Atomic Spectroscopy

Introduction
With gas-phase atoms or ions, only electronic transitions occur.
Thus, atomic emission, absorption spectra are made up of a limited number of narrow lines.
Transition to or from the ground state is called resonance transition, and resulting resonance line.
Difference among AAS, AES, and AFS

Definition:
1. AAS is the method used in Chemistry where the energy absorbed by atoms is measured.
AES is a similar technique to AAS that measures the energy emitted by the atomic species under
investigation.
2. For the sample introduction, in AAS, there is a separate chamber for atomization of the sample.
However, in AES, atomization takes place step by step upon the introduction of the sample to the
flame.
3. Different energy transfer pathway between different energy level.
Atomic Line Widths
Theoretically, atomic lines will have 0 line width.
However, atomic line widths are affected by:
Natural broadening due to the uncertainty principle,
Doppler broadening, and Pressure or collisional broadening
1. Natural broadening
natural line width - caused by finite lifetime of excited state. (10-5 nm usually)
∆𝑡∆𝜈 ≥ 1，𝜈 = 𝑐𝜆−1 → 𝑑𝜈 = −𝑐𝜆−2 𝑑𝜆
𝜆2 ∆𝜈
|∆𝜆1⁄2 | =
𝑐
2. Doppler broadening
If an atom emits radiation while moving toward the detector, the
waves will be compressed, and the wavelength will be shorter.
In addition, atoms moving toward radiation absorb at higher
frequencies; atoms moving away from radiation absorb at lower
frequencies
3. Collisional broadening
Collisions lead to deactivation of the excited state and thus
broadening the spectral line.
Temperature Effects with Boltzmann distribution
Determines the number of ground state and excited state
Boltzmann equation:
𝑁＊ 𝑔＊ −∆𝐸
= 𝑒 𝑅𝑇 𝑁: 𝑝𝑜𝑝𝑢𝑙𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑠𝑡𝑎𝑡𝑒 𝑔: 𝑑𝑒𝑔𝑒𝑛𝑒𝑟𝑎𝑐𝑦 𝑜𝑓 𝑡ℎ𝑒 𝑠𝑡𝑎𝑡𝑒
𝑁0 𝑔0
3 steps required before measurements are possible in an AAS experiment:
1. Vaporization, 2. Reduction to the elemental state and then 3. Exposure to radiation
The first two steps are accomplished by a flame.
Since flame is at high temperature might have an effect on fraction of atoms in excited state, we can
use Boltzmann equation to explain the effect of flame temperature, when temperature goes higher,
more fraction of the atoms in the flame are excited to the excited state.
Also, from Boltzmann equation, only very small proportion of the absorbing species is in the excited
state from excitation by flame; higher energy transitions much less likely than the lower ones.
Now, we can expect that in the AES experiment, temperature control is very important.
(Sensitive to flame instability for the extremely small fraction)
AAS, instead, temperature isn’t important at all. (Nearly all gaseous atoms are at ground state)
Instrumentation of atomic spectroscopy

1. Sample introduction and Atomizer (Atomization)

Several methods used to vaporize sample from solution
Flame atomization:
Sample sprayed into flame by nebulizer where it undergoes atomization and irradiation.
Graphite furnace atomization, GF (a.k.a. Electrothermal atomization, ET):
Flame is replaced by high-current heated graphite tube. Dried and ashed at lower temperature
(125℃ and 1400℃ respectively) then vaporized at higher temperature (2500℃)
Atomization efficiency is greater, to reduce matrix interference (smaller LOD).

Inductive coupled plasma atomization, ICP (for AES)

Using high temperature plasma (Ar+) for sample atomization (also excitation, 10000K)
Higher fraction of atoms exist in excited state, allowing more types of atoms to be detected, also
making ICP an ideal technique for multielement emission spectrometry.
Sample introduced:
(a) By nebulizer, as the way used in flame.
(b) Laser ablation, high energy laser pulse hit the surface of
solid sample, vaporizing the sample for ICP detection
Required RF power of 1~2 kW to maintain plasma output.
Higher frequency gives a thinner plasma with a wider dynamic
range (like low current HCL lamp) → with less self-absorption
 ICPMS (with mass spectrometry)
Advantages:
Have better limit of detection than those obtained by Graphite furnace AAS (even smaller LOD)
Due to the high temperature of ICP source, it has the ability to operating more complex data with
a minimum of matrix (Higher throughput)
The ability to obtain isotopic information

2. Light source – Why using line light source?

Problems with using continuous light source (UV light, D2 lamp):
Non-monochromatic light may cause source with others λ, which causes only small decrease in
total signal area with large amount of matrix → Atotal from D2 could be viewed as Abackground
Solution is to used light source that has light emission in range of interest (Laser or HCL lamp)
For laser, it’s hard to match with element line of interest.
The Hollow Cathode Lamp (HCL lamp): Characteristic wavelength
Use element (Ar) to detect element (Sample)
Ionized Ar gas to Ar+, then Ar+ goes to cathode (-) and hit surface.
Some of deposited element is excited and dislodged into gas phase.
Background Correction
Problem with working with flame in AAS is that light from flame and source both reach detector.
1. Continuous Source Background correction
Photometer using HCL as its light source: Measures atomic absorption + BKG absorption.
Photometer using D2 lamp as its light source: Measures only BKG absorption.

2. Smith-Hieftje Background correction (Self-absorption correction method)

This method uses the spectrum obtained by lighting with an excessive current to HCL lamp
instead of the D2 lamp light source spectrum of the previous section.
Comparison of Continuous Source and Self-absorption correction method
 3. Beam chopping
Physically block the light source to obtain the light only from the flame

4. Zeeman effect Background correction

Place gaseous atoms into magnetic field cause non-random orientation of atoms

Interference in AAS
1. Spectral interference
Absorbance spectra overlap with nearby bands (unwanted signals overlapping analyte signal)
Can be corrected by Continuous Source, Self-absorption, Zeeman effect correction method.
2. Chemical interference (Refractory compounds) – more common than spectral interference
Low volatility compound: Take Ca2P2O7 as example (Hard to atomized as Ca2+)
Releasing agent: Adding Sr3+ or La3+ forms more stable compound with PO43- than Ca2+
Protecting agent: Such as EDTA that form complex with Ca2+, can easily atomized in flame
Chemical modifier: A chemical modifier is a reagent which is added to a sample to
(a) increase the volatility of the matrix or (b) decrease the volatility of the analyte.
Take one problematic matrices NaCl as example: Adding NH4NO3 convert NaCl into easily
decomposed form to remove this salt form matrix and minimize salt interference.
Formation of Oxide (MO)
Increase temperature of flame (increase atom production) or use less oxidant
3. Ionization interference High flame temp. cause M → M+ + electron
Ionization of analyte atoms decreasing the concentration of neutral atoms
Lower temperature or add ionization suppressor (more easily ionized than analyte)
For example: K+, Na+are good suppressor; or create high electron condition shift equilibrium
4. Physical interference Viscosity, gas flow rate, etc.