IR Spectroscopy

Structural Prediction of Organic Compounds

 IR Spectra
% Trasmittance

2-Pentanone
2-Pentanone

Wavenumbers (cm-1)
 IR Spectroscopy-Basics and principle
• Molecules are flexible, atoms and groups of atoms can rotate about single
covalent bonds.
• Bonds can stretch and bend just if their atoms were joined by flexible springs.
• Infrared spectroscopy, also called IR spectroscopy, probes stretching and
bending vibrations of molecules.
• Atoms joined by bonds are not fixed in one position but rather undergo
continual vibrations relative to each other. The energies associated with
these vibrations are quantized, which means that, within a molecule, only
specific vibrational energy levels are allowed.
• The energies associated with these transitions between vibrational energy
levels in organic molecules correspond to frequencies in the infrared region
which stretches from 4000 to ~600 cm-1.
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 IR Spectroscopy-Basics and principle
• IR Spectroscopy is not used for complete structural characterization of
compounds. It is used to determine the various functional groups present in
the molecule.

• It is very difficult to assign all the peaks obtained in the IR spectra of a

compound.

• Two compounds will never show similar IR spectra (except enantiomers).

• In order to be IR active, a vibration must cause a change in the dipole

moment of the molecule.

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 Presentation of the IR Spectra
Designation Abbreviation Wavelength
Near-Infrared NIR 0.78–3 μm
Mid-Infrared MIR 3–50 μm
Far-Infrared FIR 50–1000 μm

• Wavelength of IR Radiation used in IR spectroscopy is from 2.5 μm to 17 μm

approximately.
• The position of an infrared absorption band is specified in frequencies units
by its wavenumber (n) measured in reciprocal centimetres (cm-1).
• Therefore, in terms of wavenumber in cm-1 , IR spectra range is from 4000 to
600 cm-1.
• An infrared spectrum is the graph of % transmittance versus frequency
expressed as wavenumbers.
• Each dip in a spectrum called a band or peak, represents absorption of
infrared radiations at that frequency by the sample. A 100 % transmittance
means no absorption and if all the radiation is absorbed the transmittance is
0 percent.

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(a) High Frequency Region: (4000 to 1650 cm-1)
• This region is especially useful for identification of various functional groups.
• This region shows absorption arising from stretching modes and often contains only a
few bands.
(b) Fingerprint Region: (1650 to 600 cm-1)
• It is called fingerprint region because the pattern of absorption in this region are unique
to any particular compound, just as a person’s fingerprint are unique.
• Many of the vibrational modes in the fingerprint region depend on complex vibrations
involving the entire molecule, it is impossible for any two different compounds (except
enantiomers) to have precisely the same IR spectrum.
• Both stretching and bending modes give rise to absorptions here. One therefore, cannot
correlate an individual band with a specific functional group with accuracy in this
region. 6
 Molecular Vibrations
HCl molecule as an anharmonic
oscillator vibrating at energy level E 3

• Bonds behave as if they are tiny springs

connecting the atoms.
• The vibrational motion is quantized as shown
for a diatomic molecule (HCl).
• At room temp, most of the molecules in a given
sample are in the lowest vibrational state.
• However, on absorption of light of appropriate
energy the molecule becomes excited to the
second vibrational level. In this level, the
amplitude of the molecular vibration is greater.

• For the excitation of a molecule from one vibrational energy level to another, the
molecule has to absorb IR radiation of a particular energy (i.e, radiation of particular
wavelength or frequency).
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 Molecular Vibrations

• There are two types of molecular vibrations, stretching and bending.

• A molecule consisting of n atoms has a total of 3n degrees of freedom,
corresponding to the Cartesian coordinates of each atom in the molecule.
• In a nonlinear molecule, 3 of these degrees are rotational and 3 are
translational and the remaining correspond to fundamental vibrations.
• In a linear molecule, 2 degrees are rotational and 3 are translational.
• The net number of fundamental vibrations for nonlinear and linear
molecules is therefore:

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 Symmetric and Asymmetric Vibration

Calculation reveals that a simple molecule such as propane, C3H8, has 27

fundamental vibrations, and therefore, you might predict 27 bands in an IR
spectrum!

The fundamental vibrations for water, H2O (n= 3; non linear; fundamental
vibrations = 9 – 6 = 3), are shown in picture. Water, which is nonlinear, has
three fundamental vibrations (two stretching + one bending).

Stretching vibrations require higher energy than bending vibrations and occur
at higher frequency!!
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 Stretching and Bending
Carbon dioxide, CO2, is linear and hence has four (9-5) fundamental
vibrations.

