Chem 306 Instrumental Analysis II

Prof. Dr. Şerife H. Yalçın

İzmir Institute of Technology, Chemistry Dept. 35430 İZMİR/TURKEY

Informations given in these slides are, either in part or all, recollection from the following sources,
solely for education purposes.
Principles of Instrumental Analysis, 6e/7e by Holler, Skoog & Crouch, 2007
Fundamentals of Analytical Chemistry 9e by Douglas A. Skoog, 2013. 1
 Chapter 16-17
An Introduction and Application to Infrared
Spectrometry
The infrared region of the spectrum encompasses radiation with
wavenumbers ranging from about 12,800 to 10 cm-1 or wavelengths from
0.78 to 1000 m. The infrared spectrum is divided into near-, mid-, and far-
infrared radiation.
Infrared Spectroscopy
A) Introduction
A) 1.)Infrared (IR) spectroscopy: based on IR absorption by molecules as undergo
vibrational and rotational transitions. Absorption of radiation in this region by a typical
organic molecule results in the excitation of vibrational, rotational and bending
modes, while the molecule itself remains in its electronic ground state.

rotational transitions
Potential Energy (E)

Vibrational transitions

Interatomic Distance (r)

Potential energy resembles classic Harmonic Oscillator

 2.) IR radiation is in the range of 12,800 – 10 cm-1 or l = 0.78 – 1000 m
- rotational transitions have small energy differences
• ≤ 100 cm-1, l > 100 m
- vibrational transitions occur at higher energies
- rotational and vibrational transitions often occur together

3.) Typical IR spectrum for Organic Molecule

% Transmittance

Wavenumber (cm-1)
 Wide Range of Types of Electromagnetic Radiation in nature.
1. Only a small fraction (350-780 nM is visible light).
2. The complete variety of electromagnetic radiation is used throughout spectroscopy.
3. Different energies allow monitoring of different types of interactions with matter.

E=hn = hc/l
3.) Typical IR spectrum for Organic Molecule
- many more bands then in UV-vis, fluorescence or phosphorescence
- bands are also much sharper
- pattern is distinct for given molecule
• except for optical isomers
- good qualitative tool
• can be used for compound identification
• group analysis
- also quantitative tool
• intensity of bands related to amount of compound present
- spectra usually shown as percent transmittance (instead of absorbance)
vs. wavenumber (instead of l) for convenience

Hexane

Hexene

Hexyne
B) Theory of IR Absorption

1.) Molecular Vibrations

i.) Harmonic Oscillator Model:

- approximate representation of atomic stretching
- two masses attached by a spring

E = ½ ky2

where:
y is spring displacement
k is spring constant
Vibrational frequency given by:

n  1/ 2 k / m
where:
n : frequency
k: force constant (measure of bond stiffness)
: reduced mass – m1m2/m1+m2

If know n and atoms in bond, can get k:

Single bonds:
k ~ 3x102 to 8 x102 N/m (Avg ~ 5x102)

double and triple bonds ~ 2x and 3x k for

single bond.

So, vibration n occur in order:

n k single < double < triple
 ii.) Anharmonic oscillation:
- harmonic oscillation model good at low energy levels (n0, n1, n2, …)
- not good at high energy levels due to atomic repulsion & attraction
• as atoms approach, coulombic repulsion force adds to the bond
force making energy increase greater then harmonic
• as atoms separate, approach dissociation energy and the harmonic
function rises quicker

Harmonic oscillation

Anharmonic oscillation

Because of anharmonics: at low DE, Dn =±2, ±3 are observed which cause the appearance of
overtone lines at frequencies ~ 2-3 times the fundamental frequency. Normally Dn = ± 1
iii.) Types of Molecular Vibrations

1- Fundamental Vibrations: Bond Stretching Bond Bending

Fundamental bands
are inherently intense,
make up most of the
peaks seen in mid-IR symmetric
spectra, and comprise In-plane rocking
most of the
diagnostically useful
peaks for
interpretation asymmetric
In-plane scissoring
purposes.

