CHAPTER 2

Molecular Absorption Spectroscopy:

Theory, Instrumentation and
Application
BASIC COMPONENTS OF SPECTROSCOPIC
INSTRUMENTS
 Sources of energy
 Wavelength selection

 Sample cells

 Detectors

 Signal Processors
SOURCES OF ENERGY
 Sources of
Electromagnetic
Radiation
 continuum source emits
radiation over a broad
range of wavelengths,
with a relatively smooth
variation in intensity.
 line source emits
radiation at selected
wavelengths.
 Sources of Thermal Energy
 Flames sources use the combustion of a fuel and an
oxidant to achieve temperatures of 2000–3400 K.
 Plasmas, which are hot, ionized gases, provide
temperatures of 6000–10 000 K.
 Chemical Sources of Energy
 Exothermic reactions also may serve as a source of
energy.
 In chemiluminescence the analyte is raised to a high
energy state by means of a chemical reaction,
emitting characteristic radiation when it returns to a
lower-energy state.
 In bioluminescence, the emission of radiation from
the chemical reaction results from a biological or
enzymatic reaction.
 The flash of light from a firefly are examples of
chemiluminescence and bioluminescence.
WAVELENGTH SELECTION
 A wavelength selector passes a narrow band of
radiation characterized by a nominal wavelength, an
effective bandwidth and a maximum throughput of
radiation.

 The effective bandwidth is defined as the width of the

radiation at half of its maximum throughput.

 Narrow effective bandwidth provides a higher

resolution, with spectral features separated by more
than twice the effective bandwidth being resolved.
ORIGINAL METHOD TO COMPARE COLORS
OF TWO SOLUTIONS

 Natural light passes upwards

through the samples and
standards and the analyst views
the solutions by looking down
toward the light source.
 The top view, shown on the right,
is what the analyst sees.
 To determine the analyte’s
concentration, the analyst
exchanges standards until the two
colors match.
TYPES OF WAVELENGTH SELECTOR
 An absorption or interference filter
 Absorption filters work by selectively absorbing
radiation from a narrow region of the electromagnetic
spectrum.
 Commercially available absorption filters provide effective
bandwidths of 30–250 nm, although the throughput may be
only 10% of the source’s emission intensity at the low end of
this range.
 Interference filters use constructive and destructive
interference to isolate a narrow range of
wavelengths.
 Interference filters are more expensive than absorption
filters, but have narrower effective bandwidths, typically
10–20 nm, with maximum throughputs of at least 40%.
 A monochromator is an alternative method for
selecting a narrow band of radiation that also allows
us to continuously adjust the band’s nominal
wavelength.
 commonly used in most spectrometer including UV, visible
and FTIR instruments
 An interferometer provides
an alternative approach for
wavelength selection.

 Instead of filtering or
dispersing the
electromagnetic radiation, an
interferometer allows source
radiation of all wavelengths
to reach the detector
simultaneously.

 The result is called an

interferogram, or a time
domain spectrum.
SAMPLE CELLS
 The sample compartment provides a light-tight environment that
limits the addition of stray radiation.
 Samples are normally in the liquid or solution state, and are
placed in cells constructed with UV/Vis (for example) transparent
materials, such as quartz, glass, and plastic.
DETECTORS

 Modern detectors use a sensitive transducer to convert

a signal consisting of photons into an easily measured
electrical signal.
 There are two broad classes of spectroscopic
transducers:
 Photon Transducers. Phototubes and photomultipliers
contain a photosensitive surface that absorbs radiation in
the ultraviolet, visible, or near IR, producing an electrical
current proportional to the number of photons reaching the
transducer.
 A thermal transducer, therefore, is used for infrared
spectroscopy. The absorption of infrared photons by a
thermal transducer increases its temperature, changing
one or more of its characteristic properties.
SIGNAL PROCESSORS
 A transducer’s electrical signal is sent to a signal
processor where it is displayed in a form that is
more convenient for the analyst.
 Examples of signal processors:
 Analog or digital meters
 Recorders
 Computers equipped with digital acquisition boards.

