COLOR

Elementary concepts on color

Color is the characteristic of human visual
perception described through color categories, with
names such as red, yellow, purple, or bronze. This
perception of color derives from the stimulation
of cone cells in the human eye by electromagnetic
radiation in the spectrum of light.
In the object viewing mode, the colorants present in
a material selectively absorb part of the light
illuminating it and transmit or reflect the remainder
into the eye of the observer. It is this light that
stimulates the sensation of what we call the ‘color’
of the material.
 Factors Influencing Color Perception

Color perception may vary depending on three

important factors:
(1) the wavelength distribution, or colour of the
light source illuminating the object
(2) the degree of reflection or transmission of
each wavelength of the incident light by the
object
(3) the visual response of the observer’s eye to
the wavelengths of light entering from the object.
 How we see colours
• When light hits an object – say, a banana – the object
absorbs some of the light and reflects the rest of it.
• A ripe banana absorbs wave length in the range of blue
colour but wavelengths of about 570 to 580 nanometers
bounce back. These are the wavelengths of yellow
light.
• When we look at a banana, the wavelengths of reflected
light determine what color you see. The color
representing the absorbed wave length and that for the
reflected wave length are complementary colours.
• The light waves reflect off the banana's peel and hit the
light-sensitive retina at the back of your eye.
 Complementary colours
• If we arrange some colours in a
circle, we get a "colour wheel". The
diagram shows one possible version
of this.
• Colours directly opposite each other
on the colour wheel are said to be
complementary colours. Blue and
yellow are complementary colours;
red and cyan are complementary;
and so are green and magenta.
• Mixing together two complementary
colours of light will give white light.
 Wavelength of light absorption versus
colour in organic Dyes
Wavelength Absorbed (nm) colour Absorbed colour Observed

400–435 Violet Yellow-Green

435-480 Blue Yellow

480-490 Green-Blue Orange

490-500 Blue-Green Red

500-560 Green Purple

560-580 Yellow-Green Violet

580-595 Yellow Blue

595-605 Orange Green-Blue

605-700 Red Blue-Green

Primary, secondary & tertiary color
 Primary, secondary & tertiary color
Primary Colours
These colours are the three colours that can not
be created by mixing other colours. The colours
are red, blue and yellow.
Primary colours can be combined to make
secondary colours.
 Primary, secondary & tertiary color
Secondary Colours
These colours consist of two primary colours
mixed together. The three colours secondary
colours are purple (also known as violet), green
and orange.
red + blue = purple
red + yellow = orange
yellow + blue = green
 Primary, secondary & tertiary color
Tertiary Colours
These colours are made by mixing a primary colour with
an adjacent secondary colour. When naming tertiary
colours the primary and secondary colour names are
joined by a dash (-) with the primary always being the
first colour.
yellow + orange = yellow-orange
red + orange = red-orange
blue + green = blue-green
yellow + green = yellow-green
red + purple (violet) = red-purple (red-violet)
blue + purple (violet) = blue-purple (blue-violet)
 Theory of color mixing
Additive color mixing: The three primary colors in
additive mixing are red, green, and blue. In the
absence of color or, when no colors are showing,
the result is black. If all three primary colors are
showing, the result is white.
red + green = yellow.
red + blue = magenta
Blue + green = cyan.
Additive mixing is used in television and
computer monitors to produce a wide range of
colors using only three primary colors.
 Theory of color mixing
Subtractive Mixing
The mixing of colored physical substances
corresponds to subtractive color mixing. To explain
the mechanism, let us consider mixing red paint
with yellow paint. yellow light is composed of (an
additive) mixture of red and green light. When we
mix the two paints, the yellow paint absorbs all
colors except for red and green. However, the red
paint will absorb the green reflected by the yellow
paint. The red paint can be said to subtract the green
from the yellow paint. The resulting paint reflects
only red light and so appears red to our eyes.
 Theory of color mixing

Subtractive Mixing
primary colors in subtractive mixing
are yellow, magenta and cyan; however, for a long
time painters have used yellow, red and blue in
place of these. In subtractive mixing of color, the
absence of color is white and the
presence of all three primary
colors is black. Subtractive
mixing is used in printing, painting.
 Dimension of color- hue, value &chroma
Each color has its own distinct appearance based on three elements: Hue,
Value, and Chroma. By describing a color using these three attributes, we
can accurately identify a particular color and distinguish it from any
other.
Hue(dH): When asked to identify the color of an object, we must likely
speak first its hue. Hue is we perceive an objects color. Red, Orange,
Green , Blue etc.
In CIE color space hue can be expressed by hue angle. That is to say in
CIELCH (L*C*h0) system h0 denotes hue angle as CIELCH uses polar
co-ordinates. By different hue angles i.e. different values h0 we can
express different hues as below-
When, h0=0, red h0=270, blue
h0=45, orange h0=315 , Magenta
h0=90, yellow h0=360, red
h0=180, green h0=225, cyan
 Dimension of color- hue, value &chroma
Value(dL): The second characteristic of colour describes its
luminous intensity- that is its degree of lightness. Colour can
be classified as light or dark color when comparing the
value. The scale of value ranges from zero(0) for pure black
to 100 for pure white. In CIEL*a*b* (fig.) system, L
represents value. L=0 means perfect black(total absorption)
and L=100 means perfect white (total reflection).
For example, when placing a
tomato and a radish side by side
by the red of tomato, in contrast
the radish has a dark red value.
 Dimension of color- hue, value &chroma
Chroma(dC): The vividness or dullness of color
describing its chroma. Again comparing the tomato
and radish the red of the tomato is much more vivid,
the radish appears duller.

