Instrumental Methods of Chemical

Analysis
Infrared Spectroscopy

1
 What is infrared spectroscopy?
 Modes of vibration
 Instrumentation
 Sources
 Detectors
 Dispersive IR spectrometer (scanning Instruments)
 Fourier transform-Infrared spectrometer (FT-IR)
 FT-IR Advantages?
 IR Applications
2
THE ELECTROMAGNETIC SPECTRUM
high Frequency (n) low
high Energy low

0.78-1000 ɥM

X-RAY ULTRAVIOLET INFRARED MICRO- RADIO FREQUENCY

WAVE

Nuclear
Vibrational
Ultraviolet Visible magnetic
Infrared (Mid-IR) resonance
2.5 mm 15 mm 1m 5m
200 nm 400 nm 800 nm
BLUE RED

short Wavelength (l) long

 Infrared radiation
 Infrared radiation lies between the visible and microwave portions of the
electromagnetic spectrum .
 Infrared waves have wavelengths longer than visible and shorter than
microwaves, and have frequencies which are lower than visible and higher than
microwaves.
 The Infrared region is divided into: near, mid and far-infrared.
 Near-infrared refers to the part of the infrared spectrum that is closest to
visible light and far-infrared refers to the part that is closer to the
microwave region.
 Mid-infrared is the region between these two. For chemical analysis, we are
interested in mid IR region (2.5 mm-15 mm).

 Usually, Many chemists refer to the radiation in the Mid IR in terms of

wavenumber (n)
1 1 1
ν (cm )  cm 1  10 4
λ (cm) ( )
4
Thus in terms of wavenumber, the Mid IR extends from 4000 cm-1 to 650 cm-1
PRINCIPAL MODES OF VIBRATION

Stretching

- Change in bond length resulting from change in

interatomic distance (r)

Two stretching modes

- Symmetrical and asymmetrical stretching

- Symmetrical stretching is IR-inactive (no change in µ)

PRINCIPAL MODES OF VIBRATION

Bending

- Change in bond angle or change in the position of a group of

atoms with respect to the rest of the molecule

Bending Modes
- Scissoring and Rocking
- In-plane bending modes (atoms remain in the same plane)

- Wagging and Twisting

Out-of-plane (oop) bending modes (atoms move out of plane)
PRINCIPAL MODES OF VIBRATION

3N-6 possible normal modes of vibration

N = number of atoms in a molecule

Degrees of freedom = 3N

H2O for example

- 3 atoms
- Degrees of freedom = 3 x 3 = 9
- Normal modes of vibration = 9-6 = 3
PRINCIPAL MODES OF VIBRATION

Linear Molecules

- Cannot rotate about the bond axis

- Only 2 degrees of freedom describe rotation

3N-5 possible normal modes of vibration

CO2 for example

- 3 atoms
- Normal modes of vibration = 9-5 = 4
 Radiation in the Mid IR region will cause stretching and bending vibrations of the
bonds in most covalent molecules.

Modes of Vibration
1- Stretching Vibrations 2- Bending vibrations
A- In-plane bending

Symmetric stretching
Scissoring Rocking

b- Out-of-plane bending

Asymmetric stretching
n Asym  n Sym  n Bending 9
twisting wagging
Bond Stretching
High Frequency Stretching
Low Frequency Bending
 TRANSITIONS
Fundamental

- Excitation from the ground state Vo to the first excited state V1

- The most likely transition and have strong absorption bands

V3
V2
V1

Vo
 FUNDAMENTAL TRANSITIONS
Overtone

- Excitation from ground state to higher energy states V2, V3, ….

- Result in overtone bands that are weaker than fundamental

- Frequencies are integral multiples of fundamental absorption

- Fewer peaks are seen than predicted on spectra due to IR-inactive

vibrations, degenerate vibrations, weak vibrations

- Additional peaks may be seen due to overtones

 Overtones
• The vibrations described previously are called fundamental absorptions.
(arise from ground state to the first excited state). Usually the spectrum is
complicated because of the presence of weaker overtones.

