INTRODUCTION

DYE
A dye is a colour substance that has an affinity to the substrate to which
it is being applied. The dye is generally applied in an aqueous solution,
and may require a mordant to improve the fastness of the dye on the
fiber.
Dyes are colored because they absorb only some wavelengths of
visible light. Dyes are usually soluble in water whereas. Some dyes can
be rendered insoluble with the addition of salt to produce a lake pigment.
Evolution of Dyes
The preparation and application of dye stuffs is one of the oldest forms
of human activities. Evidences of which were found by Excavation at
archaeological sites where ancient fabrics were unearthed. There is also
mention of it in the Bible and other works of classical antiquity. It was in
2600 BC when earliest written records of the use of dye stuffs were
found in China.

Perhaps one of the real breakthroughs in the history of dyes came in

1856 when a teenager who was experimenting at
his makeshift laboratory in home made a certain
discovery that acted as a sort of launching pad
for the modern chemicals industry.

William Perkin an 18-year-old student was

working on chemical synthesis of natural
products. In a classic case of serendipity, the
young William Perkin chanced upon his now
famous 'Aniline Mauve' dye while he was attempting to synthesize
quinine, the only cure for malaria. Perkin named his
colour Mauveine, after the French name of non-fast colour which was
made of natural dyes. So "Mauve" (a basic dye) was the first synthetic
dye stuff. Mauve was a derivative of coal tar. It was the first mass-
produced dye, that was commercially available and the idea was born
that a colour could be made in the factory. It was indeed a revolution.
TYPES OF DYES
Natural-Dye:
Natural dyes are simply dye substances extracted from natural
sources. Although the main source of dyes for early times, they
have largely been replaced by synthetic dyes, which are usually
more reliable, cheaper and can be supplied more readily. Natural
dyes still in use include haematoxylin, carmine, orcein.

Colouring materials have been used for many thousands of years

by man. Leather, cloth, food, pottery and housing have all been
modified in this way. Some of our most common dyes are still
derived from natural sources. These are termed natural dyes. The
Colour Index uses this as a classification and naming system.

Each dye is named according to the pattern:

Natural + base colour + number

Natural dyes are often negatively

charged. Positively charged natural dyes do exist, but are not
common. In other words, the coloured part of the molecule is
usually the anion. Although the molecular charge is often shown
on a specific atom in structural formulae, it is the whole molecule
that is charged. Many, but by no means all, natural dyes require
the use of a mordant.
Synthetic-Dye:
Dyes derived from organic or inorganic compound
are known as synthetic dyes. Examples of this
class of dyes are Direct, Acid, Basic, Reactive,
Mordant, Metal complex, Vat, Sulphure , Disperse
dye etc. Synthetic dyes quickly replaced the
traditional natural dyes.

They cost less, they offered a vast range of new

colors, and they imparted better properties to the
dyed materials dyes are now classified according
to how they are used in the dyeing process.
Acid dye:

Acid dyes are water-soluble anionic dyes, containing one or

more sulfonic acid substituents or other acidic groups. An
example of the class is Acid Yellow 36.

Acid yello36
Acid dyes are water-soluble anionic dyes that are applied to
fibers such as silk, wool, nylon and modified acrylic fibers using
neutral to acid dye baths. Acid dyes are not substantive to
cellulosic fibers. Most synthetic food colors fall in this category.
The dyeing process is reversible and may be described as
follows:
Azoic Dye:
Azoic dyes contain at least one azo group (-N=N-) attached to
one or often two aromatic rings. These dyes are used primarily
for bright red shades in dyeing and printing since most other
classes of fast dyes are lacking in good red dyes. Azoic dyes,
called Naphthols in the industry, are actually manufactured in
the fabric by applying one half of the dye. The other half is then
put on and they combine to form the finished color. Unless they
are carefully applied and well washed, they have poor fastness
to rubbing or crocking.

The production of bluish red azoic dye from the following two
components is an example.
 Properties of dyes:

 These dyes are economical dyes and are generally used

to produce dark shades such as dark greens , dark blues
and blacks.

 These dyes have good leveling and color fastness

properties.

 The interaction between fiber and dye is established

through very strong ionic bonds , which are formed
between the anionic groups of the colorant and
ammonium cations on the fiber. Chromium or the
metal ion acts as bridge between the dye and fiber ,
which gives rise to a very strong linkage , resulting into
excellent fastness properties.
Some dye application:

Name of Dyes Application

Man made fiber(Nylon),

Acid dye Natural fiber (Silk, Wool)

Man made fiber (Viscose),

Direct Dye Natural fiber (Cotton)

Man made fiber (Viscose),

Vat dye Natural fiber (Cotton, Silk, Wool)

Nylon, Polyester, Acrylic, Tri-acetate, Di-

Disperse dye acetate

Basic dye Jute, Acrylic

Reactive dye Cotton, Wool, Silk, Viscose, Nylon

Sulfur dye Cotton, Viscose

Mordant dye Cotton, Wool, Silk

Pigment Cotton, Man made fiber

Mineral Cotton, Wool, Silk

Azoic dye Cotton, Viscose

Aniline Black Cotton

Rapid and Rapidson

dye Cotton

Onium dye Cotton, Jute

Hazards of using synthetic dyes.
Synthetic Dyes find use in a wide range of industries but are of primary
importance to textile manufacturing. Wastewater from the textile
industry can contain a variety of polluting substances including dyes.
The environmental and subsequent health effects of dyes released in
textile industry wastewater are becoming subject to scientific scrutiny.
Environmental legislations are being imposed to control the release of
dyes, in particular azo-based compounds, into the environment.
Wastewater from the textile industry is a complex mixture of many
polluting substances ranging from organochlorine-based pesticides to
heavy metals associated with dyes and the dyeing process. During textile
processing, inefficiencies in dyeing result in large amounts of the
dyestuff being directly lost to the wastewater; which ultimately finds its
way into the environment.

