Infrared (IR) Spectroscopy

Definition :
• Energy absorption by molecule in infrared region

• Transition between two vibrational levels

• Extract molecular structural information by measuring molecular vibrations spectra

• Molecular fingerprints, characterize and identify the molecule

• Used in conjunction with Raman Spectroscopy

IR Spectrometer Instrumentation :
• Dispersive prism or grating

• Non-dispersive interference filters, tunable lasers sources, an interferometer (Fourier Trans-

form Infrared Spectrometer

• For IR region, front faced mirrors

• Glass and quartz absorb opaque to IR

Parts of IR spectrometer:
1. Source of Infrared radiation

• IR, heat radiation

• Heat transfer direct, do not require a direct physical medium
• Converted to heat, only on absorption by object
• Source, an incandescent solid material which has a radiant energy distribution
• Similar to theoretical black body
• Tungsten filament lamp, Glober, Nernst Glower, Nichrome heater

2. Infrared monochromator

• Means of separating source radiation wavelengths

• Prisms and gratings
• Prisms of alkali halides
• Large crystals, Prisms, windows and cells are cut from them
• N aCl 4000 − 650 cm−1
• Potassium bromide 1000 − 400 cm−1
• Cesium iodide 1000 − 260 cm−1
• Below 250 cm−1 , gratings are used, disperse the energy

3. Infrared Detector

• Thermal radiant energy into electrical energy

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 • Selective response dependent on wavelength incident radiation
• Photographic plates, photocells, photoconductive cells, infrared phosphors
• Photoconductive important, rapid response and high sensitivity
• PbS, PbSe, Lead telluride, selenium
• Increase in conductivity, with increase in IR illumination
• 0.5 3.5 microns
• Non-selective response independent of wavelength of incident radiation
• Directly proportional to incident energy
• Thermocouples, bolometers, pneumatic cell

Thermocouple

• Thermocouples: evaporating bismuth antimony, semiconductor alloys, on thin film

cellulose nitrate, in evacuated chamber with KBr window

Bolometers

• Electrical signal, change in resistance of a metallic conductor with temperature

• Faster response time due to small thermal capacity
• Thermistor bolometer, increased sensitivity
• Fused mixture of metal oxides : Ni, Co, Mn, exponential decrease in resistance with
temperature

Pneumatic detector cell

• Two cells, first 3 mm filled with a gas (Xe), connected to second cell through a tube
• One end closed with a curved diaphragm, acting as mirror
• Heat on gas changes the volume, expansion due to IR absorption
• Thereby moving mirror in other cell proportionally

Preparation of samples :

1. Gaseous samples

• No special preparation
• 10 cm long cell for gaseous samples
• Vacuum tight cells
• Connection problems
• Proper operation, due to heating and cooling cycles

2. Liquid or solution samples

• Pure liquid samples

• No solvents, as they have their own absorption spectra

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 • Liquid and solution, same type of cell
• Non-corrosive and not too viscous liquids, normally in sealed cells
• Highly viscous liquids, sandwiched as a layer between two salt plates
• Cavity cells

3. Solids

• Solid Films: solid samples into thin films, on IR transmitting window, or solid melted
and cooled into thin film, not recommended for crystalline substances
• Mull-Technique: Powdered sample mixed with a little heavy paraffin oil, nujol, mulled
into paste, transferred to rock salt plate
• Pressed Pellet Technique: Weighed solid material thoroughly mixed with KBr, pressed
into pellet under high pressure in evacuated die, resulting in transparent discs

Applications of IR Methods :

• GC-IR

• TG-IR

• Tiny samples

• Study of light emitted by sample

• Photocurrent sepctra