• Overtones results from excitation from ground state to the 2nd and 3rd
excited states and correspond to integral multiples of the frequency of the
fundamental band. Overtones occur at 2 ν , 3 ν etc. An absorption in the IR
at ν = 500 cm-1 may have an accompanying peak of lower intensity at
ν = 1000 cm-1 .

14
 COUPLING

- The interaction between vibrational modes

- Two vibrational frequencies may couple to produce a new

vibrational frequency

Combinational Band
ν1 + ν2 = ν3

Difference Band
ν1 - ν2 = ν3
 VIBRATIONAL MOTION

- Consider a bond as a spring

~ν  1 f
2πc μ
c = speed of light (cm/s)
f = force constant (dyn/cm; proportional to bond strength)
f for a double bond = 2f for a single bond
f for a triple bond = 3f for a single bond

M 1M 2
μ  reduced mass in grams 
M1  M 2

- M1 and M2 are masses of vibrating atoms connecting the bond

 DIPOLE MOMENT (µ)

µ=Qxr

Q = charge and r = distance between charges

- Asymmetrical distribution of electrons in a bond renders the

bond polar

- A result of electronegativity difference

- µ changes upon vibration due to changes in r

- Change in µ with time is necessary for a molecule to absorb

IR radiation

17
 DIPOLE MOMENT (µ)

- The repetitive changes in µ makes it possible for polar molecules

to absorb IR radiation

- Symmetrical molecules do not absorb IR radiation since they

do not have dipole moment (O2, F2, H2, Cl2)

- Diatomic molecules with dipole moment are IR-active

(HCl, HF, CO, HI)

- Molecules with more than two atoms may or may not be

IR active depending on whether they have permanent
net dipole moment

18
 IR active species
Molecular species with small energy differences between various vibrational and
rotational states ( most organic species).
A molecule must have a change in dipole moment during
vibration in order to absorb IR radiation
Only bonds which have significant dipole moments will absorb infrared radiation.
Bonds which do not absorb infrared include
• Symmetrically substituted alkenes and alkynes.
R R
R C C R
R R
• Symmetric diatomic molecules.
H2 , Cl2 , O2 , N2
• Ionic salts NaCl, KBr absorb only in the far IR region ( < 700 cm-1) so are
suitable as sample holders for most Mid-IR measurements.
19
INSTRUMENTATION

Components

- Radiation source

- Sample holder

- Monochromator

- Detector

- Computer

20
Instrumentation
Simplified Infrared Spectrophotometer
NaCl
focusing plates
mirror
Detection Electronics
and Computer

Determines Frequencies
of Infrared Absorbed and
Infrared
plots them on a chart
Source
Sample Infrared
Spectrum
% Transmittance
Absorption
“peaks”
frequency
(decreasing)
 Ideal Spectrometer system
• An ideal Spectrophotometric instrument has only five components:
– a source of illumination on the sample (a light source which provides the
electromagnetic energy required for the analysis).
– a signal sorter (a dispersion or interference device for resolving the
frequencies from each other).
– a sampling component (a method of channeling the light to the sample and
from the sample to the instrument).
– a signal detector (a transducer which converts light to a voltage or current).
– a computer (to control data acquisition and analysis).
• If each of these components performs its task properly, the instrument possesses
virtually all the advantages that one might assign to an ideal analytical device.

22
 IR spectrophotometer
1. Radiation source
Infrared radiation can be produced by electrically heating
a source, often a Nernst filament or a Globar to 1000-1800 C.
a. Nernst filament is fabricated from oxides of zirconium,
thorium and cerium.
b. The Globar is a small rod of silicon carbide.

