ELECTRONIC

CONCEPT OF DYES

Rachna - A0989222022
 WHAT ARE DYES?
Dyes are coloured organic compounds that are used to impart
colour to various substrates, including paper, leather, hair, drugs,
cosmetics, waxes, greases, plastics and textile materials.
A dye is a coloured compound, normally used in solution, which is
capable of being fixed to fabrics.

Modern/ Electronic Theories of Dye

Valence Bond Theory (VBT) Molecular Orbital Theory (MOT)

1.VALENCE BOND THEORY (VBT)
1.When a beam of light falls on a molecule, it absorbs light of appropriate energy and
gets excited.
2.The wavelength of light absorbed depends upon the difference in the energy of
ground state and excited state (E). The greater is this difference, the shorter is the
wavelength of light absorbed.
3.Example: ethylene is colourless but conjugated polyene having more double bonds
are coloured.
1.VALENCE BOND THEORY (VBT)
4.When the number of double bonds in conjugation increases the wavelength of absorption
also increases.
- Example:-

Ethylene: λmax= 175nm 1,3-Butadiene: λmax= 217nm

5. Hence, the colour of a compound will depend upon the following:
(a) Extent of conjugation

β-Carotene( pigment present in carrot)

Orange red: λmax= 478nm
1.VALENCE BOND THEORY (VBT)
(b) Presence of other groups
- Example:

Colourless: λmax= 204nm Pale yellow: λmax= 280nm Dark yellow: λmax= 375nm

(c) Steric effect

2.MOLECULAR ORBITAL THEORY (MOT)
- When an atom or molecule absorbs energy in the UV/visible region, it undergoes excitation involving transition
between electronic energy levels.
- These transitions involve promotion of an electron from an occupied orbital (Ground State) to an unoccupied
orbital (excited state).
- Generally, the most probable transition takes place from Highest Occupied Molecular Orbitals (HOMO) to
Lowest Unoccupied Molecular Orbitals (LUMO).
-HOMO -LUMO
𝞂 orbitals (𝞂 bond) 𝞂* orbitals
π orbitals (π bond) π* orbitals
n orbital ( non-bonding orbitals)
-Energy levels of various molecular orbitals
2.MOLECULAR ORBITAL THEORY (MOT)
- The order of energies for various electronic transitions is as follows-
→ → → →
𝞂 𝞂* > 𝞂 π* > π π* > n 𝞂* > n π* →
→
Decrease in energy (or increase in wavelength) of absorption.
→ →
- π π* and n π* transitions can occur in UV range.
→
- The n π* transition requires minimum energy and hence occurs at longer wavelength and such
transition is always less intense.
→ →
- Further π π* transitions are more intense than n π * transitions and hence are responsible for
colour.
Simple alkenes, such as ethylene, absorbs at 175 mm.
But 1,3-butadiene absorbs at 217 mm due to presence
of two double bonds in conjugation.

Molecular orbitals of 1,3-butadiene

 References

-John D. Robert and Marjorie C. Caserio (1977) Basic Principles of

Organic Chemistry, second edition. W. A. Benjamin, Inc. , Menlo
Park, CA

—https://paulingblog.wordpress.com/2014/09/17/a-theory-
of-the-color-of-dyes/

https://chem.libretexts.org/Bookshelves/Organic_Chemistry/Ba
sic_Principles_of_Organic_Chemistry_(Roberts_and_Caserio)/28
%3A_Photochemistry/28.05%3A_Color_and_Constitution
Thank you