SPECTROSCOPY

9. The branch of science

which describes the interactions of electromagnetic
malter is Rinown a s spectroscopy. Spectroscopy
may be defined a s aan
radiation with
molecular structure with electromagnetie
radiation. The
ared of study that probes
a molecule as a result of the interaction of
ahsorption of electromagnetic radiation by the
the radiationwith the molecule gives very valueable information regarding
molecule.
structure of the

Electromagnetic radiation is a commonly known a s

form of energy,
a s energy, the propagation and
radiant energy. Kadiant energy may be defined
matter. Light is a
transfer of which takes place as a wave motion without transfër of
form of electromagnetic radiation. The electromagnetic radiation, unlike
other wave
phenomena (say sound) does not always require a supporting medium for its
transmission and readily passes through vacuum. According to quantum mechanics,
electromagnetic radiation has the properties of both a wavé and a particle-like
discrete packets of energy, called quanta or photons. While dealing with the
interaction of electromagnetic radiation, it is the photon concept which is almost
always used.

Nature of Electromagnetic Radiation

The electromagnetic radiation (emr) is conveniently treated as an alternating

electrie field in space associated with mutually perpendicular electrical and magnetic
forces. The wave nature of electromagnetic radiation (emr) can be represented by
electrical and magnetic vector. Besides being perpendicular to each other, the two
fields are perpendicular to the direction of propagation. It is because of these
associated electric and magnetic fields that the radiation is called electromagnetic
radiation (emr). In emr, it is the electrical field that interacts with the electrons in
matter and as a result the representation of radiation by the electrical vector alone
has been found to
be
sufficient for most cases. The radiation obtained from a single
source comprises several waves which may be of equal or. unequal wavelengths. A
radiation in which all electric displacements are in one plane as the wave progresses
s said to be polarized. Emr having all the waves of a single wavelength is known
s
monochromatic, literally "one coloured". On the other hand, a polychromatic
"adiation consists of waves of various wavelengths.
An electromagnetic radiation can be characterized in different ways using
ifferent parameters as described below:
Wavelength, A. The distance between two successive crests or troughs or a

beam of electromagnetic radiation is called wavelength and is denoted by

avein a
ambda). The units commonly used for wavelength are angstrom, nanomee
icrometerand meter (lm =105 unm = 10" nm =101A)
The number of waves passing through
u.
a point on
tne pa
(nu). It is
requency, and is
d e n o t e d by
v

of radiation per second is called frequency

2am second (cps); (1 Hz
1 cps. =
T a r ccles ner
 RY
16
passing per centimeter. cO
AA common
Wave number, t is the number of waves

100 ml). + =
1/A
the reciprocal centimeter, cm-1,(1 cm-
=

unit for is
of a the distance through which a particular wave tra
w a v e is
The speed, c
is related to frequency and wavelengthh by
in one second and is denoted by c. Speed
the expression;
(1)
or

be characterized in terms of
Energy, E. Electromagnetic radiation
can ene-
onerg
each photon of radiation. The SI unit for energy is Joule (J). E
Each
possessed by
to the frequency of light.
photon has an energy which is proportional
hu hc hcv ---(2)
Ephoton = =

where h is the Planck's constant having a value 6.625 x 10°* Js andc is the velocit.
cit
of light which is 3.0 x 105 m/s.
Cosmic rays, gamma rays, X-rays, ultraviolet, visible light, infrared rays, mier
waves and radio waves, all are electroniagnetic radiation. Electromagnetic spectrum
covers a wide range of wavelengths and the radiations of different wavelengths hav
different characteristics. The whole electromagnetic spectrum can be conveniently
divided into several regions, each region can be defined by the limits of any of the
four parameters, i.e., wavelength, frequency, wave number or energy. In organi
hemistry, the important wavelength regions are the ultraviolet, visible and
nfrared.
Table 9.1 Ranges of electromagnetic radiations in spectral region
Spectral region Wavelength Frequency Wavenumber Energy
(Hz) (cm) (J)
Cosmic rays 10A 3x 1022 1012 2x 10-11

10-A 3x 1021 10l1 x 10-12

Gamma rays
10' 3x 1019 2 x 10-14

X-rays 100 (10 nm) 3 x

10 2 x 10-17

Ultraviolet
400 nm 7.5 x 104 2.5 x 10 5x 10
Visible 2.5 x 1019
800 nm (0.8 um) 3.8x 10 1.3x 10
Infrared
10 m 3 x 1011 10 2 x 10-22
Microwavve
10 um(1m) 3 x 108 102 2x 1 0 -

Radiowave
10 m 3 x 10 106 2 x 10-28
Principle of Spectroscopy

All organie compOunds interact with

arb energy. whe a molecule absorb
electromagnetic radiation, that i8, they
energv, a transformation occurs. Lower
wuy radiation may cause a
energy molecular rotation, or a bond vibration. Higher
adiation may ause the promotion of electrons to higher energy levels or enerE
bond
eleavage.

Whether thetranstormation involves molecular rotation, bond vibration,

tronie transition, the molecule absorbs only the wavelength of radiation with
electn
or
aetly the energy necessary for the transition. The absorption of wavelengths of
exactly
iatjon is selective for a particular transition which
depends on the structure ol
the olecule. By measuring the absorption spectra of known compounds we can
the mole

oarTelate the wavelengths of energy absorbed with characteristic structural features.

