Dyestuff and Color Science

Engr. Dr Faiza Safdar

Introduction
 Colorant
• A Colorant is a matter when present on a substrate they selectively
modify the reflection or transmission of incident light thus imparting
color to the matter.
• Two types of colorants:
• Dyes
• Pigments
 Pigment
• A pigment is insoluble in water and other solvents, and has no affinity
for the substrate in which it is incorporated.
• These are dispersed in application media and applied in the form of
paste or dispersion.
• Have no affinity to wards substrate.
• Require a fixer/binder to stay on the substrate.
 Dyestuff
Dye:
• An ionized aromatic compound that have the ability impart color to
the substrate on which these are applied, is termed as DYE.
• All dyes contains aromatic compounds.
• Have affinity towards substrate.
• Substrate may be textile(Fiber, fabric, paper, leather, plastics wax,
cosmetic base etc.
• Aromatic compounds are substances that consist of one or more
rings that contain alternating single and double bonds (benzene) in its
chemical structure.
• Benzene
Other Examples
• A dye is a colored substance but every colored substance is not dye.
• e.g. Azo benzene – Red in color but not Dye
Why…?
 Requisites of a true dye
• It must have a stable structure- Should not go structural change easily.
• Should be soluble in water or in any suitable media or made stable dispersion.
• It must be able to attach itself to material from solution or to be capable of fixed
on it.
Example: Azobenzene (yellow colour) – unable to fix itself to a fibre, not a
dye.
• A dye may not be able to dye all types of materials or substrates.
Example: Picric acid (yellow) – to dye silk or wool but not cotton.
• Thus a dye ether forms a chemical bond with the substrate being dyed or it may
get associated with physical interactions.
• After application should resist to certain physical/chemical action with acceptable
limits.
 What is color?
• The perception of colour is an ability of some animals, including
humans, to detect some wavelengths of electromagnetic radiation
(light) differently from other wavelengths.
• When light fall on any object it absorbs to some extant and shows
reflectance, transition and scattered.
• The potions of light in visible spectrum of light reaches to our eye is
detected as color.
 What is color?
• Color is nothing just the rays of certain wave length that detected by
our eye.
• Electrons fall to lower energy levels and give off light in the form of a
spectrum.
• These spectral lines are actually specific amounts of energy for when
an electron transitions to a lower energy level.
• Electrons can only occupy specific energy levels in an atom to be
stabilized.
• Electron jumps and release energy in form of rays of different wave
length.
Electromagnetic spectrum
• When an object absorbs some of the radiation from within that range
we see the waves that are left over, and the object appears coloured.
• In reality this range we see makes up only a very small fraction of the
electromagnetic spectrum.
• Human eye respond to wavelengths between about 400-700 nm.
What makes Dye Colored

Is It chromophore???
• The absorption of electromagnetic radiation of varying wavelengths,
depending on the energy of the electron clouds. For this reason,
chromophores do not make dyes coloured in the sense that they
confer on them the ability to absorb radiation.
• Chromophores function by altering the energy in the delocalised
electron cloud of the dye, and this alteration results in the compound
absorbing radiation from within the visible range instead of outside it.
Our eyes detect that absorption, and respond to the lack of a
complete range of wavelengths by seeing colour.
Examples of Chromophor

p-quinoid -

Azo- Nitro-
Auxochrome

Halogen
Auxochrome
• The word auxochrome is derived from two roots. The prefix auxo is
from auxein, and means increased. The second
part, chrome means colour, so the basic meaning of the word
auxochrome is colour increaser. This word was coined because it was
noted originally that the addition of ionising groups resulted in a
deepening and intensifying of the colour of compounds.
• Auxochrome themselves are unable to produce colour.
• But in presence of chromophore increases the depth of the colour.
• Both chromophores and auxochromes are linked to one another
through a conjugated system.
• There are many ways in which chromophores, auxochromes and
conjugated aromatic systems, together with other structural features
designed to confer particular application properties, are incorporated
into dye molecule.
How can a dye molecule's hue be altered?
By bathochromic shift?
By hypsochromic shift?
• By structural changes in chromophore ( add more
atoms/groups, change its position in dye molecule)
• By structural changes in the auxochrome (add more
atoms/groups, change its position in dye molecule)
• Introduce modifiers in dye molecule.
Effect of auxochrome on aromatic system
To the left is naphthalene, a colourless compound.

