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Most compounds with covalent bonds absorb different frequencies of electromagnetic
radiation in the infrared (IR) region of the electromagnetic spectrum. The wavelength range of
IR radiation varies from 0.8 m to 1000 m (or 800 nm – 1.00 mm). The IR spectrum can be
divided into three groups: Near IR (0.8 – 2.5 m), Middle IR (2.5 – 50 m), and Far IR (50 –
1,000 m).
The middle infrared range (2.5 – 40 m) of electromagnetic (EM) radiation is used in IR
spectroscopy because its frequency has enough energy to cause a change in the vibration
motion of covalent compounds. This range is sometimes referred to as vibrational EM
radiation.
In IR spectroscopy,
wavelength of EM radiation is not expressed in nm or µm, rather it expresses as the number
of wave per centimetre. And denoted as cm-1 (“reciprocal centimeter” or “centimeter to the
power minus one”), which is also known as "wavenumbers" or “number of waves per
centimeter”. It is the reciprocal of wavelength in cm scale.
Chemists prefer to use wavenumbers instead of nm of µm as the unit of wavelength in IR
spectroscopy, because they are directly proportional to energy of the EM radiation (higher
wavenumbers correspond to higher energy).
Conversion of wavelength to wave number (Mid IR range 2.5 m ~ 40 m)
• 1 m = 10-4 cm = 10-6 m
2.5 m = 2.5 x 10-4 cm = 0.00025 cm,
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• reciprocal of this wavelength is 0.00025 𝑐𝑚
= 4,000 cm-1 (wavenumbers)
40 m = 50 x 10-4 cm = 0.004 cm,
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• reciprocal of this wavelength is 0.004 𝑐𝑚
= 400 cm-1 (wavenumbers)
Therefore, Mid IR range now 4,000 cm-1 ~ 400 cm-1 in wavenumbers
The Infrared Absorption Process
For the purposes of explaining infrared spectroscopy, a molecule is viewed as being joined
by bonds which behave like springs.
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In IR absorption, energy is transferred from the incident radiation to the molecule, and a
quantum mechanical transition occurs between two vibrational energy levels, from E1 to E2 .
The difference in energy between the two vibrational energy levels (E) is related directly to
the frequency of the electromagnetic radiation (). i.e.
E = E2 – E1 or, E = h, where h is Planck’s constant (6.624 x 10-34J.s)
The most important transitions are from the ground state (V0) to the first excited levels (V1).
These allowed transitions are known as fundamentals. They usually give rise to strong
absorption bands in the infrared spectrum.
A transition from the ground state V0 to a level V2 is known as an overtone.
A transition from the ground state (V0) to a level for which vibrational quantum numbers are
Vi and Vj (where Vi = V1 and Vj=V1 and i and j are two different vibrations) is known as a
combination. This peak arises when two or more vibrations of a molecule are excited
simultaneously.
Overtones and combinations are forbidden by the simple harmonic oscillator theory of
molecular vibrations, but they become weakly allowed when anharmonicity is taken into
account. Many weak absorptions in an IR spectrum can be attributed to overtones or
combinations.
If the simple molecule HCl is examined in the gas phase, it can be seen that it has an
absorbance maximum at ca 2,900 cm-1, which results from the transition between the bottom
vibrational state V0 and the first excited state V1 (i.e. energy associate with wave of 2,900 cm-
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= E = EV1–EV0, where, EV1 = energy associate with V1 and EV0 = energy associate with V0 energy
level).
In order for the electrical component in electromagnetic radiation to interact with a bond, the
bond must have a dipole. Thus, symmetrical bonds, such as those in O 2 or N2, do not absorb
infrared radiation. However, the majority of organic molecules have plenty of asymmetry. Even
in small organic molecules the modes of vibration are complex.
The Infrared Absorption Process
Molecular Vibrations and its types:
Any slight change in the shape of a covalent molecule caused by the bending, stretching, or
internal rotation of bonds around a single bond is known as molecular vibration.
In order for the electrical component in electromagnetic radiation to interact with a bond, the
covalent bond must be polar (i.e. must have a dipole moment).
• Non-polar or symmetrical covalent bonds, such as those in O2 or N2, do not absorb
infrared radiation.
The majority of organic molecules have plenty of asymmetry, which gives rise to the polarity
of the bonds. Even in small organic molecules, the modes of vibration are complex.
When the waves of EMR interact with matter, they change the appearance of bending and/or
stretching vibrations.