 A signal processor also is used to calibrate the

detector’s response, to amplify the transducer’s
signal, to remove noise by filtering, or to
mathematically transform the signal.
UV/VIS SPECTROSCOPY
INSTRUMENT DESIGNS FOR
MOLECULAR UV/VIS ABSORPTION
 Filter Photometer
 Single-Beam Spectrophotometer
 Double-Beam Spectrophotometer
 Diode Array Spectrometer
 Sample Cells
FILTER PHOTOMETER
 The simplest instrument
for molecular UV/Vis
absorption is a filter
photometer, which uses
an absorption or
interference filter to
isolate a band of
radiation.
 The filter is placed
between the source and
the sample to prevent
the sample from
decomposing when
exposed to higher energy
radiation.
EXAMPLE OF FILTER PHOTOMETER
 A filter photometer has a single optical path between the
source and detector, and is called a single-beam
instrument.
 The instrument is calibrated to 0% T while using a shutter
to block the source radiation from the detector. After
opening the shutter, the instrument is calibrated to 100% T
using an appropriate blank. The blank is then replaced
with the sample and its transmittance measured.
 Because the source’s incident power and the sensitivity of
the detector vary with wavelength, the photometer must be
recalibrated whenever the filter is changed.
AD V A N T A G E S
AND
DISADVANTAGES OF PHOTOMETER
 Advantages:
 relatively inexpensive, rugged and easy to maintain
 portability, making it easy to take into the field.

 Disadvantages:
 inability to record an absorption spectrum
 source’s relatively large effective bandwidth, which limits the
calibration curve’s linearity.
 SINGLE-BEAM SPECTROPHOTOMETER
 An instrument that uses a
monochromator for
wavelength selection is called
a spectrophotometer.
 The simplest
spectrophotometer is a
single-beam instrument
equipped with a fixed-
wavelength monochromator.
 Single-beam
spectrophotometers are
calibrated and used in the
same manner as a
photometer.
 One example of a single-beam
spectrophotometer is Thermo
Scientific’s Spectronic 20D+.
 The Spectronic 20D+ has a
range of 340–625 nm (950 nm
when using a red-sensitive
detector), and a fixed effective
bandwidth of 20 nm.
 Battery-operated, hand-held
single-beam
spectrophotometers are
available, which are easy to
transport into the field.
 The accuracy of a single-beam
spectrophotometer is limited by
the stability of its source and
detector over time.
DOUBLE-BEAM SPECTROPHOTOMETER
 The limitations of fixed-wavelength, single-beam
spectrophotometers are minimized by using a double-beam
spectrophotometer.
 A chopper controls the radiation’s path, alternating it
between the sample, the blank, and a shutter.
 The signal processor uses the chopper’s known speed of
rotation to resolve the signal reaching the detector into the
transmission of the blank, P0, and the sample, PT. By
including an opaque surface as a shutter, it is possible to
continuously adjust 0% T.
 The effective bandwidth of a double-beam
spectrophotometer is controlled by adjusting the
monochromator’s entrance and exit slits. Effective
bandwidths of 0.2–3.0 nm are common.
 A scanning monochromator allows for the automated
recording of spectra.
 Double-beam instruments are more versatile than single-
beam instruments, being useful for both quantitative and
qualitative analyses, but also are more expensive.
DIODE ARRAY SPECTROMETER
 In a diode array spectrometer the source radiation passes
through the sample and is dispersed by a grating
 The photodiode array is situated at the grating’s focal
plane, with each diode recording the radiant power over a
narrow range of wavelengths.
 Because we replace a full monochromator with just a
grating, a diode array spectrometer is small and compact.
ADVANTAGES
 Speed of data acquisition, which allows to collect several
spectra for a single sample.
 Individual spectra are added and averaged to obtain the
final spectrum. This signal averaging improves a
spectrum’s signal-to-noise ratio.
SAMPLE CELLS
 A quartz or fused-silica cell is required when working at a
wavelength <300 nm where other materials show a
significant absorption.
 The most common path length is 1 cm (10 mm), although
cells with shorter (as little as 0.1 cm) and longer path
lengths (up to 10 cm) are available. Longer path length
cells are useful when analyzing a very dilute solution, or
for gas samples.
 The highest quality cells allow the radiation to strike a flat
surface at a 90o angle, minimizing the loss of radiation to
reflection.
 A test tube is often used as a sample cell with simple,
single-beam instruments, although differences in the cell’s
pathlength and optical properties add an additional source
of error to the analysis.
FIBER-OPTIC PROBE
 With a fiber-optic probe we can analyze samples in situ.

