteristics of Acids
Characteristic Strong Acids Weak Acids
Equilibrium position Toward ionized products Toward reactants
Ka Large Small
[H3O+] and [A-] 100% of [HA] Small percent
[HA]
Conjugate bases Weak Strong
Dissociation of Water
Dissociation of Water: 2H2O(l) H3O1+(aq) + OH1-(aq)
Ion-Product Constant for Water: Kw = [H3O1+][OH1-]
at 25°C: [H3O1+] = [OH1-] = 1.0 x 10-7 M
Kw = (1.0 x 10-7)(1.0 x 10-7) = 1.0 x 10-14
Dissociation of Water
Kw = [H3O1+][OH1-] = 1.0 x 10-14
1.0 x 10 -14
1.0 x 10 -14
[H3O1+] = [OH1-] =
[OH1-] [H3O1+]
Dissociation of Water
The pH Scale
pH = -log[H3O1+] [H3O1+] = 10 -pH
Basic solution: pH > 7
Neutral solution: pH = 7
Acidic solution: pH < 7
The pH Scale
The hydronium ion concentration for lemon juice is
approximately 0.0025. What is the pH when
[H3O1+] = 0.0025 M?
2 significant figures
pH = -log(0.0025) = 2.60
2 decimal places
The pH Scale
Calculate the pH of an aqueous ammonia solution
that has an OH1- concentration of 0.0019 M.
The pH Scale
Calculate [H3O1+] in a solution that has a pH of 4.5.
The pH in Solutions of Strong
Acids and Strong Bases
What is the pH of a 0.025 M solution of HNO3?
pOH
The pOH of a solution
• Is analogous to the pH value on the pH scale.
• Is based on the [OH−].
• Has high pOH values with low [OH−] and high
[H3O+].
• Is equal to the - log [OH-] pOH = - log [OH-].
• Added to the pH value is equal to 14.0.
pH + pOH = 14.0
The pH in Solutions of Strong
Acids and Strong Bases
What is the pH of a 0.025 M solution of NaOH?
Equilibria in Solutions of Weak
Acids
The pH of 0.250 M HF is 2.036. What is the Ka for
hydrofluoric acid?
HF(aq) + H2O(l) H3O1+(aq) + F1-(aq)
I 0
C
E
Calculating Equilibrium
Concentrations for Weak Acids
Calculate the pH of a 0.10 M HCN solution. At 25 °C,
Ka = 1.4 x 10-9.
HCN(aq) + H2O(l) H3O1+(aq) + CN1-(aq)
I
C
E
Polyprotic Acids
H2CO3(aq) + H2O(l) H3O1+(aq) + HCO31-(aq)
[H3O1+] [HCO31-]
Ka1 = = 4.3 x 10-7
[H2CO3]
HCO31-(aq) + H2O(l) H3O1+(aq) + CO32-(aq)
[H3O1+] [CO32-]
Ka2 = = 5.6 x 10-11
[HCO31-]
Polyprotic Acids
Polyprotic Acids
Calculate the pH of a 0.020 M H2CO3 solution. At
25 °C, Ka1 = 4.3 x 10-7 , Ka2 = 5.6 x 10-
H2CO3 (aq) + H2O(l) H3O1+(aq) + HCO31-(aq)
I
C
E
Equilibria in Solutions of Weak
Bases
B(aq) + H2O(l) BH1+(aq) + OH1-(aq)
Base Acid Acid Base
[BH1+][OH1-]
Base-Dissociation Constant: Kb =
[B]
NH3(aq) + H2O(l) NH41+(aq) + OH1-(aq)
[NH41+][OH1-]
Kb =
[NH3]
Equilibria in Solutions of Weak
Bases
Equilibria in Solutions of Weak
Bases
Calculate the pH of a 0.40 M NH3 solution. At 25 °C,
Kb = 1.8 x 10-5.
