IR SPECTROSCOPY
Introduction:-
Electromagnetic radiation has dual wave particle properties. A
photon is the particle of electromagnetic. In a vacuum a
photon Travels at constant velocity C =2.998 x 10⁸ms-¹. The
velocity is related to the frequency and wavelength(λ).
C = λV
The energy of a photon is proportional to its frequency (v). The
proportionality constant is Planck's Constant, h = 6.626 x 10-³⁴ Js.
E = hv = hc/λ.
Protons with wavelength from 100 nm to 800 nm (frequency
from 3.75 x 10¹⁴ s-¹ to 3.00 x 10¹⁵s-¹) are sufficiently energetic to
cause electronic transitions in molecules atoms. Their
quantized transitions give information about atomic or
molecular structure. The branch of Spectroscopy known as
electronic absorption spectroscopy is offend called UV-visible
spectroscopy.
100 - 200 nm---------- Vacuum UV ( far UV region ).
200 - 400 nm ---------- UV
400 - 800 nm----------- Visible
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
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.
V(cm-1) = 1/ λ =
v Is the frequency, divided by speed of light in unit of cm-1. The
practical range of IR spectroscopy expresses in this unit is
4000 cm-1and two 400 cm-1.
650 cm-1 to 1350 cm-1 = Fingerprint region---------
identification of compound.
1500 cm-1 = - C –O Stretching
< 3000 cm-1 = Aliphatic compound group
1700 cm-1 = ( = C= O ) group.
> 3000 cm-1 = Aromatic ring.
1400 cm-1 to 4000 cm-1 = functional group.
Functional group such as OH or C=O tend to absorb radiation in
a narrow frequency range In any compound in which they are
found. These ranges are called functional group frequencies .
For you organic compounds the functional group range lies
between 1400 cm-1 to 4000 cm-1.
The carbonyl stretching frequency is very important because
there are many classes of compounds that have this group. You
can identify which class by the detailed knowledge of how
structure variations such as ring size and π conjugation affect
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 Carbonyl group in IR spectroscopy:--------
The carbonyl group (C = O) Occurs in large number of organic
compounds (Ketones, aldehydes, carboxylic acids and their
ester, Amide, anhydride, acid chloride and thioester
derivatives). IR spectroscopy is very useful for identifying these
compounds because the carbon is stretching band is very
intense and is located in a part of I have spectrum. (1650 cm-1
to 1850 cm-1) Where there is little interference from other
functional groups. The Characteristic carbonyl compounds and
ring size and pi conjugation effects, So it is very often possible
to make an identification of the specific type of carbonyl
compound from an investigation of its IR spectrum.
Conjugation:----By conjugation reduces the carbonyl
absorption band frequency by 30 cm-1 in ketones and other
carbonyl compounds.
Ring size effect:---- Decreasing ring size (<6 membered ring)
increases C=O stretching frequency.
Cyclohexanone = cyclopentanone = Cyclobutanone =
1710 cm-1 1747 cm-1 1783 cm-1
Aldehyde: --- aliphatic aldehyde : 1725 +- 10cm-1 sharp band.
Carboxylic acid:------ Aliphatic acid:----- (1710 +- 10)cm-1
Esters: --
Broad strong C=O stretching at
A primary amide:-- NH stretch ( 2 bands ) 3370 cm-1,3190 cm-1.
C=O stretch = 1660 cm-1 - 1700 cm-1.
A tertiary amide : No NH stretch.
C=O stretch: 1640 cm-1.
Anhydride :-------- Aliphatic anhydride
Aliphatic acid chloride:--- (1820 +- 10 cm-1)
Other easily detected functional groups: ---
Alcohol: ----(R-OH)
-OH Stretch = 3200 - 3600 cm-1 strong, often broad.
-OH bend = 1050 - 1200 cm-1 strong, frequency increases in
order 1o,2o, 3o phenol.
C-O stretch = 1260 - 1410 cm-1
Nitriles…. R-C N
C N stretch: 2210 - 2260 cm-1 medium intensity, sharp.
Alkynes R-C C-R
C C stretch ::: 2100 - 2260 cm-1 variable intensity, sharp.
C-H stretch 3300 cm-1 strong terminal alkynes only.
The vibration we have been discussing are called fundamental
absorption. They arise from excitation from the ground state to
the lowest energy excited state. Usually the spectrum is
complicated because of presence of weak overtone,
combination and difference bands. Overtones result from
excitation from the ground state to the higher energy states,
which corresponds to integral multiples of the frequency of the
fundamental. For example, you might observe weak overtone
bands at 2v,3v…… etc. Any kind of physical vibration generates
overtones. If you pluck a string on a cello, listing vibrates with a
fundamental frequency. However, less intense vibrations are
also set up at several overtones Frequencies. And absorption in
the infrared at 500 cm-1 may well Have an accompanying peek
of lower intensity at 1000 cm-1 – an overtone. When two
vibrational frequencies (v1 and v2) in a molecule Couple to give
rise to a vibration of a new frequency within the molecule, and
when such a vibration is infrared active it is called a
combination band. This band is the sum of the two interacting
bands (Vcomb = V1 + V2). Not all possible combination occurs.
