InfraRed Spectros

InfraRed Spectroscopy (IR-Sp)
Wavenumbers
• wavelength is measured in "wavenumbers„
• wavenumber = 1 / wavelength
• in centimeters it is useful to divide the infra red region into three sections; near, mid
and far infra red;
Regions of wavelength range
• Wavenumber range (cm-1)
• Near 0.78 - 2.51 2800 – 4000
• Middle 2.5 – 50 4000- 200
• Far 50 -1000 200 – 10
The most useful I.R. region lies between 4000 - 670cm-1
Theory of infra red absorption
• IR radiation does not have enough energy to induce electronic transitions as seen
with UV.
• Absorption of IR is restricted to compounds with small energy differences in the
possible vibrational and rotational states.
• For a molecule to absorb IR, the vibrations or rotations within a molecule must cause
a net change in the dipole moment of the molecule.
Theory of Infrared Absorption Spectroscopy
• In order for IR absorbance to occur two conditions must be met:
1.There must be a change in the dipole moment of the molecule as a result of a molecular
vibration (or rotation). The change (or oscillation) in the dipole moment allows interaction
with the alternating electrical component of the IR radiation wave. Symmetric molecules
(or bonds) do not absorb IR radiation since there is no dipole moment.
2. If the frequency of the radiation matches the natural frequency of the vibration (or
rotation), the IR photon is absorbed and the amplitude of the vibration increases.
Dipole moment (μ) is the measure of net molecular polarity, which is the magnitude of
the charge Q at either end of the molecular dipole times the distance r between the
charges (μ=Q×r) Dipole moments tell us about the charge separation in a molecule.
DE = hn There are three types of molecular transitions that occur in IR
a)Rotational transitions
• When an asymmetric molecule rotates about its center of mass, the dipole moment
seems to fluctuate.
• DE for these transitions correspond to n < 100 cm-1
• Quite low energy, show up as sharp lines that subdivide vibrational peaks in gas
phase spectra.
b)Vibrational-rotational transitions : complex transitions that arise from changes in the
molecular dipole moment due to the combination of a bond vibration and molecular
rotation.
c)Vibrational transitions
• The most important transitions observed in qualitative mid-IR spectroscopy.
• n = 13,000 – 675 cm-1 (0.78 – 15 mM)
Vibrational Modes
1.Stretching -the rhythmic movement along a bond axis with a subsequent increase and
decrease in bond length.
2.Bending -a change in bond angle or movement of a group of atoms with respect to the
rest of the molecule.
Mechanical Model of Stretching Vibrations

1. Simple harmonic oscillator. : Hooke’s Law (restoring force of a spring is proportional
to the displacement)
F = -ky
Where: F = Force
k = Force Constant
(stiffness of spring)
y = Displacement
Natural oscillation frequency of a mechanical oscillator
depends on:
a) mass of the object
b) force constant of the spring (bond)
The oscillation frequency is independent of the amount of energy imparted to the
spring.
Anharmonic oscillators : In reality, bonds act as anharmonic oscillators because as
atoms get close, they repel one another, and at some point a stretched bond will break.
• FT-IR stands for Fourier Transform InfraRed, the preferred method of infrared
spectroscopy.
• In infrared spectroscopy, IR radiation is passed through a sample.
• Some of the infrared radiation is absorbed by the sample and some of it is passed
through (transmitted).
• The resulting spectrum represents the molecular absorption and transmission,
creating a molecular fingerprint of the sample.
So, what information can FT-IR provide?
• It can identify unknown materials
• It can determine the quality or consistency of a sample
• It can determine the amount of components in a mixture
Why FT-IR?
• Fourier Transform Infrared (FT-IR) spectrometry was developed in order to overcome
the limitations encountered with dispersive instruments.
• The main difficulty was the slow scanning process.
• A method for measuring all of the infrared frequencies simultaneously, rather than
individually, was needed.
• A solution was developed which employed a very simple optical device called an
interferometer.
• The interferometer produces a unique type of signal which has all of the infrared
frequencies “encoded”
• into it.
• The signal can be measured very quickly, usually on the order of one second or so.
• Most interferometers employ a beamsplitter which takes the incoming infrared
beam and
• divides it into two optical beams.
• One beam reflects off of a flat mirror which is fixed in place.
• The other beam reflects off of a flat mirror which is on a mechanism which allows this
mirror to move a very short distance (typically a few millimeters) away from the
beamsplitter.
• The signal which exits the interferometer is the result of these two beams
“interfering” with each other.
• The resulting signal is called an interferogram which has the unique property that
every data point (a function of the moving mirror position) which makes up the
signal has information about every infrared frequency
• which comes from the source.
The Sample Analysis Process
The normal instrumental process is as follows:
1. The Source: Infrared energy is emitted from a glowing black-body
source. This beam passes through an aperture which controls the amount
of energy presented to the sample (and, ultimately, to the detector).
2. The Interferometer: The beam enters the interferometer where
the “spectral encoding” takes place. The resulting interferogram signal
then exits the interferometer.
3. The Sample: The beam enters the sample compartment where it
is transmitted through or reflected off of the surface of the sample,
depending on the type of analysis being accomplished. This is where
specific frequencies of energy, which are uniquely characteristic of the sample, are absorbed.
4. The Detector: The beam finally passes to the detector for final measurement. The detectors
used are specially designed to measure the special interferogram signal.
5. The Computer: The measured signal is digitized and sent to the computer where the Fourier
transformation takes place. The final infrared spectrum is then presented to the user for
interpretation and any further manipulation.
Raman Spectroscopy
Light Scattering Phenomenon
When radiation passes through a transparent medium,
the species present in that medium scatter a fraction
of the beam in all directions.
Raman Effect (or Raman Scattering)
• The visible wavelength of a small fraction of the
radiation scattered by certain molecules differs from that of the incident beam.
• Furthermore, the change (shifts) in frequency depend upon the chemical structure
of the molecules responsible for the scattering
Rayleigh Scattering and Raman Scattering
The frequency of the scattered light can be:
• at the original frequency (νI) “Rayleigh scattering”
very strong.
• at some shifted frequency
(νs = νI ± νmolecule) “Raman scattering or Raman shift”
very weak (~ 10-5 of the incident beam)
Stokes and Anti-Stokes Scattering

