Dyes & Color - Fibre2fashion
Dyes & Color - Fibre2fashion
Dyes & Color - Fibre2fashion
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<strong>Dyes</strong> & color<br />
By<br />
Mansoor Iqbal<br />
Senior Research Associate, Textile<br />
PCSIR Lab Complex Karachi<br />
e-mail :<br />
mansoorprocessing@hotmail.com
<strong>Dyes</strong> & <strong>Color</strong><br />
Any coloured compound is not a Dye or <strong>Dyes</strong>tuff. A dye is a coloured<br />
organic compound that absorbs light strongly in the visible region and can<br />
firmly attach to the fiber by virtue of chemical and physical bonding between<br />
group of the dye and group on the fiber. To be of commercial importance a dye<br />
should be fast to light, rubbing and water.<br />
Colour and dye have always played an important role in the life of man<br />
from time immemorial. Preparation of a colour and dyeing of cloth date back to<br />
antiquity. Fabrics dyed in indigo were found in the tombs of predyanstic Egypt.<br />
Let us now try to understand how we get sensation of colour.<br />
Modern theory of colour:<br />
Colour is a physiological sensation associated with the wavelength of<br />
light striking the retina of the eye. The sensation of colour is produced when<br />
light having a wavelength within the visible region of electromagnetic spectrum<br />
strikes the retina of the eye.<br />
The visible region of the spectrum extends from 4000 to 7500 Å in wavelength.<br />
Ultra<br />
Viole<br />
4000 4500 5000 5500 6000 7000<br />
Violet Blue Green Yellow Orange Red Infra<br />
red<br />
High Increasing Energy Low<br />
When white light falls on a substance, the light may be completely<br />
reflected and in this case substance will appear white. If it is completely<br />
absorbed, the substance will appear black. If a substance absorbs all visible<br />
light except that corresponding to e.g. yellow, it will transmit or reflect only<br />
yellow colour and will be seen as yellow. However, it is generally seen that,<br />
light of only one colour is absorbed in which case the substance will appear to<br />
have the complementary colour. Thus, if the light is absorbed from the violet<br />
region of spectrum, the substance will be seen as yellow. If light is absorbed<br />
from the red region, the substance will appear green.
Wavelength Colour absorbed Visible colour<br />
absorbed (Å)<br />
(complementary<br />
colour)<br />
4000 – 4350 Violet Yellow Green<br />
4350 – 4800 Blue Yellow<br />
4800 – 4900 Green blue Orange<br />
4900 – 5000 Blue green Red<br />
5000 –5600 Green Purple<br />
5600 – 5800 Yellow green Violet<br />
5800 – 5950 Yellow Blue<br />
5950 – 6050 Orange Green blue<br />
6050 – 7500 Red Blue green<br />
Otto Witt theory of colour (1876):<br />
An early theory of dyes first formulated by O. Witt provided a basis for<br />
understanding the reaction between colour and structure of the molecule.<br />
According to the O. Witt colour theory a dye is made up of two essential kinds<br />
of parts, Chromophores and Auxochromes. He designated a group that produces<br />
colour as a chromophore (Gr, Kuroma. colour + Phors carrier). Chromophores<br />
are unsaturated groups. Presence of at least one such group is essential to<br />
produce a colour in an organic compound and a molecule containing such a<br />
group is called as chromogen.<br />
Some most effective chromophores are<br />
-N= 0<br />
+<br />
N<br />
0<br />
0<br />
Nitroso<br />
-N= N-<br />
Azo<br />
0 0<br />
O O<br />
P-Q uina d O-Quinad<br />
Thus for example nitrobenzene is pale yellow, azobenzene is orange-red, pquinones<br />
are yellow and o-quinones are orange or red.<br />
Certain other unsaturated groups produce colour only when several of them are<br />
present in a molecule and when they are conjugated. They are<br />
Thus though acetone is colourless, biacetyl colour.<br />
C = C<br />
Ethylene<br />
C = O<br />
Carbonyl<br />
0<br />
C = N -<br />
Azomethine
O<br />
||<br />
CH3 – C – CH3 Acetone Colourless<br />
O O<br />
|| ||<br />
CH3 – C – C – CH3 Biacetyl Yellow<br />
O O<br />
|| ||<br />
CH3 – C – CH3 – C – CH3 Acetonyl Colourless<br />
Acetone<br />
O. Witt also observed that certain groups, while not producing colour<br />
themselves, are able to intensify the colour when present in a molecule together<br />
with a chromophore. These are called auxochromes (Gr, auxanein = to<br />
increase). The most effective auxochromes<br />
H<br />
|<br />
–OH –OR –NH2 –N–R –NR2<br />
Hydroxyl Alkoxy Amino Alkylated<br />
Amines<br />
Thus nitrophenols and nitroanilines are more intensely coloured than<br />
nitrobenzene and aniline and are deep yellow to orange.<br />
Further auxchoromes are salt forming groups, i.e., they are basic or<br />
acidic and makes the coloured compound to attach itself to the fabric, so that it<br />
is fast to light, soap and water. Acidic auxochromes like – OH, --COOH and –<br />
SO2H give acidic dyes and basic auxochromes like – NH2 – NHR and – NR2<br />
gives basic dyes. Auxochromes like – SO3H group has little value as<br />
auxochrome but it has a solublishing effect. The halogen atom also functions as<br />
auxochrome and the relative order of colour intensifying effect is I>Br>Cl. It<br />
can be observed that all the auxochromic groups contain atoms with unshared<br />
pair of electrons.<br />
According to Witt theory of colour and constitution chromogen is a<br />
compound which contains a chromophore –N=N. It is a bright red compound<br />
but not a dye.<br />
C6H5 – N = N – C6H5<br />
On the other hand p-hydroxy-azo benzene is acid dye because<br />
H2O – C6H4 – N = N – C6H5<br />
It contains – OH group, an acid, auxochrome, and p-amino azobenzene is a<br />
basic dye, as it has basic auxochrome – NH2.