23
 RADIATION SOURCES
Intensity of radiation should
- Be continuous over the λ range and cover a wide λ range
- Constant over long periods of time
- Have normal operating temperatures between 1100 and 1500 K
- Have maximum intensity between 4000 and 400 cm-1
(mid-IR region)

- Modern sources include furnace ignitors, diesel engine heaters

- Sources are usually enclosed in an insulator to reduce noise

 RADIATION SOURCES

Mid-IR Sources

Nernst Glowers
- Heated ceramic rods
- Cylindrical bar
- Made of zirconium oxide, cerium oxide, thorium oxide
- Heated electrically to 1500 K – 2000 K
- Resistance decreases as temperature increases
- Can overheat and burn out
 RADIATION SOURCES

Mid-IR Sources

Globar
- Silicon carbide bar

- Heated electrically to emit continuous IR radiation

- More sensitive than the Nernst glower

 RADIATION SOURCES

Mid-IR Sources

Heated Wire Coils

- Heated electrically to ~ 1100 oC
- Similar in shape to incandescent light bulb filament
- Nichrome wire is commonly used
- Rhodium is also used
- May easily fracture and burn out
 RADIATION SOURCES

Near-IR Sources

Quartz halogen lamp

- Contains tungsten wire filament

- Also contains iodine vapor sealed in a quartz bulb

- Evaporated tungsten is redeposited on the filament

increasing stability

- Output range is between 25000 and 2000 cm-1

 RADIATION SOURCES

Far-IR Sources

High pressure Hg discharge lamp

- Made of quartz bulb containing elemental Hg

- Also contains inert gas and two electrodes

 MONOCHROMATORS

- Salt prisms and metal gratings are used as dispersion devices

- Mirrors made of metal with polished front surface

- Spectrum is recorded by moving prism or grating such

that different radiation frequencies pass through
the exit slit to the detector

- Spectrum obtained is %T verses wavenumber (or frequency)

 DETECTORS

Two classes

Thermal detectors

and

photon-sensitive detectors
DETECTORS

Thermal Detectors

- Bolometers

- Thermocouples

- Thermistors

- Pyroelectric devices
 DETECTORS

Thermal Detectors

Bolometers
- Very sensitive electrical resistance thermometer

- Older ones were made of Pt wire

(resistance change = 0.4% per oC)

- Modern ones are made of silicon placed in a wheatstone bridge

- Is a few micrometers in diameter

- Fast response time

 DETECTORS

Thermal Detectors

Thermocouples
- Made up of two wires welded together at both ends
- Two wires are from different metals
- One welded joint (hot junction) is exposed to IR radiation
- The other joint (cold junction) is kept at constant temperature
- Hot junction becomes hotter than cold junction
- Potential difference is a function of IR radiation
- Slow response time
- Cannot be used for FTIR
 DETECTORS

Thermal Detectors

Thermistors
- Made of fused mixture of metal oxides

- Increasing temperature decreases electrical resistance

which is a function of IR radiation

- Resistance change is about 5% per oC

- Slow response time

 DETECTORS

Thermal Detectors

Pyroelectric Detectors
- Made of dielectric materials (insulators), ferroelectric materials,
or semiconductors

- A thin crystal of the material is placed between two electrodes

- Change in temperature changes polarization of material

which is a function of IR radiation exposed

- The electrodes measure the change in polarization

 DETECTORS

Photon Detectors

- Made of materials such as lead selenide (PbSe),

indium gallium arsenide (InGaSa), indium antimonide (InSb)

- Materials are semiconductors

- S/N increases as temperature decreases (cooling is necessary)

- Very sensitive and very fast response time

- Good for FTIR and coupled techniques

 Infrared Instrumentation
History and development
• Types
– Scanning Instruments
• Dispersion Spectrometers (older technique)

– Multiplex Instruments
• Fourier Transform Infrared (FT-IR) Spectrometers
(Modern technique)

• Nearly all IR spectrometers, nowadays, are of the

FT type.
38
  Noise is random, it may be positive or negative.
– If “n” spectra are added S/N increases in proportion of n
This means that to improve S/N by a factor of 2, you have to add and average 4
spectra (scans). Improvement of S/N by factor of 10 needs averaging 100 spectra.
Measure signal
height

Noise

• All measurements, especially those we

carry out with instruments, generate
Noise.
• Detectors of all sorts generate electrical
noise # of scans S/N ratio 39
 Fourier Transform IR
 Fourier Transform Infrared (FT-IR) spectrometry was developed in

order to overcome the limitations encountered with dispersive

instruments mainly the slow scanning process.

