CONTENTS

• Arrhenius concept of acids and bases

• Bronsted Lowry concept
• Lewis concept
• Solvent system concept
• Lux-Flood concept
• Pearson concept
• INTRODUCTION
An acid-base reaction is a chemical
reaction that occurs between an acid
and a base. Several concepts that
provide alternative definitions for the
reaction mechanisms involved and their
application in solving related problems
exist.
• Despite several differences in definitions,
their importance becomes apparent as
different methods of analysis when applied
to acid-base reactions for gaseous or
liquid species, or when acid or base
character may be somewhat less
apparent.
• The first of these scientific concepts of
acids and bases was provided by the
French chemist Antoine Lavoisier, circa
1776.
• Lavoisier's oxygen theory of acids
Since Lavoisier's knowledge of strong
acids was mainly restricted to oxoacids,
such as HNO3 and H2SO4, which tend to
contain central atoms in high oxidation
states surrounded by oxygen, and since
he was not aware of the true composition
of the hydrohalic acids (HF, HCl, HBr, and
HI),
he defined acids in terms of their
containing oxygen, which in fact he named
from Greek words meaning "acid
• The Lavoisier definition was held as
absolute truth for over 30 years, until the
1810 article and subsequent lectures by
Sir Humphry Davy in which he proved the
lack of oxygen in H2S, H2Te, and the
hydrohalic acids.
• However, Davy failed to develop a new
theory, concluding that "acidity does not
depend upon any particular elementary
substance, but upon peculiar arrangement
of various substances
• Liebig's hydrogen theory of acids
• This definition was proposed by Justus
von Liebig circa 1838, based on his
extensive works on the chemical
composition of organic acids. This finished
the doctrinal shift from oxygen-based
acids to hydrogen-based acids, started by
Davy. According to Liebig, an acid is a
hydrogen-containing substance in which
the hydrogen could be replaced by a
metal.
• Arrhenius definition
The Arrhenius definition of acid-base
reactions is a development of hydrogen
theory of acids, devised by Svante
Arrhenius,
which was used to provide a modern
definition of acids and bases that followed
from his work with Friedrich Wilhelm
Ostwald in establishing the presence of
ions in aqueous solution in 1884, and led
to Arrhenius receiving the Nobel Prize in
Chemistry in 1903 "
• The universal aqueous acid-base
definition of the Arrhenius concept is
described as the formation of water from
hydrogen and hydroxide ions, or hydrogen
ions and hydroxide ions from the
dissociation of an acid and base in
aqueous solution:
• H+(aq) + OH−(aq)------ H2O

• This leads to the definition that in

Arrhenius acid-base reactions, a salt and
water is formed from the reaction between
an acid and a base. In other words, this is
a neutralization reaction.
• acid+ + base− → salt + water
The positive ion from a base forms a salt
with the negative ion from an acid. For
example, two moles of the base sodium
hydroxide (NaOH) can combine with one
mole of sulfuric acid (H2SO4) to form two
moles of water and one mole of sodium
sulfate.

• 2 NaOH + H2SO4 → 2 H2O + Na2SO4

• Brønsted-Lowry definition

The Brønsted-Lowry definition,

formulated in 1923, independently by
Johannes Nicolaus Brønsted in Denmark
and Martin Lowry in England , is based
upon the idea of protonation of bases
through the de-protonation of acids—that
is, the ability of acids to "donate" hydrogen
ions (H+) or protons to bases, which
"accept" them.
• Unlike the previous definitions, the Brønsted-
Lowry definition does not refer to the
formation of salt and solvent, but instead to
the formation of conjugate acids and
conjugate bases, produced by the transfer of
a proton from the acid to the base
• In this approach, acids and bases are
fundamentally different in behavior from salts,
which are seen as electrolytes, subject to the
theories of Debye, Onsager, and others. An
acid and a base react not to produce a salt
and a solvent, but to form a new acid and a
new base. The concept of neutralization is
thus absent.[
• For example, the removal of H+ from
hydrochloric acid (HCl) produces the chloride
ion (Cl−), the conjugate base of the acid:
• HCl → H+ + Cl− The addition of H+ to the
hydroxide ion (OH−), a base, produces water
(H2O), its conjugate acid:
• H+ + OH− → H2O
Although Brønsted-Lowry acid-base behavior
is formally independent of any solvent, it
encompasses Arrhenius and solvent system
definitions in an unenforced way. For
example, protonation of ammonia, a base,
gives ammonium ion, its conjugate acid:
• Lewis definition

