Chapter 12

Acids and Bases

12.1 The Nature of Acids and Bases
12.2 Acid Strength
12.3 The pH Scale
12.4 Calculating the pH of Strong Acid Solutions
12.5 Calculating the pH of Weak Acid Solutions
12.6 Bases
12.7 Polyprotic Acids
12.8 Acid-Base Properties of Salts
12.9 Acid Solutions in Which Water Contributes to the H+
Concentration (skip)
12.10 Strong Acid Solutions in Which Water Contributes to
the H+ Concentration (skip)
12.11 Strategy for Solving Acid-Base Problems: A Summary

Acids and Bases and Their Reactions

Definitions
1. Arrhenius Acids and Bases Acids are

H+ donors
Bases are OH- donors

2. Arrhenius Broadened Definition

Acids increase H+ concentration or [H+]

increases
Bases increase OH- concentration or [OH-]
increases

3. Brnsted-Lowry Acids and Bases (1923)

Acids donate H+
Bases accept H+

Arrhenius
1903
Nobel Prize

Acids-Bases
Brnsted-Lowry Acids and Bases
A Brnsted-Lowry acid is a substance that can
donate a hydrogen ion (aka H+, proton).
A Brnsted-Lowry base is a substance that can
accept a hydrogen ion.
Acids and bases occur as conjugate acid base pairs.

Conjugate Base - subtract an H+ from the acid

Conjugate Acid add H+ to the base
Examples

1. OH is the conjugate base of

2. H2O is the conjugated base of

3. H2O is the conjugated acid of

4. H3O+ (or often shown as H+) is the conjugate

CH3CO2H +

H 2O

H 3 O+ +

Acetic Acid

Pairs

CH3CO2Acetate Ion

acid

base

2
acid

1
base

Point of View #1

CH3CO2H +
acid

H 2O

H 3 O+ +

base

Conjugate acid
of H2O

CH3CO2Conjugate base of
CH3CO2H

Point of View #2

CH3CO2H
Conjugate acid
of CH3CO2-

+ H 2O
Conjugate
base of H3O+

H3O+ + CH3CO2acid

base

Nomenclature
When H+ is hydrated, it is H3O+ and is called a
hydronium ion. A hydronium ion has the same
molecular geometry as NH3.

+
111.7

HA

+ H2 O

H3O+ + A

HA = generic acid

There is Competition for the proton between two bases H 2O

and A
If H2O is a much stronger base than A the equilibrium lies
far to the right.
If A is a much stronger base than H2O the equilibrium lies
far to the left.

Acid Strength: graphical representation of the behavior of

acids of different strengths in aqueous solution.
A strong acid: equilibrium lies
far to the right

HA + H2O

H3O+ + A

A weak acid: equilibrium lies

far to the left

HA + H2O

H3O+ + A

A weak acid yields a relatively

strong conjugate base

Relationship of acid strength and conjugate base

strength

HA + H2O

H3O+ + A-

[H 3O ][A ]
Ka
[HA]

HA + H2O

H3O+ + A

SAME AS

HA

H+ + A

Ka is the Acidity constant

Autoionization of H2O
H2O
Pairs 1

H2O
2
base

acid

H3O+ + OH2
1
acid

base

Point of View #1

H2O

#1
acid

+ H 2O

#2
base

H 3 O+

Conjugate acid
of H2O #2

OHConjugate base
of H2O #1

Point of View #2

H2O +
Conjugate acid
of OH-

H2O
Conjugate
base of H3O+

H3O+ +
acid

OHbase

Amphoterism - an ion or molecule can act as an

acid or base depending upon the reaction conditions

Amphoterism - an ion or molecule can act

as an acid or base depending upon the
reaction conditions
1.) Water in NH3 serves as an acid
H2O

+ NH3

acid

base

NH4+ +
acid

OHbase

2.) Water in acetic acid serves as a base

H2O +

base

CH3CO2H
acid

H 3 O+ +
acid

CH3CO2base

Conjugate acid

Conjugate base

of H2O

of acetic acid

Water as an Acid and a Base

Autoionization of water:
[H3O+][OH-]
[H2O(l)]2

2 H2O (l)

H3O+ (aq) + OH- (aq)

Kw = [H3O+][OH-] = [H+][OH-]
Kw = 1.0 x 10-14 (at 25oC)
In pure water [H+] = [OH-]

