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Acid-Base Equilibria
18-1
Acid-Base Equilibria
18.1 Acids and Bases in Water
18-2
Table 18.1 Some Common Acids and Bases and their
Household Uses.
18-3
Arrhenius Acid-Base Definition
This is the earliest acid-base definition, which classifies
these substances in terms of their behavior in water.
18-4
Strong and Weak Acids
18-5
Figure 18.1A The extent of dissociation for strong acids.
18-6
Figure 18.1B The extent of dissociation for weak acids.
18-7
Figure 18.2 Reaction of zinc with a strong acid (left) and a
weak acid (right).
1 M HCl(aq) 1 M CH3COOH(aq)
18-8
The Acid Dissociation Constant, Ka
[H3O+][A-] [H3O+][A-]
Kc = Kc[H2O] = Ka =
[HA][H2O] [HA]
18-9
Table 18.2 Ka Values for some Monoprotic Acids at 25C
18-10
Classifying the Relative Strengths of Acids
Strong acids include
the hydrohalic acids (HCl, HBr, and HI) and
oxoacids in which the number of O atoms exceeds the number
of ionizable protons by two or more (eg., HNO3, H2SO4, HClO4.)
Weak acids include
the hydrohalic acid HF,
acids in which H is not bonded to O or to a halogen (eg., HCN),
oxoacids in which the number of O atoms equals or exceeds
the number of ionizable protons by one (eg., HClO, HNO 2), and
carboxylic acids, which have the general formula RCOOH (eg.,
CH3COOH and C6H5COOH.)
18-11
Classifying the Relative Strengths of Bases
Strong bases include
water-soluble compounds containing O 2- or OH- ions.
The cations are usually those of the most active metals:
M2O or MOH, where M = Group 1A(1) metal (Li, Na, K, Rb, Cs)
MO or M(OH)2 where M = group 2A(2) metal (Ca, Sr, Ba).
Weak bases include
ammonia (NH3),
amines, which have the general formula
18-12
Sample Problem 18.1 Classifying Acid and Base Strength from
the Chemical Formula
PROBLEM: Classify each of the following compounds as a strong
acid, weak acid, strong base, or weak base.
(a) KOH (b) (CH3)2CHCOOH
(c) H2SeO4 (d) (CH3)2CHNH2
PLAN: We examine the formula and classify each acid or base, using
the text descriptions. Particular points to note for acids are the
numbers of O atoms relative to ionizable H atoms and the
presence of the COOH group. For bases, note the nature of
the cation or the presence of an N atom that has a lone pair.
SOLUTION:
(a) Strong base: KOH is one of the group 1A(1) hydroxides.
18-13
Sample Problem 18.1
18-14
Autoionization of Water
18-15
The Ion-Product Constant for Water (Kw)
2H2O (l) H3O+ (aq) + OH- (aq)
[H3O+][A-]
Kc =
[H2O]2
In pure water,
[H3O+] = [OH-] = = 1.0x10-7 (at 25C)
18-16
A change in [H3O+] causes an inverse change in [OH-],
and vice versa.
Higher [H3O+] lower [OH-]
Higher [OH-] lower [H3O+]
18-17
Figure 18.3 The relationship between [H3O+] and [OH-] and the
relative acidity of solutions.
18-18
Sample Problem 18.2 Calculating [H3O+] or [OH-] in an Aqueous
Solution
PROBLEM: A research chemist adds a measured amount of HCl gas
to pure water at 25C and obtains a solution with [H3O+] =
3.0x10-4 M. Calculate [OH-]. Is the solution neutral,
acidic, or basic?
PLAN: We use the known value of Kw at 25C (1.0x10-14) and the
given [H3O+] to solve for [OH-]. We can then compare [H3O+]
with [OH-] to determine whether the solution is acidic, basic,
or neutral.
SOLUTION:
Kw = 1.0x10-14 = [H3O+] [OH-] so
Kw 1.0x10-14
[OH-] = = = 3.3x10-11 M
[H3O+] 3.0x10-4
18-19
The pH Scale
pH = -log[H3O+]
The higher the pH, the lower the [H3O+] and the less
acidic the solution.