 A solution was developed which employed a very simple

optical device called an interferometer. The interferometer

produces a unique type of signal which has all of the infrared
frequencies “encoded” into it. The signal can be measured very
quickly, usually on the order of one second or so.

40
 FTIR systems
1. Mechanical operation
• Encode (modulate) the spectral information using a
Michelson Interferometer.

2. Mathematical operation
• Computer processing of encoded information to
produces the spectrum (Decoding).

41
 FT SPECTROMETERS

- Based on Michelson interferometer

- Employs constructive and destructive interferences

- Destructive interference is a maximum when two beams are

180o out of phase

- An FT is used to convert the time-domain spectrum obtained into

a frequency-domain spectrum

- The system is called FTIR

 FT SPECTROMETERS

- Has higher signal-to-noise ratio

- More accurate and precise than dispersive monochromators

(Conne’s advantage)

- Much greater radiation intensity falls on the detector due

to the absence of slits
(throughput or Jacquinot’s advantage)
Optical Diagram
Michelson
Interferometer
Light He-Ne gas laser
source

Beam splitter Interferogram

Movable mirror

Sample chamber

DLATGS (deuterated L-
alanine doped triglycene
Fixed mirror sulphate)
Detector
Interferometer
44
 Interference is a superimposing of waves
Relationship between light source spectrum and the interferogram
(signal output from interferometer)
Light source spectrum Signal output from interference wave
I
(a) Monochromatic
light

Wavenumber
Time t
S I

(b) Dichroic light

u1 u2
Wavenumber Time t
I(t)

(c) Continuous
spectrum light
F(u)
Time t
Wavenumber

Frequency domain Time domain

Note that the time domain signal, even after modulation, contains the same 45
information as in the frequency domain.
 Michelson Interferometer
(Mechanical operation)
 Most interferometers employ a beamsplitter which takes the
incoming infrared beam and divides it into two optical beams.
One beam reflects on a flat mirror which is fixed in place. The
other beam reflects on a flat mirror which is on a mechanism
which allows this mirror to move a very short distance (typically a
few millimeters) away from the beamsplitter.

 Because one beam travels is a fixed length and the other is

constantly changing as its mirror moves, the signal which exits the
interferometer is the result of these two beams “interfering” with each
other. The resulting signal is called an interferogram which has the
unique property that every data point which makes up the signal has
information about every infrared frequency which comes from the
source. 46
 FT SPECTROMETERS

Focusing Mirrors of Interferometer

- Made of metal and polished on the front surface

- Gold coated to prevent corrosion

- Focus source radiation onto the beam splitter

- Focus light emitting from sample onto detector

 FT SPECTROMETERS

Beam Splitter of Interferometer

- Made of Ge or Si coated onto a highly polished

IR-transparent substrate

- Ge coated on KBr is used for mid-IR

- Si coated on quartz is used for NIR

- Mylar film is used for far-IR

- Transmits and reflects 50% each of beam (ideally)

 Fourier transform
(Mathematical Operation)
Because the analyst requires a frequency spectrum (a plot of the
intensity at each individual frequency) in order to make an
identification, the measured Interferogram signal can not be
interpreted directly. A means of “decoding” the individual
frequencies is required. This can be accomplished via a well-
known mathematical technique called the Fourier
transformation. This transformation is performed by the
computer which then presents the user with the desired spectral
information for analysis.
49
 FT--IR summary
FT

Time axis decoding Wavenumber

Frequency domain
Time domain by FFT
50
 Background Spectrum
A background spectrum (with no sample in the beam) must be collected for
all IR measurements . This can be compared to the measurement with the
sample in the beam to determine the “percent transmittance.” A single
background measurement can be used for many sample measurements
because this spectrum is characteristic of the instrument itself and its
environment .

