Introduction to Color Chemistry

In water and wastewater treatment, we make a distinction between true color

and apparent color. True color is the result of dissolved organics, minerals, or
chemicals in water, as noted above. When testing the color of a water sample,
the goal is to measure the true color of the water. However, suspended
materials in the water (turbidity) can change the apparent color of the water (the
color of the water before filtration).

Color is often caused by dissolved organic matter, e.g. humic and fulvic acids
(organic decomposition products from vegetation). It can also be a result of
impurities of minerals such as iron and manganese.

Fulvic acid

Typical humic acid 1

 Questions, Questions….
•  What’s in this flask?

•  What have you just synthesized?

•  Did my reaction Work?

•  What is present in that sample?

•  How could this reaction have possibly Failed?

•  Isolated materials?

•  Purity? Mixture? What kind of mixture?

•  Is this material suitable for the next step?

•  Best to Ask Yourself these questions!

2
 Answers!

•  Bad Answer: “…because this always works in our lab…”

•  Bad Answer #2 “..because my Professor (or some slightly older grad

student, postdoc) said so..”

•  Slightly less Bad Answer #3 “…this was done in the literature…”

•  Good Answer “…because all the spectral and other analytical data
agree with me”

•  Analytical Chemistry. If you do it right, nobody has to “take your word”

on the answers!

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 Spectroscopy in Chemistry….

•  The Chemists Eyes, Ears and Nose

•  How do we know what we have?

•  Read labels (sometimes labels lie)

•  Whose word do we have to take on it?

•  Check it out for yourself! (Get a spectrum!)

•  A spectroscopist (never the hero, just the hero’s best friend)

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 Structural Features we can address
Spectroscopically

•  Molecular weight

•  Chemical Formula

•  Functional groups

•  Skeletal Connectivity, structural isomers

•  Spatial-geometric arrangements, stereoisomerism, symmetry

•  Presence and location of chromophores

•  Chirality issues

•  Some of these are more central than others. Sometimes we can stop
when the answer is fit to purpose.
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 Spectral Techniques

Spectroscopy: It is a general term for “the science that deals with the interactions of
various types of radiation with matter”

Initially interest was laying on “interaction of electromagnetic radiation with matter”

But now-a-days, spectroscopy has been broaden to include “interactions between

matter and other forms of energy”

Spectrometry & spectrometric methods refer to “the measurements of the intensity of

radiation with a photoelectric transducers or other type of electronic device”

Most readily recognizable forms of energy being light and radiant heat

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 Molecular Spectroscopy
Light has magnetic and electric components
-oriented at 90°
-can be polarized

7
 General Terms

Frequency, ν, is the number of oscillations of the field that occurs per second

Wavelength (λ): The linear distance between any two equivalent points on successive
waves (e.g. successive maxima or minima)

Velocity of propagation (v): frequency in cycles per second × wavelength in meter per
cycles

Velocity of radiation depends on the composition of the medium

Wavenumber (ν): Reciprocal of the wavelength in cm−1, equal to kν where k is

proportionality constant

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 Electromagnetic Spectrum

X-ray: Radio waves:

core electron UV: valance IR: molecular Nuclear spin states
excitation electronic vibrations (in a magnetic field)
excitation

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300 kJ/mol 170 kJ/mol
Internal Energy of Molecules

Etotal = Etrans + Eelec + Evib + Erot + Enucl

Eelec: electronic transitions (UV, X-ray)

Evib: vibrational transitions (Infrared)

Erot: rotational transitions (Microwave)

Enucl: nucleus spin (nuclear magnetic resonance)

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 Spectroscopic Techniques and Common Uses

UV-vis UV-vis region Quantitative analysis: Beer’s Law

Atomic Absorption UV-vis region Quantitative analysis: Beer’s Law

FT-IR IR/Microwave Functional Group Analysis

Raman IR/UV Functional Group Analysis/quant

FT-NMR Radio waves Structure determination

X-Ray Spectroscopy X-rays Elemental Analysis

X-ray Crystallography X-rays 3-D structure Anaylysis

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 Why should we learn this stuff?
After all, nobody solves structures with UV any longer!

Many organic molecules have chromophore that absorbs UV

UV absorbance is about 1000 x easier to detect per mole than NMR

Useful because timescale is so fast, and sensitivity so high. Kinetics, esp. in

biochemistry, enzymology.

Most quantitative Analytical chemistry in organic chemistry is conducted using

HPLC with UV detectors

One wavelength may not be the best for all compound in a mixture.

Affects quantitative interpretation of HPLC peak heights

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 Uses for UV

Knowing UV can help you know when to be skeptical of quant results.