2- Non-fundamental Vibrations
Out-of-plane wagging
- Overtones, from v = 0 to v = 2,3,4 or higher
*For fundamentals above 2000 cm-1 their
overtones will mostly appear above 4000 cm-1
* Since overtones are weak they are Out-of-plane twisting
generally not diagnostically useful IR
features.
- Combination Tones, more than one
vibration can be excited at the same time.
Figure 3: The IR spectrum of methyl ethyl ketone, with examples of fundamental and
overtone bands marked.
Figure 4: The IR spectrum of liquid water with the scissors vibration, O-H stretch, and
combination band marked.
 symmetric asymmetric In-plane scissoring

Out-of-plane twisting In-plane rocking Out-of-plane wagging

iv.) Number of Vibrational Modes:
- for non-linear molecules, number of types of vibrations: 3N-6
- for linear molecules, number of types of vibrations: 3N-5
- why so many peaks in IR spectra
- observed vibration can be less then predicted because
• symmetry ( no change in dipole)
• energies of vibration are identical
• absorption intensity too low
• frequency beyond range of instrument

Examples:
1) HCl: 3(2)-5 = 1 mode

2) CO2: 3(3)-5 = 4 modes

- + - moving in-out of plane

See web site for 3D animations of vibrational modes for a variety of molecules
http://www.chem.purdue.edu/gchelp/vibs/co2.html
v.) IR Active Vibrations:
- In order for molecule to absorb IR radiation:
• vibration at same frequency as in light
• but also, must have a change in its net dipole moment
as a result of the vibration

Examples:
1) CO2: 3(3)-5 = 4 modes  = 0; IR inactive
d- 2d+ d-
 > 0; IR active
d- 2d+ d-
- + -  > 0; IR active
d- 2d+ d-
degenerate –identical energy single IR peak
2d+
 > 0; IR active
d- d-
Example 8: Calculate the absorption frequency for the C-H stretch with a force constant of k =
5.0x102 N/m.
 16B IR INSTRUMENTATION
Three types of instruments for IR absorption measurements are commonly
available:
(1) dispersive spectrophotometers with a grating monochromator, (Until the 1980s)
(2) FT spectrometers employing an interferometer (Section 7I), and
(3) nondispersive photometers using a filter or an absorbing gas that are used for
analysis of atmospheric gases at specific wavelengths.

(1) DISPERSIVE INSTRUMENTS

- dispersive instruments are generally double-beam instruments,
- use reflection gratings for dispersing radiation.
- the double-beam design is less demanding wrto the performance of sources and
detectors
— an important characteristic because of the relatively low intensity of IR
sources, the low sensitivity of IR transducers, and the resulting requirement for
large signal amplifications (see Section 16C).
- An additional reason for the general use of double-beam instruments in the IR
region is the elimination of the atmospheric water and carbon dioxide from the
spectra.
 Double-beam instruments
Basic Design: similar to UV-Vis, main differences are light source & detector

- a low-frequency chopper
permits the detector to
discriminate between the
signal from the source and
signals from extraneous
radiation, such as IR
emission from various bodies
surrounding the transducer.

the sample and reference

compartments located
between the source and the
MC ;
- IR radiation, in contrast to
UV-visible, is not sufficiently
energetic, no photochemical
decomposition of the sample.
- It is also advantageous that
most scattered radiation and
IR emission, generated within
the cell compartment, is
FIgure 11 Schematic diagram of a double-beam, dispersive IR effectively removed by the
spectrophotometer. The heavy black lines indicate mechanical linkages, and
MC and thus does not reach
the light lines indicate electrical connections. The radiation path is designated
by dashed lines.
the transducer.
iv.) Overall Instrument Design

-Need chopper to discriminate source light

from background IR radiation
-Monochromator after sample cell
-Not done in UV-Vis since letting in all
hn to sample may cause
photdegradation (too much energy)
-IR lower energy
-Advantage that allows
monochromator to be used to screen
out more background IR light
-Problems:
-Source weak , need long scans
-Detector response slow – rounded
peaks
2) NONDISPERSIVE INSTRUMENTS

- Generally, these instruments are less complex, more rugged, easier to

maintain, and less expensive than the instruments we have previously
described in this chapter.
- Some are simple filter photometers,
- some use filter wedges in lieu of a dispersing element to provide entire
spectra.
- Some gas analyzers use no wavelength-selection device at all.
 IR filter photometer designed for quantitative analysis of various substances in the
atmosphere. The gaseous sample is brought into
the cell by means of a battery-
operated pump at a rate of 20
L/min.
In the cell, three
gold-plated
mirrors are used
in a folded-path-
length design.
Path lengths of
0.5 m and 12.5 m
may be selected.
Detection of
many gases at
sub-parts-per-
million levels,
particularly with
the long-path-
length setting,
have been
reported with this
photometer.

