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Subject Chemistry

Paper No and Title Paper 12: Organic Spectroscopy

Module No and Title Module 9: Characteristic vibrational frequencies of functional

groups
Module Tag CHE_P12_M9_e-Text

CHEMISTRY PAPER No. 12: ORGANIC SPECTROSCOPY

Module  9:  Characteristic  vibrational  frequencies  of  functional  
groups  
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TABLE OF CONTENTS
1. Learning Outcomes
2. Introduction
3. Alkyl and Aryl halides
4. Alcohol and phenols
5. Ethers and Epoxides
6. Carbonyl compounds
6.1 Aldehydes and ketones
6.2 Cyclic ketones
6.3 Carboxylic Acids
6.4 Esters
6.5 Cyclic esters
6.6 Amides
6.7 Cyclic amides
6.8 Anhydrides
6.8 Acid chlorides
7. Amines
8. Nitro compounds
9. Nitriles, Isocynates, Imines and oximes
10. Carboxylic acid salts, Amine salts (NH4+, RNH3+, R2NH2+, R3NH+) and amino
acids
11. Summary

CHEMISTRY PAPER No. 12: ORGANIC SPECTROSCOPY

Module  9:  Characteristic  vibrational  frequencies  of  functional  
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1. Learning Outcomes
After studying this module, you shall be able to
• To understand the position, intensity and shape of absorption bands related to various
functional groups.
• To understand how mesomeric and inductive effect change the absorption frequency of
carbonyl compounds.
• To understand ring strain effect on various ring structures, cyclic ketones, lactams, lactones
etc.
• How to differentiate primary, secondary and tertiary amines on the basis of IR-spectroscopy

2. Introduction
The infrared spectrum of an organic compound contains a large number of bands due to the
stretching and bending vibrational modes of each bond. Thus it is quite difficult to assign each
and every band to a particular mode of vibration. Organic chemists generally do not try to
identify all the absorption bands in an IR spectrum. They just look at some characteristic bands
that you will be dealing in the present module. These characteristic peaks tell about the presence
of some particular functional groups present in the molecule. Now as more energy is needed to
stretch a bond than to bend it, absorption bands for stretching vibrations are found in the high
frequency region that is functional group region whereas absorption bands for bending vibrations
are typically found in the fingerprint region. Stretching vibrations, therefore, are the most useful
vibrations in determining the functionality present in a molecule. The IR stretching frequencies
associated with different types of bonds are discussed separately.
Thus, the vibrational frequencies provide important structural information about a compound and
since two same types of bonds in two different compounds would vibrate at different frequencies
and so no two compounds can have exactly same infrared spectrum especially in the finger print
region except enantiomers. This makes IR spectroscopy a simple and versatile tool for
identification of samples. Here we describe the various vibrational modes and their characteristic
absorption frequencies.

3. Alkyl and Aryl halides

It is difficult to determine the presence or the absence of a halogen in a compound by infrared
spectroscopy. The C-X absorption bands occur at very low frequencies to the extreme right to the
spectrum (fingerprint), where a number of other bands appear. Table 1 drawn below lists the
absorption regions observed for organic halogen compounds. Particular care must be taken when
fluorine is present in a compound as the C–F stretching bands observed in the region of 1350-
1100 cm−1, are very strong and may obscure any C–H bands that might be present.

CHEMISTRY PAPER No. 12: ORGANIC SPECTROSCOPY

Module  9:  Characteristic  vibrational  frequencies  of  functional  
groups  
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Table 1: C-X bond absorption frequencies

4. Alcohol and phenols

Alcohols and phenols produce characteristic infrared bands due to O–H stretching and C–O
stretching in the regions 3200-3650 cm−1 and 1000-1260 cm−1 (The presence of NH or moisture
causes similar results). For alcohols, the broad O–H stretching band is centred at 3600 cm−1,
while for phenols this band appears 50–100 cm−1 lower than the alcohols. But the frequency value
is always not much reliable as the position of the O-H band is very sensitive to hydrogen bonding.
A strong and sharp peak is observed near to 3700 cm-1 in gaseous or extremely dilute solutions. In
condensed phases (bulk liquid, KBr discs, concentrated solution etc.) the molecules are associated
through hydrogen bonding and causes shifting to lower frequencies and broadening of bands
(Figure 1,2).

