VOLUMETRIC ANALYSIS

ACID AND BASE TITRATIONS

THEORY OF THE ACID-BASE TITRATION

The point at which the number of moles of an acid (H+) that is added has fully neutralized the
number of moles of an alkali (OH-) in the conical flask is called the equivalence point. At this
point, the mole acid that reacts with the alkali is according the mole coefficient in the
stoichiometric equation. At this, the neutralization is complete.

H+ (aq) + OH- (aq) → H2O(l)

Since in acid-base titration, the products (salt and water) are usually colorless. An acid-base
indicator is added into the solution in the conical flask to detect the equivalent point of a titration.
Acid-base indicators are weak acids or bases that can appear in different colours depend on the
acidity of the solution at which it is added.
HPh(aq) ⇌ H+(aq) + Ph-(aq)
Colourless pink

For instant, if phenolphthalein (HPh) indicator is added into an alkali solution, the alkali added
neutralizes the H+ and causes the forward reaction takes place. Hence, to produce more Ph – anion
that gives the solution pink colour. However, if an acid is added, H + ion added combine with Ph–
anion to form more HPh molecule, the solution is colourless.

In the acid-base reaction, neutralization takes place at the equivalent Point, where an acid is
totally neutralized by the alkali according to the mole ration of the stoichiometric equation. At
this point the pH value of the solution changes drastically though a few drops of acid or alkali are
added.
The range of pH at which the indicator changes colour from one colour to another colour is called
the pH range of the indicator.

If the pH range of the indicator falls into the range of the change of pH at the equivalence point of
an acid-base titration, the indicator is a good choice of indicator to use in the acid-base titration.

The table below shows the pH range for several acid-base indicators.

Indicator pH range Colour change

Methyl orange 3.20 – 4,20 Red Yellow
Methyl red 4.20 – 6.30 Red Yellow
Bromothymol blue 6.00 – 7.60 Yellow Blue
Phenolphthalein 8.20 – 10.00 Colorless Pink

The choice of indicator that is used in an acid-base titration also depends on the colour of the
indicator and the type of acid-base titration. The colour change of an indicator must be obviously
and easily observed at the end point. For example, the colour change from red to yellow is
difficult to be seen compares to the colour change from colourless to pink.

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The following table shows the indicator that is used, the pH change at equivalence point and the
type of acid-base titration.
Type of acid-base titration pH change at equivalence point Indicator used

Strong acid-strong base 3.00 – 10.00 Phenolphthalein

Bromothymol blue
Methyl orange
Methyl red
Strong acid-weak base 3.00 – 6.00 Methyl orange
Methyl red
Weak acid-strong base 7.00 – 10.00 Phenolphthalein

The end point of an acid-base titration is the point at which the titration stopped as the indicator
changes its colour. The color change is refers to the changing from one colour to another colour
(example: Colourless to pink). It is not referring to the change from a darker colour to a lighter
same colour (example: light pink to dark pink).
The volume of titer (solution in burette) at the end point is calling the titer value.

The diagram below is a titration curve of a weak acid as it is titrated by a strong base. It shows
the change of pH in the solution of the weak acid as a strong base is added gradually until the end
point.

pH pH change at the equivalence point is 7.00 – 10.00.

Overlaps with the pH range of phenolphthalein (8.20 – 10.00).
At this point the colour of phenolphthalein changes from
colourless to pink. The titration is stopped. Thus, the end point,
titer V1 is very close to the equivalence point, V’.

pH change at the equivalence point is 7.00 – 10.00.

But, the pH range of methyl orange is 3.20 – 4.20.
V’ At this point the colour of methyl orange changes
from red to yellow before the equivalence point.
The titration is stopped. Thus, the end point, titer V2
is smaller then the equivalence point, V’.
Titer V2 V1 NaOH

If the acid-base indicator is selected carefully, the titer value, V at the end point of an acid-base
titration is very close to its equivalence point, V’. Thus, the titration is accurate.

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In volume-metric analysis, a few titrations are carried out in-order to find out the accurate titer
value. The first titration is carried out by adding the titer slowly from the burette to the titan
(solution in the conical flask) until the end point. The volume of titer required is recorded. This is
a rough titer value. This titer value helps to estimate the titer needed. Base on this rough value, a
few sets of accurate titration are carried out carefully to determine the exact volume of titer
needed for a complete reaction. Accurate titration is carried out by adding an approximately a
volume titer that is slightly less than the rough titer value into the titan and then add the titer drop
by drop to get the accurate end point when the colour change is clearly observed.

