IR SPECTROSCOPY

Introduction:- The Carbonyl group in IR spectroscopy:--------

Electromagnetic radiation has dual wave particle properties. A The carbonyl group (C = O) Occurs in large number of organic
photon is the particle of electromagnetic. In a vacuum a compounds (Ketones, aldehydes, carboxylic acids and their
photon Travels at constant velocity C =2.998 x 10⁸ms-¹. The ester, Amide, anhydride, acid chloride and thioester
velocity is related to the frequency and wavelength(λ). derivatives). IR spectroscopy is very useful for identifying these
C = λV compounds because the carbon is stretching band is very
The energy of a photon is proportional to its frequency (v). The intense and is located in a part of I have spectrum. (1650 cm-1
proportionality constant is Planck's Constant, h = 6.626 x 10-³⁴ Js. to 1850 cm-1) Where there is little interference from other
E = hv = hc/λ. functional groups. The Characteristic carbonyl compounds and
Protons with wavelength from 100 nm to 800 nm (frequency ring size and pi conjugation effects, So it is very often possible
from 3.75 x 10¹⁴ s-¹ to 3.00 x 10¹⁵s-¹) are sufficiently energetic to to make an identification of the specific type of carbonyl
cause electronic transitions in molecules atoms. Their compound from an investigation of its IR spectrum.
quantized transitions give information about atomic or Conjugation:----By conjugation reduces the carbonyl
molecular structure. The branch of Spectroscopy known as absorption band frequency by 30 cm-1 in ketones and other
electronic absorption spectroscopy is offend called UV-visible carbonyl compounds.
spectroscopy. Ring size effect:---- Decreasing ring size (<6 membered ring)
100 - 200 nm---------- Vacuum UV ( far UV region ). increases C=O stretching frequency.
200 - 400 nm ---------- UV Cyclohexanone = cyclopentanone = Cyclobutanone =
400 - 800 nm----------- Visible 1710 cm-1 1747 cm-1 1783 cm-1
800nm and above ---- IR

