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Topic: Color and theories of Color
Name: SAIMA LATIF
Roll No. 36 Institute Of Chemistry PU Lahore
COLOR
‘‘An attribute of things that results from the
light they reflect, transmit, or emit in so far as
this light causes a visual sensation that
depends on its wavelengths’’.
-
Chromatics
The science of color is called chromatics, colorimetry,
or simply color science.
In Chemistry, it is called ‘Color Chemistry’.
Types of Color
Primary
Color
Secondary
Color
Tertiary
Color
Law of Color Mixing
• In 1861, the James Clerk Maxwell (Additive
color) red, green and blue to produce other
colors.
• In 1868, Ducos du Hauron, (Subtractive color/
Complementary color mixing) yellow,
magenta and cyan create black.
Electro-magnetic Spectrum
• The visible region
ranges from 380
nm to 780 nm.
Interaction with light mater
Due to energy difference between excited state and ground state
According to Plank’s Equation:
E = hv
E = Energy difference b/w two states
V= frequency of absorbed light
h= Plank’s Constant
Further modify:
E = hc/λ
c= Velocity of light
Complementary Colors
Examples
Compound
Number of C=C
in conjugated
system
Main colour
absorbed
Colour
compound
appears
Vitamin A 5 Violet Yellow
β-carotene 11 Blue Orange
Lycopene 11 Green Red
OH
CH3CH3CH3H3C
CH3
CH3CH3CH3H3C
CH3
H3C
H3C
CH3
CH3CH3
Vitamin A
Beta-carotene
Lycopene
Causes of Color
• Excitation(e.g vapour lamp, neon signs),
vibration, rotation
• Transition metal compound (d-orbital involve)
• Color in organic compounds due to π-π*
transitions
• Organic molecules that are coloured
contain delocalised electrons spread over a
number of atoms. That is called conjugated
system.
HH
HH
HH
Colorant
• This term is used for both type of coloring materials e.g pigment and
dye. These distinguished on the basis of the solubility:
Pigment: insoluble in water and most of the solvents
Dyes: Soluble in water and most of the solvents
• Classification of colorants:
• Chemical classification
• Azo, carbonyl, anthraquinones, phthalocyanin et.c
• On the basis of electronic excitation
• Donor-Aceptor polyene
• Cyanin or n-π* chromogen
Attributes of Color
• Hue (Shade)
• Strength/ intensity of color
• Brightness of color
Hue (Shade)
• Hue of dye can be determined by absorbed λ of light e.g
• Bathochromic Shift:
is a change of spectral band position in the absorption, or emission spectrum
of a molecule to a longer wavelength
• Hypsochromic Shift:
is a change of spectral band position in the absorption, or emission spectrum
of a molecule to a shorter wavelength
Intensity of Color determined by using Beer-
Lambert Law:
• Most absorbing materials satisfy the Beer-Lambert Law. Intensity of
color of dye is given by ɛ.
A = ɛcl
• A= Absorbance
• C= Concentration
• l= Path length
• ɛ=molar extinction coefficient
Brightness of Color
• It is characterized by the UV- spectrum and shape of absorption
spectrum.
• Spectrum of red surface e.g (Low reflectance and hight absorption)
• Red (600-700 nm)
• Green (500-600 nm)
• Blue (400- 500 nm)
Theories OF Color
Theories of Color
Classical theory
Witt’s Theory
(Chromophore-
Auxochrome
Theory)
Bury’s Theory
of Color
Tautomeric
Theory
(Baeyer’s Theory)
Armstrong’s
Theory
(Quinonoid Theory)
Modern theory
VBT
(Resonance
Theory)
MOT
Classical theories of Color
Witt’s Theory
Chromophore‐Auxochrome theory:
In 1876, Witt put forward a theory according to which the color of a
substance is due to the presence of an unsaturated group known as
chromophores(Greek chroma‐color, and phores‐bearing).
The important chromophores are:
• ‐C = C ‐
• ‐C = N ‐
• ‐C = O ‐
• ‐N = N ‐
• ‐NO2
• ‐Quinoid rings
Auxochromes: responsible for the darkening of color
Examples:
• ‐OH or ‐NH2
• ‐‐NR2
Types of Chromophore
• Single chromophore is sufficient
to impart color to the
compound.
• Example: ‐NO, ‐NO2, ‐N=N,
=N=N‐N, o,p‐quinonoid etc.
• More than one chromophore is
required to impart the color, e.g.
>C=O, >C=C< etc.
• Example: Acetone and diketone
Diketone
Dilthey and witzinger’s Theory
• Dilthey and witzinger Refined the witt's theory
• ‘‘Stated the chromophores are EWG and auxochrome are EDG
They are linked through the conjugated system’’.