• The hydrogen requirement of Arrhenius

and Brønsted-Lowry was removed by the
Lewis definition of acid-base reactions,
devised by Gilbert N. Lewis in 1923], in the
same year as Brønsted-Lowry, In this
system, an acid does not exchange atoms
with a base, but combines with it. For
example, consider this classical aqueous
acid-base reaction:
• HCl (aq) + NaOH (aq) → H2O (l) + NaCl
• By treating acid-base reactions in terms of
electron pairs instead of specific
substances, the Lewis definition can be
applied to reactions that do not fall under
other definitions of acid-base reactions.
For example, a silver cation behaves as
an acid with respect to ammonia, which
behaves as a base, in the following
reaction:
• Ag+ + 2 :NH3 → [H3N:Ag:NH3]+ The result
of this reaction is the formation of an
ammonia-silver adduct.
• Lux-Flood definition
• This acid-base theory was a revival of oxygen
theory of acids and bases, proposed by
German chemist Hermann Lux in 1939,
further improved by Håkon Flood circa 1947
and is still used in modern geochemistry and
electrochemistry of molten salts. This
definition describes an acid as an oxide ion
(O2−) acceptor and a base as an oxide ion
donor.
• For example:
MgO (base) + CO2 (acid) → MgCO3
CaO (base) + SiO2 (acid) → CaSiO3
• Pearson definition
In 1963 Ralph Pearson proposed an
advanced qualitative concept known as Hard
Soft Acid Base principle, later made
quantitative with help of Robert Parr in 1984.
'Hard' applies to species that are small, have
high charge states, and are weakly
polarizable. 'Soft' applies to species that are
large, have low charge states and are
strongly polarizable. Acids and bases
interact, and the most stable interactions are
hard-hard and soft-soft. This theory has
found use in organic and inorganic chemistry.
 RELATIVE
STRENGTH OF
ACID AND BASES
 CONTENTS
• (i) Strength of hydro acids
• (ii) Strength of oxo acids
• (iii) Acid strength of hydrated cations
• (iv) Strength of organic acids
• (v) Effects of substituents on the strength
of Lewis acids and Lewis bases
• (vi) Advantages of Bronsted definition
 RELATIVE STRENGTH OF
ACIDS & BASES
• Our use of the symbols HA and A- for a conjugate
acid-base pair does not mean that all acids are
neutral molecules or that all bases are negative
ions. It signifies only that the acid contains an H+ ion
that isn't present in the conjugate base. Bronsted
acids or bases can be neutral molecules, positive
ions, or negative ions. Typical Bronsted Acids and
Their Conjugate Bases
• Acid Base Acid Base Acid Base
H3O+ H2O H2O OH- OH- O2-
• A compound can be both a Bronsted acid and a
Bronsted base. Water is the perfect example of this
behavior because it simultaneously acts as an acid
and a base when it forms the H3O+ and OH- ions.
• The Acid Dissociation Equilibrium Constant,
Ka
• The relative strengths of acids is often described
in terms of an acid-dissociation equilibrium
constant, Ka. To understand the nature of this
equilibrium constant, let's assume that the
reaction between an acid and water can be
represented by the following generic equation.
• HA(aq) + H2O(l) H3O+(aq) + A-(aq)
• In other words, some of the HA molecules react
to form H3O+ and A- ions
• The value of Ka for acid is calculated from the
following equation.
• When a strong acid dissolves in water, the acid
reacts extensively with water to form H3O+ and
A- ions. (Only a small residual concentration of
the HA molecules remains in solution.) The
product of the concentrations of the H3O+ and A-
ions is therefore much larger than the
concentration of the HA molecules, so Ka for a
strong acid is greater than 1.
• Example: Hydrochloric acid has a Ka of roughly
1 x 106.
• Weak acids, on the other hand, react only
slightly with water. The product of the
concentrations of the H3O+ and A- ions is
therefore smaller than the concentration of
the residual HA molecules. As a result, Ka
for a weak acid is less than 1.
• Example: Acetic acid has a Ka of only 1.8
x 10-5.
• Ka can therefore be used to distinguish
between strong acids and weak acids.
• Strong acids: Ka > 1 Weak acids: Ka < 1
• Comparing Relative Strengths of Pairs of Acids and
Bases
• The value of Ka for an acid can be used to decide whether it is
a strong acid or a weak acid, in an absolute sense. It can also
be used l to compare the relative strengths of a pair of acids.
• Example: Consider HCl and the H3O+ ion.
• HCl Ka = 1 x 106 H3O+ Ka = 55
• These Ka values suggest that both are strong acids, but HCl is
a stronger acid than the H3O+ ion.
• A high proportion of the HCl molecules in an aqueous solution
reacts with water to form H3O+ and Cl- ions. The Bronsted
theory suggests that every acid-base reaction converts an
acid into its conjugate base and a base into its conjugate acid.
• There are two acids and two bases in this reaction. The
stronger acid, however, is on the left side of the equation.
• HCl(g) + H2O(l) H3O+(aq) + Cl-(aq) stronger
acid weaker
acid
• It isn't surprising that 99.996% of the HCl molecules in
a 6 M solution react with water to give H3O+ ions and
Cl- ions. The stronger of a pair of acids should react
with the stronger of a pair of bases to form a weaker
acid and a weaker base.
• Let's look at the relative strengths of acetic acid and
the H3O+ ion.
• CH3CO2H Ka = 1.8 x 10-5 H3O+ Ka = 55
• The values of Ka for these acids suggest that acetic
acid is a much weaker acid than the H3O+ ion, which
explains why acetic acid is a weak acid in water. Once
again, the reaction between the acid and water must
convert the acid into its conjugate base and the base
into its conjugate acid.
 Now the question is how the acidity and basicity
depend upon the nature of compound , its
molecular structure or position in the periodic
table, which are discussed as below:-
1. Strength of Hydro acids.
(a) Acid strength of binary acids increases on
going from left to right across a period of the
periodic table i.e.
CH4 < NH3 < H2O < HF
PH3<H2S < HCl
This trend can be explained on the basis of
increasing electronegativity. Thus the release of
hydrogen ion becomes more easy.
(b) The relative strength of the hydro acids
of a group increases as we go down the
group i.e.
HF < HCl < HBr < HI
H2O < H2S < H2Se < H2Te
Because the acidic strength depends upon
two factors electronegativity and size of
the central atom. Here the effect of
increase in size is more than the effect of
electronegativity change. Therefore HI can
easily release H+ and HF can lose H+ with
difficulty.
The strength of hydro acids can also be explained
on the basis of relative basic strength of their
conjugate bases.

