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FTIR Lecture Slides

Fourier transform infrared (FT-IR) spectroscopy analyzes the absorption of infrared light by molecules to determine their structure. Molecular vibrations, such as bond stretching and bending, occur at specific infrared wavelengths that are characteristic of different functional groups. During FT-IR analysis, a sample is exposed to infrared radiation and the wavelengths absorbed are measured, producing a spectrum that reveals the types of bonds present in the molecule through peaks corresponding to vibrational energies. This allows identification of functional groups and molecular structure.
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0% found this document useful (0 votes)
119 views25 pages

FTIR Lecture Slides

Fourier transform infrared (FT-IR) spectroscopy analyzes the absorption of infrared light by molecules to determine their structure. Molecular vibrations, such as bond stretching and bending, occur at specific infrared wavelengths that are characteristic of different functional groups. During FT-IR analysis, a sample is exposed to infrared radiation and the wavelengths absorbed are measured, producing a spectrum that reveals the types of bonds present in the molecule through peaks corresponding to vibrational energies. This allows identification of functional groups and molecular structure.
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Fourier transform infrared ( FT– IR)

spectroscopy

Experimental Techniques Ph 764


Dr. Zulqurnain Ali
Molecular absorption processes
• Electronic transitions ~10-18 J
• UV and visible wavelengths

• Molecular vibrations
• Thermal infrared wavelengths Increasing energy

• Molecular rotations
• Microwave and far-IR wavelengths
~10-23 J

• Each of these processes is quantized


• Translational kinetic energy of molecules is unquantized
Interaction of radiation with matter

Wavelength
• If there are no available quantized energy levels matching the quantum energy of the incident
radiation, then the material will be transparent to that radiation
Molecular Vibrations

Atomic and molecular vibrations correspond to excited energy levels in quantum mechanics

Excited level

Û DE = hn

Energy
Ground level
The atom is vibrating at The atom is at least partially in an
frequency, ν. excited state.

• For a given frequency of radiation, there is only one value of quantum energy for the photons of that radiation
• Transitions between energy levels occur by absorption, emission and stimulated emission of photons
Absorption

Atoms and molecules can also absorb photons, making a transition from a lower level to a more excited one

Excited level
This photon has
been absorbed
Energy

Ground level
Emission

Before After

Spontaneous
emission

Absorption

Stimulated
emission

In 1916, Einstein showed that another process, stimulated emission, can occur
Molecular Vibrations

The IR Spectroscopic Process.


The quantum mechanical energy levels observed in IR spectroscopy are those of molecular vibration

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

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

Any change in shape of the molecule- stretching of bonds, bending of


bonds, or internal rotation around single bonds
Molecular Vibrations
• There are two types of bond vibration:
1. Stretch – Vibration or oscillation along the line of the bond

H H
C C
H H

symmetric asymmetric

2. 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

9 9
Absorption spectra of molecules

V = Vibrational quantum number

J = Rotational quantum number

• Electronic, vibrational and rotational energy levels are superimposed


• The absorption spectrum of a molecule is determined by all allowed transitions between pairs of energy
levels, and whether the molecule exhibits a sufficiently strong electric or magnetic dipole moment
(permanent or otherwise) to interact with the radiation field
Vibrational Energy Levels
Absorption frequency for a diatomic molecule

1 k ( m1 + m2 )
n=
2pC m1m2
m1, m2 = atomic mass of vibrating atoms
V = wavenumber [cm-1] Let’s consider bond strength, K:
k = force constant (bond strength) [dynes cm-1] A C≡C bond is stronger than a C=C
bond is stronger than a C-C bond
For a single bond, k = 5×105 dynes cm-1 wavenumber, cm-1
For a double bond, k = 10×105 dynes cm-1 C≡C ~2100
For a triple bond, k = 15×105 dynes cm-1 C=C ~1650
C—C ~1200

Due to the reduced mass term, these two bonds of similar strength show up in very different regions of the IR spectrum:

C─C 1200 cm-1 µ = (12 x 12)/(12 + 12) =6


C─H 3000 cm-1 µ = (1 x 12)/(1 + 12) = 0.92
Molecular Vibrations
§ Each stretching and bending vibration occurs with a characteristic frequency

§ Typically, this frequency is on the order of 1.2 x 1014 Hz


(120 trillion oscillations per sec. for the H2 vibration at ~4100 cm-1)

§ The corresponding wavelengths are on the order of 2500-15,000 nm or 2.5 – 15 microns (mm)

§ When a molecule is bombarded with electromagnetic radiation (photons) that match the frequency of one of
these vibrations (IR radiation), it is absorbed and the bonds begin to stretch and bend more strongly (emission
and absorption)

§ When this photon is absorbed the amplitude of the vibration is increased NOT the frequency
IR Spectrum
• The x-axis of the IR spectrum is in units of wavenumbers, n, which is the number of waves per centimeter in units of
cm-1 (Remember E = hn or E = hc/l)
• 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

IR spectra are observed for


what is called the Mid IR: 200-
4000 cm-1
Basic Functional Groups
bending

C-H

O-H

C=O C-O
stretching

alkenes
O-H aromatic

C-H ChC C=C C-C

4000 3000 2000 1000 400

WAVENUMBER (cm-1)
Basic Functional Group
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)

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
16
4000 cm-1 2700 cm-1 2000 cm-1 1600 cm-1 400 cm-1
FTIR Spectrum
• 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
• The position of the spectral band is dependent on bond strength and atomic size

• The intensity of the peak results from the efficiency of the coupling; e.g. vibrations that have a large change in
dipole moment create a larger electrical field with which a photon can couple more efficiently

Exact transmittance values are rarely recorded


Functional Groups and IR spectrum
Signal Characteristics : INTENSITY
Only Streching vibrations that produce a change in
dipole moment are observed as IR signal on spectrum
Signal Characteristics : INTENSITY
Signal Characteristic: SHAPE
Carbon Hydrogen Bond in IR Spectra
Structural unit Frequency, cm-1

sp C—H 3310-3320

sp2 C—H 3000-3100

sp3 C—H 2850-2950

sp2 C—O 1200

sp3 C—O 1025-1200


Carbon Hydrogen Bond in IR Spectra

sp2 C—H 3000-3100 sp C—H 3310-3320


Symetric and Asymetric Streching

Diethylamine
Do Practice and identify compounds from IR Spectra

http://orgspectroscopyint.blogspot.com/p/ir.html

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