Kw = [H3O+][OH-]

Ka/Kb/Kw

NH4+

H+ + NH3
[H ][NH 3 ]
Ka
[NH +4 ]

NH3 + H2O

OH- + NH4+

+
4

[OH ][NH ]
Kb
[NH 3 ]

Ka/Kb/Kw

NH4+

H+ + NH3
[H ][NH 3 ]
Ka
[NH +4 ]

NH3 + H2O

H2O

OH- + NH4+

+
4

[OH ][NH ]
Kb
[NH 3 ](1)

OH- + H+

K w = K a K b

[OH ][H + ]
(1)

The pH Scale
pH = -log10[H3O+]
SAME AS

pH = -log10[H+]
pH < 7 acidic solution
[H3O+] > [OH-]
pH = 7 neutral solution
[H3O+] = [OH-]
pH > 7 basic solution
[H3O+] < [OH-]
Sig figs: for logs: the number of decimal
places in the log is equal to the number of sig
figs in the original number

Calculate the pH of Strong Acid-Base Solutions

EXAMPLE

pH = -log10[H3O+]

Calculate the pH (at 25oC) of an aqueous solution that has an

OH-(aq) concentration of 1.2 x 10-6 M (i.e., mol/liter)

Solution
The concentration of H+ (aq) is
[H+][OH-] = KW
[H+] = KW/[OH-] = 10-14/1.2x10-6 = 8.3 x 10-9
pH = -log[8.3 x 10-9] = 8.1

Strong Acids
A strong acid is one that dissociates completely in water to
produce H+(aq).

E.g., Hydrochloric acid (HCl) is a strong acid:

HCl (aq) H+ (aq) + Cl- (aq)

(reaction essentially complete)

Dissolving 0.10 mol of HCl in enough water to make 1.0 L of

solution gives a final concentration of 0.10 M for H+(aq).

H2O (l)

H+ (aq) + OH- (aq)

[H+][OH-] = Kw
[OH-] = Kw / [H+] = 10-14/10-1 = 10-13

Weak Acids

Write the major species in solution and Ka

values. Which is dominant?
#1: HA

[H+][A ]
Ka
[HA]

H+ + A

#2: H2O

H + OH
+

Kw [H+][OH ]

Compare the value for Ka and Kw. Which is

larger? This is the dominate

source of H+

Problem: (a) Calculate pH and (b) the fraction of

CH3CO2H ionized at equilibrium. The concentration of
CH3CO2H is 1 M (initial, or total). The Ka for acetic acid is
1.8 x 10-5
Estimate major species in solution CH3CO2H (a weak
acid) and H2O.
CH3CO2H
H2O

H+ + CH3CO2
H+ + OH

Ka = 1.8 x 10-5
Kw = 1.0 x 10-14

Problem: (a) Calculate pH and (b) the fraction of

CH3CO2H ionized at equilibrium.
H+ + CH3CO2

CH3CO2H
Initial

1.0M

~0

Change

-y

+y

+y

Equilibrium

1.0 y

Problem: (a) Calculate pH and (b) the fraction of

CH3CO2H ionized at equilibrium.
H+ + CH3CO2

CH3CO2H
Initial

1.0M

~0

Change

-y

+y

+y

Equilibrium

1.0 y

(y)(y)
Ka
(1.0- y)
assumey << 1.0
(y)(y)
Ka
(1.0)

Problem: (a) Calculate pH and (b) the fraction of

CH3CO2H ionized at equilibrium.
H+ + CH3CO2

CH3CO2H
Initial

1.0M

~0

Change

-y

+y

+y

Equilibrium

1.0 y

(y)(y)
Ka
(1.0- y)
assumey << 1.0

(y)(y)
Ka 1.8x10
(1.0)

(y)(y)
Ka
(1.0)

y 4.3x10 3

y 1.8x10 5
checkassumption : isy << 1.0?

Effect of dilution on the % dissociation and [H+] and pH

HA

H+ + A

Le Chateliers Priniciple:

The more dilute the

weak acid solution,
the greater the
percent dissociation

If a chemical system at equilibrium

experiences a change in
concentration (or temperature,
volume, or partial pressure) then
the system shifts to counteract the
imposed change.

