CHE 320 ANALYTICAL TECHNIQUES IN STRUCTURAL DETERMINATION

SPECTROSCOPY
Is a branch of science concerned with the investigation and easements of spectra
produces when matter interacts with or emits electromagnetic radiation.
MAGNETIC PROPERTIES
On the basis of their behavior in a magnetic field, substances can be divided into two classes.
(1) Diamagnetic substances
which are slightly repelled or pushed out of the magnetic field.
Most substances belong to this class.
(2) Paramagnetic substances
which are slightly attracted or pulled into the magnetic field. Some substances belong to this
class.
A few substances are intensely paramagnetic and retain their magnetic property when removed
from the magnetic field. These are known as Ferromagnetic substances.
Examples are iron, cobalt and nickel.
Measurement of Magnetic Properties
The magnetic properties of substances can be measured with the help of a magnetic balance
Or Gouy balance

Why a Substance is Paramagnetic or Diamagnetic?

A single electron spinning on its own axis generates a magnetic field and behaves like a small
magnet. Therefore a substance with an orbital containing an unpaired electron will be attracted
into the poles of an electromagnet. It follows that any atom, ion or molecule that contains one or
more unpaired electrons will be paramagnetic. When an orbital contains two electrons (↑↓), their
spins are opposed so that their magnetic fields cancel each other. Thus an atom, ion or molecule
in which all electrons are paired will not be paramagnetic.

Magnetic Properties and Molecular Structure

A paramagnetic molecule or ion contains one or more unpaired electrons.
Each spinning electrons behaves like a magnet and has a magnetic moment.
The magnetic moment (μ) of a molecule or ion due to the spin of the unpaired electrons is
expressed by the formula (2)
μ= √ ¿ ¿ …….. 2 , where μ is the magnetic moment in magnetons and n
the number of unpaired electrons. The number of unpaired electrons can be determined by
measuring magnetic moment with the help of Gouy balance. This has proved of great use in
establishing the structure of certain molecules and complex ions.

MOLECULAR SPECTRA
We have studied previously how hydrogen atom exhibits an
atomic spectrum by interaction with electromagnetic radiation. This was explained in terms of
energy levels in the atom. An electron can pass from one energy level to another by emission or
absorption of energy from the incident radiation. When an electron drops from a higher energy
level E2 to another of lower energy E1 , the surplus energy is emitted as radiation of frequency v.
That is E2-E1= hѵ .where h ]is Planck’s constant. Each frequency of emitted radiation records a
bright line in the spectrum.
On the other hand, if the transition of an electron occurs from a lower energy level E1, to another
of higher energy E2, energy (hv) is absorbed. This records a dark line in the spectrum. A
spectrum which consists of lines of different frequencies is characteristic of atoms and is termed

Line Spectrum or Atomic Spectrum A spectrum which consists of bright lines produced by
emission of electromagnetic radiation is termed Emission Spectrum.
A spectrum which consists of dark lines produced by absorption of incident radiation is termed
Absorption Spectrum.
Similar to atoms, molecules also have energy levels. Thus molecules exhibit
Molecular spectra by interaction with electromagnetic radiations. These spectra may consist of
bright or dark bands composed of groups of lines packed together. Such spectra are termed Band
spectra.
Molecules generally exhibit spectra made of dark bands caused by absorption of incident
radiation. These are referred to as Absorption Band spectra
and provide valuable information about the chemical structure of molecules. However, molecular
spectra are relatively complex. Before taking up their systematic study, it is necessary to acquaint
the student with the Electromagnetic spectrum as also the Molecular energy levels

ELECTROMAGNETIC SPECTRUM
Visible light, X-rays, microwaves, radio waves, etc., are all electromagnetic radiations.
Collectively, they make up the Electromagnetic spectrum Electromagnetic radiations consist of
electrical and magnetic waves oscillating at right angles to each other. They travel away from the
source with the velocity of light (C) in vacuum. Electromagnetic waves are characterized by:
(1) Frequency (v) :
It is the number of successive crests (or troughs) which pass a stationary point in one
It is the reciprocal of wavelength, Its unit is cm–1

