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INFRARED SPECTROMETRY

Sampling Methods and Qualitative Analysis


CUA-NARCISO-PILAR, EXPT 7
IN THE BOOKS
Principle
Infrared excitation occurs as vibrational motion
IR spectra are obtained by detecting changes in transmittance
(or absorption) intensity as a function of frequency
For a particular vibrational mode to absorb infrared radiation, it
must produce a change in the dipole moment of the molecule
Hookes Law
Can be used to represent the molecules undergoing vibration
Given by F=(K)(u)
F: applied force
u: displacement
k: spring constant
HOOKES LAW
Fig 1. Representation of Hookes Law
Molecular Vibrations
A molecule has 3n degrees of freedom
6: translational and rotational degrees of freedom
3n - 6
3n -5: linear molecule
Remaining degrees of freedom are for normal modes of vibration
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The IR Spectra
Functional group region: stretching vibrations at 1500 cm-1
and higher
Fingerprint region: bending vibrations at 1500-500 cm-1
{ Fingerprint Region }
Fig. 2. Infrared Spectrum of propan-1-ol, CH3CH2CH2OH
Fourier Transform IR (FTIR)
Employs a beamsplitter which takes the incoming infrared beam
and divides it into two optical beams
One beam reflects off a moving mirror while the other reflects off
a fixed mirror
The signal which exits the interferometer is the result of these
two beams interfering with each other
Interferogram: every data point which makes up the signal has
information about every infrared frequency
As the interferogram is measured, all frequencies are being
measured simultaneously
Fig. 3. Fourier Transform from Interferogram to IR spectra
Fig. 4. Layout of Classical Spectrometer
Infrared Spectrometer
Fig. 5. Michelson Interferometer
Strengths and Limitations
ID of all types of organic and many types of inorganic compounds
Determination of functional groups in org materials
Determination of the molecular composition of surfaces
ID of chromatographic elluents
Quantitative determination of cmpds in mixtures
Nondestructive method
Determination of molecular conformation (structural isomers) and
stereochemistry (geometrical isomers)
Determination of molecular orientation (polymers and solutions)
General Uses
Strengths and Limitations
ID of cmpds by matching spectrum of unknown cmpds with reference
spectrum (fingerprinting)
ID of func. groups in unknown substances
ID of reaction components and kinetic studies of reaction
ID of molecular orientation in polymer films
Detection of molecular impurities or additives present in amounts of 1%
and in some cases as low as 0.01%
ID of polymers, plastics, and resins
Analysis of formulations such as insecticides and copolymers
Common Applications
Strengths and Limitations
Samples
Amount
- Almost any solid, liquid, or gas sample can be
analyzed. Many sampling accessories are available
- Solids: (50-200 mg) is desirable
- 10 ug ground with transparent matrix (i.e. KBr) is
the min for qualitative determination
- 1 - 10 ug min is reqd if solid is soluble in suitable
solvent
-Liquids: 0.5 uL is needed if neat, less if pure
-Gasesl 50 ppb is needed
Strengths and Limitations
Preparation
Analysis Time
- Little or no preparation is required
- May have to grind solid in KBr matrix or dissolve
sample in a suitable solvent (CCl4 of CS2).
- Many types of sample holders and cells are
available
- Water should be removed if possible
- Estimated time to obtain spectrum from a routine
sample varies from 1-10 min depending on the type
of instrument and the resolution required.
- Most samples can be prepared for IR analysis in 1-5
min
Strength and Limitations
General
Accuracy
Sensitivity
and
Detection
Limits
- Minimal elemental info is given for most samples
- Background solvent or solid matrix must be relatively
transparent in the spectral region of interest
- Molecule must be active in the IR region
- In analysis of mixtures under favorable conditions,
accuracy is greater than 1%
- In routine analysis, it is +- 5%
- Routine is 2%
- 0.01% under most favorable conditions and special
techniques
IN THE LABORATORY
IR apparatus
IR SPECTROMETER
Fig. 6. Components of an IR spectrometer
To take the infrared spectrum of a sample, it is necessary to measure both the sample and a "reference" (or "control" or the background). This is because each measurement is affected by
not only the light-absorption properties of the sample, but also the properties of the instrument (for example, what light source is used, what detector is used, etc.). The reference
measurement makes it possible to eliminate the instrument inuence. Mathematically, the sample transmission spectrum is divided by the reference transmission spectrum.