FIgure 16-13 A portable IR photometer designed for gas analysis. The sample is introduced
into the cell by means of a pump. The path length can be changed by altering the number of
Photometers without Filters
- Widely used to monitor gas streams for a single comp.
- Figure 16-14 to determine CO) in a gaseous mixture
- The reference cell: a non absorbing gas;
- the sample flows through a second cell of similar
length.
- The beams chopped simultaneously by the chopper.
- Selectivity is obtained by filling both compartments of
the sensor cell with the gas being analyzed, CO in this
example.
- The two chambers of the detector are separated by a
thin, flexible, metal diaphragm that serves as one plate
of a capacitor; the second plate is contained in the
sensor compartment on the left.
- In the absence of CO in the sample cell, the two
sensor chambers are heated equally by IR radiation
from the two sources.
- If the sample contains CO, however, the right-hand
beam is attenuated somewhat and the corresponding
sensor chamber becomes cooler with respect to its
reference counterpart.
- As a result, the diaphragm moves to the right and the FIgure 16-14 A nondispersive IR
capacitance of the capacitor changes. This change in photometer for monitoring CO.
capacitance is sensed by the amplifier system
- The device can be adapted to the determination
of any IR-absorbing gas (e.g., CO2, NO, or H2S).
3) FOURIER TRANSFORM IR (FTIR)
- alternative to Normal IR
- Based on the Michelson Interferometer that generates an interferogram
- This interferogram data is then mathematically transformed using a
Fourier algorithm to obtain an IR spectrum.
- FTIR is much faster and more sensitive than traditional IR spectroscopy.

- Conventional spectroscopy can be termed

frequency-domain spectroscopy in that radiant
power data are recorded as a function of frequency
or wavelength. In contrast, time-domain
spectroscopy, which can be achieved by the
Fourier transform, is concerned with changes in
radiant power with time.
- Time-domain signals, cannot be acquired
experimentally with radiation in the frequency
range that is associated with optical spectroscopy
(1012 to 1015 Hz),because there are no transducers
FIGURE 7-41 (a) Time-domain plot of two slightly different that will respond to radiant power variations at
frequencies of the same amplitude n1 and n2. these high frequencies.
(b) Time-domain plot of the sum of the two waveforms in (a).
(c) frequency-domain plot of n1. (d) frequency-domain plot of n2.
(e) frequency-domain plot of the waveform in (b).
 - Acquiring Time-Domain Spectra with a Michelson Interferometer
- A typical transducer yields a signal that corresponds to the average
power of a high-frequency signal and not to its periodic variation.
To obtain time-domain signals requires, therefore, a method of
converting (or modulating) a high-frequency signal to one of
measurable frequency without distorting the time relationships
carried in the signal; that is, the frequencies in the modulated
signal must be directly proportional to those in the original.
- Different signal-modulation procedures are used for the various
wavelength regions of the spectrum. The Michelson interferometer
is used extensively to modulate radiation in the optical region.

1) The Michelson interferometer is a device that splits a

beam of radiation into two beams of nearly equal power
and then recombines them in such a way that intensity
variations of the combined beam can be measured as a
function of differences in the lengths of the paths of the
two beams.
2) The splitted beams go to two other mirrors, one fixed
and the other movable, and are reflected to recombine at
the central mirror and pass through the sample to the
detector
3) The movement of the second mirror enables light to
travel different distances in two paths before recombining;
b) constructive & destructive interference occurs
c) as the mirror is moved, get a change in signal
Remember
Destructive Interference can be created when two waves from the same source travel different paths to get
to a point.
The difference in path lengths for the two beams, in the figure, is
called the retardation, d.

Resolution
The resolution of a Fourier transform spectrometer can
be described in terms of the difference in wavenumber
between two lines that can be just separated by the
instrument.

This equation means that resolution in wavenumbers

will improve in proportion to the reciprocal of the
distance that the mirror travels.

This may cause a difference in the phase

between the two waves.
• If the paths differ by an integer multiple of a
wavelength, the waves will also be in phase.
• If the waves differ by an odd multiple of half a
wave then the waves will be 180 degrees out of
phase and cancel out.
- a plot of Intensity vs. Distance (interferograms)
- convert to the plot of Intensity vs. Frequency by doing a Fourier Transform

- resolution Dn = 1/Dd (interval of distance traveled by mirror)

Advantages of FTIR compared to Normal IR:
1) The throughput, or Jaquinot, advantage- few optical elements and no slits to attenuate radiation, the
radiant power that reaches the detector is much greater than in dispersive instruments, and much greater
signal-to-noise ratios are observed.
2) high resolution (<0.1 cm-1); high resolving power and wavelength reproducibility that makes possible the
analysis of complex spectra
3) Fellgett, or multiplex, advantage- much faster, seconds vs. minutes- all elements of the source reach the
detector simultaneously; all frequencies are collected at once, therefore more data is collected and use of
signal averaging to increase signal-to-noise (S/N) is applied.

increase S / N  number scans

Disadvantages of FTIR compared to Normal IR:

