Organic

Spectroscopy
INTRODUCTION
 CH224: Course Content

• Ultraviolet, visible, IR, H1 and C13 – NMR,

Mass spectra
• Qualitative UV/Visible spectroscopy,
Qualitative IR
• Qualitative use of Spectroscopic methods
(IR, H1 –NMR, C13-NMR, UV, MS)
• Proof of structure of organic compounds.

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 References
1. Silverstein R.M, Webster FX, Kiemle DJ (2005)
Spectrometric Identification of Organic
Compounds. 7th Edition, John Wiley & Sons, Inc.

2. Williams D.H, Fleming I (1989) Spectroscopic

Methods in Organic Chemistry. 4th Edition,
McGraw-Hill.

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 Introduction

• Prior to the 19th century, schools of pharmacy

trained pharmacists and physicians how to prepare
medicinal remedies from natural organic products
or inorganic materials.

• Herbal medications and traditional remedies dating

back to ancient Egyptian, Greek, Roman, and Asian
societies were administered without any knowledge
of their biological mechanism of action.

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 Introduction cont.

• It was not until the early 1800s that scientists began

extracting chemicals from plants with claimed
therapeutic properties to isolate the active
components and identify them.

• By discovering and structurally characterizing

compounds with medicinal activity, chemists are
able to design new drugs with enhanced potency
and decreased adverse side effects.

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 Introduction cont.

• Drug development and synthesis is the core of

pharmaceutical/medicinal chemistry.

• Pharmaceutical chemists are involved in the

development and assessment of therapeutic
compounds.

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 Introduction cont.

• So how do we know if a compound that has been

synthesized is the correct compound?
• How do we ensure that there are no impurities
present in the compound synthesized?
• How can we tell the structure of an unknown
compound that has poisoned many people?
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 Introduction cont.

• We can answer these questions by making use of

various analytical techniques to elucidate the
structure of the compound by using Nuclear
Magnetic Resonance (NMR) Spectroscopy or check
if there is a change in the functional group by using
Infra-red (IR) Spectroscopy.

• Impurities can also be detected using thin layer

chromatography.

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 Introduction cont.

• Some of the steps that may be taken to identify a

synthesized or isolated substance are:
1. Determination of molecular weight.
2. Elemental analysis.
3. Detection of the presence or absence of a certain
functional groups (e.g. by chemical analysis):

Alkanes Alkenes Alkyl halides Alcohols

Ethers Aldehydes Ketones Carboxylic acids
Esters Acid Chlorides Cyanides Amines Phenols

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 Introduction cont.

4. Degradation to simpler compounds.

5. Conversion into derivatives.
6. Synthesis by an unambiguous route.
7. Spectroscopy.

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 SPECTROSCOPY
• Study of the interaction between electromagnetic
radiation and matter.

• Study of the absorption, emission, or scattering of

electromagnetic radiation by matter to qualitatively or
quantitatively study matter or physical processes.

• Matter involved can be atoms, molecules, atomic or

molecular ions, or solids.
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 Types of Interaction between
EM Radiation and Matter
• Absorption: A transition from a lower to higher
Energy level with transfer of energy from the
radiation field to an absorber (atom, molecule, or
solid).

• Emission: Transition from a higher to lower

Energy level with transfer of energy from the
emitter to the radiation field.

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 Types of Interaction between
EM Radiation and Matter
• Scattering: Re-direction of light due to its
interaction with matter. Scattering might or might
not occur with a transfer of energy.

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 Types of Interaction between
EM Radiation and Matter
• The group of techniques which measures the
interaction between matter and EM Radiation are
called SPECTROSCOPIC TECHNIQUES.

• Spectroscopy can be used as an analytical tool to

identify and to quantify the chemical constituents
in a sample.

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 Qualitative Spectroscopy
• The application of the measurement of interaction
(absorption, emission or scattering) between
electromagnetic radiation (EMR) and matter for its
qualitative study (study of composition of matter)

• May involve identification, structure determination,

configuration determination etc.