The appropriate "reference" depends on the measurement and its goal. The simplest reference measurement is to simply remove the sample (replacing it by air). However, sometimes a
different reference is more useful. For example, if the sample is a dilute solute dissolved in water in a beaker, then a good reference measurement might be to measure pure water in the
same beaker. Then the reference measurement would cancel out not only all the instrumental properties (like what light source is used), but also the light-absorbing and light-reecting
properties of the water and beaker, and the nal result would just show the properties of the solute (at least approximately).
A common way to compare to a reference is sequentially: First measure the reference, then replace the reference by the sample, then measure the sample. This technique is not perfectly
reliable: If the infrared lamp is a bit brighter during the reference measurement, then a bit dimmer during the sample measurement, the measurement will be distorted. More elaborate
methods, such as a "two-beam" setup (see gure), can correct for these types of effects to give very accurate results.
----
a. infrared radiation is produced by electrically heating a lament which is divided by mirrors into 2 beams, a reference beam and a sample beam. The common radiation source for the IR
spectrometer is an inert solid heated electrically to 1000 to 1800 C. Three popular types of sources are Nernst glower (constructed of rare-earth oxides), Globar (constructed of silicon
carbide), and Nichrome coil. They all produce continuous radiations, but with
different radiation energy proles
b. In the sampling area, a segmented rotating disk allows each beam to pass through alternately.
c. The reference beam and the sample beam are combined into a beam of alternating segments.
d. The monochromator is a device used to disperse a broad spectrum of radiation and provide a continuous calibrated series of electromagnetic energy bands of determinable wavelength or
frequency
range.
e. The detector measures the heat energy and the recorder records the results as a plot of percent absorption (or transmittance) as a function of wavenumber (cm
-1
) or wavelength (m).
Most detectors used in dispersive IR spectrometers can be categorized into two classes: thermal detectors and photon detectors.
Sampling Techniques
Gas, liquid, solids
IR plates
Transparent
NaCl or KBr
Clean with acetone or
organic solvent
Fig. 7.
How to
hold an IR
plate
Fig. 8. Formation of IR plate
NaCl or KBr plates were used instead of glass because of the strong absorptions of the Si-O group.
It is important to always hold the salt plate properly. The biggest enemy of salt plates is moisture.
Salt Plates
Fig. 9. Cloudy plate
Fig. 10. Types of plates produced
Moisture in air can make the salt plate cloudy
Moisture from ngers can leave a ngerpring on the plate
When more water is in contact with the plate, it can dissolve
Thus, it is important that the salt plates be kept in dessicators
Salt plates are also very fragile. It will break or shatter in areas once dropped. They can also be scratched by metal spatulas and pasteur pipettes.
IR spectra look best when run as thin even lms of compounds
When the salt plates are damaged, the IR spectra will have broader bands than expected.
- Pits and ngerprints can cause a thick and uneven lm of the sample. This will lead to the scattering of irradiation or very intense bands.
- Cloudiness causes scattering of irradiation and even prevention of radiation transmission through the sample. THis will lead to broad bands and a spectrum that is less than 100% transmission.
Fig. 11. IR spectra of isoamyl acetate from an excellent plate
Excellent plates
- sharp bands
- >90% transmission
- not curved baseline
- carbonyl peak is most intense as it should be
Fig. 12. IR spectra of isoamyl acetate from a cloudy plate
Cloudy plate
- decrease in transmission
- curving and slanting of baseline
- some broadening of the bands
Fig. 13. IR spectra of isoamyl acetate from a pitted/ngerprinted plate
Pitted/ngerprinted
- broadening of bands
- increased relative intensities
- i.e carbony overtones in bad plate
Fig. 14. Superimposed IR spectra of isoamyl acetate from an execellent,
cloudy and pitted/ngerprinted plate
Isoamyl acetate superimposed
- main diagnostic bands (CH stretch at 3000, C=O stretch at 1750, CO stretch around 1250) show up on each and they are still the same compound
- pitted plate at 3300, misinterpret an an amine or OH bond
Solids
Mull or Paste Technique
Crush 5 mg of sample with 2 drops mulling agent in a marble or
agate mortar, squeeze between 2 plates
Nujol (liquid paraffin), Fluorolube (chlorofluorocarbon polymer),
hexachlorobutadiene
(+): grinding may change the state of sample, non-hydroscopic
(-): interference from mulling agent
Mull or Paste Technique. The mull or paste technique is the most common and easiest way to prepare a solid sample. A mull is a two-phase mixture with a consistency of toothpaste. This is obtained by grinding around 5
milligrams of the sample with 1-2 drops of the mulling agent in a marble or agate mortar. The mull is the squeezed between two salt plates and the plates are mounted on a support, ready to be read under IR radiation.
