ACID-BASE CHEMISTRY

Effendy
Jurusan Kimia, FMIPA
Universitas Negeri Malang (UM)
In 1777 Antoine Lavoisier, a French
chemist, proposed that:
“All acids contain a common element:
oxygen”.
The word oxygen is derived from a
Greek phrase meaning “acid former”.
This name is used because all of
known acids before 1877 always
contain oxygen.
At that time it was known that
all acids have certain
properties related to the litmus
paper.
All acids change the color of
blue litmus paper red.
 In 1810 Sir Humphrey Davy (1778–
1829), an English Chemist, showed that
muriatic acid (hydrochloric acid) has
properties similar to the properties of
acids which contain oxygen.
Davy’s studies suggested that the
common element in acids is hydrogen,
not oxygen.
The relation between acidic behavior
and the presence of hydrogen in a
compound was described in 1887 by the
Swedish chemist Svante Arrhenius.
Arrhenius theory of acid-base
In 1887 Arrhenius (1859–1927) proposed
that acids are substances which produce
hydrogen ions (H+) in water.
Example:
in hydrochloric acid the hydrogen
chloride molecules are ionized to produce
hydrogen ions and chloride ions.
HCl(aq) → H+(aq) + Clˉ(aq)
Sulfuric acid and nitric acid also ionize in
aqueous solutions to produce hydrogen
ions.

H2SO4(aq) → 2H+(aq) + SO42ˉ(aq)

HNO3(aq) → H+(aq) + NO3ˉ(aq)

hydrochloric acid, sulfuric
acid, and nitric acid ionize
completely in the aqueous
solutions.
All of them are strong acids.
Ionization equations of strong
acids use single arrow.
 In many acids such as acetic and
formic acids only small proportion of
molecules are ionized in aqueous
solution.
These acids are called weak acids.
The equation for the ionization of weak
acids uses double arrows such as
shown below.
CH3COOH(aq) H+(aq) + CH3COO-(aq)
HCOOH(aq) H+(aq) + HCOO-(aq)
The hydrogen ions produced in aqueous
solution are sometimes represented as
H+, H+(aq), or H3O+(aq).

These different representations are used

partly because each might be useful in
certain circumstances and partly because
of doubt surrounding the nature of
protons in aqueous solution.
Besides H3O+, there is some evidence for the
formation of other species such as H5O2+ and
H9O4+ in the aqueous solution of acids.
+ +
H H H H

O :O O: O
H H H H
:

:
H H
H
O:
+
H5O2
H

:
O
H
H

H9O4+
H+ is very small because they it doesn’t
have electron.
It has positive charge.
Because the charge of H+ is located in a
very small volume, the attraction
between H+ and water molecule is
greater than for other ions.
In aqueous solution, H+ is more likely to
exist as hydronium ion (H3O+).
+
+
:

:
H + :O H O
H
H
H
H
Arrhenius proposed that a base is a
substance which produces hydroxide ion
(OHˉ) in aqueous solution.
Sodium hydroxide and potassium
hydroxide, ionic solids, are dissociated in
water to produce hydroxide ions.

NaOH(s) → Na+(aq) + OHˉ(aq)

KOH(s) → K+(aq) + OHˉ(aq)

Sodium hydroxide and potassium
hydroxide are strong bases which
dissociate completely in aqueous
solutions.
A single arrow is used to
represent their dissociation in
aqueous solution.
Ammonia (NH3) is a weak base.
Although it doesn’t contain hydroxide ion, in
aqueous solution it reacts with water
molecule to give hydroxide ion according to
the equation.
NH3(aq) + H2O(l) NH4+(aq) + OH-(aq)

The above equation indicates an aqueous

solution of ammonia consists mainly of
dissolved NH3 molecules and only relatively
small quantities (about 1%) of NH4+ and OHˉ
are present.
 Some common Arrhenius acids and bases

