UV-Visible and IR spectroscopy

Components of typical spectroscopic instruments:

1. A stable source of radiant energy (sources of
radiation).
2. A transparent container for holding the sample
(sample cell).
3. A device that isolates a restricted region of the
spectrum for measurement (wavelength
selector, monochromator or grating).
4. A radiation detector, which converts radiant
energy to a usable electrical signal.
5. A signal processor and readout, which displays
the transduced signal.
 Sources of Radiation

In order to be suitable for spectroscopic studies, a

source must generate a beam of radiation with
sufficient power for easy detection and
measurement and its output power should be
stable for reasonable periods. Sources are of two
types.
1. Continuum sources
2. Line Sources
Continuum Sources:
Continuum sources emit radiation that changes in
intensity only slowly as a function of wavelength.
It is widely used in absorption and fluorescence
spectroscopy. For the ultraviolet region, the most
common source is the deuterium lamp. High
pressure gas filled arc lamps that contain argon,
xenon, or mercury serve when a particular
intense source is required. For the visible region
of the spectrum, the tungsten filament lamp is
used universally. The common infrared sources
are inert solids heated to 1500 to 2000 K.
 Continuum source
• A source that emits radiation over a wide
range of wavelengths

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Line Sources:
Sources that emit a few discrete lines find wide
use in atomic absorption spectroscopy, atomic
and molecular fluorescence spectroscopy, and
Raman spectroscopy. Mercury and sodium vapor
lamps provide a relatively few sharp lines in the
ultraviolet and visible regions and are used in
several spectroscopic instruments. Hollow
cathode lamps and electrodeless discharge lamps
are the most important line sources for atomic
absorption and fluorescence methods.
 Line source
• A source that emits radiation at only select
wavelengths.