Figure 1: Infrared Spectrum of hexanol

CHEMISTRY PAPER No. 12: ORGANIC SPECTROSCOPY

Module  9:  Characteristic  vibrational  frequencies  of  functional  
groups  
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Figure 2: Infrared Spectrum of p-methyl phenol

Table 2: C-O and O-H stretching frequencies in various alcohols and phenols

The C-O stretching in alcohols and phenols occurs in the 1300–1000 cm−1 region. The C-O
absorptions are coupled with the adjacent C-C stretching vibrations hence the position of C-O can
be used to differentiate between primary (~1050 cm-1), secondary (~1100 cm-1) and tertiary
(~1150 cm-1) alcohols and phenols (~1220 cm-1). These compounds also produce O–H bending
vibrations, but the latter couple with other vibrations and produce complex bands in the
fingerprint region (Table 2).

5. Ethers and Epoxides

In the spectra of aliphatic ethers, the most characteristic absorption is a strong band in the 1150-
1000 cm−1 region because of asymmetric C-O-C stretching, but a band in this region is also
observed in other oxy compounds like alcohols, aldehydes, ketones, acids etc. Therefore, we
consider the possibility that a compound is ether or an epoxide only if the unknown oxy
compound shows no absorption bands in O-H (3750-3000 cm−1) or carbonyl (1850-1550 cm−1)
regions (Figure 3).

CHEMISTRY PAPER No. 12: ORGANIC SPECTROSCOPY

Module  9:  Characteristic  vibrational  frequencies  of  functional  
groups  
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Figure 3: The Infrared spectrum of diethyl ether (neat Liquid, KBr plates).

The conjugation of ether with carbon-carbon double bond or phenyl ring shifts the C-O-C
symmetric stretching to ~1250 cm−1. The resonance increases the bond order from single to
partial double bond and so higher the force constant and higher the absorption frequency. Cyclic
ethers show a C–O stretching band over a broad 1250–900 cm−1 range (Figure 4).

Figure 4: The infrared spectrum of anisole (neat Liquid, KBr plates).

6. Carbonyl compounds
Aldehydes, ketones, carboxylic acid, esters, lactones, acid halides, anhydrides, amides and
lactams show a strong C=O stretching band in the region of 1630-1870 cm-1. The different
frequencies of these functionalities can be explained by the inductive effect, mesomeric effect,
hydrogen bonding, field effect, steric effect and ring strain. These factors either increase or
decrease the stretching frequency of both the aldehydic and ketonic group compared to the
normal value 1715 cm-1 (saturated aliphatic ketone) (Table 3).

CHEMISTRY PAPER No. 12: ORGANIC SPECTROSCOPY

Module  9:  Characteristic  vibrational  frequencies  of  functional  
groups  
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Table 3: Characteristic infrared bands of oxygen containing compounds

CHEMISTRY PAPER No. 12: ORGANIC SPECTROSCOPY

Module  9:  Characteristic  vibrational  frequencies  of  functional  
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6.1. Aldehydes and ketones

Aliphatic aldehydes show a very strong C=O stretching in the region of 1740–1725 cm-1. The
conjugation of an aldehyde to a C=C or a phenyl group lowers C=O stretching by ~ 30 cm-1. This
effect is seen in benzaldehyde in which aryl group is attached directly to the carbonyl group and
shifts C=O stretch to 1701 cm-1. Aldehyde C-H stretching vibrations appear as a pair of weak
bands between 2860-2800 cm-1 and 2760-2700 cm-1. The higher C-H stretching band (2860-2800
cm-1) of aldehyde is often buried under aliphatic C-H band. But the lower C-H band at 2760-2700
cm-1 is usually used to distinguish aldehydes from other carbonyl-containing compounds. The C-
H bending vibrations appear between 945-780 cm-1 (Figure 5,6).

Figure 5: The Infrared spectrum of nonanal (neat liquid, KBr plates)

Figure 6: The Infrared spectrum of benzaldehyde (neat liquid, KBr plates)

The aliphatic acyclic ketones show C=O stretching between 1720 to 1700 cm-1 which is shifted to
lower frequencies by 20-30 cm-1 on conjugation with C=C or phenyl ring. The presence of two
conjugated groups as in benzophenone further lowers the C=O stretching frequency to 1665 cm-1.

6.2. Cyclic ketones

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The frequency of C=O group in cyclic ketones increases with decreasing the ring size. The ring
strain shift the absorption values to a higher frequency. Six-membered rings with carbonyl group
e.g. cyclohexanone absorb at normal value i.e. 1715 cm-1. Decrease in ring size increases the C=O
stretching frequency. Smaller rings require the use of more p-character to make C-C bonds for the
requisite small angles. This gives more s character to the C=O sigma bond and thus results in
strengthening of C=O double bond causing absorption at higher frequency (Figure 7).

