Chem 16 General Chemistry 1

12 Acids and Bases

Dr. Gil C. Claudio

First Semester 2014-2015
Table of Contents

Contents
1 The Arrhenius Theory

2 Brnsted-Lowry Theory of Acids and Bases

3 Self-Ionization of Water and the pH Scale

4 Strong Acids and Strong Bases

5 Weak Acids and Weak Bases

6 Polyprotic Acids

7 Lewis Acids and Bases

References
References of these notes
General Chemistry, 10th ed, by Ralph H. Petrucci, F. Geoffrey Herring,
Jeffy D. Madura, and Carey Bisonnette.
Chemistry: The Central Science, 13th ed., by Theodore L. Brown, H. Eugene
LeMay Jr., Bruce E. Bursten, Catherine J. Murphy, Patrick M. Woodward,
and Matthew W. Stoltzfus.

1 The Arrhenius Theory

Arrhenius Definition of Acids and Bases
The Arrhenius concept of acids and bases can be stated as
An acid is a substance that, when dissolved in water, increases the
concentration of H+ ions.
A base is a substance that, when dissolved in water, increases the
concentration of OH ions.
Arrhenius Theory
When the acid HCl dissolves in water
HCl(aq) H+ (aq) + Cl (aq)
When the base NaOH dissolves in water
NaOH(aq) Na+ (aq) + OH (aq)
1

The net ionic ionic equation of the neutralization reaction is

H+ (aq) + OH (aq) H2 O(l)
The essential idea of the Arrhenius theory: A neutralization reaction involves
the combination of hydrogen ions and hydroxide ions to form water.
Limitation: cannot describe some weak bases, e.g., ammonia NH3

2 Brnsted-Lowry Theory of Acids and Bases

Brnsted-Lowry Theory of Acids and Bases
According to the Brnsted-Lowry theory, an acid is a proton donor and a
base is a proton acceptor.
NH3
base

H2 O
acid

NH4+
acid

OH
base

The product is also an acid-base reaction, thus

NH3
base(1)

H2 O
acid(2)

NH4+
acid(1)

OH
base(2)

The pairs NH3 /NH4+ and H2 O/OH are called conjugate pairs.
NH4+ is the conjugate acid of the base NH3
OH is the conjugate base of the acid H2 O
Amphiprotic substances can act either as an acid or a base.
Ionization Constants
Given the reaction
NH3 (aq) + H2 O(l) NH4+ (aq) + OH (aq)
the base ionization constant is
Kb =

aNH + aOH
4

aNH3 aH2 O

[NH4+ ][OH ]
= 1.8 105
[NH3 ]

Given the reaction

CH3 COOH(aq) + H2 O(l) CH3 COO (aq) + H3 O+ (aq)
the acid ionization constant is
Ka =

aCH

3 COO

aH

3O

aCH3 COOH aH2 O

[CH3 COO ][H3 O+ ]

= 1.8 105
[CH3 COOH]

Hydronium Ion
The hydronium ion H3 O+ is the form in which protons are found in
aqueous solution.
The terms hydrogen ion and hydronium ion are often used
synonymously.
Given CH3 COOH + H2 O CH3 COO + H3 O+ , H2 O acts as a base and
H3 O+ is its conjugate acid.

B-L Acids and Bases and Their Conjugates

PHMB 10e, Example 16-1, p 701
For each of the following, identify the acids and bases in both the forward
and reverse reactions.
1. HClO2 + H2 O ClO2 + H3 O+
2. OCl + H2 O HOCl + OH
3. NH3 + H2 PO4 NH4+ + HPO42
4. HCl + H2 PO4 Cl + H3 PO4
Direction of the Reaction
In an acid-base reaction, the favored direction of the reaction is from the
stronger to the weaker member of a conjugate acid-base pair.
Some examples
HCl
acid(1)
strong

OH
base(2)
strong

Cl
base(1)
weak

H2 O
acid(2)
weak

H2 O
acid(1)
weak

I
base(2)
weak

OH
base(1)
strong

HI
acid(2)
strong

The stronger an acid, the weaker its conjugate base.