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 Laser Sources

The term ‘LASER’ is an acronym for Light

Amplification by Stimulated Emission of
Radiation. Laser are highly useful because
of their very high intensities, narrow
bandwidths, single wavelength, and
coherent radiation. Laser are widely used
in high-resolution spectroscopy.
Component of Lasers:
The important components of laser source
are lasing medium, pumping source, and
mirrors. The heart of the device is the lasing
medium. It may be a solid crystal such as
ruby, a semiconductor such as gallium
arsenide, a solution of an organic dye or a
gas such as argon or krypton.
Four processes in Lasing Mechanism:
1. Pumping
2. Spontaneous emission (fluorescence)
3. Stimulated emission
4. Absorption
1. Pumping
• Molecules of the active medium are
excited to higher energy levels
• Energy for excitation  electrical, light,
or chemical reaction
2. Spontaneous Emission
• A molecule in an excited state can lose excess
energy by emitting a photon (this is
fluorescence)
• E = h = hc/; E = Ey – Ex
• E (fluorescence) < E (absorption) 
 (fluorescence) >  (absorption) [fluorescent
light is at longer wavelength than excitation
light]
3. Stimulated Emission
• Must have stimulated emission to have lasing
• Excited molecules interact with photons
produced by emission
• Collision causes excited molecules to relax and
emit a photon (i. e., emission)
• Photon energy of this emission = photon energy
of collision photon  now there are 2 photons
with same energy (in same phase and same
direction)
4. Absorption
• Competes with stimulated emission
• A molecule in the ground state absorbs
photons and is promoted to the excited
state
• Same energy level as pumping, but now
the photons that were produced for lasing
are gone
Population Inversion:
• Must have population inversion to sustain
lasing.
• Population of molecules is inverted (relative to
how the population normally exists).
• Normally: there are more molecules in the
ground state than in the excited state (need >
50 %).
• Population inversion: More molecules in the
excited state than in the ground state.
Why is it important?
– More molecules in the ground state 
more molecules that can absorb photons
– Remember: absorption competes with
stimulated emission
– Light is attenuated rather than amplified
– More molecules in the excited state 
net gain in photons produced
 Plasma
• a state of matter similar to gas in which a certain
portion of the particles are ionized.
• Heating a gas may ionize its molecules or atoms
(reduce or increase the number of electrons in
them), thus turning it into a plasma, which
contains charged particles: positive ions and
negative electrons or ions.
• Ionization can be induced by other means, such
as strong electromagnetic field applied with a
laser or microwave generator, and is
accompanied by the dissociation of molecular
bonds, if present.
 Gas-discharge lamp
• Gas-discharge lamps are a family of artificial light
sources that generate light by sending an electrical
discharge through an ionized gas, i.e. a plasma.
• The character of the gas discharge critically depends
on the frequency or modulation of the current.
• Typically, such lamps use a noble gas (argon, neon,
krypton and xenon) or a mixture of these gases.
• Most lamps are filled with additional materials, like
mercury, sodium, and metal halides.
 Deuterium arc lamp
• A deuterium arc lamp (or simply deuterium
lamp) is a low-pressure gas-discharge light
source often used in spectroscopy when a
continuous spectrum in the ultraviolet region
is needed.
 Deuterium arc lamp
• A deuterium lamp uses a tungsten filament and anode
placed on opposite sides of a nickel box structure
designed to produce the best output spectrum.
• Unlike an incandescent bulb, the filament is not the
source of light in deuterium lamps.
• Instead an arc is created from the filament to the anode,
a similar process to arc lamps.
• Because the filament must be very hot before it can
operate, it is heated for approximately twenty seconds
before use.
• Because the discharge process produces its own heat, the
heater is turned down after discharge begins. Although
firing voltages are 300 to 500 volts, once the arc is created
voltages drop to around 100 to 200 volts
 Deuterium arc lamp
The arc created excites the molecular deuterium contained
within the bulb to a higher energy state. The deuterium then
emits light as it transitions back to its initial state. This
continuous cycle is the origin of the continuous ultraviolet
radiation.
 Tungsten incandescent lamp
• The incandescent lamp or incandescent light globe
produces light by heating a filament wire (usually made
of tungsten) to a high temperature until it glows.
• The hot filament is protected from oxidation in the air
with a glass enclosure that is filled with inert gas or
evacuated.
• The light bulb is supplied with electrical current by feed-
through terminals or wires embedded in the glass.
• Typical source of continuous visible light
 Halogen lamp
• A halogen lamp, also known as a tungsten halogen
lamp or (historically) Quartz iodine lamp (QI), is an
incandescent lamp with a tungsten filament
contained within an inert gas and a small amount of
a halogen such as iodine or bromine.
• The combination of the halogen gas and the tungsten
filament produces a chemical reaction known as a
halogen cycle which increases the lifetime of the
filament and prevents darkening of the bulb by re-
depositing tungsten from the inside of the bulb back
onto the filament.
 Halogen lamp
• In ordinary incandescent lamps, the tungsten is mostly
deposited on the bulb darkening it.
• At moderate temperatures the halogen reacts with the