HX H+ + X -
The conjugate bases of HF, HCl, HBr and
HI are F- , Cl- Br- and I- respectively. The
basic character decreases as F- > Cl- >
Br- I- due to the increase in size of the ion.
Thus a weak conjugate base (I-) has the
strongest acid (HI) and a strong conjugate
base (F-) has the weakest acid (HF) .
2. Strength of Oxo acids
Consider an oxoacid
Z–O–H
The strength of oxo-acid depends upon
(i) size of the atom (z)
(ii) electronegativity of the atom (z) and
(iii) inductive effect of the substituents present
on z.
Small size and high electlronegativity of z, allows
the proton to dissociate and make the
compound acidic.
Thus acid character decreases in the order
HClO > HBrO > HIO
H–O Cl H–O I
Greater tendency to Lesser tendency to
withdraw electrons withdraw electrons
from Oxygen from Oxygen
Similarly H2SO3 is more acidic than H2SeO3 due to
greater electronegativity of S than Se and HClO4 is
more acidic than HIO4
Acidity also increases with the increasing oxidation
number of the atom (z) e.g.
Acid HClO < HClO2 < HClO3 < HClO4
O.N. +1 +3 +5 +7
Similarly
HNO < HNO2 < HNO3
H2SO3 < H2SO4
 But among the oxo acids of Phosphorus the Oxidation Number of
Phosphorus increases in the order of
H3PO2 < H3PO3 < H3PO4
But all the oxoacids of Phosphorus are weak acids

Acid H3PO2 H3PO3 H3PO4

O.N. +1 +3 +5
PKa 2.0 2.0 2.16
This can be explained on the basis of their structures
H3PO2 (gives 1H+) H3PO3 (gives 2 H+) H3PO4 (gives 3H+)
Monobasic acid Dibasic acid Tribasic acid
There is only one unprotonated oxygen atom which influence
the acidity. Therefore overall effect of unprotonated oxygen is
more for one O – H group in H3PO2, less for two – OH
groups and least for three –OH groups. Hence the acidity
slightly decreases as
H3PO2 > H3PO3 > H3PO4
3. Strength of organic acids
The acidic strength of organic acids
particularly carboxylic acids and phenols is
influenced by the factors
Inductive effect
Resonance effect
(i) Inductive effect
R-COOH RCOO– + H+
Carboxylate ion
The strength of the carboxylic acid depends
upon the cleavage of O–H bond and the
resonance stabilization of resulting
carboxylate ion which is enhanced by –I effect
of electron-withdrawing groups such as Cl,
CN, NO2 etc.
Inductive effect increases in the number of
substituents

