Instrumental Analysis II (Chem3052)
Chapter 3
3. Instrumentation for Optical Spectroscopy
3.1 Components of optical instruments
3.1.1 Source of Radiation
3.1.2 Wavelength selectors
3.1.3 Sample containers
3.1.4 Radiation detectors
3.1.5 Readout detectors and signal amplification systems
3.2 Optical systems used in spectroscopy: single beam versus double
beam instruments
1
3.1 Components of optical instruments
Optical Instruments has the following
basic components
•Light source
•Wavelength selector
•Sample holder
•Light detector (Transducer)
•Signal Amplifiers
•Recording and display unit
2
3.1 Components of optical instruments
a) Components of Atomic Absorption Spectroscopy
Light source
3
3.1 Components of optical instruments
b) Components of Molecular absorption spectroscopy: UV-VIS & IR
S
l
i
t
Basic instrumentation for both UV and IR spectroscopy
consists of an energy source, wavelength selector, a
sample cell, a dispersing device (prism or grating) and
a detector, arranged as schematically shown in Figure
above.
4
3.1.1 Source of Radiation
a) Source of Radiation for Atomic Absorption Spectroscopy
„The atomic absorption lines are very narrow. „„For Beer’s law to be valid,
the bandwidth of the source must be narrow relative to the width of an
absorption peak. We can’t approach this narrow line width even with a
good monochromator. „
„Therefore we use a radiation source that emits the same line spectra of
the element which we are trying to detect.
This source is called Hollow Cathode Lamp (HCL). The HCL provides the
spectral line for the element of interest.
Want to look for lead? Then use a lead lamp.
„Want to look for copper? Then use a copper lamp.
5
THE HOLLOW CATHODE LAMP: Construction and mecahnism of light
generation
The hollow cathode lamp consists of an anode and a cylindrical cathode sealed in a
glass tube that is filled with an n inert gas ( inert gas (Ne or or Ar ) at a pressure of 1-5
torr. „
„The cathode is constructed of the element that is to be analyzed (Na, Ca, K, Fe...). „
Reaction in the HCL
Step 1. Potential applied by means of the electrodes to generate beam of energetic electrons
Step 2. Ionization of filler gas by the energetic electrons: Ar + e- Ar+ + 2e-
Step 3: Sputtering of cathode atoms (atoms of the element under investigation):
M(s) + Ar+ M(g) + Ar+
Step 4: Excitation of metal atoms: M(g) + Ar+ M* (g) + Ar
Step 5: Light Emission: M*(g) M(g) + hv ………. Then M(g) in flame + hv M(g)*
6
3.1.1 Source of Radiation
b) Light Source for Molecular absorption spectroscopy: UV-VIS
7
3.1.1 Source of Radiation
b) Light Source for Molecular absorption spectroscopy: UV-VIS
8
3.1.2. Wavelength Selection: Monochromator
• Used as a filter: the
monochromator will select a
narrow portion of the
spectrum (the bandpass) of a
given source
• Used in analysis: the
monochromator will
sequentially select for the
detector to record the
different components
(spectrum) of any source or
sample emitting light.
9
3.1.3 Sample containers
a) Sample containers for AA are beakers or small vials connected to
a nebulization capillary tube.
b) Unlike AAS, UV-Vis requires a specialized sample containers
Known as cuvettes (should be transparent for the light used for analysis).
Cuvettes-Sample Containers for UV-Vis Analysis
10
11
12
13
3.1.4 Radiation detectors
Detectors are transducers that transform the analog output of the spectrometer into an
electrical signal that can be viewed and analyzed using a computer. There are two
types: photon detectors and thermal detectors.
Photon detectors work generally by either causing electrons to be emitted or
development of current when photons strike the detector surface. Examples include
photovoltaic cells, phototubes, and charge-transfer transducers.
Photovoltaic cells generate electrical current on a semiconductor material when
photons in the visible region are absorbed.
Phototubes emit electrons from a photon-sensitive material.
Charge-transfer transducers (such as photodiodes) develop a charge from visible
region photon-induced electron transfer reactions within a silicon material.
In each case, it is the current, the number of electrons, or the charge that is actually
detected (not the photons themselves) and is then related to the energy/quantity of
photons that caused the change in the material.
Thermal detectors detect a temperature change in a material due to photon
absorption. Thermocouples work by measuring the difference in temperature between a
pair of junctions (usually the reference against the sample) and are generally used for
the infrared wavelengths. The temperature difference is related to a potential difference,
which is the output signal.
Pyroelectric transducers are used in infrared region and utilize a dielectric material
that produces a current when its temperature is changed by radiation absorption. 14
3.1.4 Radiation detectors Detector
Photomultiplier
The type is commonly used.
The detector consists of a
photoemissive cathode
coupled with a series of
electron-multiplying
dynode stages, and usually
called a photomultiplier.
The primary electrons ejected from the photo-cathode are
accelerated by an electric field so as to strike a small area on
the first dynode. 15
3.1.4 Radiation detectors
Principle of Photomultiplier Detector
•The impinging electrons strike with enough
energy to eject two to five secondary
electrons, which are accelerated to the second
dynode to eject still more electrons.
•A photomultiplier may have 9 to 16 stages,
and overall gain of 106~109 electrons per
incident photon.
16
3.2 Optical systems used in spectroscopy: single beam
versus double beam instruments
Single and Double Beam Spectrometer
•Single-Beam: There is only one light beam or
optical path from the source through to the
detector.
•Double-Beam: The light from the source,
after passing through the monochromator, is
split into two separate beams-one for the
sample and the other for the reference.
Reading Assignment:
a) Readout detectors and signal amplification systems
b) Display Units (Oscilloscope, LCD)
17
End of Chapter 3