1) single-beam, requires collecting blank

2) can’t use thermal detectors – too slow

COMPONENTS of IR INSTRUMENTS

i) Light Source:
- must produce IR radiation
- can’t use glass since absorbs IR radiation
- several possible types

a) Nernst Glower Zr, Ce, Th

- rare earth metal oxides (Zr, Ce, Th) heated electrically

- apply current to cylinder, has resistance to current flow generates heat (1200o – 2200o C).
- causes light production similar to blackbody radiation
- range of use ~ 670 – 10,000cm-1
- need good current control or overheats and damaged

b) Globar
- similar to Nernst Glower but uses silicon carbide rod instead of rare earth oxides
- similar usable range
c) Incandescent Wire Source

- tightly wound nichrome or rodium wire that is electrically heated

- same principal as Nernst Glower
- lower intensity then Nernst Glower or Globar, but longer lifetime

d) CO2 Laser
- CO2 laser gas mixture consists of 70% He, 15% CO2, and 15% N2
- a voltage is placed across the gas, exciting N2 to lowest vibrational levels.
- the excited N2 populate the asymmetric vibrational states in the CO2 through
collisions.
- infrared output of the laser is the result of transitions between rotational states of the CO2
molecule of the first asymmetric vibrational mode to rotational states of both the first
symmetric stretch mode and the second bending mode
- gives off band of ~ 100 cm-1’s in range of 900-1100 cm-1
- small range but can choose which band used & many compounds have IR absorbance in
this region
- much more intense than Blackbody sources

e) Others
- mercury arc (l > 50 m) (far IR)
- tungsten lamp (4000 -12,800cm-1) (near IR)
ii.) Detectors:
- three main types in common IR instruments
a) Thermal Detectors
b) Photoconducting Detectors
c) Pyroelectric Detectors metal1 metal2
hn

- +
A- Thermal Detectors IR transparent
material (NaCl)
1.) Thermocouple V

- two pieces of dissimilar metals fused together at the ends

- when heated, metals heat at different rates
- potential difference is created between two metals that varies with their difference in
temperature
- usually made with blackened surface (to improve heat absorption)
- placed in evacuated tube with window transparent to IR (not glass or quartz)
- IR “hits” and heats one of the two wires.
- can use several thermocouples to increase sensitivity.
2.) Bolometer
i
- strips of metal (Pt, Ni) or semiconductor that has a large
change in resistance to current with temperature. hn
- as light is absorbed by blackened surface, resistance
increases and current decreases
A
- very sensitive

B) PHOTOCONDUCTING DETECTORS
- thin film of semiconductor (ex. PbS) on a nonconducting glass surface and sealed in a
vacuum.
- absorption of light by semiconductor moves from non-conducting to conducting state
- decrease in resistance  increase in current hn vacuum
- range: 10,000 -333 cm-1 at room temperature

semiconductor

glass
Transparent
to IR
C) PYROELECTRIC DETECTORS
- pyroelectric (ceramic, lithium tantalate) material get polarized (separation of (+) and (-)
charges) in presence of electric field.
- temperature dependent polarization
- measure degree of polarization related to temperature of crystal
- fast response, good for FTIR
iii.) Other Components
a.) Sample Cell
- must be made of IR transparent material (KBr pellets or NaCl)

NaCl plates
Liguid Sample Holder

b.) monochromator

- reflective grating is common

- can’t use glass prism, since absorbs IR
 Chapter 17 Applications of IR Spectrometry
Mid-IR absorption and reflection spectrometry are major tools for determining the
structure of organic and biochemical species. In this section we examine mid-IR
absorption applications. Section 17B is devoted to mid-IR reflectance
measurements.1
17A-1 Sample Handling

