TABLE OF C ONTENTS

T HE A RRHENIUS T HEORY

C HEM 16 G ENERAL C HEMISTRY 1

B RNSTED -L OWRY T HEORY OF A CIDS

AND

B ASES

12 A CIDS AND B ASES

S ELF -I ONIZATION OF WATER AND THE P H S CALE

Dr. Gil C. Claudio

S TRONG A CIDS

AND

S TRONG B ASES

University of the Philippines, Diliman

W EAK A CIDS

AND

W EAK B ASES

First Semester 2014-2015

P OLYPROTIC A CIDS
L EWIS A CIDS

R EFERENCES

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.

AND

B ASES

A RRHENIUS D EFINITION OF A CIDS AND B ASES

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.

A RRHENIUS T HEORY

B RNSTED -L OWRY T HEORY OF A CIDS AND B ASES

When the acid HCl dissolves in water

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

According to the Brnsted-Lowry theory, an acid is a proton

donor and a base is a proton acceptor.
NH3
base

When the base NaOH dissolves in water

NaOH(aq) Na+ (aq) + OH (aq)

NH3
base(1)

H+ (aq) + OH (aq) H2 O(l)

Limitation: cannot describe some weak bases, e.g., ammonia

NH3

I ONIZATION C ONSTANTS

H2 O
acid

NH4+
acid

OH
base

The product is also an acid-base reaction, thus

The net ionic ionic equation of the neutralization reaction is

The essential idea of the Arrhenius theory: A neutralization

reaction involves the combination of hydrogen ions and hydroxide
ions to form water.

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.

H YDRONIUM I ON

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 3 O +

aCH3 COOH aH2 O

[CH3 COO ][H3 O+ ]

= 1.8 105
[CH3 COOH]

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 A CIDS AND B ASES AND T HEIR C ONJUGATES

D IRECTION OF THE R EACTION

PHMB 10 E , E XAMPLE 16-1, P 701

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.
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

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.

R ELATIVE S TRENGTHS OF S OME A CIDS AND B ASES

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

S ELF -I ONIZATION AND I ON P RODUCT 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

P H AND P OH

A CIDIC AND B ASIC S OLUTIONS

The potential of the hydrogen ion pH was defined in 1909 as the

negative of the logarithm of [H+ ] (or of [H3 O+ ]).

pOH = -log[OH ]
Starting from the equation of Kw we can derive

1 M NaOH (pH 14.0)

bleach

12
11

pH = -log[H3 O+ ]
The quantity pOH is defined in a similar way

14
13

pH < 7.0
pH = 7.0
pH > 7.0

acidic
neutral
basic

[H3 O+ ] > [OH ]

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

pKw = pH + pOH = 14.00

soapy water
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

3
2

orange juice
vinegar (pH 2.4-3.4)
lemon juice

gastric juices (pH 1.0-2.0)

1 M HCl(pH 0)

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

R ELATING [H 3 O + ], [OH ], P H AND P OH

S TRONG A CIDS AND S TRONG B ASES

PHMB 10 E , E XAMPLE 16-2, PP 705-706

For strong acids (bases), the ionization essentially goes to

completion, and [H3 O+ ] ([OH ]) is the concentration of the strong
acid (base).
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.

HCl + H2 O Cl + H3 O+
[H3 O+ ] ([OH ]) is the concentration of the strong acid (base)
unless the solution is extremely dilute.

ANSWERS:
1. [H3 O+ ] = 4.5 105 M
2. [OH ] = 1.9 103 M

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 .

C ALCULATING I ON C ONCENTRATIONS

C ALCULATING THE P H OF A S OLUTION

PHMB 10 E , E XAMPLE 16-3, PP 706-707

PHMB 10 E , E XAMPLE 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?

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.

ANSWER: pH = 12.64

M EASUREMENT OF P H

PK
pK is a shorthand designation for an ionization constant pK =
-log K .

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 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.

I DENTIFYING W EAK A CIDS AND B ASES

P OLYPROTIC A CIDS

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

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 a 2 > K a3

CH3 NH2 + H2 O CH3 NH3+ + OH

[CH3 NH3+ ][OH ]

Kb =
= 4.2 104
[CH3 NH2 ]

P HOSPHORIC A CID

S ULFURIC A CID

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 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
HSO4 + H2 O

H3 O+ + HSO4
H3 O+ + SO42

Ka1 = very large

Ka2 = 1.1 102

L EWIS A CIDS AND B ASES

L EWIS A CIDS AND B ASES : E XAMPLES

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.

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

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 .

Lewis acids are species with vacant orbitals that can accommodate
electron pairs. Lewis bases are species that have lone-pair electrons
available for sharing.
en.wikipedia.org/wiki/File:Calcium sulfite.png

F ORMATION OF C OMPLEX I ONS

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.

H YDRATED M ETAL I ONS : A N E XAMPLE

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.

H YDRATED M ETAL I ON AS B RNSTED A CIDS

I DENTIFYING L EWIS A CIDS AND B ASES

PHMB 10 E , E XAMPLE 16-15, P 735

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+

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