Fig.: Munsell system

 Otto Witt theory of color
(Chromophore&Auxochrome theory)

O.N. Witt observed in 1876 that coloured

compounds contain certain unsaturated groups
which he called chromophores and compound
containing a chromophore is called a chromogen.
When certain groups called auxochrome are
present in the chromogen a dye is obtained.
Chromophores can be two types:
• Independent Chromophore
• Dependent Chromophore
 Otto Witt theory of color
(Chromophore&Auxochrome theory)

Some chromophores
 Otto Witt theory of color
(Chromophore & Auxochrome theory)
Independent Chromophore:
When a single chromophore is sufficient to
impart color to the compound, such type of
chromophore is called Independent
chromophore. Some examples are as follows-
-N=O
-N=N-
-NO2
-N=N O
-N=N-NH etc.
 Otto Witt theory of color
(Chromophore & Auxochrome theory)

Dependent Chromophore:
When more than one chromophore is required to
impart color to the compound, such type of
chromophore is called dependent chromophore.
Some examples are as follows-
>C=C<
>C=O
Acetone (CH3-CO-CH3) is colorless, but
Diacetyl (CH3-CO-CO-CH3) is colored.
 Otto Witt theory of color
(Chromophore & Auxochrome theory)

• A single C=C group does not produce color in the

compound but if more than one number of them is
present in the conjugation, the color usually
appears.
CH2= CH2 is colorless, but CH3-(CH)6-CH3
• The shade of color is also influenced by the
proximity of the chromophores. If this are
separated by other groups, the compound becomes
colorless.
CH3-CO-CO-CH3 is yellow color, but
CH3-CO- CH2-CH2 CO-CH3 is colorless compound.
 Otto Witt theory of color
(Chromophore & Auxochrome theory)
Auxochrome:
This is a group of atoms attached to a chromophore
which modifies the ability of the chromophore to
absorb light and increase the intensity of color. This
increases overall polarity of dye molecule and
makes it more readily soluble. The polarity of
auxochromes enables the attraction between dye and
fibre that improves fastness property.
Some auxochromes are given below-
Amino (-NH2), Chloro (-Cl), Hydroxy (-OH),
carboxylic acid (-COOH), Sulphonic acid (-SO3H),
Acetyl (-COCH3), Acetamide (-CONH2), Cyano (-
CN) etc.
 Armstrong theory (Quinonoid theory)
Armstrong in 1885 suggested that all coloring matters
may be represented by quinonoid structures (p‐or o‐),
and thus believed that if a particular compound can be
formulated in a quinonoid form it is colored, otherwise
it is colorless. On the basis of this theory we can see
that benzene is colorless, where as benzoquinones are
colored.

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.
 Modern theory of color

The current and most important theories called

valence bond (VB) theory and molecular orbital
(MO) theory explain the relation between color and
constitution. These theories are based upon the
following concepts:
1. Quantization of light theory: Light is
quantized in the units of energy called light
quanta or photons.
 Modern theory of color
2. Absorption of radiation by molecules: A
compound appears colored if it selectively absorbs
light in the visible region. The main function of the
absorbed energy is to raise the molecule from the
ground state energy, Eo to the excited state, E1 and
the difference of energy, ΔE is the quantum of
energy given by quantum theory equation:
𝑐
ΔE = E1 - Eo = hυ= h
λ
Where, h= Planck's constant
c= velocity of light
λ = wave length of the absorbed radiation
 Modern theory of color
• The amount of energy absorbed , ΔE depends upon the
structural configuration of that dye, in other words, ΔE
depends upon how tightly the electrons are bound in the
bonds and accordingly the absorption will occur in UV or
a particular region of visible range.
• If the electrons of a molecule are tightly bound as in
saturated compounds, no light of visible region will be
absorbed but only light of UV region will be absorbed
and hence the compound will appear colorless.
• If the electrons of a molecule are loosely bound as in
saturated compounds, the absorption may occur in the
visible region and the substance will then appeared
colored.
 Absorption of Different wave length

Compounds Energy level Frequency Wave length

Saturated compounds Higher energy Higher absorb shorter

(electrons are firmly to excite frequency wave length
bound) electrons

Unsaturated Lower energy Lower absorb Longer

compounds or having to excite frequency wave length
double\triple bonds electrons
(electrons are mobile
in nature)
-
 Modern theory of color