How many sets of accurate titration should be conducted?

It is depends on the different between the 1st and the 2nd accurate titer values. The differences
between two titer values should not be more than 0.10 cm 3.

If the first accurate titer value is 25.50 and the second is 25.30, the difference between these titer
values is 0,20. Then, the third accurate titration need to be conducted. If the third accurate titer
value is 25.20, the difference of titer values (2 nd and 3rd) is 0.10. The experiment has got enough
accurate titer values (2nd and 3rd ). Stop the experiment.
The 2nd and the 3rd readings are to be considered as the accurate titer values.
An average of the titer value is to be calculated by adding these accurate titer values and divides
the sum by two as this, (25.30 + 25.20) / 2 = 25.25.

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EXPERIMENT 1

TOPIC: DETERMINING THE PERCENTAGE OF PURITY OF A CARBONATE

PURPOSE: 1. TO DETERMINE THE PECENTAGE OF PURITY FOR A SAMPLE OF

SODIUM
CARBONATA CRYSTAL

MATERIALS: VA5: solution that contents 20.00g sample Na2CO3.10H2O in 1 dm3 solution.
VA6: solution of hydrochloric acid 0.10 mol dm-3.

THEORY: In this experiment, a solution of Na2CO3.10H2O is prepares by dissolving certain

amount of Na2CO3.10H2O into 1 decimeter of distil water. A known volume of this solution is
then titrated with a dilute hydrochloric, HCl, with the help of an indicator. The volume of the acid
required for neutralization can be determined by checking it from the burette. The concentration
of mole for Na2CO3.10H2O is calculated from the mole ratio of reaction. Next, the actual mass of
Na2CO3.10H2O can be calculated from relative molecular mass of Na 2CO3.10H2O. Lastly, the
percentage of purity is determined dividing the actual mass by the mass of carbonate used in the
experiment.

PROCEDURE:
1. Fill a burette with 50 cm3 of VA6 solution.
2. Pipette 25.0 cm3 of VA5 solution and transfer this solution into a conical flask. Add 3 – 5
drops of methyl orange indicator into the flask and shake the solution gently. The
solution turns yellowish.
3. Titrate the solution, VA5 in the flask slowly with VA6 from the burette. Shake the flask
gently while the titration is going on to ensure the solution is well mixed.
4. Stop the titration promptly as the color changes from yellowish to orange in color. The
end point is reached. Check the reading of the burette, that is the titer value and record it
in the following table.
5. Repeat the titration (steps 2 – 4) for a few times to get a set of satisfactory titer values.

RESULTS:
Titration number Rough Accurate
1 2 3
3
Final reading / cm

Initial reading / cm3

Titer value / cm3

Calculate the average titer value

25.0 cm3 of VA5 required………….. cm3 of VA6 for a complete reaction.

QUESTIONS:
1. Write a balance equation for the reaction between Na 2CO3.10H2O and HCl.
2. Calculate the concentration, in mol dm-3, of Na2CO3.10H2O in VA5.
3. Calculate the mass of Na2CO3.10H2O.
4. Calculate the percentage of purity for Na 2CO3.10H2O sample.
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EXPERIMENT 2

Topic: Redox titration.

Purpose: To determine the % of purity of a sample of iron(II) sulphate

Materials: VA19 contains 3.18 g/dm3 of KMnO4

VA20 contains approximately 30.0 g/dm3 of FeSO4.7H2O

Theory:
In redox titration, a volume of an aqueous solution of a reducing agent with unknown
concentration is titrated with another aqueous solution of an oxidizing agent of known
concentration. The end point of the titration is indicated by the colour change of the indicator
used. However, when potassium manganate(VII) is used indicator is not required. Potassium
permanganate is purple in colour. At the end point, in the present of slightly excess (few drops) of
potassium manganate(VII) will change the colour of reaction mixture from one colour to pink.