Strong Bases
A strong base reacts
water to
Strongcompletely
Acids andwith
Bases
produce OH-(aq) ions.
Sodium hydroxide (NaOH) is a strong base:
Others are KOH, NH2 (amide ion) and H (Hydride ion)

NaOH (s) Na+ (aq) + OH- (aq)

(reaction essentially complete)

Dissolving 0.10 mol of NaOH in enough water to make 1.0 L

of solution gives a final concentration of 0.10 M for OH- (aq).
From this you can calculate pH and pOH.

[H+][OH-] = Kw
[H+] = Kw/[OH-] =10-14/10-1 = 10-13
[OH-] = 10-1
[H+] = 10-13
pOH = 1
pH = 13

Weak Bases
B (aq) + H2O (l)

BH+ (aq) + OH (aq)

B = Base

Kb is the basicity constant

Kb = [BH+][OH]/[B]

Calculations for solutions of weak bases are similar

to those for weak acids. Bases (B) compete with
OH, a very strong base, for H+ ions.

B (aq) + H2O (l)

BH+ (aq) + OH (aq)

Acid-Base Equilibria

Base Strength
strong acids have weak
conjugate bases
weak acids have strong
conjugate bases

The strength of a base is

inversely related to the strength
of its conjugate acid; the weaker
the acid, the stronger its
conjugate base, and vice versa

pKa + pKb = pKw

This equation applies to an acid and its conjugate base.

Weak Bases
NH3 is a base

Kb = 1.8 x 10-5

NH3 + H20 NH4+ + OHacid1 base2 acid2 base1

NH4+ is an acid

Ka = 5.6 x 10-10
NH4+
acid1

NH3 + H+
base1

Weak Bases
NH3 is a base
NH3 + H20

Kb = 1.8 x 10-5
NH4+ + OH-

NH4+ is an acid

Ka = 5.6 x 10-10
NH3 + H+

NH4+

Ka Kb = Kw = (5.6 x 10-10) (1.8 x 10-5) = 10-14

pKa + pKb = pKw = (-9.25) + (-4.75) = -14

Weak Bases with Weak Acids

NH4+ is an acid
NH4+
CH3COOH is an acid
CH3COOH

Ka(am) = 5.6 x 10-10

NH3 + H+
Ka(aa) = 1.8 x 10-5
CH3COO- + H+

change the direction of the aa reaction and add them together

NH4+ + CH3COO-

NH3 + CH3COOH

K = Ka(am)/Ka(aa) = 5.6 x 10-10/1.8 x 10-5

Assuming 0.1M NH3 initial, calculate the pH of

the resulting solution
H20 + NH3
NH4+ + OH-

Assuming 0.1M NH3 initial, calculate the pH of

the resulting solution
H2O + NH3
NH4+ + OHInit. conc.

0.1M

~0

Change

-y

+y

+y

Equil. conc.

0.1 y

Assuming 0.1M NH3 initial, calculate the pH of

the resulting solution
H20 + NH3
NH4+ + OH-

Kb

Init. conc.

0.1M

~0

Change

-y

+y

+y

Equil. conc.

0.1 y

[NH 4 ][OH - ]
y2

[NH 3 ][1]
0.1 y

K b for NH 3 1.8x10 5
assume y is small
y2
5
Kb
1.8x10
0.1
y [OH - ] [NH 4 ] 1.3x10 -3

[H+] =
Kw/[OH-] =
10-14/y
pH=-log[H+]

Polyprotic
Acids

It is always easier to remove the first proton in a

polyprotic acid than the second. That is, Ka1 > Ka2 > Ka3

Note: Sulfuric acid is a strong acid in its first dissociation step and a weak
acid in its second step.

H2SO4 (aq) H+ (aq) + HSO4 (aq)

HSO4 (aq)

H+ (aq) + SO42 (aq)

Ka1 1.0x102
Ka2 1.2x10-2

Polyprotic Acids
1.
2.
3.
4.

Polyprotic acids have more than one ionizable proton.

The protons are removed in steps, not all at once.
The extent of the steps can be calculated sequentially.
From the successive acidity constants, the equilibrium concentrations of all
species present can be calculated at any value of the pH.

