Chapter 1

Physics of color

How the eye see colors

Color is a perceptual phenomenon.
Color is caused by receptors in our eyes that are
stimulated by electromagnetic radiation of certain
wavelengths.
The production of color requires 3 elements: light
source, object, and the eye-brain system of viewer.

Electromagnetic spectrum

Visible spectrum
The visible spectrum (or sometimes optical spectrum) is the portion of
the electromagnetic spectrum that is visible to the human eye.

Sunlight spectrum

Light sources

Light object interaction

Transmission: light passes through an object without
being essentially changed transparent object

 Refraction: light goes through two media that have

different densities change direction
n1sin1=n2sin2

 Absorption: light is absorbed by an object and converted

into energy

Reflection: light bounces off an object

 If the object absorbs only part of the visible light, it

appears colored

If all light wavelengths are absorbed, it appears black, if

none of the wavelengths is absorbed, it appears white

Transparent, transluent, opaque objects

Transparent materials: almost all of it passes directly
through them. Ex. air, water, clear glass
Transluent materials: part the light is scattered as it passes
through them objects on the other side appear fuzzy
and unclear. Ex. Frosted glass, some plastic
Opaque material: no light is transmitted, most of the light
the light is either reflected by the object or absorbed and
converted to heat. Ex. Wood, stone, metal..

Lambert-Beer law
Equal amounts of absorption result when light passes
through equal amounts of absorbing material

The LambertBeer law is valid within certain concentration values, and only if
individual wavelengths of light are used; in addition, not all materials obey this law.

Color attributes
Hue : tone of color, ex. Red, green, blue, orange..

Saturation: purity of color, intensity of hue in comparison

to its own brightness.
A saturated color looks clear and bright
Unsaturated color appear pale, muddy, dull
Saturation defines a range from pure color (100%) to
gray (0%) at a constant lightness level. A pure color is
fully saturated

 Lightness: technically defined as the perceived brightness

of an object compared to that of a perfect white object .

Brightness: total light from the illuminant or reflected

from the surface.
Lightness and brightness are grouped in the term value
and commonly used interchangebly.
Lightness ranges between black and white through the
various shades of grey

Human perception of color

Retinal light detectors are composed of rods and cones.
Rods allow us to see in dim light conditions (maximum
sensitivity at 500 nm), but do not confer color vision.
Cones show less sensitivity to light but great sensitivity to
color. There are 3 types of cones: Red, Green, Blue cones.

 Each type of cone receptor has its own response curve

under the effect of a specific light wavelength and has
different wavelength of maximum sensitivity: R cones ~ 580
nm, G cones ~ 550 nm, B cones ~ 440 nm.
The mixture of these responses is interpreted by the
human brain as color.

 R, G, and B cones are not equally represented in the

fovea: 64% corresponds to R cones, 32% to G, and 4%
to B.
The combined responses of cones produce a curve with
a maximum of sensitivity at around 550 nm under
phototopic vision (daylight-adapted vision). This
maximum is between the maximum sensitivity peaks of
the R and G cones.

Instrumental color mesurement

Lovibond tinctometer: a visual colorimeter, in which standardized
Lovibond colored glasses (red, yellow, blue colors) are combined
to match a sample that is viewed at simultaneously.
used in the color measurement of lubrication oil, sugar solutions,
beer, and light-reflecting materials, such as oleomargarine

 The Lovibond Tintometer is a visual colorimeter designed to

optimise the use of Lovibond glass filters. It is arranged with two
adjacent fields of view, seen through the viewing tube, so that the
product in the sample field and a white reflective surface in the
comparison field are observed side by side, suitably illuminated. The
Lovibond glasses are introduced into the comparison field by a
simple system of sliding racks, allowing the user to compare the
colour of light which is either transmitted through or reflected from
the sample with that transmitted through the glasses.A series of
neutral glasses in racks is also supplied; these can be introduced into
the sample field to dull the colour of products which are too bright to
obtain a good colour match using Lovibond Red, Yellow or Blue
glasses. The racks are varied until a visual colour match is found for
the light from the sample and its colour can then be expressed in
Lovibond units. Modes Transmittance, reflectance Range 0.1 - 79.9
Red, Yellow; 0.1 - 49.9 Blue; 0.1 - 3.9 Neutral Resolution 0.1
Lovibond unit Optical system 11 glass-filled nylon racks containing a
graduated range of Lovibond colour glasses
Since the glasses are standardized, it is possible to make a match and
to describe the sample color in numerical terms, which can be
converted to CIE (Commission Internationale de lEclairage) color
specifications, and vice versa