Figure 7: The C=O stretching vibrations for cyclic ketones and ketene

6.3. Carboxylic Acids

Carboxylic acids (RCOOH) exist as dimers, except in dilute solution, due to strong
intermolecular hydrogen bonding. Carboxylic acids show a strong peak in the range of 1730-1700
cm−1. This band shifts to lower frequency if in conjugation with a C=C or a phenyl ring. The O–H
stretching band is appeared as a very broad peak in the 3400–2500 cm−1 range. The very broad
nature of this band is attributed to the strong hydrogen bonding present in the dimer. In dilute
solutions, the carboxylic acids attain monomeric structures and the inductive effect of oxygen
shifts the C=O absorption band to higher values (1760–1730 cm−1) than observed in ketones.
In addition, carboxylic acids show characteristic C–O stretching band near 1240 cm−1 and in-
plane and out-of-plane O–H bending bands at 1430 cm−1 and 930 cm−1, respectively. These bands
are of medium to low intensity bands.

Figure 8: The Infrared spectrum of isobutyric acid (neat liquid, KBr plates)

CHEMISTRY PAPER No. 12: ORGANIC SPECTROSCOPY

Module  9:  Characteristic  vibrational  frequencies  of  functional  
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6.4. Esters
In case of esters, two strong peaks are observed, the C=O stretching appears in the range 1750-
1730 cm−1 and the C-O stretching absorption appears in the range 1300-1000 cm−1. If the C=O
group is conjugated with C=C or a phenyl ring, the C=O frequency is shifted to lower frequency
due to conjugation. If in an ester, C-O oxygen bears electron-withdrawing groups such as vinyl,
phenyl etc. then the C=O stretching is shifted to higher values (~1770 cm−1) This increases the
electron-withdrawing ability of oxygen causing increase in carbonyl double bond character
(Figure 9).

Figure 9: The Infrared spectrum of ethyl butyrate (neat liquid, KBr plates)

6.5. Cyclic esters

In cyclic esters (lactones), C=O stretching is shifted to higher frequency with decreasing ring
size. The unstrained six membered cyclic ester, δ-valerolactone, absorbs at the same value as a
non-cyclic ester (1735 cm-1). Because of ring strain, γ-butyrolactone and β- butyrolactone show
C=O stretching at 1770 cm-1 and 1820 cm-1, respectively.

6.6. Amides
The C=O stretching frequency in amides appears in the range 1680-1630 cm-1 that is 20-50 cm-1
lower than that of C=O stretching frequency of ketones. The low frequency of amides is due to
the strong resonance participation of lone pair of electrons by amide nitrogen that weakens the

CHEMISTRY PAPER No. 12: ORGANIC SPECTROSCOPY

Module  9:  Characteristic  vibrational  frequencies  of  functional  
groups  
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carbonyl bond. The C=O stretching band in IR spectra of amide is called amide I band and N-H
bending is called amide II band.
In the solid or pure liquid state, primary amides, which are highly hydrogen bonded, exhibit two
N-H stretching bands, one at 3550 cm-1 due to N-H asymmetric stretching and other at 3180 cm-1
due to N-H symmetric stretching. In dilute solutions, due to lowering in degree of hydrogen
bonding, the absorption bands shift to higher frequencies at 3500 cm-1 and 3400 cm-1,
respectively. They also exhibit C=O stretching at 1680–1660 cm-1 (amide I band) and N-H
bending at 1650–1620 cm-1 (amide II band) (Figure 10).

Figure 10: The Infrared spectrum of propionamide (nujol mull, KBr plates). Dots
indicate the Nujol (mineral oil) absorption bands.
The secondary amides show only one N-H stretching band at near 3300 cm-1, while the carbonyl
stretching (amide I band) is observed at 1680–1640 cm−1. The amide II band for secondary
amides is due to the coupling of N–H bending and C–N stretching and appears at 1560–1530
cm−1. A weak band which is an overtone of the amide II band appears at 3100–3060 cm−1. A
broad N–H wagging band also appears at 750–650 cm−1.

Figure 11: The Infrared spectrum of N-methylacetamide (neat liquid, KBr plates)

CHEMISTRY PAPER No. 12: ORGANIC SPECTROSCOPY

Module  9:  Characteristic  vibrational  frequencies  of  functional  
groups  
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Tertiary amides show C=O stretching band in the range of 1680-1630 cm−1 but do not show any
N-H stretching band (Figure 11).

