TITRIMETRIC ANALYSIS

INTRODUCTION
Titrimetric analysis involves determination of the volume of a solution of accurately known
concentration, which is required to react quantitatively with the measured volume of the solution of
a substance, concentration of which is to be determined. The solution of accurately known
concentration is called standard solution. The mass of the substance dissolved in the solution of
unknown concentration is calculated from the volume of the standard solution used, the chemical
equation and the relative molecular masses of the reacting compounds. The reagent of known
concentration is called titrant and the substance being titrated is termed as titrand.
To carry out titrimetric analysis, standard solution is usually added from
the long-graduated tube called burette. The process of adding the standard solution to the solution
of unknown concentration until the reaction is just complete is called titration. The point at which
reaction is completed is called equivalence point. The end point is detected by the addition of an
auxiliary reagent, known as indicator.
Neutralisation reactions involve titrations of acids and bases. Standard solutions of acids (acidimetry)
and bases (alkalimetry) are used in these titrations. In quantitative estimation through titrimetric
analysis, concentration of solution is expressed in terms of molarity. A solution of exactly known
concentration is called standard solution.

INDICATORS IN ACID BASE TITRATION

Acid base indicators are sensitive to pH change.
PHENOLPHTHALEIN
Phenolphthalein is a weak acid; therefore, it does not dissociate in the acidic medium and remains in
the unionised form, which is colourless.

In the acidic medium, equilibrium lies to the left. In the alkaline medium, the ionisation of
Phenolphthalein increases considerably due to the constant removal of H+ ions released from HPh by
the OH– ions from the alkali. So, the concentration of Ph– ion increases in the solution, which imparts
pink colour to the solution.
HPh ⇌ H+ + Ph–
NaOH ⎯→ Na+ + OH–
H+ + OH– ⎯→ H2O
For a weak acid vs strong alkali titration, phenolphthalein is the most suitable indicator. In this case
alkali is dropped from the burette and acid is taken in the titration flask. Colour of the solution taken
in the titration flask changes from colourless to pink. This is so because the last drop of added alkali
brings the pH of the solution in the range in which phenolphthalein shows sharp colour change. If we
take alkali in the titration flask, the colour change will be from pink to colourless and accuracy in
noting the colour change may be less.
METHYL ORANGE
In the titration of strong acid and a weak base, methyl orange is chosen as indicator. Methyl orange
is a weak base and is yellow in colour in the unionised form. The anion formed from the indicator is
an active species, which on accepting a proton (i.e acting as Bronsted Lowry base) changes from the
benzenoid form to the quinonoid form. The quinonoid form is deeper in colour and thus is
responsible for the colour change at the end point. This is illustrated in the following manner:

In the titration of strong acid versus strong base anyone of the above indicators can be used. For the
titration of weak acid vs weak base, no indicator is available.
APPRATUS IN ACID BASE TITRATION
BURETTE
A burette is simply a long-graduated tube of uniform bore with a stopcock at one end. It is used for
measuring volume in a quantitative (titrimetric) estimation. The burette reading is noted before and
after delivering the liquid. The difference between these two readings is the volume of the liquid
delivered. The liquid should be delivered dropwise. If the liquid is allowed to run too fast, the walls
of the burette will not drain properly and some liquid may remain sticking to the surface of the
walls. This may lead to faulty reading. Measuring capacity of the burette usually used in the
laboratory is 50 mL. Before filling the solution to be used, the burette should be rinsed with the
solution to be filled. After rinsing, the solution is filled in the burette with the help of a funnel above
zero mark. Stopcock is then opened wide and the solution is allowed to run through the nozzle till
there are no air bubbles in it. For all transparent solutions in the burette, reading coinciding with the
lower meniscus is noted and for all dark coloured solutions reading coinciding with the upper
meniscus is noted. Remove the funnel from the burette before noting the reading of the burette and
ensure that the nozzle is completely filled.
PIPETTE
Pipette is used for measuring volumes of liquids, when these are to be transferred to a flask or some
other apparatus. Liquids are sucked into the pipette by applying suction through mouth or by using a
pipette filler bulb. When the liquid is above the etched mark on the pipette, remove the bulb, and
put the index finger of the hand at its place holding the pipette. Loosen the finger carefully to allow
the excess liquid to flow out so that the curvature of the meniscus reaches the mark. Carefully
remove the finger and let the liquid run into the flask After emptying the pipette do not blow out the
remaining liquid. Pipettes are so designed that the little amount of liquid, which remains
untransferred, is not taken into calibration. The pipette should always be rinsed with the solution
which is to be measured by it.
ANALYTICAL BALANCE (CHEMICAL BALANCE)
The beam is made up of a hard but light weight material. The beam pivots at its centre on a knife
edge, which rests upon a plate made of very hard material such as agate or corundum. The plate is
attached to the central beam support (central pillar). The two terminal agate knife-edges are fixed at
equal distance from the central edge and each of these supports a suspension called stirrup from
which the pans are hung. A sharp pointer is attached to the centre of the beam. The pointer moves
over a scale fixed at the bottom of the pillar and serves to point out the deflection of the beam from
central position when the balance is in operation . There, are two adjusting screws on both sides of
the beam, which are meant for adjusting the beam in the horizontal position. There are three
levelling screws at the base of the balance to make it horizontal. A plumb line hangs near the central
pillar, which helps in keeping the balance horizontal. In order to operate the balance, there is a knob
at the centre of the base
Level the balance with the help of levelling screws and plumb line. Ensure that the beam is
horizontal. Adjust the pointer at zero point with the help of screws provided on both sides of the
beam. If it is adjusted on releasing the beam arrest, the pointer moves equal divisions on both the
sides of the zero of the base scale. on the left pan in which weighing material is kept. Put
approximate weights from the weight box with the help of forceps on the right pan. Release the
beam arrest slowly and note the movement of the pointer on the scale. If its weight is not
appropriate, the pointer will move towards the lighter side. Add or remove weights according to the
requirement after bringing the pans to rest by arresting the beam with the help of the knob located
near the base. When weight on both the pans becomes equal, the pointer moves equal divisions on
both sides of the zero of the base scale. Use the rider for adjustment of weight below 10mg.

