CY 101: Titrimetric Analysis

Course Instructor: Dr. Asha Gupta

Reference Books: VOGEL’S Textbook of Quantitative Chemical
Analysis

CY 101: Crystal Field Theory &

Titrimetric Analysis
Titrations and its types, end & equivalence point, Standard
solution-Primary & Secondary. Strong acid-strong base
titration, Complexometric Titration. Hardness of water.
CaCO3 equivalence.

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 Titrimetric Analysis
The term 'titrimetric analysis' refers to quantitative chemical analysis
carried out by determining the volume of a solution of accurately known
concentration which is required to react quantitatively with a measured
volume of a solution of the substance to be determined. The solution of
accurately known strength is called the standard solution.
The reagent of known concentration is called the titrant and the
substance being titrated is termed the titrand/analyte.

The process of adding the standard solution until the reaction is just
complete is termed a titration.

The point at which this occurs is called the equivalence point or the
theoretical (or stoichiometric) end point

The completion of the titration is detected by some physical change,

produced by the standard solution itself (e.g. the faint pink color formed
by potassium permanganate) or, more usually, by the addition of an
auxiliary reagent, known as an indicator; alternatively some other physical
measurement may be used.

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Vogel’s Chapter 10, Pg 257 2
 Titrimetric Analysis
In the ideal titration the visible end point will coincide with the stoichiometric or
theoretical end point.

In practice, however, a very small difference usually occurs; this represents the titration
error.

The indicator and the experimental conditions should be so selected that the difference
between the visible end point and the equivalence point is as small as possible.

An indicator should be available which, by a change in physical properties (colour or

formation of a precipitate), should sharply define the end point of the reaction.

Equivalence point can often be achieved by measuring:

(a) the potential between an indicator electrode and a reference electrode

(potentiometric titration)

(b) The change in electrical conductivity of the solution (conductimetric titration)

(c) the current which passes through the titration cell between an indicator electrode
and a depolarised reference electrode at a suitable applied e.m.f. (amperometric
titration)

(d) the change in absorbance of the solution (spectrophotometric titration)

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 Classification
The reactions employed in titrimetric analysis fall into four main classes. The
first three of these involve no change in oxidation state as they are dependent
upon the combination of ions. But the fourth class, oxidation-reduction
reactions, involves a change of oxidation state or a transfer of electrons.

1. Neutralisation reactions, or acidimetry and alkalimetry. These include the titration of

free bases, or those formed from salts of weak acids by hydrolysis, with a standard
acid (acidirnetry), and the titration of free acids, or those formed by the hydrolysis of
salts of weak bases, with a standard base (alkalirnetry). The reactions involve the
combination of hydrogen and hydroxide ions to form water. Also under this heading
must be included titrations in non-aqueous solvents, most of which involve organic
compounds. (Acid-Base Titration)

2. Complex formation reactions. These depend upon the combination of ions, other than
hydrogen or hydroxide ions, to form a soluble, slightly dissociated ion or compound, as in
the titration of a solution of a cyanide with silver nitrate (2CN+ Ag+ ⇋ [Ag(CN)2] ) or of
chloride ion with mercury(I1) nitrate solution (2Cl + Hg2+ ⇋ HgCl2).

Ethylenediaminetetra-acetic acid, largely as the disodium salt of EDTA, is a very

important reagent for complex formation titrations and has become one of the most
important reagents used in titrimetric analysis. Equivalence point detection by the use of
metal-ion indicators has greatly enhanced its value in titrimetry. (Complexometric
Titration)
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 Classification
3. Precipitation reactions. These depend upon the combination of ions to form
a simple precipitate as in the titration of silver ion with a solution of a chloride. No
change in oxidation state occurs. AgNO3(aq) + NaCl(aq) →AgCl(s) ↓ + NaNO3(aq)

4.Oxidation-reduction reactions. Under this heading are included all reactions

involving change of oxidation number or transfer of electrons among the
reacting substances.

The standard solutions are either oxidizing or reducing agents.

The principal oxidizing agents are KMnO4, K2Cr2O7, Ce(SO4)2, iodine, potassium
iodate, and potassium bromate.

