UNIT 1 −¿

Acid-Base Equilibria
1.1 ACID-BASE CONCEPTS

1.1.1 The Arrhenius Concept of Acids and Bases

In the Arrhenius acid-base definition, acids and bases are classified in terms
of their formulas and their behavior in water: •
•An acid is a substance that has H in its formula and dissociates in water
to yield H30+ . example, perchloric acid, HClO4

Other examples of Arrhenius acids are H2 SO 4 , HI , HBr , HCl , HNO3 , HCN,

H2S and CH3COOH.
NOTE, Every hydrogen compound cannot be regarded as an acid, e.g.,
CH 4 is not an acid.
• A base is a substance that has OH in its formula and dissociates in water
to yield OH-. some typical example of Arrhenius
bases are NaOH, KOH, and Ba(OH)2

NOTE, Every hydroxide, OH compound cannot be regarded as bases, e.g

CH 3OH, C2H5OH , etc., have OH groups but they are not bases.
Although Arrhenius bases contain discrete OH- ions in their structures,
Arrhenius ac ids never contain H + ions. On the contrary, these acids
contain covalently bonded H atoms that ionize in water.

The drawbacks of the Arrhenius’ concepts of acids and bases

The Arrhenius definition of acids and bases has the following limitations.
* It defines acids and bases in terms of what happens when compounds dissolve in water.
However, similar chemistry occurs in many reactions that take place in solvents other than
water, and this definition does not work for such reactions.
* It does not explain why some compounds in which hydrogen has an oxidation number of +
1 (such as HCl) dissolve in water to give acidic solutions, whereas others (such as NH3) do
so.
*The neutralisation process is limited to those reactions which can occur
 in aqueous solutions only, although reactions involving saltformation do
occur in absence of solvent.

* Only the compounds that contain the OH– ion can be classified as Arrhenius bases.
The Arrhenius definition does not explain why compounds such as Na2CO3,NH3 , AlCl3 have
basic properties.

1.1.2 PROTON TRANSFER AND THE BRÔNSTED-LOWRY

ACID-BASE DEFINITION
According to the BrÔnsted-Lowry acid-base defnition,
• An acid is a proton donor any species that donates an H+ ion. An acid
must contain H in its formula; HN03 and H2P04- are two of many
examples. All Arrhenius acids are
Br¢nsted-Lowry acids.
• A base is a proton acceptor, any species that accepts an H+ ion.
A base must contain a lone pair of electrons to bind the H+ ion;
A few examples are NH3,CO32, and F-, as well as OH- itself.
Brönsted-Lowry bases are not Arrhenius bases, but all Arrhenius bases
contain the Br0nsted-Lowry base OH- .
From the Br0nsted-Lowry perspective, the only requirement for an acid-
base reaction is that one species donates a proton and another species
accepts it: an acid-base reaction is a proton-transfer process.
Acid-base reactions can occur between gases, in non aqueous solutions,
and in heterogeneous mixtures, as well as in aqueous solutions.
An acid and a base always work together in the transfer of a proton. In
other words, one species behaves as an acid only if another species
simultaneously behaves as a base, and vice versa. Even when an acid or
a base merely dissolves in water, an acid-base reaction occurs because
water acts as the other partner.
Consider two typical acidic and basic solutions:
1 . Acid donates a proton to water. When HCI dissolves in water, an H+
ion (a proton) is transferred from HCI to H20, where it becomes attached
to a lone pair of electrons on the 0 atom, forming H30+ . In effect, HCI
(the acid) has donated the H + , and H20 (the base) has accepted it:
HCl(g) + H2O(/)→ Cl-(aq) + H3O+(aq)
2. Base accepts a proton from water . In an aqueous solution of ammonia,
proton transfer also occurs. An H+ from H20 attaches to the N atom's
lone pair, forming NH4+ . Having transferred an H+ , the H20 becomes
 an OH- ion:

In this case, H20 (the acid) has donated the H+ , and NH3 (the base) has
accepted it. Thus, H20 is amphoteric: it acts as a base in one case and as
an acid in the other.
71
Conjugate Acid-Base Pairs
The Brønsted-Lowry definition provides a new way to look at
acid-base reactions because it focuses on the reactants and the
products as acids and bases. A Brønsted-Lowry
acid-base reaction occurs when an acid and a base react
form their conjugate base and conjugate acid, respectively:
acid1 + base2 ⥫⥬ base1 + acid2

Every acid has a conjugate base, and every base has a

conjugate acid. For any conjugate acid-base
pair,
∙ The conjugate base has one fewer H and one more negative

Conjugate base ⇌ Conjugate acid -H

charge than the acid.