• By this why donor-acceptor chromogen was born.
Armstrong’s Theory
Quinonoid theory: Armstrong in 1885 suggested that all coloring
matters have quinonoid structures, and thus believed if a compound
have quinonoid form, in a structure it is colored, otherwise it is
colorless.
Example:
• benzene and benzoquinones
Baeyer’s Theory
• In 1907, Baeyer proposed the ‘‘theory of tautomerism’’(Baeyer’s Theory) which
states that there is a rapid oscillation between two tautomeric forms of a
compound.
• Example: Doebner’s violet dye (1) (1a), with a rapid flipping of the chloride ion
from one amino group to another (see Figure 1).
unsubstitued diamino
triphenyl methane dye is
Called Doebner's violet.
Figure 1: Movement of atom
Watson’s Theory
• In 1914, Watson was proposed ‘‘Tautomerism is the basic
requirement for colored molecule and that must have
conjugated chain in a quinonoid form in all the possible
tautomers’’.
• The theories of Armstrong and Watson became invalid after the
discovery of dyes without a quinonoid structure.
Bury’s theory
• In 1935, Bury was highlighted the relationship between the color of a dye
and resonance. Bury’s theory ‘color is due to the involvement of a
chromogen in resonance in the molecule’.
• Baeyer’s idea that the color of Doebner’s violet arose from the oscillation of atoms
was disproved by Bury, who proposed that it was the electrons that moved and not
the atoms (see Figure 2).
Figure 2: Movement of electrons
Modern theories of Color
Valence Bond Theory or (Resonance
Theory)
Two assumptions apply the valence-bond approach
to color and constitution, which are:
 The ground electronic state of the dye resembles the
most stable resonance form.
 The first excited state of the dye resembles the less
stable, charge-separated form.
Postulates
• Chromophores have the π‐electrons which moved from ground
state to excited state by the absorption of radiation, thus
producing the color.
• Auxochromes are groups:
• 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.
• The dipole moment changes due to oscillation of electron pairs.
VBT
• Resonance theory explains the
• Relation of the color and
• The symmetry of the molecule
• Transition dipole of the molecule
because
High canonical str.s ∝ high color intensity ∝ high bathochromic shift
Example: 1
• EDG and EWG will effect its bathochromic shift and λmax.
Canonical forms
Example: 2
• p-nitro dyes have λmax 486 nm but o-nitro dye have λmax 462 nm
Because:
• In ortho, nitro group is out of plane ‘‘so rotation is required’’
λmax of o-nitro = 462 nm
Example:3
• Five membered heterocyclic rings
have maximum bathochrmic shift as
compare to six membered ring.
Because
• Less steric interaction
• Coplanar Geometric arrangements
• Less steric congestion
• 126ᵒ bond angle
λmax = 608 nm
λmax = 614 nm
Molecular Orbital Theory
• Molecular orbitals generates by the overlapping of
atomic orbital.
• End-to-end overlapping form ….. σ-bond
• Sideways overlapping form ……. π bond
The σ bonding orbital is the highest occupied molecular orbital
(HOMO), and the lowest unoccupied molecular orbital (LUMO)
is the σ* anti-bonding orbital.
While these organic compounds do absorb light, the energy
transitions involved in promoting an electron from σ to σ* are
very large.
Organic compounds that contain only σ bonds are colourless.
Increasingenergy
σ bonding orbital
π bonding orbital
non-bonding orbital
π* anti-bonding orbital
σ* anti-bonding orbital
These absorptions
correspond to the UV part
of the spectrum.
Molecular Orbital Theory
Possible Allows transitions are:
σ  σ* (UV- region)
π  π* (appear in visible region)
n  σ* (saturated molecule + heteroatom)
n  π* (Unsaturated molecule + heteroatom)
Molecular Orbital Theory
Increasingenergy
σ bonding orbital
π bonding orbital
non-bonding orbital
π* anti-bonding orbital
σ* anti-bonding orbital
Hückel Molecular Orbital (HMO) Method
• Method use for the calculation on conjugated molecules.
• HMO method used to find:
• Bond resonating energies (ẞ )
• Pi-electron charge density (Q)
• Pi-bond order (P)
• Degree of pi-overlap of atomic orbitals
• This method is good to calculate the electronic transition energy of
 Linear polyenes
 Aromatic hydrocarbons.
• PPP-MO approach is best over the HMO because of
• Inter-electronic interaction energies
• Along with molecular geometery
• This Method is suitable for the treatment of large molecules
• Handle the hetero-atomic species
• Help to find
• Magnitude of dipole moment
• lamda max.
