Unit V Spectroscopy

Dr. M. A. Sabitha
Assistant Professor in Chemistry
Department of Chemistry
Sadakathullah Appa College
Tirunelveli

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Electromagnetic Region:
• Radiations such as ultraviolet, visible, infrared, X-rays, radiowaves etc.
• Arrangement of EMR in the order of increasing wavelength is known as electromagnetic
spectrum.

Region Spectra Wavelength nm Frequency Hz

Radiofrequency NMR 100 3x106
1 3x108
ESR
10-1 3x109
Microwave Rotational 10-4 3x 1011
IR Vibrational 7.8x 10-7 3.8x 1014
Electronic Visible 3.8x 10-7 7.5x 1014
UV 10-8 1.5x 1016
Inner shell electronic X-ray 10-11 3x 1018
10-13 3x 1020

Nuclear reaction Γ-ray

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Spectroscopy:
• Study of interaction of electromagnetic radiation with matter.
Molecular Spectroscopy:
• Study of interaction of electromagnetic radiation with molecules.
• Spectrum is called molecular spectrum.
Types of Molecular spectra:
The three types of molecular spectra are:
• Pure rotational spectra
• Vibrational rotational spectra
• Electronic band spectra
Pure Rotational Spectra
• When a molecule absorbs a lower amount of energy that it makes a transition from one
rotational level to another within the same vibrational level.

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• Rotational spectra are observable in the spectral region of Far Infrared and Microwaves.
• Also, the energies in these spectral regions are exceedingly small. Therefore, we call rotational
spectra the microwave spectra.
Vibrational Rotational Spectra
• When a molecule absorbs sufficient energy that causes the transition of a molecule from one
vibrational level to another within the same electronic level.
• Therefore, in this case, both rotational and vibrational transition takes place. This is how we obtain
vibrational rotational spectra.
• The vibrational spectra are observable in the Near-Infrared Spectral region. We call the vibrational
rotational spectra the Infrared spectra.
Electronic Band Spectra
• When the exciting energy of the radiation is large enough to cause the transition of a
molecule from one electronic level to another electronic level. This transition is
accompanied by both rotational and vibrational level changes.
• Additionally, for each vibrational transition, a set of closely spaced lines appear.
• Because of the corresponding rotational level changes, these closely spaced lines are
known as bands. Hence, we call it the Electronic band spectra. 5
Colorimeter:
• Deals with the measurement of light absorbed by colored substances in solutions.
• The variation of color of a system with change a concentration of some component forms
the basis of colorimetric analysis.
• The intensity of the color may be compared with that of the known amount of the substance.
• The instrument which measures the intensity of the color is known as Colorimeter.
Types of colorimetric analysis:
Two types- Visual colorimetry and Photoelectric colorimetry.
Visual colorimetry:
• Simple visual technique.
• Human eye as detector and brain as amplifier and signal indicator.
• Comparison of samples with standard samples until a match is obtained with Nessler’s tube
as the comparison cell and day light as light source.
• Standard series method, Duplication method, Dilution method and Balancing method.
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Disadvantages:
• Availability of series of standards.
• Eye will not be able to match the colour in the presence of second coloured substance in
the same solution.
• Eye not sensitive to small differences in absorbance as a photoelectric device.
• Concentration differences less than 5%- difficult to detect.

Photoelectric colorimetry:
• Colorimetric analysis with eye is replaced by photoelectric cell.
• Light of narrow wavelength range obtained by passing white light through filters- source
of radiation –also known as filter photometers.
• Colorimeters using prisms and gratings – spectrophotometers.
• Spectrophotometers are classified- IR, UV, Visible or X-ray spectrophotometer on the basis
of the wavelength region used.
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Applications of Colorimeter:
• It is used in laboratories and hospitals to estimate biochemical samples such as urine,
cerebrospinal fluid, plasma, serum, etc.
• It is used in the manufacturing of paints.
• It is used in textile and food industry.
• It is used in the quantitative analysis of proteins, glucose, and other biochemical compounds.
• It is used to test water quality.
• It is used to determine the concentration of haemoglobin in the blood.
UV Spectroscopy:
Theory:
• Molecule is exposed to UV or visible light, electron of the molecule is excited from lower level
to excited state.
• Energy required for transition depends on energy difference between ground and excited state.
• Separation between two successive electronic level is very large compared to vibrational level.

