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INFRARED SPECTROSCOPY
SECTION A
IR REGION OF THE SPECTRUM AND UNITS
C
this IR region of the spectrum ranges from the end of the visible region (red @ ~ 780
nm) to about 1,000,000nm. In wave numbers, this is from ~ 12800 - 10 cm-1
three main process occur: emission, absorption reflection, due to the transition of
molecules from one vibrational or rotational energy state to another
Region
l range
(mm)
wave number (n or s)
(cm-1)
Near-IR
Mid-IR
Far-IR
0.78 - 2.5
2.5 - 50
50 - 1000
12800 - 4000
4000 - 200
200 - 10
Most used
region
2.5 - 15
4000 - 670
E = hc/l = hn
the energy of the transitions are low and are associated with vibrational and
rotational transitions
the relative positions of atoms in a molecule are not fixed but fluctuate continuously
due to different types of vibrations and rotations about the bonds in the molecule.
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the number of possible vibrations and rotations for a given molecule is related to the
number of atoms, and thus the number of bonds in the molecule
for a simple diatomic or tri-atomic molecule it is easy to define the number and
nature of these vibrations, but for larger molecules this is not easily done
thus, for most molecules, there is a multiple of quantized rotational and vibrational
levels associated with its bonds
all of the vibrations discussed can occur in a simple molecule (< 2 atoms)
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DIPOLE CHANGES
Vibration
C in order to absorb energy, a molecule must undergo a net change in dipole moment
due to its vibrational and/or rotational motions
C under these condition, the alternating electrical field of the radiation interacts with
the molecule and a transfer of energy occurs causing a change in the amplitude of
one of the motions of the molecule
C through this process, molecules absorb IR radiation and are promoted to a higher
vibrational energy level
C the absorption of energy is quantized and corresponds to the mid-IR region of the
spectrum
Rotation
C rotation of molecules around their centre of mass also results in a periodic dipole
fluctuation that can interact with radiation < 100 cm-1 , i.e., > 100 mm
homonuclear and chiral molecules
C homonuclear molecules, e.g., O2, Cl2. N2 and chiral molecules in the crystalline state
have no net change in dipole moment during their vibration or rotation, thus these
molecules cannot absorb IR radiation
Note: chiral molecules - molecules that have non-superimposable mirror images
gases, liquids, solids
C absorption spectra by gases show discrete, well-defined rotational and vibrational
absorption lines
C in liquids and solids, intramolecular collisions and interactions cause broadening of
rotational and vibrational lines into a continuum, leaving only broadened vibrational
peaks or bands
4
SECTION B
IR instrumentation
-
Source of e.m.r.
Optical materials
Detectors
ii)
Globar
iii) Incandescent
wire
5
iv) Mercury Arc
v)
Tungsten
filament
2. Optical Materials
6
4. Detectors
- three types 1. thermal
2. pyroelectric
3. photo-conducting
1. Thermal detectors
- responses depend on the heating effects of radiation on different materials
- three main types: I) thermocouple
ii) bolometer
iii) Golay tube (pneumatic)
- mechanism - radiation is absorbed by a small black body, the
temperature of the body rises, and the rise in temperature
is measured
- temperature rises are small (a few thousandths of a Kelvin)
- requirements - absorbing element must be small
- heat capacity must be small
- all radiation must be focused on the absorbing element
- other - thermal noise from the surroundings is a problem
- the detector is housed in a vacuum and shielded from other
thermal noises
- the beam of radiation is chopped so that it can be detected apart
from extraneous noise
7
ii) bolometer (see figure 2)
-
iii)
Certain crystals, e.g., triglycine sulphate (TGS), deuterated tri glycine sulphate
(DTGS), lithium tantalate, etc., have an internal electric polarization along an
axis resulting from alignment of electric dipole moments
such crystals are known as ferroelectric materials (in a ferro-electric material,
the dipole moments remain aligned in the absence of an external electric field.
This gives the material a permanent electric polarization. One face of the
crystal is positive and the other negative. This polarization is temperature
dependent)
when these crystals absorb IR radiation, they heat up. This alters the lattice
spacings of the crystals which, in turn, causes a change in the electric
polarization
if placed between electrodes consisting of metal plates connected through an
external circuit, current will flow in the circuit to balance this charge
redistribution
8
-
3. Photo-conducting detector
- consists of a thin film of semi-conductor material (e.g., lead sulphide,
mercury/cadmium telluride, indium antimonide. Lead telluride, or germanium
doped with copper or lead) deposited on a non-conducting glass and sealed in an
evacuated envelope to protect the semi-conductor from reaction with the
atmosphere.