Colorants that enter the wastewater streams normally pass through a

wastewater treatment plant where they are eliminated to a large degree
by adsorption on sludge. The extent to which residual amounts reach the
surface waters depends on the efficiency of treatment processes. Low
concentrations of dyes in waste water do not normally pose any
significant environmental hazard. Environmental problems arise mainly
from inefficient removal of dyes or disposing the untreated dye effluent
to water receiving bodies. This is normally the case in most developing
countries.
Advantages of Natural Dyes
 Minimal Environmental Impact – Because they come
from natural sources, natural dyes are not harmful to the
environment, which makes it so appealing for consumers.
Natural dyes are biodegradable and disposing them don’t
cause pollution.
 Renewable – Natural dyes are obtained from renewable
sources that can be harnessed without imposing harm to the
environment.
 Color pay-off – If you’re going for a soft hue or soothing
shade, natural dyes can help you achieve that look.
 Safe – Some natural dyes, such as carmine found in
lipsticks, will not cause harm or health problems when
ingested.
Disadvantages of Natural Dyes
 Cost – A larger amount of natural dyes may be needed in order to
dye a specific amount of fabric as opposed to synthetic dyes. For
instance, one pound of cotton may be dyed with just five grams of
synthetic dye, whereas 230 grams of natural dye are needed to dye
the same amount of material. Since that is the case, using natural
dyes is more expensive than synthetic dyes.
 Color pay-off – Color pay-off from natural dyes tend to fade
quickly. More so, quality may not be as consistent than what
synthetic dyes can deliver.
 Availability – Another issue with natural dyes is their availability.
It can be difficult to produce because the availability of raw
materials can vary from season to season, place, and species,
whereas synthetic dyes can be produced in laboratories all year
round.
 Harmful Effects – Natural dyes can also be harmful to some
extent. Logwood has ingredients, hematein and hematoxylin, that
can be have harmful effects when inhaled, ingested, or absorbed
through the skin. Bloodroot, another natural dye source, can cause
irritation and inflammation when inhaled. More so, natural dyes
may need mordants for application. While these substances help
the dye stick to fabrics, they can also be toxic. Example of
mordants used in natural dyes are aluminum, copper, iron, and
chrome.
 Sustainability – While natural dye sources are renewable,
sustainability can still be an issue for natural dyes because
producing them require vast areas of land.
 EXPERIMENT

AIM: Preparation of Phenyl-azo-β-naphthol

Theory:

2-Naphthol aniline dye or Phenyl-azo-β-naphthol is an orange-red dye. It

belongs to a large class of azo-compounds, all of which contain the
characteristic grouping

Azo compounds are all coloured compounds. For the preparation of this
dye, aniline is diazotised and then diazonium salt thus obtained is
subjected to coupling reaction with 2-naphthol.

Apparatus:

 One 100 mL conical flask

 One 100 mL beaker
 One 250 mL beaker
 Ice-bath
 Glass-rod
 Buchner funnel
 Water pump
Chemicals Required:

 Aniline = 4.5 ml
 Sodium nitrite = 4g
 2-Naphthol = 7 g
 Cone, hydrochloric acid = 10 ml
 Glacial acetic acid = 40 ml

Procedure:

1. Take a 100 ml conical flask and add 2.25 ml of aniline, 5 ml of

conc. HCl and 10 ml of water. Cool this solution to 5°C by placing
the conical flask in a trough containing ice- cold water.

2. In a 10 ml beaker dissolve 2 g of sodium nitrite in 10 ml of water

and cool this solution also to 5°C.

3. Now slowly add sodium nitrite solution to the solution of aniline in

conc. HCl.

4. Dissolve 3.5 g of 2-naphthol in 30 ml of 10% NaOH solution taken

in a 250 ml beaker and cool this solution to 5°C by placing in an ice
bath. Some crushed ice may be added directly to fecilitate cooling.

5. Now add the diazotised solution very slowly to the naphthol

solution with constant stirring. The mixed solutions immediately
develop a red colour and the phenyl-azo-β- naphthol rapidly
separates as orange-red crystals.

6. When the addition of diazo solution is complete, allow the mixture

to stand in ice-salt mixture for 30 minutes, with occasional stirring.
Filter the solution through a buchner funnel under suction from the
pump. Wash the phenyl-azo-β-naphthol with water and dry the
crystals obtained by pressing between the folds of filter paper.
 7. Recrystallise the product from glacial acetic acid. Filter the crystals
obtained at the pump. Wash with a few ml of ethanol to remove
acetic acid. Phenyl-azo-β-naphthol is obtained as orange-red
crystals. Expected yield is 1.5 g and melting point is 133°C.

Precautions:

1. The solution of the aniline hydrochloride should be cooled

to 5°C, and this temperature should be maintained
throughout the addition of the sodium nitrite solution.

2. Addition of sodium nitrite should be very slow because the

reaction is exothermic and may cause the temperature to
rise.