1

Unit-IV
Electrochemistry
Theory of electrolytes, migration of ions, transport number and electrochemical theory
of corrosion.
Theory of Electrolytes:
An electrolyte is a compound which produces an ionic solution when dissolved in an
aqueous solution. For example, a salt like KCl would produce an electrolyte solution. Those
compounds which produce a large number of ions in solution are called strong electrolytes.
KCl, because it is highly soluble, would be a strong electrolyte. On the other hand, those
compounds which produce a small number of ions in solution are weak electrolytes.

\
2
3
4
5
6
7
 8

FARDAY’S LAWS OF ELECTROLYSIS

Michael Faraday studied the quantitative aspect of electrolysis. He discovered that there exists
a definite relationship between the amounts of products liberated at the electrodes and the quantity of
electricity used in the process. In 1834, he formulated two laws which are known as Faraday’s Laws
of Electrolysis.

First Law:
The amount of a given product liberated at an electrode during electrolysis is directly
proportional to the quantity of electricity which passes through the electrolyte solution.

Second Law:
When the same quantity of electricity passes through solutions of different electrolytes, the
amounts of the substances liberated at the electrodes are directly proportional to their chemical
equivalents.
 9

Electrochemical equivalent defined in light of First law:

If m is the mass of substance (in g) deposited on electrode by passing Q coulombs of electricity, then
mαQ
We know that Q = I x t
Where I is the strength of current in amperes and t is the time in seconds for which the current has
been passed.
Therefore, m α I x t
Or m=ZxIxt
Where Z is the constant known as the Electrochemical equivalent of the substance (electrolyte).
If I = 1 ampere and t = 1 second, then
m=Z
Thus, the electrochemical equivalent is the amount of a substance deposited by 1 ampere current
passing for 1 second ( i.e., one coulomb).

The electrical unit faraday:

The quantity of electricity required to liberate one gram equivalent of a substance is 96,500 coulombs.
This quantity of electricity is known as Faraday and is denoted by the symbol F.
The quantity of electricity needed to deposit 1 mole of the substance is given by the expression.
Quantity of electricity = n x F
Where n is the valency of its ion. Thus the quantity of electricity required to discharge :
One mole of Ag+ = 1 x F = 1F
One mole of Cu2+ = 2 x F = 2F
One mole of Al3+ = 3 x F = 3F
10
11
12
13
14
 15

COROSSION

Corrosion (from Latin corrodere, “gnaw to pieces”) of metals is the spontaneous chemical
(oxidative) destruction of metals under the effect of their environment.

Corrosion is an undesirable process. Due to corrosion there is limitation of progress in many areas.
The cost of replacement of materials and equipments lost through corrosion is unlimited.

Most often it follows an electrochemical mechanism, where anodic dissolution (oxidation) of

the metal and cathodic reduction of an oxidizing agent occur as coupled reactions.

Corrosion (rusting) of metals is causing huge losses to the economy. This process affects the
metal structures of buildings and bridges, the equipment of chemical and metallurgical plants,
river and sea vessels, underground pipelines, and other structures.

A green film of basic carbonate [CuCO3 + Cu(OH)2] is formed on the surface of copper, when
it is exposed to moist-air containing carbon dioxide.

CAUSES OF CORROSION

1) Native State: The metals exist as such in the earth crust then the metals are present in a native
state. Native state means free or uncombined state. These metals are non-reactive in nature. They are
noble metals which have very good corrosion resistance. Example: Au, Pt, Ag, etc.,

2) Combined State: Except noble metals, all other metals are highly reactive in nature which
undergoes reaction with their environment to form stable compounds called ores and minerals. This is
the combined state of metals. Example: Fe2O3, ZnO, PbS, CaCO3, etc.,

3) Metallic Corrosion: The metals are extracted from their metallic compounds (ores). During the
extraction, ores are reduced to their metallic states by applying energy in the form of various
processes. In the pure metallic state, the metals are unstable as they are considered in excited state
(higher energy state). Therefore as soon as the metals are extracted from their ores, the reverse
 16

process begins and form metallic compounds, which are thermodynamically stable (lower energy
state). Hence, when metals are used in various forms, they are exposed to environment, the exposed
metal surface begin to decay (conversion to more stable compound).
17
18
 19

Electromotive Force (EMF)

20
21
22
23
24
 25

pH in textile wet processing:

In textile wet processing there are a lot of procedures, which require the use of a
reducing agent. Typical examples are the reduction of vat dyes, the reduction clearing of
disperses dyes, stripping of dyes etc. Well-known reducing agents like sodium dithionite
(hydrosulphite) are commonly used. In modern wet processing the demands go further and
additional properties are required. This includes the need for products to be liquid, for use in
automated color kitchens, and also ecology is becoming increasingly important.
 26

Effectivity in relation to pH
For most reducing agent there is a strong dependency towards the pH. This also gives
an indication of where the product can be applied. Hydrosulphite is known to have a flat pH
dependency curve. This is an advantage, since the results remain the same over a broad pH
range, for instance vat dyeing. However, a product based on thioureadioxide, is giving better
results at higher pH’s, which makes it more suitable for stripping and reduction clearing, but
not applicable for processes at neutral and acid pH, e.g. for bleaching of wool and polyamide.
These are the pH-range from slightly acid to slightly alkaline (pH 5-8). In both ranges there
are numerous applications, which are outlined below.

Reduction potential
This is a very important item. It is often misunderstood or misinterpreted. Every
chemical product, which has to be reduced, whether it is a dye or something else, needs a
very specific minimum reduction potential. Every reducing agent yields a certain reduction
potential, of course depending on pH, temperature, time etc. This means that some products
can be reduced by certain reducing agents, but other products can't. This means that there is a
strong selectivity. Increasing the amount of reducing agent will not help in this case, because
the reduction potential is only to a certain extent depending on amount. Liquid reducing
agents, in general, have lower reduction potentials than the well known powders.
 27

Enzymes are biocatalysts, they differ from normal chemical catalysts because they are
very specific in their action, are thermo-labile, have relatively low energies of activation and
are usually active only over a narrow range of pH.
The pH range from 4 to 8 is normally safe for fibroin and it has been found that alkaline
conditions are less harmful to fibroin than acid conditions. In contrast to fibroin, the solubility
of Sericin is very high at pH values between 1.5 and 2 and between 9.5 and 10.5.

Advantages
1. Lower discharge of chemicals and waste water and decreased handling of hazardous
chemicals for textile workers.
2. Improved fabric quality.
3. Traditionally, to get the look and feel of stone washed jeans, pumice stones were
used.
4. More fashion choices longer garment life/wear due to lower damage of original
fabric.
5. Reduced chemical load, reduced water consumption, lower energy consumption.