OBT751 - ANALYTICAL METHODS AND

INSTRUMENTATION

LECTURE - 2

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SPECTROMETRY BASICS
 Spectrometric methods encompass a large group of
analytical methods based on atomic and molecular
spectroscopy.

 Spectroscopy is a general term for the science of the

interactions of radiation with matter.

 Spectrometry and spectrometric methods refer to the

measurement of the intensity of radiation with a
photoelectric transducer or other type of electronic device.

 The most widely used spectrometric methods are based on

electromagnetic radiation
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PROPERTIES OF ELECTROMAGNETIC RADIATION
 The properties of electromagnetic radiation are
conveniently described by means of a classical sinusoidal
wave model, which embodies such characteristics as
wavelength, frequency, velocity, and amplitude.

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PROPERTIES OF ELECTROMAGNETIC RADIATION
 In fig (a), a plane-polarized wave is shown
propagating along the x-axis.
 The electric field oscillates in a plane perpendicular

to the magnetic field.

 If the radiation were unpolarized, a component of

the electric field would be seen in all planes.

 In fig (b), only the electric field oscillations are

shown.
 The amplitude of the wave is the length of the

electric field vector at the wave maximum, while

the wavelength is the distance between successive
maxima. 4
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1.1.1 WAVE CHARACTERISTICS

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1.1.1 WAVE CHARACTERISTICS
The characteristics of a wave are
 Amplitude
 Period
 Frequency
 Wavelength
 Velocity of Propagation
 Wave Number
 Power
 Intensity

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1.1.1 WAVE CHARACTERISTICS
 Amplitude :The amplitude A of the sinusoidal wave

is shown as the length of the electric vector at a

maximum in the wave.

 Period : The time in seconds required for the

passage of successive maxima or minima through
a fixed point in space is called the period p of the
radiation.

 Frequency : The frequency n is the number of

oscillations of the field that occur per second1 and
is equal to 1/p. 7
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1.1.1WAVE CHARACTERISTICS
 Wave Length : The wavelength l is the linear distance
between any two equivalent points on successive waves
(e.g., successive maxima or minima).

 Velocity of Propagation : Multiplication of the frequency

in cycles per second by the wavelength in meters per
cycle gives the velocity of propagation vi in meters per
second

 Wave Number : The wavenumber n, which is defined as

the reciprocal of the wavelength in centimeters. The
wavenumber is directly proportional to the frequency,
and thus the energy, of radiation.
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1.1.1 WAVE CHARACTERISTICS
 Power : The power P of radiation is the energy of
the beam that reaches a given area per second

 Intensity : the intensity I is the power per unit

solid angle.

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1.1.2 The Electromagnetic Spectrum
The electromagnetic spectrum encompasses an enormous
range of wavelengths and frequencies

Fig. Regions of the electromagnetic spectrum

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1.1.2 The Electromagnetic Spectrum
 The divisions are based on the methods used to
generate and detect the various kinds of radiation.

 The portion of the spectrum visible to the human

eye is tiny when compared with other spectral
regions.

 Spectrochemical methods using not only visible but

also ultraviolet and infrared radiation are often
called optical methods despite the human eye’s
inability
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1.1.2 The Electromagnetic Spectrum

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1.1.3 Mathematical Description of a Wave
The wave can be described by the equation for a sine wave.

where
y is the magnitude of the electric field at time t
A is the amplitude or maximum value for y
f is the phase angle
 ω is the angular velocity of the vector

Substitution of this relationship into Equation

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1.1.4 Superposition of Waves
 The principle of superposition states that when two or
more waves traverse the same space, a disturbance
occurs that is the sum of the disturbances caused by the
individual waves.
 This principle applies to electromagnetic waves, in which
the disturbances involve an electric field.
 When n electromagnetic waves differing in frequency,
amplitude, and phase angle pass some point in space
simultaneously, the principle of superposition can be
written as

Where y is the resultant field 14

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1.1.4 Superposition of Waves

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1.1.4 Superposition of Waves
 The black curve in Figure (a) shows the superimposition of two
waves of identical frequency but somewhat different amplitude and
phase angle. The resultant is a periodic function with the same
frequency but larger amplitude than either of the component
waves.
 Figure (b) differs from (a) in that the phase difference is greater; in
this case, the resultant amplitude is smaller than the amplitudes of
the component waves. A maximum amplitude occurs when the two
waves are completely in phase—a situation that occurs whenever
the phase difference between waves ( φ1 - φ2 ) is 0°, 360°, or an
integer multiple of 360°. Under these circumstances, maximum
constructive interference is said to occur.
 A maximum destructive interference occurs when
( φ1 - φ2 ) is equal to 180° or 180° plus an integer multiple of
360°. Interference plays an important role in many instrumental
methods based on electromagnetic radiation.
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1.1.4 Superposition of Waves

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1.1.4 Superposition of Waves
 The figure depicts the superposition of two waves with identical
amplitudes but different frequencies. The resulting wave is no
longer sinusoidal but does exhibit a periodicity, or beat.
 It is to be noted that the period of the beat pb is the reciprocal
of the frequency difference △‫ ט‬between the two waves. That is,

 An important aspect of superposition is that a complex

waveform can be broken down into simple components by a
mathematical operation called he Fourier transformation
Any periodic function, regardless of complexity, can be
described by a sum of simple sine or cosine terms.