- In UV-Vis, absorbance measurements in the optimal range are obtained by

suitably adjusting either the concentration or the cell length.
- Unfortunately, this approach is often not applicable for IR spectroscopy
because no good solvents are transparent throughout the region of interest. As a
result, sample handling is frequently the most difficult and time-consuming part
of an IR spectrometric analysis.
- In this section we outline some of the common techniques for preparation of
samples for IR absorption measurements.
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.
- For this purpose, a variety of cylindrical cells
are available with path lengths that range from a
few centimeters to 10 m or more.
- The longer 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 IR spectra is on solutions prepared to contain a
known concentration of sample, as is generally done in UV-visible spectrometry. This
technique is somewhat limited in its applications, however, by the availability of solvents
transparent over significant regions in the IR.
Solvents. no single solvent is transparent throughout the entire mid-IR region.
- Water and the alcohols are difficult to use as solvents in IR spectrometry.
- Water shows several strong absorption bands in the IR region, as can be seen in
Figure 17-2.
Water and alcohols also
attack alkali-metal
halides, the most
common materials used
for cell windows. Hence,
water-insoluble window
materials, such as barium
fluoride, must be used
with such solvents. Care
must also be taken to dry
the solvents shown in
Figure 17-1 before use
with typical cells.
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 used in the UV and visible regions.
- Often, relatively high sample concentrations (from 0.1% to 10%) are required because of the
short path lengths and the low molar absorptivity of IR bands.
- Liquid cells are frequently designed for easy disassembly and use Teflon spacers to allow
variation in path length (see Figure 17-3).
Fixed-path-length cells can be
filled or emptied with a
hypodermic syringe.
- A variety of window materials are
available as listed in Table 17-2.
- Window materials are often chosen on
the basis of cost, range of transparency,
solubility in the solvent, and reactivity with
the sample or solvent.
-Sodium chloride and potassium bromide
windows are most commonly used and are
the least expensive.
- Even with care, however, their surfaces
eventually become fogged because of
absorption of moisture. Polishing with a
buffing powder can, in many cases, return
them to their original condition.
- For samples that are wet or aqueous,
calcium and barium fluoride are suitable,
although neither transmits well throughout
the entire mid-IR region. Silver bromide is
often used, although it is more expensive,
is photosensitive, and is easily scratched.
Liquids
When the amount of a liquid sample is small or when a suitable solvent is unavailable, it is
common practice to obtain spectra on the pure (neat) liquid. The thickness of a very thin film
of liquid presents a sufficiently short path length to produce satisfactory spectra. Commonly,
a drop of the neat liquid is squeezed between two rock-salt plates to give a layer 0.015 mm
thick or less. The two plates, held together by capillary action, are then placed in the beam
path. This technique does not give particularly reproducible transmittance data, but the
resulting spectra are usually satisfactory for qualitative investigations.
Solids
Most organic compounds exhibit numerous absorption bands throughout the mid-IR region,
and finding a solvent that does not have overlapping bands is often impossible. Because of
this, spectra are often obtained on dispersions of the solid in a liquid or solid matrix.
Generally, in these techniques, the solid sample must be ground until its particle size is much
less than the wavelength of the radiation to avoid the effects of scattered radiation.
Pelleting. One of the most popular techniques for handling solid samples has been KBr
pelleting (other alkali-metal halides have also been used). Halide salts have the property of
cold flow, in which they have glasslike transparent or translucent properties when sufficient
pressure is applied to the finely powdered materials. In using this technique, a milligram or
less of the finely ground sample is intimately mixed with about 100 mg of dried, spectroscopic
grade, potassium bromide powder. Mixing can be carried out with a mortar and pestle or,
better, in a small ball mill. The mixture is then pressed in a special die at 10,000 to 15,000
pounds per square inch to yield a transparent disk. Best results are obtained if the disk is
formed in a vacuum to eliminate occluded air. The disk is then held in the instrument beam
for spectroscopic examination. The resulting spectra frequently exhibit bands at 3450 and
1640 cm-1 (2.9 and 6.1 μm) due to absorbed moisture.
KBr
- With many compounds, KBr pelleting produces excellent spectra that appear in many
spectral libraries.
- Being ionic, KBr transmits throughout most of the IR region with a lower cutoff of about
400 cm-1
- Although KBr is the most frequently used pelleting salt, materials such as CsI and CsBr
are sometimes used. Cesium iodide has greater transparency at low frequencies than KBr.

Mulls.
- R spectra of solids that are not soluble in an IR-trans- parent solvent or are not
conveniently pelleted in KBr are often obtained by dispersing the analyte in a mineral oil or
a fluorinated hydrocarbon mull.
Qualitative Analysis (Compound Identification)

- Use of IR, with NMR and MS, in late 1950’s revolutionized organic chemistry
► decreased the time to confirm compound identification 10- 1000 fold

- Identification of an organic compound from a spectrum of this kind is a two-step

process.
1) examine what functional groups are present by looking at group frequency region
- 3600 cm-1 to 1200 cm-1
2) A detailed comparison of the spectrum of the unknown with the spectra of pure
compounds that contain all of the functional groups found in the first step.
- The fingerprint region,
from 1200 to 600 cm-1 is
particularly useful here
because small differences
in the structure and
constitution of a molecule
result in significant changes
in the appearance and
distribution of absorption
bands in this region.
- Consequently, a close
match between two spectra
in the fingerprint region (as
well as others) constitutes
almost certain evidence
that the two compounds are
identical.
ii.) Group Frequency Region
- approximate frequency of many functional groups (C=O,C=C,C-H,O-H) can be calculated
from atomic masses & force constants
- positions changes a little with neighboring atoms, but often in same general region
- serves as a good initial guide to compound identity, but not positive proof.