Need to calibrate response factors
Assessing purity of a major peak in HPLC is improved by “diode array”
data, taking UV spectra at time points across a peak. Any differences
could suggest a unresolved component. “Peak Homogeneity” is key for
purity analysis.
Sensitivity makes HPLC sensitive
e.g. validation of cleaning procedure for a production vessel
But you would need to know what compounds could and could not be
detected by UV detector! (Structure!!!)
One of the best ways for identifying the presence of acidic or basic
groups, due to big shifts in λ for a chromophore containing a phenol,
carboxylic acid, etc.
“hypsochromic” shift “bathochromic” shift

λ 13
 The Quantitative Picture

•  Transmittance:
T = Pe/Pi Pi Pe
(power in) (power out)
•  Absorbance:
A = -log10 T = log10 Pi/Pe
l (path through sample)

•  The Beer-Lambert Law or Beer’s Law:

A =εcl
Where the absorbance A has no units, since A = log10 Pi / Pe
ε  = molar absorbtivity with units of L mol-1 cm-1
l = path length of the sample in cm
c = concentration of the compound in solution, (mol L-1 or M, molarity) 14
 The Quantitative Picture

Measurement of Transmittance and Absorbance:

The power of the beam transmitted by the analyte solution is usually compared
with the power of the beam transmitted by an identical cell containing only
solvent. An experimental transmittance and absorbance are then obtained with
the equations.

P0 and P refers to the power of radiation after it has passed through the solvent
and the analyte. 15
How Do UV spectrometers work?

Matched quartz cuvettes

Sample in solution at ca. 10-5M.
System protects PM tube from
stray light
D2 lamp-UV
Tungsten lamp-Vis
Double Beam makes it a
difference technique

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 Beer’s law and mixtures

•  Each analyte present in the solution absorbs light!

• 
•  The magnitude of the absorption depends on its ε

•  A total = A1 + A2 + … + An

•  A total = ε1c1l+ ε2c2l + … + εncnl

•  If ε1 = ε2 = εn then simultaneous determination is impossible

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 Example

Two organic components X and Y have absorption maxima at 255 nm and 330
nm respectively. For a pure solution of X, e (255) and e (330) are 4.60 and 0.46
M-1 cm-1 respectively. In the case of pure Y solution, e (255) and e (330) are 3.88
and 30.00 M-1 cm-1. The solution of 0.01 M of mixed components gives
absorption values 0.274 and 0.111 at 255 nm and 330 nm respectively (path
length 1 cm). Calculate the concentration of X and Y in the mixture.

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 Limits to Beer’s Law
•  Chemical Deviations
－absorbing undergo association, dissociation or reaction with the solvent
•  Instrumental Deviations
－non-monochromatic radiation
－stray light

Chemical Deviations
•  high concentration－particles too close
•  Average distance between ions and molecules are diminished to the point.
•  Affect the charge distribution and extent of absorption.
•  Cause deviations from linear relationship.
•  chemical interactions－monomer-dimer
equilibria, metal complexation equilibria,
acid/base equilibria and solvent-analyte
association equilibria
•  The extent of such departure can be
predicted from molar absorptivities and
equilibrium constant.
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 Limits to Beer’s Law

Instrumental Deviations

•  non-monochromatic radiation

•  Stray light
(Po' + Po")
Am = log --------------
(P' + P")

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 UV and UV-Visible Spectroscopy

§  Use of ultraviolet and visible radiation

§  Electron excitation to excited electronic level (electronic transitions)

§  Identifies functional groups (-(C=C)n-, -C=O, -C=N, etc.)

§  Access to molecular structure and oxidation state

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Single-Beam Instruments for the
Ultraviolet/Visible Region

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 Types of Instruments

Instrumental designs for UV-visible photometers or spectrophotometers. A single-

beam instrument is shown. Radiation from the filter or monochromator passes
through either the reference cell or the sample cell before striking the photodetector.

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Single beam instrument

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Double beam (most commercial instruments)

–  Light is split and directed towards both reference cell (blank) and sample
cell
–  Two detectors; electronics measure ratio (i.e., measure/calculate
absorbance)
–  Advantages:
•  Compensates for fluctuations in source intensity and drift in detector
•  Better design for continuous recording of spectra

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 Double beam (most commercial instruments)
Merits of Double Beam Instruments
1. Compensate for all but the most short
term fluctuation in radiant output of the
source
2. Compensate drift in transducer and
amplifier
3. Compensate for wide variations in
source intensity with wavelength

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Absorption

27
 Types of Transitions

In alkenes, only σ and π bonds. So, only σ, π and σ*, π* Mos are present
But amines, ketones, aldehydes& halides have N, O, X and lone pairs on it.
So we need to consider them as non-bonding electrons (n) in the MOs. 28
 Types of Transitions

•  σ→σ* and σ→π* transitions: high-energy, accessible in vacuum UV (λmax<150

nm). Not usually observed in molecular UV-Vis.

•  n→σ* and π→σ* transitions: non-bonding electrons (lone pairs), wavelength

(λmax) in the 150-250 nm region.

•  n→π* and π→π* transitions: most common transitions observed in organic

molecular UV-Vis, observed in compounds with lone pairs and multiple bonds
with λmax = 200-600 nm.

•  Any of these require that incoming photons match in energy the gap
corresponding to a transition from ground to excited state.

