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Infrared Spectrometry

Instrumental Analysis
Chapter 17

Applications of Infrared
Spectrometry

Modern infrared spectrometry is a versatile tool that is


applied to the qualitative and quantitative determination of
molecular species of all types. The applications of infrared
spectrometry can be split into three main areas:
Near-infrared 4,000 to 14,000 cm-1
Mid-infrared 670 to 4,000 cm-1
Far- infrared less than 670 cm-1

Chart on Regions
SpectralRegions

TypeMeasurement

TypeAnalysis

TypeSamples

Near-infrared

Diffuse Reflectance
Absorption

Quantitative
Quantitative

Solid, Liquid
Gaseous Mixtures

Mid-infrared

Absorption
Reflectance
Emission

Qualitative
Quantitative
Chromatographic
Qualitative
Quantitative

Solid, liquid, gas


Solid, liquid, gas
Solid, liquid, gas
Pure solid or liquid
Atmospheric sample

Absorption

Qualitative

Pure inorganic or metal


organic

Far-infrared

Gas in an Evacuated Cylinder


The

spectrum of a low-boiling liquid or gas can be


obtained by permitting the sample to expand into
an evacuated cylindrical cell equipped with
suitable windows. A variety of cylindrical cells
are available with path lengths that that range from
a couple of centimeters to 10 meters or more.
The longer the path lengths are obtained in
compact cells by providing reflecting internal
surfaces, so that the beam makes numerous passes
through the sample before exiting the cell.

Solutions
When

feasible, a convenient way of


obtaining infrared spectra is on solutions
prepared to contain a known concentration
of sample, as is generally done in
ultraviolet/visible spectroscopy.
This technique is limited due to the
availability of solvents that are transparent
over significant regions in the infrared.

Dissolved in Solvents
There

is no particular solvent that is completely


transparent in the entire mid-infrared region.
Therefore solvents are chosen on the basis of the
region the sample will absorb.
Water and alcohol are used seldom because they
absorb strongly and they attack alkali metal
halides, the most common materials used for cell
windows. The alkali metals are the most common
metals used in cell windows.

Liquid in Cell

Because of the tendency for solvents to absorb, infrared


cells are ordinarily much narrower than those employed in
the UV/Vis regions. Fixed path length cells can be filled
or emptied with a hypodermic syringe.
Sodium Chloride windows are widely used because their
surfaces. A common problem with sodium chloride cells is
that they absorb moisture and become fogged. To get rid
of the fogginess one has to polish the window with a
buffing powder returns them to their original condition.

Demountable Liquid Cell


The cells are frequently
demountable, with Teflon spacers
to allow for variation in path
length.
The thickness, b, of very narrow
infrared cells can be determined.
The maxima occur when the
radiation reflected off of the two
internal surfaces of the cell has
traveled a distance that is an
integral multiple, N, of the
wavelength of the radiation that
was transmitted with out reflection:
2b/N=

Pellets

One of the most popular techniques for handling solid


samples has been KBr pelleting. In using this technique, a
milligram or less of the finely ground sample is ultimately
mixed with about 100 mg of dried potassium bromide
powder.
Halide salts have the property of cold flow in which they
have glass like transparent or translucent properties when
sufficient pressure is applied to the finely powdered
materials. With many compounds KBr pelleting produces
excellent spectra that appear in many spectral libraries.

Pellets (cont)

The KBr pelleting system


is designed to allow the
spectroscopist to position
a KBr die in the laboratory
press without the need to
continually connect or
disconnect a vacuum tube
from an external vacuum
pump when samples are
processed.

