Experiment 6

Infrared (IR) spectroscopy

Techniques: Analyzing IR spectra

BACKGROUND: Did you ever wonder how night vision goggles work? One type depends on
the principle that warm objects emit infrared radiation, which can be detected and then displayed
as an image, called a thermogram. An example is shown below of cold butter (blue) on hot toast
(red). This technology relies on the interactions between light and matter, the study of which is
called spectroscopy.

Electromagnetic radiation (light) exhibits both wave-like properties and particle-like properties.
When viewed as a wave, electromagnetic radiation consists of perpendicular oscillating, electric
and magnetic fields.

The wavelength (λ) describes the distance between adjacent peaks, while
the frequency describes the number of wavelengths that pass a particular point in space per unit
time. Therefore, a long wavelength corresponds to a small frequency, and a short wavelength
corresponds to a large frequency. The range of all possible frequencies is known as
the electromagnetic spectrum, which is arbitrarily divided into several regions by wavelength.
Different regions of the electromagnetic spectrum are used to probe different aspects of
molecular structure.

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An important tool for the organic chemist is Infrared Spectroscopy, or "IR". IR spectra are
acquired on a special instrument, called an IR spectrometer. IR is used to gather information
about compound's structure, assess its purity, and sometimes to identify it. Infrared radiation is
the part of the electromagnetic spectrum between the visible and microwave regions. Infrared
radiation is absorbed by organic molecules and converted into energy of molecular vibration
(stretching or bending).

A typical IR spectrum is shown below. A IR spectrum is a plot of wavenumber (X-axis) vs

percent transmittance (Y-axis). The wavenumber is proportional to energy; therefore, the highest
energy vibrations are on the left. The units of wavenumber are inverse centimeters (cm−1), and
the values range from 400 to 4000 cm−1. The percent transmittance (%T) is plotted on the Y-
axis. An absorption of radiant energy is therefore represented by a “trough” in the curve: zero
transmittance corresponds to 100% absorption of light at that wavelength.

Different types of bonds, and thus different functional groups, absorb infrared radiation of
different wavelengths. IR spectra can be divided into two main regions. The diagnostic
region generally has fewer peaks and provides the clearest information. This region contains all
signals that arise from double bonds, triple bonds, and X─H bonds. The fingerprint
region contains signals resulting from the vibrational excitation of most single bonds (stretching
and bending). This region generally contains many signals and is more difficult to analyze.

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Here's the IR spectrum for ethanol (CH3CH2OH). The characteristic alcohol functional group
(O-H) is circled in blue.

TECHNIQUE:
It is not feasible to assign every band in an IR spectrum. Instead, look for characteristic bands
corresponding to particular functional groups in the diagnostic region (4000-1300 cm-1). You can
use the IR correlation chart on the last page, but we require that you memorize the distinctive
bands of the common functional bands below:

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3500-3300 cm-1 (m) N-H stretch Primary amines, RNH2, 2 bands
Secondary amines, R2NH, 1 band

3500-3200 cm-1 (s, b) O-H stretch Alcohols

3300 cm-1 (s) C-H stretch Alkynes

3100-3000 cm-1 (m) C-H stretch Alkenes

3000-2850 cm-1 (m) C-H stretch Alkanes

1850-1650 cm-1 (s) C=O stretch Ketones

Aldehydes

Esters

Carboxylic acids (also look for O-H

band)

1700-1600 cm-1 C=C stretch Alkenes

2150 cm-1 Alkynes

stretch For terminal alkynes, look for C-H
stretch at ~3300 cm-1
m=medium, s=strong, b=broad

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Analyzing IR spectra:
Begin by looking in the region from 4000-1300 cm-1. Look at the C–H stretching bands around
3000:
Indicates:
alkyl groups (present in most organic
Are any or all to the right of 3000 cm-1?
molecules)
a C=C bond or aromatic group in the
Are any or all to the left of 3000 cm-1?
molecule

Look for a carbonyl (C=O) in the region 1760-1690 cm-1. If there is such a band:
Indicates:
Is an O–H band also present? a carboxylic acid group
Is a C–O band also present? an ester
Is an aldehydic C–H band also present? an aldehyde
Is an N–H band also present? an amide
Are none of the above present? a ketone