The weight box of a chemical balance generally contains the following weights. (a) Weights for
weighing in grams :100, 50, 20, 20, 10, 5, 2, 2, 1 (b) Weights for weighing in milligrams: 500, 200,
200, 100, 50, 20, 20, 10 (c) Rider: To weigh 0.2 mg to 10 mg.
Aim
To prepare M/20 standard solution of oxalic acid and determine the concentration
(strength) of a given sodium hydroxide solution by titrating it against prepared standard
solution of oxalic acid.
Theory
In the titration of a strong acid with a strong base, the amount of acid and base becomes
chemically equivalent at the end point and the chemical reaction is called neutralization
reaction. Near the end point there is a sudden change in the pH of the solution. If
after end point even a small amount of base/acid is added the solution would become
slightly alkaline or acidic respectively. In this titration phenolphthalein (HPh) is used as an
indicator. The concentration of unknown solution is calculated in g/L.
In the titration between oxalic acid (weak acid) and sodium hydroxide (strong base),
following reaction takes place:
Procedure:
1)Weighing and preparation of standard solution
a) Weigh the empty watch glass on a chemical balance.
b) Weigh 0.63g of oxalic acid in the watch glass.
c) Transfer the weighed compound to the volumetric flask using wash bottle and funnel.
d)Add distilled water, shake the flask till the solid has dissolved and the solution is clear.
e) Now, add more distilled water to make the solution up to 100 mL mark.
f) Stopper the flask and shake the solution thoroughly to mix well.

2)Titration
a) Clean the burette thoroughly, wash it with distilled water and finally rinse it with sodium
hydroxide solution.
b) Clamp the burette vertically in a burette stand. Fill burette with given NaOH solution through a
funnel.
c)Remove the air gap, if any, from the nozzle of the burette Remove the funnel before noting initial
reading of the burette. Note the initial reading by noting the lower meniscus of the solution.
d) Wash the pipette with water and rinse with the liquid to be measured before
pipetting out the liquid. Pipette out the standard oxalic acid solution(10ml)
e) Transfer the titrant to the conical flask.
f) Add 2 drops of Phenolphthalein Indicator.
g)Titrate the acid with sodium hydroxide solution till a very faint permanent pink colour is obtained.
h) Add sodium hydroxide solution in small amounts initially and then dropwise.
i)Read the lower meniscus of the solution in the burette again and record it as final reading.
j) Repeat the procedure until three concordant readings are obtained.
k) Record readings in the table.
Precautions

Weighing
(a)Check if the hinges are proper.
(b)Do not touch the balance while the doors are open.

Titration
(a)Solution should be prepared in distilled water.
(b)Last drops in the volumetric flask should be added carefully.
(c) Never rinse the conical flask with the experimental solutions.

Pipette
(a) Lower end of the pipette should always remain dipped in the liquid while drawing the liquid.
(b) Do not blow out the last drop of the solution from the jet end of the pipette.
(c) Never use pipette with a broken nozzle.
(d) Always rinse the pipette with the solutions to be taken in them.

Burette (a) Always rinse the burette with the solutions to be taken in them.
(b) Remove the air gaps if any, from the burette.
(c) Never forget to remove the funnel from the burette before noting the initial reading of the
burette.
(d) No drop of the liquid should hang at the tip of the burette at the end point and while noting
reading.
(e) Always read the lower meniscus for recording the burette reading in the case of all colourless
solutions.
(f) Never use burette with a broken nozzle.
Aim
To determine the strength of a given solution of hydrochloric acid by titrating it against a standard
solution of sodium carbonate.

Theory
The strength of hydrochloric acid is determined by titrating it against a standard solution of sodium
carbonate. The following reaction takes place:
Na2CO3 + 2HCl→ 2 NaCl + CO2 + H2O
In this titration, methyl orange, a weak base (yellow in the unionised form) is used as an indicator.
In this experiment also, the titration follows the usual course, i.e., the proton furnished by the
addition of the acid first neutralises sodium carbonate solution. When the entire sodium carbonate
solution is neutralised, the last drop of the acid added from the burette produces the pinkish red
colour change, which is the end point. The concentration (strength) of the unknown solution is
calculated in g/L. It is calculated from the molarity of the solution.

Titration of hydrochloric acid and standard sodium carbonate solution.

a) Clean the burette thoroughly, wash it with distilled water and finally rinse it with sodium
hydroxide solution.
b) Clamp the burette vertically in a burette stand. Fill burette with given HCl solution through a
funnel.
c)Remove the air gap, if any, from the nozzle of the burette Remove the funnel before noting initial
reading of the burette. Note the initial reading by noting the lower meniscus of the solution.
d) Wash the pipette with water and rinse with the liquid to be measured before
pipetting out the liquid. Pipette out the standard sodium carbonate solution(10ml)
e) Transfer the titrant to the conical flask.
f) Add 2 drops of Methyl Orange Indicator.
g) Titrate the base with acid solution till pinkish red colour is obtained.
h) Add HCl solution in small amounts initially and then dropwise.
i)Read the lower meniscus of the solution in the burette again and record it as final reading.
j) Repeat the procedure until three concordant readings are obtained. Record your observations in
Table.