Modern Instrumental Methods of Analysis

J.R. Mudakavi
Dept. of Chemical Engineering
Indian Institute of Science, Bangalore
Qualitative analysis
Quantitative analysis
characterization
Method development
Multidisciplinary
Problem solving
Broader perspectives
Ions,organics,titrations
Gravimetry,
Limited physical properties
M.P,B.P,Viscosity
Classical & Modern
Instrumental techniques
Statistics, electronics
Computers
Quditative schemes
Tools
Routine Analysis Cutting edge Technology
Tools
ANALYTICAL SCIENCE ANALYTICAL CHEMISTRY
2. Analytical Chemistry in Action
2.1 Automobile exhaust analysis
Sub-ppb analysis of PAHS
2.2 APXS sensor on Mars
Analysis of soils and rocks on Mars by
Rutherford backscattering
X-ray fluorescence
Nuclear reactions
2.3 SPADNS Method for fluoride determination
Development of APHA standard Method
Interlaboratory and intralaboratory analysis
Development of standard Reference material(SRM)
Data handling statistical evaluation
1.Identify the problem
Determine type of information needed
(qualitative,quantitative,characterization,
or fundamental)
Identify context of the problem
2.Design the experimental procedure
Establish design criteria (accuracy,
Precision, scale of operation, sensitivity,
Selectivity, cost, ,speed )
Identify interferents
Select method
Establish validation criteria
Establish sampling strategy
5.Propose a solution
Conduct external evaluation
4.Analyze the experiment data
Reduce or transform data
Analyse statistics
Verify results
Interpret results
3.Conduct an experiment
Calibrate instruments and
equipment
Standardize reagents
Gather data
Feedback
loop
Marching ahead
Resolving the contradictory evidence of a sportsman taking steroids
Evaluating the endosulphan exposure to farmers, children and
pregnant ladies
Developing rapid and sensitive detectors for chemical warfare
agents.
Real time modeling and monitoring of an oil spill near a port.
Developing miniaturized sensors for real time air quality monitoring
Problem solving Multiple source, interactions
Accuracy,precision,sensitivity and detection limit
Amount of sample available, collection ,storage, transport and
pretreatment of the sample
Number of samples to be analysed
Validation of the method, equipment and results
Report presentation, problem solution and external evaluation
Cost considerations based on the above
Analytical inputs
What exactly is the analytical problem?
What type of input information is to be collected?
What criteria are to be considered in designing the experiment ?
What interferences are expected and how to eliminate the same?
How to collect ,store, transport and pretreat the samples
Validation of results
Can a successful solution is feasible at this stage?
Characteristic Properties Instrumental Methods
Emission of radiation
Absorption of radiation
Scattering of radiation
Refraction of radiation
Diffraction of radiation
Rotation of radiation
Electrical potential
Electrical charge
Electrical current
Electrical resistance
Mass
Mass-to-charge ratio
Rate of reaction
Thermal characteristics
Radioactivity
Emission spectroscopy (X-ray, UV, visible,
electron, Auger); fluorescence, phosphorescence,
and luminescence (X-ray, UV, and visible)
Spectrophotometry and photometry (X-ray, UV,
visible, IR); photoaccoustic , spectroscopy
;nuclear magnetic resonance and electron spin
resonance spectroscopy
Turbidimetry;nephelometry;Raman spectroscopy
Refractometry;interferometry
X-ray and electron diffraction methods
Polarimetry;optical rotary dispersion;circular
Dichroism
Potentiometry;chronopotentiometry
Coulometry
Amperometry;polarography
Conductometry
Gravimetry(quartz crystal microbalance)
Mass spectrometry
Kinetic methods
Thermal gravimetry and titrimetry;differential
scanning calorimetry;differential thermal analyses;
thermal conductometric methods
Activation and isotope dilution methods
1. ATOM IN HINDU SCRIPTURES
Ancient Hindu scriptures recognized that matter is made of tiny
discrete particIes known as Anu, paramanu, kana.
'Kana' is an aggregate of smaIIer particIes caIIed as 'Anu'. But
it is not visibIe to the naked eye. 'Anu's of each substance are
distinctive and capabIe of independent existence. 'Paramanu' is
the smaIIest discrete particIe capabIe of independent existence
but not visibIe to the naked eye. 'Paramanu' s are essentiaI
components of aII things we see around us.
The power of the 'paramanu's and 'Anu's was utiIized in
warfare as 'Astras'(warheads) described as Shakti astra,
Brahmastra etc., and in aeropIanes(Vimanas).
contd...
2 .DALTONS THEORY(1802)
Matter is compared of tiny reaI particIes caIIed atoms
which are indivisibIe and cannot be created or
destroyed.
Atoms of aII substances are identicaI in nature,
weight, size and other properties. Atoms of pure
substance differ in weight & other characteristics
from other substances.
Atoms combine in definite proportions resuIting in
chemicaI compounds.
contd...
ParticIe Notation Mass*
(AMU)
Charge*
esu 10
10
ReIative charge
EIectron e 0.0005486 -4.8029 -e
Proton P, 1.00757 +4.8029 +e
Neutron n, 1.00893 0 0
Positron 0.0005486 +4.8029 +e
Neutrino ....... 0 0
Antinutrino ...... ....... 0 0
Meson 0.156 4.8029 e
0.118 4.8029 e
Deutron d, 2.01416 + 4.8029 +e
AIpha , 4.00279 +9.6058 +2e
H
1
1
3.FUNDAMENTAL COMPONENTS OF ELEMENTARY PARTICLES
n
1
0

