Dyes

UNIT - 2

Explain the Chemistry and Applications of Dyes

 What are Dyes ?
Dyes are the coloured
substances used to colour
fibres, paper, leather,
foodstuffs etc.

https://studioresha.com/blogs/news/story-indigo-dye-make-indigo-color
 Theories of Colour and Constitution

1. Otto Witt’s Chromophore - Auxochrome Theory

The colour of organic compounds is mainly due to the presence of

unsaturated groups known as chromophores (Greek word; Chroma
means colour and Phoros means to bear). The compound bearing
chromophoric groups is called chromogen.
The greater the number of
chromophores in a chromogen, the
greater is the intensity of the colour
in the chromogen.

This effect is particularly marked

when the chromophores are in
conjugation with each other.
Certain substituents fail to produce colour by themselves but they
deepen the colour of the chromophoric units present in the
molecule. Such substituents are termed as Auxochromes.

Examples of auxochromes - NH2, NR2, OR, X, OH

The Auxochromes are generally salt forming groups and perform
two functions, namely deeping of the colour and acting as
anchoring units of the dye molecules.

Dye may be defined as a chromogen containing auxochrome.

Dye = Chromogen + Auxochrome

Dye must in addition, possess certain other groups (eg., -SO3H) to

impart water solubility.
To sum up, the colours of organic compounds according to the Witt
theory are explained in terms of the types and positions of the
chromophores present in a molecule. The more the number of
chromophores and greater the conjugation in a molecule the
deeper the colour.

For a compound to act as a dye molecule it should have both

chromophoric and auxochromic groups.
Introduction of groups like auxochromes in a chromogen shifts the
absorption band from lower to higher wavelength region. This shift
in the absorption band from lower wavelength to higher
wavelength region of electromagnetic spectrum is called
Bathochromic shift or Red shift.

Such effect is observed when the hydrogen atom of an

auxochrome is replaced by alkyl groups.
If the absorption band of a chromophore shift from higher
wavelength to lower wavelength region of electromagnetic
spectrum is called Hypsochromic shift or Blue shift.

Such effect is observed when the hydrogen atom of an

auxochrome is replaced by acyl groups.
 Hyperchromic shift

Hypsochromic shift Bathochromic shift

Hypochromic shift
2. Quinonoid Theory

Armstrong in 1885 suggested that all coloring matters may be

represented by quinonoid structures, and thus believed that if a
particular compound can be formulated in a quinonoid form it is
colored, otherwise it is colorless.
But the quinonoid theory is not sufficient to account for the coloring
characteristics of all the compounds. For example, iminoquinone and
di‐iminoquinone, both posses a quinoid structure even then they are
colorless.
3. Valence Bond Theory

According to this theory, electron pair

of a molecule in its ground state are in
a state of constant oscillation and
when placed in light, they absorb a
Photon of appropriate energy E and
gets excited. the wavelength of light
absorbed depends on the energy
difference between these two states
of the molecule. The smaller is this
difference, longer is the wavelength of
the light absorbed.
4. Molecular orbital theory

According to this theory the excitation of a molecule means the

transference of one electron from an orbital of lower energy to that of
higher energy. These electrons may be σ, π or n (non‐bonding)
electrons. The lower energy states are known as bonding molecular
orbitals and higher energy states are commonly known as
anti‐bonding orbitals.
 Classification of Dyes
There are several ways to classify dyes. The most common ways
of classifying dyes are..

★ Based on the Source

★ Based on the Structure of the chromophore
★ Based on Method of Application
 Classification Based on Source

Natural dyes are dyes that are derived from natural resources such as
plants, minerals, fungi etc..

Curcumin Hennatonnic acid

Indigo
Synthetic dyes are dyes that are synthesized in laboratories.

Fuchsine Eosin B Methylene Blue

 Classification Based on Structure

Gambine Y Gambine R

Picric acid Martius yellow

★ Azo Dyes

Methyl orange Congo Red Para Red

 Classification Based on Structure
★ Diphenylmethane Dyes

Auramine O Auramine G

★ Triphenylmethane Dyes

Malachite green Crystal Violet Rosaniline

 Classification Based on Structure
★ Anthraquinone Dyes ★ Indigo Dyes

Alizarin

★ Phthalein Dyes

Phenolphthalein

Fluorescein Eosin B
 Classification Based on Structure
★ Heterocyclic Dyes
★ Phthalocyanine Dyes
Classification Based on Method of Application
Under this classification, the dyes are classified according to the methods of
their application.

1. Direct dyes: These dyes are applied to the fabric by the direct method.
It consists of soaking the fabric in an aqueous solution of the dye,
taking it out, removing excess of the solution and then drying.

Direct dyes are strongly polar dyes used for polar fabrics (example
wool) or moderately Polar fabrics (example cotton, Ryon). This dyes are
further subdivided into acidic and basic dyes.

