Spectroscopy

Infrared spectra
By
Prashanth kumar K
M.Pharm 1st year
Pharmaceutical Analysis & QA
Lilitha college of pharmacy
 Sir William Herschel
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 Spectroscopy
“seeing the unseeable”
Using electromagnetic radiation
as a probe to obtain information
about atoms and molecules that
are too small to see.

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 Spectroscopy is the branch of science
dealing with the study of interaction of
electromagnetic radiation with matter

The most important consequence of

such interaction is that energy is
absorbed or emitted by the matter in
discrete amount called quanta

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 Electromagnetic Radiation

• Electromagnetic radiation: light and other

forms of radiant energy
• Wavelength (λ): the distance between
consecutive peaks on a wave.
• Frequency (ν): the number of full cycles of
a wave that passing through a fixed point in

a second.
• Wave number: The number of waves per
centimeter.

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The Spectrum and Molecular
Effects

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 Types of Spectroscopy
 Infrared (IR) spectroscopy measures the bond vibration
frequencies in a molecule and is used to determine the
functional group.
 Mass spectrometry (MS) fragments the molecule and
measures the masses.
 Nuclear magnetic resonance (NMR) spectroscopy
detects signals from hydrogen atoms and can be used to
distinguish isomers.
 Ultraviolet (UV) spectroscopy uses electron transitions to
determine bonding patterns.

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 IR-REGION: 12,800 - 10 cm-1
REGION WAVE WAVE NUMBER FREQUENCY
LENGTH υ (cm-1 ) RANGE
λ (μm) Hz

NEAR 0.78 - 2.5 12800 - 4000 3.8x1014 -1.2x1014

MIDDLE 2.5 - 50 4000 - 200 1.2x1014 - 6x112

FAR 50 - 1000 200 -10 6x1012 - 30x1011

MOST 2.5 - 15 4000 - 670 1.2x1014 -2x1013

USED

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 BASIC PRINCIPLE

 IR involves absorption phenomenon the absorption of radiation

depends on increasing energy of vibration or rotation associated with
covalent bond in molecule provide that such an increasing in energy
causes a change in the dipole moment of molecule.

 Hence in order to absorb IR radiation a molecule must go a net

change in dipole moment due to its vibration or rotation motion

 This means that nearly all molecules containing covalent bond will
show some degree of selective IR absorption

 Infra red spectra are usually plotted as % transmittance (%T) rather

than as absorbance as the ordinate.
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 This makes absorption band appear as dips in the curve than as
maxima as in the case of UV-Vis.

 Each dip In the spectrum is called a band or peak and represented

absorption of IR radiation at that frequency by the sample.

 The transmittance is 0% if all the radiation is absorbed and the

transmittance is 100% for no absorption.

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 IR source  sample  prism  detector

graph of % transmission vs. frequency

=> IR spectrum

100

%T

0
4000 3000 2000 1500 1000 500

v (cm-1 )

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 Infrared
InfraredSpectrum
Spectrum of
of Hexane
Hexane

100

bending
%T

C—H stretching
bending bending

CH3CH2CH2CH2CH2CH3

3500 3000 2500 2000 1500 1000 500

Wave number, cm-1
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 Use of Wave number than wavelength
offer several advantages

 Wave number are directly proportional to

frequency and are expressed in much more
convenient numbers (in this region of the
spectrum), 5000-500 cm-1

 Because the wave number is directly

proportional to frequency and energy, the use
of wave numbers allows spectra to be
displayed linear in energy, which is a distinct
aid in sorting out related vibrational transitions

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 INFRARED THEORY
- Molecular vibration can occur by 2
different mechanism

- Firstly, quanta of IR radiation can excite

atoms to vibrate directly. The absorption of
IR radiation give rise to the IR spectrum

- Secondly quanta of visible light achieve the

same result indirectly

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 Types of Vibration

Stretching Bending

Scissoring
Symmetric Wagging
In plane

Out of plane
Rocking
Asymmetric
Twisting
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 Molecular Vibrations

Covalent bonds vibrate at only certain

allowable frequencies.

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 Stretching Frequencies

 Frequency decreases with increasing

atomic weight.
 Frequency increases with increasing bond
energy.
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 Vibrational Modes

Nonlinear molecule with n atoms usually has 3n

- 6 fundamental vibrational modes.

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Fingerprint of Molecule

 Whole-molecule vibrations and bending

vibrations are also quantitized.
 No two molecules will give exactly the same
IR spectrum (except enantiomers).
 Simple stretching: 1600-3500 cm-1.
 Complex vibrations: 600-1400 cm-1, called
the “fingerprint region.”

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IR-Active and Inactive

 A polar bond is usually IR-active.

 A nonpolar bond in a symmetrical
molecule will absorb weakly or not at all.

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 INSTRUMENTATION

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Components of infrared
spectroscopy
1. Radiation source
2. Monochromator
3. Sampling area
4. Detector
5. Recorder

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An Infrared Spectrometer

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 Radiation sources

1. Nernest glower
2. Globar source
3. Incandescent wire source
4. Mercury arc
5. Carbondioxide laser source
6. Tungsten filament lamp

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 INFRARED SAMPLING
 Sample handling is the most difficult and time
consuming part of an IR spectroscopic
analysis
 Common point to the sampling of different
phases is that the sampling must be
transparent to IR radiation.
 Various phases used for ir sampling are
i) sampling of gases
ii) sampling of liquids
iii) sampling of solids

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 Solids
50-200mg required
10µg for qualitative
1-10µg soluble in suitable solvent
 Liquids
0.5µl less if pure
 Gases
50ppb

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DETECTORS or
TRANSDUCERS
 There are 3 types of detector (transducer)

 1) THERMAL DETECTOR
 2) PYROELECRIC DETECTOR
 3) PHOTON (QUANTUM) DETECTOR

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 FT-IR Spectrometer

 Uses an interferometer.
 Has better sensitivity.
 Less energy is needed from source.
 Completes a scan in 1-2 seconds.
 Takes several scans and averages them.
 Has a laser beam that keeps the instrument
accurately calibrated.

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Analysis time

 1-10 min. depending on type of instrument

and resolution
 Approx. 1-5 min.

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 Applications
 Identification of all types of organic & many types
of inorganic compounds
 Determination of functional groups
 Identification of chromatographic effluents
 Quantitative determination of compounds in
mixtures
 Determination of molecular composition &
stereochemistry
 Determination of molecular orientation
(Polymers & Solutions)
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 Identification of compounds by matching
unknown with reference spectrum(Fingerprinting)
 Detection of impurities 0.1-0.01
 Analysis of formulations such as insecticides &
copolymers

Accuracy
 Favorable conditions >1%

 Routine analysis ±5%

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 Sensitivity & Detection limits
 Routine – 2%
 Most favorable conditions & using special
techniques – 0.01%
Limitations
 Minimal element info.is given for most of

samples
 Background solvent should be transparent in
IR region
 Molecule must be active in IR region
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Complementary related
techniques
 NMR – additional detailed information on

molecular structure
 MS – molecular mass information & structure
 Raman Spectroscopy – complementary
information on molecular vibrations
Some vibrational modes of motion are IR-
inactive but Raman-active and vice versa
It also facilitates analysis of aqueous samples
& Cell window material may be regular glass

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REFERENCES
 THANK
YOU

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