• Raman shift can correspond either to rotational, vibrational or electronic frequencies.
Δν = |νI – νs|
• Radiation scattering to the lower frequency side (to the red side) of the Rayleigh line
is called Stokes scattering.
• Radiation scattering to the higher frequency side (to the blue side) of the Rayleigh
line is called anti-Stokes scattering.
1.) Raman spectroscopy: complimentary to IR spectroscopy.

- radiation at a certain frequency is scattered by the molecule
with shifts in the wavelength of the incident beam.
- observed frequency shifts are related to vibrational changes in the
molecule à associated with IR absorbance.
- Raman Scattering Spectrum Resembles IR absorbance spectrum
- Raman & IR mechanism differ
a) comparison of Raman & IR:
IR Raman
i. vibrational modes vibrational modes
ii. change in dipole change in polarizability
iii. excitation of molecule to momentary distortion of the

excited vibrational state electrons distributed around the bond
iv. asymmetric vibrations (active) symmetric vibrations (active)
4.) Instrumentation: - Basic design

i. ) Light source:
- generally a laser to get required intensity of light
Raman scattering is only 0.001% of light source
Allows use of glass/quartz sample cells & optics
UV/Vis type detectors (photomultiplier tubes)
Applications:
a) Qualitative Information
i. characteristic regions for different groups as in IR
ii. Raman correlation charts available
iii. Good for aqueous based samples
iv. Useful for a variety of samples, organic, inorganic & biological
b) Quantitative Information – not routinely used
i. fewer technical problems than IR, fewer peaks
ii. Interference from fluorescence
iii. Higher cost
iii. Signal weak – require modified Raman methods
1) Resonance Raman spectroscopy allows detection of 10-3 ->10-7M by using lasers light
with wavelength approaching electronic absorption
2) Surface enhanced Raman spectroscopy places samples on metal or rough surfaces that
increase Raman scattering
Nuclear Magnetic Resonance Spectroscopy (NMR-Sp)
What does it do?
Nuclear magnetic resonance (NMR) allows us to detect atomic nuclei and say what sort of
environment they are in, within their molecule.
NMR can easily distinguish between different sorts of hydrogen atoms present.
The technique is called 1H-NMR or proton-NMR spectroscopy.
Likewise, NMR can easily distinguish between the three different carbon atoms.
The technique is called13C-NMR or carbon-NMR spectroscopy
One can determine the entire structure of a molecule.
The nuclei of all elements carry a charge.
Every nuclei have an intrinsic value of spin quantum number,
which may have value like 0, ½, 1, 2, 3, 3/2….....
Nuclei having non zero spin quantum number spins around its axis
As nuclei has charge, spining nuclei generates a magnetic dipole
Each nuclei acts a tiny magnet
In the absence of an applied magnetic field, the nuclear spins are randomly oriented.
In an applied magnetic field, the nuclei twist and turn to align themselves with or against
the field of the larger magnet.
More energy is needed for a proton to align
against the field than with it.
Protons that align with the field are in the
lower-energy α-spin-state; protons that align
against the field are in the higher-energy β-spin-state
More nuclei are in the α-state than in the β-state.
The energy difference between the α-and β-states depends on the strength of the
applied magnetic field
The greater the strength of the magnetic field to which nucleus is exposed, the
greater is the difference in energy between the α-and β-states
Now here is an unfortunate thing about NMR
The energy difference between the nuclear spin being
aligned with the magnetic field and against it is really
very small so small that we need a very, very strong
magnetic field to see any difference at all.
 When a nuclei is subjected to a corresponding
Difference in energy between the α-and β-states, nuclei
in the α-state are promoted to the β-state.
 Because the energy difference between the states is so small only a small amount
of energy is needed to flip the spin. The radiation required is in the radiofrequency (rf)
region of the electromagnetic spectrum and is called rf radiation.
 When the nuclei undergo relaxation (i.e., return to their original state), they emit
electromagnetic signals whose frequency depends on the difference in energy
between the α- and β-states.
The NMR spectrometer detects these signals and

Displays them as a plot of signal frequency versus
intensity—an NMR spectrum.

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InfraRed Spectroscopy (IR-Sp)

Mechanical Model of Stretching Vibrations

Stokes and Anti-Stokes Scattering

1.) Raman spectroscopy: complimentary to IR spectroscopy.

iii. excitation of molecule to momentary distortion of the

4.) Instrumentation: - Basic design

The NMR spectrometer detects these signals and

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