Chapter 18

Acid-Base Equilibria

18-1 Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
 Water is a product in all the reactions between strong acids and
strong bases (neutralization reactions):
H+(aq) + OH-(aq) H2O(l) ∆Hrxno = - 55.9 kJ
Furthermore, an acid dissociates in water according to:
HA(g or l) + H2O(l) A-(aq) + H3O+(aq)
According to the ARRHENIUS ACID-BASE DEFINITION:
- an acid is a compound containing H in its formula and dissociates in
water to yield H3O+
- a base has OH in its formula and dissociates in water to yield OH-.
However, this definition is not sufficient to explain the behaviour, as
bases, of substances that have not discrete OH- in their formula (NH3,
K2CO3).

18-2
 Figure 18.2 The extent of dissociation for strong acids

Strong acids dissociate completely into ions in water; virtually, no HA

molecules are present, to say [H3O+] ≈ [HA]INIT.
Since the reaction is essentially complete, it is not very useful to express it
as an equilibrium process.

18-3
 Figure 18.3 The extent of dissociation for weak acids

Weak acids dissociate very slightly into ions in water; the great
majority of HA molecules are undissociated.
[H3O+] << [HA]INIT, to say [HA]EQ ≈ [HA]INIT and the value of KC is small.

18-4
 Strong acids dissociate completely into ions in water

HA(g or l) + H2O(l) H3O+(aq) + A-(aq)

Weak acids dissociate very slightly into ions in water

HA(aq) + H2O(l) H3O+(aq) + A-(aq)

The Acid-Dissociation Constant

[H3 O+][A-] stronger acid higher [H3O+]

Kc = Kc >> 1
[H2O][HA] larger KC

[H3O+] [A-] smaller KC lower [H3O+]

Kc[H2O] = Ka = Kc << 1
[HA] weaker acid
(10-1 to 10-12)

18-5
 Autoionization of water and the pH scale

Pure water autoionizes to a small extent so it has a low conductivity

18-6
 H2O(l) + H2O(l) H3O+(aq) + OH-(aq)

[H3O+][OH-]
Kc =
[H2O]2

The Ion-Product Constant for Water

Kc[H2O]2 = Kw = [H3O+][OH-] = 1.0 x 10-14 (at 25oC)

A change in [H3O+] causes an inverse change in [OH-].

In an acidic solution, [H3O+] > [OH-]

In a basic solution, [H3O+] < [OH-]
In a neutral solution, [H3O+] = [OH-]

18-7
 The relationship between [H3O+] and [OH-] and the
Figure 18.4
relative acidity of solutions

18-8
 SAMPLE PROBLEM 18.2 Calculating [H3O+] or [OH-] in aqueous
Solution

PROBLEM: A research chemist adds a measured amount of HCl gas to pure

water at 25oC and obtains a solution with [H3O+] = 3.0 x 10-4 M.
Calculate [OH-]. Is the solution neutral, acidic, or basic?

PLAN: Use the Kw at 25oC and the [H3O+] to find the corresponding [OH-].

SOLUTION: K = 1.0 x 10-14 = [H O+] [OH-] so

w 3

Kw 1.0 x 10-14
[OH-] = = = 3.3 x 10-11M
[H3O+] 3.0 x 10-4

[H3O+] is > [OH-] and the solution is acidic.

18-9
 The pH values of some
familiar aqueous solutions

pH = -log [H3O+]

pOH = -log [OH-]

pKW = -log KW = 14 (at 25 °C)

18-10
18-11
Figure 18.6 The relations among [H3O+], pH, [OH-], and pOH

18-12
 SAMPLE PROBLEM 18.3 Calculating [H3O+], pH, [OH-], and pOH

PROBLEM: In an art restoration project, a conservator prepares copper-

plate etching solutions by diluting concentrated HNO3 to 2.0 M,
0.30 M, and 0.0063 M HNO3. Calculate [H3O+], pH, [OH-], and
pOH of the three solutions at 25oC.

PLAN: HNO3 is a strong acid so [H3O+] = [HNO3]. Use Kw to find the [OH-]
and then convert to pH and pOH.