evaporating tungsten, the halide formed being moved around in
the inert gas filling.
• At some time it will reach higher temperature regions, where it
dissociates, releasing tungsten and freeing the halogen to
repeat the process.
• In order for the reaction to operate, the overall bulb
temperature must be higher than in conventional incandescent
lamps.
• The bulb must be made of a high-melting-point glass
 Xenon arc lamp
• A xenon arc lamp is a specialized type of
gas discharge lamp, an electric light that produces
light by passing electricity through ionized xenon gas
at high pressure to produce a bright white light that
closely mimics natural sunlight.
• In order to achieve maximum efficiency, the xenon
gas inside short-arc lamps is maintained at an
extremely high pressure — up to 30 atmospheres
(440 psi / 3040 kPa) — which poses safety concerns
• xenon short-arc lamps generate substantial
ultraviolet radiation
 Hollow-cathode lamp (HCL)
• An HCL usually consists of a glass tube containing a cathode, an
anode, and a buffer gas (usually a noble gas).
• A large voltage across the anode and cathode will cause the
buffer gas to ionize, creating a plasma.
• The buffer gas ions will then be accelerated into the cathode,
sputtering off atoms from the cathode.
• Both the buffer gas and the sputtered cathode atoms will in
turn be excited by collisions with other atoms/particles in the
plasma.
• As these excited atoms decay to lower states, they will emit
photons, which can then be detected and a spectrum can be
determined.
• Source of line spectra
 Electrodeless lamp (EDL)
• An electrodeless lamp or induction light is a light source in
which the power required to generate light is transferred from
outside the lamp envelope to inside via electromagnetic fields
, in contrast with a typical electrical lamp that uses electrical
connections through the lamp envelope to transfer power.
Advantages::
• Extended lamp life, because the electrodes are usually the
limiting factor in lamp life.
• The ability to use light-generating substances of higher
efficiency that would react with metal electrodes in normal
lamps.
• Improved collection efficiency because the source can be
made very small without shortening life, a problem in
electroded lamps
 Electrodeless lamp (EDL)
• Plasma lamps are a family of light sources that
generate light by exciting a plasma inside a closed
transparent burner or bulb using radio frequency (RF)
power. Typically, such lamps use a noble gas or a
mixture of these gases and additional materials such
as metal halides.
• They produce an intense radiation and last more
than HCL
• They need a RF generator.
 Sodium-vapor lamp
• A sodium vapor lamp is a gas discharge lamp
that uses sodium in an excited state to
produce light.
 Nernst glower
• The Nernst glower is an almost obsolete device for providing
a continuous source of (near) infrared radiation for use in
spectroscopy.
• Typically it was in the form of a cylindrical rod or tube
composed of a mixture of certain oxides such as
zirconium oxide (ZrO2), yttrium oxide (Y2O3) and erbium oxide
(Er2O3) at a ratio of 90:7:3 by weight.
• They operated by being electrically heated to about 2000 °C.
• Initially they require external heating because the material is
an insulator at room temperature.
• It has been replaced by a similar device known as a Globar
made of silicon carbide (SiC) that operates at about 1100 °C.
 Globar
• A Globar is a silicon carbide rod of 5 to 10 mm width
and 20 to 50 mm length which is electrically heated up
to 1,000 to 1,650 °C (1,832 to 3,002 °F).
• When combined with a downstream variable
interference filter, it emits radiation from 4 to 15 µm
wavelength.
•Globars are used as thermal light sources for infrared
spectroscopy
• Alternative middle-infrared luminous sources are
Nernst lamps, coils of chrome-nickel alloy or high-
pressure mercury lamps.
 Nichrome
• Nichrome is a non-magnetic alloy of nickel, chromium,
and often iron, usually used as a resistance wire.
• Patented in 1905, it is the oldest documented form of
resistance heating alloy.
• A common alloy is 80% nickel and 20% chromium, by
mass, but there are many others to accommodate
various applications.
• It is silvery-grey in colour, is corrosion-resistant, and
has a high melting point of about 1400 °C (2552 °F).
• Due to its relatively high electrical resistivity and
resistance to oxidation at high temperatures, it is
widely used in electric heating elements,
 Sample Holders
• Sample containers are required for all spectroscopic studies except
emission spectroscopy.
• In common with the optical elements of monochromators, the cells or
cuvettes that hold the samples must be made of material that passes
radiation in the spectral region of interest.
• Thus, quartz or fused silica is required for work in the ultaviolet region
(below 350 nm); both of these substances are transparent in the visible
region and to about 3 µm in the infrared region as well.
• Silicate glasses can be employed in the region between 350 and 2000
nm.
• Plastic containers have also found application in the visible region.
• Crystalline sodium chloride is the most common substance employed for
cell windows in the infrared region; th
• The best cells have windows that are perfectly normal to the
direction of the beam in order to minimize reflection losses.
• The most common cell length for studies in the ultraviolet
and visible regions is I cm
• Other path lengths, from 0.1 cm (and shorter) to 10 cm, are
also available.
• Transparent spacers for shortening the path length of l-cm
cells to 0.1 cm are also available.
• Cells for infrared studies of liquids and solutions generally
have path lengths of less than Imm.
Wavelength Selection