Acid Base

Strong acid HClO4 NaOH Strong base

H2SO4 KOH
HI Ba(OH)2
HBr Ca(OH)2
HCl
HNO3

H3PO4
HF
Weak acid CH3COOH NH3 Weak base
Degree of ionization
The fraction of acid or base ionized in
aqueous solution is expressed in degree of
ionization.
The symbol of degree of ionization is
(alpha) with its value in the range of zero
to one.
The higher the value of  the stronger the
acid or base.
The value of  is one for strong acids and
strong bases, and close to zero for weak
acids and bases.
Microscopic representation of
Arrhenius acid and base
Species present in acid and base may be
represented using microscopic
representation.
In the context of Arrhenius acid-base
theory, water molecules, (aq), bond to HA,
H+, and Aˉ may not be presented.
 = HA

= H+

=A

Microscopic representation of aqueous

solution of HA with = 0.2. Water molecules
are omitted for clarity.
 The following pictures represent aqueous
solution of three acids, HX, HY, and HZ, with
water molecules omitted for clarity. Which of
the three is the strongest acid, and which is the
weakest? Give the reasons of your answers.

HX HY HZ
Neutralization
In the Arrhenius theory, hydrogen ion (H+)
is responsible for the properties of acid,
and hydroxide ion (OHˉ) for the properties
of bases.
When an acid and a base are mixed in the
right stoichiometric proportion, both acidic
and basic properties disappear because of
neutralization reaction which produce salt
and water.
 If HA is the formula of an acid and
MOH is the formula of a base, the
neutralization reaction is as follows.

HA(aq) + MOH(aq) MA(aq) + H2O(l)

Acid Base A salt Water
Or

H+(aq) + OHˉ(aq) → H2O(l)

 Based on Arrhenius theory, in
neutralization reaction between
an acid and a base,
the acidic properties of H+ and
the basic properties of OHˉ are
neutralized when they combine
to form water molecule.
Brönsted-Lowry theory of acid-base
Arrhenius theory of acid and base
explained acid-base reactions in aqueous
solution quite well, but it did not explain
the reactions in the absence of water.
For example, Arrhenius would suggest
that in aqueous solutions, HCl and NH3
exist as ionic solutions of hydrochloric
acid and ammonium hydroxide (NH4OH).
The reaction of them gives the salt
ammonium chloride (NH4Cl) and water.
H+(aq) + Cl-(aq)+ NH4+(aq) + OH-(aq)

Hydrochloric Ammonium
acid hydroxide

NH4+(aq) + Cl-(aq) + H2O(l)

Ammonium Water
chloride
Dry gaseous HCl and NH3 also reacts to
give NH4Cl.
NH3(g) + HCl(g) → NH4Cl(s)
The formation of NH4Cl in gaseous state
cannot be interpreted based on Arrhenius
theory of acid and base because gaseous
HCl does not dissociate into H+ and Clˉ,
and NH3 does not furnish OHˉ.
Hence, in the absence of water, H+ and
OHˉ are not present to react as they are in
aqueous solution.
This limitation of the Arrhenius
acid-base theory was resolved
independently by Johannes N.
Brönsted, a Danish chemist, and
Thomas M. Lowry, an English
chemist.
The Brönsted-Lowry acid-base
theory states that an acid-base
reaction involves proton transfer.
The acid is the proton donor and
the base is the proton acceptor.
The Brönsted-Lowry acid-base
theory emphasizes the
interdependence of an acid and a
base; one is defined in term of
the other
 H _
+

: :
+ :Cl :
: :

H :Cl : +

:
O H O H
:

:
H Chloride ion

Acid Base H

Hydronium ion
Formation of ammonium chloride from
gaseous HCl and NH3 can be presented
as follows.

NH3 + HCl NH4+ + Cl

Base Acid
 H H +

: :
Cl :

: :
H N: + H H N H :Cl :

H Acid H
Ammonium chloride
Base
NH3 in water is a base because it accepts proton (H+) from
water molecule; water molecule is an acid because it
donates proton to NH3.