B e ,
D
2
1
He
4
2
*AMU - Atomic mass unit, equivalent to
+esu is the fundamental unit of electrical charges
g
24
10 6603 . 1

contd...
4.MODERN ATOMIC THEORY
An atom consists of a positiveIy charged nucIeus of
about and comparativeIy heavy.
An extra nucIear arrangement of eIectrons which is
comparativeIy Iarge and diffuse in
character.
NucIeus consists of a number of protons and
neutrons. They are formaIIy reIated as:
Neutron Proton
cm
12
10

cm
8
10

e
contd...
e

NucIear forces arise from the creation and

annihiIation of mesons by nucIear particIes
(nucIeons). During radio active decay processes,
changes in nucIear charges occur according to the
foIIowing mechanisms.
P

n
z e

contd...
NucIei with 2,8,20,28,50,82 or 126 neutrons or
protons are especiaIIy stabIe. These so caIIed magic
numbers represent cIosed sheIIs of nucIeons.
For a given eIement with Z protons a number of
species may exist with the same number of protons
but varying in the number of neutrons. Such
eIements exhibit the same chemicaI properties but
differ in atomic weight and are caIIed isotopes.
NucIei of same mass number but differing in charge
aIso exist which are caIIed as isobars. But they
do differ in their chemicaI properties. (e.g Ca & Ar)
contd...
Attractive forces exists between neutrons and
protons. Energy exchanges occur via mesons
among them. The actuaI neutron to proton ratio is
due to the baIance between the tendency towards
neutron-proton equaIisation and proton reduction.
AII the radio active decay processes are therefore
aimed at attaining stabIe nucIei. This is achieved by :
(i) B-Emission For high neutron/proton
(ii) Neutron Emission ratios
(iii) Positron Emission
(iv) OrbitaI EIectron Capture For Iow neutron/proton
(v) Proton Emission ratios
contd...
An unstabIe nucIeus (having AMU > 83) arising out
of radio active decay or nucIear reaction, readjusts
itseIf to a stabIe nucIeus by the emission of an
particIe . In the process mass is Iost by 4 AMU
` and charge is Iost by 2 units
untiI it reaches a stabIe configuration.
NucIear stabiIity is aIso attained by the absorption or
reIease of energy. The energetics of nucIear
reactions are of course associated with mass
changes according to Einstein's equation,
E = mc
2
4 A A
2 z z
contd...
The reIease of energy takes pIace either in the form
of heat or as radiations. The mass change
corresponding to the conversion of hydrogen into
heIium,
is 0.0302 AMU. This is equivaIent to 28.12 Mev of
energy per heIium atom or 6.45 x 10
8
k caI per gram
atom of heIium. This is equivaIent to the
temperatures prevaiIing on sun. Hence nucIear
reactions are of interest as
a source of energy.
Q He n H
4
2
1
0
1
1
2 2
contd...
There are 5 types of NucIear reactions:
1. Capture reactions
2. ParticIe- ParticIe reactions
3. Fission Reactions
4. SpaIIation Reactions
5. Fusion Reactions
NucIear reactions can aIso be cIassified in terms of
bombarding agent. These incIude:
1. AIpha induced reactions
2. Proton induced rations
3. Deutron induced reactions
4. Gamma and X-radiation induced reactions
5. Neutron induced rations
contd...
5. THE ELECTRONIC STRUCTURE OF THE
ATOMS
In 1904 Sir J.J. Thomson proposed the corpuscuIar theory of
matter. He pictured the positive charge of an atom distributed
uniformIy throughout a sphere of protons and neutrons of
about 10
-8
cm. Negative charge was surrounding it in a jeIIy-
Iike fashion.
Rutherford modified this theory that eIectrons revoIve around
the nucIeus in such a way that the centrifugaI force exactIy
baIances the inward attractive forces much Iike our pIanets
do around the sun. This view was aIso not tenabIe because
within the atom, particIes having opposite charges are
present. Hence regardIess of their speed, they enter the
nucIeus. Moreover the eIectron Iosing energy wouId emit
continuous radiation without any sharp breaks.
contd...
In 1903, Bohr proposed a radicaIIy different view of
the atomic structure based on the opticaI spectrum
of Hydrogen. He incIuded the postuIates of quantum
theory proposed by Max pIank.
Bohr proposed that the eIectron in a hydrogen atom
aIways described a fixed circuIar path around the
nucIeus. Such orbits named 'stationary states' may
be thought of various circIes differing in radius. The
anguIar momentum of each stationary states was an
integraI muItipIe of n.h/2 which amounts to anguIar
momentum. The anguIar momentum mvr is given by
mvr = n(h/2)
where n is an integer caIIed a quantum number
contd...
He aIso postuIated that as Iong as the eIectron
remained in a given orbit it neither radiates nor
absorbs energy. When the eIectron moves from one
orbit to another it was considered to invoIve the
absorption or emission of definite quantity of energy
depending upon whether the eIectron moved from
Iower state to higher one or vice versa. This energy
manifests as radiation and the frequency of such
radiation is manifests a a spectraI Iine which couId
be reIated to the energies of eIectron in the two
states E
1
& E
2
as:
h E E
1 2
contd...
Line spectra of hydrogen atom
Lyman series n = 2,3,4.....to n = 1
BaImer series n = 3,4,5.....to n = 2
Paschen series n = 4,5,6.....to n = 3
Brackett series n = 5,6,7.....to n = 1
Pfund series n = 6,7.....to n = 5
Origin of hydrogen spectrum scann pp 83, Morrison
Bohr's theory couId expIain the spectra of hydrogen
and etc. But it faiIed compIeteIy
when appIied to muItipIe eIectron systems. Further
it couId not account for spIitting of opticaI Iines (fine
structure) when spectroscopes of high resoIving
power were empIoyed.
2 3
, & He li Be