18-13
 SAMPLE PROBLEM 18.3 Calculating [H3O+], pH, [OH-], and pOH
continued

SOLUTION:

For 2.0 M HNO3 [H3O+] = 2.0 M -log [H3O+] = -0.30 = pH

-
Kw 1.0 x 10-14
[OH ] = = = 5.0 x 10-15 M pOH = 14.30
[H3O+] 2.0

For 0.30 M HNO3 [H3O+] = 0.30 M -log [H3O+] = 0.52 = pH

K 1.0 x 10-14
w
[OH-] = = = 3.3 x 10-14 M pOH = 13.48
[H3O+] 0.30

For 0.0063 M HNO3 [H3O+] = 0.0063 M -log [H3O+] = 2.20 = pH

Kw 1.0 x 10-14
[OH-] = = = 1.6 x 10-12 M pOH = 11.80
[H3 O+] 6.3 x 10-3

18-14
 Figure 18.7 Methods for measuring the pH of an aqueous solution

pH (indicator) paper: the paper

is impregnated with one or a
mixture of indicators

pH meter: two electrodes are

immersed in the test solution,
one provides a stable reference
voltage and the other has a thin
glass membrane that separates
a known internal [H3O+] from the
unknown external [H3O+]. The
difference in [H3O+] creates a
voltage difference across the
membrane, measured in pH
units.

18-15
 Figure 18.8 Proton transfer as the essential feature of a Brønsted-
Lowry acid-base reaction

18-16
 Brønsted-Lowry Acid-Base Definition

An acid is a proton donor (species which donates an H+).

A base is a proton acceptor (species which accepts an H+).

An acid-base reaction can now be viewed from the standpoint

of the reactants and the products.
An acid reactant will produce a base product and the two will
constitute an acid-base conjugate pair.
An acid-base reaction is a proton-transfer process.

18-17
Each reaction has an acid and a base as reactants AND as products, and
these comprise two conjugate acid-base pairs.
Acids and bases can be neutral, cationic, or anionic.
The same species can be an acid or a base (amphiprotic), depending on the
other species reacting (for example, water in reactions 1. and 4.).

18-18
 SAMPLE PROBLEM 18.4 Identifying Conjugate Acid-Base Pairs

PROBLEM: The following reactions are important environmental processes.

Identify the conjugate acid-base pairs.
(a) H2PO4-(aq) + CO32-(aq) HPO42-(aq) + HCO3-(aq)

(b) H2O(l) + SO32-(aq) OH-(aq) + HSO3-(aq)

PLAN: Identify proton donors (acids) and proton acceptors (bases).

conjugate pair1 conjugate pair2

SOLUTION: (a) H2PO4-(aq) + CO32-(aq) HPO42-(aq) + HCO3-(aq)

proton proton proton proton
donor acceptor acceptor donor
conjugate pair1 conjugate pair2

(b) H2O(l) + SO32-(aq) OH-(aq) + HSO3-(aq)

proton proton proton proton
donor acceptor acceptor donor
18-19
 Figure 18.9

Strengths of conjugate
acid-base pairs

A reaction proceeds to the

greater extent in the direction
in which a stronger acid and a
stronger base form a weaker
acid and weaker base.
In other terms, the stronger the
acid is, the weaker its
conjugate base.

18-20
 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: Write out the dissociation equation. Use pH and solution concentration
to find the Ka.

Assumptions: With a pH of 2.62, the [H3O+]HPAc >> [H3O+]water.

[PAc-] ≈ [H3O+]; since HPAc is weak, [HPAc]initial ≈ [HPAc]initial -
[HPAc]dissociation

SOLUTION: HPAc(aq) + H2O(l) H3O+(aq) + PAc-(aq)

Ka = [H3O+][PAc-]

[HPAc]

18-21
 SAMPLE PROBLEM 18.7 Finding Ka of a Weak Acid from the Solution
pH
continued

Concentration (M) HPAc(aq) + H2O(l) H3O+(aq) + PAc-(aq)

Initial 0.12 - 1 x 10-7 0

Change -x - +x +x
Equilibrium 0.12 - x - x + (<1 x 10-7) x

[H3O+] = 10-pH = 2.4 x 10-3 M which is >> 10-7 (the [H3O+] from water)

x ≈ 2.4 x 10-3 M ≈ [H3O+] ≈ [PAc-] [HPAc]equilibrium = 0.12 - x ≈ 0.12 M

(2.4x10-3) (2.4x10-3)
So Ka = = 4.8 x 10-5
0.12
1x10-7 M
Be sure to check for % error. [H3 O+] from water; x100 = 4 x 10-3 %
2.4x10-3 M
[HPAc]diss; 2.4x10-3 M
x100 = 2.0 %
0.12 M
18-22
 SAMPLE PROBLEM 18.8 Determining Concentrations 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 = 1.3 x 10-5)?