18-20
Figure 18.4
pH = -log [H3O+]
18-21
Table 18.3 The Relationship between Ka and pKa
pKa = -logKa
18-22
pH, pOH, and pKw
pH = -log[H3O+]
pKw = pH + pOH = 14.00 at 25C
pOH = -log[OH-]
18-23
Figure 18.5 The relations among [H3O+], pH, [OH-], and pOH.
18-24
Sample Problem 18.3 Calculating [H3O+], pH, [OH-], and pOH
18-25
Sample Problem 18.3
18-26
Figure 18.6 Methods for measuring the pH of an aqueous solution.
pH paper
pH meter
18-27
Brnsted-Lowry Acid-Base Definition
18-28
Figure 18.7 Dissolving of an acid or base in water as a Brnsted-
Lowry acid-base reaction.
Lone pair
binds H+
Lone pair
binds H+
18-29
Conjugate Acid-Base Pairs
In the forward reaction:
NH3 accepts a H+ to form NH4+.
18-31
Table 18.4 The Conjugate Pairs in some Acid-Base Reactions
Conjugate Pair
Conjugate Pair
18-32
Sample Problem 18.4 Identifying Conjugate Acid-Base Pairs
PLAN: To find the conjugate pairs, we find the species that donated
an H+ (acid) and the species that accepted it (base). The acid
donates an H+ to becomes its conjugate base, and the base
accepts an H+ to becomes it conjugate acid.
SOLUTION:
18-33
Sample Problem 18.4
18-34
Net Direction of Reaction
18-35
Figure 18.8 Strengths of conjugate acid-base pairs.
18-36
Sample Problem 18.5 Predicting the Net Direction of an Acid-
Base Reaction
PROBLEM: Predict the net direction and whether Kc is greater or less
than 1 for each of the following reactions (assume equal
initial concentrations of all species):
(a) H2PO4-(aq) + NH3(aq) HPO42-(aq) + NH4+(aq)
(b) H2O(l) + HS-(aq) OH-(aq) + H2S(aq)
SOLUTION:
(a) H2PO4-(aq) + NH3(aq) HPO42-(aq) + NH4+(aq)
stronger acid stronger base weaker base weaker acid
18-37
Sample Problem 18.5
18-38
Sample Problem 18.6 Using Molecular Scenes to Predict the Net
Direction of an Acid-Base Reaction
PROBLEM: Given that 0.10 M of HX (blue and green) has a pH of 2.88,
and 0.10 M HY (blue and orange) has a pH 3.52, which
scene best represents the final mixture after equimolar
solutions of HX and Y- are mixed?
PLAN: A stronger acid and base yield a weaker acid and base, so we
have to determine the relative acid strengths of HX and HY to
choose the correct molecular scene. The concentrations of the
acid solutions are equal, so we can recognize the stronger acid
by comparing the pH values of the two solutions.
18-39
Sample Problem 18.6
SOLUTION:
18-40
Solving Problems Involving
Weak-Acid Equilibria
Problem-solving approach
1.Write a balanced equation.
2.Write an expression for Ka.
3.Define x as the change in concentration that
occurs during the reaction.
4.Construct a reaction table in terms of x.
5.Make assumptions that simplify the calculation.
6.Substitute values into the Ka expression and solve
for x.
7.Check that the assumptions are justified.
18-41
Solving Problems Involving
Weak-Acid Equilibria
The assumptions
[H3O+] from the autoionization of H2O is
negligible.
A weak acid has a small Ka and its
dissociation is negligible. [HA] [HA]init.
18-42
Sample Problem 18.7 Finding Ka of a Weak Acid from the
Solution pH
PROBLEM: Phenylacetic acid (C6H5CH2COOH, simplified here as
HPAc) builds up in the blood of persons with
phenylketonuria, an inherited disorder that, if untreated,
causes mental retardation and death. A study of the acid
shows that the pH of 0.12 M HPAc is 2.62. What is the Ka
of phenylacetic acid?
