INFRARED

SPECTROSCOPY
CHM 3212 Advanced Organic Chemistry
College of Science
Pamantasan ng Lungsod ng Maynila

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OUTLINE

I. Molecular Vibrations
II. The IR Spectrum
III. IR Absorptions of Different Functional Groups
IV. IR and Structure Determination

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OBJECTIVES

• To state the factors that influence the frequency and intensity of a peak in the
IR spectrum.
• To assign functional groups to some diagnostic peaks in the IR spectrum.
• To use IR spectroscopy in the determination of an outcome of a chemical
reaction.
• To use the IR spectrum to deduce structures of simple organic compounds.

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OVERVIEW

• Infrared (IR) Spectroscopy deals with the EMR absorption of molecules in the
infrared region (2.5 μm – 25 μm)

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OVERVIEW

• Wavenumber, ν (cm-1)
• Higher wavenumber, higher energy

© 2015 Cengage Learning

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INFRARED ABSORPTION PROCESS

• Infrared absorption is a quantized process.

• The energy absorbed increases the amplitude of the vibrational motions of
the bonds in the molecule.
• For a molecule to absorb IR, it must have a dipole moment (polar).
• The frequencies of absorption are characteristic of a molecule.

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MOLECULAR VIBRATIONS

© 2005 Springer Science+Business Media

Dordrecht

Two modes of fundamental vibrations:

a. Stretching vibrations
b. Bending (deformation) vibrations

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MOLECULAR VIBRATIONS

Stretching vibrations
• For a group of 3 or more atoms where at
least 2 of which are identical, both modes
are present.
• Symmetric stretch ~2853 cm-1
• Asymmetric stretch ~2926 cm-1

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MOLECULAR VIBRATIONS

Bending vibrations

~1450 cm-1 ~1250 cm-1 ~720 cm-1 ~1250 cm-1

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MOLECULAR VIBRATIONS

Non-fundamental vibrations
• Overtones – integral multiples of the frequency of the fundamental (ν)

• Combination bands – when two vibrational frequencies couple to give rise

to a vibration of a new frequency within the molecule.

• Difference bands – difference between two interacting bands

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THE IR SPECTRUM

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THE IR SPECTRUM

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IR ABSORPTIONS
OF FUNCTIONAL
GROUPS

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IR ABSORPTIONS OF FUNCTIONAL GROUPS

A. Alkanes
• sp3 C—H stretch : ~3000-2840 cm-1
• –CH2– bending: ~1465 cm-1
• –CH3 bending: ~1375 cm-1
• CH2 bending for molecules with 4 or more CH2 groups : ~720 cm-1

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IR ABSORPTIONS OF FUNCTIONAL GROUPS

A. Alkanes

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IR ABSORPTIONS OF FUNCTIONAL GROUPS

B. Alkenes
• sp2 =C—H stretch : >3000 cm-1
• =CH out-of-plane bending: 1000-650 cm-1
• C=C stretch: 1660-1600 cm-1
o Conjugation lowers the frequency
Isolated C=C 1640-1680 cm-1
Conjugated C=C 1620-1640 cm-1
Aromatic C=C ~1600 cm-1
o Symmetrically disubstituted trans double bonds are very weak; cis are stronger

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IR ABSORPTIONS OF FUNCTIONAL GROUPS

B. Alkenes

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IR ABSORPTIONS OF FUNCTIONAL GROUPS

B. Alkenes

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IR ABSORPTIONS OF FUNCTIONAL GROUPS

B. Alkenes

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IR ABSORPTIONS OF FUNCTIONAL GROUPS

C. Alkynes
• sp ≡C—H stretch : ~3300 cm-1
• C≡C stretch: ~2150 cm-1
o Conjugation moves stretch to lower frequency

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IR ABSORPTIONS OF FUNCTIONAL GROUPS

C. Alkynes

IR Spectrum of 1-octyne COLLEGE OF SCIENCE

IR ABSORPTIONS OF FUNCTIONAL GROUPS

Carbon-carbon bonds
• The C=C stretching frequency is lowered if the alkene is strained or conjugated.