Relative Strengths of Some Acids and Bases
s
t
r
o
n
g

w
e
a
k

acid
Perchloric acid
Hydroiodic acid
Hydrobromic acid
Hydrochloric acid
Sulfuric acid
Nitric acid
Hydronium ion
Hydrogen sulfate ion
Nitrous acid
Acetic acid
Carbonic acid
Ammonium ion
Hydrogen carbonate ion
Water
Methanol
Ammonia

HClO4
HI
HBr
HCl
H2 SO4
HNO3
H3 O+
HSO4
HNO2
CH3 COOH
H2 CO3
NH4+
HCO3
H2 O
CH3 OH
NH3

w
e
a
k

s
t
r
o
n
g

conjugate base
Perchlorate ion
Iodide ion
Bromide ion
Chloride ion
Hydrogen sulfate ion
Nitrate ion
Water
Sulfate ion
Nitrite ion
Acetate ion
Hydrogen carbonate ion
Ammonia
Carbonate ion
Hydroxide ion
Methoxide ion
Amide ion

ClO4
I
Br
Cl
HSO4
NO3
H2 O
SO42
NO2
CH3 COO
HCO3
NH3
CO32
OH
CH3 O
NH2

3 Self-Ionization of Water and the pH Scale

Self-Ionization and Ion Product of Water
In the self-ionization (or autoionization) of water, for each H2 O molecule
that acts as an acid, another H2 O molecule acts as a base, and hydronium
(H3 O+ ) and hydroxide (OH ) ions are formed.
H2 O + H2 O H3 O+ + OH

K = [H3 O+ ][OH ]

At 25 C in pure water
[H3 O+ ] = [OH ] = 1.0 107 M
Thus the ion product of water Kw at 25 C is
Kw = [H3 O+ ][OH ] = 1.0 1014

pH and pOH
The potential of the hydrogen ion pH was defined in 1909 as the negative
of the logarithm of [H+ ] (or of [H3 O+ ]).
pH = -log[H3 O+ ]
The quantity pOH is defined in a similar way
pOH = -log[OH ]
Starting from the equation of Kw we can derive
pKw = pH + pOH = 14.00
Acidic and Basic Solutions
pH < 7.0
pH = 7.0
pH > 7.0

acidic
neutral
basic

[H3 O+ ] > [OH ]

[H3 O+ ] = [OH ]
[H3 O+ ] < [OH ]

14

1 M NaOH (pH 14.0)

13

bleach

12

soapy water

11

household ammonia (pH 11.9)

10

milk of magnesia(pH 10.5)

baking soda (0.1 M pH 8.4)

sea water (pH 7.0-8.5)

blood (pH 7.4)
distilled water (pH 7.0)
milk (pH 6.4)
urine (pH 5-7)

black coffee

tomato juice

orange juice
vinegar (pH 2.4-3.4)
lemon juice

2
1

gastric juices (pH 1.0-2.0)

1 M HCl(pH 0)

en.wikipedia.org/wiki/File:PH Scale.svg

Relating [H3 O+ ], [OH ], pH and pOH

PHMB 10e, Example 16-2, pp 705-706
In a laboratory experiment, students measured the pH of samples of
rainwater and household ammonia. Determine
1. [H3 O+ ] in rainwater, with pH measured at 4.35
2. [OH ] in the ammonia, with pH measured at 11.28.
ANSWERS:
1. [H3 O+ ] = 4.5 105 M
2. [OH ] = 1.9 103 M

4 Strong Acids and Strong Bases

Strong Acids and Strong Bases
For strong acids (bases), the ionization essentially goes to completion, and
[H3 O+ ] ([OH ]) is the concentration of the strong acid (base).
HCl + H2 O Cl + H3 O+

[H3 O+ ] ([OH ]) is the concentration of the strong acid (base) unless the
solution is extremely dilute.
The common strong acids and strong bases
acids: HCl, HBr, HI, HClO4 , HNO3 , H2 SO4 (first ionization only)
bases: LiOH, NaOH, KOH, RbOH, CsOH, Mg(OH)2 , Ca(OH)2 , Sr(OH)2 ,
Ba(OH)2 .
Calculating Ion Concentrations
PHMB 10e, Example 16-3, pp 706-707
Calculate [H3 O+ ], [Cl ], and [OH ] in 0.015 M HCl(aq).
ANSWERS: [H3 O+ ] = 0.015 M, [Cl ] = 0.015 M, and [OH ] = 6.7 1013
M.
Calculating the pH of a Solution
PHMB 10e, Example 16-4, pp 707-708
Calcium hydroxide (slaked lime), Ca(OH)2 , is the cheapest strong base
available. It is generally used for industrial operations in which a high
concentration of OH is not required. Ca(OH)2 (s) is soluble in water only to
the extent of 0.16 g Ca(OH)2 /100.0 mL solution at 25 C. What is the pH of
saturated Ca(OH)2 (aq) at 25 C?
ANSWER: pH = 12.64

5 Weak Acids and Weak Bases

Measurement of pH
Two ways of showing that ionization has occurred in an aqueous solution
of an acid:
1. by the color of an acid-base indicator
2. the response of a pH meter
0.1 M HCl and 0.1 M CH3 COOH in thymol blue indicator

pH < 1.2 < pH < 2.8 < pH

red
orange
yellow
pK
pK is a shorthand designation for an ionization constant pK = -log K.
pK values are useful when comparing the relative strengths of acids (pKa )
and bases (pKb ).
this equation is introduced so that very large and very small numbers
can be more easily handled.
The ionization of acetic acid
CH3 COOH(aq) H3 O+ + CH3 COO
Ka =

[H3 O+ ][CH3 COO ]

= 1.8 105
[CH3 COOH]

pKa = log Ka = 4.74

Ionization constants must be determined by experiment.