Less energetic radiation causes vibrational transitions within

molecules. This vibrational motion is also quantized. Photos of
wavelength from 1000 nm to 30000nm cause these transitions.
This infrared (IR) radiation is of longer wavelength (lower
frequency) then visible red radiation. The particle range for Aldehyde: --- aliphatic aldehyde : 1725 +- 10cm-1 sharp band.
infrared Spectroscopy of organic compound is about 2500 nm
to 20000nm.
Frequency is more commonly used as measurement in IR
spectroscopy. The wave number (cm-1) is the standard
frequency measure in IR spectroscopy. Carboxylic acid:------ Aliphatic acid:----- (1710 +- 10)cm-1
V(cm-1) = 1/ λ = Esters: --
v Is the frequency, divided by speed of light in unit of cm-1. The Broad strong C=O stretching at
practical range of IR spectroscopy expresses in this unit is A primary amide:-- NH stretch ( 2 bands ) 3370 cm-1,3190 cm-1.
4000 cm-1and two 400 cm-1. C=O stretch = 1660 cm-1 - 1700 cm-1.
650 cm-1 to 1350 cm-1 = Fingerprint region--------- A tertiary amide : No NH stretch.
identification of compound. C=O stretch: 1640 cm-1.
1500 cm-1 = - C –O Stretching Anhydride :-------- Aliphatic anhydride
< 3000 cm-1 = Aliphatic compound group Aliphatic acid chloride:--- (1820 +- 10 cm-1)
1700 cm-1 = ( = C= O ) group.
> 3000 cm-1 = Aromatic ring. Other easily detected functional groups: ---
1400 cm-1 to 4000 cm-1 = functional group. Alcohol: ----(R-OH)
Functional group such as OH or C=O tend to absorb radiation in -OH Stretch = 3200 - 3600 cm-1 strong, often broad.
a narrow frequency range In any compound in which they are -OH bend = 1050 - 1200 cm-1 strong, frequency increases in
found. These ranges are called functional group frequencies . order 1o,2o, 3o phenol.
For you organic compounds the functional group range lies C-O stretch = 1260 - 1410 cm-1
between 1400 cm-1 to 4000 cm-1. Nitriles…. R-C N
The carbonyl stretching frequency is very important because C N stretch: 2210 - 2260 cm-1 medium intensity, sharp.
there are many classes of compounds that have this group. You Alkynes R-C C-R
can identify which class by the detailed knowledge of how C C stretch ::: 2100 - 2260 cm-1 variable intensity, sharp.
structure variations such as ring size and π conjugation affect C-H stretch 3300 cm-1 strong terminal alkynes only.
the frequency of absorption.
All distinct compounds are for unique IR Spectra. A particularly
useful part of the higher frequency range for establishing
unique identifier is the range from 1350 cm-1 to 650 cm-1 .
There is some overlap with a functional group range. This
frequency range is called a fingerprint Region because it
appears that all compounds have a unique absorption
spectrum in this region.
The vibration we have been discussing are called fundamental Aromatic Rings:------
absorption. They arise from excitation from the ground state to = C-H :- Stretch for Sp2 C-H occurs at values greater than 3000
the lowest energy excited state. Usually the spectrum is cm-1 ( 3050-3010 cm-1 ).
complicated because of presence of weak overtone, =C-H :--Out of plane (oop)bending occurs at 900 -690 cm-1. These
combination and difference bands. Overtones result from bands can be used with great utility to assign the ring
excitation from the ground state to the higher energy states, substitution pattern.
which corresponds to integral multiples of the frequency of the C=C :--Ring stretch absorption often occurs in pairs at 1600 cm-1
fundamental. For example, you might observe weak overtone and 1475 cm-1 .
bands at 2v,3v…… etc. Any kind of physical vibration generates Overtone/Combination bands appear between 2000 cm-1 and
overtones. If you pluck a string on a cello, listing vibrates with a 1667 cm-1 . These weak absorption can be used to assign the ring
fundamental frequency. However, less intense vibrations are substitution pattern .
also set up at several overtones Frequencies. And absorption in Examples: ---- Toluene, ortho-diethylbenzene, meta-
the infrared at 500 cm-1 may well Have an accompanying peek ethylbenzene and para-diethylbenzene.
of lower intensity at 1000 cm-1 – an overtone. When two
vibrational frequencies (v1 and v2) in a molecule Couple to give Alcohols and phenols: -----
rise to a vibration of a new frequency within the molecule, and O-H :--The free OH stretch is a sharp peak at 3650 to 3600 cm-1.
when such a vibration is infrared active it is called a This band appears in combination with the hydrogen