contd...
6. SOMMERFELD THEORY
In 1916 SommerfeId modified Bohr's theory to
incIude eIIipticaI orbits which incIudes circuIar
orbits onIy as a speciaI case. The veIocity of an
eIectron moving in an orbit wiII be greatest when
it approaches cIosest to the nucIeus and Ieast
when it is farthest.
This introduces variabiIity in the orbit aIso
which as a whoIe wiII precess around the
nucIeus. This precessionaI movement wiII resuIt
in smaII energy changes and wiII be refIected as
fine structure in the spectrum.
contd...
SommerfeId concept permitted the subdivision of
the Bohr's stationary states of sIightIy differing
energy IeveIs corresponding to the differences in
orbit shapes.
This is the basis of modern concepts of eIectronic
configurations.
Further it projected the possibiIity of penetrating
orbits. Thus certain eIectrons may penetrate cIoser
to nucIeus than others thus permitting quaIitative
pictures of the more compIicated atoms.
contd...
7. ELECTRONIC DISTRIBUTIONS IN ATOMS
# The ruIe of 8: Inert gas atoms with the exception of
HeIium contain eight eIectrons in their outermost
arrangement .
# HeIium, Neon, argon, krypton, xenon and radon contain
2,10,18,36,54 and 86 eIectrons and represent the end of
various horizontaI series of periodic cIassification.
# C.R.Bury postuIated that maximum number of eIectrons
in the various sheIIs are 2,8,18 and 32. He aIso stated
that no sheII can contain more than 8 eIectrons unIess
another sheII further removed from the nucIeus is being
formed. This concept permitted IogicaI expIanations for
the configurations of transition and inner transition
eIements i.e fiIIing up of inner eIectronic IeveIs whiIe the
outer most ones remained constant.
contd...
# EIectronic configurations of inert gas atoms
SymboI At.No K L M N O P
He 2 2
Ne 10 2 8
Ar 18 2 8 8
Kr 36 2 8 18 8
Xe 54 2 8 18 18 8
Rn 86 2 8 18 32 18 8
contd...
8.QUANTUM DESIGNATIONS FOR
ELECTRONS
The Bohr-SommerfeId concept of eIectrons revoIving
around the atomic nucIei is Iimited to weII defined
shapes is essentiaIIy a rough pictoriaI presentation.
Modern concepts based on wave mechanics depict
comparative density of the eIectronic charges at any
given point within the atom based on the theory of
probabiIity.
EssentiaIIy this means eIectrons wiII tend to group
themseIves in a series of positions reIative to the
nucIeus which may be considered as energy IeveIs
w.r.t the nucIeus. Transitions are permitted onIy
between these energy IeveIs giving rise to spectrum.
contd...
EIectrons are best described in terms of four quantum numbers:
PrincipaI Quantum number(n) , OrbitaI quantum number(I), magnetic
quantum number(m) and Spin quantum number(s).
The energy IeveIs corresponding to n are given by
where w - energy of the eIectron
z - TotaI number of eIectrons atomic number)
e - EIectronic charge
- EIectronic mass and
h - PIanks constant
CrudeIy this amounts to the mean distance of the eIectron from the
nucIeus. PrincipIe quantum number may have vaIue from n=1 to
infinity where refers to the compIete removaI of the eIectron &
production of a positive ion. They may be designated as K sheII, L
sheII, M sheII etc.
|
.
|

