TITRATION:

The word titration comes from the Latin word "titulus", which means inscription or title. The
French word title means rank. Therefore, Titration means the determination of concentration
or rank of a solution with respect to water with a pH of 7.

The standard solution is usually added from a graduated vessel called a burette. The process
of adding standard solution until the reaction is just complete is termed as titration and the
substance to be determined is said to be titrated.

All chemical reactions cannot be considered as titrations. A reaction can serve as a basis of a
titration procedure only if the following conditions are satisfied:

1. The reaction must be a fast one.

2. It must proceed stoichiometrically.
3. The change in free energy (ΔG) during the reaction must be sufficiently large for spontaneity
of the reaction.
4. There should be a way to detect the completion of the reaction.

End point and Equivalent point:

For a reaction, a stage which shows the completion of a particular reaction is known as end
point. Equivalence point is a stage in which the amount of reagent added is exactly and
stoichiometrically equivalent to the amount of the reacting substance in the titrated solution.
The end point is detected by some physical change produced by the solution, by itself or more
usually by the addition of an auxiliary reagent known as an 'indicator'. The end point and the
equivalence point may not be identical. End point is usually detected only after adding a slight
excess of the titrant. In many cases, the difference between these two will fall within the
experimental error.

Indicator:

It is a chemical reagent used to recognize the attainment of end point in a titration. After the
reaction between the substance and the standard solution is complete, the indicator should
give a clear colour change.

When a titration is carried out, the free energy change for the reaction is always negative.
That is, during the initial stages of the reaction between A & B, when the titrant A is added to
B the following reaction takes place.

Equilibrium constant,

a = activity co-efficient.
Large values of the equilibrium constant K implies that the equilibrium concentration of A &
B are very small at the equivalence point. It also indicates that the reverse reaction is
 negligible and the product C & D are very much more stable than the reactants A & B.
Greater the value of K the larger the magnitude of the negative free energy change for the
reaction between A & B. Since,

Where,
R= Universal gas Constant = 8.314 JK-1mol-1,
T= Absolute Temperature

The reaction of the concentration of A & B leads to the reduction of the total free energy
change. If the concentrations of A & B are too low the magnitude of the total free energy
change becomes so small and the use of the reaction for titration will not be feasible.

Expressions of Concentration of Solutions:

The concentration or strength of solution means the amount of solute present in a given
amount of the solution. The concentration may be expressed in physical or chemical units.

1. Normality (N): It is defined as number of gram equivalents of the solute present in 1 litre
(1000mL.) of the solution. If W g of solute of equivalent weight E is present in V mL of the
solution, the normality of the solution is given by:

2. Molarity (M): It is defined as the number of moles of the solute present in 1 liter (or 1000 mL)
of the solution. A one molar solution contains 1 mole of the solute dissolved in 1 liter of the
solution.

3. Molality (m): It is defined as the number of moles of solute dissolved in 1000 g of the solvent.
One molal solution contains one mole of the solute dissolved in 1000 g of the solvent.
Normal solution:

A solution containing one gram equivalent weight of the solute dissolved per litre is called a
normal solution; e.g. when 40 g of NaOH are present in one litre of NaOH solution, the
solution is known as normal (N) solution of NaOH. Similarly, a solution containing a fraction
of gram equivalent weight of the solute dissolved per litre is known as subnormal solution.
For example, a solution of NaOH containing 20 g (1/2 of g eq. wt.) of NaOH dissolved per
litre is a sub
normal solution. It is written as N/2 or 0.5 N solution.

Formulae used in solving numerical problems on volumetric analysis;

1. Strength of solution = Amount of substance in g litre-1.

2. Strength of solution = Amount of substance in g moles litre-1.

3. Strength of solution = Normality × Eq. wt. of the solute = molarity × Mol. wt. of solute.

4. Molarity = Moles of solute/Volume in litre.

5. Number of moles = Wt.in g/Mol. wt = M × V (initial) = Volume in litres/22.4 at NTP (only for
gases).

6. Number of milli moles = Wt. in g × 1000/mol. wt. = Molarity × Volume in mL.

7. Number of equivalents= Wt. in g/Eq. wt. = x × No. of moles × Normality × Volume in litre
(Where x = Mol. wt./Eq. wt.).

