Chemical Methods of Analysis

Analytical methods are used in separation,

identification and quantitative estimation of materials

Physical analysis (determination of physical

quantities)

Chemical analysis (qualitative and

quantitative analysis)
Physical analysis Specific
gravity

Melting point

Purification Boiling point

Crystallization

Purification
CHEMICAL ANALYSIS
Qualitative analysis : It involves the separation
and detection of types of ions or radicals
present in a compound

It helps in identifying the elemental

composition of the material
Quantitative analysis: determination of amounts of components
in the samples

Volumetric or titrimetric analysis: Determination of

volume of solution of unknown concentration.

Gravimetric analysis: It is based on the measurement of

weight. It is concerned with the transformation of element
to be determined into a pure and stable state which is
suitable for weighing
 TYPES OF REACTIONS

1. Precipitation reaction: This reaction involves the formation of a sparingly

soluble salt. (Determination of chloride)

2. Complexometric reaction: This reaction involves the formation of a

soluble complex between the metal ion and the complexing agent. (EDTA )

3. Neutralization reaction: This reaction involves the neutralization of an

acid and a base.

4. Redox reaction: This reaction involves an oxidizing agent and a reducing

agent.
The volumetric analysis is based on the following:

1. Law of chemical equivalence: This law states that substances react with
each other in a definite ratio by mass. At a particular point called end-point,
the number of gram equivalents of the reacting substances becomes equal.

Number of gram equivalents of substance 1 = Number of gram

equivalents of substance 2

2. Normality equation: The law of chemical equivalence can be expressed in

terms of normality of the two reacting substances:
Some Terms Used in Volumetric Analysis

1. Titrant: The standard solution of accurately known strength.

2. Titrate /analyte: The solution containing the substance whose
concentration/strength is to be determined.
3. Equivalence point: The equivalence point in a titration is the point at
which the added titrant is chemically equivalent completely to the analyte in
the sample. End point is the point where the indicator changes its color.

4. Equivalence point comes before the end point.

5. End-point: The point, practically observed, at which a physical change is

observed near the equivalence point.
6. Indicator: The substance used for visual detection (by color change) on
completion of reaction at the end-point.
Types of indicators: The following types of indicators are used in volumetric
analysis: (a) Acid-base indicators (b) Redox indicators (c) Precipitation
indicators and (d) Complexometric indicators
7. Strength of the solution:

8. Normality (N):

9. Molarity (M):

10. Molality (m):

11. Parts per million (ppm) 1 mg of substance in 1 Litre of solution
12. EquivalentWeight
The weight of an element or compound that will combine with or
displace 8 grams of oxygen or 1.007 97 grams of hydrogen.
Also called: gram equivalent
13. Equivalent weight of an acid / base is to divide the molecular weight of
an acid by the number of replaceable H atoms; divide the molecular weight of
a base by the number of OH groups;

14. Equivalent weight of an oxidizing or reducing agent

The equivalent mass of an oxidising and a reducing agent may be
calculated by dividing the molecular mass of the oxidising or
reducing agent by change in oxidation number in the reaction.
15. Standard solution
Primary standard solution concentration does not change
over time
Highly stable compound
Not influenced by environment
Example: Oxalic acid, Potassium dichromate

Secondary standard solution Concentration changes over

time
Unstable
Influenced by environment
Example: NaOH, Potassium permanganate
 Neutralization
titrations

Redox titrations
Types of
Volumetric
Titrations Precipitation
titrations

Complexometric
titrations
Neutralization Titrations (AcidBase Titrations)

The titrations involving acid and alkali or in other words titrations involving
reaction between H+ and OH ions to form water are termed as neutralization
titrations or acidbase titrations.

Selection of Indicators and Their Action

1. methyl orange is pink in acidic medium and yellow in basic medium and
works within 3.14.4 pH range;
2. phenolphthalein is colorless in acidic medium and pink in basic medium and
works within 8.09.6 pH range and
3. methyl red is red in acidic medium and yellow in basic medium and works
within 4.56.5 pH range.
Redox Titrations

Involves an oxidizing agent and a reducing agent. Indicators: self (color change
in the reacting solution), internal (added to the volumetric flask), external (used
externally instead of adding to the volumetric flask)
+7

The increase in oxidation state of an atom, through a chemical reaction,

is known as an oxidation; The increase in oxidation state of an atom,
through a chemical reaction, is known as an oxidation;
Redox Indicators

1. Self Indicator ( one of the substance in the titration acts as indicator

KMnO4)

2. Internal Indicator (added inside the conical flask: diphenyl amine)

3. External Indicator (added outside the conical flast: potassium ferric

cyanide)
Potassium Permanganate Titrations

+7 +3 +2 +4

Potassium Dichromate Titrations

Iodine Titrations

Iodine is a mild oxidizing agent. It acts as an oxidizing agent in neutral aqueous

medium as per the following reaction:

Iodine titrations can be classified as:

1. Iodometry: (indirect titration of iodine with reducing agent) Titrations

in which iodine liberated during the oxidation of iodide ions by strong
oxidizing agent, is titrated with a reducing agent and the strength of the
oxidizing agent is estimated are called iodometric titrations.

2. Iodimetry: Titrations involving the direct titration of iodine with a reducing

agent are termed as iodimetric titrations. (reaction of sulphite with iodine)
Complexometric Titrations

Complexometric titrations refer to those titrations which are based on the

formation of a soluble complex between the metal ion and the complexing agent
(ligand). These titrations are generally used for the estimation of calcium and
magnesium by ethylenediamine tetraacetic acid (EDTA).

Selection of Indicators

Indicator for complexometric titration is selected such that it forms a less stable
complex with metal atom than the metalligand complex and releases the metal
ion at equivalence point resulting in a color change, thus indicating the end-point.
Most widely used indicator is Eriochrome Black T (EBT). It is known as metal
ion indicator because it forms intensely colored complexes with metal ions which
are visible to the eye even at low temperatures.
Estimation of Hardness of Water by EDTA Method

When the indicator is added to the hard water, the indicator EBT forms a pink
colored complex with the Ca2+ ions. When EDTA is added to the solution, it
chelates Ca2+ leaving the indicator EBT uncomplexed, which is blue in color.
Precipitation Titrations

Argentometric Titration (estimation of chloride ion in solution)

1. Mohrs method: (direct titration)

2. Volhards method: (back of titration)

 Substance dissolved in a solvent

Precipitate
Precipitation
Method Dried, filtered, purified, converted into
compound of known stoichiometric
composition
Compound weighed and analyte
Gravimetric
determined
Analysis
Sample dried or heated to separate volatile
and non volatile content
Volatilization Non-volatile residue is weighed
Method
Dried, filtered, purified, converted into
compound of known stoichiometric
composition