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Atom Spec

Chapter 8 introduces atomic spectrometry, focusing on three main methods: optical, mass, and x-ray spectrometry, with an emphasis on optical spectrometry for analyzing elemental composition. The chapter discusses the principles of atomic spectra, energy transitions, and factors affecting line widths, such as Doppler and pressure broadening. It also covers sample introduction methods, highlighting pneumatic nebulization and graphite tube furnaces as key techniques for producing neutral atoms or ions for analysis.

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Özge Vural
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7 views17 pages

Atom Spec

Chapter 8 introduces atomic spectrometry, focusing on three main methods: optical, mass, and x-ray spectrometry, with an emphasis on optical spectrometry for analyzing elemental composition. The chapter discusses the principles of atomic spectra, energy transitions, and factors affecting line widths, such as Doppler and pressure broadening. It also covers sample introduction methods, highlighting pneumatic nebulization and graphite tube furnaces as key techniques for producing neutral atoms or ions for analysis.

Uploaded by

Özge Vural
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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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Chapter 8: Introduction to Atomic Spectrometry

Read: pp. 215 – 228 Problems: 2,4,5,6,9

• Why choose atomic spectrometry?

• Three major types of spectrometric methods for identifying


elements present in matter:
– optical spectrometry (Chap. 8, 9, 10)
– mass spectrometry (Chap. 11)
– x-ray spectrometry (Chap. 12)

• In optical spectrometry, the elements present in a sample are


converted to gaseous atoms or elementary ions and then
analyzed by optical methods.
403.08
Mn
403.31
403.45

Wavelength (nm)

Notice high resolution!

Excellent series of methods for determining elemental


composition in environmental samples, foods and drinks,
potable water, biological fluids, and materials.
Atomic Spectra

• Outer shell or valence electrons


are promoted to unoccupied
atomic orbitals by incident
radiation.
E = hν = hc/λ

• Small energy differences


between the different transitions
– so high resolution instruments
are needed. Na

• Transitions are observed only


between certain energy states.
Figure 8-1a
Na Mg+

Figure 8-1
Mg

Figures 8-2 and 8-3


Chemical Problem

The first excited state of Mg is reached by absorption of 457.1 nm light.


Calculate the energy difference (kJ/mol) between the ground and
excited states.

E = hν = hc/λ

(6.62 x 10 -34 J s)(3.00 x 108 m/s)


E= -9
= 4.34 x 10-19 J/photon
(457.1 nm)(1.00 x 10 m/nm)

(4.34 x 10-19 J/photon)(6.02 x 1023 photons/mol) = 2.62 x 105 J/mol

(2.62 x 105 J/mol) (1 kJ/1000 J) = 262 kJ/mol


Atomic Line Widths

Sources of Line Broadening


1. Uncertainty effect
2. Doppler effect
3. Pressure or collisional
effects
4. Electric and magnetic field
effects

Figure 8-6
Uncertainty Effect
• Spectral lines have finite widths because lifetimes of one or
both transition states are finite, which leads to uncertainties in
transition times.
∆ν • ∆t ≥ 1

• To know ∆ν with high accuracy, then time of measurement,


∆t, must be very long!
• Lifetime of ground state is long, but lifetime of excited state is
short, 10-8 s.
• Line widths due to uncertainty broadening, sometimes called
natural line widths, are on the order of 10-4 Å.
Doppler Broadening
∆λ/λo = v/c v = velocity of moving atom

Encounter wave crests more frequently Encounter wave crests less frequently

Maximum None Mixed

Wavelength of radiation emitted or absorbed by rapidly moving atom


decreases if motion is toward the detector and increases if motion
is away from the detector. Broadening on the order of 10-2 to 10-1 Å.
Pressure Broadening

• Broadening arises from collisions of the absorbing or


emitting species with other atoms or ions in the heated
medium.

• Collisions cause small changes in the ground state


energy levels and, thus, a range of absorbed or emitted
wavelengths.

• Broadening on the order of 10-1 Å.


Temperature Effects

• Temperature influences velocity and, thus, the extent of


Doppler broadening and pressure broadening.

• Temperature also influences the number of atoms in the


ground (N0) and excited (Nj) states

Nj gj ⎛ − Ej ⎞
= exp ⎜⎜ ⎟⎟
N0 g0 ⎝ kT ⎠
where g0 and gj are statistical factors and Ej is the
energy difference between states.

• So temperature should be maintained constant, as


much as possible.
Least effect on atomic absorbance and fluorescence
measurements, because fraction of atoms in ground
state is large.
Greatest effect on atomic emission measurements,
because fraction in excited state is small.
Sample Introduction Methods

• Goal is to produce neutral atoms or simple ions in the gas


phase

• Sample may be gas, liquid/solution, slurry, or solid

• Sample introduction may be continuous or discrete

• Great challenge – generally limits accuracy, precision, and


detection limits of atomic spectrometric methods
Steps in Sample Introduction Process

Several methods for introduction of liquid samples, main one is


pneumatic nebulization:

Figure 8-10
Pneumatic Nebulizer Designs

Concentric Tube Cross-Flow

Figure 8-11
Graphite Tube Furnace

Sample • Liquid or solid samples


• Smaller sample volumes
• More efficient atomization
• Lower detection limits
• Poorer precision
• Slow – requires heat cycles
to dry, ash, atomize

hν

Figure 9-6a

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