314: Instrumentation Analysis

OPTICAL METHODS OF ANALYSIS

A) WAVE CHARACTERISTICS:
Amplitude, A length of the electric vector at a maximum in the wave.
Peroid, p time in seconds required for the passage of successive maxima or minima
through a fixed point in space of the radiation
Velocity of propagation, c radiation travelling through a vacuum
c = 2.9979x108 m/s
Frequency, v the number of oscillations of the field that occur per second
1 Hz = 1 cyle/s
Wavelength, the linear distance between any two equivalent points of successive
waves. (cm, nm, m)
= c/v
Energy content of a photon, E = hv =hc/
Where:
h = Plancks Constant = 6.6254 x 10-34 J-s
c = 2.9979 x 108 m/s
1 J = 6.24 x 1018 eV
Wavenumber, v reciprocal of the wavelength in centimeters, another way of
describing electromagnetic radiation. The unit for v in cm-1 of Kaiser.
Monochromatic beam beam of radiation whose rays have identical wavelengths.
Polychromatic beam beam is made up of different wavelengths.

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314: Instrumentation Analysis

B) DIFFRACTION OF RADIATION
Diffraction process in which parallel beam of radiation is bent as it passes by a sharp
barrier or through narrow opening.

C) TRANSMISSION OF RADIATION
Refractive Index, n one measure of its interaction with radiation.
n=

c
v

Where: n = refractive index at a specified frequency

= 1.3 to 1.8 (liquids)
= 1.3 to 2.5 (solids)
v = velocity of radiation in the medium
c = velocity in a vacuum
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314: Instrumentation Analysis

Polarization temporary deformation of the electron clouds associated with atoms or

molecules that is brought about by the alternating electromagnetic field of the radiation.
Dispersion the splitting up of white light to seven constituent colors on passing
through a transparent medium.

D) REFRACTION OF RADIATION
Refraction this is when radiation passes at an angle through the interface between
two transparent media that have different densities, an abrupt change in direction. The
beam is observed as a consequence of a difference in velocity of the radiation in the two
media.
The extent of refraction is given by Snells Law:
sin n v
= =
sin n v

E) REFLECTION OF RADIATION
Reflection this occurs when radiation crosses an interface between media that differ
in refractive index. The fraction of reflected radiation becomes greater with increasing
differences in refractive index.
For a beam that enters an interface at right angles, the fraction reflected is given by:
I (nn)
=
I (n+ n)
Where:
I = is the intensity of the incident beam
I = reflected intensity
n & n = refractive indexes of the two media.
Example:

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314: Instrumentation Analysis

Calculate the percentage loss of intensity due to reflection of a perpendicular beam of

yellow light as it passes through a glass cell that contains water. Assume that for yellow
radiation the refractive index of glass is 1.5, of water is 1.33, and of air is 1.00.

F) SCATTERING OF RADIATION
Rayleigh Scattering Scattering by molecules or aggregates of molecules with
dimension significantly smaller than the wavelength of the radiation. Its intensity is
proportional to the inverse fourth power of the wavelength.
Raman Scattering these changes are the results of vibrational energy level
transitions that occur in the molecules as a consequence of the polarization process.

G) ENERGY STATES OF CHEMICAL SPECIES

The quantum theory was first proposed in 1990 by Max Planck, a German Physicist,
to explain the properties of radiation emitted by heated bodies. The theory was later
extended to rationalize other types of emission and absorption processes. Two important
postulates of quantum theory include the ff:
1. Atoms, ions, and molecules can exist only in certain discrete states, characterized by
definite amounts of energy. When a species changes it state, it absorbs or emits an
amount of energy exactly equal to the energy difference between states.
2. When atoms, ions, or molecules absorb or emit radiation in making the transition from
one energy state to another, the frequency v or the wavelength of the radiation is
related to the energy difference between the states by the equation
EE=hv =

hc

Where:
E = the energy of the higher state
E = the energy of the lower state

Ground State - lowest energy state of an atom or molecule

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314: Instrumentation Analysis

Excited State Higher energy state of an atom or molecule

H) EMISSION OF RADIATION
Electromagnetic radiation is produced when excited particles (atoms, ions, or molecules)
relax to lower energy levels by giving up their excess energy as photons
Excitation can be brought about by a variety of means, including:
1. Bombardment with electrons or other elementary particles, which generally leads
to the emission of X-radiation.
2. Exposure to an electric current, an ac spark, or an intense heat source (flame, dc
arc, or furnace), producing ultraviolet, visible, or infrared radiation.
3. Irradiation with a beam of electromagnetic radiation, which produces fluorescence
radiation
4. An exothermic chemical reaction that produces chemiluminescence(excitation of
the analyte by a chemical reaction).

I) ABSORPTION OF RADIATION
Absorption process in which electromagnetic energy is transferred to the atoms, ions,
or molecules composing the sample.
Absorption Methods:
Transmittance, T = P/Po=Psoln/Psolvent
Where:
Po=Incident Radiant Power measurement before the beam has passed through the
medium that contains analyte
P= Transmitted Radiant Power measurement after the beam has passed through the
medium that contains analyte
Absorbance, A = -log[T] = log [Po/P]=log[Psolvent/Psoln]
*In contrast to transmittance, the absorbance of a medium increases as attenuation of
the beam becomes greater.

J) BEERs LAW

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314: Instrumentation Analysis

For monochromatic radiation, absorbance is directly proportional to the path length b

through the medium and the concentration c of the absorbing species. These
relationships are given by
A = abc = log [Po/P]
Where:
a = proportionality constant, absorptivity, L/g-cm
b = width of the cuvette/cell, cm
c = concentration, g/L
Application to Beers Law to Mixtures
Beers Law also applies to a medium containing more than one kind of absorbing
substance. Provided that the species do not interact, the total absorbance for a
multicomponent system is given by:
Atotal = A1 + A2 + + An
Atotal = 1bc + 2bc + + nbc
A. Deviations to Beers Law due to Polychromatic Radiation
~for the wavelength,
P = Po 10-bc
~for the wavelength,
P = Po 10-bc
When an absorbance measurement is made with radiation composed of both
wavelengths, the power of the beam emerging from the solution is the sum of the
powers emerging at the two wavelengths, P + P. Likewise, the total incident power is
the sum Po + Po. Therefore, the measured absorbance Am is
Am = log

(P' + P )} over {( {P} ^ {'} +P)

B. Deviations to Beers Law due to Stray Radiation

Stray Light defined as radiation from the instrument that is outside the nominal
wavelength band chosen for the determination. These is the result of scattering and
reflection off the surfaces of gratings, lenses or mirrors, filters, and windows.
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314: Instrumentation Analysis

A = log

P+ P
P+ P

Where:
Ps = power of nonabsorbed stray radiation
Photometer used for measuring the transmittance and absorbance of aqueous
solution with a filtered beam of visible radiation.
Here the radiation from a tungsten bulb passes through a colored glass filter that
restricts the radiation to a limited band of contiguous wavelengths. The beam then
passes through a variable diaphragm that permits adjustments of the power of the
radiation that reaches the transparent cell that contains the sample. A shutter can be
imposed in front of the diapraghm that completely blocks the beam. With the shutter
open, the radiation impinges on a photoelectric transducer that converts the radiant
energy of the beam to a direct current that is measured with a microammeter.

| Prepared by Engr. Benedict S. Marzan