• Increasing bond order leads to higher frequencies

C-C 1200 cm-1
C=C 1600-1680 cm-1
C≡C 2200 cm-1

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IR ABSORPTIONS OF FUNCTIONAL GROUPS

C—H bending vibrations for methyl and methylene

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IR ABSORPTIONS OF FUNCTIONAL GROUPS

D. Aromatic Rings
• =C-H stretch: >3000 cm-1
• =C-H out-of-plane: 900-690 cm-1
• C=C ring stretch: often occur in
pairs near 1600 and 1475 cm-1
(strong absorption)
• Overtone/combination bands
(weak) at 2000-1667 cm-1

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IR ABSORPTIONS OF FUNCTIONAL GROUPS

D. Aromatic Rings

IR Spectrum of methylbenzene COLLEGE OF SCIENCE

IR ABSORPTIONS OF FUNCTIONAL GROUPS

D. Aromatic Rings

IR Spectrum of m-diethylbenzene COLLEGE OF SCIENCE

IR ABSORPTIONS OF FUNCTIONAL GROUPS

D. Aromatic Rings

IR Spectrum of p-diethylbenzene COLLEGE OF SCIENCE

IR ABSORPTIONS OF FUNCTIONAL GROUPS

E. Alcohols and Phenols

• O—H stretch (Free): sharp, medium peaks at 3650-3600 cm-1
• O—H stretch (Hydrogen-bonded): broad, distinct peaks at 3400-3300 cm-1
o Intermolecular H-bonding weakens the O—H bond → lower ν
• C—O—H bend: broad and weak peak at 1440-1220 cm-1
• C—O stretch: strong peaks at 1260-1000 cm-1
o 1° ROH ~1050 cm-1
o 2° ROH ~1100 cm-1
o 3° ROH ~1150 cm-1
o Phenols ~1220 cm-1
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IR ABSORPTIONS OF FUNCTIONAL GROUPS

E. Alcohols and Phenols

IR Spectrum of hexanol COLLEGE OF SCIENCE

IR ABSORPTIONS OF FUNCTIONAL GROUPS

E. Alcohols and Phenols

Free and H-bonded (in

H-bonded Free and H-bonded very dilute solution)
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IR ABSORPTIONS OF FUNCTIONAL GROUPS

F. Ethers
• C—O stretch: 1300-1600 cm-1
o Epoxides: strong bands at 950-815 cm-1 and 880-750 cm-1
o Phenyl alkyl ethers: two strong bands at ~1250-1040 cm-1
o Aliphatic ethers: one strong band at ~1120 cm-1

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IR ABSORPTIONS OF FUNCTIONAL GROUPS

F. Ethers

IR Spectrum of dibutyl ether COLLEGE OF SCIENCE

IR ABSORPTIONS OF FUNCTIONAL GROUPS

G. Carbonyl Compounds
• C=O stretch: strong, prominent peak at 1850-1650 cm-1

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IR ABSORPTIONS OF FUNCTIONAL GROUPS

G. Carbonyl Compounds: Aldehydes

• C=O stretch
o Aliphatic aldehydes: strong peak at 1740-1725 cm-1
o Conjugated aldehydes: 1700-1680 cm-1
o Aromatic conjugated aldehydes: 1700-1660 cm-1
o Longer conjugated system: 1680 cm-1
• Aldehydic C—H stretch
o Pair of weak bands at 2860-2800 cm-1 and 2760-2700 cm-1

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IR ABSORPTIONS OF FUNCTIONAL GROUPS

G. Carbonyl Compounds: Aldehydes

IR Spectrum of nonanal COLLEGE OF SCIENCE

IR ABSORPTIONS OF FUNCTIONAL GROUPS

G. Carbonyl Compounds: Ketones

• C=O stretch
o Aliphatic ketones: strong peak at 1720-1708 cm-1
o Conjugated ketones: 1700-1675 cm-1
o Aromatic conjugated ketones: 1700-1680 cm-1

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IR ABSORPTIONS OF FUNCTIONAL GROUPS

G. Carbonyl Compounds: Ketones

IR Spectrum of acetophenone COLLEGE OF SCIENCE

IR ABSORPTIONS OF FUNCTIONAL GROUPS

G. Carbonyl Compounds: Carboxylic Acids

• C=O stretch: strong, broad peak at 1730-1700 cm-1
• C—O stretch: medium peak at 1320-1210 cm-1
• O—H stretch: very broad (strongly H-bonded) at 3400-2400 cm-1

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IR ABSORPTIONS OF FUNCTIONAL GROUPS