Pariser, Parr and Pople (PPP) Molecular
Orbital Method
PPP-MO Method
THANKS

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Color and theories of color

  • 1. Topic: Color and theories of Color Name: SAIMA LATIF Roll No. 36 Institute Of Chemistry PU Lahore
  • 2. COLOR ‘‘An attribute of things that results from the light they reflect, transmit, or emit in so far as this light causes a visual sensation that depends on its wavelengths’’.
  • 3. - Chromatics The science of color is called chromatics, colorimetry, or simply color science. In Chemistry, it is called ‘Color Chemistry’.
  • 5. Law of Color Mixing • In 1861, the James Clerk Maxwell (Additive color) red, green and blue to produce other colors. • In 1868, Ducos du Hauron, (Subtractive color/ Complementary color mixing) yellow, magenta and cyan create black.
  • 6. Electro-magnetic Spectrum • The visible region ranges from 380 nm to 780 nm.
  • 7. Interaction with light mater Due to energy difference between excited state and ground state According to Plank’s Equation: E = hv E = Energy difference b/w two states V= frequency of absorbed light h= Plank’s Constant Further modify: E = hc/λ c= Velocity of light
  • 9. Examples Compound Number of C=C in conjugated system Main colour absorbed Colour compound appears Vitamin A 5 Violet Yellow β-carotene 11 Blue Orange Lycopene 11 Green Red OH CH3CH3CH3H3C CH3 CH3CH3CH3H3C CH3 H3C H3C CH3 CH3CH3 Vitamin A Beta-carotene Lycopene
  • 10. Causes of Color • Excitation(e.g vapour lamp, neon signs), vibration, rotation • Transition metal compound (d-orbital involve) • Color in organic compounds due to π-π* transitions • Organic molecules that are coloured contain delocalised electrons spread over a number of atoms. That is called conjugated system. HH HH HH
  • 11. Colorant • This term is used for both type of coloring materials e.g pigment and dye. These distinguished on the basis of the solubility: Pigment: insoluble in water and most of the solvents Dyes: Soluble in water and most of the solvents • Classification of colorants: • Chemical classification • Azo, carbonyl, anthraquinones, phthalocyanin et.c • On the basis of electronic excitation • Donor-Aceptor polyene • Cyanin or n-π* chromogen
  • 12. Attributes of Color • Hue (Shade) • Strength/ intensity of color • Brightness of color
  • 13. Hue (Shade) • Hue of dye can be determined by absorbed λ of light e.g • Bathochromic Shift: is a change of spectral band position in the absorption, or emission spectrum of a molecule to a longer wavelength • Hypsochromic Shift: is a change of spectral band position in the absorption, or emission spectrum of a molecule to a shorter wavelength
  • 14. Intensity of Color determined by using Beer- Lambert Law: • Most absorbing materials satisfy the Beer-Lambert Law. Intensity of color of dye is given by ɛ. A = ɛcl • A= Absorbance • C= Concentration • l= Path length • ɛ=molar extinction coefficient
  • 15. Brightness of Color • It is characterized by the UV- spectrum and shape of absorption spectrum. • Spectrum of red surface e.g (Low reflectance and hight absorption) • Red (600-700 nm) • Green (500-600 nm) • Blue (400- 500 nm)
  • 16. Theories OF Color Theories of Color Classical theory Witt’s Theory (Chromophore- Auxochrome Theory) Bury’s Theory of Color Tautomeric Theory (Baeyer’s Theory) Armstrong’s Theory (Quinonoid Theory) Modern theory VBT (Resonance Theory) MOT
  • 18. Witt’s Theory Chromophore‐Auxochrome theory: In 1876, Witt put forward a theory according to which the color of a substance is due to the presence of an unsaturated group known as chromophores(Greek chroma‐color, and phores‐bearing). The important chromophores are: • ‐C = C ‐ • ‐C = N ‐ • ‐C = O ‐ • ‐N = N ‐ • ‐NO2 • ‐Quinoid rings Auxochromes: responsible for the darkening of color Examples: • ‐OH or ‐NH2 • ‐‐NR2
  • 19. Types of Chromophore • Single chromophore is sufficient to impart color to the compound. • Example: ‐NO, ‐NO2, ‐N=N, =N=N‐N, o,p‐quinonoid etc. • More than one chromophore is required to impart the color, e.g. >C=O, >C=C< etc. • Example: Acetone and diketone Diketone
  • 20. Dilthey and witzinger’s Theory • Dilthey and witzinger Refined the witt's theory • ‘‘Stated the chromophores are EWG and auxochrome are EDG They are linked through the conjugated system’’. • By this why donor-acceptor chromogen was born.
