INFRARED SPECTROSCOPY

(IR)
Theory and Interpretation of
IR spectra
ORGANIC STRUCTURE DETERMINATION

How do we know:
• how atoms are connected together?
• Which bonds are single, double, or triple?
• What functional groups exist in the
molecule?
• If we have a specific stereoisomer?
The field of organic structure determination attempts
to answer these questions.
 INSTRUMENTAL METHODS OF
STRUCTURE DETERMINATION
1. Nuclear Magnetic Resonance (NMR) – Excitation of the nucleus of
atoms through radiofrequency irradiation. Provides extensive
information about molecular structure and atom connectivity.
2. Infrared Spectroscopy (IR) – Triggering molecular vibrations
through irradiation with infrared light. Provides mostly information
about the presence or absence of certain functional groups.
3. Mass spectrometry – Bombardment of the sample with electrons
and detection of resulting molecular fragments. Provides information
about molecular mass and atom connectivity.
4. Ultraviolet spectroscopy (UV) – Promotion of electrons to higher
energy levels through irradiation of the molecule with ultraviolet light.
Provides mostly information about the presence of conjugated p
systems and the presence of double and triple bonds.
 ELECTROMAGNETIC SPECTRUM
Most organic spectroscopy uses electromagnetic energy, or radiation,
as the physical stimulus.

Electromagnetic energy (such as visible light) has no detectable mass

component. In other words, it can be referred to as “pure energy.”

Other types of radiation such as alpha rays, which consist of helium

nuclei, have a detectable mass component and therefore cannot be
categorized as electromagnetic energy.
EFFECT OF ELECTROMAGNETIC RADIATION ON MOLECULES
Nu bar
 Problems
a. Which is higher in energy, electromagnetic radiation with wavenumber 100
cm-1 or with wavenumber 2000 cm-1 ?

b. Which is higher in energy, electromagnetic radiation with wavelength 9 μm or

with wavelength 8 μm?

c. Which is higher in energy, electromagnetic radiation with wavenumber 2000

cm-1 or with wavelength 2 μm?

Answer
a. 200 cm-1 (the larger wavenumber, the higher the energy).

b. 8 μm (The shorter wavelength, the higher the energy).

c. 2 μm, because 2 μm = 5000 cm-1(5000 cm-1 wavenumber is higher than

2000 cm-1)
 Infrared radiation is largely thermal energy.
It induces stronger molecular vibrations in covalent bonds, which can
be viewed as springs holding together two masses, or atoms.

Specific bonds respond to (absorb) specific frequencies

Graphics source: Wade, Jr., L.G. Organic Chemistry, 5th ed. Pearson Education Inc., 2003
 VIBRATIONAL MODES
• Covalent bonds can vibrate in several modes, including stretching,
rocking, and scissoring.
• The most useful bands in an infrared spectrum correspond to
stretching frequencies, and those will be the ones we’ll focus on.

Graphics source: Wade, Jr., L.G. Organic Chemistry, 5th ed. Pearson Education Inc., 2003
 TRANSMISSION vs. ABSORPTION
When a chemical sample is exposed to the action of IR LIGHT, it can
absorb some frequencies and transmit the rest. Some of the light can
also be reflected back to the source.

Transmitted light
IR Chemical
Detector
source sample

From all the frequencies it receives, the chemical sample

can absorb (retain) specific frequencies and allow the
rest to pass through it (transmitted light).

The detector detects the transmitted frequencies, and by doing so also reveals the
values of the absorbed frequencies.
 AN IR SPECTRUM IN ABSORPTION MODE
The IR spectrum is basically a plot of transmitted (or absorbed) frequencies
vs. intensity of the transmission (or absorption). Frequencies appear in the
x-axis in units of inverse centimeters (wavenumbers), and intensities are
plotted on the y-axis in percentage units.

The graph above shows a spectrum in absorption mode.

 AN IR SPECTRUM IN TRANSMISSION MODE

The graph above shows a spectrum in transmission mode.