Mulls

Mulls are formed by grinding 2 to 5 mg of the finely powdered sample


in the presence of one or two drops of a heavy hydrocarbon oil (Nujol).
If hydrocarbon bands are likely to interfere, fluorolube, a halogenated
polymer can be used instead. The disadvantage of Nujol is that
hydrocarbon bands may interfere with analyte absorbances. A second
method of forming a mull involves grinding the powdered analyte with
dry potassium bromide and forming a disk.
The ratio of analyte to potassium bromide is usually about 1:100. The
materials are ground together using a mortar and pestle or a small ball
mill. The mixture is then pressed in a die at 10,00015,000 psi to form
a small transparent disk and analyzed. Care must be taken when
preparing the disk to protect it from moisture. It is very common to see
absorbencies for moisture when using potassium bromide disks.

Mid-Infrared Absorption
Spectrometry

Mid-infrared absorption and reflection spectrometry are major tools


for determining the structure of organic and biochemical species.
Mid-infrared light (2.5 - 50 m, 4000 - 200 cm-1 See Diagram Below)
is energetic enough to excite molecular vibrations to higher energy
levels.

The wavelength of many IR absorption bands are characteristic of


specific types of chemical bonds, and IR spectroscopy finds its
greatest utility for qualitative analysis of organic and organometallic
molecules. IR spectroscopy is used to confirm the identity of a
particular compound and as a tool to help determine the structure of a
newly synthesized molecule (with NMR spectroscopy and mass
spectrometry).

Absorption Spectrometry

The visible region of the


electromagnetic spectrum
consists of photons with
wavelengths from approximately
400 to 700 nm. The short
wavelength cutoff is due to
absorption by the lens of the eye
and the long wavelength cutoff is
due to the decrease in sensitivity
of the photoreceptors in the
retina for longer wavelengths.
Light at wavelengths longer than
700 nm can be seen if the light
source is intense.

Electromagnetic Spectrum
TypeofRadiation

FrequencyRange(Hz)

WavelengthRange

TypeofTransition

gamma-rays

1020-1024

<1 pm

nuclear

X-rays

1017-1020

1 nm-1 pm

inner electron

ultraviolet

1015-1017

400 nm-1 nm

outer electron

visible

4-7.5x1014

750 nm-400 nm

outer electron

near-infrared

1x1014-4x1014

2.5 m-750 nm

outer electron molecular vibrations

infrared

1013-1014

25 m-2.5 m

molecular vibrations

microwaves

3x1011-1013

1 mm-25 m

molecular rotations, electron spin flips*

radio waves

<3x1011

>1 mm

nuclear spin flips*

Qualitative Analysis

The mid-infrared region is further broken down into the group


frequency region (1,280 to 5,000 cm-1) and the fingerprint region (670
to 1,280 cm-1). Since most organic molecules have single bonds, the
region below 1500 cm-1 can become quite complex and is often
referred to as the 'fingerprint region'.
If you are dealing with an unknown molecule which has the same
'fingerprint' in this region, that is considered evidence that the two
molecules may be identical. The fingerprint region is useful because
small differences in the structure and constitution of a molecule result
in significant changes in the appearance and distribution of absorption
peaks in this region. A close match between two spectra in the
fingerprint region constitutes almost certain evidence for the identity of
the compounds yielding the spectra.

Quantitative Analysis

The use of highly concentrated solutions (not necessarily


highly concentrated in the absorber).
Poor monochromaticity of the radiation beam.
"Stray light" within the instrument.
Changes in chemical speciation.
Quantitative infrared absorption methods differ somewhat
from UV/VIS molecular spectroscopic methods because of
the greater complexity of the spectra, the narrowness of the
absorption bands, and the instrumental limitations of
infrared instruments.

Quantitative Analysis

Even when there is full confidence that Beer's Law can be


applied, there are random errors in absorbance
measurements to be considered. Random instrumental
errors arise primarily from electronic noise and, hence, vary
somewhat with instrument design.
A useful rule of thumb for absorbance measurements is to
keep measured A values within the range 0.5 - 1.0. Some
modern instruments give optimum precision near A = 1.5
but it is always best to avoid measuring below A = 0.1
(small difference between large numbers) or above A = 2.0
(where only 1% of light is transmitted and stray light
becomes important).

References
Chem

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Science Magazine
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