5

Identifying Weak Acids and Bases

Most acids are weak acids. A large number of weak acids have the carboxyl
group, -COOH.
Many weak bases are derived from ammonia, and these are called amines
(RNH2 , RR NH). For example, the ionization of methylamine is
CH3 NH2 + H2 O CH3 NH3+ + OH
Kb =

[CH3 NH3+ ][OH ]

= 4.2 104
[CH3 NH2 ]

6 Polyprotic Acids
Polyprotic Acids
A polyportic acid is capable of losing more than a single proton per
molecule in acid-base reactions. Protons are lost in a stepwise fashion, with
the first proton being the most readily lost.
K a1 > K a2 > K a3

Phosphoric Acid
Phosphoric acid, H3 PO4 , is a triprotic acid.
H3 PO4 + H2 O
H2 PO4 + H2 O
HPO42 + H2 O

H3 O+ + H2 PO4
H3 O+ + HPO42
H3 O+ + PO43

Ka1 = 7.1 103

Ka2 = 6.3 108
Ka3 = 4.2 1013

Some observations
Ka1 Ka2 Ka3 , thus essentially all the H3 O+ is produced in the first
step.
We can assume that [H2 PO4 ] = [H3 O+ ]
Thus [HPO42 ] Ka2
Sulfuric Acid
Sulfuric acid differs from most polyprotic acids since it is a strong acid in
its first ionization and a weak acid in its second.
H2 SO4 + H2 O H3 O+ + HSO4 Ka1 = very large
HSO4 + H2 O H3 O+ + SO42
Ka2 = 1.1 102

7 Lewis Acids and Bases

Lewis Acids and Bases
A Lewis acid is a species (atom, ion or molecule) that is an electron pair
acceptor. A Lewis base is species that is an electron pair donor.
A reaction between a Lewis acid (A) and a Lewis base (B:) results in the
formation of a covalent bond between them.
The product of a Lewis acid-base reaction is called an adduct (or addition
compound).
B: + A B-A
Lewis acids are species with vacant orbitals that can accommodate electron
pairs. Lewis bases are species that have lone-pair electrons available for
sharing.
6

Lewis Acids and Bases: Examples

The OH ion and NH3 , a Brnsted-Lowry bases, are also a Lewis bases.
HCl is not a Lewis acid, however H+ is a Lewis acid.
An example of octet completion is the reaction of BF3 and NH3 .

commons.wikimedia.org/wiki/File:NH3-BF3-adduct-bond-lengthening-2D-no-charges.png

The reaction of lime (CaO) and sulfur dioxide SO2 to produce calcium sulfite
CaSO3 .

en.wikipedia.org/wiki/File:Calcium sulfite.png

Formation of Complex Ions

A complex is a polyatomic cation, anion, or neutral molecule in which
groups (molecules or ions) called ligands are bonded to a central metal atom
or ion. A complex ion is a complex having a net electrical charge.
Hydrated metal ions form in aqueous solution because the water acts as
a Lewis base and the metal ions as a Lewis acid.
Hydrated Metal Ions: An Example
When anhydrous AlCl3 is added to water, heat is evolved in the formation
of the hydrated metal ion [Al(H2 O)6 ]3+ (aq).
The interaction between the metal ion and H2 O is so strong that when
the salt is crystallized from the solution, the water molecules crystallize along
with the metal ion, forming the hydrated salt AlCl3 6 H2 O.

Hydrated Metal Ion as Brnsted Acids

In aqueous solution, the hydrated metal ions can act as Brnsted acids
[Al(H2 O)6 ]3+ + H2 O [Al(OH)(H2 O)5 ]2+ + H3 O+

Identifying Lewis Acids and Bases

PHMB 10e, Example 16-15, p 735
According to the Lewis theory, each of the following is an acid-base
reaction. Which species is the acid and which is the base?
1. BF3 + F BF4
2. OH (aq) + CO2 (aq) HCO3 (aq)
ANSWERS:
1. BF3 is the acid and F is the base
2. CO2 is the acid and OH is the base