IR SPECTROMETER IN EVERDAY LIFE

Infrared radiation is that part of the electromagnetic spectrum

between the visible and microwave regions. Infrared radiation is
absorbed by organic molecules and converted into energy of
molecular vibration, either stretching or bending. Different types of
bonds, and thus different functional groups, absorb infrared
radiation of different wavelengths. A IR spectrum is a plot of
wavenumber (X-axis) vs percent transmittance (Y-axis). (Note:
wavelength can be used instead of wave number and absorbance
instead of percent transmittance. IR spectra are acquired on a special instrument,
called an IR SPECTROMETER
Infrared spectroscopy is widely used in industry as well as in research. It is a simple and
reliable technique for measurement, quality control and dynamic measurement. It is also
employed in forensic analysis in civil and criminal analysis.
Some of the major applications of IR spectroscopy are as follows:
1. Identification of functional group and structure elucidation
Entire IR region is divided into group frequency region and fingerprint region. Range of
group frequency is 4000-1500 cm-1 while that of finger print region is 1500-400 cm-1.
In group frequency region, the peaks corresponding to different functional groups can be
observed. According to corresponding peaks, functional group can be determined.
Each atom of the molecule is connected by bond and each bond requires different IR region
so characteristic peaks are observed. This region of IR spectrum is called as finger print
region of the molecule. It can be determined by characteristic peaks.

2. Identification of substances
IR spectroscopy is used to establish whether a given sample of an organic substance is
identical with another or not. This is because large number of absorption bands is observed
in the IR spectra of organic molecules and the probability that any two compounds will
produce identical spectra is almost zero. So if two compounds have identical IR spectra then
both of them must be samples of the same substances.
IR spectra of two enatiomeric compound are identical. So IR spectroscopy fails to
distinguish between enantiomers.
For example, an IR spectrum of benzaldehyde is observed as follows.
C-H stretching of aromatic ring- 3080 cm-1
C-H stretching of aldehyde- 2860 cm-1 and 2775 cm-1
C=O stretching of an aromatic aldehyde- 1700 cm-1
C=C stretching of an aromatic ring- 1595 cm-1
C-H bending- 745 cm-1 and 685 cm-1
No other compound then benzaldehyde produces same IR spectra as shown above.

3. Studying the progress of the reaction

Progress of chemical reaction can be determined by examining the small portion of the
reaction mixure withdrawn from time to time. The rate of disappearance of a characteristic
absorption band of the reactant group and/or the rate of appearance of the characteristic
absorption band of the product group due to formation of product is observed.
4. Detection of impurities
IR spectrum of the test sample to be determined is compared with the standard compound.
If any additional peaks are observed in the IR spectrum, then it is due to impurities present
in the compound.
5. Quantitative analysis
The quantity of the substance can be determined either in pure form or as a mixure of two
or more compounds. In this, characteristic peak corresponding to the drug substance is
chosen and log I0/It of peaks for standard and test sample is compared. This is called base
line technique to determine the quantity of the substance.

It is possible to obtain an IR spectrum from samples in many different forms, such as liquid,
solid, and
gas. However, many materials are opaque to IR radiation and must be dissolved or diluted in a
transparent matrix in order to obtain spectra. Alternatively, it is possible to obtain reflectance or
emission
spectra directly from opaque samples. Some popular sampling techniques and accessories are
discussed
here.
Liquid cells are used for dilute solutions of solid and liquid samples that are dissolved in
relatively
IR-transparent solvents. Sampling in solution results in enhanced reproducibility and is often the
preferred choice. Unfortunately, no single solvent is transparent through the entire mid IR region.
The analyst usually chooses solvents that have transparent windows in the region of interest. The
conventional
popular solvents are carbon tetrachloride for the region between 4000 and 1330 cm
–1
and carbon disulfide for the region between 1330 and 625 cm
–1
Both solvents are quite toxic, and thus must be handled .
carefully. One may replace carbon tetrachloride with the less-toxic tetrachloroethylene or
methylene
chloride and substitute carbon disulfide with n-hexane or n-heptane. Polar solvents such as water
and
alcohols are seldom used because they absorb strongly in the mid IR range and react with alkali-
metal
halides, such as NaCl, commonly used for cell windows.
Acquiring acceptable IR spectra of aqueous samples requires use of special types of liquid cells
such as thin cells of BaF2
, AgCl, or KRS-5(a mixed thallium bromide–thallium iodide). Aqueous solution measurements
can also be accomplished with attenuated total reflectance (ATR) accessories,
which are discussed later in this chapter.
Typically, solutions of 0.05 to 10% in concentration are handled in IR cells of 0.1 to 1 mm in
thickness. Concentration of 10% and cell path length of 0.1 mm represent one practical
combination. In a
double-beam spectrometer, a compensating cell is filled with pure solvent and placed in the
reference
beam. In the single-beam FT instrument, the solvent bands are mostly removed by obtaining the
difference spectra through subtraction of solvent spectra from sample spectra. Both fixed-
thickness and variable-thickness liquid cells are available commercially. They normally consist
of metal frame plates, IRtransmitting windows, and gaskets that determine the path length of the
cells.
Salt plates of IR-transmitting materials can be used for semivolatile and nonvolatile liquid
samples. Sodium chloride disks are the most popular and economical choice for nonaqueous
liquids. Silver chloride or barium fluoride plates may be used for samples that dissolve or react
with NaCl plates.
A drop of the neat sample is squeezed between two salt plates to form a film of approximately
0.01
mm in thickness. The plates can be held together by capillary attraction, or they may be clamped
in a
screw-tightened holder or pressed to form a good contact in a press fit O-ring supported holder.
It is
also possible to place a film of samples on salt plates by melting a relatively low-melting solid
and
squeezing it between two plates. Sodium chloride salt plates can usually be cleaned with dry
methylene chloride or acetone. This smear technique is one of the simplest ways to obtain IR
spectra.
Thin films of nonvolatile liquids or solids can be deposited on an IR-transmitting salt plate by
solvent evaporation. The sample is first dissolved in a reasonably volatile solvent. A few drops
of the resulting solution are placed on the plate. After evaporating off the solvent, a thin film of
sample is
obtained for subsequent spectra acquisition.