The CIE system

developed by the International Commission on
Illumination.
three elements are involved in color evaluation: source
of light, object, and observer.

 CIE common standard light sources

Standard Illuminant D65:
Average daylight (including
ultraviolet wavelength region) with a correlated color
temperature of 6504K
Standard Illuminant C: Average daylight (not including
ultraviolet wavelength region) (6774K);
Standard Illuminant A Incandescent light (~2856K);.

CIE color matching functions

The color matching functions are the tristimulus values of
the equal-energy spectrum as a function of wavelength.
These functions are intended to correspond to the
sensitivity of the human eye.
Ther are two sets of three color matching functions are
specified for the 2 Standard Observer and 10
Supplementary Standard Observers.

CIEXYZ
X, Y, Z - CIE Tristimulus Values: Amounts of the three
components (approximately red, green, blue) necessary in a
three-color additive mixture required for matching a color.
The curve for the Y tristimulus value is equal to the curve that
indicates the human eye's response to the total power of a
light source. For this reason the value Y is called the
luminance factor and the X Y Z values have been normalized
so that Y always has a value of 100.

however, tristimulus values X, Y, Z correlate poorly with visual attributes. While Y relates to
value (lightness), X and Z do not correlate to hue and chroma.

CIE Yxy
Y: lightness, the color (hue, saturation) may be specified by
plotting x, y on a horsehoe-shaped chromaticity diagram.

Non-uniformity equal changes in x, y or Y do not

correspond to equal perceived differences.

CIELAB
one of the most popular color space for measuring
object color and is widely used in virtually all fields.
It is one of the uniform color spaces defined by CIE in
1976 in order to reduce one of the major problems of
the original Yxy color space
L: lightness,
a (red green) and b (yellow blue): chromaticity
coordinates.
The center is achromatic; from the center out, the
saturation increase

CIELCh
uses the same diagram as Labcolor space, but uses
cylindrical coordinates instead of rectangular coordinates
L:lightness, the same as the Lof the Labcolor space,
C: chroma, h: hue angle

UV-Vis absorption of an organic molecule

The absorption of UV or visible radiation corresponds to the
excitation of outer electrons. There are three types of
electronic transition which can be considered:
Transitions involving p, s, and n electrons
Transitions involving charge-transfer electrons
Transitions involving d and f electrons
When an atom or molecule absorbs energy, electrons are
promoted from their ground state to an excited state. In a
molecule, the atoms can rotate and vibrate with respect to
each other. These vibrations and rotations also have discrete
energy levels, which can be considered as being packed on
top of each electronic level.

 Absorbing species containing p, s, and n electrons

Absorption of UV-Vis radiation in organic molecules is restricted to
certain functional groups (chromophores) that contain valence
electrons of low excitation energy. Possible electronic transitions of
p, s, and n electrons are;

 s - s* Transitions : required large energy, not seen in

typical UV-Vis. spectra (200 - 700 nm) (eg. methane
max 125 nm)
n - s* Transitions: can be initiated by light
wavelength in the range 150 - 250 nm. The number
of organic functional groups with n - s* peaks in the
UV region is small.
n - p* and p - p* Transitions: absorption peaks fall in
an experimentally convenient region of the spectrum
(200 - 700 nm).
Most absorption spectroscopy of organic compounds
is based on these transitions.
Molar absorbtivities from n - p* transitions are
relatively low, and range from 10 to 100 L mol-1 cm-1 .
p - p* transitions normally give molar absorbtivities
between 1000 and 10,000 L mol-1 cm-1 .