PLAN: Write out the dissociation equation and expression; make whatever
assumptions about concentration that are necessary; substitute.
Assumptions: For HPr(aq) + H2O(l) H3O+(aq) + Pr -(aq)
x = [HPr]diss = [H3O+]from HPr= [Pr-] Ka = [H3O+][Pr -]

SOLUTION: [HPr]

Concentration (M) HPr(aq) + H2O(l) H3O+(aq) + Pr-(aq)

Initial 0.10 - 0 0
Change -x - +x +x
Equilibrium 0.10 - x - x x

Since Ka is small, we will assume that x << 0.10

18-23
 SAMPLE PROBLEM 18.8 Determining Concentrations from Ka and
Initial [HA]
continued

[H3O+][Pr -] (x)(x)
1.3 x 10-5 = =
[HPr] 0.10

x = (0.10)(1.3x10−5 ) = 1.1 x 10-3 M = [H3O+]

1.1 x 10-3M
Check: [HPr]diss = x 100 = 1.1%
0.10 M

18-24
 [HA]dissociated
Percent HA dissociation = x 100
[HA]initial

Polyprotic acids (acids with more than one ionizable proton)

-((aq)) [H3O+][H2PO4-]
H3PO4((aq)) + H2O(
O(l)) H2PO4 + H3 O+((aq)) Ka1 = = 7.2 x 10-3
[H3PO4]

-(aq) 2-(aq) [H3O+][HPO42-]

H2PO4 + H2O(l) HPO4 + H3 O+(aq) Ka2 = = 6.3 x 10-8
[H2PO4-]

2-(aq) 3-(aq) [H3O+][PO43-]

HPO4 + H2O(l) PO4 + H3 O+(aq) Ka3 = = 4.2 x 10-13
[HPO42-]
Ka1 > Ka2 > Ka3
18-25
 SAMPLE PROBLEM 18.9 Using Molecular Scenes to Determine the
Extent of HA Dissociation

PROBLEM: A 0.15 M solution of acid HA (blue and green) is 33%

dissociated. Which scene represents a sample of that solution
after it is diluted with water ?

PLAN: Calculate percent dissociation for each scene. Percent dissociation

increases as an acid is diluted.

SOLUTION: Solution 1: 4/(5 + 4) x 100 = 44%

Solution 2: 2/(7 + 2) x 100 = 22%
Solution 3: 3/(6 + 3) x 100 = 33%
Therefore, scene 1 is the diluted solution.
18-26
 WEAK BASES
The bases accept protons and to do this they must have a lone electron
pair.
[BH+][OH-]
B(aq) + H2O(l) BH+(aq) + OH-(aq) KC =
[B] [H2O]
[BH+][OH-] BASE-IONIZATION CONSTANT (but no base
KB =
[B] dissociates in the process !)

pKB = -log KB it decreases with the increasing base strength

18-27
 AMMONIA AND THE AMINES

NH3(aq) + H2O(l) NH4+(aq) + OH-(aq) KB = 1.76 x 10-5 (at 25 °C)

Abstraction of a proton from water by methylamine: it acts as a base in

water by accepting a proton.

18-28
 THE RELATION BETWEEN KA AND KB
HA + H2O H3O+ + A-
A- + H2O HA + OH-
2 H2O H3O+ + OH-
AUTOIONIZATION OF WATER
[H3O+] [A-] [HA] [OH-]
[HA] [H2O] [A-] [H2O]
Ka x Kb = KW
This relationship allows to calculate Ka of BH+, the cationic conjugate
acid of a molecular weak base, or Kb of A-, the anionic conjugate base of
a molecular weak acid.