∙ The conjugate acid has one more H and one fewer negative

Conjugate acid ⇌ Conjugate base H

charge than the base.

From Brønsted-Lowry acid-base reactions. Note these points:

∙ Each reaction has an acid and a base as reactants and as
products, comprising two
conjugate acid-base pairs.
∙ Acids and bases can be neutral molecules, cations, or anions.
∙ The same species can be an acid or a base (amphiprotic),
depending on the other species reacting. Example H2O ,
H2P04-, HPO4- , HC03-
SAMPLE P ROBLEM Identifing Conjugate Acid-Base Pairs.
(a) H2P04-(aq) + C032-(aq) ⥫⥬ HC03-(aq) + (aq)
(b) H20(l) + S032-(aq) ⥫⥬ OH-(aq) + HS03-(aq).
Solution

a.H2P04- has one more H+ than HPO4; C032-has one fewer

H+ than HC03-. Therefore, H2P04- and HC03- are the acids,
and HPO4- and CO3- are the bases. The conjugate acid-base
pairs are H2P04-¿HP042- and HC03-/C032-.
(b) H2O has one more H+ than OH-; S032- has one fewer H+
than HS03-. The acids are H20 and HS03-; the
bases are OH- and S032-. The
conjugate acid-base pairs are H20/OH- and HS03-/S032-.

Utility of Bronsted – Lowry concept

(i) Bronsted – Lowry concept is not limited to molecules but
includes even the ionic species to act as acids or bases.
(ii) It can explain the basic character of the substances like
Na2CO3, NH 3 etc.
(iii) It can explain the acid-base reactions in the non-aqueous
 medium or even in the absence of a solvent (e.g., between HCl
and NH3)

Limitations of Bronsted lowry concept

(i) The protonic definition cannot be used to explain the
reactions occuring in non-protonic solvents such as COCl2,
SO2, N2O4, etc.

(ii) It cannot explain the reactions between acidic oxides like CO 2,

SO 2,SO 3 etc and the basic oxides like CaO, BaO, MgO etc which
take place even in the absence of the solvent e.g., CaO SO3
CaSO4
There is no proton transfer in the above example.
(iii) Substances like BF3, AlCl3 etc, do not have any hydrogen
and hence cannot give a proton but are known to behave as
acids.

Relative Strengths of Conjugate Acid-Base

Pairs and the Net Direction of Reaction
The net direction of an acid-base reaction depends on the
relative strengths of the
acids and bases involved.
A reaction proceeds to the greater extent in the direction in
which a stronger acid and stronger base form a weaker
conjugate acid and weaker conjugate base respectively.
•An acid is strong if it has high tendency to donate electron
pair and if its conjugate base is weak or vice versa.

i.e, stronger acid ⥫⥬ weaker conj

ugate base
i.e, weaker acid ⥫⥬ stronger conjugate base
• A base is strong if it has great tendency to accept proton and if
its conjugate acid is weak or vice versa.

i.e, stronger base ⥫⥬ weaker conjugate acid

i.e, weaker base ⥫⥬ stronger conjugate acid
If the stronger acid and base are written on the left, the net

stronger acid + stronger base ⟶ weaker conjugate base +

direction is to the right, so Kc > 1 .

