Spectroscopy
Spectroscopy is an analytical technique which helps determine structure. It destroys little or no
sample. The amount of light absorbed by the sample is measured as wavelength is varied.
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.
Electromagnetic Spectrum
Most organic spectroscopy uses electromagnetic energy, or radiation, as the physical stimulus.
Electromagnetic energy (such as visible light) has no detectable mass component. In other words,
it can be referred to as “pure energy.”
Examples: X rays, microwaves, radio waves, visible light, IR, and UV.
Other types of radiation such as alpha rays, which consist of helium nuclei, have a detectable mass
component and therefore cannot be categorized as electromagnetic energy.
The important parameters associated with electromagnetic radiation are:
• Frequency and wavelength are inversely proportional.
• c = ln, where c is the speed of light.
Energy per photon = hn, where h is Planck’s constant.
The Spectrum and Molecular Effects
Infrared radiation
• Infrared radiation is largely thermal energy.
• It induces stronger molecular vibrations in covalent bonds, which can be viewed as springs
holding together two masses, or atoms.
IR Region
• Just below red in the visible region.
• Wavelengths usually 2.5-25 mm.
• More common units are wave numbers, or cm-1, the reciprocal of the wavelength in centimeters.
• Wave numbers are proportional to frequency and energy.
IR-Spectroscopy involves the interaction of infrared radiation with matter. It covers a range of
techniques mostly based on absorption spectroscopy. As with all spectroscopic techniques, it can be
used to identify and study chemicals. Samples may be solid, liquid or gas.
When IR absorption occur?
1. IR absorption only occurs when IR radiation interacts
with a molecule undergoing a change in dipole moment
as it vibrates or rotates.
2. Infrared absorption only occurs when the incoming IR photon has sufficient energy for the
transition to the next allowed vibrational state.
• Note if the 2 rules above are not met, no absorption can occur.
IR Spectrometer
• The method or technique of infrared spectroscopy is conducted with an instrument called an
infrared spectrometer (or spectrophotometer) to produce an infrared spectrum. An IR
spectrum can be visualized in a graph of infrared light absorbance (or transmittance) on the
vertical axis v/s frequency or wavlength on the horizontal axis.
What happen when a molecule absorbs infrared radiation?
• Absorption of IR radiation corresponds to energy changes on the order of 8 to 40 kJ/mole.
• Radiation in this energy range corresponds to stretching and bending vibrational frequencies of
the bonds in most covalent molecules.
• In the absorption process, those frequencies of IR radiation which match the natural vibrational
frequencies of the molecule are absorbed.
• The energy absorbed will increase the amplitude of the vibrational motions of the bonds in the
molecule.
ALL bonds in a molecule are capable of absorbing IR energy?
• NOT ALL bonds in a molecule are capable of absorbing IR energy. Only those bonds that
have change in dipole moment are capable to absorb IR radiation.
• The larger the dipole change, the stronger the intensity of the band in an IR spectrum.
What is a dipole moment?
It is a measure of the extent to which a separation exists between the centers of positive and
negative charge within a molecule.
Principle of Infrared Spectroscopy
• The IR spectroscopy theory utilizes the concept that molecules tend to absorb specific
frequencies of light that are characteristic of the corresponding structure of the molecules.
The energies are reliant on the shape of the molecular surfaces, the associated vibronic
coupling, and the mass corresponding to the atoms.
• For instance, the molecule can absorb the energy contained in the incident light and the
result is a faster rotation or a more pronounced vibration.
Regions of the Infrared spectrum
• Most of the bands that indicate what functional group is present are found in the region
from 4000 cm-1 to 1300 cm-1. Their bands can be identified and used to determine the
functional group of an unknown compound.
• Bands that are unique to each molecule, similar to a fingerprint, are found in the fingerprint
region, from 1300 cm-1 to 400 cm-1. These bands are only used to compare the spectra of
one compound to another.
Molecular Vibrations
Covalent bonds vibrate at only certain allowable frequencies.
Stretching Frequencies
• Frequency decreases with increasing atomic weight.
• Frequency increases with increasing bond energy.
Vibrational Modes
Nonlinear molecule with n atoms usually has 3n - 6 fundamental vibrational modes. Linear
molecule has 3n-5 vibrational modes
Vibrational Modes
IR-Active and Inactive
Carbon-Carbon Bond Stretching
• Stronger bonds absorb at higher frequencies:
– C-C 1200 cm-1
– C=C 1660 cm-1
– C≡C 2200 cm-1 (weak or absent if internal)
• Conjugation lowers the frequency:
– isolated C=C 1640-1680 cm-1
– conjugated C=C 1620-1640 cm-1
– aromatic C=C approx. 1600 cm-1
Carbon-Hydrogen Stretching
Bonds with more s character absorb at a higher frequency.
– sp3 C-H, just below 3000 cm-1 (to the right)
– sp2 C-H, just above 3000 cm-1 (to the left)
– sp C-H, at 3300 cm-1
An Alkane IR Spectrum
An Alkene IR Spectrum
An Alkyne IR Spectrum
O-H and N-H Stretching
• Both of these occur around 3300 cm-1, but they look different.
– Alcohol O-H, broad with rounded tip.
– Secondary amine (R2NH), broad with one sharp spike.
– Primary amine (RNH2), broad with two sharp spikes.
No signal for a tertiary amine (R3N)
An Alcohol IR Spectrum
An Amine IR Spectrum
Carbonyl Stretching
• The C=O bond of simple ketones, aldehydes, and carboxylic acids absorb around 1710
cm-1.
• Usually, it’s the strongest IR signal.
• Carboxylic acids will have O-H also.
Aldehydes have two C-H signals around 2700 and 2800 cm-1.
A Ketone IR Spectrum
An Aldehyde IR Spectrum
O-H Stretch of a Carboxylic Acid
This O-H absorbs broadly, 2500-3500 cm-1, due to strong hydrogen bonding.
Variations in
C=O Absorption
• Conjugation of C=O with C=C lowers the stretching frequency to ~1680 cm-1.
• The C=O group of an amide absorbs at an even lower frequency, 1640-1680 cm-1.
• The C=O of an ester absorbs at a higher frequency, ~1730-1740 cm-1.
• Carbonyl groups in small rings (5 C’s or less) absorb at an even higher frequency.
An Amide IR Spectrum
Carbon – Nitrogen Stretching
• C - N absorbs around 1200 cm-1.
• C = N absorbs around 1660 cm-1 and is much stronger than the C = C absorption in
the same region.
• C ≡ N absorbs strongly just above 2200 cm-1. The alkyne C ≡ C signal is much weaker
and is just below 2200 cm-1 .
A Nitrile IR Spectrum
Summary of IR Absorptions
Strengths and Limitations
• IR alone cannot determine a structure.
• Some signals may be ambiguous.
• The functional group is usually indicated.
• The absence of a signal is definite proof that the functional group is absent.
• Correspondence with a known sample’s IR spectrum confirms the identity of the
compound.