8. Number of mill equivalents (meq.) = Wt. in g × 1000 / Eq. wt. = normality × volume in mL.

9. Normality = x × No. of mill moles (Where x = valency or change in oxi. number).

10. Normality formula, N1V1 = N2V2, (Where N1, N2 → Normality of titrant and titrate
respectively, V1, V2 → Volume of titrant and titrate respectively).

11. % by weight = Wt. of solvent/Wt. of solution × 100 .

A solution is a homogeneous mixture of two or more components, the composition of which

may be changed. The substance which is present in smaller proportion is called the solute,
while the substance present in large proportion is called the solvent.

Volumetric Analysis:

It involves the estimation of a substance in solution by neutralization, precipitation, oxidation

or reduction by means of another solution of accurately known strength. This solution is
known as standard solution.

Volumetric analysis depends on measurements of the volumes of solutions of the interacting

substances. A measured volume of the solution of a substance A is allowed to react
completely with the solution of definite strength of another substance B. The volume of B is
noted. Thus we know the volume of the solutions A and B used in the reaction and the
strength of solution B; so the strength of the other solution A is obtained. The amount (or
concentration) of the dissolved substance in volumetric analysis is usually expressed in terms
of normality. The weight in grams of the substance per litre of the solution is related to
normality of the solution as,
Weight of the substance (g per litre) = Normality × gram equivalent weight of the
substance.

Conditions of Volumetric Analysis:

1. The reaction between the titrant and titrate must be expressed.
2. The reaction should be practically instantaneous.
3. There must be a marked change in some physical or chemical property of the solution
at the end point.
4. An indicator should be available which should sharply define the end point.
 EXPERIMENT-1
AIM: To determine the percentage composition of the given mixture of NaCl and NaOH,
8gms of which is dissolved per litre of the solution.
Apparatus Requirements: Burett, Pipett, Conical flask, Beaker.
Chemical Requirement: 0.1NHCl, Sodium Hydroxide, Sodium chloride.
Indicator: Phenolphthalein
Theory
For the titration of a solution of NaOH and NaCl the other solution need is HCl solution.
NaOH react with HCl solution whereas NaCl will remain as such.

NaOH + HCl → NaCl + H2O

The mixture solution will be titrated with the acid solution of HCl and we can find out the
normality and strength of NaOH. By dividing the strength of NaOH from the total known
strength of the solution we will find out the strength of NaCl and hence find the %
composition.
Indicator: Phenolphthalein
End point: Pink to colourless.
Procedure:
1. Rinse the burette with the given N/10 HCl solution.
2. Take the HCl in the burette and note the initial reading.
3. Pipette out the 10 ml of the solution in the conical flask
4. Add a drop of indicator in the solution
5. Add the acid solution from burette in to the conical flask till solution become colourless
6. Note the burette reading
7. Repeat the experiment to get three concordant reading
Observations:
Normality of the HCl solution = 0.1 N
Volume of the mixture of the in conical flask= 10 ml

TABLE I.
S. Volume of Burette Reading Volume 0.1 N
No. given HCl used (ml)
mixture Initial Readings Final Readings
taken(ml)

1. 10 0.0 10.0 10

2. 10 10 20.1 10.1

3. 10 10 20.0 10

Calculations:
By the law of chemical equivalents
N1V1 = N2V2
N2 = N1V1 / V2
= 0.1V1 / 10 = V1 / 100

Strength of given NaOH solution = N2 x 40 gm/l = y g/l

Amount of NaCl in the mixture = (8 – y) g/L = z g/L
% of the NaOH = y/8 x 100
% of NaCl = z/8 x 100

Result:
Normality of Sodium Hydroxide solution =……N.
Strength of Sodium Hydroxide solution = ……gms/l.
The percentage of the NaOH = y/8 x 100,
The percentage 0f NaCl = z/8 x 100

Viva-Voce
Q1. What do you mean by back- titration?
Q2. What is the colour of phenolphthalein in acidic and base medium?
Q3. What is the structure of phenolphthalein?
Q4. What is the procedure to prepare a 0.1 N solution of NaOH?