Chapter 4

Electronic Spectroscopy:
UV-Vis molecular absorption spectroscopy

(10-200-380-780) nm
Type of electronic transitions:

The absorption of UV or visible radiation

corresponds to the excitation of outer electrons.
Generally, There are three types of electronic
transition which can be considered;

1.Transitions involving , , and n electrons

2.Transitions involving charge-transfer electrons
3.Transitions involving d & f electrons
Type of electrons in the molecule:
Closed Core electrons no absorption in UV-Vis regions
shell
electrons
σ- (single bonds in saturated Require too high energy of excitation
electrons hydrocarbons, -CH2-CH2-)
n- (paired nonbonding electrons , exited in UV-Vis regions because they
electrons e.g. N, O, S & Halogens) are less tightly held than σ- electrons

π- ( in double and triple bonds) are responsible for electronic spectra

electrons in UV-Vis regions
The common transitions in the UV-Vis region :

Molecular
energy levels
Which compounds show UV-Vis spectra:

compounds possess n → σ* transitions only do not absorb UV-Vis :

Examples :

• Ethers ( R - O – R’) CH3OC2H5

• Thioether ( R – S – R’)
• Disulphides ( R – S – S – R’)
• Alkyl amines ( R – NH2 )
• Alkyl halides ( R – X )

- All these transitions are transparent in the UV-Vis regions i.e. have no absorption
bands in the UV-Vis regions because absorption occurs at λ < 200 nm.

- The oxygen non-bonding electrons in alcohols and ethers do not give rise to G.R.
absorption above 160 nm. Consequently, pure alcohol and ether solvents may be
used for UV-vis spectroscopic studies.
Compounds possess n → * and  → * transitions can absorb UV-Vis :

Examples:

The spectrum of the unsaturated ketone illustrates:

• The  → * absorption located at 242 nm is
very strong, with an ε = 18,000.
• The weak n → * absorption near 300 nm has
an ε = 100.

Transitions in Ketones, alkane,

alkenes, dienes ?

σ → σ* and n → σ* occurs at λ < 200 nm

n → π* and π → π* occur at λ > 200 nm

 Expressions in UV-Vis spectra:

Chromophore:

the absorbing group in a molecule (functional group usually containing unshared

electrons i.e. unsaturated group ex. C=O, N=O, C ≡ C, C=C, …).

Auxochrome:

does not itself absorb, usually a saturated group but if present in a molecule, it
can enhance the absorption by a chromophore or shift the wavelength of
absorption, e.g. –OH, -NH2, X (Cl, Br…..).They possess n electrons that can
interact with π electron in the chromophore.
 Bathochromic shift: (RED shift)

absorption maximum is shifted to longer wavelength.

Hypsochromic shift: (Blue shift)

absorption maximum is shifted to shorter wavelength.

“hypsochromic” shift “bathochromic” shift

Hyperchromism/ Hyperchromic: an increase in molar absorptivity or absorbance

Hypochromism/ Hypochromic: a decrease in molar absorptivity or absorbance

Relation between UV-Vis spectra and structure :

Presence of conjugated double bond

• Where multiple ( = or ≡ ) bonds are separated by just one single

bond.

• It results in a bathochromic shift (RED) and a general increase

in intensity (hyperchromism).
Example:

Extending conjugation generally results in bathochromic and

hyperchromic shifts in absorption
Relation between UV-Vis spectra and structure :

pPresence of Auxochrome

An auxochrome is a saturated group of atoms attached to the

chromophore which modifies the ability of the chromophore (to
absorb light, altering the wavelength or intensity of the
absorption. If auxochromes are in direct conjugation with the pi-
system of the chromophore, they may increase the wavelength
(bathochromic or red shift ) at which the light is absorbed and
intensify the absorption (hyperchromism).
Example:

O NH2
O NH2

PURPLE
ORANGE
O OH
O
Substituents attached to a chromophore that
cause a red shift are called “auxochromes”

O NHCH3

BLUE

O NHCH3
Does a minor change in the structure of the chromophore affect
the spectrum? What is the effect of addition of single bonds on
chromophores?

• Ans. > > The spectrum is not affected

Example:

Acetone and 2-butanone give spectra similar in shape and

intensity.
O O
║ ║
CH3 – C – CH3 CH3 – C – CH2CH3
Acetone 2- Butanone
What is the effect of existence of isolated chromophores in a
molecule?
• The spectral effects of two isolated chromophores in a molecule
(separated by at least 2 single bonds) are independent and additive.

