Chapter 16

Acid-Base Equilibria

Acids and Bases: A Brief

Review
Acids: taste sour and cause dyes to change color.
Bases: taste bitter and feel soapy.
Arrhenius: acids increase [H+], bases increase [OH-] in
solution.
Arrhenius: acid + base salt + water.
Problem: the definition confines us to aqueous solution.

Brnsted-Lowry Acids and

Bases
The H+ Ion in Water
The H+(aq) ion is simply a proton with no electrons.
(H has one proton, one electron, and no neutrons.)
In water, the H+(aq) joins a water molecule to become
H3O+(aq).
Generally we use H+(aq) and H3O+(aq) interchangeably.

Proton Transfer Reactions

Focus on the H+(aq).
Brnsted-Lowry: acid donates H+ and base accepts H+.
Brnsted-Lowry base does not need to contain OH-.
Consider HCl(aq) + H2O(l) H3O+(aq) + Cl-(aq):
HCl donates a proton to water. Therefore, HCl is an acid.
H2O accepts a proton from HCl. Therefore, H2O is a base.

Water can behave as either an acid or a base.

Amphoteric substances can behave as acids and bases.

Conjugate Acid-Base Pairs

Whatever is left of the acid after the proton is donated is
called its conjugate base.
Similarly, whatever remains of the base after it accepts a
proton is called a conjugate acid.
Consider HA(aq) + H2O(l)
H3O+(aq) + A-(aq)
After HA (acid) loses its proton it is converted into A- (base).
Therefore HA and A- are a conjugate acid-base pair.
After H2O (base) gains a proton it is converted into H3O+ (acid).
Therefore, H2O and H3O+ are a conjugate acid-base pair.

Conjugate acid-base pairs differ by only one proton.

Example Identify the acid and the base in each equation,

and identify each acid-base pair.
1. HNO3 + NH3 NO3- + NH4+

2. CH3COOH + OH- H2O + CH3COO-

Identify the acid and base for the reverse reaction in each
example.

Relative Strengths of Acids and Bases

The stronger the acid, the weaker the conjugate base.
H+ is the strongest acid that can exist in equilibrium in
aqueous solution.
OH- is the strongest base that can exist in equilibrium in
aqueous solution.

Relative Strengths of Acids and Bases

Any acid or base that is stronger than H+ or OH- simply
reacts stoichiometrically (to completion) to produce H+
and OH-.
The conjugate base of a strong acid (e.g. Cl-) has
negligible acid-base properties (we consider it a neutral
species).
Similarly, the conjugate acid of a strong base (e.g. H2O or
Na+) has negligible acid-base properties (we consider it a
neutral species).

The Autoionization of
Water
The Ion Product of Water
In pure water the following equilibrium is established
H2O(l) + H2O(l)
H3O+(aq) + OH-(aq)
at 25 C
[H 3O + ][OH - ]
K eq =
2
[ H 2 O]

K eq [H 2 O]2 = [H 3O + ][OH - ]
K w = [H 3O + ][OH - ] = 1.0 10 14
The above is called the autoionization of water.

The pH Scale
In most solutions [H+(aq)] is quite small.
We define
pH = log[H3O + ] = log[H + ]
pOH = log[OH- ]
In neutral water at 25 C, pH = pOH = 7.00.
In acidic solutions, [H+] > 1.0 10-7, so pH < 7.00.
In basic solutions, [H+] < 1.0 10-7, so pH > 7.00.
The higher the pH, the lower the pOH, the more basic the
solution.

Other p Scales
In general for a number X,
p X = log X
For example, pKw = -log Kw.
K w = [H + ][OH- ] = 1.0 1014

pK w = log [H + ][OH- ] = 14
log[H + ] log[OH - ] = 14
pH + pOH = 14

 Most pH and pOH values fall between 0 and 14.

There are no theoretical limits on the values of pH or
pOH. (e.g. pH of 2.0 M HCl is -0.301.)
Examples:
1. Consider a solution with [H+] = 6.2 x 10-3.
Calculate the pH, pOH, and [OH-]
Is this solution acidic or basic?
2. Consider a solution with pOH = 13.65
Calculate the pH, [H+], and [OH-]
Is this solution acidic or basic?

Measuring pH
Most accurate method to measure pH is to use a pH
meter.
However, certain dyes change color as pH changes.
These are indicators.
Indicators are less precise than pH meters.
Many indicators do not have a sharp color change as a
function of pH.