PLAN: We start with the balanced dissociation equation and write
the expression for Ka. We assume that [H3O+] from H2 is
negligible and use the given pH to find [H3O+], which equals
[PAc-] and [HPAc]dissoc. We assume that [HPAc] [HPAc]init
because HPAc is a weak acid.
SOLUTION: HPAc(aq) + H2O(l) H3O+(aq) + PAc-(aq)
Ka = [H3O+][PAc-]
[HPAc]
18-43
Sample Problem 18.7
Concentration (M) HPAc(aq) + H2O(l) H3O+(aq) + PAc-(aq)
Initial 0.12 - 0 0
Change -x - +x +x
Equilibrium 0.12 - x - x x
[H3O+] = 10-pH = 2.4x10-3 M which is >> 10-7 (the [H3O+] from water)
0.12 M
18-44
Sample Problem 18.8 Determining Concentration from Ka and
Initial [HA]
PROBLEM: Propanoic acid (CH3CH2COOH, which we simplify as
HPr) is a carboxylic acid whose salts are used to retard
mold growth in foods. What is the [H3O+] of 0.10 M HPr
(Ka = 1.3x105)?
Ka = [H3O+][Pr]
[HPr]
18-45
Sample Problem 18.8
Since Ka is small, we will assume that x << 0.10 and [HPr] 0.10 M.
[H3O+][Pr-] x2
Ka = 1.3x10 =
-5
=
[HPr] 0.10
x= = 1.1x10-3 M = [H3O+]
1.1x10-3 M
Check: [HPr]diss = x 100 = 1.1% (< 5%; assumption is justified.)
0.10 M
18-46
Concentration and Extent of Dissociation
[HA]dissoc
Percent HA dissociated = x 100
[HA]init
18-47
Sample Problem 18.9 Using Molecular Scenes to Determine
the Extent of HA Dissociation
18-48
Sample Problem 18.9
SOLUTION:
In each case, remember that each unit of H3O+ is produced from one unit
of HA, so [HA]init = [HA] + [H3O+].
[H3O+] x 100
% dissociation =
[HA] + [H3O+]
18-49
Polyprotic Acids
A polyprotic acid is an acid with more than one ionizable
proton. In solution, each dissociation step has a different
value for Ka:
[H3O+][H2PO4-]
H3PO4(aq) + H2O(l) H2PO4 (aq) + H3O (aq)
- +
Ka1 = = 7.2x10-3
[H3PO4]
[H3O+][HPO42-]
H2PO4-(aq) + H2O(l) HPO42-(aq) + H3O+(aq) Ka2 = = 6.3x10-8
[H2PO ]4
-
[H3O+][PO43-]
HPO (aq) + H2O(l)
4
2-
PO (aq) + H3O (aq)
4
3- +
Ka3 = = 4.2x10-13
[HPO42-]
18-50
Table 18.5 Successive Ka values for Some Polyprotic Acids at
25C
18-51
Sample Problem 18.10 Calculating Equilibrium Concentrations
for a Polyprotic Acid
PROBLEM: Ascorbic acid (H2C6H6O6; H2Asc for this problem), known
as vitamin C, is a diprotic acid (Ka1 = 1.0x10-5 and Ka2 =
5x10-12) found in citrus fruit. Calculate [H2Asc], [HAsc-],
[Asc2-], and the pH of 0.050 M H2Asc.
PLAN: We first write the dissociation equations and the associated
Ka expressions. Since Ka1 >> Ka2, we can assume that the first
dissociation produces almost all the H3O+. Also, since Ka1 is
small, the amount of H2ASc that dissociates can be
neglected. We set up a reaction table for the first dissociation,
with x equal to [H2Asc]dissoc, and solve for [H3O+] and [HAsc-].
