Dyes

Prepared by

CH-3 Dr. Khalid Ahmad Shadid

Chemistry Department
Islamic university in madinah
 Definition of dye 2
• Definition: it’s a stable coloring matter which can be applied on the substrate in the form of
solution or dispersion and which can import color to substrate.

• Prorerties of a good dye:

(1) it should have affinity for the fibres.

(2) Resistance to the action of water, dilute acids and alkalis, various organic solvents used in
dry cleaning.

(3) it should have attractive color, once applied to substrate it should be not easily removed.

(4) it should be soluble in water or the medium through which it is applied fibres, it should form
fine and stable dispersion in that medium.
 Classification of dyes 3

• Dyes are classified in two ways:

(1) according to their chemical constitution.

(2) by their method of application to the fibre.

• (1) Chemical classification: It is rather difficult to classify the dyes in distinct

groups because the chemical constitution of dyes is very much varied. However,

they are classified as : Nitro, Nitroso, Azo, Triaryl methane, Anthraquinone,

Indigoid, Phthalocyanine, Acridine, Sulphur dyes etc.

 2. Classification according to application: 4
(i) Acid dyes: These are sodium salts of sulphonic acid and carboxylic acids. They
can be applied to wool, silk, polyamides and acrylic fibres.
(ii) Basic dyes: These are salts of the colour bases.
(iii)Mordant dyes: These cannot be fixed on the fibre directly but require the help
of a mordant. For acidic dyes, metal hydroxides Al(OH)3, Cr(OH)3, Fe(OH)3, etc
are used as mordants. For basic dyes, tannin ( tannic acid ) is used as a
mordant. The metal salts formed are termed as ‘lakes‘.
(iv) Vat dyes: These are applied to the fibre in their reduced form (Leuco
compounds) After the application to the fibre, the leuco compound is
reoxidised to the dye. They are mainly used with the cotton fibres. Indigo is a
very well-known example of a vat dye.
 2. Classification according to application: 5
v. Disperse dyes: These are water-insoluble dyes and are used with synthetic
fibres. Before application they are dispersed with suitable reagents.
vi. Azoic dyes: These are insoluble azo dyes Hence they are produced on the fibre
itself. Cellulose fibres are mainly dyed with them.
vii. Reactive dyes: They contain a reactive group which combines directly with
cellulosic fibres.
viii.Sulphur dyes: These are mainly used with cellulosic fibres.
ix. Metal complex dyes: These are different from the mordant dyes. They are
prepared as complexes which are then applied to the fibres.
x. Organic pigments: pounds and are used as pigments for colouring paints. When
made water-soluble, they are used as dyes.
 Method of application of dyes: 6
It is already said earlier that the method of application of a dye to a fibre depends
upon the nature of the fibre as well as that of the dye. Fibres may be natural or
synthetic. Natural fibres may be of vegetable origin ( e.g. cotton, linnen, hemp,
Jute etc) or of animal origin (e.g, Wool, Silk, leather, fur etc.) Vegetable fibres are
cellulosic in nature while animal fibres are protein in nature.

Synthetic fibres are high polymers that are built of various types of monomeric
units. They may be polyamides (Nylons), polyesters (Terylene), polyacrylo nitriles
(Orlon) etc. Before dyeing, fibres are treated chemically.

The dye molecule can bind to the fibre in four ways : (i) by covalent bonds (ii) by
hydrogen bonds (iii) by ionic bonds and (iv) by van der Waals forces. The type of
bonding of the dye to the fibre depends largely on the nature of the fibre.
 Synthesis of some typical dyes: 7
(1) Methyl orange (helianthin or Orange III) : Methyl orange is prepared by
coupling diazotised sulphanilic acid with dimethylaniline:
H3OS N N ClH N(CH3)2

Diazotised sulphanilic acid

Dimethylaniline
(p-sulphonic benzene diazonium chloride) NaOH

H3OS N N N(CH3)2

O3S N N N(CH3)2 Methyl orange

Orange Methyl orange is an acid azo dye. However it is not used
as a dye but rather as am acid-base indicator, being
O3S HN