 The probe consists of two bundles of fiber-optic cable.

 One bundle transmits radiation from the source to the

probe’s tip, which is designed to allow the sample to flow
through the sample cell. Radiation from the source passes
through the solution and is reflected back by a mirror.

 The second bundle of fiber-optic cable transmits the

nonabsorbed radiation to the wavelength selector.
QUANTITATIVE APPLICATIONS
 Determination of an analyte’s concentration based on its
absorption of ultraviolet or visible radiation

 Many organic and inorganic compounds have strong

absorption bands in the UV/Vis region of the
electromagnetic spectrum.
 If an analyte does not absorb UV/Vis radiation—or if its
absorbance is too weak—we often can react it with
another species that is strongly absorbing.
 It is relatively easy to adjust experimental and
instrumental conditions so that Beer’s law is obeyed.
SOME OF THE APPLICATIONS
 Environmental applications
 analysis of waters and wastewaters
 Clinical applications
 determination of serum barbiturates
 Industrial analysis
 analysis of a diverse array of industrial samples
including pharmaceuticals, food, paint, glass, and
metals
 Forensic applications
 analysis of narcotics and for drug testing
QUANTITATIVE ANALYSIS FOR A
SINGLE ANALYTE
 To determine the concentration of a an analyte we measure
its absorbance and apply Beer’s law using standardization
methods.

 Normal calibration curve using external standards and

the method of standard additions.
 A single point standardization (standard addition
method) is also possible, although we must first verify
that Beer’s law holds for the concentration of analyte in
the samples and the standard.
A calibration curve plot showing limit of detection
(LOD), limit of quantification (LOQ), dynamic range,
and limit of linearity (LOL).
EXAMPLE
 The determination of Fe in an industrial waste stream was
carried out by the o-phenanthroline. Using the data in the
following table, determine the mg Fe/L in the waste
stream.
ANSWER
 Linear regression of
absorbance versus the
concentration of Fe in the
standards gives a calibration
curve with the following
equation.
A = 0.0006+0.1817× (mg Fe/L)

 Substituting the sample’s

absorbance into the calibration
expression gives the
concentration of Fe in the
waste stream as 1.48 mg Fe/L
ST A N D A R D A D D IT IO N M E T H O D
 The method of standard addition is a type of quantitative
analysis approach often used in analytical chemistry
whereby the standard is added directly to the aliquots of
analyzed sample.
 This method is used in situations where sample matrix also
contributes to the analytical signal, a situation known as
the matrix effect, thus making it impossible to compare the
analytical signal between sample and standard using the
traditional calibration curve approach.
 Experimentally, equal volumes of the sample solution are
taken, all but one are separately ‘spiked’ with known and
different amounts of the analyte, and all are then diluted to
the same volume.
 The instrument signals are then determined for all these
solutions and the results plotted.
 As usual, the signal is plotted on the y-axis; in this case the
x-axis is graduated in terms of the amounts of analyte
added (either as an absolute weight or as a concentration).
 The (unweighted) regression line is calculated in the
normal way, but space is provided for it to be extrapolated
to the point on the x-axis at which y = 0. This negative
intercept on the x-axis corresponds to the amount of the
analyte in the test sample.
 EXAMPLE
 Standard addition plot
used to determine the
concentration of calcium
in an unknown sample.
 The point at zero
concentration added Ca
is the reading of the
unknown, the other
points are the readings
after adding increasing
amounts ('spikes') of
standard solution.
 The absolute value of
the x-intercept is the
concentration of Ca in
the unknown, in this
case 1.69E-6 g/mL.
IR SP E C T R O S C O P Y
BASIC PRINCIPLES IN IR SPECTROSCOPY
 Electromagnetic spectrum
 Energy of IR photon insufficient to cause electronic excitation
but can cause vibrational excitation.
 IR radiation causes the excitation of the vibrations of
covalent bonds within that molecule.
 These vibrations include the stretching and bending modes.
 IN F R A R E D (IR) S P E C T R O S C O P Y D E A L S
WITH THE
INTERACTION OF INFRARED RADIATION
WITH MATTER.