This information is then used to determine the structure of unknown compounds.
During absorption sóme of the molecules falling in the path of the incdent
heam, collide with photons of radiant energy. However, only those photons get
absorbed whose energy exactly equals the difference in energy, AE between the ground
and the excited states of the molecules.
AE = hu = hc/
Spectrophotometer. The instrument used to measure the amount of
electromagnetie radiation absorbed by a compound is called spectrophotometer or
spectrometer. It consists of light source of radiation, with a prism that can select
the desired wavelengths which are passed through a sample of the compound being
investigated. The radiation that is absorbed by the sample is detected and is
recorded on a chart against the wavelength or wave number. Absorption peaks are
plotted as minima in infrared, and usually as maxima in ultraviolet spectroscopy.

A-H
Light Source Prism Selector Sample Detector Spectrum

Fig. 9.1 Basic compohents of a spectrophotomer

When a beam of polychromatic light is passed through a prism, it splits up
nto seven different colour. The set of colours thus obtained is called a spectrum.
ne distribution among various wavelengths of the radiant energy emitted or

bsorbed by an object is called spectrum.

Classification of Spectra
oi spectra namely emission spectrum and
There are two maii classes
absorption spectrum.
emitted by a substance is passed through a
Emis
Ssion spectrum. When the light obtained is known as
examined directly with a spectroscope, the spectrum
and is further classified depending upon its
ssion spectrum. Emission spectrum
Ppearance as line, band and continuous spectrum.
ADsorption spectrum. When white light is passed through an absorbing s
and then examined through a spectroscope, it is observed that certain wa substance
ne
are missing and dark lines appear at their places. The spectrum thus ahtoi
called absorption spectrum. These dark lines or bands depend upon the natura .o
of the
absorbing material.
Interaction of electromagneticeradiation with
matter

The interaction of electromagnetic radiation with matter gives a varie

rnety of
phenomenon which may occur as follows:

1. If the photons of radiation possess the appropriate energies, they may

absorbed by the matter and result in electronic transitions, rotational chanae
Lges,
vibrational changes or combination of these. After absorption, atoms n
molecules become excited. They lose energy quickly either in the form of heat ur

by reemitting electromagnetic radiation.

2. The radiation passing through the matter is not absorbed completely. The
portion of electromagnetic radiation that passes into matter, instead of beina
absorbed, may undergo scattering or reflection or may be re-emitted at the
same or different wavelength.
3 When electromagnetic radiation is neither absorbed nor seattered, it may
undergo changes in orientation or polarization.

Electronic energy levels in an atom

The electrons in any atom occupy the lowest energy level and this
arrangement refers to the ground state of the atom. Excitation of atoms by

absorption of radiation occurs corresponds to subsequent changes in their electronie

energy levels. The electrons can be excited by radiant energy to higher energy state
The process of transfer of an electron from one energy level to the other is referred to
as electronic transition.
The energy of the photons which are preferably absorbed differ from one

element to another. The amount of energy change in any one absorption interacir
of this type depends both upon what the atom or ion is and upon what electro

orbital in that atom or ion are involved in the change. In general, it has been toune
that absorption involving the outer electronic energy levels need photons of enerE
corresponding to UV and visible region of electromagnetic spectrum.

Excited atoms or molecules are relatively short lived and return to t

01
the
ground state spontan2ously. The life time of the excited state is generally
order of 10 seconds. While returning to the ground state the atom emits ce
SPECTROSCOPY 519
energy which difference between two energy levels. Both
corresponds processes follow the law oI conservation of energy and
xcitation and de-excitation
to the

moves to the next energy level (e.g, from 2s to 2p) and *hen returns to the ground
State, the transition is known as resonance radiation and it is on this phenomenon

that the atomic

absorption method is based on.
When the emission of light is instantaneous, the phenomenon is called
ffuorescence, but if it after some time, it is called phosphorescence. When
occurs

the absorbed energy is stored by the atom or molecule and used in producing some
chemical reaction, fluorescence and phosphorescence disappear and the resulting
chemical reaction is called photochemical reaction.
Different Transitions possible in atoms and molecules
 unoccupied n orbitals of the ligand.
Spectroscopic Techniques
is a uniqua
with a particular substance
The study of energy levels associated
and determines the frequercies at which
characteristic of that substance
absorbed. Qualitative information
electromagnetic radiation c a n be emitted or
is obtained through a study of
regarding the composition and structure of a sample
lines o r bands. Quantitative
the positions and relative intensities of spectral
between the intensity of a
analysis is possible because of the direct proportionality
o r molecules undergoing the
particular line or band and the number of atoms
used for analytical
transition The various spectroscopic techniques commonly
a r e given below in
the table.
purposes and the type of information they provide
Table-9.2: Analytical Spectroscopic Techniques

Name of Technique Principle Major Applications

Qualitative and quantitative
Arc/spark spectrometry or
determination of metals,
spectrography Atomic emission minor or trace
largely as

constituents.

Quantitative determination of
Flame Photometry minor or trace
metals as
constituents.

Qualitative and quantitative

X-ray flucrescence
determination of elements
spectrometry nitrogen as trace
heivier than

to major constituents.
Atomic fluorescence
Emission Quantitative determination o'
Atomicfluorescence trace
trace
metals as minor or

spectrometry constituents.
Atomic absorption
Atomic absorption Quantitative determination of
spectroscopy
metals as minor or trace
constituents.

y-spectrometry
Nuclear emissioon Qualitative and quantitative
determination of elements at
trace levels.
Ultraviolet (UV)
Quantitative determination of
spectroscopy
elements and compounds at
trace levels.

Visibie spectroscopy Molecular absorption Quantitative determination of

elements and compounds,
mainly as trace and minor
constituents.

Infrared (IR) spectroscopy Molecular absorption Identification and structural

analysis of organic compounds
Nuclear magnetic Nuclear absorption Identification and structural
resonance (NMR) analysis of organic compounds
spectroscopy

Mass spectrometry Structural Identification and structural

fragmentation analysis of organic compounds