Ultraviolet/Visible Molecular

Absorption Spectrometry III

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Outline
• The magnitude of molar absorptivities
• UV/Vis absorbing species
– Absorbing species containing π, σ, n electrons
– Absorbing species containing d and f electrons
– Charge-transfer absorption
• Quantitative analysis by UV/Vis absorption
measurements
– General aspects
– Analysis of mixtures of absorbing substances
– Photometric titration

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The magnitude of molar absorptivities
Molar absorptivity: 0 to around 105

ε = 8.7 x 1019 P A

P: transition probability (0 to 1)
A: cross sectional target area in cm2 (~ 10-15 cm2 for
organic molecules, determined from electron diffraction
and X-Ray studies).

forbidden transition: P = 0.01; ε = 103

allowed transition: P = 0.1 to 1
P=0.01, ε~103
P=0.1, ε~104
P=1, ε~105

strong absorption: ε = 104 to 105 L/ (mol*cm)

weak absorption: ε =103 L/ (mol*cm) 3
 Types of light absorbing electrons

Uv/vis absorption Æ electronic transitions involving valence electrons.

Valence electrons: electrons in the outermost shell of an atom.

1. π, σ and n electrons 2 atomic orbitals combine to form a bonding

and an antibonding orbitals.
2. d and f electrons
3. charge transfer electrons

Overlapping of
atomic orbitals

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Example: Formaldehyde molecular orbital
The lowest energy transition
for formaldehyde is n Æ π*

(a) nÆ π* (S), 397nm

(green-yellow) low
probability
(a) nÆ π* (S), 355 nm, higher (b) nÆ π* (S), 355 nm,
probability, intense UV higher probability,
absorption intense UV absorption
(b) nÆ π* (T), 397 nm, (green- 5
yellow) low probability
 Electronic transitions involving π, σ, and n electrons

Four types of electronic

transitions

σÆ σ* (vaccum UV)
π Æ π* (200-700 nm)
n Æ σ* (150-250 nm)
n Æ π* (200-700 nm)

Electronic molecular energy levels.

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 Electronic transitions involving π, σ, and n electrons

1). absorption maxima due to σ Æσ* transitions (around 125 nm) have
never been observed in the ordinary, accessible UV region.

2). n Æσ* transitions (from 150 to 250 nm): depend primarily upon the
kind of bond and to a lesser extent upon the structure of the molecule.
Molar absorptivity: 100 to 3000 L/ (mol*cm).

3). π Æ π*, n Æ π* transitions (from 200 to 700 nm): both transitions

require the presence of an unsaturated functional group to provide the
π orbital.

4). Molar absorptivity for n Æ π* is low: 10 to 100 L/(mol*cm); blue shift

with increasing solvent polarity due to increased solvation of the
unbonded electron pair.

5). Molar absorptivity for π Æ π* is high: 1000 to 10,000 l/ (mol*cm). Red

shift with increasing solvent polarity.

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 Absorption by organic compounds

• All organics are capable of absorbing electromagnetic

radiation because all contain valence electrons
– σ-σ* in CH4: 125 nm
– σ-σ* in C2H5: 135 nm
– Water also absorbs here. Æ interference
• Useful wavelength: λ>185 nm
• Inorganics: nÆπ* (nitrate (313 nm), CO32- (217 nm), NO2-
(360, 280 nm)

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nÆσ*
Organics containing N, O, X
Example functional groups: C=O, OH,
C-O, C-N, C-Cl, C- I, etc.)
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The position of λmax is affected by structural details and solvent.

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Absorption
spectra for
typical
organic
compounds.
Conjugation lowers E of
π* This leads to lower
πÆπ* transition E Æ λmax
red shift

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Additive if
non-conjugate

Red shift

Similar λmax

Red shift

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 Effect of common ring substituents

Auxochrome is a functional group that does not itself absorbs in the UV/vis region, but has
the effect of shifting chromophore peaks to longer wavelength.
Examples; -OH, -NH2. (They have non-bonding electrons interacting with π electrons of the
ring. The effect is to stablize π*).
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 Absorption involving d electrons

Electron –density
distribution of d-orbitals

Splitting of the d-orbitals occurs when complex formation occurs in solution.

Reason: Differential forces of electrostatic repulsion between the e pairs of the donor and
electrons in the various d orbitals of the central metal ion. 14
Absorption involving d electrons

The ions and complexes of elements in the first two

transition series absorbs broad bands of visible radiation,
as a result, colored.
Absorption involves transitions between filled and unfilled
d-orbitals with energies that depend on the ligands
bonded to the metal ions.
The energy differences between these d-orbitals, thus
the λmax position, depend on the position of the element
in the periodic table, its oxidation state, and the nature of
the ligand bonded to it.

Absorption spectra of aqueous 15

solutions of transition metal ions
 Absorption involving f electrons

…4d104f115s25p6

The electrons responsible for absorption by lanthanides

…4d104f125s25p6
and actinides are 4f and 5f electrons, respectively.
These f electrons are shielded from external influences
by electrons that occupy orbitals with larger principal
quantum numbers. Æ Their energy levels are Little
effected by the type of ligand associated with the metal
…4d104f35s25p6
ions. Æ Absorption band tend to be narrow and
relatively unaffected by the species bonded by the outer
electrons.

…4d104f65s25p6

Absorption spectra of aqueous 16

solutions of rare earth ions
Charge-Transfer Absorption

Of analytical utility because of large ε (εmax>10,000).

One component has e-donor characteristics, the
other component has e-acceptor properties.
Radiation absorption transfers an e from the donor to
an orbital largely assocaied with the acceptor., i.e.,
internal oxidation/reduction.
Example: Fe(SCN)2+,
e- donor: SCN-, e- acceptor, Fe (III)Æ Fe (II)

Absorption spectra of aqueous

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Charge transfer complexes
Quantitative analysis by absorption measurements

1) Selection of wavelength: peak wavelength

(maximum sensitivity; good adherence to Beer's law; less
sensitive to uncertainties);

2) Variables that influence absorbance: solvents; pH of the

solution; temperature; high electrolyte concentrations; presence of
interfere species;

3) Cleaning the cell: lens paper soaked in methanol is used to

wipe cell surfaces;

4) Relationship between A and c: using standard solutions

to obtain A vs. c curve;

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 Analysis of mixtures of absorbing
substances
At λ’

A' = ε 'M bCM + ε ' N bC N

At λ”

A" = ε "M bCM + ε "N bC N

ε’M,ε’N,ε”M, ε”N: can be obtained from
single analyte standard.
A’, A”: experimentally measurable.
Choose λ’, and λ” at which εM and εN
differ most.
Figure 14-9 Absorption spectrum of a two-component
mixture. Optimum wavelenghs λ’ and λ″ for the
determination of the two components are indicated by
the vertical dashed lines. 19
 Photometric titration

A+tÆP

A = ε AbC A + ε t bCt + ε p bC p

Figure 14-12 Typical photometric titration curves. Molar

absorptivities of the substance titrated, the product, and the
titrant are given by εA, εp, εt, respectively. 20
Photometric titration: example

Bi 3+ + EDTA = Bi − ( EDTA) complex

cu 2+ + EDTA = Cu − ( EDTA) complex

At 745 nm,
εBi=0
εBi-EDTA=0
εCu-EDTA>0

Photometric titration curve of 100 mL of a solution that was 2.0 × 10-3 M in

Bi3+ and Cu2+. Wavelength: 745 nm.

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