combination band. This band is the sum of the two interacting bonded O-H peaks when alcohol is dissolved in a solvent.
bands (Vcomb = V1 + V2). Not all possible combination occurs. The hydrogen bonded O-H band is abroad peak at 3900 -
3300 cm-1 . This band is usually the only one present in
Characteristics vibrational frequencies an alcohol that has not been dissolved in a solvent .
Alkanes: ---- When the alcohol is dissolved in a solvent the free OH
The spectrum is usually simple with few peaks. and hydrogen bonded O-H baonds are present together,
C-H = Stretch occurs around 3000. In alkanes (expected with the relatively weak free O-H on the left .
strained ring compounds) Sp3 C-H absorption always C-O-H :--Bonding appears as a broad and wesk peak at 1400 -
occurs at frequency less than 3000 cm-1 (3000 - 2840 cm-1). 1200 cm-1 , often observed by the CH3 bonding .
If a compound vinylic, aromatic, acetylenic or cyclopropyl C-O :--Stretching vibration usually occurs in the range 1260 -
hydrogens, the C-H absorption is greater than 3000 cm-1 , 1000 cm-1 . This band can be used to assign a primary,
these compounds have sp2 and sp hybiridization. secondary or tertiary structure to an alcohol.
C-H2 = Methylene groups have a characteristic bending Example:----The hydrogen bonded O-H stretch is present in the
absorption of approximately 1465 cm-1. pure liquid samples of 1-hexano, 2-butanol and para cresol.
CH3 = Methyl groups have a characteristic bending absorption
of approximately 1375 cm-1. Ethers :---
CH2 = The bending (rocking) motion associated with four or C-O :--The most prominent band is that due to C-O stretch , 1300
more CH2 groups in an open chain occurs at about 720 - 1000 cm-1 . Absence of C-O and O-H is required to
cm-1 ( called a long chain bond ) . ensure that C-O stretch is not due to an Ester or alcohol.
C-C = Stretch not interpretively useful, many weak peaks. Phenyl alkyl ether give two strong bands at about 1250
Example: ---- decane and mineral oil and cyclohexane. cm-1 and 1040 cm-1 .While aliphatic ethers give one
strong band at about 1120 cm-1 .
Alkenes :-- Examples :------- diethyl ether and anisole.
=C-H :- Stretch for Sp2 C-H occurs at value greater than 3000
cm-1. Amines: -----
=C-H :--Out of plane bending occurs in the range 1000 cm-1 to N-H :--Stretch occurs in the range 3500-3300 cm-1. Primary
650 cm-1. These bands can be used to determine the amines have two bands . Secondary amines have one band a
degree of substitution on the double bond . vanishing weak one for aliphatic compounds and stronger one
C = C :--Stretch occurs at 1660 - 1600 cm-1 , often conjugation for aromatic secondary amines. Tertiary amines have no N-H
moves C=C stretch to lower frequencies and increase the stretch .
intensity. Symmetrically substituted bonds ( 2,3- N-H :--Bend in primary amounts result in a broad band in the
dimethyl-2-butene ) do not absorb in the infrared ( no range 1640-1560 cm-1 . Secondary amines absorb near
dipole change ) . Symetrically disubstituted ( trans ) 1500 cm-1.
double bond are often vanishingly week in absorption, N-H :--Out of plane, bending absorption can sometimes be
sis are stronger. observed near 800 cm-1 .
Examples:----- hexene, cyclohexene, sis-2-pentene and trans- C-N:---Stretch occurs in the range 1350-1000 cm-1.
2-pentene. Examples:---- butylamine, dibutylamine, tributylamine and N-
Alkynes:--- methylaniline.
C-H :--- Stretch for Sp C-H usually occurs near 3300 cm-1 .
C C :--- Stretch occurs near 2100 cm-1, conjugation moves Nitriles :--- R-C=N
states to lower frequency. Disubstituted or -C=N :--Stretch Is a medium intensity sharp absorption near
symmetrically unsubstituted or substituted triple 2250 cm-1 . Conjugation with double bonds or aromatic
bonds you either know absorption or weak absorption. rings move the absorption to a lower frequency.
Examples :---- 1-Octyne and 4-Octyne. Examples :- butyronitrile and benzonitrile.
 Nitro compounds :--- The medium intensity absorption in nonanal at 1460 is due to
Aliphatic ----- assymetric stretch (strong) the scissoring (bending) vibration of the CH2 Group to the
1600-1530 cm-1, symmetric stretch carbonyl group. Methylene group often absorb more strongly
(medium) 1390-1300 cm-1. when they are attached directly to carbonyl group.
Aromatic -----(Conjugated) assymetric
stretch (strong) 1550-1490 cm-1. Symmetric Ketones: ----
stretch (strong) 1355-1315 cm-1. C=O stretch appears in range 1720-1708
Examples:---- 1-nitrobenzene and nitrobenzene. cm-1. For normal aliphatic range.

