An Introduction To Infrared and UV-Visible Spectros

An Introduction to Infrared and
UV-Visible Spectroscopy
LEARNING OBJECTIVES
 Describe the principal regions of the electromagnetic
spectrum.
 Describe the principles of infrared spectroscopy.
 Describe the principles of UV-Vis spectroscopy.
 Describe and explain the principal factors that govern the
vibrational frequencies of bonds.
 Describe and explain the principal factors that govern the
electronic absorption process in UV-Vis spectroscopy.
 Experimental and instrumental
THE ELECTROMAGNETIC
SPECTRUM
WHAT IS SPECTROSCOPY?
 Atoms and molecules interact with electromagnetic
radiation (EMR) in a wide variety of ways.
 Atoms and molecules may absorb and/or emit EMR.
 Absorption of EMR stimulates different types of motion
in atoms and/or molecules.
 The patterns of absorption (wavelengths absorbed and to
what extent) and/or emission (wavelengths emitted and
their respective intensities) are called ‘spectra’.
 The field of spectroscopy is concerned with the
interpretation of spectra in terms of atomic and molecular
structure (and environment).
INFRARED SPECTROSCOPY
 Infrared radiation stimulates molecular

vibrations.
 Infrared spectra are traditionally displayed as
%T (percent transmittance) versus wave
number (4000-400 cm-1).
 Useful in identifying presence or absence of
functional groups.
C
O O CH3
C
HO
Wavenumber = 1/ wavelength
 In the IR region of
the electromagnetic
spectrum, the
absorption of
radiation by a sample
is due to changes in
the vibrational
energy states of a
molecule.
 Methane H H H H H H
C C C
H H H H H H
Asymmetrical Symmetrical Bending or scissoring

stretching stretching
H H H H H H
C C C
H H H H H H
Rocking or in Twisting or out- Wagging or

plane bending of-plane out-of-plane
bending bending
 Only vibrations that cause a change in ‘polarity’ give rise
to bands in IR spectra – which of the vibrations for CO2
are infrared active?
O C O
Symmetric stretch
O C O Asymmetric stretch
Bending (doubly
O C O O C O
degenerate)
What is a vibration in a molecule?

 Any change in shape of the molecule- stretching of bonds,
bending of bonds, or internal rotation around single bonds
What vibrations change the dipole moment of a

molecule?
 Asymmetrical stretching/bending and internal rotation change
the dipole moment of a molecule. Asymmetrical
stretching/bending are IR active.
 Symmetrical stretching/bending does not. Not IR active

 Human Breath
100
80
O O
60 H H
%T
H H
40
20 O C O
0
4000 3500 3000
O C O
2500 2000 1500 1000 O 500 C O
-1
wavenumber/cm
 How much movement occurs in the vibration of a C-
C bond?
stretching vibration 154 pm For a C-C bond with a
bond length of 154
pm, the variation is
about 10 pm.
10 pm
For C-C-C bond angle
bending vibration a change of 4o is
4o 10 pm typical. This moves a
carbon atom about 10
pm.
What wavelength of electromagnetic radiation is

involved in causing vibrations in molecules?
 Infrared (IR) electromagnetic radiation causes vibrations in
molecules (wavelengths of 2500-15,000 nm or 2.5 – 15 mm)
How does the mass influence the vibration?
 The greater the mass - the lower the wavenumber
H2 I2
Ethane Chloroethane
POSITION REDUCED MASS LIGHT ATOMS HIGH

FREQUENCY
BOND STRENGTH STRONG BONDS HIGH

FREQUENCY
(STIFFNESS)
STRENGTH CHANGE IN STRONGLY POLAR

‘POLARITY’ BONDS GIVE INTENSE
BANDS
WIDTH HYDROGEN BONDING STRONG HYDROGEN
BONDING GIVES
BROAD BANDS
 In general
Bond C-H C-D C-O C-Cl

→
ν /cm-1 3000 2200 1100 700
→
Bond C≡ O C=O C-O

→
ν /cm-1 2143 1715 1100
→
4000-3000 3000-2000 2000-1500 1500-1000
cm-1 cm-1 cm-1 cm-1
O-H C≡ C C=C C-O