6.7. Cyclic amides

The C=O stretching frequency is shifted to higher frequency with decreasing ring size. The
unstrained six membered cyclic amide, δ-valerolactam, absorbs at 1760 cm−1 whereas γ-
butyrolactam and β-propiolactam show C=O stretching at 1770 cm−1 and 1745 cm−1, respectively
due to ring strain.

6.8. Anhydrides
The acid anhydrides show two absorption bands due to carbonyl group in the region of 1840-
1800 cm−1 (symmetric stretching) and at 1780-1740 cm−1 (asymmetric stretching). Conjugation
shifts each of these bands to lower frequencies (about 30 cm−1 each). Ring strain moves the
absorptions to a higher frequency. Anhydrides also show a strong and broad C–O stretching band
in the range of 1300-900 cm−1 for open-chain anhydrides (Figure 12).

Figure 12: The Infrared spectrum of propionic anhydride (neat liquid, KBr plates).

6.9. Acid chlorides

Aliphatic acid chloride shows a very strong band due to C=O group in the range of 1810-1775
cm−1. The high frequency region in case of acid chloride is attributed to the high electronegativity
of chlorine. Conjugation lowers the frequency to 1780-1760 cm−1. The C-Cl stretching vibrations
occur in the range of 730-550 cm−1.

CHEMISTRY PAPER No. 12: ORGANIC SPECTROSCOPY

Module  9:  Characteristic  vibrational  frequencies  of  functional  
groups  
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Figure 13: The Infrared spectrum of acetyl chloride (neat liquid, KBr plates)

7. Amines
The N-H stretching frequency occur the range of 3500-3200 cm-1. Primary (–NH2), secondary (–
NH) and tertiary (no hydrogen attached to N) amines may be differentiated by using infrared
spectra. Primary amines, R-NH2, show two N-H stretching bands in the range 3500-3300 cm-1,
whereas secondary amines, R2N-H, show only one band in that region. Tertiary amines do not
show an N-H stretch. Table 4 summarizes the main infrared bands for amines.

Table 4: Characteristic Infrared bands of amines

In neat liquid samples, the N-H bands are weaker and sharper than an O-H band. Primary (–NH2)
amines show two absorption bands (symmetric and asymmetric stretch) at near 3400 cm-1 and
3300 cm-1. It is not possible to assign the symmetric and asymmetric bands by inspection but it is
assumed that the higher frequency band is due to the asymmetric vibration, whereas the lower
frequency band results from a symmetric vibration. In dilute solutions, the two frequencies are

CHEMISTRY PAPER No. 12: ORGANIC SPECTROSCOPY

Module  9:  Characteristic  vibrational  frequencies  of  functional  
groups  
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shifted to higher values. Aliphatic secondary amines show only one N–H stretching band at 3300
cm-1, whereas an aromatic secondary amine gives a stronger N-H band near 3400 cm-1. Tertiary
amines do not show N-H stretching band (Figure 14).

Figure 14: The Infrared spectrum of butylamine (neat liquid, KBr plates)

Figure 15: The Infrared spectrum of dibutylamine (neat liquid, KBr plates)

Figure 16: The Infrared spectrum of tributylamine (neat liquid, KBr plates)
CHEMISTRY PAPER No. 12: ORGANIC SPECTROSCOPY
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The N-H bending mode (scissoring) appears as a medium to strong intensity (broad) band in the
range from 1640 to 1560 cm-1. In aromatic secondary amines, the band shifts to a lower frequency
and appears near 1500 cm-1. However, in aliphatic secondary amines the N-H bending vibration is
very weak and usually is not observed. The N-H vibrations in aromatic compounds often overlap
the aromatic C=C ring absorption, which also appear in this region. Sometimes an out-of-plane
N-H bending vibration also appears as a broad band in the range 850-750 cm-1 for primary and
secondary amines. These bands appear in the spectra of compounds determined as neat liquids
and are seen most easily in aliphatic amines.

The C-N stretching absorption occurs in the region from 1350 to 1000 cm-1 as a medium to strong
band for all amines. Aliphatic amines absorb from 1250 to 1000 cm-1, whereas aromatic amines
absorb from 1350 to 1250 cm-1. The C-N absorption occurs at a higher frequency in aromatic
amines because resonance increases the double-bond character between the ring and the attached
nitrogen atom (Figure 15,16).

