Infrared Spectroscopy

Instrumentation……
• The usual optical materials, glass or quartz absorb strongly in the infrared region.
Thus the apparatus used in infrared spectroscopy is different from that used in
visible and ultraviolet regions. The main parts of Infrared Spectrometer are

→IRradiation sources.
→Monochromators.
→Sample cells and sampling of substances.
→Detectors.
• Infrared •
region Instrumentation
is divided into 3 basic segments
with the dividing points based on the instrumental
capabilities.
Region of Electromagnetic Spectrum
Near-Infrared Mid-Infrared Far-Infrared
Wave no. cm-1 12500-4000 4000-200 200-10
Wavelength µm 0.8 – 2.5 2.5 – 50 50 – 1000
Radiation Source Tungsten Filament Lamp Nernst Glower, Globar, or High Pressure Mercury Arc
coil of Nichrome wire, Lamp

Optical System 1 or 2 Quartz Prisms or 2-4 plane diffraction with Double beam grating
Prism-grating double either fore prism instruments for use to 700
Monochromator monochromator or infrared µm, interferometric
filters spectrometers for use to
1000 µm

Detector Lead Sulfide Thermopile, Thermistor or Golay or Pyroelectric

Photoconductive Pyroelectric
 • Radiation Sources
• In order to be suitable for spectroscopic studies a source must generate a beam of radiation
with sufficient power for ready detection and measurement. In addition, its output should be
stable. Should extend over desired wavelengths.
• Commonly used is the Tungsten filament lamp for near infrared region.
• A close wound nichrome coil can be raised to incandescence by resistive heating. A black
oxide film is coated around the coil which gives acceptable emissivity.
• Can tolerate temperature up to 11000 C. Requires no water cooling and is on low maintenance
with long service.
• RECOMMENDED WHERE RELIABILITY IS ESSENTIAL SUCH AS IN
NONDISPERSIVE PROCESS ANALYZERS OR FILTER PHOTOMETERS.
• This source is less intense than other infrared sources.
• A hotter, therefore brighter, source is the Nernst glower which has an operating temperature as high as
15000C.
• These are constructed from a fused mixture of oxides of zirconium, yttrium and thorium, molded in form of
hollow rods 1 -3 mm in diameter and 2-5 cm in length.
• The radiation energy is twice that of Nichrome and Globar sources except in the near-infrared region.
• Globar Source is a rod of silicon carbide 6-8 mm in diameter and 50 mm in length. It possesses
characteristics intermediate between heated wire coil and Nernst glower. It is self starting and has an operating
temperature of 13000C.
• In very far-infrared, beyond 50 µm (200 cm-1), black body type sources lose their effectiveness since their
radiation decreases with the fourth power of wavelength. Here, high pressure Mercury Arc, with extra
quartz jacket to reduce the thermal loss, give intense radiation in this region. Output is similar to that from
blackbody sources but additional radiation is emitted from plasma which enhances the long-wavelength output.
• Visuals

• Tungsten Filament Lamps

• Visuals

•Nernst Glower
• Visuals

•Mercury Arc Lamps

• Monochromators
• It is necessary to select a desired frequency from a radiation source and reject
radiation of other frequencies. This can be achieved by the use of monochromators
which are of TWO types
• A: - Prism Monochromator and
• B: - Grating Monochromator.
• Prism Monochromator
• Prism used as a dispersive device is constructed of various metal
halide salts which transmits Infrared.
• Because of its high dispersion in the region of 4-15 µm, a region
which is of special importance for functional group studies, sodium
chloride is probably the most common prism salt. Only we have to
consider the mechanical, thermal instability and the water solubility.
• Single-pass and Double-pass Monochromator: -

Parabolic Exit Slit

Littrow
Mirror. Source

• Sample is kept at or near the focus of the beam, just before the entrance slit to the monochromator.
• Radiation from the source after passing through the sample and entrance slit, strikes off the
Parabolic Littrow mirror which renders the radiation parallel and sends to Prism. Then it returns
back to prism second time from the Littrow and focuses into the exit slit of the monochromator,
which finally passes into the Detector.
• The double pass monochromator gives 4 passes of Radiation through prism and produces more
resolution and then it finally passes on to the detector.
• Grating Monochromator
• To achieve a higher dispersion, a prism monochromator is replaced by a grating
monochromator.
• Grating is an assembly of series of parallel straight lines cut into a plane surface.
• Dispersion by a grating follows the law of diffraction.
• The mathematical equation:
• nλ = d(Sin i ± Sin θ)
• Where
• n = order (generally a whole number)
• λ = wavelength of the radiation
• d = distance between the grooves
• i = angle of incident beam of IR radiation
• θ = angle of dispersion of light of a particular wavelength.
• For different wavelengths, the angle of dispersion is different. At a
grating, separation of light occurs because of wavelengths dispersed at
different angles.

• Grating Monochromators possesses following advantages over prism

monochromator
• 1. it can be made with materials like aluminium which are not attacked
by moisture, while metal salt prisms are subject to etching from
atmospheric moisture
• 2. it can be used over a considerable range of wavelengths.
• Visuals

θ
i