Atomic Spectroscopy Atomization and Excitation

Atomic Absorption Spectrometry A photon of light promotes an outer electron to a higher energy level Absorption only occurs in the gas phase Involves both atoms and ions Involves discrete energy transfers

Excitation and Emission

Atomic Emission Spectroscopy The heat from a flame or an electrical discharge promotes an electron to a higher energy level As the electron falls back to ground state, it emits a wavelength characteristic of the excited atom or ion

From Skoog et al. (2004); Figure 28-1, p.840

Atomic Absorption and Emission

1. Atoms can exist only in certain discrete states: Non-continuous energy levels. 2. When an atom changes its state, it absorbs or emits energy EXACTLY equal to (E. 3. When the absorbed or emitted energy is EM radiation, (E = hR = hc/P 4. Different atoms, ions have their distinct (Es, thus absorbing or emitting EM(light) at distinct frequencies or wavelengths (lines). Every species has its own barcode. Because of their line spectra, atomic spectroscopy can be used to pinpoint elements directly and easily.

Atomic Line Spectra

Each spectral line is characteristic of an individual energy transition

c h E = hR! n P

Sodium Lines
Absorption

There is no small energy levels such as vibration and rotation levels to be involved. Only electronic energy levels are involved. Even with certain splitting, generally line spectra are generated.

Splitting of Sodium Line

j=l + s
Orbital Angular Momentum : l Spin angular Momentum: s Total angular Momentum: j

Line Width----Figure of Merit: Effective Bandwidth (P1/2

Line Broadening
1. Heisenberg Uncertainty Principle 2. Doppler effect 3. Pressure effect 4. Electric and Magnetic fields effect

Uncertainty Rule: No escape

(t(E uh (t (Rf u1

Upper Limit: life time of the excited state

Lower limit of uncertainty in frequency: (Rf = 1/tlife

Doppler Effect

two order of magnitude larger than uncertainty effect

Pressure Effect
Increased pressure induces increased collision, causing more small changes in ground state energy: Starting points varies.

Atomic Absorption Spectroscopy Instrumentation

Atomizer: Flame or graphite furnace

Atomization Methods

Introduction of Samples

Flame AAS Atomizer

Atomization occurs in a flame created by mixing a fuel with an oxidant. Analyte and background ions are atomized simultaneously. Only a small percentage of the aqueous sample is atomized much of the sample goes to waste

Flame

MOx
Rich in free atoms Most used

Blue luminescence Seldom used

Flame Absorbance Profile

Types of Flame

A range in atomization temperatures can be achieved by changing and varying the fuel/oxidant mixtures

Performance Characteristics of Flame Atomizers

1. Best reproducibility: precision 2. Low sampling efficiency and sensitivity: drain and short time in path 3. Most sensitive part of flame for AAS varies with analyte: sensitivity varies with element must adjust burner position makes simultaneous multi-element detection difficult 4. Different types of analytes require different types of flames: temperature 5. Other non-atomic species are produce in flame: interference and low sensitivity 6. Sample in solution or gas only

Electrothermal or Graphite Furnace Atomizer

Atomization occurs in an electrically heated graphite tube The graphite tube is flushed with an inert gas (Ar) to prevent the formation of (non-absorbing) metal oxides
graphite tube

Graphite Furnace Process

A. Evaporation of solvents at low T B. Ashing - removal of organics, volatile hydroxides, sulfates, carbonates at higher T C. Atomization of remaining analyte at high T.

Performance Characteristics
Entire sample atomized rapidly ( T soar to 2000-3000 oC within ms-s) Sample spends up to 1 s in light path Superior sensitivity (10-10-10-13 g analyte) : QL of solution required Diminished oxidation Solid sample OK Lower precision (5-10 %) Narrower dynamic range

Radiation Source: Requirement

Atomic absorption lines: narrow 0.002-0.005 nm The resolution of the best monochromators: 0.01 nm

Continuous light source

Consequence of continuous light source: 1. Interference: deviation from Beers law Beers law requires single wavelength: the bandwidth of source narrower than an absorption peek 2. Poor sensitivity: only a small fraction absorbed; small slope

Light Source: Emission line from the metal itself

AAS should be very selective - each element has different set of energy levels and lines very narrow BUT for linear calibration curve (Beers' Law) need bandwidth of absorbing species to be broader than that of light source: difficult with ordinary monochromator Solved by using very narrow line radiation sources minimize Doppler broadening pressure broadening lower P and T than atomizer Lasers are also used in research instruments. Since lasers are intense enough to excite atoms to higher energy levels, they allow AA and atomic fluorescence measurements in a single instrument. and using resonant absorption Na emission at 589.6 nm used to probe Na in analyte

Hollow Cathode Lamp

tungsten Metal of interest

HCL Process
300 V potential

* Some consist of several metals

Ne ions bombard cathode and sputter cathode atoms Fraction of sputtered atoms excited, then fluoresce Cathode made of metal of interest (Na, Ca, K, Fe...) different lamp for each element restricts multielement detection Hollow cathode to maximize probability of redeposition on cathode restricts light direction

Spectral Interference
1. Emission or absorption lines overlap, separation < 0.1 : very rare

Al : 3082.15 V : 3082.11

3092.7

Spectral Interference
2. Combustion products that absorb broadly or scatter : diminishing transmittance, positive errors Correction: blank

3. Sample matrix absorption or scattering Positive errors Correction: change to high T flame Others

Chemical Interferences
1. Formation of compounds of low volatility negative errors Correction: A. Higher T flame B. Releasing agent Ca3(PO4)2 + La3+ + Cl- p CaCl2 + LaPO4 stable, non-volatile
To be atomized

C. Protective agent: Ca3(PO4)2 + EDTA p Ca-EDTA + PO43Stable More volatile

Chemical Interferences
2. Reversal of atomization equilibria

In presence of

HCl

H +

Cl

Chemical Interferences
3. Ionization (significant in high T flames) hotter atomization means: more ionization emission from interferents Reducing sensitivity Correction: supply more free electrons But how: Add a metal that can be ionized more easily (ionization suppressor)

Ionization of Metals