H2SO3 (aq) + H2O (l) H3O+ (aq) + HSO3- (aq)

Ka1 = 103
HSO3- (aq) + H2O (l)

H3O+ (aq) + SO32- (aq)

Ka2 = 1.2 x 10-2

Polyprotic Acids
pH calculations for solutions of Polyprotic acids
appear complicated, most common cases (with
weak acids) are surprising straightforward.
Setup equations, K values, set up ICE type
table, assume dissociation is small (check
assumption) and solve.
For typical weak Polyprotic acids.
Ka1 >> Ka2 >> Ka3
The first dissociation step dominates the H+
concentration and thus the pH

A plot of the fractions of H2CO3, HCO-3 and CO32At pH = 9.00 H2CO3 0%, HCO-3 = 95% and CO32- = 5%
At pH = 10.00 H2CO3 0%, HCO-3 = 68% and CO32- = 32%

Acid-Base Properties of Salts

Hydrolysis

Hydrolysis is a Brnsted-Lowry Acid

and Base Reaction
Anion: A + H2O HA + OH
Cation: M+2 + H2O H3O+ + M(OH)+
E.g., Cations Ni+2 and Fe+2

 Hydrolysis is a term applied to reactions of

aquated ions that change the pH from 7
When NaCl is placed in water, the resulting solution
is observed to be neutral (pH = 7)
However when sodium acetate (NaC2H3O2) is
dissolved in water the resulting solution is basic
Other salts behave similarly, NH4Cl and AlCl3 give
acid solutions.
These interactions between salts and water are
called hydrolysis

Example problem:
Suppose a 0.1 mole solution sodium acetate is
dissolved in 1 liter of water. What is the pH of the
solution?

CH3CO2 + H2O CH3CO2H + OH

base

acid

acid

Init. conc.

0.1M

conc.

-y

+y

Equil. conc.

0.1 y

1. Find Kb
2. Find [OH-]
3. Find [H+]
4. Find pH

base
~0
+y
y

1. Find Kb

Example problem:

2. Find [OH-]
3. Find [H+]

What is the pH of the solution?

4. Find pH

CH3CO2 + H2O CH3CO2H + OH

Init. conc.

0.1M

conc.

-y

0
+y

Equil. conc. 0.1 y

Ka x Kb = K w

~0
+y
y

 Hydrolysis is a term applied to reactions of aquated ions

that change the pH from 7
When NaCl is placed in water, the resulting solution is
observed to be neutral (pH = 7)
However when sodium acetate (NaC2H3O2) is dissolved in
water the resulting solution is basic (Problem: found at 0.1M
NaAc, pH =8.89)
a non-hydrolyzed cation (Na+)
a hydrolyzed anion (acetate ion)
Other salts behave similarly, NH4Cl and AlCl3 give acid
solutions.
a non-hydrolyzed anion (Cl-)
a hydrolyzed cation (NH4+ or Al+3)
These interactions between salts and water are called
hydrolysis

Hydrolysis of

Result

Anions
Cations

Raise pH
Lower pH

Non-Hyrolyzed Ions (a few)

7 Anions, not hydrolyzed
Cl , Br , I , HSO4, NO3, ClO3, ClO4
10 Cations, not hydrolyzed
Li+, Na+, K+, Rb+, Sc+, Mg++, Ca++, Sr++, Ba++,
Ag+

Hydrolysis of

Result

Anions
Cations

Raise pH
Lower pH

Predict pH of salts in water (relative pH)

Na33PO44? is basic (raised pH)
(a non hydrolyzed cation and a hydrolyzed anion)
FeCl33? is acidic (lowers pH)
(a hydrolyzed cation and a non hydrolyzed anion)

Summary
Acid-Base Properties of Salts
Hydrolysis

Summary
Acid-Base Equilibrium Problems
Which major species are present
Does a reaction occur that can be assumed to go to
completion?
Which equilibrium dominates the solution?
Set up ICE type table
Solve for equilibrium concentrations using know K
values
Check any simplifying assumptions
Typically solve for pH or % species in solution

Chapter 7
Acids and Bases
7.1 The Nature of Acids and Bases
7.2 Acid Strength
7.3 The pH Scale
7.4 Calculating the pH of Strong Acid Solutions
7.5 Calculating the pH of Weak Acid Solutions
7.6 Bases
7.7 Polyprotic Acids
7.8 Acid-Base Properties of Salts
7.9 Acid Solutions in Which Water Contributes to the H+
Concentration (skip)
7.10 Strong Acid Solutions in Which Water Contributes to the
H+ Concentration (skip)
7.11 Strategy for Solving Acid-Base Problems: A Summary