- group frequencies and correlation charts serve as a starting point in the identification
process.
- charts permit intelligent guesses as to what functional groups are likely to be present or
absent in a molecule.
Abbreviated Table of Group Frequencies for Organic Groups
Bond Type of Compound Frequency Range, cm-1 Intensity
C-H Alkanes 2850-2970 Strong
C-H Alkenes H 3010-3095 Medium
C C
675-995 strong

C-H Alkynes C C H 3300 Strong

C-H Aromatic rings 3010-3100 Medium

690-900 strong
0-H Monomeric alcohols, phenols 3590-3650 Variable
Hydrogen-bonded alchohols, phenols 3200-3600 Variable, sometimes broad
Monomeric carboxylic acids 3500-3650 Medium
Hydrogen-bonded carboxylic acids 2500-2700 broad
N-H Amines, amides 3300-3500 medium
C=C Alkenes 1610-1680 Variable
C=C Aromatic rings 1500-1600 Variable
C C Alkynes 2100-2260 Variable
C-N Amines, amides 1180-1360 Strong
C N Nitriles 2210-2280 Strong
C-O Alcohols, ethers,carboxylic acids, esters 1050-1300 Strong
C=O Aldehydes, ketones, carboxylic acids, esters 1690-1760 Strong
NO2 Nitro compounds 1500-1570 Strong
1300-1370
iii.) Fingerprint Region (1200-700 cm-1)
- region of most single bond signals
- many have similar frequencies, so affect each other & give pattern characteristics of
overall skeletal structure of a compound
- exact interpretation of this region of spectra seldom possible because of complexity
- complexity  uniqueness Fingerprint Region
iv.) Computer Searches
- many modern instruments have reference IR spectra on file (~100,000 compounds)
- matches based on location of strongest band, then 2nd strongest band, etc
overall skeletal structure of a compound
- exact interpretation of this region of spectra seldom possible because of complexity
- complexity  uniqueness

Bio-Rad SearchIT database

of ~200,000 IR spectra
2.) Quantitative Analysis
- not as good as UV/Vis in terms of accuracy and precision
► more complex spectra
► narrower bands (Beer’s Law deviation)
► limitations of IR instruments (lower light throughput, weaker detectors)
► high background IR
► difficult to match reference and sample cells
► changes in e (A=ebc) common
- potential advantage is good selectivity, since so many compounds have different IR
spectra
► one common application is determination of air contaminants.

Contaminants Concn, ppm Found, ppm Relative error, %

Carbon Monoxide 50 49.1 1.8

Methylethyl ketone 100 98.3 1.7

Methyl alcohol 100 99.0 1.0

Ethylene oxide 50 49.9 0.2

chloroform 100 99.5 0.5

 Baseline method.
- An alternative way of obtaining P0 and T for a single absorption band is the baseline method.
For an instrument that displays transmittance, the solvent transmittance is assumed to be
constant or at least to change linearly between the shoulders of the absorption peak, as
illustrated in Figure 17-9. The quantities T0 and Ts are then obtained as shown in the figure.
- For direct absorbance readout, as is shown in Figure 17-7, the absorbance is assumed to be
constant or to change linearly under the absorption band. The peak absorbance is then
obtained by subtracting the baseline absorbance.
Example 9: The spectrum is for a substance with an empirical formula of C3H5N. What is the
compound?

Nitrile or No aromatics
Aliphatic
alkyne group One or more
hydrogens
alkane groups
 17B MID-IR REFLECTION SPECTROMETRY
- IR reflection spectrometry has found a number of applications, particularly for dealing with;
- solid samples that are difficult to handle, e.g. polymer films and fibers, foods, rubber-
based materials, agriculture products, and many others.
- Mid-IR reflection spectra, although not identical to the corresponding absorption spectra,
are similar in general appearance and provide the same information as do their
absorption counterparts.
- Reflectance spectra can be used for both qualitative and quantitative analysis. Most
instrument manufacturers now offer adapters that fit into the cell compartments of IR
absorption instruments and make it possible to obtain reflection spectra readily.