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1.1.4 Superposition of Waves
where n takes values of 3,
5, 7, 9, 11, 13, and so
forth.

A graphical representation of the summation process is shown:

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1.1.5 Diffraction of Radiation
 Diffraction, is a process in which a parallel beam of radiation is bent
as it passes by a sharp barrier or through a narrow opening.
Diffraction is a wave property that can be observed not only for
electromagnetic radiation but also for mechanical or acoustical waves.

•When the slit is wide relative to

the wavelength , diffraction is
slight and difficult to detect.
•On the other hand, when the
wavelength and the slit
opening are of the same order
of magnitude, diffraction
becomes pronounced.
•Here, the slit behaves as a new
source from which waves
radiate in a series of nearly
180° arcs. The direction of the
wave front appears to bend as
a consequence of passing the
two edges of the slit.

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1.1.5 Diffraction of Radiation
 Inferference phenomena cause diffraction. This relationship is
most easily understood by considering an experiment,
performed first by Thomas Young in 1800, in which the wave
nature of light was demonstrated unambiguously.

A parallel beam of light is

allowed to pass through a
narrow slit A (or in Young’s
experiment, a pinhole) after
which it is diffracted and
illuminates more or less
equally two closely spaced
slits or pinholes B and C; the
radiation emerging from
these slits is then observed
on the screen lying in a plane
XY. If the radiation is
monochromatic, a series of
dark and light images
perpendicular to the plane of
the page is observed.
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1.1.5 Diffraction of Radiation
Fig. b is the plot of the
intensities of the bands
as a Function of distance
along the length of the
screen.
If the width of the slit,
approaches the
wavelength of radiation,
the band intensities
decreases.

In Figure (a) , the appearance of the central band E, which lies in the shadow of
the opaque material separating the two slits, is readily explained by noting that
the paths from B to E and C to E are identical. Thus, constructive interference of
the diffracted rays from the two slits occurs, and an intense band is observed.

 The conditions for maximum constructive interference, which result in the

other light bands, can be derived.
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1.1.5 Diffraction of Radiation
 The angle of diffraction u is the angle formed by the lines OE (the
normal) and OD, where D is the point of maximum intensity.
 The black lines BD and CD represent the light paths from the slits
B and C to this point.
 The lines BD, OD, and CD are, parallel.
 Line BF is perpendicular to CD and forms the triangle BCF, which
is, similar to DOE. The angle CBF is equal to the angle of
diffraction Ɵ.

 Line CF corresponds to the wavelength of the radiation; that is,

Reinforcement also occurs when the additional path length

corresponds to 2l, 3l, and so forth.
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1.1.5 Diffraction of Radiation
 a more general expression for the light bands surrounding the
central band is

 where n is an integer called the order of interference.

Substituting in the above equation

The above equation permits the calculation of the wavelength

from the three measurable quantities.

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1.1.5 Coherent Radiation
 The conditions for coherence are that
1) The two sources of radiation must have identical
frequencies (or sets of frequencies) and
2) The phase relationships between the two beams must
remain constant with time.

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1.1.5 Coherent Radiation
 The two slits in Figure is illuminated with individual tungsten
lamps.
 Under this circumstance, the well-defined light and dark
patterns disappear and are replaced by a more or less uniform
illumination of the screen.
 This behavior is a consequence of the incoherent character of
filament sources.
 With incoherent sources, light is emitted by individual atoms or
molecules, and the resulting beam is the summation of
countless individual events, each of which lasts on the order of
10-8 s.
 A beam of radiation from this type of source is not
continuous but instead is composed of a series of wave
trains that are a few meters in length
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1.1.5 Coherent Radiation
 Because the processes that produce trains are random, the
phase differences among the trains must also be variable.
 A wave train from slit B may arrive at a point on the screen in
phase with a wave train from C so that constructive
interference occurs; an instant later, the trains may be totally
out of phase at the same point, and destructive interference
occurs.
 Thus, the radiation at all points on the screen is governed by
the random phase variations among the wave trains; uniform
illumination, which represents an average for the trains, is the
result.
 Sources of Electromagnetic radiation that produce coherent
sources are
1. radio-frequency oscillators,
2. Microwave sources,
3. Optical lasers. 27
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