Example:

CH3CH2CNS and SNCCH2CH2CH2CNS

In ethyl thiocyanate CH3CH2CNS, an absorption maximum due to CNS occurs
at 245nm with ε = 800.
In SNCCH2CH2CH2CNS, absorption maximum occurs at 247 nm with ~ double

intensity ε = 2000.
Assignment: Account for the
isolated chromophores in a
molecule.
 What if the molecule doesn’t absorb radiation:

Idea: Prepare a derivative that absorbs.

❑ Ex. 1: Proteins form colored complex in alkaline medium with

copper(II) (biuret reagent)

❑ Ex. 2: Creatinine (is a waste product removed from the body by

the kidneys) in the blood is reacted with picrate ion in alkaline
solution to give a colored product which absorbs at λ = 490 nm

❑ Ex. 3: Iron (Fe II) is reacted with bathophenanthroline to give a

colored product that being measured at λ = 535 nm
 What if the molecule doesn’t absorb radiation:
❑ Ex. 4: Uric
acid is oxidized with alkaline phosphotungstate to gives
blue reduction product of phosphotungstate that is measured at λ =
680 nm

❑ Ex. 5: Inorganicphosphate is reacted with molybdenum(VI), the

complex formed is reduced to “molybdenum blue” Mo (V) that
absorbs at λ = 660 nm

❑ Ex. 6: Barbiturates are determined in alkaline solution at λ = 252 nm

❑ Ex. 7:Monitoring many enzyme reactions by following change in

absorbance at λ = 340 nm due to changes in the reduced form of
NADH*(nicotinamide adenine dinucleotide is a co-enzyme required
for the production of energy in cells.).
bathophenanthroline Uric acid
alkaline phosphotungstate
Assignment: how to treat protein,
creatinine and uric acid samples to
be measured with UV-Vis
spectroscopy?
 Polyenes, and Unsaturated
Carbonyl groups
R.B. Woodward 1941, L.F. Fieser 1948 and others
Predict max for π* in extended conjugation systems to
within ca. 2-3 nm.

Homoannular diene
All are in one cycle , base 253 nm

Acyclic, base 217 nm

Heteroannular diene
Each is in a cycle , base 214 nm
 215 202

 b g d,+
Extended diene C=C +30
b b
exocyclic C=C +5

alkyl +10 +12 +18 +18

O
OH +35 +30 +50
OAcyl +6 +6 +6 +6

O-alkyl +35 +30 +17 +31 x
Cl/Br +15/+25 +12/+30
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 ß alkyl subst. 24
total 239
Obs. 237
 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
exo DB 5
total 278
Obs. 278
HO2C
Predict max for the following compounds:

Ans. 239 Ans. 283

Ans. 256
Ans. 363
UV-Visible spectroscopy for
Inorganic Compounds
 Transition metal (d-block):

❑ Most transition-metal ions absorb in the ultraviolet or

visible region of the spectrum.
❑ The first and second transition-metal series, the 3d and
4d electrons are responsible for the absorption.

Examples:

Fe+3: [Ar] 4s0 3d5

Cu+2 [Ar]4s0 3d9

 Inorganic anions:

Inorganic anions have broad UV absorption bands

from non-bonding electrons.

Examples:
 Complexes:

L: → □ M

The absorption of UV-Vis radiation can be due to:

1-Excitation of the metal ion (Mn+):
usually has very low ε ~ 1 -100.
2-Excitation of the ligand (L):
most ligands are organic chelating agents that exhibit
absorption due to π → π * and n →π * transitions.
3-Charge transfer transition:
intense absorption bands (ε > 10,000)
Electron density distribution of d - orbitals
dxy, dxz, dyz are between axes
dx2-y2, dz2 are along the axes
❑ Complexation removes the degeneracy of the five d orbitals.
❑ Electronic transitions take place from lower energy d orbital to
higher energy d orbital, upon absorption of the proper
frequency of light. (d → d* transitions)
❑ The light required for these transitions ranges from the near IR
to UV region.
The amount of splitting between d orbitals depends on the ligand field
strength, i.e. the energy difference between d orbitals depends on the
nature of the ligand, the oxidation state of the metal and the symmetry.

Ligand field strength increase ↑ splitting increase and λ ↓ max

CN- causes d orbital to split more than I-; hence, more energy is required for
a transition for a cyano complex than for an iodo complex.
 Charge-transfer of complexes

• one of the components is electron-donor and the other is

electron-acceptor . Electron absorbs light and transfers to
acceptor via internal red-ox process

• Generally: Ligand-to-metal charge transfer (LMCT)

Mn+ acts as electron acceptor while L as electron donor,
ex: Fe3+ ≠ SCN‾.
• Exceptions:Metal-to-ligand charge transfers (MLCT)
Mn+ acts as electron donor while L as electron acceptor
ex: Fe2+ ≠ 1,10-phenanthroline.

