IR Spectroscopy

I. Introduction
8. The entire electromagnetic spectrum is used by chemists:
Frequency, n in Hz
~1019 ~1017 ~1015 ~1013 ~1010 ~105

Wavelength, l
~.0001 nm ~0.01 nm 10 nm 1000 nm 0.01 cm 100 m

Energy (kcal/mol)
> 300 300-30 300-30 ~10-4 ~10-6
Click to add text

g-rays X-rays UV IR Microwave Radio

nuclear core electronic molecular molecular Nuclear Magnetic
excitation electron excitation vibration rotation Resonance NMR
(PET) excitation (p to p*) (MRI)
(X-ray
cryst.)

Visible
IR Spectroscopy

I. Introduction
C. The IR Spectroscopic Process
1. The quantum mechanical energy levels observed in IR spectroscopy are those of
molecular vibration

2. We perceive this vibration as heat

3. When we say a covalent bond between two atoms is of a certain length, we are
citing an average because the bond behaves as if it were a vibrating spring
connecting the two atoms

4. For a simple diatomic molecule, this model is easy to visualize:

IR Spectroscopy

I. Introduction
C. The IR Spectroscopic Process
5. There are two types of bond vibration:
• Stretch – Vibration or oscillation along the line of the bond

H H
C C
H H

symmetric asymmetric

• Bend – Vibration or oscillation not along the line of the bond

H H H H
C C C C
H H H
H
scissor rock twist wag
in plane out of plane
Infrared Spectroscopy

C.The IR Spectroscopic Process

6.As a covalent bond oscillates – due to the oscillation of the dipole
of the molecule – a varying electromagnetic field is produced

7.The greater the dipole moment change through the vibration, the
more intense the EM field that is generated
Infrared Spectroscopy

C. The IR Spectroscopic Process

8. When a wave of infrared light encounters this oscillating EM
field generated by the oscillating dipole of the same frequency,
the two waves couple, and IR light is absorbed

9. The coupled wave now vibrates with twice the amplitude

IR beam from spectrometer

“coupled” wave

EM oscillating wave
from bond vibration
Quantum mechanics: The frequency (n) depends on the energy gap between vibrational
levels
E = hn= hc/l(cm-1)

Only the natural frequency will be absorbed

The natural frequency (8.67 x 1013 s-1) is absorbed selectively

 What does the absorption intensity depend on?

The absorption intensity depends on how efficiently the energy of

an electromagnetic wave of frequency n can be transferred to the
atoms involved in the vibration

The greater the change in dipole moment during a vibration, the

higher the intensity of absorption of a photon
 Dipole Moment Must Change during for
a vibration to be “IR active”!

• In order to interact
strongly with the EM
radiation, the motion
of the molecule must
be such that the dipole
moment changes.

Which of the vibrations are “IR” active”?

 Does O=C=O absorb IR light?

Ans: vibrations of O=C=O which cause a change in the dipole moment of the
molecular absorb IR light

vibrations of O=C=O which do not cause a change in the dipole moment of the
molecular DO NOT absorb IR light

No dipole Dipole
generated generated
What is the intensity of an IR signal of:
O2 or N2 or H2?

Ans: In order to absorb infrared radiation, a molecular

vibration must cause a change in the dipole moment of
the molecule

O2, N2 and H2 DO NOT ABSORB IR LIGHT!

Vibration levels are quantized, like
everything else

Like a harmonic oscillator

With L-H, L moves most easily
From Skoog and West Can couple to other springs but heavy atoms can
block or minimize this effect
IR: Masses, Atoms and Springs
A Model: Picture the atoms of a diatomic molecule as point masses connected by springs
(bonds).

As a first approximation use Hooke’s Law

F = -kx
F = force, restoring back to equilibrium
position

k = characteristic stretching constant

x = displacement from the equilibrium

position
 Infrared Spectroscopy
IR Absorptions

• Where a particular bond absorbs in the IR depends on bond strength and

atom mass.

• Hooke’s Law describes the relationship of frequency to mass and bond

length.

14
 Vibrations, potential energy and motion

X Y X Y F = d PE/ dr
a b

X Y X Y
PE
c d

r re re

Internuclear Internuclear
separation separation
X Y X Y

Light atoms Heavy atoms

and / or and /or
strong bonds weak bonds
 Examples of stretching frequencies and correlations with bond strengths (bond
order)

Bond strength* Bond order n

350 1 1000 cm-1

C-C

600 2 1600 cm-1

C=C

3 2200 cm-1
840
C C

*In kJ/mol For same reduced mass!

