Applications of infrared Spectrometry

Infrared Spectrometry

the study of interaction of infrared light with matter, which can be used to identify unknown
materials, examine the quality of a sample or determine the amount of components in a
mixture.

it is a versatile tool that is applied to the qualitative and quantitative determination of

molecular species of all types.

Three Categories based on IR spectral regions:

Mid-IR

- most widely used region.

- extends from about 670 to 4000cm-1 (2.5 to 14.9 m )

- absorption, reflection, and emission spectra are employed for both qualitative and
quantitative analysis.

Three Categories based on IR spectral regions:

Near-IR

- 4000 to 14,000 cm-1 (0.75 to 2.5 m)

- also finds considerable use for the routine quantitative determination of certain species,
such as water, carbon dioxide, sulfur and many other simple compounds of interest in
agriculture and industry.

- often based on diffuse-reflectance measurements of untreated solid or liquid

samples or absorption studies of gases.

Three Categories based on IR spectral regions:

Far-IR

- (15 to 1000 m)

- primary use is for the determination of the structures of inorganic and metal-organic
species based on absorption measurements.

Mid-IR Absorption Spectrometry

major tool for determining the structure of organic and biochemical species.

Mid-IR Absorption Applications

Sample Handling

- frequently the most difficult and time- consuming part of an IR spectrometric analysis.
 - samples of different phases must be treated differently.

- the only common point to the sampling of different phases is that the material
containing t he sample must be transparent to IR radiation.

Mid-IR Absorption Applications

Gases

- the spectrum of a low boiling point liquid or gas can be obtained by permitting the
sample to expand into an evacuated cylindrical cell equipped with suitable windows.

- the end walls of the cell are usually

made of sodium chloride which is transparent to infrared.

Mid-IR Absorption Applications

Solutions

- when feasible, a convenient way of obtaining IR spectra is on solutions prepared to

contain a known concentration of sample, as is generally done in ultraviolet visible
spectrometry.

- this technique is limited in its applications depending on the availability of solvents.

Mid-IR Absorption Applications

Solvents

- no single solvent is transparent throughout the entire mid-IR region.

- water and alcohols are difficult to use as solvents in IR spectrometry.

- Chloroform is considered to be an important solvent and is frequently used because it

shows absorptions though it is less symmetric molecule than carbon tetrachloride and
carbon disulphide.

Mid-IR Absorption Applications

Cells

- because of the tendency for solvents to absorb IR radiation, IR liquid cells are
ordinarily much narrower (0.01 to 1 mm) than those employed in the ultraviolet and visible
regions.

- liquid cells are frequently designed for easy disassembly and use Teflon spacers to allow
variation of path length .

Mid-IR Absorption Applications

 Mid-IR Absorption Applications

Liquids

- when the amount of liquid sample is small or when a suitable solvent is unavailable, it is
common practice to obtain spectra on the pure (neat) liquid.

- this method is most useful for qualitative

work only because the sample thickness cannot be controlled.

Mid-IR Absorption Applications

For Solids

- the solid sample must be ground until its particle size is less than the wavelength of the
radiation to avoid the effects of scattered radiation.

Mid-IR Absorption Applications

Pelleting

- in this technique a small amount of finely ground solid sample is intimately mixed with
about 100 times its weight of powdered KBr, in a vibrating ball mill.

- one of the most popular techniques for handling solid samples has been KBr.

- with many compounds, KBr pelleting produces excellent spectra that appear in many
spectral libraries.

Mid-IR Absorption Applications

Mull

- in this technique a small quantity of sample is thoroughly ground in a clean mortar until
the powder is very fine.

- 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).

Mid-IR Absorption Applications

Other Methods for Solids

- the IR behavior of solids can also be obtained by reflectance techniques and by the
photoacoustic method.

Qualitative Analysis

Group Frequencies

- are seldom totally invariant because of interactions with other vibrations associated
with one or both of the atoms composing the group.
 - interaction effects are ordinarily small; as a result, a range of frequencies can be
assigned within which it is highly probable that the absorption maximum for a given
functional group will be found.

Qualitative Analysis

The Fingerprint Region

- well suited for identifying compounds based on spectral comparisons.

- most single bonds give rise to absorption bands at these frequencies; because their
energies are about the same, strong interaction occurs between neighboring bands.

Qualitative Analysis

Limitations to the Use of Correlation Charts

- the unambiguous establishment of the identity or the structure of a compound is

seldom possible from correlation charts alone.

- uncertainties frequently arise from overlapping group frequencies, spectral

variations as a function of the physical state of the sample and instrumental limitations.

Qualitative Analysis

Collections of Spectra

- correlation charts seldom suffice for the positive identification of an organic

compound from its IR spectrum.

- several catalogs of IR spectra are available that assist in qualitative identification by

providing comparison spectra for a large number of pure compounds.

- computer based systems are widely used.

Qualitative Analysis

Computer Search Systems

- IR instrument manufacturers now offer computer search systems to aid in

identifying compounds from stored IR spectral data.

- computer matches profiles and prints a list of compounds having spectra similar to that of
the analyte.

Quantitative Applications

Quantitative IR absorption methods differ somewhat from ultraviolet visible molecular

spectroscopic methods because of the greater complexity of the spectra.

Quantitative data obtained with older dispersive IR instruments were generally significantly
inferior in quality to data obtained with UV visible spectrophotometers.
 Quantitative Applications

Disadvantages and Limitations to Quantitative IR Methods

- the richness of spectral features enhances the probability of overlapping absorption bands.

- the narrow path length cells required for many analyses are inconvenient to use and may
lead to significant analytical uncertainties.

- the analytical errors associated with a quantitative IR analysis often cannot be reduced to
the level associated with ultraviolet and visible methods, even with considerable care and effort.

Mid-IR Reflection Spectrometry

IR reflection spectrometry has found a number of applications, particularly for dealing with
solid samples that are difficult to handle, such as polymer films and fibers, foods, rubbers,
agriculture products and many others.

Reflectance spectra can be used for both qualitative and quantitative analysis.

Types of Reflection

Specular Reflection

- occurs when the reflecting medium is a smooth polished surface.

Diffuse Reflection

- occurs when the reflecting medium is a rough surface.

Internal Reflection

- interaction of the electromagnetic radiation on the interface between the sample and a
medium with ahigher refraction index is studied.

External Reflection

- arise from the radiation reflected from the sample surface.

Diffuse-Reflectance Spectrometry

An effective way of directly obtaining IR spectra on powdered samples with a minimum of

sample preparation.

It permits conventional IR spectral data to be gathered on samples not appreciably altered

from their original state..

A complex process that occurs when a beam of radiation strikes the surface of a finely
divided powder.

ATR Spectrometry
 Internal reflection spectroscopy is a technique for obtaining IR spectra of samples that are
difficult to deal with, such as solids of limited solubility, films, threads, pastes, adhesives and
powders.

ATR Spectra

Similar but not identical to ordinary absorption spectra. In general, although the same bands
are observed, their relative intensities differ.

One of major advantages of ATR spectroscopy is that the absorption spectra are readily
obtainable on a wide variety of sample types with a minimum of preparation.