• Two non-metallic components, ex: quinone and

hydroquinone
 Spectra of Lanthanides and Actinides

• The transitions responsible for absorption by elements of the lanthanide

series involve 4f electrons, while it is the 5f electrons of the actinide
series.
• The bands represent f → f* transitions. sharp peaks caused by “screening”
of the f electrons by other orbitals
 Solvents for Spectrometry

In choosing a solvent, consideration must be given not only to its transparence, but also to its
possible effects upon the absorbing system.

• The solvent used to prepare the sample must not absorb in the λ region where the
measurement is being made.
• The positions of absorption maxima are influenced by the nature of the solvent.
• The same solvent must be used when comparing absorption spectra for identification
purposes.
• In Vis. region, water and many transparent solvents are used.
• In UV, water can be used, ethanol, hexane
• In IR region, carbon tetrachloride CCl4 and
carbon disulphide CS2 are used but
Water exhibits strong absorption bands in the IR .

Give reason: Water can’t be

used as solvent in IR
measurement
Applications of absorption measurement
and photometric titration
Spectrophotometric and photometric
titrations

Spectrophotometric / photometric
measurements are useful for
locating the equivalence points of
titrations. If the titrand, titrant, or
the reaction product absorbs
radiation in the UV-Vis region,
absorbance measurements can be
used to locate the end point of the
titration.
 • The absorbance of the titrand solution is measured after each
addition of the titrant and the end point of the titration is located
from a plot of the absorbance of the titrand solution as a function
of the volume of added titrant.

• The curve consists of two straight-line regions with different slopes, one
occurring at the outset of the titration and the other located beyond the
equivalence point region; the end point is taken as the intersection of
extrapolated linear portions of the two lines.
.
 Experimentally notes

• Before a titration curve is plotted, absorbance readings

must be corrected for volume changes by multiplying
the observed absorbance by (V + v) / V, where V is the
original volume of the titrand and v is the volume of the
added titrant.

• The absorbance can be measured by removing a

fraction of the titrand from the titration vessel and
placing it in the absorptive cell or performing the
titration inside the cell by a microburette.
Example 1:
Let’s consider the analysis of hydrogen peroxide with potassium permanganate in an acidic
solution.
The potassium permanganate or MnO4- is the only colored substance in the reaction. (It can serve
as its own indicator.)
How would the absorbance change as titrant was added?

5H2O2 + 2MnO4- + 6H+ → 5O2 (g) + 2Mn+2 + 8H2O

absorbance

purple

Equivalence point
MnO4- reacting,
color disappears excess MnO4-
accumulates

Volume of titrant (mL KMnO4)

Notice you do not need to have a data point at the equivalence point.
Equivalence point located by extrapolation of the two lines.
Example 2:
• Titrate a protein with Fe3+ where product (complex) has red color
• Product has an absorbance maximum at 465 nm
• As more Fe3+ is added, red color and absorbance increases,
• When the protein is saturated with iron, no further color can form
• End point – intersection of two lines
• As more Fe3+ is added, concentration changes due to dilution
• Need to correct absorbance for dilution.
 total volume 
Corrected absorbance =  (observed absorbance )
 initial volume 

Analyte titrant (red)

(colorless) (colorless)
As Fe3+ binds protein

solution turns red

When all the protein is bound to Fe3+,

no further increase in absorbance.

As Fe3+ continues to bind protein

red color and absorbance increases.
The shape of the titration curve varies with the absorbing species in the solution, for example:

Curve d is the titration of a non absorbing species with an absorbing titrant that is
decolarized by the reaction, e.g. titration of ferrous ion with potassium
permenganate.
Example 3: In the successive photometric
titration of bismuth(III) and copper(II) at
745nm with EDTA

❑ the cations, the reagent, and the

bismuth complex formed in the first part
of the titration do not absorb but the
copper complex does.

❑ Thus, the solution exhibits no

absorbance until essentially all the
bismuth is complexed followed by an
increase in the absorbance due to the
formation of the copper complex.
 Problems on Chapter 4

1- Draw the titration curve in the following cases:

a) KMnO4 ≠ NO2− b) Both titrant and titrand absorb

2- Which of the following has an absorbance at longer max

A) [Cr(en)3]3+
B) [Cr(CN)6]3-
C) [CrCl6]3-
D) [Cr(NH3)6]3+