Infrared Spectroscopy

Theory and Applications

ANKIT JAIN M.TECH. INDUSTRIAL BIOTECHNOLOGY ROLL NO..11IB05F

What is Infrared?
An Electromagnetic Radiation Lies between the visible and microwave portions of the electromagnetic spectrum The Infrared region is divided into: near, mid and far-infrared. far-

IR ABSORPTIONS
Atoms within a molecule are never still. They vibrate in a variety of ways (modes). modes). Atoms may be considered as weights connected by springs. Absorption of IR radiation excitation of vibrational and rotational energy levels not sufficient energy for electronic excitation Vibrational energy states are of greatest importance for IR spectroscopy
asymmetric stretch CO2 symmetric stretch

bending

Correct wavelength of radiation Vibrational mode involves a change in dipole moment An induced dipole moment is observed in polar molecules Magnitude of dipole moment depends on overlap of electron densities in molecule Vibration results in change in internuclear distance and therefore fluctuations in magnitude of dipole Homonuclear diatomic molecules (e.g. H2, N2, O2) dont absorb IR radiation, b/c of no dynamic dipole moment no dipole no dipole symmetric stretch

asymmetric stretch
change in dipole - IR active

bending
change in dipole - IR active

CO2 IR spectra
100

Transmittance /%
0 2800

The bigger the change in dipole, dipole, the more intense the absorption

2400

2000

1600

1200

800

400

Wavenumber /cm-1

Stretching higher energy than bending The symmetric stretch is not IR active (no change in dipole)

FT Optical System Diagram

Light source

He-Ne gas laser

(ceramic) Beam splitter Movable mirror Sample chamber

Fixed mirror Interferometer

Detector

INFRA RED SPECTRUM

Four regions in the spectrum:

4000 3500 3000 2500 2000

Wavenumber / cm-1
1500 1000

O-H N-H C-H stretching

C C C O C N N O stretching N-H bending

other stretching, bending and combination bands: fingerprint region

C C C N X Y Z stretching

INFRA RED SPECTRUM

Group frequency region:
Simple stretching: 1600-3500 cm-1 1600Can be calculated from Hookes law Factor influencing:  Coupling  Electronic effects  Hydrogen bonding

Fingerprint region:
Sensitive to structure Bending vibrations: 600-1500 cm-1 600Stretching vibrations :C-C,C-O and C-N :CMolecules containing the same functional group shows different spectra in this region

Group frequecy table for organic groups

Qualitative Analysis
Step One : Identify functional groups (group frequency region) Step Two : Compare with standard spectra containing these functional groups
fingerprint region play important role

isopropyl alcohol, CH(CH3)2OH Spectrum

An Alkane IR Spectrum

An Alkene IR Spectrum

An Alkyne IR Spectrum

Chapter 12

An Amide IR Spectrum

=>

A Nitrile IR Spectrum

Quantitative Analysis
Use Beer- Lambert law Convert transmittance value to corresponding value Plot calibration graph of absorbance against concentration Multi-component sample mixture can be analyse

Strengths and Limitations

IR alone cannot determine a structure. Some signals may be ambiguous. The functional group is usually indicated. The absence of a signal is definite proof that the functional group is absent. Correspondence with a known samples IR spectrum confirms the identity of the compound.

Applications of Infrared Analysis

Identification and quantification of organic solid, liquid or gas samples. Structure Determination: probable structure can be predicted if some chemical data is available Qualitative analysis of functional groups Study of a chemical reaction Study of Keto-Enol tautomerism KetoGeometrical isomerism Detection of impurity in a compound Analysis of powders, solids, gels, emulsions, pastes, pure liquids and solutions, polymers, pure and mixed gases. Infrared used for research, methods development, quality control and quality assurance applications.

References
Koulis, Cynthia, et. al. Comparison of Transmission and Internal Reflection Infrared Spectra of Cocaine. Journal of Forensic Sciences, 2001. Skoog, Holler, and Nieman. Principles of Instrumental Analysis. 5th edition, 1998 Engel and Reid. Physical Chemistry. Pearson Education, 2006. http://wwwchem.csustan.edu/Tutorials/INFRARED.HTM http://www.micromemanalytical.com/ATR_Ken/ATR.htm

THANKS.