=
s cm
s cm
f
Computer needed to turn complex interferograms into spectra.
Measuring processes
very high resolution (< 0.1 cm
1
)
Two closely spaced lines only separated if one complete "beat" is recorded. As
lines get closer together, o must increase.
Av(cm
1
) = 1/o
Mirror motion is 1/2 o
Resolution governed by distance movable mirror travels
very high sensitivity (nanogram quantity)
can be coupled with GC analysis (> measure IR spectra in gas-phase)
High S/N ratios - high throughput
Few optics, no slits mean high intensity of light
Rapid (<10 s)
Reproducible and Inexpensive
Advantages of FTIR
Usually to improve resolution
decrease slit width but less light
makes spectrum "noisier" - signal
to noise ratio (S/N)
n # scans
S/N improves with more scans
(noise is random, signal is not!)
n
N
S
S S
S
n
N
S
i
=
2
) (
To improve S/N ratio
For routine instrument calibration, run the spectrum of
polystyrene film (or indene) at resolution 2 cm
-1
. Band
positions are available in the literature.
Higher resolution calibrations may be made from gas-
phase spectra (e.g. HCl gas).
Spectrum calibration
Sample preparation techniques
The preparation of samples for infrared spectrometry is often the most
challenging task in obtaining an IR spectrum. Since almost all substances absorb
IR radiation at some wave length, and solvents must be carefully chosen for the
wavelength region and the sample of interest.
Infrared spectra may be obtained for gases, liquids or
solids (neat or in solution)
A gas sample cell consists of a cylinder of glass or sometimes a metal.
The cell is closed at both ends with an appropriate window materials
(NaCl/KBr) and equipped with valves or stopcocks for introduction of the
sample.
Long pathlength (>10 cm) cells used to study dilute (few molecules)
or weakly absorbing samples.
Multipass cells more compact and efficient instead of long-pathlength
cells. Mirrors are used so that the beam makes several passes through
the sample before exiting the cell. (Effective pathlength > 10 m).
To resolve the rotational structure of the sample, the cells must be
capable of being evacuated to measure the spectrum at reduced
pressure.
For quantitative determinations with light molecules, the cell is
sometimes pressurized in order to broaden the rotational structure and
all simpler measurement.
Gas samples
Pure or soluted in transparent solvent not water (attacks windows)
The sample is most often in the form of liquid films (sandwiched
between two NaCl plates)
Adjustable pathlength (0.015 to 1 mm) by Teflon spacer
Liquid samples
Regions of transparency for common infrared solvents.
The horizontal lines indicate regions where solvent transmits at least
25% of the incident radiation in a 1-mm cell.
Solid samples
Spectra of solids are obtained as alkali halide discs (KBr), mulls
(e.g. Nujol, a highly refined mixture of saturated hydrocarbons) and
films (solvent or melt casting)
Alkali halide discs:
1. A milligram or less of the fine ground sample mixed with about
100 mg of dry KBr powder in a mortar or ball mill.
2. The mixture compressed in a die to form transparent disc.
Mulls
1. Grinding a few milligrams of the powdered sample with a mortar
or with pulverizing equipment. A few drops of the mineral oil
added (grinding continued to form a smooth paste).
2. The IR of the paste can be obtained as the liquid sample.
1. Fundamental chemistry
Determination of molecular structure/geometry.
e.g. Determination of bond lengths, bond angles of
gaseous molecules
2. Qualitative analysis simple, fast, nondestructive
Monitoring trace gases: NDIR.Rapid, simultaneous
analysis of GC, moisture, N in soil. Analysis of fragments
left at the scene of a crime
Quantitative determination of hydrocarbons on filters, in
air, or in water
Main uses of IR spectroscopy:
Near-infrared and Far-infrared absorption
The techniques and applications of near-infrared (NIR) and
far-infrared (FIR) spectrometry are quite different from those
discussed above for conventional, mid-IR spectrometry.
Near-infrared: 0.8 -2.5 m, 12500 - 4000 cm
-1
Mid-infrared: 2.5 - 50 m, 4000 - 200 cm
-1
Far-infrared:
50 - 1000 m, 200 - 10 cm
-1
Near-infrared spectrometry
NIR shows some similarities to UV-visible spectrophotometry and
some to mid-IR spectrometry. Indeed the spectrophotometers
used in this region are often combined UV-visible-NIR ones.
The majority of the absorption bands observed are due to
overtones (or combination) of fundamental bands that occur in
the region 3 to 6 m, usually hydrogen-stretching vibrations.
NIR is most widely used for quantitative organic functional-group
analysis. The NIR region has also been used for qualitative
analyses and studies of hydrogen bonding, solute-solvent
interactions, organometallic compounds, and inorganic
compounds.
Far-infrared spectrometry
Almost all FIR studies are now carried out with FTIR
spectrometers.
The far-IR region can provide unique information.
i) The fundamental vibrations of many organometallic and
inorganic molecules fall in this region due to the heavy atoms
and weak bonds in these molecules.
ii) Lattice vibrations of crystalline materials occur in this region,
iii) Electron valence/conduction band transition in
semiconductors often correspond to far-IR wavelengths.
References:
J. Workman, A.W. Springsteen, Applied Spectroscopy, Academic
Press, 1998.
J.M. Hollas, Modern Spectroscopy, John Wiley&Sons, 1996.
B. Stuart, W.O. George, D.J. Ando, Modern Infrared Spectroscopy,
John Wiley&Sons, 1997.
N.N. Colthup, L.H. Daly, S.E. Wiberly, S.E. Wiberly, Introduction to
Infrared and Raman Spectroscopy, Academic Press, 1997.
B. Schrader, D. Bougeard, Infrared and Raman Spectroscopy: Methods
and Applications, John Wiley&Sons, 1995.
Infrared Spectrum of CCl
4