Reaction: Reduction: MnO4– + 5e + 8H+ → Mn2+ + 4H2O

Oxidation: Fe2+ → Fe3+ + e

In this reaction , iron(II) ion is easily oxidized to iron(III) ion by the permanganate ion. Thus,
heating of the reaction mixture is not required.
When of the redox reaction is slow, where involved ethanedioic ion,
Oxidation : C2O42- → 2CO2 + 2e
heating is required to ensure the complete oxidation. Example, when the ethanedioic acid is used,
the acid solution need to be heated to a certain temperature before it is titrated by the potassium
manganate(VII) solution.

The reaction takes place in acidic solution is to ensure MnO 4- ion is oxidized to Mn2+. If acid is
not used, MnO4- may only be oxidized to MnO2 . It is also important to note that the acid is stable
and it is not oxidized by the the permanganate. Therefore, a stable and non reducing acid like the
sulphuric acid is used. The sulphate ion of the sulphuric acid is not oxidized by the
manganate(VII) ion.

The reaction involved the maganate(VII) ion is autocatalytic. Thus, the reaction is slow in the
beginning and becomes faster after a while where the catalyst, Mn 2+ ion is produced. Thus, it is
important to add the potassium manganate(VII) solution slowly and shake the mixture of reaction
well in the beginning of the titration. After the catalyst is formed, speed up the adding of
potassium manganate(VII) solution.

Procedure:
1. Pipette 25.0 cm3 of VA20 and transfer the solution into a clean conical flask.
2. Add approximately 25 cm3 of dilute sulfuric acid into VA20 in the conical flask using a
measuring cylinder.
3. Fill a clean burette with VA19.
4. Titrate the acidified VA20 in the conical flask with VA19 from the burette.
5. The colour changes from colourless to pink at the end point.
6. Repeat step 1 to 5 until a set of satisfactory titer value is obtained.

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Result:

Titration number Rough Accurate

1 2 3
Final reading / cm3

Initial reading / cm3

Titer value / cm3

Calculate the average titer value

........... cm3 of VA20 required ............. cm3 of VA19 for complete reaction.

Questions:
1. Write a balanced half equation for the oxidation of iron(II) ion to iron(III) ion.
2. With the half equation of the manganate(VII) ion and the iron(II) ion, write a balanced
overall equation for the reaction.
3. Calculate the concentration of iron(II) ion in VA20.
4. Calculate the mass of iron(II) sulphate in 1.0 dm 3 of VA20 solution.
5. Calculate the % of purity of the iron(II) sulphate sample given.

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EXPERIMENT 3

Topic: Redox titration.

Purpose: To determine the mass of ethanedioic acid H2C2O4.2H2O is VA22.

Materials: VA21 contains 3.18 g/dm3 of KMnO4

VA22 contains approximately 5.00 g of H2C2O4.2H2O in 1.0 dm3 of distilled water.

Theory:
As experiment 6

Procedure:
1. Pipette 25.0 cm3 of VA22 and transfer the solution into a clean conical flask.
2. Add approximately 25 cm3 of dilute sulfuric acid into VA22 in the conical flask using a
measuring cylinder.
3. Fill a clean burette with VA21.
4. Heat the mixture in the conical flask up to approximately 60 oC, and titrate it with VA21
from the burette.
5. The colour changes from colourless to pink at the end point.
6. Repeat step 1 to 5 until a set of satisfactory titer value is obtained.

Result:

Titration number Rough Accurate

1 2 3
Final reading / cm3

Initial reading / cm3

Titer value / cm3

Calculate the average titer value

........... cm3 of VA22 required ............. cm3 of VA21 for complete reaction.

Questions:
1. Write a balanced half equation for the oxidation of ethanedioate ion, C 2O42- to carbon
dioxide.
2. With the half equation of the manganate(VII) ion and the half equation of ethanedioate
ion, write a balanced overall equation for the reaction.
3. Calculate the concentration of ethanedioate ion in VA22.
4. Calculate the mass of ethanedioate ion in VA22.

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Experiment 1: VA5: NaOH 0.10M ; VA6 : HCl 0.10M
Experiment 2: VA19: KMnO4 0.020M ; VA20 : 20.0g Fe2SO4
Experiment 3: VA21: KMnO4 0.020M ; VA22 : 5.0g of ethanedioic acid, H2C2O4.2H2O.