Strong Acids
The strongest common acids are HCl, HBr, HI, HNO3,
HClO4, and H2SO4.
Strong acids are strong electrolytes.
All strong acids ionize completely in solution:
HNO3(aq) + H2O(l) H3O+(aq) + NO3-(aq)
Since H+ and H3O+ are used interchangeably, we write
HNO3(aq) H+(aq) + NO3-(aq)

Strong Acids and Bases

Strong Acids
In solutions the strong acid is usually the only source of
H+. (If the molarity of the acid is less than 10-6 M then
the autoionization of water needs to be taken into
account.)
Therefore, the [H+] of the solution is the initial molarity
of the acid. (pH = -log [H+])
Strong Bases
Group 1 and soluble group 2 hydroxides are strong bases
(e.g. NaOH, KOH, and Ca(OH)2).

 Strong bases are strong electrolytes and dissociate

completely in solution.
The pOH of a strong base is given by the initial molarity
of the hydroxide ion. Be careful of stoichiometry.
In order for a hydroxide to be a base, it must be soluble.
Bases do not have to contain the OH- ion:
O2-(aq) + H2O(l) 2OH-(aq)
H-(aq) + H2O(l) H2(g) + OH-(aq)
N3-(aq) + H2O(l) NH3(aq) + 3OH-(aq)

Examples: Calculate the pH and pOH of each:

1.
2.
3.
4.
5.
6.

0.25 M NaOH
12.00 M HCl
6.00 M KOH
0.0050 M HNO3
6.5 x 10-12 M RbOH
0.10 M HClO4

Examples: Calculate the pH and pOH of each:

pH
pOH
1. 0.25 M NaOH
13.40
0.60
2. 12.00 M HCl
-1.08
15.08
3. 6.00 M KOH
14.78
-0.78
2.30
11.70
4. 0.0050 M HNO3
7.00
7.00
5. 6.5 x 10-12 M RbOH
1.00
13.00
6. 0.10 M HClO4

Weak Acids
Weak acids are only partially ionized (dissociated) in
solution.
There is a mixture of ions and unionized acid in solution.
Therefore, weak acids are in equilibrium:
HA(aq) + H2O(l)
H3O+(aq) + A-(aq)
[H3O+ ][A - ]
Ka =
[HA]
HA(aq)

H+(aq)

A-(aq)

[H + ][A - ]
Ka =
[HA]

 Ka is the acid dissociation constant.

Note [H2O] is omitted from the Ka
expression. (H2O is a pure liquid.)
The larger the Ka the stronger the acid
(i.e. the more ions are present at
equilibrium relative to unionized
molecules).
If Ka >> 1, then the acid is completely
ionized and the acid is a strong acid.

Calculating Ka from pH
Weak acids are simply equilibrium calculations.
The pH is used to calculate the equilibrium concentration
of H+.
Write the balanced chemical equation clearly showing the
equilibrium.
Write the equilibrium expression.
Use an ICE Chart
Find the value for Ka.

Examples: Calculate Ka.

1. A 0.25 M solution of a hypothetical acid, HA, has a pH
of 4.06.
3.0 x 10-8

2. A 0.10 M solution of acetic acid (CH3COOH) has a pH

of 2.87.
1.8 x 10-5

Percent Ionization
Percent ionization is another method to assess acid
strength.
For the reaction
HA(aq) + H2O(l)

H3O+(aq) + A-(aq)
+

% ionization =

[H 3O ]eq
[HA]0

100

Using Ka to Calculate pH
Percent ionization relates the equilibrium H+ concentration,
[H+]eqm, to the initial HA concentration, [HA]0.
The higher percent ionization, the stronger the acid.
Percent ionization of a weak acid decreases as the molarity
of the solution increases.
For acetic acid, 0.05 M solution is 2.0 % ionized whereas a
0.15 M solution is 1.0 % ionized.
Use ICE Charts to determine [H+]
-log [H+] = pH

Substitute into the equilibrium constant expression and solve.

Remember to turn x into pH if necessary.