why water can not be used as solvent in IR SPECTROMETRY

Water absorbs strongly at 3710cm-1 due to O-H stretch and 1630 cm-1 due to O-H bending.
These absorptions may overlap with the absorption bands due to the sample under examination.
Hence water cannot be used as solvent in IR spectra and also the sample has to dry.

Beer–Lambert law,

the law states that there is a logarithmic dependence between the transmission (or transmissivity), T, of
light through a substance and the product of the absorption coefficient of the substance, α, and the
distance the light travels through the material (i.e. the path length), ℓ. Theabsorption coefficient can, in
turn, be written as a product of either a molar absorptivity (extinction coefficient) of the absorber, ε, and
theconcentration c of absorbing species in the material, or an absorption cross section, σ, and the
(number) density N' of absorbers.

the amount of radiation absorbed may be measured in a number of ways:

Transmittance, T = P / P0
% Transmittance, %T = 100 T

Absorbance,
A = log10 P0 / P
A = log10 1 / T
A = log10 100 / %T
A = 2 - log10 %T
the last equation, A = 2 - log %T , is worth remembering because it allows you
10

to easily calculate absorbance from percentage transmittance data.

A=ε bc

%T = 100 P/P0 = e -ε bc
where:
A=Absorbance
c= Concentration
e= extinction coefficient
l = optical path length (typically 1 cm)

limitations of beer's law

Deviations from Beer's Law can be caused by:
(a) Stray light, which is any light striking the detector whose wavelength is outside the spectral
bandpass of the monochromator or which has not passed through the sample;
(b) Polychromatic light effect, which occurs if the absorber's absorption coefficient alpha varies
over the wavelength interval of light passing through the sample;
(c) unequal light path lengths across the light beam;
(d) unequal absorber concentration across the light beam;
(e) changes in refractive index of the solution at high analyte concentration;
(f) light-scattering by the sample matrix, especially in turbid samples, resulting in a significant
absorption signal even when the absorber's concentration is zero;
(g) shifts in chemical equilibrium involving the absorber as a function of concentration;
(h) changes in pH as a function of concentration.
(i) fluorescence of the absorber, in which some of the absorbed light is re-emitted and strikes the
detector;
(j) chemical reactions caused by the absorption of light, including photolysis, dimerization,
polymerization, and molecular phototropism (change in molecular shape when the molecule
absorbs light).
(k) if the light intensity is extremely high (like a focused laser), it's possible to observe non-linear
optical effects, which are a fundamental failure of the Beer-Lambert Law.

The most common of these are (a) and (b), which both result in a concave-down curvature of the
Beer's Law plot; (c) and (d) are easily avoided by proper experiment and instrument design
(square cuvettes, well-mixed solutions); (e) is only a problem at very high concentrations; (f) is
pretty common in real-world applications to complicated samples, but can be minimized by
special measurement techniques and instrument designs; (g) and (h) can be avoided by buffering
the solutions to constant pH and adjusting the concentration of reagents; (i) and (j) occur rarely
with some particular absorber molecules and must be treated on a case-by-case basis; (k) never
occurs in standard laboratory instruments with conventional light sources..