1

2)An introduction to spectrometric/photometric

methods(Spectrophotometric).

-Wave properties of electromagnetic radiation.

-Quantum mechanical properties of radiation,

-Components of optical instrument.

Spectrometry:
-Spectrometry comprises large group of analyticalmethods, i.e. those methods based on atomic &
molecular spectroscopy.
Spectroscopy:
-A branch of science that deals with the interaction of various types of radiation with matter.
-Consequence of such interaction is that energy is absorbed or emitted by the matter in discrete
amount called quanta or photons .
-Intensity of the absorbed or emitted radiations are measured with a photoelectric transducer or other
types of electronic devices.
Radiation types:

-Electromagnetic radiation(most widely used).

Gamma rays, x-rays, ultraviolet, visible, IR, microwave, and radio frequency radiation etc.

Nowadays ,

spectroscopy comprises additionally:

-Acoustic waves, beams of particles(ions, electrons).
Spectrometer:
-Equipped with optical devices to produce light of a definite wavelength

(or to produce the dispersion of electromagnetic radiation)
(The aim of the dispersion is to produce light of a definite WL)


2


Photometer:
-A device for measuring the intensity of transmitted (or absorbed) radiation.
Spectrophometer:
-Spectrometer and photometer are combined to form Spectrophotometer.

-In spectrophotometer, these are employed conjointly to produce a signal corresponding to the
difference between the transmitted radiation of a reference and that of sample at the selected
wavelengths(or at variable WLs).
UV-vis absorption spectroscopy (UV-Vis)

FT-IR absorption/transmission spectroscopy (FTIR)

Atomic absorption spectroscopy (AAS)

Atomic fluorescence spectroscopy (AFS)

X-ray fluorescence spectroscopy (XFS)
General properties of electromagnetic radiation:
-Electromagnetic radiation is a form of energy that is transmitted through space at an
enormous velocity.
-Requires no medium to pass in contrast to sound.
-Passes readily in vacuum.
-Many properties are described by a classical sinusoidal wave model(wavelength,
frequency, velocity, amplitude etc)
-The wave model fails to account the phenomena associated with the absorption &
emission of radiant energy.
-Not only waves, it acts as a stream of discrete particlesor wave packets of energy
called photons.

Energy of photons frequency of radiation.

-Dual nature of the radiation(Wave & particle) is complementary to each other.

-Visible light is a type of Electromagnetic radiation.

3


Electromagnetic Radiation(Wave Properties)

Components of EM radiation: Electric&magnetic fields

-The both fields undergo in-phase sinusoidal oscillations at right angles to
each other & direction of propagation.

-Plane polarized EM field(either electric or magnetic) oscillates in a single
plane.

4





-The above first figure is a representation of a single ray plane-polarized
electromagnetic radiation.

-The second figure is a two-dimensional representation of the electric component of
the ray.

-The ordinate is for electric field(as a vector),
(Its length is proportional to the field strength)

-The abscissa is for either time as the radiation passes a fixed point in space or
distance when time is held constant.
-Electric component is responsible for phenomena
viz.
transmission,

reflection,

refraction,
5



diffraction &interference

absorption.

-Magnetic component is accounted for the absorption ofradio frequency waves in
nuclear magnetic resonance(NMR).

Wave properties of electromagnetic radiation
a.Amplitude(A) , b.Period(P). , c.Frequency() ,d.Wavelength().

Wave components:
a. Amplitude(A) is the length of the electric vector of the sinusoidal
wave at a maximum in the wave.

b. Period(P) is the time in seconds required for the passage of
successivemaxima or minima through a fixed point in space.
(or time required for the completion of one cycle or oscillations)

c.Frequency() is the number of oscillations of the field that occur
per second(unit time)& is equal to 1/P.
The dimension of frequency is reciprocal time(T
-1
) .
6


Its usual unit is sec
-1
i.e. cycles per second(cps) or hertz(Hz)
*Frequency() is more fundamental but cumbersome(very large
number) to use in practice.
*Hence, wave number ()is used instead.
It is the number of waves per centimeter in vacuum.
= 1/(cm
-1
), reciprocal of wavelength

d.Wavelength() is the linear distance between any two equivalent
points on successive waves(successive maxima crest&
minimaTrough).
It can be expressed in centimeter(cm) or as follows:
Units in practice:

1 angstrom() = 10
-8
cm = 10
-10
m

1 nanometer(nm) = 10
-9
m = 10
-7
cm = 10 ()

1 micrometer(m) =10
4
=10
-6
m = 10
-4
cm.