The addition of a single hydroxyl group to naphthalene

produces 1-naphthol which is also a colourless
compound, but one which can ionise.

If instead of a hydroxyl group we add the nitro

group, which is a chromophore, we get the
compound 2,4-dinitronaphthalene. The addition of
this chromophore has caused it to become pale
yellow.
If instead of a hydroxyl or nitro groups, both a
hydroxyl and nitro groups are added, we get the deep
yellow dye, martius yellow.
Modifiers
• Groups that alter the colour of dyes by altering the energy in the
delocalized electrons.
• They themselves cannot do this enough to cause absorption in the
visible range, but they can affect the shade significantly when
absorption is already in that range. Adding more of a particular
modifier results in a progressive alteration of colour.
• Example - the Methyl violet series*.
Modifier
Without any methyl groups the parent dye is
called pararosanilin and is red.

When four methyl groups are added we get

the reddish purple dye methyl violet.

As more methyl groups are added we get the

purple blue dye crystal violet which has six
such groups.

If a seventh methyl group is added, the

resulting dye ismethyl green.
 Colour and Constitution
Witt’s theory or Auxochrome-chromophore theory:
• According to this theory, dye is made up of two parts –Chromophores
and auxochromes
• Chromophore: Colour of the substance is mainly due to the presence
of an unsaturated groups known as chromophores.
• The compounds possessing chromophores are known as
chromogens.
Terms associated with Dyes
 Hue
• When asked to identify the color of an object, you’ll
most likely speak first of its hue.

• Quite simply, hue is how we perceive an object’s color

Hue: The degree of stimuli of absorbing specific
wavelength.
These are the family of twelve purest colors.
• Three Primary Colors (RGB)
• Three Secondary Colors(?)
• Six Tertiary Colors(?)

For understanding, any of basic these basic color is Hue

Secondary Colors
Strength: Absorbance of Dye at a particular Wavelength.
A dye with batter strength have deeper shade% at low concentration.
Bathochromic Shift
• A structural change which causes the absorption band to longer
wavelengths.
• Also called red shift.
(i.e. yellow -> orange -> red, violet -> blue -> green) is called
a bathochromic shift.
Example: Halogens, alkyl and aryl groups
Hypsochromic effect
• A structural change which causes the absorption band to shorter
wavelengths.
• Also called blue shift.

• Chromophors- Electron withdrawing groups

• Auxochrome- Electron donating groups
A bathochromic shift may be caused by increasing the electron-withdrawing
power of the chromophore (X or Y), increasing the electron-donating power
of the auxochrome (Y or X) and by increasing the length of the conjugated
system connecting the two.
• The position of the chromophore and auxochrome also has an
effect. In general, the meta position (M) has the shortest wavelength,
and the para (P) and ortho (O) absorption wavelengths are
approximately equal, and longer than meta.
• Even larger bathochromic shifts are provided when there is an
electron-releasing group in one aromatic ring and an electron-
withdrawing group in the other, i.e., a typical donor–acceptor
chromogen
Groups-cause more bathochromic shift
Photochromism
• Chromic materials, which are chemical species that respond to
various external stimuli by exhibiting reversible colour change.

• Specific colour change phenomena are named using the suffix

chromism and a prefix that describes the stimulus causing the change
Photochromism
• Photochromism is commonly defined as a process in which a compound
undergoes a reversible change between two chemical species with
different absorption spectra, i.e., with different colours, on irradiation with
light.
• Most photochromic dyes convert reversibly from colourless into coloured
when exposed to UV light.
• Can be used for functional textiles, can be used for both fashion effect and
smart textiles such as UV sensors

General scheme for reversible photochromism

Two broad types
• T-type dyes, the reverse reaction is thermally-driven, i.e., occurs
when the light source is removed,
• P-type dyes, the reverse reaction is photochemically-induced using
light of a different wavelength.
• Dyes must have good fatigue resistance.
• It is considered a fault in textile.
• It is due to different isomeric position of stable dye structure initiated
by exposure to light, the two geometrical isomers of dyes having
noticeably different colours.
• Firstly found in azo disperse dyes.
Cis/Trans Isomerisim
The terms “cis” and “trans” are from Latin, in which cis means "on this
side"[ and trans means "on the other side" or "across".
As with any double bond, the planar -N=N- bond shows geometrical
isomerism (tautomerism)

Trans Cis
• Trans form is more stable than cis.

• Strong polar group, less will be photochromism