SOLUTION:
[HAsc-][H3O+]
H2Asc(aq) + H2O(l) HAsc (aq) + H3O (aq)
- +
Ka1 = = 1.0x10-5
[H2Asc]
[Asc2-][H3O+]
HAsc-(aq) + H2O(l) Asc2-(aq) + H3O+(aq) Ka2 = = 5x10-12
[HAsc-]
18-52
Sample Problem 18.10
[HAsc-][H3O+] x2 x2
Ka1 = = 1.0x10-5 =
[H2Asc] 0.050 - x 0.050
18-53
Sample Problem 18.10
Checking assumptions:
1. [H3O+] << [H3O+]
from HAsc -
from H2Asc : For any second dissocation,
[H3O+] = = 6x10-8 M
from HAsc-
18-54
Weak Bases
A Brnsted-Lowry base is a species that accepts an H+.
For a weak base that dissolves in water:
18-55
Figure 18.9 Abstraction of a proton from water by the base
methylamine.
Lone pair of N
pair binds H+
18-56
Table 18.6 Kb Values for Some Molecular (Amine) Bases at 25C
18-57
Sample Problem 18.11 Determining pH from Kb and Initial [B]
18-58
Sample Problem 18.11
x = [OH-] = 3.0x10-2 M
Check assumption:
3.0x10-2 M x 100 = 2.0% (< 5%; assumption is justified).
1.5 M
18-59
Sample Problem 18.11
Kw 1.0x10 -14
[H3O+] = = = 3.3x10-13 M
[OH ]
- 3.0x10-2
18-60
Anions of Weak Acids as Weak Bases
[HA][OH-]
A-(aq) + H2O(l) HA(aq) + OH-(aq) Kb = [A-]
18-61
If NaF is dissolved in H2O, it dissolves completely, and F-
can act as a weak base:
18-62
Ka and Kb for a Conjugate Acid-Base Pair
HA + H2O H3O+ + A-
A- + H2O HA + OH-
2H2O H3O+ + OH-
18-63
Sample Problem 18.12 Determining the pH of a Solution of A-
PLAN: Sodium salts are soluble in water and acetate is the anion of
HAc so it acts as a weak base. We write the base dissociation
equation and the expression for Kb, and solve for [OH-]. We
recall that any soluble ionic salt dissociates completely in
solution, so [Ac-]init = 0.25 M.
[HAc][OH-]
Kb =
[Ac-]
18-64
Sample Problem 18.12
Kw 1.0x10-14
Kb = = = 5.6x10 -10
M
Ka 1.8x10 -5
[HAc][OH-] x2
Kb = 5.6x10 -10
= so x = [OH-] = 1.2x10-5 M
[Ac ]
-
0.25
18-65
Sample Problem 18.12
Kw 1.0x10 -14
[H3O+] = = = 8.3x10-10 M
[OH ]
- 1.2x10-5
18-66
Acid Strength of Nonmetal Hydrides
18-67
Figure 18.10 The effect of atomic and molecular properties on
nonmetal hydride acidity.
6A(16) 7A(17)
Electronegativity
H2O HF increases, so
acidity increases
decreases, so acidity
H2S HCl
Bond strength
increases
H2Se HBr
H2Te HI
18-68
Acid Strength of Oxoacids
All oxoacids have the acidic H bonded to an O atom.
18-69
Figure 18.11 The relative strengths of oxoacids.
18-70
Hydrated Metal Ions
18-71
Figure 18.12 The acidic behavior of the hydrated Al3+ ion.
18-72
Salts that Yield Neutral Solutions
NaNO3
18-73
Salts that Yield Acidic Solutions
NH4Cl
18-74
Salts that Yield Basic Solutions
CH3COONa
18-75
Sample Problem 18.13 Predicting Relative Acidity of Salt Solutions
from Reactions of the Ions with Water
PROBLEM: Predict whether aqueous solutions of the following are
acidic, basic, or neutral, and write an equation for the
reaction of any ion with water:
(a) Potassium perchlorate, KClO4 (b) Sodium benzoate, C6H5COONa
(c) Chromium(III) nitrate, Cr(NO3)3
PLAN: We identify the cation and anion from the formula for each
salt. Depending on an ions ability to react with water, the
solution will be neutral (strong-acid anion with strong-base
cation), acidic (weak-base cation with strong-acid anion), or
basic (weak-acid anion and strong-base cation).