 IR spectrum provides…..
 Important information about its chemical
nature and molecular structure

 IR applicability for…..
 Analysis of organic materials
 Polyatomic inorganic molecules
 Organometallic compounds

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IR REGION SUBDIVIDED INTO 3 SUB-REGIONS
A. Near IR region (Nearest to the visible)
780 nm to 2.5 μm (12,800 to 4000 cm-1)
N
B. Mid IR region E
A
2.5 to 50 μm (4000 – 200 cm-1) R

infrared
I
D
C. Far IR region
F
50 to 1000 μm (200 – 10cm-1) A
R

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 MOLECULAR VIBRATION

divided into
Involve change involves change
in the length of in bond angles
bond
back & forth
stretching movement bending

wagging
scissoring

symmetrical asymmetrical rocking twisting

out of
in-plane plane
vibratio vibration
n

18
STRETCHING
BENDING
http://en.wikipedia.org/wiki/Infrared_spectroscopy
 Frequency decreases with increasing atomic weight.
- heavier atoms vibrate more slowly than lighter atoms.
- example: C-C bond had lower frequency than a C-H bond.

 Frequency increases with increasing bond energy.

- stronger bonds are stiffer, requiring more force to stretch or compress.
- stronger bonds usually vibrate faster than weaker bonds
- example: O-H bonds are stronger than C-H bonds, so, O-H bonds vibrate at
higher frequencies.
- strengthens of bonds: triple bonds > double bonds > single bonds
EACH VIBRATION MODE HAS ITS ON FREQUENCY
INSTRUMENT DESIGNS FOR
INFRARED ABSORPTION
 Filter Photometer
 The simplest instrument for IR absorption
spectroscopy is a filter photometer similar to that for
UV/Vis absorption.
 These instruments have the advantage of portability,
and typically are used as dedicated analyzers for
gases such as HCN and CO.
 Double-beam spectrophotometer
 Infrared instruments using a monochromator for
wavelength selection use double-beam optics similar
to that for UV-Vis.
 Double-beam optics are preferred over single-beam
optics because the sources and detectors for infrared
radiation are less stable than those for UV/Vis
radiation.
 It is easier to correct for the absorption of infrared
radiation by atmospheric CO2 and H2O vapor when
using double-beam optics.
 Resolutions of 1–3 cm–1 are typical for most
instruments.
 Fourier transform
spectrometer
 In a Fourier transform
infrared spectrometer, or
FT–IR, the
monochromator is
replaced with an
interferometer.
 In comparison to other
instrument designs, an
FT–IR provides for rapid
data acquisition, allowing
an enhancement in signal-
to-noise ratio through
signal-averaging.
 Sample Cells
 Infrared spectroscopy is routinely used to analyze
gas, liquid, and solid samples.
 Sample cells are made from materials, such as NaCl
and KBr, that are transparent to infrared radiation.
 Gases are analyzed using a cell with a path length of
approximately 10 cm. Longer path lengths are
obtained by using mirrors to pass the beam of
radiation through the sample several times.
Three examples of IR sample cells:
(a) NaCl salts plates;
(b) fixed pathlength (0.5 mm) sample cell with NaCl windows;
(c) disposable card with a polyethylene window that is IR
transparent with the exception of strong absorption bands at 2918
cm–1 and 2849 cm–1.
 The analysis of solution samples is limited by the solvent’s IR
absorbing properties. CCl4, CS2, and CHCl3 are the most common
solvents.
 Solutions are placed in cells containing two NaCl windows
separated by a Teflon spacer. By changing the Teflon spacer,
pathlengths from 0.015–1.0 mm can be obtained.
 Transparent solid samples can be analyzed directly by placing
them in the IR beam.
 Most solid samples, however, are opaque, and must be
dispersed in a more transparent medium before recording
the IR spectrum. If a suitable solvent is available, then the
solid can be analyzed by preparing a solution and
analyzing as described above.
 When a suitable solvent is not available, solid samples may
be analyzed by preparing a mull of the finely powdered
sample with a suitable oil. Alternatively, the powdered
sample can be mixed with KBr and pressed into an
optically transparent pellet.
 The analysis of an aqueous sample is complicated by the
solubility of the NaCl cell window in water.
1. Gases
 Using evacuated cylindrical
cells equipped with suitable
windows.
2. Liquid
 sodium chloride windows.
 “neat” liquid
3. Solid
 Pellet (KBr)
 Mull
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 a drop of the pure (neat) liquid is squeezed
between two rock-salt plates to give a layer
that has thickness 0.01mm or less.