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 Electromagnetic radiation can be
Polychromatic
• Electromagnetic radiation of more than one
wavelength.
Monochromatic
• Electromagnetic radiation of a single
Wavelength

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• Nominal wavelength: The wavelength which a
wavelength selector is set to pass.
• Effective bandwidth: The width of the band of
radiation passing through a wavelength
selector measured at half the band’s height.
• Resolution: In spectroscopy, the separation
between two spectral features, such as
absorption or emission lines.

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 Wavelength Selectors
Filter
• A wavelength selector that uses either absorption, or
constructive and destructive interference to control the range of
selected wavelengths.
• Absorption filters are restricted to the visible region of the
spectrum.
• Interference filters, on the other hand, are available for
ultraviolet, visible, and infrared radiation.
Monochromator
• A wavelength selector that uses a diffraction grating or prism, and
that allows for a continuous variation of the nominal wavelength.

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Monochromator

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Grating

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 Interferometer
• A device that allows all wavelengths of light to be measured
simultaneously, eliminating the need for a wavelength
selector.

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Advantages of using a Interferometer
• The first advantage, which is termed Jacquinot’s
advantage, results from the higher throughput of
source radiation. (Better signal to noise)
• The second advantage, which is called Fellgett’s
advantage, reflects a savings in the time needed to
obtain a spectrum (hundreds times). Since all
frequencies are monitored simultaneously, an entire
spectrum can be recorded in approximately 1 s, as
compared to 10–15 min with a scanning
monochromator.
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 Detectors
Transducer
• A device that converts a chemical or physical
property, such as pH or photon intensity, to an
easily measured electrical signal, such as a
voltage or current.
S = kP + D
Dark current (D): The background current present in a
photon detector in the absence of radiation from the
source

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 Photon Transducers

• Phototubes
• Photomultipliers
• Photodiode array: A linear array of
photodiodes providing the ability to detect
simultaneously radiation at several
wavelengths.

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• Thermal Transducers: Infrared radiation
generally does not have sufficient energy to
produce a measurable current when using a
photon transducer. A thermal transducer,
therefore, is used for infrared spectroscopy

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 Signal processor
• A device, such as a meter or computer, that
displays the signal from the transducer in a
form that is easily interpreted by the analyst

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Spectroscopy Based on Absorption

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• The first requirement is that there must be a
mechanism by which the radiation’s electric field or
magnetic field interacts with the analyte. For
ultraviolet and visible radiation, this interaction
involves the electronic energy of valence electrons. A
chemical bond’s vibrational energy is altered by the
absorbance of infrared radiation.
• The second requirement is that the energy of the
electromagnetic radiation must exactly equal the
difference in energy, ΔE, between two of the
analytes quantized energy states.

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 UV-Visible
• When white light falls upon a sample, the light may be totally reflected,
in which case the substance appears white.
• Or the light may be totally absorbed, in which case the substance will
appear black.
• If, however, only a portion of the light is absorbed and the balance is
reflected, the color of the sample is determined by the reflected light.
• Thus, if violet is absorbed, the sample appears yellow-green and if yellow
is absorbed, the sample appears blue. The colors are described as
complementary.
• However, many substances which appear colorless do have absorption
spectra. In this instance, the absorption will take place in
• the infra-red or ultraviolet and not in the visible region. The following
Table illustrates the relationship between light absorption and color.
UV-Vis
UV-Vis…
 UV-Visible Spectroscopy

• Electronic transitions
– Molecular Orbital Theory
 UV-Visible Spectroscopy

• d-d Transitions
– 3d and 4d 1st and 2nd
transitions series
• Partially occupied d
orbitals
– Transitions from lower to
higher energy levels
 UV-Visible Spectroscopy
• 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 absorption of UV or visible radiation by a metal complex can be ascribed to
one or more the following
1- Excitation of the metal ion.
2- Excitation of the ligand.
3- Charge transition.
• These absorption depend upon the oxidation state of the elements and of ligand
bonded to its ions.
 UV-Vis…
• The functional groups of organic compounds (ketones, amines, nitrogen
derivatives, etc.), responsible for absorption in UV/Vis are called chromophores
• Chromophores: are unsaturated group, absorbing groups in molecule
responsible of π→π* and n→ π* electronic transitions and imparts color to the
molecules.
• A molecule containing a chromophore is called a chromogen.

• Auxochromes: are saturated groups which possess unshared electrons; they

alter both the wavelength and the intensity of absorption maxima when
attached to the chromophore present in the molecule.
• Examples are hydroxyl groups, amino groups and halogens. These possess
unshared (n) electrons that can interact with π electrons in the chromophore (n
π conjugation).
List of common chromophores and their
transitions
 Spectral changes can be classed as follows:

1- bathochromic shift: The shift of λmax to longer wavelength; known

by red shift, due to substitution and /or solvent effect.