  • 21. Armstrong’s Theory Quinonoid theory: Armstrong in 1885 suggested that all coloring matters have quinonoid structures, and thus believed if a compound have quinonoid form, in a structure it is colored, otherwise it is colorless. Example: • benzene and benzoquinones
  • 22. Baeyer’s Theory • In 1907, Baeyer proposed the ‘‘theory of tautomerism’’(Baeyer’s Theory) which states that there is a rapid oscillation between two tautomeric forms of a compound. • Example: Doebner’s violet dye (1) (1a), with a rapid flipping of the chloride ion from one amino group to another (see Figure 1). unsubstitued diamino triphenyl methane dye is Called Doebner's violet. Figure 1: Movement of atom
  • 23. Watson’s Theory • In 1914, Watson was proposed ‘‘Tautomerism is the basic requirement for colored molecule and that must have conjugated chain in a quinonoid form in all the possible tautomers’’. • The theories of Armstrong and Watson became invalid after the discovery of dyes without a quinonoid structure.
  • 24. Bury’s theory • In 1935, Bury was highlighted the relationship between the color of a dye and resonance. Bury’s theory ‘color is due to the involvement of a chromogen in resonance in the molecule’. • Baeyer’s idea that the color of Doebner’s violet arose from the oscillation of atoms was disproved by Bury, who proposed that it was the electrons that moved and not the atoms (see Figure 2). Figure 2: Movement of electrons
  • 26. Valence Bond Theory or (Resonance Theory) Two assumptions apply the valence-bond approach to color and constitution, which are:  The ground electronic state of the dye resembles the most stable resonance form.  The first excited state of the dye resembles the less stable, charge-separated form.
  • 27. Postulates • Chromophores have the π‐electrons which moved from ground state to excited state by the absorption of radiation, thus producing the color. • Auxochromes are groups: • 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. • The dipole moment changes due to oscillation of electron pairs.
  • 28. VBT • Resonance theory explains the • Relation of the color and • The symmetry of the molecule • Transition dipole of the molecule because High canonical str.s ∝ high color intensity ∝ high bathochromic shift
  • 29. Example: 1 • EDG and EWG will effect its bathochromic shift and λmax.
  • 31. Example: 2 • p-nitro dyes have λmax 486 nm but o-nitro dye have λmax 462 nm Because: • In ortho, nitro group is out of plane ‘‘so rotation is required’’ λmax of o-nitro = 462 nm
  • 32. Example:3 • Five membered heterocyclic rings have maximum bathochrmic shift as compare to six membered ring. Because • Less steric interaction • Coplanar Geometric arrangements • Less steric congestion • 126ᵒ bond angle λmax = 608 nm λmax = 614 nm
  • 33. Molecular Orbital Theory • Molecular orbitals generates by the overlapping of atomic orbital. • End-to-end overlapping form ….. σ-bond • Sideways overlapping form ……. π bond
  • 34. The σ bonding orbital is the highest occupied molecular orbital (HOMO), and the lowest unoccupied molecular orbital (LUMO) is the σ* anti-bonding orbital. While these organic compounds do absorb light, the energy transitions involved in promoting an electron from σ to σ* are very large. Organic compounds that contain only σ bonds are colourless. Increasingenergy σ bonding orbital π bonding orbital non-bonding orbital π* anti-bonding orbital σ* anti-bonding orbital These absorptions correspond to the UV part of the spectrum. Molecular Orbital Theory
  • 35. Possible Allows transitions are: σ  σ* (UV- region) π  π* (appear in visible region) n  σ* (saturated molecule + heteroatom) n  π* (Unsaturated molecule + heteroatom) Molecular Orbital Theory Increasingenergy σ bonding orbital π bonding orbital non-bonding orbital π* anti-bonding orbital σ* anti-bonding orbital
  • 36. Hückel Molecular Orbital (HMO) Method • Method use for the calculation on conjugated molecules. • HMO method used to find: • Bond resonating energies (ẞ ) • Pi-electron charge density (Q) • Pi-bond order (P) • Degree of pi-overlap of atomic orbitals • This method is good to calculate the electronic transition energy of  Linear polyenes  Aromatic hydrocarbons.
  • 37. • PPP-MO approach is best over the HMO because of • Inter-electronic interaction energies • Along with molecular geometery • This Method is suitable for the treatment of large molecules • Handle the hetero-atomic species • Help to find • Magnitude of dipole moment • lamda max. Pariser, Parr and Pople (PPP) Molecular Orbital Method