G. Carbonyl Compounds: Carboxylic Acids

IR Spectrum of isobutyric acid COLLEGE OF SCIENCE

IR ABSORPTIONS OF FUNCTIONAL GROUPS

G. Carbonyl Compounds: Amides

• C=O stretch: 1700-1640 cm-1
• N—H stretch
o 1° amides: two bands near 3350 and 3180 cm-1
o 2° amides: one band only at ~3300 cm-1
• N—H bend: ~1640-1550 cm-1
• C—N stretch: ~1400 cm-1

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IR ABSORPTIONS OF FUNCTIONAL GROUPS

G. Carbonyl Compounds: Amides

IR Spectrum of propionamide COLLEGE OF SCIENCE

IR ABSORPTIONS OF FUNCTIONAL GROUPS

G. Carbonyl Compounds: Acid Chlorides

• C=O stretch: 1810-1775 cm-1 (saturated acid chlorides)
• C—Cl stretch: 730-550 cm-1

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IR ABSORPTIONS OF FUNCTIONAL GROUPS

G. Carbonyl Compounds: Acid Chlorides

IR Spectrum of acetyl chloride COLLEGE OF SCIENCE

IR ABSORPTIONS OF FUNCTIONAL GROUPS

G. Carbonyl Compounds: Esters

• C=O stretch:
o Aliphatic esters: 1750-1735 cm-1
o Conjugated esters: 1740-1715 cm-
1 (for C=C, 1640-1625 cm-1)

o Conjugated with phenyl: 1740-

1715 cm-1 (for ring C=C, 1600-
1450 cm-1)

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IR ABSORPTIONS OF FUNCTIONAL GROUPS

G. Carbonyl Compounds: Esters

IR Spectrum of ethyl butyrate COLLEGE OF SCIENCE

IR ABSORPTIONS OF FUNCTIONAL GROUPS

G. Carbonyl Compounds: Anhydrides

• C=O stretch: two bands
o 1830-1800 cm-1
o 1775-1740 cm-1
o Conjugation moves the absorption to lower frequency
o Ring strain moves the absorption to higher frequency
• C—O stretch: multiple bands in the range of 1300-900 cm-1

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IR ABSORPTIONS OF FUNCTIONAL GROUPS

G. Carbonyl Compounds: Anhydrides

IR Spectrum of propionic anhydride COLLEGE OF SCIENCE

IR ABSORPTIONS OF FUNCTIONAL GROUPS

H. Amines
• N—H stretch: 3500-3300 cm-1
o 1° amines: two bands
o 2° amines: one band (weak for aliphatic, strong for aromatic)
• C—N stretch: 1350-1000 cm-1
• N—H bend: medium to strong band (broad)
o 1° amines: 1640-1560 cm-1
o 2° aromatic amines: ~1500 cm-1
o 2° aliphatic amines: weak or almost absent

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IR ABSORPTIONS OF FUNCTIONAL GROUPS

H. Amines

IR Spectrum of butylamine COLLEGE OF SCIENCE

IR ABSORPTIONS OF FUNCTIONAL GROUPS

H. Amines

IR Spectrum of dibutylamine COLLEGE OF SCIENCE

IR ABSORPTIONS OF FUNCTIONAL GROUPS

I. Nitriles, Isocyanates, Isothiocyanates, and Imines

• Nitriles
o —C≡N stretch: sharp, medium intensity near 2250 cm-1
• Isocyanates
o —N=C=O stretch: broad, intense absorption near 2270 cm-1
• Isothiocyanates
o —N=C=S stretch: one or two broad, intense absorptions centering near 2125 cm-1
• Imines
o Stretch in an imine, oxime, and so on gives a variable-intensity absorption near
1690-1640 cm-1

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IR ABSORPTIONS OF FUNCTIONAL GROUPS

I. Nitriles, Isocyanates, Isothiocyanates, and Imines

• Nitriles
o —C≡N stretch: sharp, medium intensity near 2250 cm-1
• Isocyanates
o —N=C=O stretch: broad, intense absorption near 2270 cm-1
• Isothiocyanates
o —N=C=S stretch: one or two broad, intense absorptions centering near 2125 cm-1
• Imines
o Stretch in an imine, oxime, and so on gives a variable-intensity absorption near
1690-1640 cm-1

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IR ABSORPTIONS OF FUNCTIONAL GROUPS