 IR Stretching Frequencies of two
bonded atoms:
What Does the Frequency, n, Depend
On?
 Example

Calculate the approximate wavenumber and wavelength of the fundamental absorption

peak due to the stretching vibration of a carbonyl group C=O

k The mass of the carbon atom in kg is given by

12
n  5.3x 10
 12 x 10  3 kg / mol
M1  x 1 atom
23
6.02 x 10 atoms / mol
M1M 2
   2.0x 10  26 kg
M1  M 2

26 26 Similar, for oxygen

2.0 x10 kg x 2.7 x10 kg
 (16 x 10  3 )
(2.0  2.7) x10  26 kg M2   2.7x 10  26 kg
(6.02 x 10 23 )
 1.1x10  26 kg
The force constant for the typical double
bond is about 1x103 N/cm. Substituting
12 1x 10 3 N / cm this value and  into eq. (5) gives
n  5.3x 10 s / cm
1.1x 10  26 kg
 1.6x 10 3 cm 1

The carbonyl stretching band is found experimentally to be in the region of 1600 to 1800 cm -1
(6.3 to 5.6 m)
 Infrared Spectroscopy
IR Absorptions
• Bonds absorb in four predictable regions of an IR spectrum.

19
 Infrared Spectroscopy
IR Absorptions

20
 Infrared Spectroscopy
IR Absorptions

21
 Regions of Frequencies
Spectral Region Frequency(Hz) Wavenumber(cm-1) Wavelength (l,m)
Near -to 3.8 x 1014 to 1.2 12800 to 4000 0.78 to 2.5
visible- IR x 1014
(NIR)
Combination
bands
Mid Infrared 1.2 x 1014 to 6.0 4000 to 200 2.5 to 50
Fundmental x 1012
bands for
organic
molecules
Far IR 6.0 x 1012 to 3.0 200 to 10 50 to 1000
Inorganics x 1011
organometallics

After Table 16-1 of Skoog and West, et al. (Chapter 16)

23
Infrared Spectroscopy

D. The IR Spectrum
1. Each stretching and bending vibration occurs with a characteristic frequency as
the atoms and charges involved are different for different bonds

The y-axis on an IR In regions where

spectrum is in units of % no osc. bond is
transmittance interacting with IR
light, transmittance
nears 100%
In regions where the EM
field of an osc. bond
interacts with IR light of
the same n –
transmittance is low (light
is absorbed)
IR Spectroscopy

D. The IR Spectrum
3. This unit is used rather than wavelength (microns) because wavenumbers are
directly proportional to the energy of transition being observed –
chemists like this, physicists hate it

High frequencies and high wavenumbers equate higher energy

is quicker to understand than
Short wavelengths equate higher energy

4. This unit is used rather than frequency as the numbers are more “real” than the
exponential units of frequency

5. IR spectra are observed for what is called the mid-infrared: 400-4000 cm-1

6. The peaks are Gaussian distributions of the average energy of a transition

Infrared Spectroscopy

E. The IR Spectrum – The detection of different bonds

7. As opposed to chromatography or other spectroscopic methods, the
area of a IR band (or peak) is not directly proportional to concentration
of the functional group producing the peak

8. The intensity of an IR band is affected by two primary factors:

Whether the vibration is one of stretching or bending

Electronegativity difference of the atoms involved in the bond

• For both effects, the greater the change in dipole moment in a

given vibration or bend, the larger the peak.

• The greater the difference in electronegativity between the atoms

involved in bonding, the larger the dipole moment

• Typically, stretching will change dipole moment more than

bending
Infrared Spectroscopy

E. The IR Spectrum – The detection of different bonds

9. It is important to make note of peak intensities to show the effect of
these factors:

• Strong (s) – peak is tall, transmittance is low (0-35 %)

• Medium (m) – peak is mid-height (75-35%)

• Weak (w) – peak is short, transmittance is high (90-75%)

• * Broad (br) – if the Gaussian distribution is abnormally broad

(*this is more for describing a bond that spans many energies)

Exact transmittance values are rarely recorded

Infrared Spectroscopy

II. Infrared Group Analysis

A. General
1. The primary use of the IR spectrometer is to detect functional
groups

2. Because the IR looks at the interaction of the EM spectrum with actual

bonds, it provides a unique qualitative probe into the functionality of a
molecule, as functional groups are merely different configurations of
different types of bonds

3. Since most “types” of bonds in covalent molecules have roughly the

same energy, i.e., C=C and C=O bonds, C-H and N-H bonds they
show up in similar regions of the IR spectrum