Examples Calculate pH, pOH and percent dissociation

for each of the following:
1. 0.35 M HF (Ka = 7.2 x 10-4)
pH = 1.80, pOH = 12.20, 4.5% ionized
2. 0.75 M HF
pH = 1.63, pOH = 12.37, 3.1% ionized
3. 0.62 M NH4+ (from NH4Cl) (Ka = 5.6 x 10-10)
pH = 4.73, pOH = 9.27, .0030% ionized
4. 1.08 M HNO2 (Ka = 4.0 x 10-4)
pH = 1.68, pOH = 12.32, 1.9% ionized
5. 6.00 M HNO3
pH = -0.78, pOH = 14.78, 100% ionized

Polyprotic Acids
Polyprotic acids have more than one ionizable proton.
The protons are removed in steps not all at once:
H2SO3(aq)

H+(aq) + HSO3-(aq)

Ka1 = 1.7 x 10-2

HSO3-(aq)

H+(aq) + SO32-(aq)

Ka2 = 6.4 x 10-8

It is always easier to remove the first proton in a

polyprotic acid than the second.
Therefore, Ka1 > Ka2 > Ka3 etc.
For calculations, we will generally only consider the first
dissociation (the others contribute very little to [H+]
EXCEPTION: H2SO4

Dilute Sulfuric Acid Solutions

First Dissociation is Strong (large Ka)
Second Dissociation is weak (Ka2 = 1.2 x 10-2)
Make ICE chart for second dissociation initial [H+] is equal
to initial [HSO4-]
Determine x (using quadratic if necessary)
Solve for [H+]eq

Example Calculate the pH of 0.010 M H2SO4

Polyprotic Acids

Examples: Calculate pH, pOH, and % dissociation

1. 0.15 M H3PO4
pH = 1.47, pOH = 12.53, 22% ionized

2. 0.30 M NaH2PO4
pH = 3.87, pOH = 10.13, .045% ionized

3. 0.61 M H2CO3
pH = 3.29, pOH = 10.71, .084% ionized

Weak Bases
Weak bases remove protons from substances.
There is an equilibrium between the base and the
resulting ions:
Weak base + H2O
conjugate acid + OH Example:
NH3(aq) + H2O(l)
NH4+(aq) + OH-(aq)
The base dissociation constant, Kb, is defined as
+
[ NH 4 ][OH ]
Kb =
[ NH3 ]

Types of Weak Bases

Bases generally have lone pairs or negative charges in
order to attack protons.
Most neutral weak bases contain nitrogen.
Amines are related to ammonia and have one or more NH bonds replaced with N-C bonds (e.g., CH3NH2 is
methylamine).
Anions of weak acids are also weak bases. Example:
OCl- is the conjugate base of HOCl (weak acid):

ClO-(aq) + H2O(l)

HClO(aq) + OH-(aq) Kb = 3.3 x 10-7

Calculating pH and pOH of Weak Base Solutions

Use ICE Chart to determine [OH-]eq
Use [OH-] to find pOH, and thus pH

Examples Calculate pOH and pH of each of the

following solutions:
1. 0.15 M NH3 (Kb = 1.8 x 10-5)
pH = 11.22

pOH = 2.78

2. 0.38 M HONH2 (Kb = 1.1 x 10-8)

pH = 9.81
pOH = 4.19

Relationship Between Ka
and Kb
We need to quantify the relationship between strength of
acid and conjugate base.
When two reactions are added to give a third, the
equilibrium constant for the third reaction is the product
of the equilibrium constants for the first two:
Reaction 1 + reaction 2 = reaction 3
has
K3 = K1 K 2

 For a conjugate acid-base pair

K w = K a Kb
Therefore, the larger the Ka, the smaller the Kb. That is,
the stronger the acid, the weaker the conjugate base.
Taking negative logarithms:
pK w = pK a + pK b

Acid-Base Properties of
Salt Solutions
Nearly all salts are strong electrolytes.
Therefore, salts exist entirely of ions in solution.
Acid-base properties of salts are a consequence of the
reaction of their ions in solution.
The reaction in which ions produce H+ or OH- in water is
called hydrolysis.
Anions from weak acids are basic.
Anions from strong acids are neutral.

An Anions Ability to React with Water

Anions, X-, can be considered conjugate bases from
acids, HX.
For X- comes from a strong acid, then it is neutral.
If X- comes from a weak acid, then
X-(aq) + H2O(l)
HX(aq) + OH-(aq)
The pH of the solution can be calculated using
equilibrium!

A Cations Ability to React with Water

Polyatomic cations with ionizable protons can be
considered conjugate acids of weak bases.
NH4+(aq) + H2O(l)
NH3(aq) + H3O+(aq)
Some metal ions react in solution to lower pH.
Combined Effect of Cation and Anion in Solution
An anion from a strong acid has no acid-base properties.
An anion that is the conjugate base of a weak acid will
cause an increase in pH (basic ion).