 2 plates held together by capillary mounted

in the beam path.

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PREPARATI
ON OF
LIQUID
SAMPLES
(NEAT
LIQUIDS)
CLEAN THE Use a Pasteur pipette to
USING SALT PLATES WITH A place a drop of liquid on
PLATE SMALL AMOUNT one salt plate
OF ACETONE.

or

Put the second salt plate

Place the sandwich in the IR salt plate on top so that the liquid
holder and then in the FTIR spreads into a thin film.
spectrophotometer.
TH E R E ARE 2 W AYS TO
PREPARE SOLID SAMPLE FOR IR
SPECTROSCOPY.

1. Solid that is soluble in solvent . The

most commonly IR solvent is carbon
tetrachloride (CCl4), benzene,
cyclohexane, etc.
2. Solid that is insoluble in CCl4 or any
other IR solvents can be prepared
either by KBr pellet or Mulls.
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 KBR PELLET
 The finely ground solid sample is mixed
with potassium bromide (KBr). The
mixture is pressed under high pressure
(10,000 – 15,000 psi) in special die to
form a pellet.
 KBr pellet then can be inserted into a
holder
 in the IR spectrometer.

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 PR E P A R A T IO N OF KBR
PELLET

Grind
sample with Put the sample Put the die set into
KBr (1:80) into die set. hydraulic press gauge.
Press until pressure up to
7000 psi.

Put the KBr pellet

into a pellet
holder for
analysis.
Transparent
disk
 MULLS

 2-5 mg finely powdered sample is ground

(grind) together with the presence 1 or 2
drops of a heavy hydrocarbon oil called
Nujol to form a Mull.
 Mull is then examined as a film between flat
salt plates.
 Mulls method is applied when solid not
soluble in an IR transparent solvent and solid
is not convenient to be pelleted with KBr.

33
 PR E P A R A T IO N O F NU JO L
MULLS

Mix the fine sample with 1 or 2

drops of a heavy hydrocarbon oil. Add a drop Put the second salt
The resulting mull should be of mixture plate on top so that
transparent with no visible to one salt the liquid spreads
particles. (KBr) plate. into a thin film.
WHAT IS MULL
A THICK PASTE FORMED BY GRINDING AN
INSOLUBLE SOLID WITH AN INERT LIQUID AND
USED FOR STUDYING SPECTRA OF THE SOLID.

What is Nujol
A trade name for a heavy medicinal liquid
paraffin. Extensively used as a mulling agent
in spectroscopy.

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 IR spectrum is due to specific structural
features, a specific bond, within the
molecule, since the vibrational states of
individual bonds represent 1 vibrational
transition.