The asymmetrical stretch of CO2 gives a strong band in the IR at 2350 cm–1.
You may notice this band in samples which you run on the instruments in the
labs, since CO2 is present in the atmosphere.

The two scissoring or bending vibrations are equivalent and therefore, have
the same frequency and are said to be degenerate, appearing in an IR
spectrum at 666 cm–1.

The symmetrical stretch of CO2 is inactive in the IR because this vibration

produces no change in the dipole moment of the molecule.
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 Stretching and Bending
Symmetric stretching Antisymmetric stretching

Stretching Vibrations

Rocking Wagging Twisting

Scissoring

Bending Vibrations 11
 Different stretching modes in acetic acid

• Apart from these characteristic absorptions (stretching vibrations) which throw light
on the general nature and the presence of functional groups in the compound there
are other absorption bands (bending vibrations) as well.

• Vibrational bending modes are Scissoring, Wagging, Twisting, and Rocking.

• Order of energy; asymmetric stretching>symmetric stretching> bending

• Neither there is necessity nor time for a skilled chemist to interpret these
absorptions because of the complexity of vibrational modes!
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 Role of Dipole Moment in IR

• In order to be IR active, a vibration must cause a change in the dipole

moment of the molecule.

• The reason for this involves the mechanism by which the photon transfers
its energy to the molecule, which is beyond the scope of this discussion.

• Carbon monoxide (CO) and iodine chloride (I-Cl) absorb IR radiation, but
hydrogen (H2), nitrogen (N2), Chlorine (Cl2) and other symmetrical
diatomics do not.

• In general, the larger the dipole change, the stronger the intensity of the
band in an IR spectrum.

• Bands of hydrocarbons which are only composed of carbon and hydrogen

atoms are weak, whereas bands associated with bonds connecting atoms
differing considerably in electronegativity, e.g., C=O are usually quite
strong.

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Trans dichloroethylene shows no C=C stretching around 1640 cm-1, whereas, the cis
isomer shows this band. It may be noted that both isomers show bands for C-H and
C-Cl stretchings.

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 Calculation of Vibrational Frequencies

The frequency of vibration is dependant on two quantities, the

masses of the atoms and the stiffness of the bond. Vibrational
frequencies can be calculated by applying Hooke’s Law.

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• The actual range for C–H absorptions is 2850–3100 cm–1.

• The region of an IR spectrum where bond stretching vibrations are seen

depends primarily on whether the bonds are single, double, or triple or
bonds to hydrogen.

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From the knowledge of bond dissociation energies, one knows that a C-H bond (104
kcal/mole, i.e., 435 kJ/mol) is only slightly stronger than a C-C bond ( 88 kca/mol, i.e.,
368.2 kJ/mol, ethane). Even then, the difference is nicely reflecting in the stretching
frequencies of these two bonds (2950 and 1200 cm-1, respectively).

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18
SIMPLIFIED CORRELATION CHART

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SIMPLIFIED CORRELATION CHART

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• It is easy to remember these values if you start simply and
then slowly increase your familiarity with and ability to
interpret the finer details of an infrared spectrum.

• Remember the formula for calculating the stretching

frequencies.

• Memorize a “typical absorption value”- a single number that can be used a pivotal value for
each of the functional groups in this pattern.
• For, e.g., start with a simple aliphatic ketone as a model for all typical carbonyl compounds. The
typical aliphatic ketone has a carbonyl absorption of about 1715  10 cm-1. Without worrying
about the variation, keep in mind 1715 cm-1 as the base value for carbonyl absorption.
• Then slowly, familiarize yourself with the extent of the carbonyl range (1700 – 1800 cm -1) and
intensity.
• Learn how factors such as ring size and conjugation affect the base values (i.e, in which direction
the values are shifted) 21
 Normal base values for the C=O stretching vibrations for carbonyl groups

• The C=O frequency of a ketone, which is approximately in the middle of the range, is usually considered the
reference point for comparison of these values. The range of values given above may be explained through
the use of electron-withdrawing effects (inductive effects), resonance effects, and hydrogen bonding.

• An electronegative element may tend to draw in the electrons between the carbon and oxygen atoms
through its electron-withdrawing effect, so that the C=O bond becomes somewhat stronger and a higher
frequency absorption results.

• Since oxygen is more electron electronegative than carbon, this effect dominates in an ester to raise the C=O
frequency above that of a ketone.