3. Dipole moment: The dipole moment plays an

important role in the transition of the molecule
because a molecule can absorb light only if its
dipole moment changes. For example, the more
symmetrical the molecule, the smaller is the
probability of transition dipole and therefore the
light is absorbed by the molecule very slowly.
Similarly, it is shown that the greater the transition
dipole, the greater is the absorption of intensity.
 Valence bond theory (Resonance theory)
The various postulates of this theory are as follows:
• Chromophores are groups of atoms, the π‐electrons of
which may get transferred from ground state to excited
state by the absorption of radiation, thus producing the
color.
• Auxochromes are groups, which tend to increase
resonance by interacting the unshared pair of electrons on
nitrogen or oxygen atoms of the auxochromes with the π
electrons of the aromatic ring.
• This increase in resonance increases the intensity of
absorption of light and also shifts the absorption band to
longer wavelength. Hence there occurs the deepening of
the color. From this it is evident that increase in resonance
must deepen the color and actually it has been found to be
 Valence bond theory (Resonance theory)
Benzene is colorless, Nitro benzene is pale yellow, p-
nitro aniline is dark yellow.

• This is a charged structure , so, absorption is shifted

to longer wave length (blue), there by producing a
pale yellow color which is the complementary color
of the blue band.
• The absorption of nitro benzene is increased due to
the loss of symmetry of the molecule.
 Valence bond theory (Resonance theory)
Benzene is colorless, Nitro benzene is pale yellow, p-
nitro aniline is dark yellow.

In p- nitroaniline, the contribution of the charged

structure is still larger and hence the light of longer
wave length is absorbed, thus deepening the color to
the dark yellow.
 Modern theory (molecular orbital theory) of color
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 higher energy states are commonly
known as anti‐bonding orbitals. The anti‐bonding
orbitalsassociated with σ and π bonds are called σ *
and π* orbitalsrespectively. However, there are no
anti‐bonding orbitalsassociated with n (non‐bonding)
electrons because they do not form bonds. Chart of
the simplest form, the essential types of energy are
giveninthe next slide:
Modern theory (molecular orbital theory) of color
 Electronic transitions

The electronic transitions can occur by the absorption of

ultraviolet and visible radiation. Although transitions are
possible, only the following types are allowed:
n →σ*
n → π* and π → π*
A σ → σ* transition takes place when a bonding σ –electron
is excited to an anti-bonding σ –orbital, i.e. σ*. This type of
transition requires a very large amount of energy as σ –
electrons are very tightly bond. Hence the compounds like
saturated hydrocarbons which do not have any π or σ
electrons may undergo only σ → σ* transitions. However,
these transitions do not take place by absorbing in the
ordinary ultra‐violet region, e.g., ethane absorbs at 135 mμ.
 Effect of conjugation
• Regarding the requirement of a
chromophore generating colour in
organic compounds, it is important to CH3-N=N-CH3
note that the chromophore must be
part of a conjugated system. Colourless
• This is illustrated through the
examples in figure where it can be
seen that placement of an azo group
between methyl groups produces a
colourless compound, while a yellow-
-N=N -
orange colour is obtained when the
azo group is placed between aromatic
rings. Orange colour
 Bathochromic Shift
• When the absorption of light by a compound
is shifted to the longer wavelength is called a
bathochromic shift. It is also called red shift.
• It can be done by-
1)Introduction of side chains of
conjugated double bonds.
2)Introduction of electron attracting
groups (-N=N,=C=O, nitroso etc) or electron
donating groups (-OH,-OCH3,-NH2 etc)
Absorption Of Different wave length

When a molecule of a coloured compound absorbs

light in the visible region and Ultra violet region,
the electrons present in the molecule are excited
and their vibrational energy is increased.

Absorptions move to longer wavelengths as the

amount of delocalisation in the molecule increases.
 Try Yourself
• Consider these three molecules:

CH2=CH2 CH2=CH-CH=CH2
Ethene buta- 1,3-diene

CH2=CH-CH=CH-CH=CH2
Hexa-1,3,5-triene

1.WHICH ONE WILL ABSORB THE LONGEST

WAVE LENGTH ?
2.WHICH COLOR WILL BE SEEN BY US ?
 Solution
• Ethene contains a simple isolated carbon-carbon double bond, but
the other two have conjugated double bonds. In these cases, there is
delocalisation of the pi bonding orbitals over the whole molecule
• Now look at the wavelengths of the light which each of these
molecules absorbs

molecule wavelength of maximum absorption (nm)

ethene 171

buta-1,3-diene 217

hexa-1,3,5-triene 258

All of the molecules give similar UV-visible absorption spectra - the

only difference being that the absorptions move to longer and longer
wavelengths as the amount of delocalisation in the molecule increases.
No colour will seen as wave length below 400-700 nm.