Introduction to Optical Atomic Spectroscopy

Identification and Quantification of Elements

X-ray spectrometry: core electrons Mass Spectrometry: trajectories of ions in magnetic fields Optical Spectrometry
Ultraviaolet-visible atomic absorption (AA) Ultraviaolet-visible atomic Emission (AE) Ultraviaolet-visible atomic Fluorescence (AF) Atomization required

Atomic Optical Spectra

Possible Transitions for Na

Terms SPDFG: total orbital quantum number S: L=0 P: L=1 D: L=2 Subscripts (S): total spin quantum number Superscript: spin multiplicity: (2S+1)

Atomic linewidths
Quantum states involved in the transition have single discrete energies. Why do atomic spectra signals (absorption, emission, etc) have a finite width covering a narrow range of energies? Sources of line broadening
Uncertainty principle Doppler broadening Pressure effects due to collision Electric and magnetic fields

Uncertainty
Transition states have a finite lifetime The breath of a line apporaches zero only if the lifetimes of th etwo states involved in the transition approach infinity Line widths due to uncertainty broadening are called natural line widths
~10-4

t 1 1 t h t

Et h

Doppler Broadening
Motion affects the frequency perceived by a detector If the particle movement is toward the detector the wavelength is shorted (high frequency) If the particle movement is away from the detector the wavelength is lengthened (low frequency) For an ensemble of particles in random motion there arises a symmetrical distribution around the source unaffected wavelength to higher and lower wavelengths Doppler broadening increases the line width by two orders of magnitude higher than the natural line width

v c

0 : unshifted
v : velocity of atom

Pressure Broadening
Collisions between atoms or ions causes small changes in energy levels, thus a range of absorbed or emitted wavelengths Pressure broadening increases the line width by two to three order of magnitude In Hollow cathode lamps, broadening is dominated by pressure effect High pressure mercury and Xenon lamps : pressure broadening leads to continuum spectra

Temperature Effect on Atomic Spectra

Boltzmann equation Temperature determines the distribution of species between energy states Example 8-2
Nj N0 = Ej gJ exp kT g0

N 0 : ground state N j : excited state T : absolute temperature E j : difference in energy k : Boltzmann con tan t = 1.38 10 23 J / K g : statistical weights

 Calculate the ration of sodium atoms in the 3p excited state to the number in the ground state at 2500 and 2510K. The wavelength emitted by atoms excited to the 3p state is 589.3 nm. Small fraction thermally excited: 0.017%: minimal effect on absorption or fluorescence methods Emisson (at this temperature) results from only the small fraction of atoms excited Increase of temperature by only 10K results in an increase of 4% in the population of the excited state
E j = h = h gj g0 Nj N0 Nj N0 = 6 =3 2 c

= 6.626 10 34 Js

3.00 108 m / s 589.3 10 9 m

= 3.37 10 19 J

3.37 10 19 J = 1.72 10 4 = 3 exp 1.38 10 23 J / K 2500 K 3.37 10 19 J = 1.79 10 4 = 3 exp 1.38 10 23 J / K 2510 K

Temperature Effects
In atomic absorption an increase in temperature usually increases efficiency of the atomization process and hence increases the total number of atoms in the vapor. Line broadening increases at high temperature. The Doppler effect is increased as atoms are moving faster. Ionization increases as the temperature increases

Atomization Methods
Flame: 1700-3150C Electrothermal vaporization: 1200-3000C Inductively Coupled Plasma: 4000-6000C