This is the most commonly used representation and the one found in most
chemistry and spectroscopy books. Therefore we will use this representation.
 Obtaining an Ifrared Spectrum
• The instrumental used to obtained an infrared spectrum is
called an IR Spectrometer.
• Infrared spectrum is obtained by passing infrared radiation
through a sample of the compound.
• Detector generate a plot of percent transmission of radiation
versus the wavenumber.
• At 100 % transmission, all the energy of the radiation passes
through the molecule.
• Lower values of percent transmission mean that some of the
energy is absorbed by the compound.
• Each spike in the IR spectrum represent absorption of energy
• The spike are called absorption bands.
• Steretching and bending vibration of organic molecules have
energy with wavenumber from 4000 to 600 cm-1.
An IR spectrum can be divided into two areas
 Functional group region: is the left-hand of an IR spectrum
4000-1400 cm-1.
 Fingerprint region: is the right-hand third of the IR
spectrum 1400-600 cm-1. it is characteristic compound as a
whole.
 THE FINGERPRINT REGION
Although the entire IR spectrum can be used as a fingerprint for the purposes of
comparing molecules, the 600 - 1400 cm-1 range is called the fingerprint region.
This is normally a complex area showing many bands, frequently overlapping each
other. This complexity limits its use to that of a fingerprint, and should be ignored by
beginners when analyzing the spectrum. As a student, you should focus your
analysis on the rest of the spectrum, that is the region to the left of 1400 cm-1.

Focus your analysis on this region. This is where most stretching Fingerprint region: complex and difficult to
frequencies appear. interpret reliably.

Graphics source: Wade, Jr., L.G. Organic Chemistry, 6th ed. Pearson Prentice Hall Inc., 2006
Two different molecules may have similar functional group
regions because they have similar functional groups, but they will
always have a different fingerprint region. we will only focus on
the functional group region when identifying the structures of
molecules. This is because the fingerprint region, which extends
from about 1450 cm-1 to 400 cm-1 , is very complex. It has many
absorptions and makes it quite difficult for students and scientists
to make precise bond assignments. Because, it takes more
energyto stretch a bond than to bend it, absorption bands for
stretching are found in the functional group region wherease
absorption bands for bending vibration are found in the fingerprint
region.

Therefore, stretching vibration are the most useful vibration in

determination what kinds of bonds a molecule has. Thus, we tend
to ignore bending.
• 2-pentanol and 3-pentanol have the same funcitional groups, so
they show similar absorption band in the functional group region.
Their fingerprint regions are different.
 CLASSIFICATION OF IR BANDS
IR bands can be classified as strong (s), medium (m), or weak (w),
depending on their relative intensities in the infrared spectrum. A strong
band covers most of the y-axis. A medium band falls to about half of the
y-axis, and a weak band falls to about one third or less of the y-axis.
 INFRARED ACTIVE BONDS
Not all covalent bonds display bands in the IR spectrum. Only polar
bonds do so. These are referred to as IR active.
The intensity of the bands depends on the magnitude of the dipole
moment associated with the bond in question:
• Strongly polar bonds such as carbonyl groups (C=O) produce strong
bands.
• Medium polarity bonds and asymmetric bonds produce medium
bands.
• Weakly polar bond and symmetric bonds produce weak or non
observable bands.
INFORMATION OBTAINED FROM IR SPECTRA

• IR is most useful in providing information about the presence or

absence of specific functional groups.

• IR can provide a molecular fingerprint that can be used when

comparing samples. If two pure samples display the same IR
spectrum it can be argued that they are the same compound.

• IR does not provide detailed information or proof of molecular

formula or structure. It provides information on molecular fragments,
specifically functional groups.

• Therefore it is very limited in scope, and must be used in conjunction

with other techniques to provide a more complete picture of the
molecular structure.
FUNCTIONAL GROUPS AND IR TABLES
The remainder of this presentation will be focused on the IR
identification of various functional groups such as alkenes, alcohols,
ketones, carboxylic acids, etc. Basic knowledge of the structures and
polarities of these groups is assumed. If you need a refresher please
turn to your organic chemistry textbook. The inside cover of the Wade
textbook has a table of functional groups, and they are discussed in
detail in ch. 2, pages 68 – 74 of the 6th edition.

