BRUKE TENSOR

TM
Series
Perkin Elmer
TM

Spectrum One
Instrumentation
Dispersive instruments: with a monochromator to be used in
the mid-IR region for spectral scanning and quantitative
analysis.
Fourier transform IR (FTIR) systems: widely applied and
quite popular in the far-IR and mid-IR spectrometry.
Nondispersive instruments: use filters for wavelength
selection or an infrared-absorbing gas in the detection system
for the analysis of gas at specific wavelength.
Dispersive IR spectrophotometers
Simplified diagram of a double beam infrared spectrometer
Modern dispersive IR spectrophotometers are invariably double-beam
instruments, but many allow single-beam operation via a front-panel
switch.
Double-beam operation compensates for atmospheric absorption, for the
wavelength dependence of the source spectra radiance, the optical
efficiency of the mirrors and grating, and the detector instability, which
are serious in the IR region.single-beam instruments not practical.
Double-beam operation allows a stable 100% T baseline in the spectra.
Dispersive spectrophotometers Designs
Null type instrument
Components of dispersive spectrophotometers
Nernst Glower heated rare earth oxide rod
(~1500 K)
1-50 m
(mid- to far-IR)
Globar heated SiC rod (~1500 K) 1-50 m
(mid- to far-IR)
W filament lamp 1100 K 0.78-2.5 m
(Near-IR)
Hg arc lamp plasma 50 - 300 m
(far-IR)
CO2 laser stimulated emission lines 9-11 m
1. IR source
Thermocouple thermoelectric effect -
dissimilar metal junction
cheap, slow,
insensitive
Bolometer Ni, Pt resistance
thermometer (thermistor)
Highly sensitive
<400 cm
-1

Pyroelectric Tri glycine sulfate
piezoelectric material
fast and sensitive
(mid IR)
Photoconducting PbS, CdS, Pb Se light
sensitive cells
fast and sensitive
(near IR)
2. Detector / transducer
3. Optical system
Reflection gratings ( made from various plastics): the groove
spacing is greater (e.g. 120 grooves mm
-1
). To reduce the effect of
overlapping orders and stray radiation, filters or a preceding prism
are usually employed. Two or more gratings are often used with
several filters to scan a wide region.
Mirrors but not lenses are used to focus and collimate the IR
radiation. Generally made from Pyrex or another material with low
coefficient of thermal expansion. Front surfaces coated with a
vacuum-deposited thin metal film of Al, Ag, or Au.

Windows are used for sample cells and to permit various compartment
to be isolated from the environment.
transparent to IR over the wavelength region
inert to the various chemicals analyzed
capable of being shaped, ground, and polished to the desired
optical quality
The Fourier transform method provides an alternatives to the use
of monochromators based on dispersion.
In conversional dispersive spectroscopy, frequencies are separated
and only a small portion is detected at any particular instant, while
the remainder is discarded. The immediate result is a frequency-
domain spectrum.
Fourier transform infrared spectroscopy generates time-domain
spectra as the immediately available data, in which the intensity is
obtained as a function of time.
Direct observation of a time-domain spectrum is not immediately
useful because it is not possible to deduce, by inspection,
frequency-domain spectra from the corresponding time-domain
waveform (Fourier transform is thus introduced).
Fourier Transform Infrared Spectrometer (FTIR)
In one arm of the interferometer, the IR source radiation travels through the beam
splitter to the fixed mirror back to the beam splitter through the sample and to the
detector. In the other arm, the IR source radiation travels to the beam splitter to the
movable mirror, back through the beam splitter to the sample and to the detector. The
difference in pathlengths of the two beams is the retardation o. An He-NE laser is used
as a monochromatic reference source. The laser beam is sent through the interferometer
in the opposite direction to that of the IR beam.
Single-beam FTIR Spectrometer
Double-beam FTIR
Spectrometer
Interferometer
Michelson interferometer
If moving mirror moves 1/4 (1/2 round-trip) waves are out of phase at beam-
splitting mirror - no signal
If moving mirror moves 1/2 (1 round-trip) waves are in phase at beam-splitting
mirror signal
...
Interferograms
Difference in pathlength called retardation o
Plot o vs. signal - cosine wave with frequency proportional to light
frequency but signal varies at much lower frequency
One full cycle when mirror moves distance /2 (round-trip = )
Frequency of signal:

Substituting =c/v

If mirror velocity is 1.5 cm/s

Bolometer, pyroelectric, photoconducting IR detectors can "see changes
on 10
-4
s time scale!

MM MM
V V
f
2
2 /
= =
v
c
V
f
MM
2
=
V
MM
velocity of moving mirror
v v
10
10
10
/ 10 3
/ 3

=
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