NH3 + H2O NH4+ + OH

Base Acid
Hydroxide ion
Ammonium ion

H +
H
H

H N: + O

: :
:

: H N H + :O H
H
Hydroxide ion
H Acid H
Base Ammonium ion
 H _
+

: :
: : + :Cl :
H :Cl : +

:
O H O H

:
:
H Chloride ion

Acid H
Base
Hydronium ion

NH3 + H2O NH4+ + OH

Base Acid
Hydroxide ion
Ammonium ion
Species such as water molecule which can donate
or accept proton indicates amphiprotic behavior.
Conjugate acid-base pairs

In the Brönsted-Lowry theory, an acid

which has donated a proton has the
potential to react as a base.
Similarly, a base, after it has received a
proton, has the potential to react as an
acid.
 The conjugate acid is formed
when a base accepts a proton.

The conjugate base is formed

when an acid loses its proton.
In the reaction:
CH3COOH(aq) + OH (aq) CH3COO (aq) + H2O(l)
Acid Base Conjugate Conjugate
base acid

H2O/OHˉ pair is described as a conjugate

acid-base pair, while CH3COOˉ/ CH3COOH
as a conjugate base-acid pair.
 Conjugate base of a strong acid is a
weak base because this conjugate base
has only a negligible tendency to
combine with a proton.
Inversely, conjugate base of a weak
base is a strong acid because this
conjugate base has a very high
tendency to combine with a proton.
 HCl + H2O H3O+ + Cl
Acid Base Conjugate Conjugate
(Strong) (Weak) acid base
(Strong) (Weak)

CH3COOH + H2O H3O+ + CH3COO-

Acid Base Conjugate Conjugate
(Weak) (Weak) acid base
(Strong) (Strong)
Predicting reactions between
acids and bases
According to Brönsted-Lowry acid-base
theory, acid-base reactions are
essentially reactions involving the
competition of proton.
Generally, strong acids will react with
strong bases to form weaker conjugate
base and weaker conjugate acid.
HCl(aq) + Fˉ(aq) → HF(aq) + Clˉ(aq)
HCl is stronger acid than HF;
Cl‾ is weaker base than F‾

HF(aq) + NH3(aq) → NH4+(aq) + Fˉ(aq)

HF is stronger acid than NH4+;
F‾ is weaker base than NH3
NH4+(aq) + H2O(l) H3O+(aq) + NH3(aq)

H3O+ is stronger acid than NH4+;

H2O is weaker base than NH3
 Microscopic representation of acid and base
solutions based on Brönsted-Lowry acid-base theory

= H3O+

= Cl

Microscopic representation of aqueous solution of HCl

based on Brönsted-Lowry acid-base theory.
Water molecules are omitted for clarity.
 = HA

= H3O+

=A

The microscopic representation of aqueous solution

of weak acid HA with degree of ionization of 0.1.
Water molecules are omitted for clarity.
Lewis theory of acid-base
A Lewis acid is an electron-pair acceptor,
while a Lewis base is an electron-pair
donor.
The Lewis acid-base theory also
emphasizes the interdependence of an
acid and a base; one is defined in term of
the other.
 :

:
:F : H :F : H

: :
B + :N H :F B N H

:F : :F :
H :F : H
:

:
Lewis acid Lewis base Lewis acid-base adduct
 Based on Lewis acid-base theory, formation of
NH4Cl from gaseous NH3 and HCl is explained as
follows.

