CHE 231 AN INTRODUCTION TO LABORATORY

PRACTICES IN ORGANIC CHEMISTRY

Department of Chemistry, Illinois State University, Normal, IL 61790-4160, USA

Infrared Spectroscopy

Table of Contents
Alkanes 2
Alkenes 4
Alkynes 6
Aromatic systems 9
Alcohols 12
Ethers 13
Phenols 14
Amines 15
Aromatic amines (anilines) 18
Ketones 19
Aromatic ketones 20
Aldehydes 21
Aromatic aldehydes 22
Carboxylic acids 24
Esters 25
Amides 26
Nitriles 27
Nitro compounds 28

2015 Department of Chemistry, Illinois State University, Normal, IL 61790-4160 Page 1

The Infrared Spectra of Alkanes
C(sp3)-H stretching 2800 to 2960 cm-1
CH2 bending 1440 to 1500 cm-1

Infrared spectrum of n-heptane: 2961, 2926, 1468, 1379 cm-1.

SDBSWeb: http://sdbs.db.aist.go.jp (National Institute of Advanced Industrial Science and Technology, January 8, 2015)

Infrared spectrum of nujol (paraffin wax, long chain hydrocarbon, CnH2n+2):

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2015 Department of Chemistry, Illinois State University, Normal, IL 61790-4160 Page 2

The Infrared Spectra of Alkanes
Different structural arrangements of methyl groups can be tentatively identified by inspection
of the fingerprint region. These peaks should not be used as final diagnostics as there are
other signals that may appear in this region.

The umbrella deformation of the methyl group.

Infrared spectrum of 2,4-dimethylpentane: 2968, 2935, 1466, 1368, 1361 cm-1.

C-H stretching vibration

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2015 Department of Chemistry, Illinois State University, Normal, IL 61790-4160 Page 3

The Infrared Spectra of Alkenes
Dominant Observable Vibrations
Stretching vibrations
C (sp2)-H stretching ~3000 to 3100 cm-1
C=C double bond stretch ~1600 to 1675 cm-1

Out of plane C-H bending vibrations

monosubstituted alkenes 910 and 990 cm-1

dibsubstituted terminal alkene 890 cm-1

trans-alkene bending vibration 960-980 cm-1
cis-alkene bending vibration 675-730 cm-1

trisubstituted alkenes 800-840 cm-1

tetrasubstituted alkenes no C-H bending vibrational signal

An infrared spectrum of 1-octene: 3079, 2998, 1823, 1642, 994, 910 cm-1.

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2015 Department of Chemistry, Illinois State University, Normal, IL 61790-4160 Page 4

The Infrared Spectra of Alkenes
cis and trans-Alkenes may be distinguished based on two key features, the carbon-carbon
double bond vibration and the out of plane bending of the vinylic protons.

An infrared spectrum for cis-2-octene

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An infrared spectrum for trans-2-octene

out of plane bending

964 cm-1

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2015 Department of Chemistry, Illinois State University, Normal, IL 61790-4160 Page 5

The Infrared Spectra of Alkynes
Dominant Observable Vibrations
Stretching vibrations
C(sp)-H stretching vibration ~3250-3350 cm-1
C≡C stretching vibration ~2100-2200 cm-1

Out of plane C-H bending vibrations

C(sp)-H bending vibration ~610-700 cm-1

Infrared spectrum of 1-octyne (a terminal alkyne): 3323, 3024, 2926, 1636, 1466, 630 cm-1

C C stretching

out of plane bending

630 cm-1

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2015 Department of Chemistry, Illinois State University, Normal, IL 61790-4160 Page 6

The Infrared Spectra of Alkynes
The infrared spectrum of 5-methyl-1-hexyne is illustrated below. The expected peaks are
present. Notice the presence of the isopropyl group “doublet” at 1368 and 1388 cm-1.

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Infrared spectrum of 2-octyne (an internal alkyne): the alkyne C≡C stretching vibration is very weak and not
observable due to symmetry and lack of changing dipole moment.

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 A review of the aliphatic hydrocarbons
Infrared spectrum of 1-octane: A saturated hydrocarbon

Infrared spectrum of 1-octene: An unsaturated hydrocarbon

Infrared spectrum of 1-octyne: An unsaturated hydrocarbon

2015 Department of Chemistry, Illinois State University, Normal, IL 61790-4160 Page 8

The Infrared Spectra of Aromatic Rings
Dominant Observable Vibrations
Stretching vibrations
C(sp2)-H stretching vibration ~3000-3100 cm-1

C=C stretching vibration ~1500-1600 cm-1

Out of plane C-H bending vibrations

The substitution of aromatic rings can be tentatively assigned based on the observed aromatic
out of plane CH bending overtones.