4. Remember all organic functional groups are made of multiple bonds

and therefore show up as multiple IR bands (peaks)
Infrared Spectroscopy

II. Infrared Group Analysis

A. General
5. The four primary regions of the IR spectrum

Bonds to H Triple bonds Double bonds Single Bonds

O-H single bond C≡C C=O C-C

N-H single bond C≡N C=N C-N
C-H single bond C=C C-O

Fingerprint
Region

4000 cm-1 2700 cm-1 2000 cm-1 1600 cm-1 400 cm-1
Infrared Spectroscopy

Specific groups
1. Alkanes – combination of C-C and C-H bonds
• Show various C-C stretches and bends between 1360-1470 cm-1 (m)
• C-C bond between methylene carbons (CH2’s) 1450-1470 cm-1 (m)
• C-C bond between methylene carbons (CH2’s) and methyl (CH3)
1360-1390 cm-1 (m)
• Show sp3 C-H between 2800-3000 cm-1 (s) cm -1

Octane
Infrared Spectroscopy

Specific groups
2. Alkenes – addition of the C=C and vinyl C-H bonds
• C=C stretch occurs at 1620-1680 cm-1 and becomes weaker as substitution
increases
• vinyl C-H stretch occurs at 3000-3100 cm-1
• Note that the bonds of alkane are still present!
• The difference between alkane and alkene or alkynyl C-H is important! If the
band is slightly above 3000 it is vinyl sp2 C-H or alkynyl sp C-H if it is below it
is alkyl sp3 C-H

1-Octene
Infrared Spectroscopy

Specific groups
3. Alkynes – addition of the C=C and vinyl C-H bonds
• C≡C stretch occurs between 2100-2260 cm-1; the strength of this band
depends on asymmetry of bond, strongest for terminal alkynes, weakest for
symmetrical internal alkynes (w-m)
• C-H for terminal alkynes occurs at 3200-3300 cm-1 (s)
• Remember internal alkynes ( R-C≡C-R ) would not have this band!

1-Octyne
Infrared Spectroscopy

Specific groups
4. Aromatics
• Due to the delocalization of electrons in the ring, where the bond order
between carbons is 1 ½, the stretching frequency for these bonds is slightly
lower in energy than normal C=C
• These bonds show up as a pair of sharp bands, 1500 (s) & 1600 cm -1 (m),
where the lower frequency band is stronger
• C-H bonds off the ring show up similar to vinyl C-H at 3000-3100 cm-1 (m)

Ethyl benzene
Infrared Spectroscopy

Specific groups
4. Aromatics
• If the region between 1667-2000 cm-1 (w) is free of interference (C=O
stretching frequency is in this region) a weak grouping of peaks is observed
for aromatic systems
• Analysis of this region, called the overtone of bending region, can lead to a
determination of the substitution pattern on the aromatic ring

Monosubstituted
G
G
1,2 disubstituted (ortho or o-)

G 1,2 disubstituted (meta or m-)

G

1,4 disubstituted (para or p-)

G
Infrared Spectroscopy

Specific groups
5. Unsaturated Systems – substitution patterns
• The substitution of aromatics and alkenes can also be discerned through
the out-of-plane bending vibration region
• However, other peaks often are apparent in this region. These peaks
should only be used for reinforcement of what is known or for
hypothesizing as to the functional pattern.
cm-1 cm-1
R
985-997 730-770
C CH2 905-915 R
690-710
H

R H
C C 960-980 R 735-770
H R
R
R R
C C 665-730 860-900
H H R 750-810
680-725
R
R
C CH2 885-895
R
R R 800-860
R R
C C 790-840
R H
Infrared Spectroscopy

Specific groups
6. Ethers – addition of the C-O-C asymmetric band and vinyl C-H bonds
• Show a strong band for the antisymmetric C-O-C stretch at 1050-1150 cm-1

• Otherwise, dominated by the hydrocarbon component of the rest of the

molecule

Diisopropyl ether

O
Infrared Spectroscopy

Specific groups
7. Alcohols
• Show a strong, broad band for the O-H stretch from 3200-3400 cm-1 (s, br)
this is one of the most recognizable IR bands
• Like ethers, show a band for C-O stretch between 1050-1260 cm-1 (s)
• This band changes position depending on the substitution of the alcohol: 1°
1075-1000; 2° 1075-1150; 3° 1100-1200; phenol 1180-1260
• The shape is due to the presence of hydrogen bonding