 The strong background absorption from water and carbon dioxide in the
atmosphere can be reduced by purging the optical bench with an inert gas
or with dry carbon dioxide – scrubbed air .
51
FT FT

Using computer Using computer

The ratio

52
Schematic illustration of
FTIR system

53
 FT--IR Advantages
FT
1- Fellgett's (multiplex) Advantage
 Fast : All frequencies of the source reach the detector simultaneously (all of
the energy is on the detector all of the time), instead of analyzing a sequence
of small wavebands available from the monochromator in dispersing IR
instruments.
 Get data for the entire spectrum in one second or less.

 Improve signal to noise ratio (S/N ratio):

Fast scans enable recording and averaging many scans.

54
 FT--IR Advantages (Contd.)
FT
2- Connes Advantage (Frequency accuracy advantage)
• Why is there a laser in FT-instruments?
Interferogram is not recoded continuously, but sampled at discrete intervals to give
different data points. The closer the spacing between data points, the greater the
wavenumber range of the spectrum.

Monochromatic visible He-Ne laser beam is passed along with the polychromatic IR
light to provide a single wavelength interferogram that oscillates much more quickly
than anything in the IR (shorter wavelength).

The laser is used as an internal clock to

IR Interferogram
trigger data points acquisition events.

Output of a Laser interferometer

IR data points might be taken at
Data points
every zero point of the laser
interferogram. 55
Optical path difference 
 Connes Advantage (Contd.)
• FTIR instruments employ a He-Ne laser as an internal wavelength
calibration standard. These instruments are self-calibrating and
never need to be calibrated by the user.

• The precise reproduction of wavenumber positions from one

spectrum to the next will increase the resolution of the spectrum,
and make it easy to differentiate between adjacent peaks too close
to each other (high resolving power).

• Frequency accuracy makes signal averaging highly precise and thus

adds further improvement in S/N ratio.

56
 FT--IR Advantages (cont. )
FT
3- Jacquinot (throughput) Advantage
• Few optical elements and no slits (greater throughput of
radiation)
– The detector receives up to 50% of the energy of original
light source (much larger than the dispersion spectrometer)
– This will enhance the sensitivity of measurement and
causes further improvement in the S/N ratio.

57
 FT--IR Advantages (cont. )
FT

4- No stray light
• Because the FT experiment modulates the source radiation and
then detects only modulated radiation, there is essentially no stray
light problems as there are with scanning instruments.

• Any stray light that reaches the detector is not incorporated into
the spectrum since it is unmodulated. Thus there is no possibility
of errors occurring during measurement (accurate quantitative
analysis).
58
 Summary of FT-
FT-IR Advantages
• Speed Because all of the frequencies are measured simultaneously.

• Sensitivity is dramatically improved with FT-IR ; detectors are much more

sensitive, the optical throughput is much higher, higher signal to noise ratio.

• Mechanical Simplicity The moving mirror in the interferometer is the only

continuously moving part in the instrument. Thus, there is very little
possibility of mechanical breakdown.

• Internally Calibrated These instruments employ a He-Ne laser as an internal

wavelength calibration standard .These instruments are self-calibrating and
never need to be calibrated by the user.

59
TRANSMISSION (ABSORPTION) TECHNIQUE

- Can be used for both qualitative and quantitative analysis

- Provides very high sensitivity at relatively low cost

- Sample cell material must be transparent to IR radiation

(NaCl, KBr)

- Samples should not contain water since materials are

soluble in water
TRANSMISSION (ABSORPTION) TECHNIQUE

Solid Samples

Three sampling techniques

Mulling, pelleting, thin film

Mulling
- Samples are ground to power with a few drops of viscous
liquid like Nujol (size < 2 µm)

- 2-4 mg sample is made into a mull (thick slurry)

- Mull is pressed between salt plates to form a thin film

TRANSMISSION (ABSORPTION) TECHNIQUE

Solid Samples

Three sampling techniques

Mulling, pelleting, thin film

Pelleting
- 1 mg ground sample is mixed with 100 mg of dry KBr powder

- Mixture is compressed under very high pressure

- Small disk with very smooth surfaces forms (looks like glass)
TRANSMISSION (ABSORPTION) TECHNIQUE