8. Nitro compounds
The Nitro group (NO2) gives two strong bands in the infrared spectrum. In aliphatic nitro
compounds, the asymmetric stretching vibration occurs in the range from 1600 to 1530 cm-1, and
the symmetric stretching band appears between 1390 and 1300 cm-1. For example, 1-nitrohexane
absorbs at about 1500 cm-1 and 1380 cm-1. Normally, its lower-frequency band is less intense than
its higher-frequency band. In contrast with aliphatic nitro compounds, aromatic compounds give
two bands of nearly equal intensity. Conjugation of a nitro group with an aromatic ring shifts the
bands to lower frequencies: 1550-1490 cm-1 and 1355-1315 cm-1. For example, nitrobenzene
absorbs strongly at 1525 cm-1 and 1350 cm-1. The nitroso group (R-N=O) gives only one strong
band that appears in the range from 1600 to 1500 cm-1 (Figure 17).

Figure 17: The Infrared spectrum of 1-nitrohexane (neat liquid, KBr plates)

9. Nitriles, Isocynates, Imines and oximes

CHEMISTRY PAPER No. 12: ORGANIC SPECTROSCOPY
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The C=N group in a nitrile group gives an intense, sharp band in the region of 2280-2200 cm-1.
Aliphatic nitriles absorb at about 2250 cm-1 whereas their aromatic counterparts absorb at lower
frequencies, near 2230 cm-1. Aromatic nitriles absorb at lower frequencies with increased
intensity because of conjugation of the triple bond with the ring. Isocynates also contain an sp-
hybridized carbon atom (R-N=C=O) and hence gives a absorption band in the nearby region at
about 2270 cm-1 and are broad and intense bands.
An imine (R-CH=N-R) gives a C=N absorption band in the range of 1690-1650 cm-1. The
intensity of the C=N band varies in intensity from compound to compound. An oxime (R-CH=N-
O-H) gives a C=N absorption in the range 1690 to 1640 cm-1 and a broad O-H absorption between
3650 cm-1 and 2600 cm-1 (Figure 18,19).

Figure 18: The Infrared spectrum of butryonitrile (neat liquid, KBr plates)

Figure 19: The Infrared spectrum of benzyl isocyanate (neat liquid, KBr plates)

10. Carboxylic acid salts, Amine salts (NH4+, RNH3+, R2NH2+, R3NH+)
and amino acids

CHEMISTRY PAPER No. 12: ORGANIC SPECTROSCOPY

Module  9:  Characteristic  vibrational  frequencies  of  functional  
groups  
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In carboxylic acid salts, the C=O stretching frequency appear little bit lower value (1600-1400
cm-1) from the value found for the parent carboxylic acid due to partial carbon–oxygen double
bond character. Band due to the asymmetric stretching (strong) occurs near 1600 cm-1, while
symmetric stretching (strong) occurs near 1400 cm-1.

The amine salts show a N-H Stretching frequency in the range 3300-2600 cm-1 as a broad band.
The ammonium ion absorbs to the extreme left in this range, while the tertiary amine salt absorbs
to the extreme right. Primary and secondary amine salts absorb in the middle of the range, 3100-
2700 cm-1. The bending N-H vibrations (strong) occur at 1610-1500 cm-1. Primary (two bands) is
asymmetric at 1610 cm-1, symmetric at 1500 cm-1. Secondary absorbs in the range 1610-1550 cm-
1
. Tertiary absorbs only weakly. All the amine salts show bands due to the C-N vibrations in the
fingerprint region but these bands are weaker (Figure 20).
Amino acids exist as zwitter ions and exhibit characteristic absorption due to carboxylate and
primary amine salts. They show absorption bands of NH3+ stretch (very broad), N-H bend
(asymmetric /symmetric) and COO- stretch (asymmetric /symmetric).

Figure 20: IR-spectrum of leucine

11. Summary
• The vibrational frequencies provide important structural information about a compound
and except for enantiomers no two compounds have the same vibrational frequencies.

• These characteristic peaks tell about the presence of some particular functional groups
present in the molecule. This makes IR spectroscopy a simple and versatile tool for
identification of samples.

• We have described here the characteristic absorption frequencies of some functional

groups like alkyl and aryl halides, alcohols and phenols, ethers and epoxides, carbonyl
CHEMISTRY PAPER No. 12: ORGANIC SPECTROSCOPY
Module  9:  Characteristic  vibrational  frequencies  of  functional  
groups  
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compounds, aldehydes and ketones, cyclic ketones, carboxylic acids, esters, cyclic esters,
amides, cyclic amides, anhydrides, acid chlorides, amines, nitro compounds, nitriles,
isocyanates, imines and oximes, carboxylic acid salts and amine salts.

CHEMISTRY PAPER No. 12: ORGANIC SPECTROSCOPY

Module  9:  Characteristic  vibrational  frequencies  of  functional  
groups