Analytical Chemistry

Acid-Base Titration

Acid is a specie that donates hydrogen ions (H+). For example, HCl, RCOOH etc.

Hydrochloric acid is a strong mineral acid and dissociates as:

HCl → H+ + Cl-

Base is a specie that donates hydroxyl ions (OH-). Examples include NaOH, Ca(OH)2 ,
Ba(OH)2 . Ca(OH)2

Sodium hydroxide is dissociated to give hydroxyl ion

NaOH → Na+ + OH-

Titration is derived from a French word ‘titalus’ meaning rank or concentration. With the
help of a titration reaction, we can find the concentration of an unknown substance in a
solution by knowing the concentration of another substance or compound which is used as a
standard solution called titrant. The solution whose unknown concentration is to be found is
called analyte or titre.

Characteristics of a titration reaction:

Not every reaction is a titration reaction. But a titration reaction has following characteristics
that it should be a;

1. Fast Reaction

Reaction may be slow or fast depending upon speed. A titration reaction must be a fast
reaction that all reactants are immediately converted into products. It shows the increased rate
of reaction. All titration reactions are categorised as fast reactions.

2. Stechiometric Reaction

The reaction should provide stechiometric calculations that all the reactants and products in
the reaction must combine with each other in a proper mole ratio. In a titration reaction,
balancing of chemical equation must provide us appropriate data to follow the standard
titration equation:

M1V1/n1 = M2V2/n2

3. Spontaneous Reaction
Every reaction has a particular free energy (ΔG ¿ reaction. As a result of a titration reaction,
there must be a huge free energy change ¿). It means that free energy change is negative as -
Δ G .It is the indication of a spontaneous reaction.

All these conditions must be fulfilled for a titration reaction to be verified.

Neutralization Reaction

When an acid reacts with base, there is salt formation with the release of water molecule.
This type of reaction is called neutralization reaction.

Acid + Base → Salt + Water

For example,

HCl + NaOH → NaCl + H2O

In acid base titration, either acid or base can act as titrant or titre. When titrant and titre react
with each other, a point comes when they equalize the concentration of each other. It means
that during reaction when we mix titrant and titre for reaction, the concentration of both
species become equal to each other after some chemical or physical change.

Equivalent Point and End Point:

The point where a sufficient amount of titrant mixes up titre is called equivalent point.

We can understand it well in acid-base titration equivalent point reaches when the
concentration of hydroxyl ions (OH-) being produced in base becomes equal to the
concentration of hydrogen ions (H+) being produced in acid.

End point gives the results of the reaction being performed. It shows the completion of
reaction by any physical change. For example by the addition of indicator, color change is the
physical change leading to the end point. Both are the possibilities that end point and
equivalent point of a reaction can be same or not depending upon the conditions.

Acid-Base Titration
 Acidimetry Alkalimetry

- Standard Acid - Standard Base

- Analyte Base - Analyte Acid

● Base as a Titrant, Acid as a Titre

When we are given the concentration of base and we are supposed to find the concentration
of acid, this type of measurement is called alkalimetry.

● Acid as a Titrant, Base as a Titre

If the concentration of acid is given and by using acid as a standard solution we have to find
the concentration of base, this is called acidimetry.

Indication of the end point:

We can determine the end point of the reaction by using:

A. pH metre

In acid-base titration, when we add titrant into titre and mix them, there is a change in
concentration of both species. By the change in concentration there must be a visible change
in pH (because hydrogen ion concentration in acid is altered). The change in pH is measured
with the help of pH metre.

B. Acid-Base Indicator

Acid-base indicator is a weak organic acid or base. To understand the chemistry of acid-base
indicator, have a look on Methyl orange which is a commonly used acid-base indicator which
is a weak organic acid and can easily donate hydrogen ions (pH change directly depends
upon the concentration of hydrogen ions). Methyl orange represents different composition in
acidic and basic media. In acidic medium, it contains hydrogen ion in its structure. When it is
exposed to the basic media, the hydrogen ion is donated and a double bond appears between
two nitrogen atoms.
The structure of methyl orange in acidic medium is in association form, without any take up
or dissolution. When due to some reason, indicator experiences basic medium, this structure
is its dissociated form with removed hydrogen ion.

As the net change in both the structures is only because of the presence or absence of
hydrogen ion, we can represent it as follows:

HIn → H+ + In-

In undissociated form, this indicator has red color. But in dissociated form it is yellow in
color.

Provision of acidic medium means a lot of hydrogen ions are available. HIn form is
preferable because indicator carries a charge over it by which it attracts opposite charges
towards itself and neutralizes itself in associated form. It means that dominant specie is red in
color in acidic medium. In case of basic medium, same equilibrium exists but with the excess
of hydroxyl ions not of hydrogen ions. These hydroxyl ions combine with hydrogen ions and
release water molecules. We know water is colorless and does not not determine any color
change. Now the dominant specie In- is free of hydrogen in basic medium and has yellow
color showing the completion of reaction.

The overall observed effect is of change in concentration of hydrogen ions and pH change.
All the acid base indicators work at a particular pH and identify the pH change which
represents end point according to the requirement. Methyl orange identifies the end point of a
titration reaction if the pH change ranges from 3.1- 4.4.

Types of Acid-Base Titration

Acid-base titration may have any of the following type:

 ● Strong Acid with Strong Base

The common example of a strong acid with strong base neutralization reaction is:

HCl + NaOH → NaCl + H2O

When titrant is mixed with titre, to check the progress of the reaction, show the readings and
results graphically putting volume of titrant on x-axis and pH on y-axis. First there will be a
gradual increase in pH till 4, after it there will be abrupt change in pH upto 7. At this point,
we can say that the end point is reached. The indicator used must give a proper physical
change at pH range of 7-9. Examples of indicators include methyl orange, phenophthalene,
methyl red etc.

● Weak Acid with Strong Base

Acetic acid is a weak organic acid. The reaction is given as:

CH3COOH + NaOH →CH3COONa + H2O

Sodium acetate formed represents a particular color change, also represents pH change at 8-
10 pH. So the indicator being used here must give a reading of change at a pH ranging from
8-10. Use standard titration equation for further calculations.

● Strong acid with weak Base

Have a look on the following reaction:

HCl + NH4OH → NH4Cl + H2O

Ammoniun Chloride salt gives a particular reading of pH change from 6-4. From the list of
indicators, select the indicator which gives reading at this pH range.

● Weak Acid with Strong Base

When weak acid reacts with weak base:

CH3COOH + NH4OH →CH3COONH4 + H2O

Observe the change by ammonium acetate and select a relative indicator. By knowing the
concentration change and molar ratios, follow M1V1/n1 = M2V2/n2 equation to find
unknown concentration or molarity.