 A cation that is the conjugate acid of a weak base will

cause a decrease in the pH of the solution (acidic ion).
Metal ions will cause a decrease in pH except for the
alkali metals and alkaline earth metals.
When a solution contains both cations and anions from
weak acids and bases, use Ka and Kb to determine the
final pH of the solution.
Use ICE charts to calculate pH and pOH (as for weak
acid and weak base solutions)

Amphoteric Substances
Determine Ka and Kb for the substance (ion)
If Ka > Kb, then the ion is acidic
If Ka < Kb, then the ion is basic
Use the appropriate constant to calculate pH and pOH

Examples State whether each will be acidic, basic, or

neutral in aqueous solution:
1. NaOCl
2. Fe(NO3)3
3. KBr
4. LiClO4
5. NaHCO3
6. CaCl2
7. NH4NO3
8. NiI2

Examples State whether each will be acidic, basic, or

neutral in aqueous solution:
1. NaOCl
basic
2. Fe(NO3)3
acidic
3. KBr
neutral
neutral
4. LiClO4
basic
5. NaHCO3
neutral
6. CaCl2
acidic
7. NH4NO3
acidic
8. NiI2

Examples Calculate pH and pOH for each solution:

1. 0.25 M NH4Cl

2. 0.60 M KBr

3. 0.18 M KC2H3O2

4. 0.50 M NaHCO3

Acid-Base Behavior and

Chemical Structure
Factors that Affect Acid Strength
Consider H-X. For this substance to be an acid we need:
H-X bond to be polar with H+ and X- (if X is a metal
then the bond polarity is H-, X+ and the substance is a
base),
the H-X bond must be weak enough to be broken,
the conjugate base, X-, must be stable.

Binary Acids
Acid strength increases across a period and down a
group.
Conversely, base strength decreases across a period and
down a group.
HF is a weak acid because the bond energy is high.
The electronegativity difference between C and H is so
small that the C-H bond is non-polar and CH4 is neither
an acid nor a base.

Binary Acids

Oxyacids
Oxyacids contain O-H bonds.
All oxyacids have the general structure Y-O-H.
The strength of the acid depends on Y and the atoms
attached to Y.
If Y is a metal (low electronegativity), then the substances are
bases.
If Y has intermediate electronegativity (e.g. I, EN = 2.5), the
electrons are between Y and O and the substance is a weak
oxyacid.

 If Y has a large electronegativity (e.g. Cl, EN = 3.0), the

electrons are located closer to Y than O and the O-H bond is
polarized to lose H+.
The number of O atoms attached to Y increase the O-H bond
polarity and the strength of the acid increases (e.g. HOCl is a
weaker acid than HClO2 which is weaker than HClO3 which is
weaker than HClO4 which is a strong acid).

Oxyacids

Carboxylic Acids
Carboxylic acids all contain the COOH group.
All carboxylic acids are weak acids.
When the carboxylic acid loses a proton, it generate the
carboxylate anion, COO-.

O
R

OH

Lewis Acids and Bases

Brnsted-Lowry acid is a proton donor.
Focusing on electrons: a Brnsted-Lowry acid can be
considered as an electron pair acceptor.
Lewis acid: electron pair acceptor.
Lewis base: electron pair donor.
Note: Lewis acids and bases do not need to contain
protons.
Therefore, the Lewis definition is the most general
definition of acids and bases.

 Lewis acids generally have an incomplete octet (e.g.

BF3).
Transition metal ions are generally Lewis acids.
Lewis acids must have a vacant orbital (into which the
electron pairs can be donated).
Compounds with -bonds can act as Lewis acids:
H2O(l) + CO2(g) H2CO3(aq)

Hydrolysis of Metal Ions

Metal ions are positively charged and attract water
molecules (via the lone pairs on O).
The higher the charge, the smaller the metal ion and the
stronger the M-OH2 interaction.
Hydrated metal ions act as acids:
Fe(H2O)63+(aq)
Fe(H2O)5(OH)2+(aq) + H+(aq)
Ka = 2 x 10-3
The pH increases as the size of the ion increases (e.g.
Ca2+ vs. Zn2+) and as the charge increases (Na+ vs. Ca2+
and Zn2+ vs. Al3+).

Hydrolysis of Metal Ions