ANALYTICAL

CHEMISTRY
(Acid Base Equilibria)
Dr.S.SURESH
Assistant Professor
Email:avitsureshindia@gm
ail.com

pH and pOH
The strength of acids and bases
can be compared with pH and pOH
values. These are related to the
[H3O+] and [OH] by the following
equations.
pH = log [H3O+]
pOH = log [OH]
pH value of strong acid
In the case of strong acids which are
completely
ionised
at
all
concentrations the concentration of
H3O+ ions can be directly calculated
from the acid concentration. If the

pH value of weak acid

Weak acids are partially ionised and
hence the concentration of H3O+ in such
solutions depends on the concentration
of the weak acid and also the extent of
dissociation. Therefore, we can write in
solution of weak acid.
[H3O+]
= degree of dissociation
concentration of the
weak acid

Buffer solution
Pure water is neutral and it has pH value
of 7. If a small amount of HCl is added,
the pH value becomes less than 7 and if
a small amount of NaOH is added, the pH
becomes greater than 7.
If we take a mixture of acetic acid and
sodium acetate, the pH of the mixture does
not change considerably even after the
addition of small amount of HCl or NaOH.
Such a mixture whose pH remains constant
even after the addition of small amount of
acid or base is called buffer solution.

Buffer action
The
reactions
responsible
for
maintaining
constant pH on the addition of acid or base in
buffer solution are called buffer action. The buffer
action of acetic acid and sodium acetate mixture
can be explained as follows.

Acetic acid is a weak acid and is partially

ionised in solution.

CH3COOH
H3O+

+ H2O

CH3COO

Sodium acetate is a strong electrolyte and

is completely ionised.
CH3COONa

CH3COO + Na+

Buffer action
When a small amount of acid is added to this
mixture, H+ ions of the acid combines with
equal number of acetate ions to form acetic
acid molecule. Therefore, the net pH remains
constant.
CH3COO
H 2O

H+

CH3COOH

When a small amount of base is added, the

OH ions of the base neutralise acid
molecules to form sodium acetate. Therefore,
the net pH remains constant.
CH3COOH
H 2O

OH

CH3COO

Henderson Equation
HA(aq)
H
logK a

(aq)

H A

Ka

(aq)

A
log H log

HA

A
pH log

HA

pK a

pH pK a

HA

base
log
acid

pH pK a

when A- HA

Preparation of acidic and

basic buffers

ACETIC ACID-SODIUM ACETATE BUFFER

REAGENTS REQUIRED:
Acetic Acid 0.2M: 1.5 ml of glacial acetic acid is
made upto 100ml with distilled water.
Sodium Acetate Solution: 0.64 gm of sodium
acetate or 2.72gm of sodium acetate trihydrate is
dissolved in 100ml Distilled water.
PROCEDURE:
Pipette out exactly 36.2ml of sodium acetate
solution into 100ml of standard flask and add
14.8ml of glacial acetic acid, make the volume
100ml using distilled water using distilled water.
This gives 0.2 M of acetic acid and sodium acetate
buffer. The pH is measured with pH meter. The pH
meter is first standararised with pH buffer. Wash
electrode with distilled water and introduced into
0.2M acetic acid-sodium acetate buffer prepared,
the pH of solution is 4.6.

Preparation of basic buffer

Ammonium
chloride-Ammonium
hydroxide buffer:
Weigh 67.5g of Ammonium chloride
and it is dissolved in 570 ml of
ammonia and it is made upto 1 litre
using distilled water.
This buffer is used to maintain the pH
in estimation of hardness by EDTA
method.

Relative strength of Acids

The constant (ka) is known as the dissociation
constant of the acid and is given by

[H ][A ]
Ka
[HA]

The above equation for the dissociation

constant of a weak acid can also be expressed
in terms of the degree of dissociation () and
the total molar concentration (C) of the acid.
Original concn.

CH3COOH
Eqilibrium concn. C(1-)
c

CH3COO +
c

H+

Relative strength of Acids

[ H 3 O ][CH 3COO ]
Ka
[CH 3 COOH ]

Ka

[C ][C ]
[C (1 )]

[C 2 ]
Ka
[(1 )]

Since for weak acids is very small, 1- in the

denominator may be taken as 1. The above
expression therefore reduces to
Ka =
C
2k a / C

Neutralisation titration
curve
Strong Acid with Strong
Base
You
should
already
be
familiar with the titration
curve generated when a
strong acid is titrated with a
strong base. The net ionic
equation for the reaction is
H3O+(aq)
2H2O(l)

OH-(aq)

---->

The titration curve and a

summary picture of the
species in solution are given
below.

Indicators for Acid-Base titrations

In a neutralisation titration, endpoint
detection is based upon the change in pH
that occurs close to the equivalence point.
The pH range within which such a change
occurs varies from titration to titration and
is determined by the nature and the
concentration of the analyte and the titrant.
An indicator can be selected with proper
knowledge of the pH changes which occur
Indicator
pHThe
range colourColour
changeand
throught
the
titration.
change
S.No
the
pH Methyl
range
of some3.2-4.5
common indicators
orange
Pink to yellow are
1
tabulated below:
2

Phenolphthalein

8.3-10.5

Colourless to pink

THEORY OF INDICATORS:
1. Ostwald's theory:
Phenolphthalein: It can be represented as HPh. It ionises
in solution to a small extent as:
HPh H+ +
Ph
Colourless
Pink
The undissociated molecules of phenolphthalein are
colourless while Ph ions are pink in colour. In presence of an
acid the ionisation of HPh is practically negligible as the
equilibrium shifts to left hand side due to high concentration
of H+ ions. Thus, the solution would remain colourless. On
addition of alkali, hydrogen ions are removed by OH ions in
the form of water molecules and the equilibrium shifts to
right hand side. Thus, the concentration of Ph ions increases
in solution and they impart pink colour to the solution.

THEORY OF INDICATORS:
Quinonoid theory:
According to this theory:
(a) The acid-base indicators exist in two tautomeric forms
having different structures. Two forms are in equilibrium. One
form is termed benzenoid form and the other quinonoid form

(b) The two forms have different colors. The color change in
due to the interconversation of one tautomeric form into other.

Theory of Indicators
Phenolphthalein: This is colourless in
undissociated acid form and pink the
dissociated base form.

Titrations with Ethylene diamine tetra acetic

acid (EDTA)

Metallochromic Indicators
The metallochromic indicators are organic
molecules which form stable, brightly
coloured complexes with most metal ions of
analytical interest. They function as acid
base indicators also. This ability combined
with the ability to form coloured complexes
is utilized to obtain the indicator behaviour
required in EDTA titrations. A common
metallochromic indicator is Eriochrome
Black T(EBT).