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• Vibrational and rotational transitions take place during electronic transitions.
∆ETotal = ∆Eelec + ∆Evib + ∆Erot

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σ- σ* transition:
• Transition from bonding σ orbital of molecule to higher energy antibonding sigma orbital.
• Transition corresponds to higher excitation energy, since σ bond is strongest.
• Observed in saturated hydrocarbons and bands appear in vacuum UV region (<200 nm).
Methane-λmax= 122 nm, ethane- λmax= 135 nm.

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n- σ*:
• Transition from non-bonding ground state to anti-bonding sigma orbital.
Saturates halides, amines, alcohols.
• Methyl alcohol- λmax= 174 nm, methyl chloride- λmax= 169 nm.
π- π*:
• Transition from pi bonding orbital to pi* antibonding orbitals.
• Unsaturated compounds- alkynes, alkenes, carbonyl compounds.
• 1, 3-butadiene- λmax=217 nm, Acetophenone- λmax=240 nm.
n- π*:
• Transition from non-bonding pi orbital to anti-bonding pi* orbital.
• Saturated aliphatic ketones and aldehydes.
• Acetone- λmax=270 nm, Acetaldehyde- λmax=293 nm.
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Single Beam Spectrophotometer:
• Radiation from source pass through the sample and then through the entrance slit of
monochromator.
• The transmitted radiation is then passed through NaCl prism.
• It is passed through exit slit and then through filter.
• The beam is focused on the detector.
• The detector measures the intensity of radiation.
• According to Beer-Lambert’s law,
• It/ Io = transmittance
• Io- Intensity of radiation is measured when is no sample in the light beam. It- Intensity of
radiation is measured when is no sample in the light beam, knowing Io and It at different
wavelengths, transmittance is determined.
Double Beam Spectrophotometer:
• Source beam is separated into sample and reference beams.
• Reference beam passes through reference cell (solvent) and sample beam passes
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through sample cell.
• The radiation is passed through exit slit and filter. Beam is focused on detector. The
signal from the detector is amplified and recorded.

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Double Beam Spectrophotometer

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Applications of UV spectroscopy:
• Quantitative determination of compounds using Beer-Lambert’s law.
• Measuring intensities of characteristic absorption peaks from time to time, the rate of the
reaction is calculated. Reaction intermediated can be characterized in a few reactions.
• Benzene and iodine in molar ratio of 1:1, new absorption band is formed due to charge
transfer complex between donor benzene and acceptor iodine.
• Distinguish between conjugated and non-conjugated dienes. Acyclic conjugated dienes
show π- π* absorption band more than 217 nm. 1,3- penta diene- λmax=223 nm, 1,4- penta
diene- λmax= 182 nm.
• When number of conjugated double bonds increases, λmax shifts to longer wavelength.
Ethylene- λmax= 165 nm, 1,3- butadiene- λmax=217 nm, 1,3- pentadiene- λmax=223 nm,
1,3,5-hexatriene- λmax= 254 nm.

λmax = 296 nm λmax = 280 nm

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A1 λmax = 325 nm, A2 λmax = 287, 351 nm

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IR Spectroscopy:
Principle:
• Energy required to produce vibrational change (0.1 eV) is greater than energy required to
produce rotational changes (0.005 eV).
• So, during vibrational change rotational change also occurs.
• Energy absorbed or emitted is the sum of the two energy changes.
• Spectroscopy is known as vibrational-rotational spectroscopy.
Applications:
Hydrogen bonding:
• Ethyl alcohol in CCl4 gives two absorption bands at 3360 cm-1 (broad) and 3620 cm-1
(sharp).
• Band at higher frequency is due to free OH and other band is due to strong hydrogen
bonded OH.
• Solution is diluted, more intensed free OH band than hydrogen bonded OH.
• Hydrogen bonding weakens the OH group and lowers the frequency of vibrations. 17
• Used to distinguish between intermolecular and intramolecular hydrogen bonding.
• Intermolecular hydrogen bonding decreases with dilution whereas intramolecular hydrogen
bonding has no effect.
Aldehyde and ketone:
• Aldehyde γC=O stretch at 1740-1695 cm-1. Acetaldehyde- 1730 cm-1 and benzaldehyde-
1710 cm-1.
• Ketones γC=O stretch at 1725-1700 cm-1. Acetone- 1725 cm-1, Acetophenone- 1683 cm-1.
• Acetophenone has C=O in conjugation with C=C. Hence absorption is at lower
wavenumber region.

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