N-H C≡ N C=O C-F
C-H C-Cl
deformations
Increasing energy
Increasing frequency
INTERPRETATION OF INFRARED SPECTRA
 An element of judgement is required in interpreting IR spectra but you
should find that it becomes relatively straightforward with practice.
 It is often possible to assign the peaks in the 1600-3600 cm-1 region by
consulting tables or databases of IR spectra. When making an assignment,
give both the type of bond and the type of vibration, e.g. O-H stretch or C-
H bending vibration.
 The most useful regions are as follows:
 1680-1750 cm-1:C=O stretches feature very strongly in IR spectra and
the type of carbonyl group can be determined from the
exact position of the peak.
 2700-3100 cm-1: different types of C-H stretching vibrations.
 3200-3700 cm-1: various types of O-H and N-H stretching vibrations.
 Too many bonds absorb in the region of 600-1600 cm-1 to allow confident
assignment of individual bands. However, this region is useful as a
fingerprint of a molecule, i.e. if the spectrum is almost identical to an
authentic reference spectrum then the structure can be assigned with some
confidence.
INTERPRETATION OF INFRARED SPECTRA
Ethanoic acid
Infrared Instrumentation
Sample
IR Source compartment Detector
 All modern instruments are Fourier Transform
instruments.
 In all transmission experiments radiation from a
source is directed through the sample to a detector.
 The measurement of the type and amount of light
transmitted by the sample gives information about the
structure of the molecules comprising the sample.
Infrared Experimental
 To obtain an IR spectrum, the sample must be
placed in a “container” or cell that is transparent
in the IR region of the spectrum.
 Sodium chloride or salt plates are a common
means of placing the sample in the light beam of
the instrument.
InfraredExperimental
IR transparent Salt Plates

 These plates are made
of salt and must be
stored in a water free
environment such as the
dessicator shown here.
 The plates must also be
handled with gloves to
avoid contact of the
plate with moisture
from one’s hands.
 To run an IR spectrum of a
liquid sample, a drop or two
of the liquid sample is
applied to a salt plate.
 A second salt plate is placed
on top of the first one such
that the liquid forms a thin
film “sandwiched” between
the two plates.
 The cell holder is then
placed in the beam of the
instrument.
 The sample is then scanned
by the instrument utilizing
predestinated parameters.
 A satisfactory spectrum has
well defined peaks-but not
so intense as to cause
flattening on the bottom of
the peaks.
Benzoic acid
 The salt plates are cleaned
by rinsing into a waste
container with a suitable
organic solvent-commonly
cyclohexane - NEVER
WATER!
 Cloudy plates must be
polished to return them to a
transparent condition.
 To polish cloudy windows,
rotate salt plate on polishing
cloth.
 Ultraviolet radiation stimulates molecular
vibrations and electronic transitions.
 Absorption spectroscopy from 160 nm to 780
nm
 Measurement absorption or transmittance
 Identification of inorganic and organic species
H3C H3CO
N C
O
O
O C
Cocaine
 Electronic transitions occur when the molecule
absorbs energy
Electronic transitions:
 p, s, and n electrons
 d and f electrons
 Charge transfer
Electronic Transitions in
Formaldehyde
 Electronic transitions
 Molecular Orbital Theory
 d-d Transitions
 3d and 4d 1st and 2nd
transitions series
 Partially occupied d
orbitals
 Transitions from lower
to higher energy levels
 Charge Transfer
 Electron donor and acceptor characteristics
 Absorption involves e- transitions from donor to acceptor
 SCN- to Fe(III)
 Fe(II) and neutral SCN
 Metal is acceptor
 Reduced metals can be exception
 THE BEER-
LAMBERT LAW I I 
T= t %T =  t  x 100
Io Io  Io 
 For a light absorbing
medium, the light
light intensity (I)

intensity falls
exponentially with
Io It
sample depth.
 For a light absorbing l
medium, the light
intensity falls It cuvette
exponentially with
increasing sample
concentration. l Sample depth
A = ε λ cl A = − log10 T
Absorbance
 The negative logarithm of T is called

the absorbance (A) and this is
directly proportional to sample depth
(called pathlength, l) and sample
concentration (c). The equation is
called the Beer-Lambert law.
ε is called the molar
absorption coefficient
and has units of dm3
Concentration mol-1 cm-1
 Beer-Lambert Law
limitations
 Polychromatic Light
 Equilibrium shift
 Solvent
 pH
UV-Visible Instrumentation
 Several types of spectrometer
UV-Visible Instrumentation
 Light source
 Deuterium and hydrogen lamps
 W filament lamp
 Xe arc lamps
 Sample containers
 Cuvettes
 Plastic
 Glass
 Quartz
Open-topped rectangular
LYCOPENE
LYCOPENE
standard cell (a) and
apertured cell (b) for limited
sample volume
 Acknowledgements
 Bette Kreuz, Ruth Dusenbery at Department of Natural
Sciences UM-Dearborn.
 Dr David J McGarvey at Keele University
 Hewlett Packard
 Andrew Jackson at Staffordshire University

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An Introduction to Infrared and

 Infrared radiation stimulates molecular

Asymmetrical Symmetrical Bending or scissoring

Rocking or in Twisting or out- Wagging or

What is a vibration in a molecule?

What vibrations change the dipole moment of a

 Symmetrical stretching/bending does not. Not IR active

What wavelength of electromagnetic radiation is

POSITION REDUCED MASS LIGHT ATOMS HIGH

BOND STRENGTH STRONG BONDS HIGH

STRENGTH CHANGE IN STRONGLY POLAR

Bond C-H C-D C-O C-Cl

Bond C≡ O C=O C-O

O-H C≡ C C=C C-O

IR transparent Salt Plates

 Fe(II) and neutral SCN

light intensity (I)

 The negative logarithm of T is called

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