Molecules

Transitions

max (nm)

s - s*

135

s - s*
n - s*

150
183

p - p*

175

p - p*

254

n - p*

290

The spectrum of a molecule containing these chromophores is

complex. This is because the superposition of rotational and
vibrational transitions on the electronic transitions gives a
combination of overlapping lines. This appears as a continuous
absorption band.

Chromophore
Chromophore: a covalently unsaturated group responsible for n
*, and * electronic absorption in the near UV and visible
regions (most value for diagnostic quantitative analysis)
Chromophore

Example

Transition

max/nm

e/L.mol-1cm-1

Ethylene

p - p*

165

15000

Acetylene

p - p*

173

6000

Acetone

p - p*
n p*

188
279

900
15

Acetoxime

p- p*

190

5000

Azomethane

n - p*

347

4.5

Nitrozobutane

p- p*
n - p*

300
665

100
20

Nitromethane

n- p*

271

18.6

 Auxochrome: saturated substituents (usually contain nonbonding electrons), which do not absorb UV radiation but their
presence shifts the absorption maximum to longer wavelength,
eg. OH, -NH2, -Cl..

Bathochromic shift (red shift): shift max to longer wavelength

Hypsochromic shift (blue shift): shift max to shorter
wavelength, eg. Solvent effect
Hyperchromic effect: an increase in absorption intensity
Hypochromic effect: a decrease in absorption intensity

Bathochromic shift

max = 255 nm
Hypsochromic shift

max = 265 nm

max = 280 nm

max = 265 nm

Hyperchromic shift

Pyridine
max = 257 nm
e max = 2750

2- methylpyridine
max = 262 nm
e max = 3356

Hypochromic shift

naphthalene
max = 250 nm
e max = 19000

2- methyl naphthalene
max = 237 nm
e max = 10250

Conjugation of polyenes
The increase in conjugation results in bathochromic shift and
increase the intensity of absorption.
The greater the number of conjugated multiple bonds a compound
contains, the longer will be the wavelength at which the compound
absorbs light.

 -carotene has eleven conjugated double bonds its absorption

maximum has shifted out of the ultraviolet and into the blue region
of the visible spectrum appears bright orange

Substance

Absorption
Peak

Ethylene(CH2=CH2)
1.3-butadiene
Vitamin A
-carotene

180nm
217nm
328nm
450nm

10000
21000
51000
140000

Benzene
Naphthalene
Anthracene
Naphthacene

255nm
286nm
375nm
477nm

180
360
7100
110000

Ethylene
max = 171 nm

Acetone
max = 279 nm

Molar Absorption
Coefficient

Crotonaldehyde
max = 290 nm

Carbonyl chromophore
Carbonyl compounds have two principal UV radiations, the allowed
* transitions and the forbidden n * transitions.
In amides, acids, esters or acid halides, the substituents NR2, OH,
OR, or X on carbonyl group show pronounced hypsochromic effect
on the n * transitions (shift to 200-215 nm range relative to 270
nm of aldehyde and ketones) due to inductive effect of nitrogen,
oxygen or halogen atoms. The heteroatom withdraws electrons
from carbonyl carbon and makes carbonyl oxygen lone pair of
electrons more stabilized due to its involvement in increasing C=O
bond order.
Conjugation of the carbonyl group with double bond shifts both n
* and * transitions to longer wavelengths. The effect on
* band is more pronounced.

Aromatic chromophore
Substituents with non-bonding electrons on aromatic ring increase
the length of -system through resonance and shift the primary
and secondary absorption bands to longer wavelength.

 Conjugation of the aromatic ring also shifts the bands to longer

wavelengths.

 In case of disubstituted benzene derivatives, if one group is

electron-releasing and other is electron-withdrawing, the
magnitude of red shift is grater compared to the effect of single
substituent individually.

 In case of polycyclic aromatic hydrocarbons, due to extended

conjugation, absorption bands are shifted to longer wavelength.