Chem 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, λ – the linear distance between any two equivalent points of successive waves. (cm, nm,
µm)

λ = c/v

Energy content of a photon, E = hv =hc/ λ

Where:

h = Planck’s 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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 Chem 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.

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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 Chem 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 Snell’s Law:

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:

Where:

I = is the intensity of the incident beam

I = reflected intensity

n & n = refractive indexes of the two media.

Example:

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.

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 Chem 314: Instrumentation Analysis

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

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

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:

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 Chem 314: Instrumentation Analysis

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) BEER’s LAW
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

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 Chem 314: Instrumentation Analysis

Application to Beer’s Law to Mixtures

Beer’s 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 = ε1bc + ε2bc +… + εnbc

A. Deviations to Beer’s Law due to Polychromatic Radiation

~for the wavelength, λ’

P’ = Po’ 10-ε’bc

~for the wavelength, λ”

P” = Po” 10-ε”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 P o’ + Po”. Therefore, the measured
absorbance Am is

Am = log

B. Deviations to Beer’s 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.

A = log

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
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 Chem 314: Instrumentation Analysis

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.

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