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 • A resonance effect may be observed when the
unpaired electrons on a nitrogen atom conjugate
with the carbonyl group, resulting in increased
single-bond character and a lowering of the C=O
absorption frequency. This effect is observed in an
amide. Since nitrogen is less electronegative than
an oxygen atom, it can more easily accommodate a
positive charge.
• In acid chlorides, the highly electronegative halogen atom
strengthens the C=O bond through an enhanced inductive effect
and shift the frequency to values even higher than are found in
esters. Anhydrides are likewise shifted to frequencies higher than
are found in esters because of a concentration of electronegative
oxygen atoms. In addition, anhydride give two absorption bands
that are due to symmetric and asymmetric stretching vibrations.

• A carboxylic acid exists in monomeric form in very dilute

solution, and it absorbs at about 1760 cm-1 because of the
electron-withdrawing effect. However, acids in concentrated
solution, in the form of near liquid, or in the solid state tend to
dimerize via hydrogen bonding. This dimerization weakens the
C=O bond and lower the stretching force constant K, resulting
in lowering of the carbonyl frequency of saturated acids to
about 1710 cm-1.
• Ketones absorb at lower frequency than aldehyde because of
their additional alkyl group, which is electron donating (compare
to H) and supplies electrons to the C=O bond. This electron-
releasing effect weakens the C=O bond in the ketone and lowers
the force constant and the absorption frequency.
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 How to approach the analysis of a spectrum?
(or what you can tell at a glance)
First look for the presence (or absence) of a few major functional group. The C=O, O-H,
N-H, C-O, C=C, CC, CN, and NO2 peaks are most conspicuous and give immediate
structural information if they are present.
Do not try to make a detailed analysis of C-H absorptions near 3000 cm -1, almost all
compounds have these absorptions.
Following is a major checklist of the important gross features :
1.) Is a carbonyl group present? The C=O group gives rise to a strong absorption in the region 1820-
1660 cm-1. The peak is often the strongest in the spectrum and of medium width. You can’t miss it.
2.) If C=O is present, check the following types (if it is absent, go to 3).
a) ACID: Is O-H also present?
Broad absorption near 3400-2400 cm-1 (usually overlaps C-H)
b) AMIDES: Is N-H also present?
Medium absorption near 3400 cm-1; sometimes double peaks with
equivalent halves.
c) ESTERS: Is C-O also present?
Strong intensity absorption near 1300-1000 cm-1.
d) ANHYDRIDES: Two C=O absorptions near 1810 and 1760 cm-1.
e) ALDEHYDES: Is aldehyde C-H present?
Two weak absorptions near 2850 and 2750 cm-1 on right side of the aliphatic
C-H absorptions.
f) KETONES: The preceding five choices have been eliminated. 24
3.) If C=O is absent:

ALCOHOLS, PHENOLS: Check for O-H.

Broad absorption near 3400-3300 cm-1
Confirm this by finding C-O near 1300-1000 cm-1.
AMINES: Check for N-H.
Medium absorption(s) near 3400 cm-1.
ETHERS: Check for C-O near 1300-1000 cm-1 (and absence of O-H near 3400 cm-1.

4.) Double bonds and/or aromatic rings:

 C=C is a weak absorption near 1650 cm-1.
 Medium to strong absorptions in the region 1600-1450 cm -1; these often imply an aromatic ring.
 Confirm the double bond or aromatic ring by consulting the C-H region; aromatic and vinyl C-H
occurs to the left of 3000 cm-1 (aliphatic C-H occurs to the right of this value).
5.) Triple bonds:
 CN is a medium, sharp absorption near 2250 cm-1.
 CC is a weak, sharp absorption near 2150 cm-1.
 Check also for acetylenic C-H near 3300 cm-1.
6.) Nitro groups:
 Two strong absorptions at 1600-1530 cm-1 and 1390-1300 cm-1.

7.) Hydrocarbons:
 None of the preceding is found.
 Major absorptions are in C-H region near 3000 cm -1.
 Very simple spectrum; the only other absorptions appear near 1460 and 1375 cm -1. 25
OVERTONE, COMBINATION AND DIFFERENCE BANDS

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 IMPORTANT NOTE

The beginning students should resist the idea

of trying to assign or interpret every peak in
the IR spectrum. You simply will not be able
to do it. Concentrate first on learning major
peaks and recognizing their presence or
absence. This is best done by carefully
studying the illustrative spectra in the
coming slides.

