Filters

Interference filters Absorption filters

Use constructive and destructive Selectively absorbing radiation from
interference to isolate a narrow a narrow region of the
range of wavelengths electromagnetic spectrum

Limitation: has a fixed nominal wavelength, then need two different

filters for measuring at two different wavelengths.
 Monochromators
Monochromator is an alternative method for selecting a narrow band of
radiation that also allows to continuously adjust the band’s nominal
wavelength.

Using prism
using diffraction grating

 Monochromator converts a polychromatic source of radiation to a

monochromatic source
 By rotating the diffraction grating, which wavelength exits the monochromator
is determined.
 Monochromator converts a polychromatic source of radiation
to a monochromatic source of finite effective bandwidth.
 A narrower exit slit provides a smaller effective bandwidth
and better resolution, but allows a smaller throughput of
radiation.
 Monochromators are classified as either fixed-wavelength or
scanning.
 In a fixed-wavelength monochromator: we select the
wavelength by manually rotating the grating. A fixed-
wavelength monochromator is used for a quantitative
analysis.
 A scanning monochromator includes a drive mechanism that
continuously rotates the grating, allowing successive
wavelengths to exit from the monochromator. Scanning
monochromators are used to acquire spectra, and, when
operated in a fixed-wavelength mode, for a quantitative
analysis.
Video of wavelength selection
Interferometers
- As the moving mirror changes
position, the wavelengths of
light experiencing maximum
constructive interference and
maximum destructive
interference also changes.
- The signal at the detector
shows intensity as a function of
the moving mirror’s position,
expressed in units of distance
or time. The result is called an
interferogram, or a time domain
spectrum

The time domain spectrum is

converted mathematically, by a
process called a Fourier
transform, to a spectrum,
showing intensity as a function
of the radiation’s energy
An interferometer allows source radiation of all wavelengths to
reach the detector simultaneously
In comparison to a monochromator, an interferometer has two
significant advantages:
 higher throughput of source radiation, and less noise.
 savings in the time needed to obtain a spectrum.
Detector
S, is a linear function of the electromagnetic radiation’s power, P,
S = kPD
k is the detector’s sensitivity, and D is the detector’s background current when
we prevent the source’s radiation from reaching the detector
There are two broad classes of spectroscopic transducers:
• Thermal transducers
• Photon transducers
Photon Transducers
Phototubes and photomultipliers: contain a photosensitive surface that absorbs
radiation in the ultraviolet, visible, or near IR, producing an electrical current
proportional to the number of photons reaching the transducer.
Semiconductor: When the semiconductor absorbs photons, valence electrons move
to the semiconductor’s conduction band, producing a measurable current.

Thermal Transducers (used for infrared spectroscopy).

A pneumatic transducer, for example, is a small tube of xenon gas with an IR
transparent window at one end and a flexible membrane at the other end. Photons
enter the tube and are absorbed by a blackened surface, increasing the temperature
of the gas. As the temperature inside the tube fluctuates, the gas expands and
contracts and the flexible membrane moves in and out. Monitoring the membrane’s
displacement produces an electrical signal.
Signal Processors
A transducer’s electrical signal is sent to a signal processor where it is displayed in a
form that is more convenient for the analyst

A signal processor also is used to calibrate the detector’s response, to amplify the
transducer’s signal, to remove noise by filtering, or to mathematically transform the
signal.
Spectroscopy Based on Absorption

In absorption spectroscopy, a beam of electromagnetic radiation passes

through a sample. Much of the radiation passes through the sample without
a loss in intensity. At selected wavelengths, however, the radiation’s
intensity is attenuated. This process of attenuation is called absorption
Absorbance Spectra
Two requirements for an analyte’s
absorption of electromagnetic
radiation:
 The 1st: there must be a
mechanism by which the
radiation’s electric field or
magnetic field interacts with the
analyte.
UV-Vis radiation: absorption of a
photon changes the energy of
the analyte’s valence electrons
IR radiation: bond’s vibrational
energy is altered by the absorption of
photon.
 The The 2nd: that the photon’s E0 : the analyte’s ground electronic state
energy, h, must exactly equal the E1: the analyte’s first electronic excited state
difference in energy, E, between 0–4 : five vibrational energy levels
two of the analyte’s quantized
energy states.
 Interaction of EMR with matter

1. Electronic Energy Levels:

• At room temperature the molecules are in the lowest energy levels
E0.
• When the molecules absorb UV-visible light from EMR, one of the
outermost bond / lone pair electron is promoted to higher energy
state such as E1, E2, …En, etc is called as electronic transition and
the difference is as:
∆E = h ν = En - E0 , where (n = 1, 2, 3, … etc)
∆E = 35 to 71 kcal/mole
2. Vibrational Energy Levels:
• These are less energy level than electronic energy levels.
• The spacing between energy levels are relatively small i.e. 0.01 to 10
kcal/mole.
• e.g. when IR radiation is absorbed, molecules are excited from one
vibrational level to another or it vibrates with higher amplitude.
3. Rotational Energy Levels:
• These energy levels are quantized & discrete.
• The spacing between energy levels are even smaller than
vibrational energy levels.

∆Erotational < ∆Evibrational <∆Eelectronic

Electronic Transitions
Organic materials

The bonds and functional groups that give rise to the absorption of
ultraviolet and visible radiation are called CHROMOPHORES.
The possible electronic transitions are

1 • σ → σ* transition
2 • π → π* transition

3 • n → σ* transition
4 • n → π* transition
5 • σ → π* transition
6 • π → σ* transition
Inorganic metal-ligand complexes
 Inorganic metal–ligand complexes is charge transfer, in which absorption
of a photon produces an excited state in which there is transfer of an
electron from the metal, M, to the ligand, L.

 Charge-transfer absorption in
which an electron moves
from the ligand to the metal
also is possible

UV/Vis spectrum for the metal–ligand

complex Fe(phen)3 2+, where phen is
the ligand o-phenanthroline.
Transition metal ions
The transitions giving rise to this
absorption are 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.
For example, in an octahedral complex of
Cu(H2O)62+. The six water molecules
perturb the d-orbitals into two groups.
The resulting d–d transitions for transition Splitting of the d-orbitals in an
octahedral field.
metal ions are relatively weak.
UV-Vis spectra for atoms
Absorption of a photon cause a change in an atom’s valence electron
configuration.
Photon absorption causes Excitation of an electron from a lower-energy
atomic orbital to an orbital of higher energy.

Valence shell energy level Atomic absorption spectrum for sodium

diagram for sodium
Transmittance and Absorbance
As light passes through a sample, its power decreases as some of it is ab-
sorbed. This attenuation of radiation is described quantitatively by two
separate, but related terms: transmittance and absorbance.

= hay % = .100

A = - log T= −
( 0  A  2)
Absorbance and Concentration:
Beer’s Law
 

A = . C. L

: molar absorptivity, which has units of cm–1 M–1

A = . C. L