Frequently used reducing agents are iron(Il) and tin(Il) compounds, sodium
thiosulphate, arsenic(IIl) oxide, mercury(l) nitrate, vanadium(Il) chloride or
sulphate, chromium(Il) chloride or sulphate, and titanium(IIl) chloride or sulphate.

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 Standard Solution
The solution of accurately known strength is called the standard solution.

The word 'concentration' is frequently used as a general term referring to a

quantity of substance in a defined volume of solution.

Standard solutions are now commonly expressed in terms of molar conc. or

molarity (M).

In titrimetry, certain chemicals are used frequently in defined

concentrations as reference solutions. Such substances are referred to as
primary standards or secondary standards.

A primary standard is a compound of sufficient purity from which a

standard solution can be prepared by direct weighing of a quantity
of it, followed by dilution to give a defined volume of solution.

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 Primary Standard Solution
Should satisfy the following requirements.

1. It must be easy to obtain, to purify, to dry (preferably at 110-120 OC), and to preserve in
a pure state. (This requirement is not usually met by hydrated
substances, since it is difficult to remove surface moisture completely without effecting
partial decomposition.)

2. Should be unaltered in air during weighing; this condition implies that it should not be
hygroscopic, oxidized by air, or affected by carbon dioxide. The standard should maintain
an unchanged composition during storage.

3. Should be capable of being tested for impurities by qualitative and other tests of known
sensitivity. (The total amount of impurities should not, in general, exceed 0.01-0.02 per
cent.)

4. It should have a high relative molecular mass so that the weighing errors may be
negligible. (The precision in weighing is ordinarily 0.1-0.2 mg; for an accuracy of 1 part in
1000, it is necessary to employ samples weighing at least about 0.2 g.)

5. The substance should be readily soluble under the conditions in which it is employed.

6. The reaction with the standard solution should be stoichiometric and practically
instantaneous. The titration error should be negligible, or easy to determine accurately by
experiment.

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 Primary Standard Solution
In practice, an ideal primary standard is difficult to obtain, and a compromise between the
above ideal requirements is usually necessary. The substances commonly employed as
primary standards are indicated below:

(a) Acid-base reactions - sodium carbonate Na2CO3, sodium tetraborate Na2B4O7,

potassium hydrogen phthalate KH(C8H4O4), constant boiling point hydrochloric acid,
potassium hydrogeniodate KH(IO3)2, benzoic acid (C6H5COOH).

(b) Complex formation reactions - silver, silver nitrate, sodium chloride, various metals
(e.g. spectroscopically pure zinc, magnesium, copper, and manganese) and salts,
depending upon the reaction used.

(c) Precipitation reactions - silver, silver nitrate, sodium chloride, potassium chloride,
and potassium bromide (prepared from potassium bromate).

(d) Oxidation-reduction reactions - potassium dichromate K2Cr2O7, potassium bromate

KBrO3, potassium iodate KIO3, potassium hydrogen iodate KH(IO3)2, sodium oxalate
Na2C2O4, arsenic(III) oxide As2O3 and pure iron.

Hydrated salts, as a rule, do not make good standards because of the difficulty of
efficient drying. However, those salts which do not effloresce, such as sodium
tetraborate Na2B4O7.10H2 O , and copper sulphate CuSO4.5H2 O, are found by
experiment to be satisfactory secondary standards.

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 Secondary Standard Solution
A secondary standard is a substance which may be used for
standardizations, and whose content of the active substance has been
found by comparison against a primary standard. It follows that a
secondary standard solution is a solution in which the concentration of
dissolved solute has not been determined from the weight of the
compound dissolved but by reaction (titration) of a volume of the solution
against a measured volume of a primary standard solution.

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 Neutralization of a Strong Acid with a Strong Base

HCl
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 Neutralization of a Strong Acid with a Strong Base

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 Neutralization of a Strong Acid with a Strong Base

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 Neutralization of a Strong Acid with a Strong Base

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 Complexometric Titration

Pg.310-Vogel’s
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 Complexometric Titration

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 Complexometric Titration

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 Hardness of Water

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 Hardness of Water

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 Hardness of Water

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 Hardness of Water

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 Hardness of Water

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 Hardness of Water

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 Hardness of Water

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 Hardness of Water

Most common complexing agent used for determining the hardness of water

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 Hardness of Water

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 Hardness of Water

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 Hardness of Water

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 Hardness of Water

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