\
|

=
2 2
4 2 2
1 2
n h
e z
w
t
contd...
OrbitaI Quantum number I is a measure of the orbitaI
anguIar momentum of the eIectron which is a vector
quantity
The vaIues of I vary from zero to (n-1). Hence for
n = 1 , I vaIue is 0
n = 2 I vaIue is 0,1
n = 3, I vaIue is 0,1,2
n = 4, I vaIue is 0,1,2,3
2
) 1 ( l l h
contd
CustomariIy these IeveIs are named after the
spectraI terms nameIy s(I=0), p(I=1), d(I=3) and f(I=4)
etc and the eIectrons present in these orbitaIs are
referred as s, p, d and f eIectrons.
A wave function associated with the orbitaI
motion of an eIectron is caIIed an orbitaI. Thus we
have s, p, d, f orbitaIs aIso.
Magnetic Quantum number
some spectraI Iines spIit if the source is kept in
a magnetic fieId. This is known as Zeeman Effect.
The orbitaI anguIar momentum vector undergoes a
precessionaI movement and describes a cone about
an axis in the direction of the fieId the magnitude of
which is given by mI(h/2).
contd

l
m
The magnetic quantum number is an integraI vaIue
and varies from -I to +I. Thus for s eIectron
s eIectron I= 0 and m
I
= 0
p eIectron I= 1 and m
I
= -1,0,+1
d eIectron I= 2 and m
I
= -2,-1,0,+1,+2
f eIectron I= 3 and m
I
= -3,-2,-1,0,+1,+2,+3
contd
Spin Quantum Number (s)
An eIectron aIso rotates on its own axis. Hence it has
its own anguIar momentum amounting to:
where s = 1/2 or -1/2 depending upon whether it is
precessing aIong the appIied magnetic fieId or
opposing it. For each vaIue of m
I
there are two
eIectrons differing in spin.
No two eIectrons within any atom can have same 4
Quantum numbers. This is known as PauIi excIusion
PrincipIe. Each eIectron differs from every other
eIectron in a given atom in its totaI energy.
2
) 1 ( s s h
contd
9. ELECTRONIC CONFIGURATION OF THE
ELEMENTS
For K sheII, n=1, I=0 , m
I
=0 and hence it is a singIe
orbitaI. OnIy two eIectrons are permitted with
differing spins. The orbitaI is of S type.
SimiIarIy for L sheII, 8 eIectrons are possibIe
according to PauIi excIusion principIe. For M, N, O
sheIIs 18, 32, 50 eIectrons can be accomodated.
According to the principIe of maximum muItipIicity
when an eIectron enters a IeveI of fixed n and I
vaIues, avaiIabIe orbitaIs are occupied singIy untiI
each orbitaI is occupied before any pairing occurs.
contd
10. KnowIedge of the exact order in which
atomic orbitaIs are occupied is based on the
interpretation of atomic spectra in terms of
how spectraI Iines resuIt from permitted
eIectronic transitions. Heavier atoms have
compIicated atomic spectraI patterns and
overIaps occurring in the simiIar systems.
contd
contd
11.Atomic orbitaIs
contd
12.Energy LeveI Diagram
13. Energy IeveI diagram for atomic orbitaI
contd
14.Periodic tabIe
contd
INTERACTION OF ELECTROMAGNETIC
RADIATION WITH MATTER
Spectroscopy is the measurement and interpretation of
eIectromagnetic radiation resuIting in the absorption,
emission, refIection, refraction, diffraction and scattering
by atoms, moIecuIes or other chemicaI species. AII these
processes are associated with changes in the energy
states of the species or modification or its direction or
intensity.
An eIectromagnetic radiation may be considered as a
wave which carries energy from one Iocation to another
at a finite veIocity (3x10
10
cm). As the name suggests an
e.m.radiation has two components: eIectric fieId and
magnetic fieId which are perpendicuIar to each other.
POLARIZED ELECTROMAGNETIC WAVE
Wave nature of a singIe frequency eIectromagnetic radiation
Many properties of the eIectromagnetic radiation are
convenientIy described by considering it as a cIassicaI
sinusoidaI wave modeI with characteristic waveIength,
frequency, veIocity and ampIitude. E.M radiations pass through
vaccum aIso unIike sound waves.
However some properties of the eIectromagnetic radiations
(possessing a quantified amount of energy) are both described
best as a number of streaming particIes traveIing in a wave
form referred to corpuscIes discrete particIes) or photons.
According to Heisenberg's principIe it is impossibIe to measure
the wave and particIe properties of a photon simuItaneousIy
and exactIy.
Therefore it is convenient to imagine photons as particIes
having specific amount of energy radiating from a source and
characterized by an eIectromagnetic wave
The waveIength of radiation can be visuaIized as
the distance between two maxima of either eIectricaI
or magnetic component.
The frequency ' ' is the number of waves that
pass any fixed point P per unit time. When a photon
passes a particuIar region of space the eIectric and
magnetic fieId osciIIate with frequency.
Therefore onIy frequency is truIy characteristic of
a particuIar radiation.