Look for a broad O–H band in the region 3500-3200 cm-1. If there is such a band:
Indicates:
Is an O–H band present? an alcohol or phenol

Look for a single or double sharp N–H band in the region 3400-3250 cm-1. If there is such a
band:
Indicates:
Are there two bands? a primary amine
Is there only one band? a secondary amine

Other structural features to check for:

Indicates:
an ether (or an ester if there is a carbonyl
Are there C–O stretches?
band too)
Is there a C=C stretching band? an alkene
Are there aromatic stretching bands? an aromatic

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Is there a C≡C band? an alkyne
Are there -NO2 bands? a nitro compound

If there is an absence of major functional group bands in the region 4000-1300 cm-1 (other than
C–H stretches), the compound is probably a strict hydrocarbon. Also check the region from 900-
650 cm-1. Aromatics, alkyl halides, carboxylic acids, amines, and amides show moderate or
strong absorption bands (bending vibrations) in this region.

You should not try to assign or interpret every peak in the spectrum. Concentrate on learning the
major bands and recognizing their presence and absence in any given spectrum.

In the organic chem labs, you usually know what compound you started with and what
compound you are trying to make. For instance, if you are oxidizing an alcohol to a ketone, your
product should show a carbonyl band but no hydroxyl band. If no carbonyl band is present, the
experiment was not successful. If both carbonyl and hydroxyl bands are present, the product is
not pure.

PROCEDURE:
You will be provided a set of IR spectra and molecular structures. Your task is to assign each
molecule to the correct spectra.

Here’s an example analysis for an IR spectrum:

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Table of Characteristic IR Absorptions

frequency, cm–1 bond functional group

3640–3610 (s, sh) O–H stretch, free hydroxyl alcohols, phenols
3500–3200 (s,b) O–H stretch, H–bonded alcohols, phenols
3400–3250 (m) N–H stretch 1˚, 2˚ amines, amides
3300–2500 (m) O–H stretch carboxylic acids
3330–3270 (n, s) –C≡C–H: C–H stretch alkynes (terminal)
3100–3000 (s) C–H stretch aromatics
3100–3000 (m) =C–H stretch alkenes
3000–2850 (m) C–H stretch alkanes
2830–2695 (m) H–C=O: C–H stretch aldehydes
2260–2210 (v) C≡N stretch nitriles
2260–2100 (w) –C≡C– stretch alkynes
1760–1665 (s) C=O stretch carbonyls (general)
1760–1690 (s) C=O stretch carboxylic acids
1750–1735 (s) C=O stretch esters, saturated aliphatic
1740–1720 (s) C=O stretch aldehydes, saturated aliphatic
1730–1715 (s) C=O stretch α, β–unsaturated esters
1715 (s) C=O stretch ketones, saturated aliphatic
1710–1665 (s) C=O stretch α, β–unsaturated aldehydes, ketones
1680–1640 (m) –C=C– stretch alkenes
1650–1580 (m) N–H bend 1˚ amines
1600–1585 (m) C–C stretch (in–ring) aromatics
1550–1475 (s) N–O asymmetric stretch nitro compounds
1500–1400 (m) C–C stretch (in–ring) aromatics
1470–1450 (m) C–H bend alkanes
1370–1350 (m) C–H rock alkanes
1360–1290 (m) N–O symmetric stretch nitro compounds
1335–1250 (s) C–N stretch aromatic amines
1320–1000 (s) C–O stretch alcohols, carboxylic acids, esters, ethers
1300–1150 (m) C–H wag (–CH2X) alkyl halides
1250–1020 (m) C–N stretch aliphatic amines
1000–650 (s) =C–H bend alkenes
950–910 (m) O–H bend carboxylic acids
910–665 (s, b) N–H wag 1˚, 2˚ amines
900–675 (s) C–H “oop” aromatics
850–550 (m) C–Cl stretch alkyl halides
725–720 (m) C–H rock alkanes
700–610 (b, s) –C≡C–H: C–H bend alkynes
690–515 (m) C–Br stretch alkyl halides

m=medium, w=weak, s=strong, n=narrow, b=broad, sh=sharp