Solid Samples

Three sampling techniques

Mulling, pelleting, thin film

Thin Film
- Molten sample is deposited on the surface of KBr or NaCl plates

- Sample is allowed to dry to form a thin film on substrate

- Good for qualitative identification of polymers but not

good for quantitative analysis
TRANSMISSION (ABSORPTION) TECHNIQUE

Liquid Samples

- Many liquid samples are analyzed as is

- Dilution with the appropriate solvent may be necessary

(CCl4, CS2, CH3Cl)

- Solvent must be transparent in the region of interest

- Salt plates are hygroscopic and water soluble (avoid water)

- Special cells are used for water containing samples (BaF2, AgCl)
 INTERPRETATION OF IR SPECTRA

Functional Group Region

- Strong absorptions due to stretching from hydroxyl, amine,
carbonyl, CHx

4000 – 1300 cm-1

Fingerprint Region
- Result of interactions between vibrations

1300 – 910 cm-1

 Infrared Spectrum
IR radiation is passed through a sample. Some of the infrared radiation is absorbed ,
the rest is transmitted. The resulting spectrum represents the molecular absorption
and transmission, creating a molecular fingerprint of the sample. No two unique
molecular structures produce the same infrared spectrum. This makes infrared
spectroscopy useful for several types of analysis.

C-H < 3000 cm-1 C=O 1715 cm-1

66
High Frequency to Low Frequency

Functional Groups Region Fingerprint Region

4000 - 1400 cm -1 1400-600 cm -1
 General Trends:

i) Stretching frequencies are higher than

corresponding bending frequencies. (It is easier to
bend a bond than to stretch or compress it.)
ii) Bonds to hydrogen have higher stretching
frequencies than those to heavier atoms.
iii) Triple bonds have higher stretching
frequencies than corresponding double bonds,
which in turn have higher frequencies than single
bonds. (Except for bonds to hydrogen).
INTERPRETATION OF IR SPECTRA

Hydrocarbons

- Absorption bands are due to the stretching or bending of

C−H and C−C bonds

- C−C stretching vibrations are distributed across the

fingerprint region (not useful for identification)

- C−C bending vibrations occur below 500 cm-1

(not useful for identification)

- Observed bands are due to C−H stretching or bending

IR Spectrum of Octane
Decane
2,2,4-Trimethylpentane
Hybridization of Carbon Affects n
of Absorption
 INTERPRETATION OF IR SPECTRA

Cyclic Alkanes
- No peak around 1375 cm-1 due to absence of methyl groups

- Two peaks at ~ 900 cm-1 and 860 cm-1 due to ring deformation

Alkenes
- Contain many more peaks than alkanes

- Peaks of interest are due to stretching and bending of C−H

and C=C bonds

- C=C band will not appear if there is symmetrical substitution

about the C=C bond
Hexane and Hexene
1-Pentene
1-Dodecene
2-Methyl-1,3-butadiene
(Isoprene)
INTERPRETATION OF IR SPECTRA

Alkynes
- C≡C peak appears around 2100 – 2200 cm-1
- Terminal alkyne ≡C−H stretch occurs near 3300 cm-1

Aromatic Hydrocarbons
- C→H absorption occurs above 3000 cm-1

- Aromatic C=C ring stretching absorption around

1400 – 1600 cm-1 appears as doublet

- Aromatic C↓H oop band around 690 – 900 cm-1

- Overtones around 1660 – 2000 cm-1

 Terminal Alkynes are
Readily Identifiable with IR
1-Heptyne
 Aromatics

• C-H str (sp2) at 3050-3100 cm-1

• C-C str (breathing) 1600 & 1500 cm-1

H
Toluene
o-Xylene
 INTERPRETATION OF IR SPECTRA

Alcohols

- OH band in neat aliphatic alcohols is a broad band centered

at ~ 3300 cm-1 due to hydrogen bonding (3100 – 3600 cm-1)