TYPES OF MOLECULAR SPECTRA

To obtain a molecular spectrum, the substance under examination is exposed to electromagnetic
radiations of a series of wavelengths. Molecules of the substance absorb certain wavelengths in
order to be excited to higher electronic, vibrational or rotational energy levels.
The series of wave lengths absorbed in each case gives a distinct molecular spectrum.
Thus there are three main types of molecular spectra.
(1) Electronic Spectra
These are caused by absorption of high energy photons which can send electrons to higher
energy levels. The electronic spectra are within the visible or ultraviolet regions of the
electromagnetic spectrum.
(2) Vibrational Spectra
Lower energy photons cause changes in vibration energy levels. The spectra thus obtained
are referred to as vibration spectra . These are in the near infrared region (near to the visible
region).
(3) Rotational Spectra
Still lower energy photons cause changes in the rotational levels in the molecules. These spectra
are called the rotational spectra. These spectra are in the far infrared or microwave region. In
order to use numbers of reasonable size, different units are used for different types of spectra. In
ultraviolet and visible spectra the radiation is stated as a wavelength in nm or as a wave-number
in cm–1 . In infrared spectra, wave-numbers in cm–1 are often used. In microwave or NMR
spectra, frequencies are expressed in Hz (or MHz)

ROTATIONAL SPECTRA
Rotational spectra are used to determine the bond lengths in hetero nuclear molecules, A–B.
Such molecules have a permanent dipole moment and while rotating produce electric field. Thus
Electromagnetic radiations interact with these molecules and produce rotational spectra. The
Rotational spectra are observed in the far infrared and microwave regions.

VIBRATIONAL SPECTRA
Atoms in a molecule are in constant vibration motion about mean or equilibrium positions. The
modes of vibration may be bond stretching, bond bending, rocking motions and the like.
.
INFRARED SPECTROSCOPY
An infrared (IR) spectrometer subjects a compound to infrared radiation in the 5000-667 cm-
1(2μm) range. Although this radiation is weak, it does supply sufficient energy for bonds in the
molecule to vibrate by Stretching or Bending as linked by springs that are set in motion by the
application of energy. As the molecule is subjected to the individual wavelengths in the 5000-
667 cm-1 range, it absorbs only those possessing exactly the energy required to cause a particular
vibration. Energy absorptions are recorded as bands (peaks) on chart paper. Since different
bonds and functional groups absorb at different wavelengths, an infrared spectrum is used to
determine the structure of organic molecules. For example, carbon-carbon triple-bond is stronger
than a carbon-carbon double bond and requires a shorter wavelength (greater energy) to stretch.
The same considerations apply to carbon-oxygen and carbon-nitrogen bonds.

An infrared spectrum is usually studied in two sections:

(1) Functional Group Region. The area from 5000 cm-1 to 1300 cm-1 is called the functional
group . The bands in this region are particularly useful in determining the type of functional
groups present in the molecule

(2)Fingerprint Region. The area from 1300 cm-1 to 667 cm-1 is called the fingerprint region. A
Peak-by-peak match of an unknown spectrum with the spectrum of the suspected compound in
this region can be used, much like a fingerprint, to confirm its identity.

SOME CHARACTERISTIC IR ABSORPTION BANDS

Range in cm-1
Bond (Remarks) 1050-1400 C– O (in ethers, alcohols, esters)
1050-1400 C– N (in amines)
1315-1475 C–H (in alkanes)
1340-1500 NO2 (two peaks)
1450-1600 C=C (in aromatic rings ; several peaks)
1620-1680 C= C (in alkenes)
1630-1690C =O (in amides)
1690-1750 C= O aldehydes, ketones, esters)
1700-1725 C=O (in carboxylic acids)
1770-1820 C=O (in acid chlorides)
2100-2200 C≡C
2210-2260 C≡N
2500 S–H
2700-2800 C–H (of aldehyde group)
2500-3000 O – H (of COOH group)
3000-3100C–H (C is part of aromatic ring)
3330 C–H (C is part of C≡C)
3020-3080 C– H (C is part of C=C
2800-3000 C–H (in alkanes)
3300-3500 N– H (in amines, amides)
3200-3600 O – H (in H-bonded ROH)
3600-3650 O –H