•  Energies correspond to a one photon of 300 nm light are ca. 95 kcal/mol

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 σ → σ*, n → σ*, n → π* and π → π* Transitions
•  An electron in a bonding σ orbital is excited to the corresponding antibonding
orbital. The energy required is large. For example, methane (which has only C-
H bonds, and can only undergo σ → σ* transitions) shows an absorbance
maximum at 125 nm. Absorption maxima due to σ → σ* transitions are not
seen in typical UV-VIS spectra (200 - 700 nm)

•  Saturated compounds containing atoms with lone pairs (non-bonding electrons)

are capable of n → σ* transitions. These transitions usually need less energy
than σ → σ* transitions. They can be initiated by light whose wavelength is in
the range 150 - 250 nm. The number of organic functional groups with n → σ*
peaks in the UV region is small.

•  Most absorption spectroscopy of organic compounds is based on transitions of

n or π electrons to the π* excited state. These transitions fall in an
experimentally convenient region of the spectrum (200 - 700 nm). These
transitions need an unsaturated group in the molecule to provide the p
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electrons.
σ → σ*, n → σ*, n → π* and π → π* Transitions

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 Transition in Ethylene
Example: π→π* transitions responsible for ethylene UV absorption at ~170 nm
calculated with ZINDO semi-empirical excited-states methods (Gaussian 03W):

hν 170nm photon

LUMO
HOMO
πg antibonding molecular orbital
πu bonding molecular orbital

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 Solvents for UV
(showing high energy cutoffs)

Sovent λmax (nm)

Sovent λmax (nm)
Water 205
THF 220
CH3C≡N 210
CH2Cl2 235
C6H12 210
CHCl3 245
Ether 210
CCl4 265
EtOH 210
benzene 280
Hexane 210
Acetone 300
MeOH 210
Dioxane 220

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 n → σ*, n → π* and π → π* Transitions

Chromophore Excitation λmax, nm Solvent

C=C π→π* 171 hexane

n→π* 290 hexane

C=O
π→π* 180 hexane

n→π* 275 ethanol

N=O
π→π* 200 ethanol

C-X   n→σ* 205 hexane

X=Br, I n→σ* 255 hexane

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n → π* and π → π* Transitions

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Example for π → π*

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 An Example--Pulegone
Frequently plotted as log of molar extinction

So at 240 nm, pulegone has a molar extinction of 7.24 x 103

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Antilog of 3.86
 Can we calculate UVs?
Molar Absorptivity (l/mol-cm) Electronic Spectra
50243

40194

30146

20097

10049

nacindolA

0 Wavelength (nm)
220 230 240 250 260 270 280 290 300

Molar Absorptivity (l/mol-cm) Electronic Spectra

51972

41578

Semi-empirical (MOPAC) at AM1, 31183

then ZINDO for config. interaction

level 14
20789

Bandwidth set to 3200 cm-1 10394

Nacetylindol

0 Wavelength (nm)
220 230 240 250 260 270 280 290 300

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 The orbitals involved

Molar Absorptivity (l/mol-cm) Electronic Spectr a

55487

44390

33292 Showing atoms

whose MO’s
22195 contribute most
to the bands
11097
Nacetylindol

0 Wavelength (nm)
200 210 220 230 240 250 260 270 280 290 300
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Polyenes, and Unsaturated Carbonyl groups;
an Empirical triumph
R.B. Woodward, L.F. Fieser and others
Predict λmax for π⇒π* in extended conjugation systems to within ca. 2-3 nm.

Homoannular, Attached group increment, nm

base 253 nm Extend conjugation +30
Addn exocyclic DB +5
Acyclic, base 217 nm Alkyl +5
O-Acyl 0
S-alkyl +30
Heteroannular,
base 214 nm O-alkyl +6
NR2 +60
Cl, Br +5
40
 Similar for Enones
O O
β β

215 202 227 239

Ο
α Base Values, add these increments…
α β γ δ,+
X=H 207
x Extnd C=C +30
X=R 215 +5
Add exocyclic C=C
X=OH 193
Homoannular diene +39
X=OR 193 alkyl +10 +12 +18 +18

With solvent OH +35 +30 +50

correction of….. OAcyl +6 +6 +6 +6
Water +8
O-alkyl +35 +30 +17 +31
EtOH 0
CHCl3 -1 NR2
Dioxane -5 S-alkyl
Et2O -7
Cl/Br +15/+25 +12/+30 41
Hydrcrbn -11
Some Worked Examples

Base value 217

2 x alkyl subst. 10
exo DB 5
total 232
Obs. 237

Base value 214

3 x alkyl subst. 15
exo DB 5
total 234
Obs. 235

O Base value 215

2 β alkyl subst. 24
total 239
Obs. 237
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 Distinguish Isomers!

Base value 214

4 x alkyl subst. 20
exo DB 5
total 239
Obs. 238
HO2C

Base value 253

4 x alkyl subst. 20
total 273
Obs. 273

HO2C
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Generally, extending conjugation leads to red shift

“particle in a box” QM theory; bigger box

Substituents attached to a chromophore that cause a red shift are called
“auxochromes”
Strain has an effect…

λmax 253 239 256 248

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Important Example

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Important Example

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Important Example

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Important Example

48
Important Example

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