 From IR spectrum we could predict the

present of atoms or group of atoms or
functional groups such as the present of an
O-H bond or a C=O or an aromatic ring.
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•Located at 4000-1300 cm-1 •Located at 1300-400 cm-1
•Peaks in this region are characteristic of •Pattern in the fingerprint region is
specific kinds of bonds and can be used to completely different and use to identify
identify specific funtional groups compound 7
8
 Focus on functional groups in frequency region

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 HO W TO AN ALYZE IR S P E C T R A

1. Begin by looking in the region from 4000-

1300. Look at the C–H stretching bands
around 3000.

Indicates
Are any or all to the above alkyl groups (present in
of 3000? most organic molecules)
Are any or all to the below a C=C bond or aromatic
of 3000? group in the molecule

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 2. LOOK FOR A CARBONYL IN THE REGION 1760-
1690.
IF THERE IS SUCH A BAND:
Indicates
Is an O–H band also present? a carboxylic acid
group
Is a C–O band also present? an ester
Is an aldehyde C–H band also an aldehyde
present?
Is an N–H band also present? an amide
Are none of the above present? a ketone

(also check the exact position of the carbonyl band for clues as to
the type of carbonyl compound it is)
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3. LOOK FOR A BROAD O–H BAND IN THE
REGION 3500-3200 CM-1. IF THERE IS SUCH A
BAND:

Indicates
Is an O–H band present? an alcohol or phenol

4. Look for a single or double sharp N–H band

in the region 3400-3250 cm-1. If there is such
a band:
Indicates
Are there two bands? a primary amine
Is there only one band? a secondary amine

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5. OTHER STRUCTURAL FEATURES TO
CHECK FOR

Indicates
Are there C–O stretches? an ether (or an ester if there
is a carbonyl band too)
Is there a C=C stretching an alkene
band?
Are there aromatic an aromatic
stretching bands?
Is there a C≡C band? an alkyne
Are there -NO2 bands? a nitro compound
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 HOW TO ANALYZE IR SPECTRA
 If there is an absence of major functional group
bands in the region 4000-1300 cm-1 (other than C–
H stretches), the compound is probably a strict
hydrocarbon.
 Also check the region from 900-650 cm-1.
Aromatics, alkyl halides, carboxylic acids, amines,
and amides show moderate or strong absorption
bands (bending vibrations) in this region.
 As a beginning student, you should not try to
assign or interpret every peak in the spectrum.
Concentrate on learning the major bands and
recognizing their presence and absence in any
given spectrum.
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8
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8
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 H H H

H C C C H

H H H
n

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CH Stretch for sp3 C-H around 3000 – 2840 cm-1.
CH2 Methylene groups have a characteristic bending absorption
at approximate 1465 cm-1
CH3 Methyl groups have a characteristic bending absorption at
approximate 1375 cm-1
CH2 The bending (rocking) motion associated with four or more
CH2 groups in an open chain occurs at about 720 cm-1
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H H
C C
H H

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 ALKENE

=C-H Stretch for sp2 C-H occurs at values greater than 3000 cm-1.
=C-H out-of-plane (oop) bending occurs in the range 1000 – 650 cm-1
C=C stretch occurs at 1660 – 1600 cm-1;
often conjugation moves C=C stretch to lower frequencies
and increases the intensity.
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ALKYNE

HC CH

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 ALKYNE

CH Stretch for sp C - H occurs near 3300 cm-1.

C C Stretch occurs near 2150 cm-1; conjugation moves stretch to

lower frequency.

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 AROMATIC RINGS

C H Stretch for sp2 C-H occurs at values greater than 3000 cm-1.

Ring stretch absorptions occur in pairs at 1600 cm-1 and

C C 1475 cm-1.

C H Bending occurs at 900 - 690cm-1.