1-butanol

HO
Infrared Spectroscopy

Specific groups
8. Amines - Primary
• Shows the –N-H stretch for NH2 as a doublet between 3200-3500 cm-1 (s-m);
symmetric and anti-symmetric modes
• -NH2 group shows a deformation band from 1590-1650 cm-1 (w)
• Additionally there is a “wag” band at 780-820 cm-1 that is not diagnostic

2-aminopentane

H2N
Infrared Spectroscopy

Specific groups
9. Amines – Secondary
• -N-H band for R2N-H occurs at 3200-3500 cm-1 (br, m) as a single sharp
peak weaker than –O-H
• Tertiary amines (R3N) have no N-H bond and will not have a band in this
region

pyrrolidine

NH
Infrared Spectroscopy

Specific groups
10. Aldehydes
• Show the C=O (carbonyl) stretch from 1720-1740 cm-1(s)
• Band is sensitive to conjugation, as are all carbonyls (upcoming slide)
• Also displays a highly unique sp2 C-H stretch as a doublet, 2720 & 2820 cm -1
(w) called a “Fermi doublet”

Cyclohexyl carboxaldehyde
O

H
Infrared Spectroscopy

Specific groups
11. Ketones
• Simplest of the carbonyl compounds as far as IR spectrum – carbonyl only
• C=O stretch occurs at 1705-1725 cm-1 (s)

3-methyl-2-pentanone
O
Infrared Spectroscopy

Specific groups
12. Esters
1. C=O stretch occurs at 1735-1750 cm-1 (s)
2. Also displays a strong band for C-O at a higher frequency than ethers or
alcohols at 1150-1250 cm-1 (s)

Ethyl pivalate
O

O
Infrared Spectroscopy

Specific groups
13. Carboxylic Acids:
• Gives the messiest of IR spectra
• C=O band occurs between 1700-1725 cm-1
• The highly dissociated O-H bond has a broad band from 2400-3500 cm-1 (m,
br) covering up to half the IR spectrum in some cases

4-phenylbutyric acid
O

OH
Infrared Spectroscopy

B. Specific groups
14. Acid anhydrides
• Coupling of the anhydride though the ether oxygen splits the carbonyl band
into two with a separation of 70 cm -1.
• Bands are at 1740-1770 cm-1 and 1810-1840 cm-1 (s)
• Mixed mode C-O stretch at 1000-1100 cm-1 (s)

Propionic anhydride
O O

O
Infrared Spectroscopy

Specific groups
15. Acid halides
• Dominant band at 1770-1820 cm-1 for C=O (s)
• Bonds to halogens, due to their size (see Hooke’s Law derivation) occur at
low frequencies, where their presence should be used to reinforce rather
than be used for diagnosis, C-Cl is at 600-800 cm-1 (m)

Propionyl chloride
O

Cl
Infrared Spectroscopy

Specific groups
16. Amides
• Display features of amines and carbonyl compounds
• C=O stretch occurs from 1640-1680 cm-1
• If the amide is primary (-NH2) the N-H stretch occurs from 3200-3500 cm-1
as a doublet
• If the amide is secondary (-NHR) the N-H stretch occurs at 3200-3500 cm-1
as a sharp singlet

pivalamide
O

NH2
Infrared Spectroscopy

Specific groups
17. Nitro group (-NO2)
• Proper Lewis structure gives a bond order of 1.5 from nitrogen to each oxygen
• Two bands are seen (symmetric and asymmetric) at 1300-1380 cm-1 (m-s)
and 1500-1570 cm-1 (m-s)
• This group is a strong resonance withdrawing group and is itself vulnerable to
resonance effects

2-nitropropane
O
O
N
Infrared Spectroscopy

Specific groups – Hydrocarbons

18. Nitriles (the cyano- or –C≡N group)
• Principle group is the carbon nitrogen triple bond at 2100-2280 cm-1 (s)
• This peak is usually much more intense than that of the alkyne due to the
electronegativity difference between carbon and nitrogen

propionitrile
N
C
Infrared Spectroscopy

Effects on IR bands
1. Conjugation – by resonance, conjugation lowers the energy of a double or triple
bond. The effect of this is readily observed in the IR spectrum:
O
O

1684 cm -1 1715 cm -1
C=O C=O

• Conjugation will lower the observed IR band for a carbonyl from 20-40 cm-1
provided conjugation gives a strong resonance contributor
O
C X X= NH 2 CH 3 Cl NO 2
H3C
1677 1687 1692 1700 cm-1

O O
O
N C
H 2N C CH 3 vs.
CH3
O

Strong resonance contributor Poor resonance contributor

(cannot resonate with C=O)
• Inductive effects are usually small, unless coupled with a resonance
contributor (note –CH3 and –Cl above)
Infrared Spectroscopy