H H +

: :
Cl :

: :
H N: + H H N H :Cl :

Lewis acid

H H

Lewis base Ammonium chloride

The properties of acids
Aqueous solution of acids such as nitric,
hydrochloric, acetic, and sulfuric acids
exhibit a range of common properties.
The common properties of aqueous
solution of acids are as follows:
(1) turn blue litmus red.
(2) conduct an electric current.
(3) taste sour.
(4) react with most metals to give a salt and
hydrogen gas.
Metal + acid → salt + H2
(5) react with carbonate salt and hydrogen
carbonate salts to give a salt, water and
carbon dioxide gas.
Acid + carbonate salt →
salt + H2O + CO2
Acid + hydrogen carbonate salt →
salt + H2O + CO2
(6) react with metal oxides to give a salt
and water.
Acid + metal oxide → salt + H2O
(7) react with aqueous solution of metal
hydroxide to give a salt and water.
Acid + metal hydroxide → salt + H2O
The properties of bases
Aqueous solution of bases which are
mostly metal hydroxides exhibits a range
of common properties. The common
properties of aqueous solution of metal
hydroxides are as follows:
(1) turn red litmus blue.
(2) conduct an electric current.
(3) taste bitter.
(4) react with acid to produce a salt and
water.
(5) react with amphoteric metals such as
aluminum, chromium, and zinc to produce a
coordination compound and hydrogen gas.
Example:
2NaOH(aq) + 2Al(s) + 6H2O(l) →
2Na[Al(OH)4](aq) + 3H2(g)
or
2OHˉ(aq) + 2Al(s) + 6H2O(l) →
2[Al(OH)4]ˉ(aq) + 3H2(g)
Metals exhibit amphoteric properties if they can
react both with acids and bases.
The term amphoteric comes from Greek word
amphoteros, meaning “in both ways”.
(6) strong bases dissolve amphoteric
metal hydroxides such as Al(OH)3,
Cr(OH)3, and Zn(OH)2 to produce a
coordination compound or complex
compound.
Example:
NaOH(aq) + Al(OH)3(s) →
Na[Al(OH)4](aq)
or
OHˉ(aq) + Al(OH)3(s) → [Al(OH)4]ˉ(aq)
Amphoteric bases behave as base when
they react with acids, but behave as acid
when react with strong base.
The basic property of aluminum
hydroxide is shown in the following
reaction.

3HNO3(aq) + Al(OH)3(s) →
Al(NO3)3 (aq) + 3H2O(l)
Formulas of complex ion of amphoteric metals aluminum,
chromium,and zinc, or their bases obtained from their
reaction with strong bases.
Metal Base Complex Name of complex ion
ion
Al Al(OH)3 [Al(OH)4]ˉ Tetrahydroxoaluminate(III) ion
Cr Cr(OH)3 [Cr(OH)4]ˉ Tetrahydroxochromate(III) ion
Zn Zn(OH)2 [Zn(OH)4]2ˉ Tetrahydroxozincate(II) ion
Relation of acid-base strength with their
electrolyte property
Aqueous solutions of strong acids and
bases behave as strong electrolytes.
Aqueous solutions of weak acids and
bases behave as weak electrolytes.
Summary
(1) Antoine Lavoisier proposed that all acids
contain a common element: oxygen.
(2) Sir Humphrey Davy showed the common
element in acids is hydrogen, not oxygen.
(3) Based on Arrhenius theory, acids are
substances which produce hydrogen ions (H+)
in water; bases are substances which
produce hydroxide ion (OHˉ) in aqueous
solution.
(4) Based on Arrhenius theory, reaction of an
acid and a base in the right stoichiometric
proportion produces salt and water. This
reaction is called neutralization reaction. In
this reaction acidic properties of acid and basic
properties of base disappear.
(5) According to Brönsted-Lowry theory an
acid is the proton donor and the base is
proton acceptor.
(6) Lewis proposed that acid is an electron-pair
acceptor, while a Lewis base is an electron-
pair donor.
(7) The strength of acids and bases are directly
related to their electrolyte property. Aqueous
solutions of strong acids and bases behave
as strong electrolytes. Aqueous solutions of
weak acids and bases behave as weak
electrolytes