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2015 Department of Chemistry, Illinois State University, Normal, IL 61790-4160 Page 9

The Infrared Spectra of Aromatic Rings
Cumene (isopropylbenzene): There are a number of peaks that appear for aromatic systems. These peaks
include aromatic C-H stretching, C=C from the aromatic ring, and out of plane bending. There are also out
of plane CH bending overtones that appear between 2000 and 1667 cm-1. The intensity and shape of these
peaks varies with the substitution of the aromatic ring.

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Disubstituted aromatic rings
Infrared spectrum of ortho-bromotoluene: 3061, 3016, 2924, 1470, 1031, 745 cm-1

Infrared spectrum of meta-bromotoluene: 3061, 3017, 2932, 1564, 834, 770, 681 cm-1

Infrared spectrum of para-bromotoluene: 3081, 3026, 2923, 1487, 1013, 801 cm-1

2015 Department of Chemistry, Illinois State University, Normal, IL 61790-4160 Page 11

The Infrared Spectra of The Alcohols (ROH)
Dominant Observable Vibrations:
O-H stretching ~3200-3600 cm-1
C-O stretching ~1000-1200 cm-1
Infrared spectrum of 1-octanol

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Hydrogen bonding is an important phenomenon in the infrared spectra of alcohols. The frequency and shape of the
peak is directly proportional to the level of hydrogen bonding.

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2015 Department of Chemistry, Illinois State University, Normal, IL 61790-4160 Page 12

The Infrared Spectra of The Ethers
Dominant Observable Vibrations
Stretching vibrations

strong band due to asymmetrical stretching, 1150-1085 cm–1 (usually 1125 cm–1)

weak band due to symmetrical stretching, 820-890 cm–1

Infrared spectrum of di-n-propyl ether (CH3CH2CH2-O-CH2CH2CH3)

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The Infrared Spectra of The Phenols
Dominant Observable Vibrations
Phenols will have an appearance that is very similar to that of alcohols. There is a broad absorption that
appears in the region of 3600 to 3100 cm-1. The following infrared spectrum is that of 2-bromo-4-
methylphenol.

Spectrum obtained from SDBSWeb: http://sdbs.db.aist.go.jp (National Institute of Advanced Industrial Science and Technology, December 16, 2014).

2015 Department of Chemistry, Illinois State University, Normal, IL 61790-4160 Page 14

The Infrared Spectra of The Amines
Dominant Observable Vibrations:
N-H stretching ~3200-3500 cm-1
N-H bend ~1550-1650 cm-1

Comments:

Shows the –N-H stretch for NH2 as two signals between 3200-3500 cm-1 (s-m); symmetric
and anti-symmetric modes NH2 group shows a deformation band from 1590-1650 cm-1.
Additionally there is a “wag” band at 780-820 cm-1 that is not diagnostic

The N-H stretching vibration varies in intensity.

Primary amines have two N-H signals in the region between 3200 and 3500 cm-1.

Secondary amines have only one N-H signal in this region.

Tertiary amines do not have an N-H signal.

Sometimes, amines are mistaken for alkenes because of the N-H bending vibration that
appears near 1600 cm-1.

2015 Department of Chemistry, Illinois State University, Normal, IL 61790-4160 Page 15

The Infrared Spectra of Amines
The infrared spectra of amines have only a few peaks that can be considered to be of
diagnostic value. The symmetric and asymmetric N-H stretch is of greatest value. The NH2
scissoring peak will vary in intensity and may be obscured by other peaks.

Primary amine: n-hexylamine

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 The Infrared Spectra of the Amines (primary, secondary, tertiary)

Primary amine: Infrared spectrum of n-pentyl amine

Secondary amine: Infrared spectrum of di-n-butyl amine

Tertiary amine: Infrared spectrum of tri-n-butyl amine

2015 Department of Chemistry, Illinois State University, Normal, IL 61790-4160 Page 17

The Infrared Spectra of Aromatic Amines (Anilines)
The following example represents an aromatic primary amine. Notice that the NH2 symmetric and anti-
symmetric stretches near 3400 cm-1 are significantly larger than the corresponding peaks in the aliphatic
amines.