The mulling agent is used to suspend the solid particles, which helps to produce a closer match of the refractive index between the sample particles and the surrounding medium. The mulling agent should be properly
choses because it is important to identify absorptions that result from the mulling agent and those from the vibrations of the sample being analyzed. The most common mulling agents used are usually Nujol (1333-4000
cm-1) or liquid paraffin, Fluorolube (1333-4000 cm-1), a chlorofluorocarbon polymer, or hexachlorobutadiene. Nujol is a brand of purified mineral oil that consists of C20-C30 alkanes. This causes the bands in the CH
stretching region to be lost because of the absorptions of Nujol. In contrast, hexachlorobutadiene is a good mulling agent for analyzing CH bands, but it reacts with organometallic compounds. Sometimes, it is best to use
multiple mulling agents or run different mulls to obtain a full IR spectrum for it to be free from mulling agent bands.
The mulling technique is often employed because it is non-hydroscopic and can be used for solid samples that are not soluble in a liquid medium. However, this technique is at a disadvantage because of interference from
the mulling agent.
Errors may surface when the sample particle size is not reduced to 2 um or less. This can easily cause absorption rather than transmission. If the mull is not ground as well as it should be, band distortion may occur.
Solids
Case or Solid Film
Dissolve sample in non-aq solvent
Place drop of solution on IR plates
Solvent evaporated to dryness
Solvent should be based on its transparency in IR region of interest
CCl4 (4000 to 1330 cm-1), CS2 (1330 to 625 cm-1)
Can result in non-representative spectra
Thin Solid Film. The thin solid film method employs the use of a thin layer of the solid sample is spread through a salt plate. This is done by dissolving the sample in a non-aqueous solvent. A drop of the sample is then
placed on IR plates, and the solvent is allowed to evaporate to dryness. This will leave a thin film of the solute, and eliminates the effect of the solvent in the spectra.
The non-aqueous solvent should be chosen so that there will be no chemical interaction between the solvent and the sample, and it will not dissolve the plate. Also, the solvent should not absorb in the IR range to
be studied. The solvent carbon tetrachloride, for example, is a useful solvent in the region 4000-1333 nm-1. Carbon disulfide can be used in the IR region 1333-400 nm-1. Changing the concentration and path length of
the solution can be used to record the spectrum that is most useful in obtaining the desired chemical information. Changing the concentrations of CCl4 can be used to distinguish between inter- and intramolecular
hydrogen bonding.
It has been found, however, that this technique can result in non-representative spectra. This is why an IR run of the solvent is usually done to take into consideration any variations found to be caused by the
solvent, and not the sample.
Thin film + how to use IR
Thin film + how to use IR
Mull + cavi ty cell?
Solids
Pellet Technique or KBr discs
Grind small amount of sample with KBr in 100 times its weight.
Compressed into a thin transparent wafer or disc
Used for sample difficult to melt or dissolve in any suitable IR-solvent
Can lead to formation of artifacts and distortions
Application of pressure can change appearance of spectrum
Water contaminant will lead to OH stretch at 3500 cm-1
KBr Pellets. Potassium bromide pellets are dilute suspensions of a solid in a solid. This is obtained by grinding a small amount of sample with KBr in 100 times the samples weight. The mixture is the compressed into a
thin transparent wafer or disc by placing the powdered mixture in a pellet die under a pressure of about 6000-10000 psi.
Potassium bromide is used because it is totally transparent in the mid-IR and near IR region. It can also be compressed under high pressures with or without a vacuum to from transparent discs. It should
however be taken in consideration that the KBr is equally dispersed or distributed. Also, the sample mixture should not be ground as much because it can induce water into the mixture.