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 Alkanes

• C–H stretch from 3000–2850 cm-1

• C–H bend or scissoring from 1470-1450 cm-1
• C–H rock, methyl from 1370-1350 cm-1
• C–H rock, methyl, seen only in long chain alkanes, from 725-720 cm-1

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 Alkenes

• C=C stretch from 1680-1640 cm-1

• =C–H stretch from 3100-3000 cm-1
• =C–H bend from 1000-650 cm-1

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Alkane vs. Alkenes

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 Alkynes

• –C≡C– stretch from 2260-2100 cm-1

• –C≡C–H: C–H stretch from 3330-3270 cm-1
• –C≡C–H: C–H bend from 700-610 cm-1

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 Alkyl Halides

• C–H wag (-CH2X) from 1300-1150 cm-1

• C–X stretches (general) from 850-515 cm-1
◦ C–Cl stretch 850-550 cm-1
◦ C–Br stretch 690-515 cm-1

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 Aromatics

• C–H stretch from 3100-3000 cm-1

• overtones (ground vibrational level to second level), weak, from 2000-1665 cm-1
• C–C stretch (in-ring) from 1600-1585 cm-1
• C–C stretch (in-ring) from 1500-1400 cm-1
• C–H "oop (out of plane)" from 900-675 cm-1

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 Alcohols

• O–H stretch, hydrogen bonded 3500-3200 cm-1

• C–O stretch 1260-1050 cm-1 (s)

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 Ketones

• C=O stretch:
◦ aliphatic ketones 1715 cm-1
◦ alpha, beta-unsaturated ketones 1685-1666 cm-1

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 Aldehydes

• H–C=O stretch 2830-2695 cm-1

• C=O stretch:
◦ aliphatic aldehydes 1740-1720 cm-1
◦ alpha, beta-unsaturated aldehydes 1710-1685 cm-1

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 Aromatic Aldehydes

• H–C=O stretch 2830-2695 cm-1

• C=O stretch:
◦ aliphatic aldehydes 1740-1720 cm-1
◦ alpha, beta-unsaturated aldehydes 1710-1685 cm-1

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 Carboxylic Acids

• O–H stretch from 3300-2500 cm-1

• C=O stretch from 1760-1690 cm-1
• C–O stretch from 1320-1210 cm-1
• O–H bend from 1440-1395 and 950-910 cm-1

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 Esters
• C=O stretch
◦ aliphatic from 1750-1735 cm-1
◦ α, β-unsaturated from 1730-1715 cm-1
• C–O stretch from 1300-1000 cm-1
 Aromatic Esters
• C=O stretch
◦ aliphatic from 1750-1735 cm-1
◦ α, β-unsaturated from 1730-1715 cm-1
• C–O stretch from 1300-1000 cm-1

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 Amines
• N–H stretch 3400-3250 cm-1
◦ 1° amine: two bands from 3400-3300 and 3330-3250 cm-1
◦ 2° amine: one band from 3350-3310 cm-1
◦ 3° amine: no bands in this region
• N–H bend (primary amines only) from 1650-1580 cm-1
• C–N stretch (aromatic amines) from 1335-1250 cm-1
• C–N stretch (aliphatic amines) from 1250–1020 cm-1
• N–H wag (primary and secondary amines only) from 910-665 cm-1

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 Amines
• N–H stretch 3400-3250 cm-1
◦ 1° amine: two bands from 3400-3300 and 3330-3250 cm-1
◦ 2° amine: one band from 3350-3310 cm-1
◦ 3° amine: no bands in this region
• N–H bend (primary amines only) from 1650-1580 cm-1
• C–N stretch (aromatic amines) from 1335-1250 cm-1
• C–N stretch (aliphatic amines) from 1250–1020 cm-1
• N–H wag (primary and secondary amines only) from 910-665 cm-1

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 Amines
• N–H stretch 3400-3250 cm-1
◦ 1° amine: two bands from 3400-3300 and 3330-3250 cm-1
◦ 2° amine: one band from 3350-3310 cm-1
◦ 3° amine: no bands in this region
• N–H bend (primary amines only) from 1650-1580 cm-1
• C–N stretch (aromatic amines) from 1335-1250 cm-1
• C–N stretch (aliphatic amines) from 1250–1020 cm-1
• N–H wag (primary and secondary amines only) from 910-665 cm-1

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 Nitro Groups
• N–O asymmetric stretch from 1550-1475 cm-1
• N–O symmetric stretch from 1360-1290 cm-1

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 Aromatic Nitro Groups

• N–O asymmetric stretch from 1550-1475 cm-1

• N–O symmetric stretch from 1360-1290 cm-1

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