specular reflection

attenuated total reflectance

Reflected radiation internal reflection
(ATR)

diffuse reflection
Specular Reflection;
- a smooth polished surface,
- the angle of reflection is identical to the
incident angle of the radiation.
- If the surface is made up of an IR
absorber, the relative intensity of
reflection is less for wavelengths that
are absorbed than for wavelengths that
are not.
- Thus, a plot of reflectance R, which is
the fraction of the incident radiant
energy reflected, versus wavelength or
wavenumber provides a spectrum for a Still water can also exhibit specular reflection.
compound similar in general
appearance to a transmission spectrum
for the species.
- Specular reflection spectra find some
use for examining and characterizing
the smooth surfaces of solids and
coated solids but are not as widely
used as diffuse- and total-reflection
spectra. We will, therefore, focus on the
latter two types of spectra.
 17B-2 Diffuse-Reflectance Spectrometry
- Diffuse reflectance is an excellent sampling tool for
powdered or crystalline materials in the mid-IR and NIR
spectral ranges with a minimum of sample preparation
- Diffuse reflection is a complex process that occurs when a
beam of radiation strikes the surface of a finely divided
powder. With this type of sample, specular reflection occurs
at each plane surface. However, because there are many of
these surfaces and they are randomly oriented, radiation is
reflected in all directions. The intensity of the reflected
radiation is roughly independent of the viewing angle.
- Diffuse-reflectance IR Fourier transform spectrometry - In addition to saving time in
(DRIFTS) sample preparation, it permits
conventional IR spectral data to
be gathered on samples not
appreciably altered from their
original state.
- Some powders may be analyzed by diffuse reflectance as neat samples (coal samples,
soil samples, diffuse coatings on a reflective base).
- Usually, the sample must be ground and mixed with a non-absorbing matrix such as
KBr. The sample to matrix ratio should be between 1 to 5% (by weight). Diluting
ensures a deeper penetration of the incident beam into the sample which increases the
contribution of the scattered component in the spectrum and minimizes the specular
reflection component.

Diffuse reflective spectra showing greatly improved results from sample dilution
 Instrumentation:
- Currently, most manufacturers of FTIR instruments offer adapters that fit in cell compartments
and permit diffuse-reflectance measurements.
- The collimated beam from the interferometer is directed to an ellipsoidal mirror and then to the
sample. The sample is usually ground and mixed with KBr or KCl as a diluent. The mixture is
then placed in a sample cup 3–4 mm deep and about 10–15 mm in diameter. A complex
combination of reflection, absorption, and scattering occurs before the beam is directed to the
detector.

- To obtain a spectrum with a single-beam

instrument, the signal for the sample is first
stored. A reference signal with a good reflector,
such as finely ground KBr or KCl, is then
recorded in place of the sample. The ratio of
these signals is then taken to give the
reflectance.
- Even with all these sample preparation practices, the The Kubelka-Munk equation
raw diffuse reflectance spectra will appear different from
its transmission equivalent (stronger than expected
absorption from weak IR bands). A Kubelka-Munk
conversion can be applied to a diffuse reflectance R is the absolute reflectance
spectrum to compensate for these differences. This k is the molar absorption coeff.
s is the scattering coefficient
conversion is available in most FTIR software packages.
- The Kubelka-Munk converted spectrum shows excellent
comparison with the transmission spectrum and is easily
identified using a library search of a transmission
spectral data base.
- - Diffuse reflectance can also be used for the analysis of
liquid samples. In this application a small amount of the
sample is dispensed directly onto the KBr powder and
analyzed.
Comparison of Absorption and Reflection Spectra:

Figure 17-12 compares the

conventional IR absorption spectrum
for carbazole obtained by means of a
KBr pellet with the diffuse-reflectance
spectrum of a 5% finely ground
mixture of carbazole in potassium
chloride. Note that the peak locations
are the same in the two spectra but
that the relative peak heights differ
considerably. The differences are
typical, with minor peaks generally
appearing larger in reflection spectra

FIGURE 17-12 Comparison of the absorption

spectrum (a) for carbazole with its diffuse-
reflectance spectrum (b).
 17B-3 Attenuated Total Reflection, ATR, Spectrometry
- When a beam of radiation passes from a more dense to a less dense medium, reflection occurs.
- ATR uses a property of total internal reflection resulting in an evanescent wave.
- The fraction of the incident beam reflected increases as the angle of incidence becomes larger; beyond a
certain critical angle, reflection is complete

- 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,
polymers and powders.

- during the reflection process the beam penetrates a small distance into the less dense medium before
reflection occurs.
- The depth of penetration, which varies from a fraction of a wavelength up to several wavelengths,
depends on the wavelength, the index of refraction of the two materials, and the angle of the beam with
respect to the interface.
- The penetrating radiation is called the evanescent wave. At wavelengths where the less dense medium
absorbs the evanescent radiation, attenuation of the beam occurs, which is known as attenuated total
reflectance, or ATR. The resulting ATR spectrum resembles that of a conventional IR spectrum with some
differences.
 https://youtu.be/QW2uh1BQuGw

17C PHOTOACOUSTİC İR SPECTROSCOPY

NOT INCLUDED
 17D NEAR-IR SPECTROSCOPY
The near-IR (NIR) region of the spectrum extends from the upper wavelength end of the
visible region at about 770 nm to 2500 nm (13,000 to 4000 cm21).17 Absorption bands in
this region are overtones or combinations (Section 16A-4) of fundamental stretching
vibrations that occur in the region of 3000 to 1700 cm-1. The bonds involved are usually
C-H, N-H, and O-H. Because the bands are overtones or combinations, their molar
absorptivities are low and detection limits are on the order of 0.1%.