Azobenzene, anthraquinone, dinitro benzene are chromogens<br />
O O<br />
|| ||<br />
and are coloured due to the presence of –N=N, --C--C, --NO2, groups<br />
respectively. The chloromogens, on reduction give the colourless compounds,<br />
for examples azobenzene, a bright red compound, on reduction forms the<br />
colourless hydrazobenzene.<br />
C6H5 – N = N – C6H5 C6H5 – NH – NH –C6H5<br />
Azobenzene Hydrazobenzene<br />
Sometimes the conversion is reversible. In this case the reduction<br />
products are called “Lecuo compounds”.<br />
H2<br />
Azobenzene Red Hydrazobenzene (colourless)<br />
Oxidation<br />
H2<br />
H2<br />
Indigo Blue Indigo white (colourless)<br />
Oxidation<br />
Sometimes reduction completely decomposes the coloured compound,<br />
such reduction products are called “Leuco compounds”.<br />
Valence bond approach to colour:<br />
Like many other theories, the Witt theory has also been replaced by<br />
modern electronic theory. According to this theory, it is the resonance<br />
stabilization of excited states that is responsible for the absorption in the visible<br />
region. When ultraviolet or visible light is absorbed by a molecule, an electron<br />
is excited, that is, it is promoted to an orbital of higher energy. The wavelength<br />
of light absorbed depends on the energy difference between the excited and<br />
ground states of the molecule. The smaller difference between the two states,<br />
the longer is the wavelength of the light absorbed.<br />
The energy required to promote an electron depends upon the<br />
environment of the electron. Sigma (σ) bond electrons are firmly held and very<br />
high energy (or short wavelength) is necessary to promote electrons and may at<br />
times break the molecule and form free radical.<br />
Pi (π) electrons are less firmly held and require less energy (or longer<br />
wavelength) to excite. Electrons belonging to conjugated systems required even<br />
less energy (still longer length). Conjugation and resonance stabilize the<br />
excited state by sharing and delocalizing higher energy of the excited electron.
As conjugation and resonance increases, the wavelength of light absorbed also<br />
increases and when the wavelength is long enough to be in the visible region,<br />
we observe colour. This can be explained with the help of following example.<br />
Ethylene absorbs light in the ultraviolet part of the spectrum 1800 Å.<br />
Butadiene, with two conjugated double bonds, absorbs at 8170 Å (a wavelength<br />
closer to visible region) and hexatriene, with three conjugated double bonds,<br />
absorbs at 2580 Å (a wavelength still closer to visible region). But all the three<br />
compounds are colourless. However, as the number of conjugated double<br />
bonds increases, the absorption falls in the visible region, for example in βcarotene<br />
there are eleven conjugated double bonds and absorbs at 4510 Å, that<br />
is, in the visible region. The light absorbed is blue and we see the<br />
complementary orange colour.<br />
H2C + CH2<br />
Ethylene<br />
(Colourless)<br />
H<br />
3CH3 H<br />
2C<br />
H<br />
2C<br />
C<br />
CH2 = CH – CH = CH – CH = CH2<br />
1: 3: 5 Hexantriene<br />
(Colourless)<br />
H2<br />
H<br />
3<br />
H3 H3 H3 H3<br />
CCH=CHC=CHCH=CHC=CHCH=CHCH=CCH=CHCH=CCH=CHC<br />
CH2=CH–CH = CH2<br />
1: 3 Butadiene<br />
(Colourless)<br />
H<br />
3CC<br />
H<br />
3CH3 Β-CAROTENE<br />
Benzene absorbs light at 2550 Å and is colourless. Aniline, which<br />
absorbs light at about 3000 Å, is also colourless; nitrobenzene absorbing light<br />
slightly above 4000 Å is pale yellow and p-nitro aniline absorbing light at 4500<br />
Å is a yellow compound.<br />
Bathochromic effect:<br />
In this case benzene ring may be considered to be chromophore, while amino<br />
group and nitro group auxochromes. When they are conjugated, the longer<br />
resonance system decreases the energy gap between the ground state and<br />
excited state transitions, thus producing visible colour. All these groups, which<br />
lengthen wavelength of absorption, are bathochrome groups. Thus<br />
displacements (or shift) to longer wavelength are known as bathochromic<br />
effects or bathochromic shift and displacements to shorter wavelength are<br />
hypsochromic. Hypsochromes are groups which decrease resonance. This is<br />
done by forcing the pi (π) orbitals out of planarity. For example when alkayl<br />
group on benzene ring is ortho to adjacent rings or chains, the molecule is<br />
distorted out of planarity and resonance is decreased. As the number of fused<br />
C<br />
H2<br />
H2<br />
H2
ings increases, the absorption in the visible region also increases e.g.<br />
naphthacene absorbs in blue region and is yellow. Pentacene absorbs in orange<br />
region and is blue. Graphite, which is a sheet of benzene rings is black, it<br />
absorbs all colours almost completely.