Characteristics vibrational frequencies
Alkanes: ----
The spectrum is usually simple with few peaks.
C-H = Stretch occurs around 3000. In alkanes (expected
strained ring compounds) Sp3 C-H absorption always
occurs at frequency less than 3000 cm-1 (3000 - 2840 cm-1).
If a compound vinylic, aromatic, acetylenic or cyclopropyl
hydrogens, the C-H absorption is greater than 3000 cm-1 ,
these compounds have sp2 and sp hybiridization.
C-H2 = Methylene groups have a characteristic bending
absorption of approximately 1465 cm-1.
CH3 = Methyl groups have a characteristic bending absorption
of approximately 1375 cm-1.
CH2 = The bending (rocking) motion associated with four or
more CH2 groups in an open chain occurs at about 720
cm-1 ( called a long chain bond ) .
C-C = Stretch not interpretively useful, many weak peaks.
Example: ---- decane and mineral oil and cyclohexane.
Alkenes :--
=C-H :- Stretch for Sp2 C-H occurs at value greater than 3000
cm-1.
=C-H :--Out of plane bending occurs in the range 1000 cm-1 to
650 cm-1. These bands can be used to determine the
degree of substitution on the double bond .
C = C :--Stretch occurs at 1660 - 1600 cm-1 , often conjugation
moves C=C stretch to lower frequencies and increase the
intensity. Symmetrically substituted bonds ( 2,3-
dimethyl-2-butene ) do not absorb in the infrared ( no
dipole change ) . Symetrically disubstituted ( trans )
double bond are often vanishingly week in absorption,
sis are stronger.
Examples:----- hexene, cyclohexene, sis-2-pentene and trans-
2-pentene.
Alkynes:---
C-H :--- Stretch for Sp C-H usually occurs near 3300 cm-1 .
C C :--- Stretch occurs near 2100 cm-1, conjugation moves
states to lower frequency. Disubstituted or
symmetrically unsubstituted or substituted triple
bonds you either know absorption or weak absorption.
Examples :---- 1-Octyne and 4-Octyne.
Aromatic Rings:------
= C-H :- Stretch for Sp2 C-H occurs at values greater than 3000
cm-1 ( 3050-3010 cm-1 ).
=C-H :--Out of plane (oop)bending occurs at 900 -690 cm-1. These
bands can be used with great utility to assign the ring
substitution pattern.
C=C :--Ring stretch absorption often occurs in pairs at 1600 cm-1
and 1475 cm-1 .
Overtone/Combination bands appear between 2000 cm-1 and
1667 cm-1 . These weak absorption can be used to assign the ring
substitution pattern .
Examples: ---- Toluene, ortho-diethylbenzene, meta-
ethylbenzene and para-diethylbenzene.
Alcohols and phenols: -----
O-H :--The free OH stretch is a sharp peak at 3650 to 3600 cm-1.
This band appears in combination with the hydrogen
bonded O-H peaks when alcohol is dissolved in a solvent.
The hydrogen bonded O-H band is abroad peak at 3900 -
3300 cm-1 . This band is usually the only one present in
an alcohol that has not been dissolved in a solvent .
When the alcohol is dissolved in a solvent the free OH
and hydrogen bonded O-H baonds are present together,
with the relatively weak free O-H on the left .
C-O-H :--Bonding appears as a broad and wesk peak at 1400 -
1200 cm-1 , often observed by the CH3 bonding .
C-O :--Stretching vibration usually occurs in the range 1260 -
1000 cm-1 . This band can be used to assign a primary,
secondary or tertiary structure to an alcohol.
Example:----The hydrogen bonded O-H stretch is present in the
pure liquid samples of 1-hexano, 2-butanol and para cresol.
Ethers :---
C-O :--The most prominent band is that due to C-O stretch , 1300
- 1000 cm-1 . Absence of C-O and O-H is required to
ensure that C-O stretch is not due to an Ester or alcohol.
Phenyl alkyl ether give two strong bands at about 1250
cm-1 and 1040 cm-1 .While aliphatic ethers give one
strong band at about 1120 cm-1 .
Examples :------- diethyl ether and anisole.
Amines: -----
N-H :--Stretch occurs in the range 3500-3300 cm-1. Primary
amines have two bands . Secondary amines have one band a
vanishing weak one for aliphatic compounds and stronger one
for aromatic secondary amines. Tertiary amines have no N-H
stretch .
N-H :--Bend in primary amounts result in a broad band in the
range 1640-1560 cm-1 . Secondary amines absorb near
1500 cm-1.
N-H :--Out of plane, bending absorption can sometimes be
observed near 800 cm-1 .
C-N:---Stretch occurs in the range 1350-1000 cm-1.
Examples:---- butylamine, dibutylamine, tributylamine and N-
methylaniline.