Eg., Martius Yellow

Classification Based on Method of Application
Mordant Dyes : Certain dyes have no natural affinity for the fabric and
therefore they cannot be applied directly but are applied with the help of
other agents known as mordants. Such dyes are called mordant dyes.

Salts of metals like Al, Fe and Cr and acidic substances like tannic acid may
be used as mordants.

Acidic dyes require basic mordants of metal oxides whereas basic dyes
require acidic mordants.
A fabric is first treated with a mordant and then with the dye solution.
The mordant at first combines with the acidic or basic groups in the
fabric and this then combines with the basic or acidic dyes.

Alizarin is an example of mordant dye.

Mordant dyeing is most suitable for wool and nylon.

 Classification Based on Method of Application

VAT Dyes: These dyes are insoluble in water but on reduction with sodium
hyposulphite in a VAT form a colourless soluble compound which have great
affinity for cotton and other cellulose fibres.

The fibre is soaked in the solution of a reduced dye and then hung in air or
treated with oxidants. As a result the colorless compound is oxidized back to
the insoluble dye which is bound to the fabric.

Indigo is a typical example of vat dye.

 Classification Based on Method of Application

Ingrain Dyes: The water insoluble azo dye may be produced in the fibre itself.
For this the cloth is first soaked in the solution of a coupling reagent like
phenol or naphthol. It is then immersed in the solution of an appropriate
diazonium salt. The dye developed in the fabric bind fast to it through the
auxochromes.

This dying is particularly suitable for cotton and other cellulosic fibres but may
also be used for nylon.

These dyes can be used for making printed fibres.

 Classification Based on Method of Application

Disperse Dyes: These dyes are insoluble in water but may be dispersed in a
colloidal form in water. The fabric is dispersed in the colloidal dispersion of the
dye.

The fine particles are absorbed Into the crystal structure of the fabric, in other
words the dye forms a solid solution in the fibre.

1-amino-4-hydroxy anthraquinone is an example of disperse dyes.

These dyes are useful for dyeing less polar fibres like Dacron or Orlon.
Bismarck Brown
Methyl Orange

Sulphanilic acid

Methyl orange is not a satisfactory dye for textiles

because it is sensitive to acids. It is used as an
indicator in acid-base titrations. It is golden yellow
in basic solution (pH < 4.4) while orange red in
acidic solution (pH > 3.1).
Malachite Green

H2SO4

Leuco Base (Colourless)

Used in dilute solution as a local antiseptic, Effective against fungi and gram
positive bacteria, Used as a dye for silk, wool, Jute etc.
Fluorescein
It is prepared by heating resorcinol (2 molecules) and phthalic anhydride (1
molecule) with zinc chloride at 190°C.

As a Marker in industries for detecting cracks

In ophthalmology for detecting dye eye
As fluorescent markers
Phenolphthalein

It is prepared by heating phenol (2 molecules) and phthalic anhydride (1

molecule) with zinc chloride at 190°C.
Phenolphthalein is not a dye. Phenolphthalein is insoluble in water, but
dissolves in alkalis to form deep red solutions. This is due to the
formation of a sodium salt, the ion of which is coloured because of
resonance. When excess of strong alkali is added, the solution of
phenolphthalein becomes colourless. This is attributed to the formation
of a trisodium salt, the jots of which is colourless because of loss of
resonance and quinoid structure.
Indigo Dye

Heumann's First Indigo Synthesis (1890). This involves the

condensation of aniline with chloroacetic acid to give
N-phenylglycine. The phenylglycine is then fused with sodium
hydroxide and sodamide at 250°C to form indoxyl, which on oxidation
by air yields the dye.
Alizarin Dye

It is 1, 2-dihydroxyanthraquinone. It is prepared from phthalic

anhydride by the following six steps.

Step I. Phthalic anhydride is

treated with benzene in the
presence of AlCl3 to give
o.benzoylbenzoic acid.
Step 2. o.Benzoylbenzoic acid is cyclized by
treatment with conc. H2SO4 to form
anthraquinone.

Step 3. Anthraquinone is heated with

fuming sulphuric acid at 180°C to give
anthraquinone-2-sulphonic acid.

Step4. Anthraquinoue-2-sulphonic
acid is converted into its sodium salt
by treatment with sodium hydroxide
Step 5. Sodium salt of
anthraquinone-2-sulphonic acid is fused
with sodium hydroxide in the presence of
potassium chlorate at 200°C under
pressure to give sodium salt of 1,
2-dihydroxyanthraquinone. The purpose
of potassium chlorate is to provide oxygen
for the oxidation of the carbon atom at C-I.

Step 6. Sodium salt of

1.2-dihydroxyanthraquinone is treated
with sulphuric acid to yield Alizarin.
Indigo Dye