May 16, 2021

SPECTROSCOPIC
IDENTIFICATION OF
ORGANIC COMPOUNDS 2
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SPECTRA
• All electromagnetic radiation travels in waves at the same
velocity, commonly known as the speed of light.

• In a vacuum this value is known to be 2.998 x 108 m/s.

• Electromagnetic radiation differs in wavelength ( ) and

frequency .

• The product of the wavelength and frequency is equal to

the speed of light.
C=
• The energy of a wave is proportional to its frequency:
E =h

where h = Planck's constant or 6.626 x 10-34 J s.

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Spectra and Organic Molecules

• When light strikes an organic molecule, some of its
energy is absorbed.

• Molecules are affected in various ways depending on

the energy of the light.

• If the light has a wavelength in the range of 400 to 700

nm, it falls in the visible region.

• When light of a particular wavelength is absorbed,

colour is observed. This is especially true of organic
dyes.

• If electromagnetic radiation with wavelengths outside of

the visible region is absorbed, absorption can only be
detected with a spectrometer.
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Infrared Spectroscopyhttps://www.youtube.com/watch?v=dDEr1C-8Ung
(IR)
Generally, IR radiation is not energetic enough to bring
about the kinds of electronic transitions encountered with
UV and visible radiation. Absorption of IR is thus confined
largely to molecular species for which small energy
differences exist between various vibrational and
rotational states.
In order to absorb IR radiation, a molecule must undergo
a net change in dipole moment as a consequence of
its vibrational or rotational motion. No net change in
dipole moment occurs during the vibration or rotation of
homonuclear species such as O2, N2 or Cl2; consequently
such compounds cannot absorb in the infrared.
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Vibrations fall into the basic categories of stretching and

bending. A stretching vibration involves a continous
change in interatomic distance along the axis of the
bond between two atoms. Bending vibrations are
characterized by a change in the angle between two
bonds.
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* Simple diatomic molecules (HCl, HBr, HI) can only

vibrate when the bond stretches.
HCl bond has the highest frequency of these three as
it has the largest bond energy and the halogen atom
with the smallest relative atomic mass.

* In more complex molecules, different types of vibration

occur, such as bending.
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Example: The three vibrational modes of H2O molecule

These three modes of vibration results in a change in

dipole of the molecule, they can be detected with IR
spectroscopy.
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Example: The four vibrational modes of CO2 molecule

The symmetric stretch is IR inactive as it produces no

change in dipole moment. The dipoles of both C = O
bonds are equal and opposite throughout the vibration.
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• Many of the functional groups that are found in organic

molecules absorb infrared at characteristic frequencies.

• This energy that is absorbed is converted to various kinds

of molecular vibrations including the rhythmic stretching of
chemical bonds.

• Each type of chemical bond has a characteristic

absorbance in the infrared region.

• The exact frequency of absorption depends on the specific

environment of the bond.
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The natural frequencies of some covalent bonds

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MATCHING WAVENUMBERS WITH BONDS

The wavenumber is the number of waves in one centimeter and
has the units of reciprocal centimeters (cm-1). Since the
wavenumber is inversely proportional to wavelength, it is directly
proportional to frequency and energy which makes it more
convenient to use.
DATA BOOKLET - TABLE 26 INFRARED DATA
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Absorption frequencies depend on functional groups

For example, the absorption frequencies for a hydroxyl
group, -OH, appear in approximately the same location
whether it was in an alcohol or a carboxylic acid, but
obviously it would not appear in an alkanone or ester.
Both acids and alkanones show a strong absorption
frequency for the carbonyl group C=O.

** Hydrogen bonds can be detected by a broadening of

the absorption. For example, hydrogen bonding between
hydroxyl groups changes the O - H vibration; it makes the
absorption much broader and shifts it to a lower
frequency.
http://media.pearsoncmg.com/intl/ema/9781447959762_ChemHL_Brown_Ford/
animations/Chapter11p569/index.html
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