-Velocity of propagation is product of the frequency in cycles per
second & the wavelength of single wave(in meter)
v =
*In the eqn. ,the frequency of a beam of radiation is determined by
7


the source& remains invariant.

*The velocity of radiation is affected by the composition of the
medium through which it passes(Due to interaction between the
EM radiation & the bound electrons in the matter.)

*Consequently wavelength of the radiation also depends on the
medium.

-Velocity(c) of radiation at its maximum in vacuum& is
independent to wavelength vacuum

- c is nearly equal in vacuum & air, i.e.
c= = 3.00X 10
8
m/s

Effect of medium on wavelength:

-Wave number is widely used in IR spectroscopy.
8


-In contrast to wavelength, wave number is directly proportional to
frequency & the energy of radiation.
= k
Where, k(proportionality const.) is reciprocal of velocity and
depends on medium.

Radiant power & intensity:

i)Radiant power(P):
-It is the energy of a beam that reaches a given area
per unit time.

-Its unit is watt(W).

ii)Intensity:
-It is the radiant power-per unit solid angle.

BOTH QUANTITIES ARE PROPORTIONAL TO THE
SQUARE OF THE AMPLITUDE OF THE ELECTRIC
FIELD.
Electromagnetic spectrum:
The entire range over which electromagnetic radiation exists is
known as electromagnetic spectrum.
-It encompasses an enormous range of wavelength & frequencies
9


( and energies).
-All electromagnetic radiation is fundamentally similar, regardless
of its wavelength.
-The division between the different spectral regions
* for convenience
* for partly to indicate the origin of radiation & partly for
experimental(instrumental) reasons.

Electromagnetic spectrum:
. .
Approximate wavelength Region of spectrum
region(cm) .
10
-12
10
-11
Cosmic rays
10
-11
10
-8
Gamma rays
10
-8
10
-6
X rays
10
-6
10
-5
Ultraviolet
10
-5
10
-4
Visible
10
-4
10
-2
Infrared
10
-2
10 Microwave
10 10
8
Radio frequency
10



The electromagnetic radiation ranges of spectroscopic interest:
Region Wavelength range
Far ultraviolet 100-200nm
Ultraviolet 200-400nm
Visible 400-750nm
Near infrared 0.75-4 m
Infrared 4-25m
-White light contains radiation of all wavelengths within the visible
region.

-The colour of a visible light can be correlated with its WL.

-Monochromatic light can be selected from white light(withprism or
diffraction gratings).

-If white light is deprived of one of its colours (by absorption), the
resulting light will appear as the complement of that colour.
-If blue light(450-480nm) is removed from white light, the resulting
radiation will be yellow (575-590nm).



11



Correlation of colour with wavelength of visible light
Wavelength(nm) Colour Complement
400-450 Violet Yellow-green
450-480 Blue Yellow
480-490 Green-blue Orange
490-500 Blue-green Red
500-560 Green Purple
560-575 Yellow-green Violet
575-590 Yellow Blue
590-625 Orange Green-blue
625-750 Red Blue-green

-The list of the wavelength & frequency ranges that important for analytical
purposes:
Types of Usual wavelength Usual Types of quantum
spectroscopy range wavenum.Transition
( cm
-1
)
Gamma ray 0.005-1.4 - Nuclear inner
emission electron

X-ray absorption, 0.1-100 -
emission, fluorescence,
and diffraction.

Vacuum UV absorption 10-180nm 1X10
6
to 5X10
4
Bonding electron

12


UV-Vis absorption, 180-780nm 5X10
4
to 1.3X10
4
Bonding electron
emission, &
fluorescence

Infrared absorption & 0.78-300m 1.3X10
4
to 3.3X10
1
Rotation/vibration
Raman scattering of molecules

Microwave 0.75-375mm 13.0-0.03 Rotation of absorption
molecules

Electron spin 3.0cm 0.33 Spin of electrons
resonance in a magnetic field

Nuclear magnetic 0.6-10m 1.7X10
-2
Spin of nuclei in a
resonance to 1X 10
3
magnetic field