Nitriles :--- R-C=N
-C=N :--Stretch Is a medium intensity sharp absorption near
2250 cm-1 . Conjugation with double bonds or aromatic
rings move the absorption to a lower frequency.
Examples :- butyronitrile and benzonitrile.
 Nitro compounds :---
Aliphatic ----- assymetric stretch (strong)
1600-1530 cm-1, symmetric stretch
(medium) 1390-1300 cm-1.
Aromatic -----(Conjugated) assymetric
stretch (strong) 1550-1490 cm-1. Symmetric
stretch (strong) 1355-1315 cm-1.
Examples:---- 1-nitrobenzene and nitrobenzene.
Aldehydes:----
C=O stretch appears in range 1740-1725 cm-
1
for normal aliphatic aldehydes.
Conjugation of C=O with alpha beta C=C
1700-1680 cm-1. For C=O and 1640 cm-1 for
C=C.
Conjugation of C=O with phenyl. 1700-1660
cm-1 for C=O and 1600-1450 cm-1 for a ring
C=C.
Longer conjugated system; 1680 cm-1 for
C=O.
C-H :----- Stretch aldehyde hydrogen Cho consist of a pair of
weak bonds one at to 860-2800 and the other at to
760-2700 . It is easier to _________ the band at the
lower frequency because it is not observed by the
usual C-H bonds from the alkyl chain. The higher
frequency aldehyde C-H stretch is often buried in the
aliphatic C-H band.
Examples:---- crotonaldehyde and benzaldehyde.
Discussion :--
The spectrum of nonanal Exhibits the normal aldehyde
stretching frequency at 1725 cm-1. Since the position of this
absorptions are not very different from those of ketones,It may
not be easy to distinguish between aldehydes and ketones on
this basis .Conjugation of carbonyl group with aryl or an Alpha
beta double bond shift the normal C=O stretching to a lower
frequency(1700-1680 cm-1) as predicted {Conjugated
effect}.This effect is seen in crotonaldehyde which has alpha
beta saturation and in benzaldehyde in which an aryl group is
attached directly to the carbonyl group. Halogenation on the
alpha carbon leads to an increased frequency for the carbonyl
group.
The C-H Stretching vibration found in aldehydes (-CHO) at
about 2750 cm-1 and 2850 cm-1 are extremely important for
distinguishing between ketones and aldehydes. Typical range
ranges for the pairs of C-H bands are 2860 cm-1- 2800 cm-1 and
2760-2700 cm-1. The bands at 275 cm-1 is probably the more
useful of the pair Because it appears in a region where other
C-H absorptions are absent. The 2850 cm-1 band overlaps the
other C-H bands and is not as easy to see if the 2750 cm-1 band
is present together with the proper absorption value and Cho
functional group is almost certainly indicated .
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.
The medium intensity absorption in nonanal at 1460 is due to
the scissoring (bending) vibration of the CH2 Group to the
carbonyl group. Methylene group often absorb more strongly
when they are attached directly to carbonyl group.
Ketones: ----
C=O stretch appears in range 1720-1708
cm-1. For normal aliphatic range.
Conjugation of C=O with alpha and beta
C=C; 1700-1675 cm-1. For C=O and 1644-
1617 cm-1 for C=C.
Conjugation with two aromatic rings; 1670
– 1600 cm-1 for C=O.
Cyclic ketones; C=O frequency increases
with decreasing ring size.
Bending appears as a medium intensity
peak in the range 130-1100 cm-1.
Examples :---- 3-methyl-2-butanone,acetophenone,
cyclopentanone and 2,4-pentandione.
Discussion :----
Normal C=O bonds
The spectrum of 3-methyl-2-butanone Exhibits a normal or
unconjugated ketone stretching frequency at 1715 cm-1. A Very
weak overtone band from the C=O (1715 cm-1) appears at
twice the frequency of the C=O absorption (3430 cm-1). Small
bands of this type should not be confused with 0-H
Absorptions, which also appear near this value. The O-H
stretching absorptions are much more intense.
Conjugation effects :---
Conjugation of the carbonyl group with an aryl or alpha beta
Double bond shift the normal C=O Stretching band (1715 cm-1)
to a lower frequency (1715-1675 cm-1) As predicted. Rotational
isomer may lead to a splitting or broadening of carbonyl band.
The effect of conjugation in the C=O Band is seen in mesityl
oxide; which has alpha beta unsaturation and in
acetonephenone in which an aryl group is attached to the
carbonyl group. Both exhibit C=O stretching vibrations which
demonstrate the influence of conjugation.
Cyclic ketones ( ring strain ):----
Some values for the C=O absorption for cyclic ketones ring
strain ship the absorption values to a higher frequency as
predicted.
Amides:---
C=O :--Stretch occurs at approximately 1680-1630cm-1.
N-H :---- Stretch in primary amides(-NH2) Gives two bands near
3350 and 3180 cm-1. Secondary amides have one band (-
NH) at about 3300 cm-1.
N-H :--- Bending occurs around 1640-150 cm-1 for primary and
secondary amides.
Examples:--- Propionamide and N-methylacetamide.
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.