Ultravolet-Visible Spectroscopy

for Inorganic Compound, Coordination Compound and

Inorganic Material

Electromagnetic Spectrum

UV-Visible
Spectroscopy
The radiation which is absorbed has an
energy which exactly matches the energy
difference between the ground state and
the excited state.
These absorptions correspond to electronic
transitions.

UV-Visible
Spectroscopy

Electron Spectra
The UV/Vis spectra are used to determine
the value of o for the complex.
The spectra arise from electronic transitions
between the t2g and eg sets of molecular
orbitals.
Electron-electron interactions can greatly
complicate the spectra.
Only in the case of a single electron is
interpretation of the spectrum
straightforward.

Obtaining o
For a d1 configuration, only a single peak is seen.
It results from the electron promotion from the t 2g
orbitals to the eg orbitals.
The toothed appearance of the peak is due to a
Jahn-Teller distortion of the excited state.
The energy of the peak = o.

General
Observations
d1, d4, d6 and d9
usually have 1
absorption.

General
Observations
d2, d3, d7 and d8
usually have 3
absorptions, one
is often obscured
by a very
intense charge
transfer band.

General Observations
d5 complexes consist of very weak,
relatively sharp transitions which are
spin-forbidden, and have a very low
intensity.

Electronic Transitions
Absorption of light occurs when electrons
are promoted from lower to higher energy
states.
Interactions between electrons causes
more than one peak in the UV/Vis spectra
of these complexes.
The electrons are not independent of each
other, and the spin angular momentum
and orbital angular momentum interact.

Spectroscopy
Absorption spectroscopy from 160 nm to 780 nm
Measurement of transmittance
Conversion to absorbance

A = -log T = log(IO/I) = b c
A = Absorbance (optical density)
T = Transmittance
IO = Intensity of light on the sample cell
I = Intensity of light leaving the sample cell
c = molar concentration of solute
b = length of sample cell (cm)
= molar absorptivity (molar extinction
coefficient)

UV-Visible
Spectroscopy

The Beer-Lambert Law is rigorously

obeyed when a single species is
present at relatively low
concentrations.

UV-Visible
Spectroscopy
The Beer-Lambert Law is not obeyed:
High concentrations
Solute and solvent form complexes
Thermal equilibria exist between the
ground state and the excited state
Fluorescent compounds are present in
solution

UV-Visible
Spectroscopy
The size of the absorbing system and
the probability that the transition will
take place control the absorptivity ().
Values above 104 are termed high
intensity absorptions.
Values below 1000 indicate low
intensity absorptions which are
forbidden transitions.

UV-Visible
Spectroscopy
Highest occupied molecular orbital
(HOMO)
Lowest unoccupied molecular orbital
(LUMO)

UV-Visible
Spectroscopy

Terminology for Absorption Shifts

Nature of Shift

Descriptive Term

To Longer Wavelength

Bathochromic

To Shorter Wavelength

Hypsochromic

To Greater Absorbance

Hyperchromic

To Lower Absorbance

Hypochromic

UV-Visible
Spectroscopy
1. Bathochromic shift (red
shift)
lower energy, longer wavelength

CONJUGATION.

2. Hypsochromic shift (blue

shift)
higher energy, shorter wavelength.

3. Hyperchromic effect
increase in intensity

4. Hypochromic effect

Absorbance

Hyperchromi
c

Bathochromi
c

Hypsochromi
c

Hypochromic

max
Terminology of shifts in the position of an
absorption band

UV-Visible
Spectroscopy
Quantitative Analysis for
Inorganic species (Colorimetric
Analysis)

UV-Visible
Spectroscopy
The ions and complexes of
elements of the first two
transition series absorb broad
bands of visible radiation in at
least one of their oxidation states
and are, as a consequence,
coloured.

UV-Visible
Spectroscopy

UV-Visible
Spectroscopy
Absorption involves transitions
between filled and unfilled dorbitals.
The energy differences between
the d-orbitals (and thus the
position of the corresponding
absorption peak) depend upon
the the position of the element in
the periodic table, its oxidation

UV-Visible
Spectroscopy

UV-Visible
Spectroscopy
Charge transfer absorption is of
particular interest to analytical
chemists because molar
absorptivities are usually large
(max > 10,000).
Methods based upon this type of
absorption are highly sensitive.

UV-Visible
Spectroscopy
Many organic and inorganic
complexes exhibit charge transfer
absorption and are known as
charge transfer complexes.
Thiocyanate and phenolic
complexes of iron(III).

UV-Visible
Spectroscopy

UV-Visible
Spectroscopy
Charge transfer complexes
generally contain both an electron
donor group and an electron
acceptor group.
Absorption of radiation involves
the transfer of an electron from
the donor group to an orbital
associated with the acceptor

UV-Visible
Spectroscopy
Six criteria for a successful
analysis
Specificity of the colour reaction
Proportionality between colour and
concentration
Stability of the colour
Reproducibility
Clarity of the solution
High sensitivity.

UV-Visible
Spectroscopy
Specificity of the colour reaction
Very few reactions are specific for a
particular substance.
However, many only give colours for a
small group of related substances.
Therefore they can be considered to be
selective.
Alteration of oxidation states and pH
enhances selectivity.

UV-Visible
Spectroscopy
Proportionality between colour and
concentration
It is desirable that the system under investigation
follows the Beer-Lambert law.

Stability of the colour

- Not all complexes are stable with respect to
time.
- The stability of the complex should be
sufficient to allow precise measurements to

UV-Visible
Spectroscopy
Reproducibility
The colorimetric procedure must give
reproducible results under the
experimental conditions.
The reaction need not represent a
stoichiometrically quantitiative change.

UV-Visible
Spectroscopy
Clarity of the solution
The solution must be free of
precipitates.
Turbidity scatters and absorbs light.

High sensitivity
It is desirable that the colour reaction
be highly sensitive.
i.e. is very large.

UV-Visible
Spectroscopy
Steps in carrying out a colorimetric
analysis.
Choose the wavelength of maximum
absorbance.
Prepare a calibration curve using known
quantities of the complex measured at this
wavelength.
Measure the absorbance of your unknown
sample.
Calculate the concentration from the

UV-Visible
Spectroscopy
Calibration
Curves
4

y = 1.2469x - 0.0219

Abs

R2 = 0.9992

2
1
0

Nickel Concentration (mg/l)

UV-Visible
Spectroscopy
Advantages of colorimetric
analysis.
Better at low concentrations than
titrimetric or gravimetric analysis.
Can be applied under conditions
where there are no satisfactory
titrimetric or gravimetric
procedures.
Very rapid once a calibration curve
as been obtained.