SOLUTION:
(a) K+ is the cation of a strong base (KOH) while ClO4- is the anion of
a strong acid (HClO4). This solution will be neutral.
18-76
Sample Problem 18.13
(b) Na+ is the cation of a strong base (NaOH) while the benzoate
anion (C6H5COO-) is the anion of a weak acid (benzoic acid). The
benzoate ion will react with H2O to produce OH- ions:
C6H5COO-(aq) + H2O(l) C6H5COOH(aq) + OH-(aq)
(c) NO3- is the anion of a strong acid (HNO3) and will not react with
H2O to any great extent. Cr3+ is a small metal cation with a fairly
high charge density. It will become hydrated and the hydrated ion
will react with H2O to form H3O+ ions:
Cr(H2O)63+(aq) + H2O(l) Cr(H2O)5OH2+(aq) + H3O+(aq)
18-77
Salts of Weakly Acidic Cations and
Weakly Basic Anions
If a salt that consists of the anion of a weak acid and the
cation of a weak base, the pH of the solution will
depend on the relative acid strength or base strength of
the ions.
NH4CN
18-78
The reaction that proceeds farther to the right determines the
pH of the solution, so we need to compare the Ka of NH4+
with the Kb of CN-.
Kw 1.0x10-14
Ka of NH4 =
+
= = 5.7x10-10
Kb of NH3 1.76x10-5
Kw 1.0x10 -14
Kb of CN =
-
= = 1.6x10-5
Ka of HCN 6.2x10-10
18-79
Table 18.7 The Acid-Base Behavior of Salts in Water
18-80
Sample Problem 18.14 Predicting the Relative Acidity of Salt
Solutions from Ka and Kb of the Ions
PROBLEM: Determine whether an aqueous solution of zinc formate,
Zn(HCOO)2, at 25C is acidic, basic, or neutral.
PLAN: Zn2+ is a small, highly charged metal cation, while HCOO - is
the anion of a weak acid. Both will react with H2O, so to
determine the acidity of the solution we must compare the Ka
of the hydrated Zn2+ ion with the Kb of the HCOO- ion.
SOLUTION:
Zn(H2O)62+(aq) + H2O(l) Zn(H2O)5OH+(aq) + H3O+(aq)
HCOO-(aq) + H2O(l) HCOOH(aq) + OH-(aq)
Ka of Zn(H2O)62+ = 1x10-9 (from Appendix C.)
Kw 1.0x10-14
Kb of HCOO =-
= = 5.6x10-11
Ka of HCOOH 1.8x10 -4
18-81
The Leveling Effect
18-82
The Lewis Acid-Base Definition
18-83
Lewis Acids and Bases
A Lewis base must have a lone pair of electrons to
donate.
Any substance that is a Brnsted-Lowry base is also a Lewis base.
18-84
Electron-Deficient Molecules as Lewis Acids
B and Al often form electron-deficient molecules, and
these atoms have an unoccupied p orbital that can accept
a pair of electrons:
18-85
Lewis Acids with Polar Multiple Bonds
18-86
Metal Cations as Lewis Acids
A metal cation acts as a Lewis acid when it dissolves in
water to form a hydrated ion:
18-87
Figure 18.13 The Mg2+ ion as a Lewis acid in chlorophyll.
18-88
Sample Problem 18.15 Identifying Lewis Acids and Bases
PROBLEM: Identify the Lewis acids and Lewis bases in the following
reactions:
(a) H+ + OH- H2O (b) Cl- + BCl3 BCl4- (c) K+ + 6H2O K(H2O6)+
(b) BCl3 accepts an electron pair from Cl-. Cl- is the Lewis base and
BCl3 is the Lewis acid.
18-89