- OH band in dilute solutions of aliphatic alcohols is a sharp

peak ~ 3600 cm-1

- C−C−O stretch ~ 1048 cm-1 for primary alcohols

- Decreasing frequency by 10 cm-1 in the order 1o>2o>3o

- Methyl bending vibrations at ~ 1200 – 1500 cm-1

 Alcohols
O-H str at 3600-3200 cm-1
C-O str at 1050-1150 cm-1
Cyclohexanol
O-H Stretch
2-Methyl-1-butanol
Benzyl alcohol
 INTERPRETATION OF IR SPECTRA

Nitrogen-Containing Compounds

- 1o amines (NH2) have scissoring mode and low

frequency wagging mode

- 2o amines (NH) only have wagging mode (cannot scissor)

- 3o amines have no NH band and are characterized by C−N

stretching modes ~ 1000 – 1200 cm-1 and 700 – 900 cm-1

- 1o, 2o, 3o amides are similar to their amine counterparts

but have additional C=O stretching band
 INTERPRETATION OF IR SPECTRA

Nitrogen-Containing Compounds

- C=O stretching called amide I in 1o and 2o amides and

amide II in 3o amides

- N−H stretch doublet ~ 3370 – 3291 cm-1 for 1o amines

- 1o N−H bend at ~ 1610 cm-1 and 800 cm-1

- Single N−H stretch ~ 3293 cm-1 for 2o but absent in 3o amine

- C−N stretch weak band ~ 1100 cm-1

1o Amines
2-Methylpentanediamine
2o Amine
Dipropylamine
 INTERPRETATION OF IR SPECTRA

Carboxylic Acids, Esters, Ketones, Aldehydes

- Characterized by very strong carbonyl (C=O) stretching

band between 1650 cm-1 and 1850 cm-1

- Fermi resonance seen in aldehydes

(doublet due to resonance with an overtone of the aldehydic
C−H bend at 1390 cm-1)
Carbonyl Compounds
Acetone
Cycloheptanone
Acetophenone
Conjugation Lowers n of
Absorption
Ketone and Aldehyde
Octanal
INTERPRETATION OF IR SPECTRA

Aliphatic Acids

- Broad OH band around 2900 cm-1

- C−H stretching bands from CH3 and CH2 stick out at the
bottom of the broad OH band

- C=O stretch ~ 1710 cm-1

- In-plane C −O−H bend ~ 1410 cm-1 and

oop C −O−H bend ~ 930 cm-1

- C −C−O stretch dimer at ~ 1280 cm-1

Carboxylic Acid
Hexanoic Acid
Phenyl Acetate, an Ester
Ethyl Butanoate
Methyl Benzoate
Benzoic Anhydride, an
Acid Anhydride
Butanamide, an Amide
 Analytical information
obtained using IR techniques
I) Qualitative
a) Structural Elucidation through interpretation of functional
group region ( 4000- 1300 cm-1), fingerprint region ( 1300-
910 cm-1), aromatic region ( 910- 650 cm-1).
b) Compound Identification to find a reference IR spectrum
that matches that of the unknown compound.
c) IR mostly used for rapid qualitative but not quantitative
analysis.
116
II ) Quantitative
A=abc
The intensity of an absorption band is linearly proportional
to the concentration of analyte of interest at a certain
frequency.

 Quantification parameters include peak height , peak area

; integration of band area should be done carefully to ensure
maximum accuracy, near IR region is better suited for
quantitation.

117
 Applications of Infrared Analysis
 Analysis of petroleum hydrocarbons , oil and grease
content ( detection of Freons).
 Determination of air contaminants.
 Determination of protein, starch, oil , lipids and
cellulose in agricultural products .
 Far- Infrared region is particularly useful for
inorganic studies ( crystals and semiconducting
materials ).

118
General Applications of
Infrared Analysis
 Pharmaceutical research.
 Forensic investigations.
 Polymer analysis.
 Lubricant formulation and fuel additives.
 Foods research.
 Quality assurance and control.
 Environmental and water quality analysis
methods.
 Biochemical and biomedical research.
 Coatings and surfactants.
119
 Resources and references
Recommended further reading:

“Principles of instrumental analysis, 5th ed. by Skoog, Holler, Nieman”

Chapter 16 , 17.

Spectrometric Identification of organic compounds , By Silverstein

120