weaker conjugate acid

In effect, the extent of acid (HA) dissociation in water can be
viewed as the result of a competition for the proton between
the two bases, A- and H2O. Strong and weak acids give
different results:
1. Strong acids. When the strong acid HNO3 dissolves, it
completely transfers an
H+ to the base, H2O, forming the conjugate base NO3- and the
conjugate acid H3O+:

stronger acid + stronger base ⟶ weaker base +

HNO3 + H2O ⥫⥬ NO3- + H3O+

weaker acid
Even though we show an equilibrium arrow here, the net
direction is so far to the
right that Kc >> 1 and the reaction is essentially complete.
HNO3 is a stronger acid
than H3O+, and H2O is a stronger base than NO3-. Thus, with a
strong HA, H2O wins the competition for the proton because A-
is a much weaker base. 2. Weak acids. when weak
acids such as HF, the A- (F- for this example) wins the
competition because it is a stronger base than H2O and the net
direction is to the left (Kc < 1), with the net result that only a
small percentage of HF molecules dissociate:

weaker acid + weaker base ⟵ stronger base +

HF + H2O ⥫⥬ F- + H3O+

stronger acid
 Based on the expermental results of many such reactions, we
can rank conjugate pairs in terms of the ability of the acid to
transfer its proton
Note, especially, that a weaker acid has a stronger conjugate
base. the acid gives up its proton less readily because its
conjugate base holds it more strongly. We can use this list to
predict the direction of a reaction between any two pairs, that
is, whether the equilibrium position lies predominantly to the
right (Kc > 1 ) or to the left (Kc < 1 ).
• H3O+ is the strongest acid and OH– is the strongest base
that can exist in water.

Chart 1.1 page 9

Auto-ionisation of Substances

The auto-ionization (self-ionization) of a substance involves the transfer of a

proton from one molecule of the substance to another molecule of the same
substance. For example,water undergoes auto-ionization as shown below:
H2O(l)+ H 2 O(l) →H3O+(aq) + OH–(aq)

Note that, in this reaction, some water molecules behave as acids, donating protons, while
the other water molecules behave as bases, accepting protons.
Amphiprotic Species
Many molecules and ions gain or lose a proton, under appropriate conditions.
Such species are said to be amphiprotic. For example,
HCO3– (aq) ⥫ ⥬ H+(aq) + CO32–(aq)
HCO3–(aq) + H+(aq) ⥫⥬ H2CO3(aq)

1.1.3 Lewis Concept of Acids and Bases

The Lewis acid-base concept includes many reactions that do not involve
proton- transfer reactions.
According to Lewis theory, electron pair acceptor is an acid
while electron pair donor is a base.
• The neutralization between Lewis acids and bases is due to
the formation of coordinate bond or dative bond.
 • A Lewis acid must possess a vacant orbital to accept the lone
pair.
• Simple cations like Ag+, Co3+, Al3+, Na+, Cu2+ zn2+, etc.
which can combine with electron pair donors by accepting lone
pair of electrons are Lewis acids.
• Compounds whose central atom has an incomplete octet or
the electron-defcient molecules such as BF3, AlCl3, FeCl3,
etc. are Lewis acids.
• Compounds whose central atom have vacant d-orbitals and
can acquire more than an octet in their outermost orbit like
PF3, PF5, SF4, SeF4, SiCl4, SnCl4, etc.
are Lewis acids.
• Molecules with multiple bonds between atoms of dissimilar
electronegativities like O C O, O S O, SO3, NO2, etc
are Lewis acids.
• Elements with electron sexet like oxygen and sulphur are
Lewis acids.
• All simple negative ions such as F–, Cl–, OH–, CN–,NH2,
SO32, etc. which can donate lone pair of electrons are Lewis
bases.
• All the molecules with one or more unshared electron
pairs like:NH3 H 2O: , ROH , ROR, RSR, RNH2 etc. areLewis
bases.

• Compounds with multiple bonds which can form coordinate

covalent bonds with transition metal ions are Lewis bases, e.g.,
CO, NO, CH ≡CH, CH2 CH2,
pyridine, etc.
limitations of lewis Theory
• Lewis theory cannot explain the strength of acids and bases.
Acids such as HCl and H2SO4 cannot form coordinate bonds.
Acid–base reactions are fast but Lewis acid–base reactions are
slow. The catalytic activity of H+ ions and neutralization of
 normal acids and bases where coordinate bonds are not formed
cannot be explained by Lewis theory.

1.2 IONIC EQUILIBRIA OF WEAK ACIDS AND BASES

1.2.1 The Equilibrium Nature of Autoionization: The Ion-
Product
Constant for Water (Kw)