Types of various vibration modes in methylene ( ) residue of a covalent
compound can be classified as follows:
1. Stretching vibration
2. Bending vibration
1. Stretching:
The vibration along the line of bond is known as stretching vibrations. These vibrations
occur in a radial direction and change bond length either by increasing or decreasing it.
Such vibrations require higher energy and appear at shorter wavelengths or higher
wavenumber (4000–1250 cm1). Stretching vibrations are of two types:
a) Symmetric stretching:
b) Asymmetric stretching:
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a) Symmetric stretching:
When the interatomic distance between the two bonds in a molecule
increases or decreases simultaneously, that is called symmetric
stretching.
b) Asymmetric stretching:
When the interatomic distance or bond length of one bond increases
and the length of another bond decreases simultaneously, this is
called asymmetric stretching.
2. Bending vibration: This is a type of vibrational motion where the bond angle between
two atoms changes, but the bond lengths remain constant.
Bending vibrations can be classified into two categories:
1. In-plane bending vibrations: The movement occurs within the plane of the
molecule.
2. Out-of-plane bending vibrations: The movement occurs perpendicular to the plane
of the molecule.
These vibrations require less energy, so they easily happen at lower wavenumbers.
In-plane bending: These are of the following two types:
a. Scissoring Vibration
Scissoring vibration happens when two
atoms approach each other. The bond
angles are decreased in this type of
vibration
b. Rocking Vibration
Rocking vibration occurs when atoms move in the same direction without changing
the relative bond angle of two bonds.
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Out-of-plane bending: These are of the following two types:
a. Wagging Vibration
Wagging vibration happens when two atoms
move toward the same side of the
plane. They move either up or down the
plane.
b. Twisting Vibration
Twisting vibration happens when two atoms
move to opposite sides of a plane. One atom moves up from the plane, and
the second moves down from the plane.
Summery:
Calculation of Stretching Frequencies using Hooke’s Law:
A diatomic molecule can be considered as two vibrating masses connected by a
spring. The bond distance continually changes, but equilibrium or average bond
distance can be defined. Whenever spring is stretched or compressed beyond this
equilibrium distance, the potential energy of the system increases.
The natural frequency of vibration of a bond is given by the following equation which
is derived from Hooke’s Law for vibrating springs:
Here,
ν = wavenumber in cm-1
c = velocity of light = 3×1010 cm/s
K = force constant (which reflects the stiffness of the spring)
μ = Reduced mass of the two atoms (The reduced mass is a way of simplifying the
two-body problem by treating the system as a single object.)
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where masses of atoms in grams.
This equation can be simplified as follows to determine the stretching wavenumber
of any covalent bonds.
Calculation of Stretching Frequencies of carbon-carbon double bond (C=C)
Calculation of Stretching Frequencies of an aliphatic carbon-hydrogen bond (C-H)
Calculation of Stretching Frequencies of carbon-deuterium bond (C-D)
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Factors affecting the vibrational frequencies
1. Stronger bonds have a larger force constant, K , and vibrate and absorbs at higher
wavenumbers (frequencies) than weaker bonds
2. Bonds between atoms of higher masses (larger reduced mass, µ) vibrate and absorbs at
lower wavenumbers (frequencies) than bonds between lighter atoms.
Triple bonds are stronger than double or single bonds between the same two atoms and
have higher frequencies of vibration (higher wavenumbers):
The C-H stretch occurs at about 3000 cm-1. As the atom bonded to carbon increases in
mass, the reduced mass (m) increases, and the frequency of vibration decreases
(wavenumbers get smaller):
Hybridization also affects the force constant K. Bonds are stronger in the order sp > sp2 >
sp3.
Resonance has the effect of reducing the force constant K, and the absorption moves to a
lower frequency
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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.
IR bands can be classified or described as
IR bands can be classified or described as
1. Broad U shape peak
2. Sharp spike peaks
3. V-shape peak
4. W shape peak
5. Shoulder peak
INFRARED ACTIVE BONDS
IR ABSORPTION RANGE
The typical IR absorption range for covalent bonds is 400 - 4000 cm-1. The following graphs
show the regions of the spectrum where the following types of bonds normally absorb.
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THE FINGERPRINT REGION
Although the entire IR spectrum can be used as a fingerprint to compare molecules, but the
600 - 1400 cm-1 range is called the fingerprint region.
This is normally a complex area showing many bands, frequently overlapping with each
other. This complexity limits its use to that of a fingerprint and should be ignored by
beginners when analyzing the spectrum.
Diethyl succinate and ethylene glycol dipropionate have similar functional groups. So, their
wavenumbers of stretching absorption are similar, even though they are two different
compounds. However, their spectra in the fingerprint region are different.