I. Nitriles, Isocyanates, Isothiocyanates, and Imines

IR Spectrum of butyronitrile COLLEGE OF SCIENCE

IR ABSORPTIONS OF FUNCTIONAL GROUPS

I. Nitriles, Isocyanates, Isothiocyanates, and Imines

IR Spectrum of benzyl isocyanate COLLEGE OF SCIENCE

IR ABSORPTIONS OF FUNCTIONAL GROUPS

J. Nitro Compounds
• Two strong bands: one near 1550 cm-1 and 1350 cm-1
o Aliphatic
1. Asymmetric stretch (strong) : 1600-1530 cm-1
2. Symmetric stretch (medium) : 1390-1300 cm-1
o Aromatic
1. Asymmetric stretch (strong) : 1550-1490 cm-1
2. Symmetric stretch (medium) : 1355-1315 cm-1

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IR ABSORPTIONS OF FUNCTIONAL GROUPS

J. Nitro Compounds

IR Spectrum of nitrohexane COLLEGE OF SCIENCE

IR ABSORPTIONS OF FUNCTIONAL GROUPS

K. Sulfur Compounds
• Mercaptans (R—S—H)
o S—H stretch (weak) : near 2550 cm-1
• Sulfoxides
o S=O stretch (strong) : near 1050 cm-1
• Sulfides
o No significant absorption
• Sulfones
o Two bands (strong) near 1300 cm-1 and 1150 cm-1

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IR ABSORPTIONS OF FUNCTIONAL GROUPS

K. Sulfur Compounds
• Sulfonyl Chlorides (R—S—H)
o S=O stretch: two bands (strong) near 1375 cm-1 and 1185 cm-1
• Sulfonates
o S=O stretch: two bands (strong) near 1350 cm-1 and 1175 cm-1
o S—O stretch: several strong bands at 1000-750 cm-1
• Sulfonamides
o S=O stretch: two bands (strong) near 1325 cm-1 and 1140 cm-1
o N—H stretch

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IR ABSORPTIONS OF FUNCTIONAL GROUPS

K. Sulfur Compounds

IR Spectrum of methyl p-toluenesulfonate COLLEGE OF SCIENCE

IR ABSORPTIONS OF FUNCTIONAL GROUPS

K. Sulfur Compounds

IR Spectrum of benzenethiol COLLEGE OF SCIENCE

IR ABSORPTIONS OF FUNCTIONAL GROUPS

L. Alkyl and Aryl halides

• Fluorides
o C—F stretch: strong band at 1400-1000 cm-1
• Chlorides
o C—Cl stretch: 785-540 cm-1
o Multiple substitution on a single C atom increases the frequency of this stretch
o CH2—Cl bend: 1300-1230 cm-1
• Bromides
o C—Br stretch: strong band at 650-510 cm-1
o CH2—Cl bend: 1250-1190
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IR ABSORPTIONS OF FUNCTIONAL GROUPS

L. Alkyl and Aryl halides

• Iodides
o C—I stretch: strong band at 600-485 cm-1
o CH2—I bend: 1200-1150 cm-1

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IR ABSORPTIONS OF FUNCTIONAL GROUPS

L. Alkyl and Aryl halides

IR Spectrum of chloroform COLLEGE OF SCIENCE

IR ABSORPTIONS OF FUNCTIONAL GROUPS

L. Alkyl and Aryl halides

IR Spectrum of carbon tetrachloride COLLEGE OF SCIENCE

IR ABSORPTIONS OF FUNCTIONAL GROUPS

M. Phosphorus Compounds
• Phosphines
o P—H stretch: sharp, strong band at 2320-2270 cm-1
o PH2 bend: medium bands at 1090-1075 cm-1 and 840-810 cm-1
o P—CH2— bend: medium band at 1440-1400 cm-1
• Phosphine oxides
o P=O stretch: very strong band at 1210-1140 cm-1

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IR AND STRUCTURE
DETERMINATION

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IR ABSORPTIONS OF FUNCTIONAL GROUPS

D. Aromatic Rings
• =C-H stretch: >3000 cm-1
• =C-H out-of-plane: 900-690 cm-1
• C=C ring stretch: often occur in
pairs near 1600 and 1475 cm-1
(strong absorption)
• Overtone/combination bands
(weak) at 2000-1667 cm-1

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IR ABSORPTIONS OF FUNCTIONAL GROUPS

C—H bending vibrations for methyl and methylene

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