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 Electromagnetic Radiations
• Electromagnetic radiation (EM radiation or EMR) are self-
propagating waves consisting of electric and magnetic field
components in a vacuum or through matter.

• The electric and magnetic field components oscillate in phase

perpendicular to each other and perpendicular to the direction of
Energy propagation.

• The components are of the same Energy and move in the same
direction.

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 Electromagnetic Radiations
• EM radiation exhibits both wave and particle
properties at the same time (refer to wave-particle
duality concept).

• Depending on the circumstances, electromagnetic

radiations may behave as a wave or particle.

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EM radiation Wave

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 EM radiation properties
• As a wave, EMR is characterized by;
• Velocity/speed.
• Wavelength.
• Frequency.
• Amplitude.

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 EM radiation properties
1. Wavelength (λ): The distance between repeating points
on the wave.

2. Amplitude: The distance between the highest (or lowest)

point on a wave and the center of the wave.

• Two waves can have different wavelengths but have the

same amplitudes.
• Considering light, in the visible region, the amplitude
controls the brightness of light.
• The larger the amplitude of the wave the brighter the light.

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 EM radiation properties
3. Frequency (v): Is the number of waves which pass a
point in space per unit time.

• The units of frequency are cycles per second (cps) or

Hertz (Hz).

• Obtained by dividing the number of waves passing a

point by the time in seconds.

• The shorter the wavelength for the EMR the higher the
frequency and vice versa is true.
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 EM radiation properties
4. Velocity (c) of a wave is a measure of speed of a
wave.
• It is the product of number of waves passing a
particular point per unit time (v) and the distance
between the tops of the waves ().

vx = c

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 EM radiation properties

• Regardless of the circumstances, ALL EMR

always travel at the same speed in a vacuum.
c = 3 x108 m/s

• In other medium (other than vacuum), the velocity

factor or refractive index must be considered.

• Since c is constant,  is inversely related to v

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 EM radiation Energy
• When considered as particle, EMR are known as photons,
and each has an energy (E) related to the frequency of the
wave given by Planck's relationship.

E = h.v
E = h.c/

h = 6.626 X 10-34 J.s

• Thus the shorter the  and the higher the v of a wave, the
higher the E and vice versa is true.

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 Classification of EMR
• Can be classified according to Frequency or Ionization capability.

1. FREQUENCY.
• EMR is commonly classified according to the frequency of its wave.
• These types of EMR include, in order of increasing Energy,
frequency and decreasing wavelength;

• Radio waves (AM, FM, TV, and Shortwaves).

• Microwaves.
• Infra-red, Visible, Ultraviolet radiation
• X-rays and Gamma rays.

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 Classification of EMR

Decreasing wavelength () in meters (m)

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 Classification of EMR
2. IONIZATION.
• Electromagnetic radiation can also be classified into
ionizing radiation and non-ionizing radiations.

• This is based on whether it is capable of ionizing

atoms or molecules and breaking chemical bonds.

• Higher frequency EMR, such as X-rays or Gamma

are ionizing.

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 Classification of EMR
• Lower energy EMR such as UV-Visible rays cannot
ionize molecules, but can cause electronic,
vibrational, and rotational excitations in molecules.

• IR radiations cannot ionize molecules or cause

electronic excitations but can cause vibrational, and
rotational excitations in molecules.

• Vibrational and rotational excitations cause thermal

excitation (heating) of a molecule.

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 Classification of EMR
• Radio and microwaves cause mainly vibrational and
rotational excitations.

• UV, Visible, IR and radiofrequency radiations are

typically used to study the composition of chemical
species.

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 Sources of EMR
• Long radio waves are produced by large antennas
e.g. those used by broadcasting stations.

• Much shorter visible light waves are produced by

the motions of electronic charges within atoms.

• The shortest waves e.g. gamma radiations, result

from changes within the nucleus of the atom.