NH3(aq) + H2O(l) NH41+(aq) + OH1-(aq)
I
C
E
Relation Between Ka and Kb
NH41+(aq) + H2O(l) H3O1+(aq) + NH3(aq) Ka
NH3(aq) + H2O(l) NH41+(aq) + OH1-(aq) Kb
2H2O(l) H3O1+(aq) + OH1-(aq) Kw
[H3O1+][NH3] [NH41+][OH1-]
Ka x Kb = x = [H3O1+][OH1-] = Kw
[NH41+] [NH3]
= (5.6 x 10-10)(1.8 x 10-5) = 1.0 x 10-14
Relation Between Ka and Kb
Ka x Kb = Kw
conjugate acid-base pair
Kw Kw
Ka = Kb =
Kb Ka
pKa + pKb = pKw = 14.00
Buffer Solutions
Buffer Solution: A solution which contains a weak
acid and its conjugate base and resists drastic
changes in pH.
Weak acid CH3CO2H + CH3CO21-
For HF + F1-
+
Example: NH41+ + NH3
H2PO42- + HPO42-
Conjugate base
Buffer Solutions
CH3CO2H(aq) + H2O(l) H3O1+(aq) + CH3CO21-(aq)
Weak acid Conjugate base
(NaCH3CO2)
Addition of OH1- to a buffer:
100%
CH3CO2H(aq) + OH1-(aq) H2O(l) + CH3CO21-(aq)
Addition of H3O1+ to a buffer:
100%
CH3CO21-(aq) + H3O1+(aq) H2O(l) + CH3CO2H(aq)
pH Titration Curves
Titration: A procedure for determining the concentration
of a solution by allowing a carefully measured volume to
react with a solution of another substance (the standard
solution) whose concentration is known.
standard solution
buret
(known concentration)
Erlenmeyer unknown concentration solution
flask
An indicator is added which changes
color once the reaction is complete
Strong Acid-Strong Base
Titrations
Equivalence Point: The point at which stoichiometrically
equivalent quantities of acid and base have been mixed
together.
Strong Acid-Strong Base
Titrations
1. Before addition of Any NaOH
0.100 M HCl
Strong Acid-Strong Base
Titrations
2. Before the Equivalence Point
100%
H3O1+(aq) + OH1-(aq) 2H2O(l)
Excess H3O1+
Strong Acid-Strong Base
Titrations
3. At the Equivalence Point
The quantity of H3O1+ is
equal to the quantity of
added OH1-.
pH = 7
Strong Acid-Strong Base
Titrations
4. Beyond the Equivalence Point
Excess OH1-
The Henderson-Hasselbalch
Equation
[Base]
pH = pKa + log [Acid]
pOH = pKb + log [Acid]
[Base]
Weak Acid-Strong Base
Titrations
Weak Acid-Strong Base
Titrations
1. Before Addition of Any NaOH
CH3CO2H(aq) + H2O(l) H3O1+(aq) + CH3CO21-(aq)
0.100 M CH3CO2H
Weak Acid-Strong Base
Titrations
2. Before the Equivalence Point
100%
CH3CO2H(aq) + OH1-(aq) H2O(l) + CH3CO21-(aq)
Excess CH3CO2H
Buffer region
Weak Acid-Strong Base
Titrations
3. At the Equivalence Point
CH3CO21-(aq) + H2O(l) OH1-(aq) + CH3CO2H(aq)
pH > 7
Notice how the pH at the
equivalence point is
shifted up versus the
strong acid titration.
Weak Acid-Strong Base
Titrations
4. Beyond the Equivalence Point
Excess OH1-
Notice that the strong
and weak acid titration
curves correspond after
the equivalence point.
Weak Acid-Strong Base
Titrations
Weak Base-Strong Acid
Titrations
1. Before Addition of Any HCl
0.100 M NH3
Weak Base-Strong Acid
Titrations
2. Before the Equivalence Point
100%
NH3(aq) + H3O1+(aq) NH41+(aq) + H2O(l)
Excess NH3
Buffer region
Weak Base-Strong Acid
Titrations
3. At the Equivalence Point
NH41+(aq) + H2O(l) H3O1+(aq) + NH3(aq)
pH < 7
Weak Base-Strong Acid
Titrations
4. Beyond the Equivalence Point
Excess H3O1+
Polyprotic Acid-Strong Base
Titrations