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CHEM F313: Instrumental Methods of Analysis: Energy & Electromagnetic Spectrum

This document discusses electromagnetic waves and spectroscopy. It covers: 1. Key terms related to electromagnetic waves like wavelength, frequency, and wave number. 2. The electromagnetic spectrum and the different types of molecular transitions that occur at different energy levels, such as molecular vibration, valence electrons, and spin orientation. 3. Factors that contribute to line broadening in spectra, including collision broadening, Doppler broadening, and the Heisenberg uncertainty principle. 4. Factors that control the intensity of spectral lines, including transition probability, population of states, and path length of the sample.

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0% found this document useful (0 votes)
42 views

CHEM F313: Instrumental Methods of Analysis: Energy & Electromagnetic Spectrum

This document discusses electromagnetic waves and spectroscopy. It covers: 1. Key terms related to electromagnetic waves like wavelength, frequency, and wave number. 2. The electromagnetic spectrum and the different types of molecular transitions that occur at different energy levels, such as molecular vibration, valence electrons, and spin orientation. 3. Factors that contribute to line broadening in spectra, including collision broadening, Doppler broadening, and the Heisenberg uncertainty principle. 4. Factors that control the intensity of spectral lines, including transition probability, population of states, and path length of the sample.

Uploaded by

radhika
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© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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CHEM F313: Instrumental Methods of Analysis

Lecture 02
Energy & Electromagnetic Spectrum
BITSPilani, Pilani Campus
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
BITSPilani, Pilani Campus
Electromagnetic spectrum
Energy Change

Nuclear Inner shell Ionization Molecular Spin Orientation


electrons of Atoms & Vibration
Molecules (stretch, bend)

Valance Electrons
BITSPilani, Pilani Campus
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.

BITSPilani, Pilani Campus


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.

BITSPilani, Pilani Campus


UV-Vis: Instrumentation
(details later)

BITSPilani, Pilani Campus


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
BITSPilani, Pilani Campus

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