- when IR radiation is absorbed by these materials some of the electrons in the
bound non-conducting valence levels are promoted to a higher energy conducting
state, resulting in a decrease in the resistance of the material.
- the photo-conductor is placed in series with a voltage source and a load resistor,
and the voltage drop across the load resister is measured - this is a measure of
the power of the IR beam of radiation.
- the lead sulphide photo-conductor detector is used widely in the near-IR (1 - 3
um, 10,000 -333 cm-1) region. It can be used at room temperature.
- the mercury/cadmium telluride photo-conductivity detector is used in the mid- and
far-IR regions.
- must be cooled in liquid nitrogen (77 K) to minimize thermal noise
- it has fast response times
- useful for Fourier Transform IR instruments
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SECTION C
1. Dispersive IR Spectrophotometer (see figure 5)
- double-beam, recording instruments, that use reflection gratings for dispersion
- double-beam
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2. Interferometric (multiplexed) Spectrometers
- two main types:
I) Fourier transform
ii) Hadamard transform (not widely used)
I) Fourier Transform Spectrometer (see figure 6)
- may be based on several types of optical systems
- will describe the Michelson interferometer (most widely used)
- consists of two plane mirrors (one fixed and the other moveable) set at right
angles to each other, with a beam splitter at 45o to the mirrors
- modulated light from the source is collimated and passed to the beam splitter
where one-half of the beam is reflected to the fixed mirror and the other onehalf passes through to the moving mirror
- when the mirrors are positioned such that the optical path lengths of the
reflected and transmitted beams are the same when they return to the beam
splitter, they will interact constructively
- if the moveable mirror is displaced 1/4 of a wavelength, when the beams return
to the beam splitter there will be a difference of -wavelength in their path
lengths, i.e., they will be 180o out of phase, and they will interact destructively
- if the moveable mirror is displaced another 1/4 of a wavelength, i.e., a total
displacement of of a wavelength, when the beams return to the beam
splitter there will be a difference of one wavelength in their path lengths, i.e.,
they will be in phase, and they will interact constructively
- as the mirror continues to move, there will be a series of constructive and
destructive interference patterns for each 1/4 wavelength displacement of the
mirror
- when the interferometer is illuminated by monochromatic radiation of
wavelength L, and the mirror moves at a velocity v , the signal from the
detector has a frequency, f=2v/L
- a plot of signal versus mirror distance is a cosine wave
11
Advantages -
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3. Non-Dispersive IR Photometers
- no monochromator (dispersive device) is used for wavelength discrimination
- several types:
- simple filter
- filter wedges - provides the entire spectrum
- no wavelength selection device
- the instruments are simple, rugged, easy to use and maintain, and costs are low
- used for quantitative analysis
- Non-Filter Photometer (see figure 7)
- no wavelength-restricting device is used
- widely used to monitor gas streams for a single component, e.g., CO2 in
automobile exhaust gases
- reference cell - filled with a non-absorbing gas
- sample cell - same length as the reference cell
- sample flows through the cell
- chopping
- beams from identical sources are chopped (~ 5 cps)
simultaneously
- serves to provide a modulated signal which, reduces the effect
of extraneous noise, and is less sensitive to drift and
1/frequency noise
- an attenuator is used to equalize the response of the sensors when both
reference and sample cells contain the same non-absorbing gas
- when an IR absorbing gas, e.g., CO2, is present in the sample cell, it absorbs
radiation and the radiation reaching the sensor in the sample beam path is
reduced
- the difference between the radiation reaching the sensor in the reference
beam path and the sample beam path is measured and corresponds to the
amount/concentration of the absorbing gas in the sample cell
- the sensors can be of several types - two widely used sensors are a thermal
sensor and a pneumatic sensor
- in this instrument the sensors act as the discriminating device
13
SECTION D
Attenuated Total Reflection (ATR)
-
when a beam of radiation enters a plate or prism, it will be reflected internally if the
angle of incidence at the interface between sample and plate is greater than the
critical angle (a function of refractive index)
on internal reflection all of the energy of the beam of radiation is reflected
the beam, however appears to penetrate slightly (from a fraction of a wavelength to
several wavelengths) beyond the reflecting surface, and before returning
if a material that can absorb IR radiation is placed on the reflecting surface, it will
absorb IR radiation thus reducing (attenuating) the intensity of the returning beam of
radiation
this attenuated radiation when measured and plotted against wavelength, gives an
absorbance spectrum that is, in fact, the IR spectrum of the material
reflection crystals used in ATR must have a high index of refraction, e.g. AgCl
applications - samples that - cannot be studied by normal transmission methods
- have very strong absorption
- resist preparation as thin films
- are non-transparent
- contain suspended matter
- aqueous solutions can be analysed without having to compensate for
very strong absorption (due to water)