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IR SPECTRUM OF ALKANES
Alkanes have no functional groups. Their IR spectrum displays only C-C and C-H bond
vibrations. The most useful of these are the C-H bands, which appear around 3000 cm-1.
Note: Since most organic molecules have such bonds, most organic molecules will display
those bands in their spectrum.
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IR SPECTRUM OF ALKENES
In addition to the presence of C-H bonds, alkenes show sharp, medium bands corresponding
to the C=C bond stretching vibration at about 1600-1700 cm-1. Some alkenes might also
show a band for the =C-H bond stretch, appearing around 3080 cm-1 as shown below.
IR SPECTRUM OF ALKYNES
The most prominent band in alkynes corresponds to the carbon-carbon triple bond. It shows
as a sharp, weak band at about 2100 cm-1. The reason it’s weak is because the triple bond is
not very polar. In some cases, such as in highly symmetrical alkynes, it may not show at all
due to the low polarity of the triple bond associated with those alkynes. Terminal alkynes have
C-H bonds involving the sp carbon (the carbon that forms part of the triple bond). Therefore,
they may also show a sharp, weak band at about 3300 cm-1 corresponding to the C-H stretch.
Internal alkynes, that is those where the triple bond is in the middle of a carbon chain, do not
have C-H bonds to the sp carbon and therefore lack the aforementioned band.
The following slide compares an unsymmetrical terminal alkyne (1-octyne) to a symmetrical
internal alkyne (4-octyne).
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IR SPECTRUM OF A NITRILE
In a manner very similar to alkynes, nitriles show a prominent band around 2250 cm -1 caused
by the CN triple bond. This band has a sharp, pointed shape just like the alkyne C-C triple
bond, but because the CN triple bond is more polar, this band is stronger than in alkynes.
IR SPECTRUM OF ALDEHYDES AND KETONES
Carbonyl compounds are those that contain the C=O functional group. In aldehydes, this
group is at the end of a carbon chain, whereas in ketones it’s in the middle of the chain. As a
result, the carbon in the C=O bond of aldehydes is also bonded to another carbon and a
hydrogen, whereas the same carbon in a ketone is bonded to two other carbons. Aldehydes
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and ketones show a strong, prominent, stake-shaped band around 1710 - 1720 cm-1. This
band is due to the highly polar C=O bond. Because aldehydes also contain a C-H bond to the
sp2 carbon of the C=O bond, they show a pair of medium-strength bands positioned about
2700 and 2800 cm-1. These bands are missing in the spectrum of a ketone because the sp2
carbon of the ketone lacks the C-H bond.
The following slide shows a spectrum of an aldehyde and a ketone.
IR SPECTRUM OF A CARBOXYLIC ACID
A carboxylic acid functional group combines the features of alcohols and ketones because it
has both the O-H bond and the C=O bond. Therefore, carboxylic acids show very strong
broadband covering a wide range between 2800 and 3500 cm-1 for the O-H stretch. At the
same time, they also show a strong absorption band in the middle of the spectrum, around
1710 cm-1, corresponding to the C=O stretch.
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IR SPECTRUM OF AN ALCOHOL
The most prominent band in alcohols is due to the O-H bond, and it appears as a strong, broad
band covering the range of about 3000 - 3700 cm-1.
Infrared (IR) Spectroscopy and Carbonyl-Containing Compounds
Infrared (IR) spectroscopy is a powerful technique for identifying different carbonyl-containing
compounds, as each type has characteristic absorption frequencies for the C=O bond.
Aldehydes (R-CHO): - Aldehydes can be identified by a C=O stretch absorption peak located
between 1725 and 1740 cm⁻¹. Additionally, they exhibit two weak C–H stretch bands around
2720 and 2820 cm⁻¹.
Example: Acetaldehyde (CH₃CHO) shows a strong absorption peak around 1730 cm⁻¹ for the
C=O stretch and the characteristic doublet near 2700 cm⁻¹ for the C–H stretching of the
aldehyde hydrogen.
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Ketones (R₂C=O): - Ketones can be identified by a C=O stretch absorption peak in the range of
1725–1740 cm⁻¹. Unlike aldehydes, ketones do not exhibit C–H stretching bands around 2700
cm⁻¹.
Example: Acetone (CH₃COCH₃) has a strong C=O stretch around 1715 cm⁻¹, without any peaks
near 2700 cm⁻¹.
Carboxylic Acids (R-COOH): - Carboxylic acids can be identified by a C=O stretch absorption
peak ranging from 1725 to 1740 cm⁻¹. They also exhibit broad and strong O–H stretch
absorption around 2500–3300 cm⁻¹, due to the hydrogen-bonded O–H group.