18-29
 SAMPLE PROBLEM 18.10 Determining pH from Kb and Initial [B]

PROBLEM: Dimethylamine, (CH3)2NH, a key intermediate in detergent

manufacture, has a Kb of 5.9 x 10-4. What is the pH of 1.5 M
(CH3)2NH?
PLAN: Perform this calculation as you did for acids. Keep in mind that you
are working with Kb and a base.

Assumptions: Kb >> Kw so [OH-]from water is neglible

[(CH3)2NH2+] = [OH-] = x ; [(CH3)2NH] - x ≈ [(CH3)2NH]initial

18-30
 SAMPLE PROBLEM 18. 10 Determining pH from Kb and Initial [B]
continued

SOLUTION:
Concentration (M) (CH3)2NH(aq) + H2O(l) (CH3)2NH2+(aq) + OH-(aq)
Initial 1.5 - 0 0
Change -x - +x +x
Equilibrium 1.5 - x - x x

[(CH ) NH +][OH-] x2
3 2 2
Kb = 5.9 x 10-4 = 5.9 x 10-4 = x = 3.0 x 10-2 M = [OH-]
[(CH3)2NH] 1.5
Check assumption: 3.0 x 10-2 M
x 100 = 2%
1.5 M
Kw 1.0 x 10-14 M
[H3O+] = -13
[OH-] = 3.0 x 10-2M = 3.3 x 10 M
pH = -log 3.3 x 10-13 = 12.48

18-31
 SAMPLE PROBLEM 18.11 Determining the pH of a Solution of A-

PROBLEM: Sodium acetate (CH3COONa, or NaAc for this problem) has

applications in photographic development and textile dyeing.
What is the pH of 0.25 M NaAc? Ka of acetic acid (HAc) is 1.8 x
10-5.
PLAN: Sodium salts are soluble in water so [Ac-] = 0.25 M.
Write the association equation for acetic acid; use the Ka to find the Kb.

SOLUTION:

Concentration Ac-(aq) + H2O(l) HAc(aq) + OH-(aq)

Initial 0.25 - 0 0
Change -x - +x +x
Equilibrium 0.25 - x - x x

[HAc][OH-] Kw 1.0 x 10-14

Kb = = Kb = = 5.6 x 10-10 M
[Ac-] Ka 1.8 x 10-5

18-32
 SAMPLE PROBLEM 18.11 Determining the pH of a Solution of A-
continued

[Ac-] = 0.25 M - x ≈ 0.25 M

[HAc][OH-]
Kb = x2
[Ac-] 5.6 x 10-10 =
0.25 M
x = 1.2 x 10-5 M = [OH-]
1.2 x 10-5 M
Check assumption: x 100 = 4.8 x 10-3 %
0.25 M
Kw 1.0 x 10-14
[H3O+] = = = 8.3 x 10-10 M
[OH-] 1.2 x 10-5

pH = -log (8.3 x 10-10) pH = 9.08

18-33
 Figure 18.11 The effect of atomic and molecular properties on
nonmetal hydride acidity

18-34
 Figure 18.13 The acidic behavior of the hydrated Al3+ ion

18-35
18-36
 SAMPLE PROBLEM 18.13 Predicting the Relative Acidity of a Salt
Solution from Ka and Kb of the ions

PROBLEM: Determine whether an aqueous solution of zinc formate,

Zn(HCOO)2, is acidic, basic, or neutral.
PLAN: Both Zn2+ and HCOO- come from weak conjugates. In order to find
the relative acidity, write out the dissociation reactions and use the
information in Appendix C.

SOLUTION:
Zn(H2O)62+(aq) + H2O(l) Zn(H2O)5OH+(aq) + H3O+(aq)

HCOO-(aq) + H2O(l) HCOOH(aq) + OH-(aq)

Ka Zn(H2O)62+ = 1 x 10-9
Kw 1.0 x 10-14
Ka HCOO- = 1.8 x 10-4 ; Kb = = = 5.6 x 10-11
Ka1.8 x 10-4
Ka for Zn(H2O)62+ >>> Kb HCOO-, therefore, the solution is acidic.

18-37