Infrared Spectroscopy

What is Infrared Spectroscopy?

Infrared spectroscopy (IR spectroscopy) is the spectroscopy that deals with the infrared region of the electromagnetic spectrum that is light with a longer wavelength and lower frequency than visible light. It covers a range of techniques, mostly based on absorption spectroscopy. As with all spectroscopic techniques, it can be used to identify and study chemicals. The infrared portion of the electromagnetic spectrum is usually divided into three regions; the near-, mid- and far- infrared, named for their relation to the visible spectrum. The higher-energy near-IR, approximately 140004000 cm1 (0.82.5 m wavelength) can excite overtone or harmonic vibrations. The mid-infrared, approximately 4000 400 cm1 (2.525 m) may be used to study the fundamental vibrations and associated rotational-vibrational structure. The far-infrared, approximately 40010 cm1 (25 1000 m), lying adjacent to the microwave region, has low energy and may be used for rotational spectroscopy.

What are the purpose of IR spectroscopy?

Identification of all types of organic and many types of inorganic compounds Determination of functional groups in organic materials Determination of the molecular composition of surfaces Identification of chromatographic effluents Quantitative determination of compounds in mixtures Nondestructive method Determination of molecular conformation (structural isomers) and stereochemistry (geometrical isomers) Determination of molecular orientation (polymers and solutions).

How does it work?

Infrared spectroscopy exploits the fact that molecules absorb specific frequencies that are characteristic of their structure. These absorptions are resonant frequencies, i.e. the frequency of the absorbed radiation matches the frequency of the bond or group that vibrates. The energies are determined by the shape of the molecular potential energy surfaces, the masses of the atoms, and the associated vibronic coupling.

Infrared Spectroscopy of Organic Molecules:

1. IR region is lower in photon energy than visible light (below red produces heating as with a heat lamp) 2. 2.5 106 m to 2.5 105 m region used by organic chemists for structural analysis 3. IR energy in a spectrum is usually measured as wave number (cm-1), the inverse of wavelength and proportional to frequency: 4. Wave number (cm-1) = 1/l(cm) 5. Specific IR absorbed by organic molecule is related to its structure

Infrared Energy Modes:

1. IR energy absorption corresponds to specific modes, corresponding to combinations of atomic movements, such as bending and stretching of bonds between groups of atoms called normal modes 2. Energy is characteristic of the atoms in the group and their bonding 3. Corresponds to molecular vibrations

Characteristic IR absorptions of some functional groups: Single Bonds to Hydrogen:

Bond C-H =C-H C-H O=C-H O-H O-H (free) N-H Wavenumber (cm-1) Notes 3000-2850 3100 - 3000 3300 2800 and 2700 3400 - 3000 ~3600 3450 - 3100 Saturated alkanes, limited value as most organic compounds contain C-H Unsaturated alkene or aromatic Terminal Alkyne Aldehyde, two weak peaks Alcohols and Phenols. If hydrogen bonding present peak will be broad 3000-2500 (e.g. carboxylic acids) Amines: Primary - several peaks, Secondary one peak, tertiary - no peaks

Double Bonds:
Bond C=O C=O C=O C=O C=O C=O Wavenumber (cm-1) Notes 1840 - 1800 & 1780 - 1740 1815 1760 1750 1715 1740 1680 1725 1665 1720 1670 Anhydrides Acyl halides Esters Aldehydes Ketones Carboxylic acids

C=O C=C C=N N=O

1690 1630 1675 1600 1690 - 1630 1560 - 1510 & 1370 - 1330

Amides Often weak Often difficult to assign Nitro compounds

Triple Bonds:
Bond CC CN Wavenumber (cm-1) Notes 2260 2120 2260 - 2220 Alkynes, bands are weak Nitriles

Single Bonds (not to Hydrogen):

Bond C-C C-O, C-N C-Cl C-Br, C-I Wavenumber (cm-1) Notes Variable 1400 1000 800-700 Below 650 No diagnostic value Difficult to assign Difficult to interpret Often out of range of instrumentation

Bending Vibrations:
Bond R-N-H R-C-H Wavenumber (cm-1) Notes 1650 1500 1480 1350 Take care not to confuse N-H bend with the C=O stretch in amides Saturated alkanes and alkyl groups

R-C-H

1000 - 680

Unsaturated alkenes and aromatics

Regions of the Infrared Spectrum:

1. 4000-2500 cm-1 N-H, C-H, O-H (stretching) a) b) 3300-3600 N-H, O-H 3000 C-H

2. 2500-2000 cm-1 CC and C N (stretching) 1. 2000-1500 cm-1 double bonds (stretching) a) b) C=O 1680-1750 C=C 1640-1680 cm-1

2. Below 1500 cm-1 fingerprint region

Differences in Infrared Absorptions:

1. Light objects connected to heavy objects vibrate fastest (at higher frequencies): C-H, N-H, O-H 2. For two heavy atoms, stronger bond requires more energy (higher frequency): C C, C N > C=C, C=O, C=N > C-C, C-O, C-N, C-halogen 3. Molecules vibrate and rotate in normal modes, which are combinations of motions (relates to force constants) 4. Bond stretching dominates higher energy (frequency) modes

Infrared Spectra of Hydrocarbons:

C-H, C-C, C=C, C C have characteristic peaks:

 Hexane:

Infrared Spectra of Some Common Functional Groups:

Alcohols:

Amines:

Carbonyl Compounds:
1. Strong, sharp C=O peak 1670 to 1780 cm1 2. Exact absorption characteristic of type of carbonyl compound a) 1730 cm1 in saturated aldehydes b) 1705 cm1 in aldehydes next to double bond or aromatic ring

 C=O in Ketones:
1. 1715 cm1 in six-membered ring and acyclic ketones 2. 1750 cm1 in 5-membered ring ketones 3. 1690 cm1 in ketones next to a double bond or an aromatic ring

C=O in Esters:
1. 1735 cm1 in saturated esters 2. 1715 cm1 in esters next to aromatic ring or a double bond

Aromatic Compounds:
1. Weak CH stretch at 3030 cm1 2. Weak absorptions 1660 - 2000 cm1 range 3. Medium-intensity absorptions 1450 to 1600 cm1

 Phenylacetylene:

Uses and applications:

Infrared spectroscopy is a simple and reliable technique widely used in both organic and inorganic chemistry, in research and industry. It is used in,

Quality control Dynamic measurement Monitoring applications Forensic analysis in both criminal and civil cases Measuring the degree of polymerization in polymer manufacture.