In contrast to mid-IR spectrometry, the most important uses of NIR radiation are for the
routine quantitative determination of species, such as water, proteins, low-molecular-mass
hydrocarbons, and fats, in products of the agricultural, food, petroleum, and chemical
industries. Both diffuse-reflection and transmission measurements are used, although
diffuse reflectance is by far the more widely used.

Instrumentation: - use tungsten-halogen lamps with quartz

- Grating instruments windows.
- filter instruments - Cells for absorption measurements are usually
- acousto-optic tunable filter (AOTF) quartz or fused silica transparent up to about
instruments 3000 nm.
- Fourier transform spectrometers - Cell lengths vary from 0.1 to 10 cm.
- Detectors range from PbS and PbSe
- Several commercial UV-visible photoconductors to InSb and InAs photodiodes.
spectrophotometers are designed to - Array detectors, such as InGaAs detectors,
operate from 180 to 2500 nm and can have also become available for the region.
thus be used to obtain NIR spectra.
17D-2 Data Processing in NIR Spectrometry

- NIR spectral bands are normally broad and often overlapping. There are rarely clean
spectral bands that allow simple correlation with analyte concentration. Instead,
multivariate calibration techniques are used; partial least squares, principal components
regression, and artificial neural networks
- Such calibration involves the development of a calibration model through obtaining
results on a “training set” that includes as many of the conditions encountered in the
samples as possible.
-
 17E FAR-IR SPECTROSCOPY
- The far-IR region is particularly useful for inorganic studies because absorption due to
stretching and bending vibrations of bonds between metal atoms and both inorganic and
organic ligands generally occurs at frequencies lower than 650 cm-1 (>15 µm).
- For example, heavy-metal iodides generally absorb radiation in the region below 100 cm-
1, and the bromides and chlorides have bands at higher frequencies. Absorption frequen
cies for metal-organic bonds ordinarily depend on both the metal atom and the organic
portion of the species.
- Far-IR studies of inorganic solids have also provided useful information about lattice
energies of crystals and transition energies of semiconducting materials. Molecules
composed only of light atoms absorb far-IR radiation if they have skeletal bending modes
that involve more than two atoms other than hydrogen.
- Important examples are substituted benzene derivatives, which generally show several
absorption bands. The spectra are frequently quite specific and useful for identifying a
particular compound. There are also characteristic group frequencies in the far-IR region.
Pure rotational absorption by gases is observed in the far-IR region, provided the
molecules have permanent dipole moments. Examples include H2O, O3, HCl, and AsH3.
- Absorption by water is troublesome; elimination of its interference requires
evacuation or at least purging of the spectrometer. Prior to the advent of Fourier
transform spectrometers, experimental difficulties made it difficult to obtain good
far-IR spectra.
- The sources available in this region are quite low in intensity. Order-sorting filters
are needed with grating instruments in this region to minimize radiation diffracted
from higher grating orders. These reduced the already low throughputs of
dispersive spectrometers.
- It is no surprise that Fourier transform spectrometry was first applied in this
spectral region. The high throughput of interferometers and the relatively low
mechanical tolerances required combine to make it fairly simple to obtain FTIR
spectra in the far-IR region with good signal-to-noise ratios.
 17F IR EMISSOIN SPECTROSCOPY
- Molecules that absorb IR radiation are also capable of emitting characteristic IR wavelengths
when they are heated.
- The principal deterrent to the analytical application of this phenome non has been the poor
signal-to-noise characteristics of the IR emission signal, particularly when the sample is at a
temperature only slightly higher than its surroundings.
- With interferometry, however, interesting and useful applications have appeared in the
literature. An early example of the application of IR emission spectroscopy is found in a
paper that describes the use of a Fourier transform spectrometer for the identification of
microgram quantities of pesticides.
- Samples were prepared by dissolving them in a suitable solvent followed by evaporation on
a NaCl or KBr plate. The plate was then heated electrically near the spectrometer entrance.
- Pesticides such as DDT, malathion, and dieldrin were identified in amounts as low as 1 to 10
µg.
- Equally interesting has been the use of interferometry for the remote detection of
components emitted from industrial smokestacks. In one of these applications, an
interferometer was mounted on an 8-inch reflecting telescope.25 With the telescope focused
on the plume from an industrial plant, CO2 and SO2 were readily detected at a distance of
several hundred feet.