MathematicaIIy an eIectromagnetic wave can be

described as a sine wave
where A is the ampIitude at any point
A
o
is the peak ampIitude
is the continuous variabIe
sin
o
A A
AIternateIy
Where t = , is the anguIar veIocity radians/unit time.
A compIete cycIe occurs when t changes from 0-360
0.
This is caIIed one compIete osciIIation or one period.
Hence the time over which one compIete occurs is
given by
or
sin
o
A A t
cycle
cycle
t 2
1 2
= frequency = =
t

For any wave moving at a constant veIocity v, we can write

where v is the frequency in ms
-1
is in Hertz (cycIes per second or s
-1
) and
in meters
The frequency is proportionaI to the energy E of the photon given by
where h = 6.62 x 10
-27
ergs when E is expressed in ergs and
= 6.63 x 10
-34
jouIes. E is expressed as jouIes.
Sometimes it is convenient to use "wave number" denoted by to
describe the radiation for exampIe in infra red spectrometry. Then the
photon energy is expressed as,

v =

= h E

E = hc
PROPERTIES OF E.M. RADIATION
X-ray,-ray
E
eV EIectron
voIt
+
Radiofrequency (Iess common in
current Iiterature)
Cps CycIes per s
Radiofrequency ,microwave Hz Hertz
Infrared, UV- visibIe (Iess common)
/c
cm
-1
, wavenumber
(reciprocaI
cm)
Infrared (common in physics
Iiterature)

m Micron,
Micrometer
VisibIe (in oIder work) m MiIimicron+
X-ray, UV-visibIe (in oIder work)

Angstrom+
UV, visibIe, near=infrared Nm Nanometer
Used in Unit for SymboI Name of the
unit
v
v
v
0
A
Spectromet
ric region
J
MHz
eV
1.986x10
-23
2.9979x10
4
1.240x10
-4
10
8
10
7
Cm
-1
1.986x10
-15
2.9979x10
12
1.240x10
4
10
8
.1
1.986x10
-16
2.9979x10
11
1.240x10
3
10
7
10 nm
J* MHz eV Cm
-1
nm
0
A
It may be noted that regardIess of the units of expression any
eIectromagnetic radiation of frequency wiII have unique
waveIength and energy.
The Ionger the waveIength, the Iower is the energy and
frequency.
Energy is cIoseIy reIated to temperature of any object, it can be
expressed as
E K
B
T
where K
B
= BoItzmann's constant
= 1.380x10
-16
ergs K
-1
atom
-1
or 1.380x10
-23
jouIe K
-1
atom
-1
If we consider energy per moIe of the materiaI
E RT
where R = the gas constant
= 8.3145x10
7
erg K
-1
moI
-1
or 8.3145 jouIe K
-1
moI
-1

The energy of the photons shouId not be confused with

brightness or intensity of the source. But it reIates to the coIour
of the Iight.
The power of a Iight source is given by
It is the energy of a beam of radiation that reaches a given area
per second.
Intensity (I) of a source of radiation is the power emanating per
unit soIid angIe.
! # $%&'() *+ ,-*.*$/ 0 ,-*.*$ ($()12
ELECTROMAGNETIC SPECTRUM
TRANSMISSION OF RADIATION
The rate of propagation of eIectromagnetic radiation through a
transparent materiaI (such as atoms, ions, moIecuIes, particIes)
is Iess than that of vaccum. However frequency change wiII not
be observed which means that permanent energy transfer to
the medium does not occur.
Therefore the interaction invoIved must be onIy temporary
deformation of the eIectronic cIouds associated with the atoms
and moIecuIes ( 10
-14
to 10
-15
s). Since the veIocity of radiation
in the media is waveIength dependent the refractive index of
the media aIso must change. The variation of R.I with
waveIength is caIIed 'dispersion'.
Dispersion is a compIex phenomena. Dispersion curves usuaIIy
show two regions. NormaI dispersion in which there is a
graduaI increase in refractive index with increasing frequency.
AnomaIous dispersion occurs at frequencies in which sharp
changes occur coinciding with naturaI harmonic frequency of
some part of a moIecuIe, atom or ion Ieading to the absorption
of the beam.
In spectroscopy, dispersion curves are important for opticaI
components such as Ienses. Most suitabIe components for the
manufacture of Ienses are those in which refractive index
shouId be high and constant. This resuIts in reduced chromatic
aberrations.
For the fabrication of prisms refractive index shouId be
Iarge but aIso highIy frequency dependent.
REFLECTION OF RADIATION
Mirrors refIect the radiation faIIing on them. Without any Ioss of the
incident radiant power. Hence they are used as opticaI components of a
spectrum. Concave mirrors refIect the radiation as weII as concentrate
the refIected radiation at its focaI point.
When radiation crosses an interface between media differing in
refractive index refIection aIways occurs. For a beam entering an
interface at rt.angIes the fraction refIected is given by
where I
o
intensity of the incident beam and
I
r
is the refIected intensity,
n
1
& n
2
are the refractive indexes of the two media.


2
2 1
2
2 1
n

n
r
o
n
I
I
n

REFRACTION PHENOMENA
When radiation passes at an angIe through the interface
between two media having differing densities an abrupt change
in the direction occurs. This is caIIed as refraction owing to the
changes in the veIocity of the radiation in the two media.
The extent of refraction is given by SneIIs Iaw
In vaccum V
1
=0 and n
1
is unity. Hence
Refractive indices of materiaIs are measured with air as one
medium and avaiIabIe in data bases.