This method is used for samples that are difficult to melt or dissolve in any suitable IR-solvent. Moreover, only a small amount of the sample is needed to proceed with this technique. However, the application of
high-pressure and force can lead to the formation of artifacts and distortions in the spectrum. If the sample is not crystalline enough, it can lead to poor quality pellets. The pellets are also prone to moisture contamination.
Bands near 3500 nm-1 and 1700 nm-1 can be from moisture and not from the sample. Freeze-drying the sample can prevent such deviations from the theoretical IR spectrum from the samples. A Nujol run can also be
employed. The two spectra should be similar, but because Nujol is a hydrocarbon and it has no affinity for water, any absorption from Nujol at 3500 nm-1 and/or 1700 nm-1 is from the sample, and not from moisture.
-
KBr pellet
Solid sample
Liquids
Can be run neat or by dissolving in a solvent
Thin film
Organic solvent
For semi-volatile and non-volatile samples: drop of solution
placed on disk and allowed to evaporate
Liquid/Cavity cells: to examine liquid samples in solution
IR cards
Liquid samples can be run neat or dissolved in a solvent under infrared radiation. Whether neat or treated, a drop of the liquid sample can be sandwiched using discs of purified alkali halides or the salt plates. Another
method is done by allowing a drop of the liquid sample to evaporate on the salt plate to deposit a thin film of crystal that will transmit sufficient light to provide an acceptable IR spectrum. This is usually used for semi-
volatile and non-volatile samples.
In order to get a good infrared spectrum, the sample concentration and path length should be selected so as to obtain a transmittance of 15%-70%. For neat samples, the path or cell length should be around 0.02
mm, while for liquid solutions, the concentration of the sample should be about 1-% and the cell length should be around 0.1mm.
For liquid solutions, as in other methods, the solvent should be organic, because aqueous solutions can dissolve alkali halides.
Liquids can also be analyzed in a bulk solution form by using liquid cavity cells with transparent windows with a spacer between them. The thickness of the spacer will determine the path length. The path length is
significant or related to the molecular weight of the sample. For low molecular weight liquid samples, shorter pathlengths are needed. The blank used should be placed in line with the reference beam so that any
absorption from the solvent is cancelled. If a blank is not used, the signal may easily overlap and there will be no clear distinction of band splits and their relative intensities. If the sample is volatile, the cell should be
covered.
IR cards are also used for non- or low volatility liquids. IR cards are non-hygroscopic, cheap, and disposable supports prepared from thin polyethylene polymer substrates. They absorb only in well-known, narrow
bands. The clean substrate is used as a background. The absorptions are then ratioed out in the final step of sample spectrum generation.
Gases
May be placed in sample cell
made of transparent NaCl or KBr
windows
Need for longer path length
because gases absorb weakly
White cell
Long path gas phase
spectroscopy cell used to
measure low-concentration
components in gases or liqid
Fig. 15. Diagram of a white cell
Gaseous samples may be placed in sample cells made out of transparent NaCl or KBr windows. Longer path lengths are needed because gases absorb quickly. It is preferred that the variable path length cell walls be
coated with a s polymeric substance, such as polytetrafluorothylene, to prevent the absorption of the chemical under the surface of the metallic cell body or support. Sometimes, the cell must be heated or quenched in nitrogen or
dry air in order to remove absorbed chemical molecules.
Usually, a white cell is used for obtaining IR spectra of gaseous samples. A white cell is a multiple-pass cell or a long path gas phase spectroscopy cell that is used to measure low-concentration components in gases and
liquids. This cell increases the length of the optical path through the cell while keeping the sample volume constant. The cell uses spherical concave mirrors with the same radius of curvature. The mirror are arranged to minimize
optical distortions by increasing the number or passes to allow for more traversals. This increases the total optical path length in comparison to the volume of the cell.
RESULTS AND DISCUSSION
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Comparison of Methods
Mulling Cast Film KBr Pellet
Halogen exchange
with KBr (i.e. base
HCl)
No effect of solvent
Important bands in
mid-IR region
Structural data
required (i.e.
polymorphism)
Structural data
required (i.e.
polymorphism)
Samples difcult to
melt/dissolve
Interference from
mulling agent
Structural data
required (i.e.
polymorphism)
Water contamination
(OH stretch at 3500
cm-1)