Red
N N(CH3)2
orange in alkaline solution, and red in acid solution.
 (2) Alizarine (1,2-dihydroxy anthraquinone) 8
• It is an anthraquinoid dye and one of the most important of the class.
• It is the chief constituent of the madder root. (Rubia tinctorum). Alizarin was valued for its
Turkey Red shade.
• Preparation: It is prepared by sulphonating anthraquinone with fuming sulphuric acid at
elevated temperature and fusing sodium anthraquinone-2-sulphonate with NaOH and the
calculated quantity of KClO3 at 180-200 ͦ C under pressure. The function of KClO3 is to provide
oxygen for the oxidation of carbon atom one to -C-OH- group.
• Alizarin forms ruby red crystals (m.p. 290°C). It dissolves in alkali to give a purple
solution. It is a mordant dye and the colour of the lake depends upon the mordant used.
Thus, with Al(OH)3 mordant, it gives red lake (Turkey red), with Fe (0H)3, a violet black
and with Cr(OH)3, a brown violet. Aluminium and Iron lakes are used for dyeing cotton
and for printing while Al and Cr lakes are employed for dyeing of wood. Dyeing with
Alizarin is almost obsolete now.
 sulphonating anthraquinone with fuming sulphuric acid at elevated
temperature and fusing sodium anthraquinone-2-sulphonate with NaOH 9
and The calculated quantity of KCl03 at 180-200 ͦ C under pressure
O
Na C o o
2 r
2O7
HS H
2 O SO3H
4
Anthracene Conc. H2S O4
O 150 °C
O
H -H2

O o o
Anthraquinone
H
Benzene
O NaOH
Phtalic anhydride

o OH o
OH (i) fusion with NaOH and
SO3Na
KClO3

(ii) HCl

o o
Alizarine
The function of KClO3 is to provide oxygen for the oxidation of carbon atom
one to -C-OH- group.
 (3) Indigo (Indigotin) 10
• It is a vat dye. It is one of the ancient dyes and was formerly obtained from the
leaves of the Indigo plant, specially cultivated for the purpose.
• Indigo does not occur as such in the plant but is derived from the colourless glucoside
indican. HO

O
O
OH
indican
OH
HO N
H

• Natural indigo has been almost completely replaced by synthetic indigo.

 (3) Indigo (Indigotin) 11

• Preparation: Indigo can be prepared by various methods. Below are given two
commercial syntheses.
(1) From aniline: Aniline is heated with chloroacetic acid and the phenyl glycine
formed is fused with sodamide and a mixture of NaOH and KOH at 200 ˚C to get
indoxyl which on exposure to air (O2) gives indigo.

HO O fusion with O
NaNH2, NaOH
ClCH2COOH
KOH, 200°C
NH2 N N
H
H
Indoxyl
 HO O fusion with NaO O
NaNH2, NaOH
ClCH2CH2OOH
KOH, 300°C
NH2 N N
H H
O O O

Oxidation
CH2 O2 H2C CH2

N N N
H H H

O
H
N

C C

N
H O
Indigo 12
 (3) Indigo (Indigotin) 13

• Indigo is a dark blue powder with a metallic lustre of copper. It is insoluble in water
When its paste is agitated with alkaline sodium hydrosulphite in vats, it gets reduced
to soluble colourless leuco compound.

•
 (3) Indigo (Indigotin) 14
The cloth to be dyed is soaked in this solution and then exposed to air when the indigo
is regenerated on the cloth by atmospheric oxidation. Thus Two geometrial forms, cis
and trans, are possible for Indigo. But the trans form is more stable.
O O O
H
N

N N N
H H H
Trans form
O
Cis form
The o-quinonoid charged structure shown below is possibly responsible for the colour
of Indigo. O H
O
H
N
N
Intermolecular Hydrogen bond
(trans form –stable) N
N H
O
H O Chromophore- conjugated system
THANK YOU •