1
2
2
s i n
s i n
v a c
v a c
n

1 2 2
2 1 1
s i n
s i n
n V
n V

SCATTERING OF RADIATION
Momentary absorption of radiant energy by atoms, ions, or moIecuIes
foIIowed by reemission of the radiation in aII directions in known as
scattering. ParticIes having comparabIe dimensions to that of the
incident radiation removes most of the reemitted radiation by
destructive interference except those traveIing in the originaI
direction. A very smaII fraction of the radiation is transmitted at aII
angIes from the originaI path & its intensity increases with particIe
size.
Scattering by moIecuIes or aggregates having smaIIer dimensions
than the incident radiation is caIIed RayIeigh scattering.
Larger moIecuIes scatter radiations in different quantities in different
direction. This is caIIed as Mie Scattering.
When the scattered radiation is quantized Iike those occurring in
vibrationaI energy IeveI transitions in moIecuIes as a consequence of
poIarization process, it is caIIed as Raman Scattering.
POLARIZATION OF RADIATION
Ordinary radiation consists of a bundIe of eIectro magnetic waves in which
vibrations are equaIIy distributed among a huge number of pIanes centered
aIong the path of the beam.
Viewed end on it Iooks Iike an infinite set of eIectric vectors fIuctuating from
zero to a maximum ampIitude A.
The vector in any one pIane say XY can be resoIved into two mutuaIIy
perpendicuIar components. RemovaI of one of the two resoIved pIanes of
vibration produces a pIane poIarized beam. It occupies a singIe pIane. Radio
waves emanating from an antenna and micro waves produced by a KIystron
tube are pIane poIarized.
PoIarized uItravioIet and visibIe radiation is produced by passing the e.m
beam through a media that seIectiveIy absorbs, refIects or refracts that
vibrates in onIy one pIane.
POLARIZATION OF LIGHT WAVES
DISPERSION OF E.M RADIATION
Dispersion is a compIex phenomena. Dispersion curves usuaIIy
show two regions:
NormaI dispersion in which there is a graduaI increase in
refractive index with increasing frequency.
AnomaIous dispersion occurs coinciding with naturaI harmonic
frequency of some part of a moIecuIe, atom or ion Ieading to
the absorption of the beam.
In spectroscopy dispersion curves are important for opticaI
components such as Ienses. Most suitabIe components for the
manufacture of Ienses are those in which refractive index
shouId be high and constant. This resuIts in reduced chromatic
aberrations.
For the fabrication of prisms refractive index shouId be Iarge
but aIso highIy frequency dependent.
DISPERSION CURVE
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DIFFRACTION OF RADIATION
Diffraction refers to the bending of a paraIIeI beam of
eIectromagnetic radiation as it passes through a
sharp barrier or a narrow opening. It is a
consequence of interference which can be easiIy
demonstrated in the Iaboratory.
When a paraIIeI beam of Iight is aIIowed to pass
through a pin hoIe, two cIoseIy spaced pin hoIes are
seen on a screen pIaced across it.
If the radiation is monochromatic a series of dark
and Iight image appear perpendicuIar to the pIane of
the radiation.
PIN HOLE DIFFRACTION
In the above figure it can be shown that
For two beams to be in phase at D, it is necessary that
ShouId correspond to the waveIength of the radiation. Hence
Since reinforcement aIso occur at 2, 3 etc. Hence,
where n is an integer caIIed the order of the interference.
CF
sin BC CF
sin BC n
sin BC CF
When the phase differences remain entireIy constant with time the
system is said to be coherent. Then onIy a reguIar diffraction pattern
is observed.
The spacing of the bands depends on the distance between the
sIits ' d ' and the foIIowing reIation hoIds:
If two different waveIengths of red & bIue are used, the two coIors wiII
be separated on the screen. If white Iight is used a number of smaII
rainbows containing aII the coIors wiII appear.
By pIacing a moving sIit across the screen any coIor or waveIength
can be seIected. This principIe is used in gratings. We wiII study more
about gratings and their uses in spectrophotometry .
sin d n
PRISMS AS A DISPERSIVE DEVICES
A prism disperses the incident radiation depending
on its refractive index and its variation with
waveIength. A prism can be used to disperse