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 Spectroscopic Techniques of
Analytical Importance
• Spectroscopic techniques of pharmaceutical analytical
importance involve those which measures radiation
selectively absorbed or emitted by atoms or molecules
of organic compounds

• Includes;
• UV, Visible Spectroscopy.
• Fluorescence.
• Infrared Spectroscopy.
• Atomic absorption and emission.
• NMR Spectroscopy.
• Mass Spectrometry etc.
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 Spectroscopic Techniques of
Analytical Importance
• Spectroscopic methods are commonly employed in;

a) Determination of structures of molecules (qualitative).

b) Identification of organic compounds including drugs.
c) Quantitative determinations.

• There are four spectroscopic techniques most commonly employed in

pharmaceutical analysis i.e.

1. UV – Visible spectroscopy .
2. Infrared Spectroscopy.
3. NMR Spectroscopy.
4. Mass Spectrometry (MS).

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 Spectroscopic Techniques of
Analytical Importance
• The first three techniques rely on the selective absorption
of electromagnetic radiation by organic molecules.

• MS is not a truly spectroscopic method. It produces ions

and weighs them. It measures mass to charge(m/e) ratios.

• These Techniques differ by;

• Region of spectrum used.
• Type of radiation-matter interactions i.e. absorption, emission or
scattering.
• What is analyzed (molecules or atoms).

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 Absorption of EMR
• Molecules absorb EMR in discrete packets called
‘quanta’ of Energy(E).
• Absorbing species are excited from ground to excited
state
• This absorption is measurable by various
spectroscopic techniques.
• Absorption occurs only when the radiation supplying
the exactly right quanta of E interacts with a the
compound of interest.
• If E of radiation does not match, no EMR absorption.
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 Absorption of EMR
• A molecule is associated with several types of motion:
a. Whole molecule rotation.
b. Vibration along the bonds.
c. Movement of electrons.

• Each of these motions are ‘quantized’ i.e. each molecule can exist
only in distinct states which correspond to discrete energy content.

• Each state is characterized by ΔE.

• Thus spectroscopy is a technique which measures the ΔE between

the allowed energy states.

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 Measurement of EMR absorption

• Each type of motion (E state) corresponds to the

absorption of light in different regions of the EMR.

• UV-Visible EMR cause movement of valence electrons.

• The E needed for this lies in the range 40 – 300kCal/mol

• This is supplied by by UV- Visible EMR of λ = 200 –

800 nm

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 Measurement of EMR absorption

• Infra red EMR cause vibrational exitation of the

molecular framework of a compound (ΔE = 2-10
kCl/mol)

• Microwave EMR cause rotation around bonds (ΔE

= 10-4 kCal/mol )

• Radio-wave EMR re-orient nuclear spins (ΔE = 10-

6 kCal/mol) = NMR spec

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 Measurement of EMR absorption

• An absorption spectrum is a graph of absorption

intensity versus ν or λ.

• Spectrum yields information about spacing of

energy levels and hence structure of a molecule.

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 Summary of Spectroscopic
techniques
UV – Visible Spectroscopy
• λ = 10-7 – 10-6 m
• Used to detect conjugated systems
• Absorption of EMR in this region promotes (excites)
electrons of such systems from ground to excited state.

IR Spectroscopy
• λ = 10-5 m
• Used to detect and identify vibrations of molecules along
their bonds especially those of triple and double bonds
present in many functional groups.
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 Summary of Spectroscopic
techniques
NMR Spectroscopy
• λ = 0.6 - 10 m
• Use a longer λ to detect changes in alignment of nuclear magnets e.g. 1H,
13
C in strong magnetic fields.
• Detects nuclear spin transitions.

Mass Spectrometry
• It measures the mass to charge ( m/e) ratio of organic ions created by
electron bombardment.
• Fragmentation of molecules following ionization can give a clue as to the
likely molecular structures from the m/e ratios of the fragment ions.

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