Aldehydes:---- Conjugation of C=O with alpha and beta

C=O stretch appears in range 1740-1725 cm- C=C; 1700-1675 cm-1. For C=O and 1644-
1
for normal aliphatic aldehydes. 1617 cm-1 for C=C.

Conjugation of C=O with alpha beta C=C Conjugation with two aromatic rings; 1670
1700-1680 cm-1. For C=O and 1640 cm-1 for – 1600 cm-1 for C=O.
C=C.
Cyclic ketones; C=O frequency increases
Conjugation of C=O with phenyl. 1700-1660 with decreasing ring size.
cm-1 for C=O and 1600-1450 cm-1 for a ring
C=C. Bending appears as a medium intensity
peak in the range 130-1100 cm-1.
Longer conjugated system; 1680 cm-1 for Examples :---- 3-methyl-2-butanone,acetophenone,
C=O. cyclopentanone and 2,4-pentandione.

C-H :----- Stretch aldehyde hydrogen Cho consist of a pair of Discussion :----
weak bonds one at to 860-2800 and the other at to Normal C=O bonds
760-2700 . It is easier to _________ the band at the The spectrum of 3-methyl-2-butanone Exhibits a normal or
lower frequency because it is not observed by the unconjugated ketone stretching frequency at 1715 cm-1. A Very
usual C-H bonds from the alkyl chain. The higher weak overtone band from the C=O (1715 cm-1) appears at
frequency aldehyde C-H stretch is often buried in the twice the frequency of the C=O absorption (3430 cm-1). Small
aliphatic C-H band. bands of this type should not be confused with 0-H
Examples:---- crotonaldehyde and benzaldehyde. Absorptions, which also appear near this value. The O-H
stretching absorptions are much more intense.
Discussion :-- Conjugation effects :---
The spectrum of nonanal Exhibits the normal aldehyde Conjugation of the carbonyl group with an aryl or alpha beta
stretching frequency at 1725 cm-1. Since the position of this Double bond shift the normal C=O Stretching band (1715 cm-1)
absorptions are not very different from those of ketones,It may to a lower frequency (1715-1675 cm-1) As predicted. Rotational
not be easy to distinguish between aldehydes and ketones on isomer may lead to a splitting or broadening of carbonyl band.
this basis .Conjugation of carbonyl group with aryl or an Alpha The effect of conjugation in the C=O Band is seen in mesityl
beta double bond shift the normal C=O stretching to a lower oxide; which has alpha beta unsaturation and in
frequency(1700-1680 cm-1) as predicted {Conjugated acetonephenone in which an aryl group is attached to the
effect}.This effect is seen in crotonaldehyde which has alpha carbonyl group. Both exhibit C=O stretching vibrations which
beta saturation and in benzaldehyde in which an aryl group is demonstrate the influence of conjugation.
attached directly to the carbonyl group. Halogenation on the Cyclic ketones ( ring strain ):----
alpha carbon leads to an increased frequency for the carbonyl Some values for the C=O absorption for cyclic ketones ring
group. strain ship the absorption values to a higher frequency as
The C-H Stretching vibration found in aldehydes (-CHO) at predicted.
about 2750 cm-1 and 2850 cm-1 are extremely important for
distinguishing between ketones and aldehydes. Typical range Amides:---
ranges for the pairs of C-H bands are 2860 cm-1- 2800 cm-1 and C=O :--Stretch occurs at approximately 1680-1630cm-1.
2760-2700 cm-1. The bands at 275 cm-1 is probably the more N-H :---- Stretch in primary amides(-NH2) Gives two bands near
useful of the pair Because it appears in a region where other 3350 and 3180 cm-1. Secondary amides have one band (-
C-H absorptions are absent. The 2850 cm-1 band overlaps the NH) at about 3300 cm-1.
other C-H bands and is not as easy to see if the 2750 cm-1 band N-H :--- Bending occurs around 1640-150 cm-1 for primary and
is present together with the proper absorption value and Cho secondary amides.
functional group is almost certainly indicated . Examples:--- Propionamide and N-methylacetamide.
The doublet that is observed in the range to 2860-2700 cm-1
For an idea is a result of Fermi resonance. The second band
appears when the aldehyde Ch stretching vibration is coupled
with the first overtone of the medium intensity aldehyde Ch
bonding vibration appearing in the range 1400-1350 cm-1.
Acid Chloride:-----
C=O :---Stretch occurs in the range 1810-1755 cm-1 in
unconjugated Lower the frequency to 1780-1760 cm-1.
C-Cl :--- Stretch occurs in the range 730-550 cm-1.
Examples :--- acetyl chlorides and benzoyl chlorides.

Anhydrides:---
C=O :--State always has two bands 1830-1800 cm-1 and 1775-
1774 cm-1 with variable relative intensity. Conjugation
moves the absorption to lower frequency. Ring strain (
cyclic anhydride ) moves the absorption to higher
frequency.
C-O :-Stretch ( multiple bonds ) occur in the range 1300-900
cm-1.
Examples:--- propionic anhydride.

Discussion :----
The characteristic pattern for noncyclic and saturated
anhydrides in the appearance of two strong bands, not
necessarily of equal intensities in the region from 1830-1800 Cyclic amides (lactams) give the expected increase, the C=O
cm-1 and from 1775-1740 cm-1. The two bands result from frequency for decreasing ring size as shown.
assymetric and symmetric Stretch.
Conjugation shift the absorption to a lower frequency while
cyclization (ring strain) Shift the absorption to a higher
frequency. The strong and broad C-O stretching vibration
occurs in the region from 1300-900 cm-1.

Cycllc Esters (Lactones):---

The C=O Vibrations are shifted to a higher frequency with
decreasing ring size . The unstrained, 6 membered cyclic Ester
δ-Valero lactone. Absorbs at About some value as a noncyclic
Ester. (1735 cm-1). Because increased angle strain, δ-
butyrolactone absorbs at about 35 cm-1 higher than δ-
valerolactone.

δ-valerolactone δ-butyrolactone

Effect of ring size, α β-unsaturation and conjugation with

oxygen on the C=O vibrations is lactones.