CHEM F313: Instrumental Methods of Analysis

Lecture 02
Energy & Electromagnetic Spectrum
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Electromagnetic waves

TWO principle methods for signal enhancement

1. Wavelength, l 6. Monochromatic/Polychromatic
2. Frequency, 7. Interference
3. Wave number, 8. Polarised/non-polarized
4. Radiant Power, P
5. Intensity, I
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Electromagnetic spectrum
Energy Change

Nuclear Inner shell Ionization Molecular Spin Orientation

electrons of Atoms & Vibration
Molecules (stretch, bend)

Valance Electrons
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 Width of Spectral Lines
Irrespective of the improvement of the instrumentation (thin slit) the
line width of the spectra are often blurred. Natural line width is
governed by,
Collision Broadening: Due to continual motion in liquid & gas phase,
molecules/atoms collide frequently. Vibration & rotation spectra are
usually affected.
Doppler Broadening: Due to collisions. Random motion creates both
higher and lower frequencies. More effective in gases then liquids
Heisenbergs Uncertainly Principle: E x t = /2 ~ 10-34 J.s ,
which means that lowest energy state is most certain.
E.g. lifetime of excited electronic state is ~ 10-8 s, so, E ~ 10-28 J,
and hence = 108 Hz. This is typically small w.r.t. source (~ 1016
Hz).
For excited electronic spin state lifetime = 10-7 s, which shows
= 107 Hz. But this is comparable with the frequency of such
transitions ~109 Hz, hence a considerably broad signal.

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 Intensity of Spectral Lines
Three important factors controlling the intensity of lines
Transition Probability: governed by the selection rules, easy to
understand pictorially
Population of States: Higher the population of the lower energy
state, higher is the intensity of the line.
Path Length of sample: The relation can be expressed as
I/I0 = e-kcl This is certainly not linear.

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UV-Vis: Instrumentation
(details later)

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Fundamental Laws
If a monochromatic radiation of radiant power P0 travels an infinitesimal distance dx, of
an absorber then, at a constant concentration,

The number of absorbent is proportional to the distance but independent of P

k depends on the wavelength

or, Lamberts Law

Also, the relation between radiant power and concentration can be found out at a
constant distance travelled and a fixed wavelength,

Beers Law
The number of absorbent is proportional to the concentration, C

Combining, and converting to base 10,

or,
is called absorptivity [Lg-1cm-1] if C is in g.L-1 and l is in cm
Or, molar absorption coefficient [Lmol-1cm-1] if C is in molL-1 and l is in cm
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