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AROMATIC RINGS

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 ALCOHOL
H H
H OH H
H C C OH
H C C C H
H H
H H H
Primary alcohol 10
Secondary alcohol 20
CH3
H3C C OH
CH3 Tertiary alcohol 30

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 O-H 3600 cm-1 (alcohol, free)
 O-H 3300 cm-1 (alcohols & acids,
H-bonding)
broadens
shifts

FREE H-BONDED

3600 3300
 Free
OH
Free C-H
OH

H-bonded H-bonded
OH C-H OH C-H

4000 3600 3200 2800 4000 3600 3200 2800 4000 3600 3200 2800

(a) Pure Liquid (b) Dilute Solution (c) Very Dilute Solution
“neat”
1-Butanol
 ALCOHOL

O-H The hydrogen-bonded O-H band is a broad peak at 3400 – 3300 cm-1.
This band is usually the only one present in an alcohol that
has not been dissolved in a solvent (neat liquid).
C-O-H Bending appears as a broad and weak peak at 1440 – 1220 cm-1
often obscured by the CH3 bendings.
C-O Stretching vibration usually occurs in the range 1260 – 1000 cm-1.
This band can be used to assign a primary, secondary or tertiary
structure to an alcohol.
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PHENOL
OH

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 PHENOL

O-H appears at 3600-3200 cm-1. (broad)

C = C (aromatic rings) appears at 1600,1500 cm-1.
C-O appears at 1400-1890 cm-1.

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1
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 ETHER

R O R'
C-O The most prominent band is that due to C-O stretch,
1300 – 1000 cm-1.

Absence of C=O and O-H is required to ensure that C-O stretch

is not due to an ester or an alcohol.

Phenyl alkyl ethers give two strong bands at about

1250 – 1040 cm-1,
while aliphatic ethers give one strong band at about 1120 cm-1.

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2
1
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3
 CARBONYL COMPOUNDS

cm-1

1810 1800 1760 1735 1725 1715 1710 1690

Anhydride Acid Chloride Anhydride Ester Aldehyde Ketone Carboxylic acid
Amide
(band 1) (band 2)

Normal base values for the C=O stretching vibrations for

carbonyl groups.

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 ALDEHYDE
R C
HO
R C
C=O stretch appear in range 1740-1725 cm-1 for
HO normal aliphatic aldehydes

Ar C Conjugation of C=O with phenyl; 1700 – 1660 cm-1 for C=O

HO and 1600 – 1450 cm-1 for ring (C=C)

C-H Stretch, aldehyde hydrogen (••-CHO), consists of weak

bands, one at 2860 - 2800 cm-1 and
the other at 2760 – 2700 cm-1.
1
0
5
1
0
6
 KETONE
R C
R' O
R C
C=O stretch appear in range 1720-1708
R' O
cm-1 for normal aliphatic ketones

Ar C
Conjugation of C=O with phenyl at 1700 –
R' O
1680 cm-1 for C=O
and 1600 – 1450 cm-1 for ring (C=C)

1
0
7
1
0
8
 R C
OH O

CARBOXYLIC ACID

1
0
9
1
1
0
 ESTER
R C O R
O
R C O R C=O stretch appear in range 1750-1735 cm-1 for
O normal aliphatic esters

Ar C O R Conjugation of C=O with phenyl; 1740 – 1715 cm-1

O for C=O
and 1600 – 1450 cm-1 for ring (C=C)

C –O Stretch in two or more bands, one stronger and

one broader than the other,
occurs in the range 1300 – 1000 cm-1
1
1
1
1
1
2
 AMIDE
O O O
H H R
R C N R C N R C N
H R R
10 20 30

1
1
3
AMIDE

11
4
 H
R N R
Secondary amine , 20

H R N R
R N
H R
Primary amine, 10 Tertiary amine, 30

1
1
5
N –H Stretching occurs in the range 3500 – 3300 cm-1.
Primary amines have two bands.
Secondary amines have one band, a vanishingly weak
one for aliphatic compounds and a stronger one for
aromatic secondary amines.
Tertiary amines have no N – H stretch.
N –H Bending in primary amines results in a broad band in the
range 1640 – 1560 cm-1.
Secondary amines absorb near 1500 cm-1

N –H Out-of-plane bending absorption can sometimes

be observed near 800 cm-1

C–N Stretch occurs in the range 1350 – 1000 cm-1

11
6
Secondary Amine

1
1
7
Aromatic Amine

1
1
8
93
94
95