Solids sampling in IR spectroscopy with video tutorial.

1. PRESENTATION ON
SAMPLING OF SOLIDS
IN INFRARED SPECTROSCOPY
T.Manoj Kumar

2. INTRODUCTION:
• IR spectroscopy refers broadly to that region of electromagnetic
spectrum which lies between visible and microwave regions.
• This region is divided into different sections:

3. BASIC PRINCIPLE:
• A chemical substance shows marked selective absorption in IR
region.
• After absorption of IR radiation the molecules of chemical
substance vibrate at many rates of vibration giving rise to closely
packed absorption spectrum called as IR absorption spectrum.
• Various bands present in the IR spectrum corresponds to
characteristic functional group and bonds present in the chemical
substance.
• Thus IR spectrum of a chemical substance is fingerprint for its
identification.

4. SAMPLE HANDLING TECHNIQUES IN IR SPECTROSCOPY:
• Samples of different phases have to be treated differently.
• The only common point to the sampling of different phases is that the
material containing the sample must be transparent to IR radiation.
• This condition restricts our selection to only certain salts like NaCl or
KBr.
• However, a final choice of salt will depend on the wavelength range to
be studied.
• Miller (1965) developed appropriate methods to handle samples in the
gas, liquid and solid phase.

5. SAMPLE CELL:
• Sample handling presents a number of problems in IR region.
• There is rugged window material for cuvette that is transparent
and also inert over this region.
• The alkali halides are widely used, particularly NaCl, KBr and
ThBr which is transparent at wavelength as long as 625 cm -1.
• AgCl cells are used for aqueous and moist samples but it is soft
and easily gets deformed and darkens on exposure to visible light.

6. • Cells made up of Teflon and polyethylene can be used, but Teflon
shows bands due to C-C & C-F.
• For frequencies less than 600 cm-1, a polyethylene cell is used.
Because of the tendency of solvents to absorb, IR cells are
ordinarily much narrower (0.1-1 mm) than those employed in UV
and visible regions.
• Sample concentrations required is from 0.1-10%.

7. Precautions:
• Cell windows are easily fogged by exposure to moisture and
require frequent polishing with buffer powder which returns
them to their original condition.
• Since alkali metal halides, with which cell is made up of are
hygroscopic so must be protected from moisture by working at a
suitable temperature.

8. SAMPLING OF SOLIDS:
Generally 4 techniques are employed for preparing solid
samples:
1. Solids run in solution.
2. Solid Films.
3. Mull technique.
4. Pressed pellet technique.

9. SOLIDS RUN IN SOLUTION
• Solids may be dissolved in non-aqueous inert solvent and a
drop of this solution is placed on an alkali metal disc and
solvent is allowed to evaporate, leaving a thin film of solute
(or the entire solution is placed in a liquid sample cell) which
is then mounted in spectrometer.
• If the solution of solid can be prepared in a suitable solvent
then the solution is run in concentration of cells for liquids.
• Some solvents used are chloroform, carbon tetrachloride,
acetone, Cyclohexane etc.

10. Demerit:
• This method can’t be used for all solids because suitable
solvents are limited in number & there is no single solvent
which is transparent throughout IR region.
Precautions:
• Solute chemical interaction with the solvent must be taken
into consideration especially for compounds having property
of H-bonding.
• The solvent should not absorb in the studied range.

11. SOLID FILMS
• If a solid is polymer resins & amorphous solids, the sample is
dissolved in any reasonable volatile solvent & this solution is poured
on a rock salt plate (Nacl or KBr) & solvent is evaporated by gentle
heating.
• If solid is non-crystalline, a thin homogenous film is deposited on
the plate which can be mounted and scanned directly.
• Sometimes polymers can be “hot pressed” onto plates.
Merit and Demerit:
• This method is useful for rapid qualitative analysis but becomes
useless for carrying out quantitative analysis.

12. MULL TECHNIQUE:
• In this technique a small quantity of sample is thoroughly ground
in a clean mortar until the powder is very fine.
• After grinding, the mulling agent (mineral oil or Nujol) is
introduced in small quantities just sufficient to take up the powder
(mixture approximates the consistency of a toothpaste).
• The mixture is then transferred to the mull plates & the plates are
squeezed together to adjust the thickness of the sample between
IR transmitting windows.
• This is then mounted in a path of IR beam and the spectrum is
run.

14. Demerit:
• Although Nujol is transparent throughout IR region, yet it has a
disadvantage that it has absorption maxima at 2915, 1462, 1376
& 719 cm-1.
• So when IR spectrum of solid sample is taken in Nujol mull,
absorption bands of solid sample that happen to coincide with
the absorption bands of the Nujol mull will be hidden (but
others will be clearly seen in IR spectrum) and then interferes
with the absorption of the sample.

15. • This interference can be avoided by using Hexachlorobutadiene
in combination with nujol which absorbs in regions 1630-1510
cm -1, 1200-1140 cm-1, 1010-760 cm-1 and thus permits the
recording of IR spectra of only the sample.
• This method is good for qualitative analysis but not for
quantitative analysis.

16. Pressed pellet technique:
• In this technique a small amount of finely ground solid sample is
intimately mixed with about 100 times its weight of powdered
Potassium bromide, in a vibrating ball mill.
• This finely ground mixture is then pressed under very high
pressure (25000 p sig) in evacuable die or minipress to form a
small pellet (about 1-2 mm thick and 1cm in diameter).
• The resulting pellet is transparent to IR radiation and is run as
such.

17. Preparing a KBr Disk

20. • The powder (KBr + sample) is introduced in between the 2
bolts and the upper screw A is tightened until the powder is
compressed to a thin disc.
• After compressing the sample bolts A & A1 are removed and
a steel cylinder with pellet inside it is placed in path of the
beam of IR spectrometer and a blank KBr pellet of identical
thickness is kept in the path of reference beam.

23. Advantages of this technique over mull technique:
• The use of KBr eliminates the problem of bands which appear
in IR spectrum due to the mulling agent as in this case no such
bands appear.
• KBr pellets can be stored for longer periods of time.
• As concentration of the sample can be suitably adjusted in
pellets, it can be used for quantitative analysis.
• The resolution of spectrum in KBr is superior to that obtained
with mulls.

24. Demerits:
• It always has a band at 3450 cm-1, from –OH group of moisture
present in the sample.
• The high pressure involved during the formation of pellets may
bring about polymorphic changes in crystallinity in the samples,
(Especially inorganic complexes) which may cause complications
in IR spectrum. In some cases, even substitution of the ligand by
bromide may be possible in inorganic complexes.
• This method is not successful for some polymers which are
difficult to grind with KBr.

25. CONCLUSION:
• Form the discussion, one may draw the important conclusion
that one may employ the Nujol mull technique may be applied
for crystalline compounds (including complexes) in solid state
& may reserve the pellet technique for remaining solid
samples.

26. REFERENCES:
1. Instrumental methods of chemical analysis, 5th edition,
Gurdeep.R.Chatwal & Sham.K.Anand, Pg.No.2.29.
2. Instrumental methods of analysis, 7th edition, Willard, Merritt,
Dean & Settle, Pg. no. 305-310.
3. Instrumental methods of chemical analysis, 26th edition,
B.K.Sharma, Pg.No.262-264.
4. Organic spectroscopy, third edition, William Kemp, pg. no. 51.