NH2
OCH3

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The following example represents an aromatic secondary amine.

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The Infrared Spectra of The Ketones
Dominant Observable Vibration
The most important vibration associated with ketones is the C=O stretching vibration. This
vibration occurs in the region of ~1710-1725 cm-1. The frequency of the carbonyl peak will
vary based on the structure of the carbonyl.

Infrared spectrum of 4-heptanone: key carbonyl vibration at 1713 cm-1.

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The Infrared Spectra of Aromatic ketones
The frequency of the C=O stretching vibration for ketones will decrease to about 1690-1666 cm-1 if the C=O
functional group is immediately next to an alkene or an aromatic ring.

Infrared spectrum of propiophenone:

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Infrared spectrum of benzophenone:

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The Infrared Spectra of the Aldehydes
The most important vibration associated with ketones is the C=O stretching vibration. This
vibration occurs in the region of ~1725-1735 cm-1. The frequency of the carbonyl peak will
vary based on the structure of the carbonyl.

-C=O stretching ~1725-1735 cm-1

Aldehydic C-H ~2700-2800 cm-1

Infrared spectrum of n-hexanal:

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The Infrared Spectra of the Aromatic Aldehydes
Aromatic Aldehydes
The frequency of the C=O stretching vibration for aldehydes will decrease to about 1685-1666 cm-1 if the
C=O functional group is conjugated to an alkene or an aromatic ring.

Infrared spectrum of 4-methoxybenzaldehyde (para-anisaldehdye)

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The Ketones and the Aldehydes: A Comparison
The Ketones
Infrared spectrum of 4-heptanone:

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The Aldehydes
The Aldehyde C-H stretch at ~2700-2800 cm-1 serves as a marker in terms of distinguishing aldehydes from ketones.

Infrared spectrum of n-hexanal:

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The Infrared Spectra of Carboxylic Acids
C=O stretching ~1710 cm-1 O-H stretching ~2500-3100 cm-1

Infrared spectrum of octanoic acid:

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Comparison with aliphatic alcohols

Both carboxylic acids and alcohols possess the –OH group, although their reactivities are very different as
the carboxylic acid –OH group is bound to a carbonyl group. The vibrational frequency of an –OH group of
an alcohol is shifted to higher frequencies.

Alcohol Carboxylic acid

2015 Department of Chemistry, Illinois State University, Normal, IL 61790-4160 Page 24

The Infrared Spectra of Esters
C=O stretch
• saturated aliphatic esters: C=O: 1750–1735 cm–1
• formates, a,b-unsaturated, and benzoate esters: 1730-1715 cm–1
• phenyl or vinyl esters: 1770-1780 cm–1

C–O stretches (strong absorptions; asymmetrical coupled vibrations)

• saturated aliphatic esters (except acetates): C–O: 1210–1163 cm–1
• acetates: 1240 cm–1
• α,β-unsaturated esters: 1300–1160 cm–1
• benzoate esters: 1310–1250 cm–1

Infrared spectrum of isopropyl acetate:

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The Infrared Spectra of Amides
Dominant Observable Vibrations:
C=O stretching ~1660-1680 cm-1
N-H stretching ~3200-3500 cm-1

Infrared spectrum of octanamide:

Amide I band (C=O)

Amide II band (NH bending)

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The Infrared Spectra of Nitriles
-C≡N triple bond stretch ~2240-2280 cm-1
Infrared spectrum of heptanenitrile:

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Comparison with terminal alkynes (R-C≡C-H)

Both alkynes and nitriles possess triple bonded functional groups that appear in nearly the
same region in the infrared spectrum. A key difference is that the alkynes (if they are
terminal alkynes) will possess additional features that should readily allow for diagnostic
confirmation for one functional group or the other.
1-octyne (a terminal alkyne): 3323, 3024, 2926, 1636, 1466, 964 cm-1.

2015 Department of Chemistry, Illinois State University, Normal, IL 61790-4160 Page 27

The Infrared Spectra of Nitrocompounds
Dominant Observable Vibrations

Two bands are observed in the spectrum (symmetric and asymmetric) at 1300-1380 cm-1 (m-
s) and 1500-1570 cm-1 (m-s).

Infrared spectrum of meta-nitrotoluene

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2015 Department of Chemistry, Illinois State University, Normal, IL 61790-4160 Page 28