INFRARED

SPECTROSCOPY

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REGION PROCESS
X-ray Bond-breaking
UV/Visible Electronic
Infrared Vibrational
Microwave Rotational
Radio Frequency (nmr) Nuclear and
Electronic Spin

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Infrared Spectrometer

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 Molecular vibrations
• IR-Tutor available in CB 280 is great!
• Basically two types
stretching vibrations
bending vibrations

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 IR TUTOR
• Select Chemistry Applications icon
• Select Structure Drawing icon
• Select Spectroscopy icon
• Select IR Tutor icon

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Typical Infrared Absorption
Regions

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 C-H stretching region
• Alkanes C-H sp3 stretch < 3000 cm-1
• Alkenes C-H sp2 stretch > 3000 cm-1
• Alkynes C-H sp stretch ~ 3300 cm-1
 C-H bending region
• CH2 bending ~ 1460 cm-1
• CH3 bending (asym) appears near the
same value
• CH3 bending (sym) ~ 1380 cm-1
 Hexane

CH3 bend
CH2 bend

C-H stretch CH3 CH2 CH2 CH2 CH2 CH3

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How do you think the infrared
spectrum of polyethylene would
differ from the spectrum of
hexane?????
 1650 - 1450 cm-1
• The C=C is found at about 1650 cm-1.
Monomers would be expected to show the
C=C bond, but in polymers the double
bond will be absent, unless there is a
benzene ring.
• The double bonds in a benzene ring are
found in the range of about 1600 to 1450
cm-1

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 1-Hexene

sp2
C-H
C=C
stretch
out of plane
sp3 bendings (oops)
C-H stretch CH2 CH CH2 CH2 CH2 CH3

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 Toluene

sp2 sp3
C-H C-H CH3 aromatic
C=C

aromatic oops

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 O-H stretching region
• O-H 3300 cm-1 (alcohol). Common
polymers with O-H: cellulose and PVA
• O-H 3300 cm-1 (acid, broad and ugly).
Dicarboxylic acids are monomers. When
the carboxylic acid is polymerized with an
diol, you get an polyester.
 Cyclohexanol

OH bending
O-H
stretch C-O
stretch
sp3 C-H stretch

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 Butanoic Acid

CH3 CH2 CH2 C OH

O-H stretch C=O stretch

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 2250 cm-1
• C≡N 2250 cm-1

The only common polymers with this functional

group: polyacrylonitrile and ABS

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 Propanenitrile

CH 3 CH 2 C N
sp3 C-H C≡N

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 N-H stretching region
• 3300 - 3400 cm-1
• –NH2 Primary amines give a pair of peaks.
You don’t see primary amines in polymers.
• -NH Secondary amines give a single peak
The N-H in polyamides and polyurethanes
show a very prominent singlet peak!
 1-Butanamine

N-H
bend CH2
N-H
stretch CH3
doublet bend

sp3 C-H stretch CH3 CH2 CH2 CH2 NH2

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 3-Methylbenzenamine

sp2 & sp3

NH2
C-H
N-H
stretch Aromatic
N-H bend C=C
CH3

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 N-Ethylbenzenamine

N-H sp2 & sp3 C-H

stretch NH CH CH
2 3

Aromatic C=C

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 1770 - 1670 cm-1
• This is the carbonyl region!! All bands are
very strong!!
• The following polymers would be expected
to show prominent C=O peaks:
• Polyesters
• Acrylics
• Polyamides and polyurethanes
• Poly ether ketone (PEEK)
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C=O Stretching in monomers
and polymers
Functional Group Frequency (cm-1)

Ester 1735 to 1700

Ketone 1715 to 1680

Carboxylic acid 1710

Amide 1690

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 2-Butanone

sp3 C-H
stretch O
C=O stretch CH3 C CH2 CH3

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 4-Methyl-2-pentanone
C-H < 3000, C=O @ 1715 cm-1

CH3 O

CH3 CH CH2 C CH3

C-H stretch C=O stretch

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 Ethyl Butanoate

C-O stretch
sp3 C-H
O

C=O stretch C
CH3 CH2 CH2 O CH2 CH3

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 Butanoic Acid

CH3 CH2 CH2 C OH

O-H stretch C=O stretch

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 Propanamide

sp3 C-H

O
C=O and
C
N-H stretch CH3 CH2 NH2
N-H bend
(pair)

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 Conjugation of C=O with C=C
• Conjugation of a carbonyl with a C=C
bond shifts values to lower frequencies
• For ketones and esters, subtract about 30
cm-1 for conjugation with C=O
• Conjugated ketone = 1690 to 1680 cm-1
• Conjugated ester = 1710 to 1700 cm-1
• C=C becomes quite strong!!

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4-Methyl-3-penten-2-one

C-H stretch
O

CH3 C CH3
C C C=O C=C
CH3 H stretch stretch

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 Acetophenone

C-H stretch

C CH3 aromatic C=C

conj C=O

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 C-X stretching region
• C-Cl 785 to 540 cm-1, often hard to find
amongst the fingerprint bands!!
• C-Br and C-I appear outside the useful
range of infrared spectroscopy.
• C-F can be found easily, but aren’t that
common - exception!
polytetrafluoroethylene

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Carbon Tetrachloride

no C-H!

Cl

Cl C Cl

Cl
C-Cl stretch

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