Effects on IR bands
1. Steric effects – usually not important in IR spectroscopy, unless they reduce the
strength of a bond (usually p) by interfering with proper orbital overlap:
O O

CH 3
C=O: 1686 cm-1 C=O: 1693 cm-1

• Here the methyl group in the structure at the right causes the carbonyl
group to be slightly out of plane, interfering with resonance

2. Strain effects – changes in bond angle forced by the constraints of a ring will
cause a slight change in hybridization, and therefore, bond strength

O O O
O O

1815 cm-1 1775 cm-1 1750 cm-1 1715 cm-1 1705 cm-1

• As bond angle decreases, carbon becomes more electronegative, as well

as less sp2 hybridized (bond angle < 120°)
Infrared Spectroscopy

Effects on IR bands
1. Hydrogen bonding
• Hydrogen bonding causes a broadening in the band due to the creation of
a continuum of bond energies associated with it
• In the solution phase these effects are readily apparent; in the gas phase
where these effects disappear or in lieu of steric effects, the band appears
as sharp as all other IR bands:

Gas phase spectrum of

1-butanol

Steric hindrance to H-bonding

in a di-tert-butylphenol
OH

• H-bonding can interact with other functional groups to lower frequencies

H
O O

C=O; 1701 cm-1

 A Functional Group Chart
4000 3600 3200 2800 2400 2000 1600 1200 800 group
O-H str

NH str
COO-H
=C-H str
Csp3-H
C-H
-(C=O)-H

CN
CC
C=O
-C=N
-C=C
phenyl
C-O
C-N
F Cl C-X I
Br
http://sdbs.db.aist.go.jp/sdbs/cgi-bin/direct_frame_top.cgi
MID-INFRARED ABSORPTION SPECTROMETRY
Sample Handling
No good solvents exist that are transparent
throughout the region of interest. As a
consequence, sample handling is frequently the
most difficult and time-consuming part of an
infrared spectrometric analysis.
Gases: The spectrum of a low-boiling liquid or
gas can be obtained by permitting the sample to
expand into an evacuated cylindrical cell
equipped with suitable windows.
 Sample Handling
Solutions: A convenient way of obtaining
infrared spectra is on solutions prepared to
contain a known concentration of sample. This
technique is somewhat limited in its applications,
however, by the availability of solvents that are
transparent over significant regions in the
infrared.
Solvents: No single solvents is transparent
throughout the entire mid-infrared region. Water
and alcohols are seldom employed, not only
because they absorb strongly, but also because
they attack alkali-metal halides, the most
common materials used for cell windows.
 Sample Handling
Cells: Sodium chloride windows are most commonly
employed; even with care, however, their surfaces
eventually become fogged due to absorption of
moisture. Polishing with a buffing powder returns them
to their original condition.
Liquids: When the amount of liquid sample is small or
when a suitable solvent is unavailable, it is common
practice to obtain spectra on the pure (neat) liquid. A
drop of the neat liquid is squeezed between two rock-
salt plated to give a layer that has a thickness of 0.01
mm or less. The two plates, held together are then
mounted in the beam path. Such a technique does not
give reproducible transmittance data, but the resulting
spectra are usually satisfactory for qualitative
investigations.
 Sample Handling
Solids: Most organic compounds exhibit numerous
absorption peaks throughout the mid-infrared region,
and finding a solvent that does not have overlapping
peaks is often impossible. As a consequence, spectra are
often obtained on dispersions of the solid in a liquid or
solid matrix.
Pelleting: One of the most popular techniques for
handling solid samples has been KBr pelleting. A
milligram or less of the finely ground sample is
intimately mixed with about 100 mg of dried potassium
bromide powder. The mixture is then pressed in a die at
10,000 to 15,000 pounds per square inch to yield a
transparent disk. The disk is then held in the instrument
beam for spectroscopic examination.
 Sample Handling

Mulls: Infrared spectra of solids that are not

soluble in an infrared-transparent solvent or are
not conveniently pelleted in KBr are often
obtained by dispersing the analyte in a mineral
oil or fluorinated hydrocarbon mull. Mulls are
formed by grinding 2 to 5 mg of the finely
powdered sample in the presence of one or two
drops of a heavy hydrocarbon oil (Nujol). If
hydrocarbon bands interfere, Fluorolube, a
halogenated polymer, can be used. The
resulting mull is then examined as a film
between flat salt plates.
Empirical Formula C3H6O
Empirical Formula C9H10O
MW 56