uItravioIet, visibIe and infrared radiation. The materiaI
of construction depends on the waveIength region.
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A prism can be constructed by fusing
together two 30
0
prisms. This is caIIed as
Cornu type. Another arrangement is to use a
30
0
prism with a mirrored bIack. In Cornu
mounting the dispersed radiation is coIIected
across the prism and in Littrow mounting it
is coIIected on the same side. Here refraction
takes pIace twice on the same side with Iess
materiaI coupIed with saving of space.
MONOCHROMATOR SLITS ...
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MONOCHROMATOR SLITS
The sIits of a monochromator pIay an important
roIe in determining its performance characteristics
and quaIity. UsuaIIy two sIits are empIoyed: one as
the entrance sIit which serves as the Iight source
and another as the exit sIit on which the image of
the entrance sIit is formed.
If the radiation source consists of a discrete
waveIengths a series of rectanguIar images appears
on the exit pIane which appear as bright Iines
corresponding to differing waveIengths. Movement
of the monochromator setting in one direction or
the other produces a continuous decrease in
emitted intensity when the entrance sIit image has
moved a distance equaI to its fuII width.
MONOCHROMATOR SLITS
IIIumination of the exit sIit with the desired
waveIength is invariabIy associated with some
unwanted radiation as shown here(
1
&
2
). This is
known as " bandwidth ".
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The effective bandwidth aIso caIIed as
spectraI band pass or spectraI sIit width is
" haIf of the bandwidth " when the two sIit
widths are identicaI.
When the effective bandwidth is decreased
to one haIf the waveIength of the three
beams compIete resoIution can be achieved.
THE PHOTOELECTRIC EFFECT...
The photoeIectric effect(1887) was discovered by
Heinrich Hertz who reported that a spark jumped
more readiIy between two charged spheres when
their surfaces were iIIuminated with Iight.
Einstein offered a simpIe and eIegant expIanation for
the photoeIectric effect in 1905, but experimentaI
confirmation came onIy in 1916 with MiIIikan's
systematic studies.
SCHEMATIC DIAGRAM OF PHOTOELECTRIC EFFECT
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When monochromatic Iight faIIs on a photocathode (A cathode
coated with aIkaIi metaIs), eIectrons of varying kinetic energies
are emitted from its surface and fIy over to anode in the
phototube as Iong as the voItage V appIied between the anode
and cathode is positive, producing a current I in the circuit.
When the voItage across the phototube is adjusted such that
the anode is negative, the photoeIectrons are repeIIed by the
anode and photocurrent decreases.
The photoeIectric current measured as a function of the
appIied voItage V
o
at which photoeIectric current reaches zero
muItipIied by the eIectronic charge(1.60x10
-19
CouIombs) gives
the kinetic energy of the most energetic eIectrons in jouIes.
When maximum kinetic energy for various coatings are pIotted
as a function of the radiation frequency, we get a straight Iine
response with a sIope of h (PIanks constant = 6.6254x10
-34
jouIe
second) with an intercept w which is known as work function.
The pIots can be described by the equation,
The work function -w is characteristic of the surface materiaI
and represents the minimum energy of binding the eIectron to
the metaI atom. It is aIso equaI to the energy of the
eIectromagnetic radiation (photon energy) required to eject the
photo eIectron from the irradiated surface.
Therefore it can be concIuded that no eIectron can be ejected
untiI the sum of the work function K.E
m
is reaIized. Therefore
the energy is not uniformIy distributed over the beam front but
concentrated in packets or bundIes of energy, which is a
thumping confirmation of the Quantum mechanicaI theory.
This equation permits the caIcuIation of the energy of any
eIectromagnetic radiation of known frequency or waveIength
and vice versa.
m
or E = KE /
m
KE h w w hc
ExampIe 1
CaIcuIate the energy of the 5.5A
0
X-ray photon.
SoIution:
we write
Substituting the vaIues we get,
/ E h hc
34 8
0 10 0
-16 8
3
(6.63 10 . ) (3.00 10 / )
(5.5 )(10 / )
= 3. 6163 10 6.24 10 /
= 2.26 10 eV

