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E10 INFRARED & RAMAN SPECTROMETRY : Principles & INSTRUMENTATION KEY NOTES Principal:-Vibrational Transition In Molecules Cause Absorption

In The Infrared
Region Of The Electromagnetic Spectrum. They may also be studied using the technique of raman spectrometry, where they scatter exciting radiation with an accompanying shift in its wavelength.

Group Frequencies:- Vibrational Spectra Give Information About The


Functional Groups In Molecules, And The Observed Group Frequencies Are Affected By Molecular Interactions Such As Hydrogen Bonding.

Instrumentation:- Infrared And Raman Instruments Include A Radiation Source, A Means Of Analyzing The Radiation And Detection And Data Processing System. Additionally, sampling methods to deal with gases, liquids, solids, micro samples and mixtures are available.

Related topics :-Infrared And Raman Spectrometry


Applications (E 11) Gas chromatography infrared Spectrometry (F4)

Principles:- The vibrational levels of molecules are separated by energies in the


infrared (1R) region of the electromagnetic spectrum. That is, in the wavenumber range from 13000 to 10 cm, or between0.8 and 1000 um on the wavelength scale .For convenience, this large region is divided into near IR, or NIR (13000-4000cm1), mid IR(4000-400cm-1) and far IR (400-10cm-1).

Molecules contain bonds of specific spatial orientation and energy. These bonds are seldom completely rigid, and when energy is supplied, they may bend, distort or stretch. A very approximate model compares the vibration to that of a harmonic oscillator, such as an ideal spring. If the spring has a force constant, k, and masses m at the ends, then the theoretical vibration frequency v is given by: V=(1/2n) (k/) Where =m m /(m + m ) is called the reduced mass. Each type of molecular vibration is characterized by a vibrational quantum number, v. For a simple stretching vibration, there is a series of levels whose energy is given approximately by E=hv ,(v+1/2) This means there is a set of levels spaced in energy by hv or in wavenumber by v . The selection rule for an ideal harmonic oscillator allows transitions where Av =+_1, giving a single, fundamental vibrational absorption peak. However, when bonds are stretched they weaken, so a better model takes this into account, and the molecules are treated as anharmonic oscillators. This where high energies are involved, large energy transition may occur, where v = +2, +3, etc, giving the first overtone at a wavenumber approximately double that of the fundamental, & so on. The electrical field associated with the electromagnetic radiation will interact with the molecules to change its electrical properties. Some molecules (for example, HCI) have a dipole moment due to change separation & will interact with the field others may acquire a dipole when they vibrate, for example, molecules, CH4 HAS No Dipole, But When One Of The Ch Bonds Stretched, The molecules will develop a temporary dipole. even if the molecules does not have a dipole, the electric fields ,E, may distort the electron distribution and polarize the molecules =a E

where is the dipole induced by fields ,E and a is the polarizability of the molecules The rules governing transitions in the infrared region of the spectrum require that ,in order to absorb, the dipole of molecule must change during the vibration. Such vibrations said to be IR active. For transitions to be active in the Raman region, it is required that the polarizability must change using the vibration. The transitions are then Raman active, or R active (fig. 1). Consider two simple diatomic molecules, nitrogen and carbon monoxide. These molecules have only one fundamental vibration frequency, vo. For nitrogen it is 2360 cm-1, and for carbon monoxide 2168 cm-1. Since carbon monoxide has a permanent dipole, which will increase and decrease as he molecule stretches and compresses, the vibration will interact with IR radiation, and an absorption peak will be observed close to 2168 cm-1. Nitrogen has no dipole, and vibration does not produce one. Therefore, it will not absorb IR radiation. This is of great importance, since IR spectra may be recorded in air without interference. However, when the nitrogen molecule vibrates, he bonding electrons are distorted and the polarizability is changed. Therefore, it will give a spectrum using the Raman technique. In order to excite Raman transitions, energy comparable to the difference between electronic energy levels must be supplied. This may be visible laser light

or NIR radiation. If the exciting wavelength matches the energy difference between the electronic levels of the sample, the Raman signal is greatly enhanced by the resonance Raman effect. Rayleigh scattering re-emits the exciting line. There ore intense emission due to fluorescence effects may mask the weak Raman signal, but with NIR radiation fluorescent interference is much less. As molecules become more complex. The number of possible vibrations increases. For example, carbon monoxide, co2 , has three atoms arranged in a line: O=C=O. this molecule does not have a dipole and may vibrate in three ways. I. The symmetric stretch, denoted by v is where both oxygen are equidistant from the central carbon, but the C-O bonds lengthen and contact together. The dipole does not change, but the polarizability does . so this vibration is IR inactive, but R active. The antisymmetric stretch, v has one C-O bond stretching, while the other contact. The carbon atom moves as well so that the centre of mass of the molecules remains stationary. The dipole changes but the polarizability does not so this is IR active but R active The bending vibrations may be resolved into two identical and mutually perpendicular components corresponding to two transitions of the same energy ( degenerate ). It is necessary to think in three dimension: considering the page as plane, then if the two oxygen go equally down the page while the carbon goes up the page to balance this is in plane bending .if the oxygen go into the page the carbon out of the page this is out of plane bending. These changes will be reversed as the vibration progresses . This vibration is IR active R inactive

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III.

The triangular molecule of water HO also has three different vibration corresponding to the same vibrational types. However each involved change in dipole so all three are IR active. The Raman spectrum shows only one line due to the symmetric stretch. These vibrations are shown schematically in figure 2. It is possible to extend these arguments to more complex molecules, but this is

only of value for student of structural parameters such as the length and