2- Hypsochromic shift: The shift of λmax to shorterwavelength; known

by blue shift, due to substitution and /or solvent effect.

3- Hyperchomic effect: An increase in absorption intensity

(absorptivity).

4- Hypochomic effect: An decrease in absorption intensity

(absorptivity).
Spectral nomenclature of shifts
 Infrared Spectra for Molecules and
Polyatomic Ions
• The energy of infrared radiation is sufficient to
produce a change in the vibrational energy of
a molecule or polyatomic. As shown in former
Figure, vibrational energy levels are quantized;
that is, a molecule may have only certain,
discrete vibrational energies.

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• The magnitude of the change in energy
depend on the type of bond.
• For example, a carbon–carbon single bond (C
—C) absorbs infrared radiation at a lower
energy than a carbon–carbon double bond
(C=C) because a C—C bond is weaker than a
C=C bond.

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Fourier transform infrared spectrum (FT-IR) of polyvinylchloride.

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 UV/Vis Spectra for Molecules and Ions

• When a molecule or ion absorbs ultraviolet or

visible radiation it undergoes a change in its
valence electron configuration.
• Chromophore: The specific bonds or
functional groups in a molecule responsible
for the absorption of a particular wavelength
of light.

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79
• Many transition metal ions, such
as Cu2+ and Co2+, form solutions
that are colored because the
metal ion absorbs visible light. The
transitions giving rise to this
absorption are due to valence
electrons in the metal ion’s d-
orbitals. For a free metal ion, the
five d-orbitals are of equal energy.
In the presence of a complexing
ligand or solvent molecule,
however, the d-orbitals split into
two or more groups that differ in
energy
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 Charge-Transfer absorption
• A more important source of UV/Vis absorption for
inorganic metal–ligand complexes is charge transfer,
in which absorbing a photon produces an excited
state species that can be described in terms of the
transfer of an electron from the metal,

• Charge-transfer absorption is important because it

produces very large absorbances, providing for a
much more sensitive analytical method.

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 UV/Vis spectrum for
Fe ― o-phenanthroline (Charge-transfer)

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 UV/Vis Spectra for Atoms
• The energy of ultraviolet and visible
electromagnetic radiation is sufficient to cause
a change in an atom’s valence electron
configuration. Sodium, for example, with a
valence shell electron configuration of [Ne]
3s1, has a single valence electron in its 3s
atomic orbital.

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Emission spectrum of sodium

84
 Transmittance and Absorbance
• Transmittance: The ratio of the radiant power
passing through a sample to that from the
radiation’s source (T).

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Absorbance and Concentration: Beer’s Law

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 Example
• A 5.00 x10–4 M solution of an analyte is placed in a
sample cell that has a pathlength of 1.00 cm. When
measured at a wavelength of 490 nm, the
absorbance of the solution is found to be 0.338.
What is the analyte’s molar absorptivity at this
wavelength?
SOLUTION
• Solving equation 10.5 for ε and making appropriate
substitutions gives

87
Beer’s Law and Multicomponent Samples

• Beer’s law can be extended to samples

containing several absorbing components
provided that there are no interactions
between the components. Individual
absorbances, Ai, are additive.

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Limitations to Beer’s Law

89
 Chemical Limitations to Beer’s Law
• Chemical deviations from Beer’s law can occur when the
absorbing species is involved in an equilibrium reaction.
Consider, as an example, an analysis for the weak acid, HA. To
construct a Beer’s law calibration curve, several standards
containing known total concentrations of HA, Ctot, are
prepared and the absorbance of each is measured at the
same wavelength. Since HA is a weak acid, it exists in
equilibrium with its conjugate weak base, A–

90
 Instrumental Limitations to Beer’s Law
• The first limitation is that Beer’s law is strictly valid
for purely monochromatic radiation; that is, for
radiation consisting of only one wavelength.
• Stray radiation (Any radiation reaching the detector
that does not follow the optical path from the
source to the detector) is the second contribution to
instrumental deviations from Beer’s law.

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