A table relating IR frequencies to specific covalent bonds can be

found on p. 851 of your laboratory textbook. Pages 852 – 866 contain
a more detailed discussion of each type of bond, much like the
discussion in this presentation.
 IR ABSORPTION RANGE
The typical IR absorption range for covalent bonds is 600 - 4000 cm-1. The graph
shows the regions of the spectrum where the following types of bonds normally
absorb. For example a sharp band around 2200-2400 cm-1 would indicate the
possible presence of a C≡N or a C ≡ C triple bond.

Graphics source: Wade, Jr., L.G. Organic Chemistry, 5th ed. Pearson Education Inc., 2003
 INFRARED BAND SHAPES
Infrared band shapes come in various forms. Two of the most common
are narrow and broad. Narrow bands are thin and pointed, like a
dagger. Broad bands are wide and smoother.

A typical example of a broad band is that displayed by O-H bonds, such

as those found in alcohols and carboxylic acids, as shown below.
Factors affecting vibrational frequencies in IR
The position of absorption pand
• The smaller atoms give bonds that vibrate at
higher frequencies, thereby corresponding to a
higher wavenumber of absorption. For example,
compare the following bonds. The C-H bond
involves the smallest atom (H) and therefore
appears at the highest wavenumber.
Effect of bond order
 Electronic effects on vibration frequencies
Whenever we discuss about the IR band, a range of frequency for each stretch is
usually assigned as the exact position of the absorption band depends on other
structural features of the molecule, such as electron delocalization, the electronic
effect of neighbouring substituents, and hydrogen bonding. Important details about
the structure of a compound can be revealed by the exact position of the absorption
band. For example, the IR bands for the carbonyl group in 2-pentanone, 2-
cyclohexenone appears at different frequencies. The 2-Cyclohexenone absorbs at a
lower frequency because the carbonyl group has less double-bond character due to
electrondelocalization. If you put an atom other than hydrogen (aldehyde) or carbon
(ketone) next to the carbonyl group, it also causes the shifting of the position of the
carbonyl absorption band. Whether it shifts to a lower or to a higher frequency
depends on the electronic effect (inductive and mesomeric effect) of the atom.
Different substituents on carbonyl carbon changes
the electronegativity of carbonyl group due to the
inductive effect arises due to the different
electronegativities of the carbonyl carbon and of the
substituent in compounds of the type RCOZ. It
involves the electrons in the sigma bonds.
The mesomeric effect involves the electrons in
the pie and nonbonding orbitals and it operates
in general opposite to the inductive effect. These
effects cannot be isolated from one another and
at a time only one of them can be applied to
determine approximate results.
• Aldehydes are typically more reactive than ketones because the carbonyl carbon in
aldehydes generally has more partial positive charge than in ketones due to the
electron-donating nature of alkyl groups. Aldehydes only have one e- donor group
while ketones have two. Electron-withdrawing groups lead to a C=O stretch at larger
wavenumbers, whereas electron-donating groups have the opposite effect.
If we talk about the C-O stretching frequency it appears in the range of 1250-
1050 cm-1. If C-O bond is in an alcohol or in ether, the stretching frequency
will be toward the lower end of the range. If this C-O bond is a part of a
carboxylic group, the stretching frequency will occur at the higher end of the
range. The position of the absorption varies because the bond in an alcohol is a
pure single bond, whereas the bond in a carboxylic acid has partial double bond
character that is due to resonance electron donation by OH group in acids.
Esters show stretches at both ends of the range because esters have two single
bonds, one that is a pure single bond and one that has partial double-bond
character.
The predominant effect of the nitrogen of an amide is electron donation by
resonance. Therefore, the carbonyl group of an amide has less double bond
character than the carbonyl group of a ketone and hence amide has low C=O
bond IR frequency than the ketone. In contrast, the predominant effect of the
oxygen of an ester is inductive electron withdrawal, therefore the carbonyl
group of an ester has more double bond character than the carbonyl group of a
ketone, so the former appears at larger frequency value.