Example: Acetic acid (CH₃COOH) displays a C=O stretch around 1710 cm⁻¹ and a broad, strong
O–H absorption band extending from 2500 to 3300 cm⁻¹.
Esters (RCOOR'): - Esters can be identified by a C=O stretch absorption peak around 1735–
1750 cm⁻¹, which is higher than those of ketones and aldehydes.
Example: Ethyl acetate (CH₃COOCH₂CH₃) has a C=O stretch near 1740 cm⁻¹, along with two
C–O stretches around 1050–1300 cm⁻¹.
Amides (R-CONH₂, R-CONHR, R-CONR₂): - Amides can be identified by a C=O stretch
absorption peak in the range of 1630–1690 cm⁻¹, which is lower than that of other carbonyl
compounds. They also show N–H stretch absorption peaks; primary or secondary amides
display one or two peaks around 3300–3500 cm⁻¹.
Example: Acetamide (CH₃CONH₂) shows a C=O stretch around 1670 cm⁻¹ and two N–H
stretches near 3200–3400 cm⁻¹.
Acid Anhydrides (RCO-O-COR)**: - Acid anhydrides can be identified by two C=O stretch
absorption peaks around 1800–1850 cm⁻¹ and 1740–1790 cm⁻¹, resulting from asymmetrical
and symmetrical stretches.
Example: Acetic anhydride ((CH₃CO)₂O) displays two C=O stretching bands near 1820 and
1760 cm⁻¹.
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INFRARED SPECTROSCOPY: DISPERSIVE AND FOURIER TRANSFORM SPECTRA
Infrared spectra can be obtained by either dispersive or interferometric methods.
The wavelength (2.5 ~ 25 µm) or wavenumber (400 – 4000 cm-1) is scanned sequentially by rotating
the prism or diffracting grating to measure the intensity of the transmittance radiation of different
wavelengths (wave number) over time. The recorder simultaneously plots on paper the Intensity
of the transmittance radiation against each wave number, thus producing an IR spectrum.
Dispersive Infrared Spectrometers
Although instrument manufacturers no longer manufacture dispersive IR spectrometers,
these instruments are still in use and are important in the historical development of IR
spectroscopy.
A dispersive IR spectrometer consists of four basic parts:
(1) Source of EM radiation of Mid IR range:
a source of continuous IR radiation, such as a coil of wire heated to high
temperatures,
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(2) monochromator:
a monochromator to disperse the radiation into its spectrum
(3) Detector: a sensitive thermocouple to detect IR radiation.
(4) recorder:
• The sample is placed usually between the source and the monochromator.
• The monochromator contains a grating that disperses the continuous radiation into
its spectrum of monochromatic components.
• A mechanical scanning device passes the component frequencies sequentially and
continuously to the detector.
• the detector senses which frequencies have been absorbed or partially absorbed by
the sample and which frequencies have been unaffected.
Fourier transform infrared (FT-IR) spectrometer
It used interferometric methods to measure the IR spectrum. The design of an FT-IR
spectrometer's optical pathway produces a pattern of radiation called an interferogram. The
interferogram is a complex signal, but its wave-like pattern contains electromagnetic radiation
(EM) of all the wavelengths of the infrared region. An interferogram is a plot of the intensity of
a signal versus time; that means it is a time-domain signal or spectrum.
The human brain cannot understand the time-domain spectrum but needs the frequency-
domain spectrum. A mathematical operation known as a Fourier transform (FT) can convert
the time-domain spectrum to the frequency-domain spectrum. Thus, it can produce a
spectrum virtually identical to that obtained with a dispersive spectrometer. This type of
instrument is known as a Fourier transform infrared spectrometer, or FT-IR.
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The advantage of an FT-IR instrument is that it acquires the
interferogram in less than a second. Thus, it is possible to
collect dozens of interferograms of the same sample and
accumulate them in a computer's memory. When a Fourier
transform is performed on the sum of the accumulated
interferograms, a spectrum with a better signal-to-noise ratio
can be plotted. An FT-IR instrument is, therefore, capable of
greater speed and greater sensitivity than a dispersion
instrument
A schematic diagram of an FT-IR.
In the interferometer, the source radiation passes through a beam splitter. It is split into two
perpendicular beams, one undeflected and the other-oriented at a 90° angle, by a mirror placed
at a 45° angle to the incoming radiation.
The beam oriented at 90° goes to a stationary or “fixed” mirror and is returned to the beam
splitter. The undeflected beam goes to a moving mirror and returns to the beam splitter. The
mirror's motion causes the second beam's path length to vary. When the two beams
recombine at the beam splitter, their differing path lengths cause constructive and destructive
interferences, creating an interferogram.
