Acid-Base Titration & Indicators

Indicator: The completion of the titration should be detectable by the addition of an

auxiliary reagent, known as an indicator. After the reaction between the substances and
the standard solution is particularly complete, the indicator should give a visible color
change in the liquid being titrated.

Example: - Phenolphthalein indicator, whose pH range is 8 to 10

Mixed Indicator: Mixed indicator refers to the suitable mixture of indicators. They are
generally selected for their pK value are close together and the overlapping colors are
complementary to an intermediate pH values.

Example: - Methyl yellow + Methyl blue, whose pH value is 3.25; color change from blue
to green.
Universal Indicator: It is one kind of mixed indicator. It is prepared by suitable mixture of
certain indicators, change in color may over a considerably portion of pH.

It may be employed for the determination of the approximate pH of a solution by the

colorimetric method.
Composition of Universal indicator:
Phenolphthalein 0.1 gm + Methyl red 0.2 gm + Methyl yellow 0.3 gm + Bromothymol

blue 0.4 gm + Thymol blue 0.5 gm all are dissolve in 500ml of absolute ethanol and
NaOH solution is added until the color is yellow.

Indicator Theory: There are two theories to explain the indicator action in acid-base
titrations. Such that Ostwald theory, Quinonoid theory.

1. Ostwald Theory: According to this theory, an acid-base indicator is either a weak acid
(HIn) or weak base (InOH). The unionized indicator (HIn) has a color, different from the
In- ions produced by the ionization of HIn indicator in aqueous solution. And the degree
of ionization of the indicator determines the visible color of the indicator.

Explanation: Let us consider a weak organic indicator, which represented as HIn. In

aqueous solution it will dissociate

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HIn
Undissociated color

H + + In (poorly dissociated)
Dissociated color

If the indicator take place in an acid solution (HA), then following equilibrium will exist.
HIn In + H + (Dissociation decreased)
HA A + H + (common ion)

Due to common ion effect (H+), the dissociation of HIn further decreased.
If the indicator take place in an alkali solution, the dissociation of HIn will be increased
as shown below

HIn In + H +

MOH M + + OH

H + + OH - H2O (Dissociation Increased)

The concentration of In- ions will be thereby greater than the concentration of HIn. So,
the color exhibited will be that of In- ion, i.e. the dissociation color.
By applying the law of mass action

So, the actual color of the indicator, which depends upon the ratio of the ionized and
unionized forms, directly related to the hydrogen ion concentration.
Example: - Phenolphthalein (HPh) is a weak acid. In the unionized form it is colorless
while ph- ion has a pink color.

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HPh
Colorless

H+ + Ph- .. (I)
Pink color

In acid solution, due to common ion effect, the dissociation of indicator is suppressed. So
most of it present in the unionized form, consequently the solution remains colorless.

On the other hand addition of strong solution of alkali (NaOH), the OH - ions form.
It combines with the H+ ions from HPh to form H2O, so that the equilibrium is disturbed
and more HPh ionized to restore this equilibrium. The ph - ions so produced combine with
Na+ ions to form strongly ionized Na-salt and thus remain in the solution in the ionic
state and produce pink color to it.

Equation (I) + Equation (II)

NaOH Na+ + OH- (II)

H+ + OH - H2O

Na+ + ph- Na+ph-

2. Quinonoid Theory: According to this theory, indicator changes its color on the basis of
intramolecular change or structure. It is believed that, an indicator consists of an
equilibrium mixture of at least two tautomeric forms (quinonoid & benzenoid form)

One of them can exist in an acidic solution and another in alkaline solution. The two

forms possess different color. The quinonoid form is usually deeper in color than the
benzenoid form.

Example: - Phenolphthalein exists in two tautomeric form.

1. The benzenoid form, which is yellow/colorless in acidic solution.

2. The quinonoid form, which is pink in alkaline solution.

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Mechanism:

In the presence of dilute alkali the lactone ring in (I) opens to yield (II)
The triphenylcarbinol structure (II) undergo loss of water to produce resonating
ion (III) which is pink in color.
If phenolphthalein is treated with excess of concentrated alcoholic alkali, the pink
color first produced disappears owing to the formation of (IV).

Color change Interval: The acid base neutralizing indicators change color according to
the pH of the solution containing them. However the color change does not occur
suddenly, rather take place within a small interval of pH. This is termed as color change
interval of the indicators.

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Explanation: Consider a weak organic acid indicator (HIn) and in aqueous solution it is
poorly dissociated.
HIn H + + In (poorly dissociated)

And the color change equilibrium at any particular ionic strength can be expressed by
. (I)
From the equation (I) it is obvious that, the ratio

is governed by the pH of the

solution, in which the indicator is placed.

Now, If HIn and In- both are present, our eye cannot detect their colors.
However, If the pH of the solution is such that [In -] = 10[HIn], the color of In- ion.
i.e. alkali color will be clearly visible.

Similarly, When [HIn] = 10[In-], the color of [HIn]. i.e. the acid color will be clearly
visible.

From the above equation,

When pH = pKin + 1, the solution has the color of In- ion.
When pH = pKin 1, the solution has the color of HIn.
Thus, the color change interval is a pH range of K in 1.
Q. Why less amount of indicator is used?

Since, indicator is a weak acid or weak base, the amount should be kept minimal so that

it does not contribute apparently to the pH and so only small amount of titrant is needed
to cause the color change. i.e. the color change will be sharper when the concentration
is lower because less acid or base is needed to convert it one form to the other.

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Q. Why phenolphthalein is not a suitable indicator in the titration of a strong acid with
weak bases?
Phenolphthalein is a weak acidic indicator, whose pH range is 8 to 10. In acidic solution
it is colorless and in alkaline solution it appears pink color. Its composition is
5gm phenolphthalein + 500ml ethanol + 500ml water
Phenolphthalein is not a suitable indicator in the titration of a strong acid with a weak
base, like NH4OH. Because
1. The weak base, NH4OH gives very few OH- ions, which combine with H+ ions of the
phenolphthalein.

HPh H+ + Ph- . (I)

NH4OH NH4+ + OH- . (II)

H+ + OH- H2O; NH4+ + OH- NH4OH

The equilibrium /equation (I) is not sufficiently disturbed.

2. The salt produced by the combination of NH4+ and Ph- gets hydrolyzed.
NH4Ph + H2O NH4+ + Ph + H2O HPh + NH4OH

Because of this, pink color does not appear until sufficient NH 4OH has been added.

As NH4OH is added, the pH of the titration solution increases gradually.

Around the equilibrium point, a sharp rise in pH occurs approximately from 3 to
8, the curve become vertical.
The pH of the phenolphthalein is 8 to 10, so it is not suitable in this titration.

Because, if it is used as indicator the experimental end point will be reached earlier than
the equivalence point, and the indicator change its color.

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