J s m s
E
A m A
ev J

ExampIe 2
CaIcuIate the energy of the 430nm photon of visibIe radiation
SoIution:
Energy of the radiation is usuaIIy expressed in KJ/moIe

-34 8
-9
-19
(6.63 10 . ) (3 10 / )
E =
430 10 /
= 4.6255 10
J s m s
nm m nm

23
-19 3
6.02 10
E = 4.6255 10 / 10
= 278.4551 /
photons KJ
J photon
mol J
KJ mol

THE PHOTOELECTRIC EFFECT...
Thus the quantum theory originaIIy proposed for bIack body
radiation was extended to expIain the emission and absorption
processes. The essentiaI postuIates of quantum theory are:
1. The ions, atoms and moIecuIes exist onIy in certain discrete energy
states. When it changes its state it absorbs or emits an amount of
energy exactIy equaI to the energy difference between the states.
2. During transition from energy state to another, the frequency
or the waveIength of the radiation emitted or absorbed is reIated
the energy difference between the states by the equation
where E
1
is the energy of the higher state and E
2
is the energy of the
Iower state.
1 2
E / E h hc

THE PHOTOELECTRIC EFFECT..

For atoms or ions in the eIementaI state, the energy of any state
arises from the movement of the eIectrons around the nucIeus.
Such energy IeveIs are caIIed eIectronic energy IeveIs.
MoIecuIes in addition to the eIectronic states exhibit quantized
vibrationaI and rotationaI states arising from the rotation of
moIecuIes or functionaI groups of moIecuIes around their
centre of mass.
The Iowest energy state of an atom or moIecuIe exists at room
temperature. It is caIIed ' ground state '. Higher energy states
are termed as excited states.
Detectors used in spectrophotometers, I.R, fIuorescence, HPLC
etc., work on the principIe of photoeIectric effect. These incIude
barrier Iayer photovoItaic ceIIs, vacuum phototubes, photo
muItipIier tubes, diode array detectors etc.
NATURE OF INTERACTION OF RADIATION
AND MATTER
A sampIe can be subjected to a chemicaI stimuIi in the form of
heat, eIectricaI energy or Iight, bombardment, or a chemicaI
reaction.
The stimuIus causes the anaIyte species to move from one
energy state to another energy state. In the process energy is
absorbed or emitted or scattered. Information about the anaIyte
can be obtained by measuring the eIectromagnetic radiation.
EMISSION PROCESS
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ABSORPTION PROCESS
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EMISSION OF RADIATION
When excited atoms, ions or moIecuIes return to ground state the excess energy
is reIeased as heat or in the form of photons. The excitation can be brought about
by:
i) Bombardment with eIectrons or other eIementary particIes. This gives
rise to X-radiation.
ii) EIectric current , ac spark or heat source such as dc arc, or furnace.
This gives rise to uItravioIet, visibIe or infra red radiation.
iii) Beam of eIectromagnetic radiation. This produces fIuorescence.
iv) Exothermic chemicaI reaction which produces chemiIuminiscence.
TYPES OF SPECTRA
The atomic and moIecuIar spectra are usuaIIy pIotted as the
function of the reIative power of the emitted radiation with
respect to the waveIength or frequency. A typicaI spectra wiII
have three components: Iines, bands and a continuum.
Line spectra are a series of weII defined peaks. Band spectrum
consists of a severaI groups of cIoseIy spaced but not weII
resoIved peaks. The continuum part of the spectrum does not
show any peaks but Iine and band spectra are super imposed
in the spectrum.
LINE SPECTRA
Line spectrum of atomic particIes are
preferabIy obtained in the gas phase.
TypicaI widths of the peaks are about
10
-5
nm (10
-4
A
0
).
X-ray Iine spectra are produced by the
transitions of eIectrons to inner most
orbitaIs. Therefore it is a characteristic of
the eIement but not of the compound.
BAND SPECTRA
RadicaIs and smaII moIecuIes usuaIIy exhibit band
spectra. The peaks are associated with vibrationaI
energy IeveIs. The Iife time of vibrationaI energy
state is 10
-15
sec compared with that of an
eIectronic state (10
-8
sec).
Therefore transition aIways occurs from the Iowest
vibrationaI energy of the excited state to any of the
vibrationaI energy IeveI of the ground state. The
Ioss of energy from vibrationaI IeveIs to the Iowest
vibrationaI energy occurs through the coIIision with
other moIecuIes.

CONTINUUM SPECTRA
Radiation from the bIack body when
heated to incandescence produces
continuum spectrum.
The energy peaks shift to shorter
waveIengths with increasing
temperature. Heated soIids are
important sources of uv, visibIe and
infrared radiations.
ABSORPTION OF SPECTRUM
Absorption of eIectromagnetic energy by the atoms, ions and moIecuIes
promotes them to higher energy excited states according to the Iaws of
quantum mechanics. The energy difference corresponding to each
excitation is unique for each species thus permitting the
characterization of the sampIe. This is usuaIIy accompIished by pIotting
absorbance as a function of waveIength or frequency.
Absorption spectra differ wideIy in appearance from sharp peaks to
smooth continuous curves depending on the physicaI state, compIexity
of the moIecuIe and the environment of the sampIe (matrix).
Atomic spectra of an eIement resuIts in onIy a few simpIe and as
excitation can occur onIy at eIectronic energy IeveIs of the outermost or
bonding eIectrons onIy.
MoIecuIar absorption spectra are usuaIIy more compIex invoIving
quantized vibrationaI and rotationaI energy states. The energy of
vibrationaI transition is much more than that of rotationaI transitions.
MoIecuIar absorption peaks invoIving eIectronic energy fairIy
broad owing to the presence of a number of vibrationaI and
reIationaI energy IeveIs associated with them. As a resuIt the
spectrum of a compound consists of a number of cIoseIy
spaced absorption Iines that constitute a broad smooth
absorption band giving the impression of a continuous
spectrum.
Absorption of pure vibrationaI energy is the basis of infrared
spectroscopy.
Pure rotationaI absorption spectra are observed in the micro
wave region.
EIectronic spectraI transitions in ions and moIecuIes gives rise
to spectrophotometry. The waveIength of the energy source
does not change here. OnIy the change in the intensity of the
incident beam and transmitted radiation are measured.
Sometimes the absorbed energy of a moIecuIe is reemitted as a
radiation of Iower frequency or Ionger waveIength. This resuIts
in fIuorescence phenomenon.
Energy changes occurring in the eIectrons and nucIei under a
strong magnetic fieId are best studied by nucIear magnetic
resonance or eIectron spin resonance.