CH3 COOH < ClCH2 COOH < Cl2 CHCOOH<Cl3CCOOH

acidic strength increases

Similarly electron-releasing substituents like CH3

and OCH3 (having +I effect) decrease the acidic
strength as it intensify the electron density
making carboxylate ion less stable

CH3–COOH > CH3 CH2 COOH > (CH3)2 CH COOH > (CH3)3 C COOH
ii) Resonance Effect In aromatic acids, the resonance effects
are more important than inductive effects in determining the
acidic strength.
 (Effect of Substituents on the strengths of Lewis acids and
bases
1) Inductive effect of the substituents
In general an electron-withdrawing group (-I effect) will
increase the acidic strength and decrease the basic strength.
On the other hand an electron-releasing group (+I effect) will
decrease the acidic strength and increase the basic strength.
Therefore, acidic strength of Me3B , BH3 and BF3 follow the
order :
Electron withdrawing group increases Lewis acid strength
Electron releasing group decreases Lewis acid strength
Me3B < BH3 < BF3

Electron releasing Electron withdrawing

group decreases group increases Lewis
Lewis acid strength acid strength
The relative order of basic strength of Me3N , NH3 and NF3 is
Me3 N > NH3 > NF3
Electron Electron
releasing group withdrawing group
increases Lewis decreases Lewis
basic strength basic strength

2. Resonance Effect
Boron trihalides act as lewis acid and since fluorine is
most electronegative the acidic strength should follow
the order
BF3 > BCl3 > BBr3
However, experimentally this order is found to be
BF3 < BCl3 < BBr3
This anomalous behaviour can be explained on the
basis of resonance stabilization and tendency of the
halogen atom to back-donate its electrons to the boron
atom.
This results into the transference of the fluorine
electrons into the vacant 2p orbital of the boron
atom. In other words an additional pp-pp bond is
formed between boron and fluorine atoms and
B-F bond, thus acquires some double bond
character.
As a result of the back-donation of electrons
from F to B the electron deficiency of Boron
atom get compensated and its lewis acid
character decreases.
The tendency to form pp-pp is maximum in case
of BF3 and decreases for BCl3 and BBr3 due to
the inability of vacant 2p orbital of boron to
overlap effectively with the 3p orbital of chlorine
in B-Cl bond or with 4p orbital of bromine in B-Br
bond because of appreciable differences in their
energy levels.
3. Steric Effect
To understand steric effects let us compare basic
strengths of pyridine, to methyl pyridine ( 2-picoline) and
4-methylpyridine (4 picoline) with the same acid
trimethylborane, BMe3.
The order of basicity has been found to be
pyridine ~ 4-methylpyridine > 2-methylpyridine
The lower basic strength of 2-methylpyridine may be
attributed steric hindrance between the CH3 group of
2-methylpyridine and CH3 groups on BMe3.
Such an effect is known as front or F-strain.
There is another type of steric hindrance
known as back-strain or B-strain. This is
due to structural necessity for the donor
atom to change its structure so that its
lone pair can be bonded effectively.
• The Advantages of the Bronsted
Definition
• The Bronsted definition of acids and bases
offers many advantages over the
Arrhenius and operational definitions.
• It expands the list of potential acids to
include positive and negative ions, as well
as neutral molecules.
• It expands the list of bases to include any
molecule or ion with at least one pair of
nonbonding valence electrons.
• It explains the role of water in acid-base
reactions: Water accepts H+ ions from acids
to form the H3O+ ion.
• It can be expanded to include solvents other
than water and reactions that occur in the gas
or solid phases.
• It links acids and bases into conjugate acid-
base pairs.
• It can explain the relationship between the
strengths of an acid and its conjugate base.
• It can explain differences in the relative
strengths of a pair of acids or a pair of bases.
• It can explain the leveling effect of water the
fact that strong acids and bases all have the
same strength when dissolved in water.