This interferogram contains all of the radiative wavelengths from the source and is directed
toward the sample by the beam splitter. As it passes through the sample, it absorbs all the
wavelengths normally found in its infrared spectrum.
The modified interferogram signal that reaches the detector contains information about the
amount of energy absorbed at every wavelength. The computer compares the modified
interferogram to a reference laser beam for a standard comparison. The final interferogram
contains all of the information in one time-domain signal. A computer uses a mathematical
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process called a Fourier transform to convert the time domain signals of the interferogram to
frequency domain signals that were absorbed and reconstruct a typical infrared spectrum.
The Basic Differences Between Dispersive and Fourier Transform Infrared (FT-IR)
Spectrometers
The basic differences between dispersive infrared (IR) and Fourier transform infrared (FT-IR)
spectrometers are based on their operational principles, speed, and sensitivity.
A dispersive IR spectrometer utilizes a monochromator (a prism or diffraction grating) to
separate IR radiation into individual wavelengths. This type of spectrometer scans one
wavelength at a time and measures its transmittance.
In contrast, an FT-IR spectrometer employs an interferometer to collect all wavelengths of IR
radiation simultaneously. It produces an interferogram or time-domain spectrum. A computer
then performs a mathematical transformation known as the Fourier Transform on this time-
domain spectrum to convert it into a frequency-domain spectrum, equivalent to the data
obtained from a dispersive IR instrument.
The dispersive IR method is slower because it scans the spectrum one wavelength at a time,
while FT-IR is significantly faster since it collects data for all wavelengths simultaneously.
Additionally, FT-IR enhances the signal-to-noise ratio through signal averaging by performing
repetitive scans.
PREPARATION OF SAMPLES FOR INFRARED SPECTROSCOPY
To determine the infrared spectrum of a compound, one must place the compound in a
sample holder, or cell.
In infrared spectroscopy, this immediately poses a problem. Glass and plastics absorb
strongly throughout the infrared region of the spectrum. Cells must be constructed of ionic
substances—typically sodium chloride or potassium bromide. Potassium bromide plates are
more expensive than sodium chloride plates but have the advantage of usefulness in the
range of 4000 to 400 cm-1. Sodium chloride plates are used widely because of their relatively
low cost. The practical range for their use in spectroscopy extends from 4000 to 650 cm-1.
The sample preparation method for infrared (IR) spectroscopy varies depending on the
sample's state—solid, liquid, or gas—and its characteristics.
Solid Samples can be prepared using the following methods:
1. KBr Pellet Method: Finely grind a small amount of the solid sample (1–2 mg) with
approximately 100 mg of potassium bromide (KBr), which is IR-transparent. Compress the
mixture into a pellet using a hydraulic press.
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2. Nujol Mull Method: Mix the finely powdered solid sample with a drop of mineral oil known
as Nujol. Grind the mixture to create a paste or "mull," then spread it between two IR-
transparent NaCl salt plates. While this method is convenient, it may result in some
interference bands from the oil.
3. Attenuated Total Reflectance (ATR): Place the solid sample in contact with an ATR crystal
made of diamond, ZnSe, or Ge. The IR beam penetrates the sample surface, allowing for
spectra collection without extensive sample preparation.
Liquid Samples can be prepared using the following techniques:
1. Neat Method: Place a small drop of the liquid sample between two NaCl discs to form a
thin film. Clamp the plates together, allowing IR light to pass through the liquid layer.
2. Solution Method: Dissolve the sample in a non-absorbing solvent (e.g., CCl₄ or CS₂) that
does not interfere with the IR regions of interest. Place the solution in a cell made of NaCl
salt plates with a known path length.
Gas Samples can be measured using the Gas Cell method. Simply introduce the gas sample
into a long-path gas cell and take the measurement.
Note of the Use of Attenuated Total Reflectance (ATR) accessory
The ATR method provides a convenient and efficient way to obtain spectra without the need
for extensive sample preparation.
When using the ATR accessory, you must directly apply a small amount of liquid or solid to the
diamond without prior preparation. The diamond is cut and mounted at precise angles so that
the incoming beam of infrared radiation bounces back and forth off the internal surfaces of
the crystal. When the beam reflects off the surface where the sample has been applied, it
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penetrates the sample slightly, and the vibrational frequencies of the sample are somewhat
absorbed, thereby “attenuating” the beam. The IR spectrometer detects the attenuated light,
and the resulting spectrum is obtained.
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