Elemental Analysis - Atomic Spectroscopy

Based on the breakdown of a sample into atoms, followed by the measurement of the atoms absorption or emission of light. - Deals with absorbance fluorescence or emission (luminescence) of atoms or elemental ions rather then molecules - atomization: process of converting sample to gaseous atoms or elementary ions - Provides information on elemental composition of sample or compound - UV/Vis, IR, Raman gives molecular functional group information, but no elemental information. - Basic process the same as in UV/Vis, fluorescence etc. for molecules

h
Absorbance

E1 Eo
Fluorescence

Types of Atomic Spectroscopy - AAS

Atomic Absorption Spectroscopy absorption of electromagnetic radiation promotion of electron to higher energy state log of transmittance is proportional to concentration

AA

Lamp

Atomizer+Sample

Monochromator

Detector

Types of Atomic Spectroscopy - AES

Atomic Emission Spectroscopy thermal excitation

M M*

radiative decay to lower energy level

M* M + h

emission signal directly proportional to concentration

AE
Atomizer+Sample Monochromator

Detector

Types of Atomic Spectroscopy - AFS

Atomic Fluorescence Spectroscopy excitation caused by absorption of EMR followed by radiative decay to lower energy state fluorescence signal is directly proportional to concentration

Lamp

AF

Atomizer+Sample

Monochromator

Detector

Most Common AA/AE Techniques

Flame AA and AE Furnace (Electrothermal) AA only Inductively Coupled Plasma (ICP) AE only

Most Common AA/AE Techniques

Flame AA and AE Well established Good speed Moderate sensitivity Few interferences (well understood) Low-moderate cost Operating temperature: 1700-3200C

Most Common AA/AE Techniques

Furnace (Electrothermal) AA only Well established Slow Single element Excellent sensitivity Many interferences Moderate-high cost Operating temperature: 1200-3000C

Most Common AA/AE Techniques

Inductively Coupled Plasma (ICP) AE only Established and growing Fast Multi-element Moderate sensitivity Spectral interferences High cost Operating temperature: 6000-8000C

Atomic Absorption Spectrometry

General Uses
Quantitative (~70 metals, any sample type) Low Concentrations (ppb) Microliter volumes or microgram masses. Well-established and accepted. Biological, medical, clinical Environmental Steel and Metal industry Pharmaceuticals Food industry

Common Applications

Atomic Absorption Spectrometry II

Samples
Almost any liquid, solid or gaseous sample. Microliter volumes or microgram masses. Aqueous samples can be analyzed directly. Complex solutions
Diluted Solvent extraction

Solids can be dissolved/digested

Analysis Time
Sample preparation (0 sec to 24 hr) Analysis after calibration 10 -120 sec.)

Limitations
No information on chemical form of metal Sample prep can be tedious Limited to metals/metalloids Destructive

Atomic Absorption Spectrometry III

Accuracy
Depends on complexity of matrix. Homogeneous solution at 10 LOD 1% Reduced to ~ 3% at LOD.

Linear Range
In single metal mode: 103 above LOD For higher concentrations use dilution.

Detection Limits
Flame AA : 0.1 to 1.0 g/mL Furnace AA : 0.01 to 0.1 g/mL

Flame AAS
Advantages Robust. Easy to use. Fast analysis time. Modest cost. Disadvantages Flammable gases. Detection limits.

Furnace AAS
Advantages g masses & L volumes. LOD 10-100 < flame. No gases. Easily automated. Disadvantages Longer analysis times. Interferences. Higher cost. Lower accuracy (1-5%).

Schematic of AA/AE
AE

AA

Laminar Flow Burner

- adjust fuel/oxidant mixture for optimum excitation of desired compounds
- usually 1:1 fuel/oxidant mix but some metals forming oxides use increase fuel mix - different mixes give different temperatures.

Laminar nonturbulent streamline flow Sample, oxidant and fuel are mixed Only finest solution droplets reach burner Most of sample collects in waste Provides quite flame and a long path length

Types of Flame/Flame Structure Selection of right region in flame important for optimal performance
- primary combustion zone (blue due to emission from C2, CH & other radicals) - not in thermal equilibrium and not used - interconal region - region of highest temperature (rich in free atoms)
- often used in spectroscopy - can be narrower in some flames (hydrocarbon) tall in others (acetylene)

- outer cone - cooler region

- rich in O2 (due to surrounding air) - gives metal oxide formation

Temperature varies significantly across flame need to focus on part of the flame

Primary region for spectroscopy

Not in thermal equilibrium and not used for spectroscopy

Flame profile: depends on type of fuel and oxidant and mixture ration

Maximum Flame Temperature

, , , , , ,

, , , , ,

Most sensitive part of flame for AAS varies with analyte

Consequences: - Sensitivity varies with element - must maximize burner position - multi-element detection difficult

The Flame Process

- For atomic absorbance, fluorescence or emission need to break sample up into atom to observe atomic spectra - Basic steps involved in atomization of solution sample
a) nebulization solution sample, get into fine droplets by spraying thru thin nozzle or passing over vibrating crystal. M+ + A- (solution) M+ + A- (aerosol) b) desolvation - heat droplets to evaporate off solvent just leaving analyte and other matrix compounds. M+ + A- (aerosol) MA (solid) c) vaporization convert solid analyte/matrix into gas phase. MA (solid) MA (gas) d) atomization break-up molecules into atoms. MA (gas) Mo + Ao (gas) e) excitation with light, heat, etc. for spectra measurement. Mo M* f) ionization cause the atoms to become charged. M* M+ + e-

Hollow Cathode Lamp

Process: uses element to detect element 1. ionizes inert gas to high potential (300V) Ar Ar+ + e2. Ar+ attracted to - cathode & hits surfaces 3. As Ar+ ions hit cathode, some of the deposited element is excited and dislodged into gas phase (sputtering) 4. excited element relaxes to ground state and emits characteristic radiation - advantage: sharp lines specific for element of interest - disadvantage: can be expensive, need to use different lamp for each element tested.

Electrothermal (Lvov or Graphite furnace) - place sample drop on platform inside tube - heat tube by applying current, resistance to current creates heat - heat volatilizes sample, atomizers, etc. inside tube - pass light through to measure absorbance

Po

P
Place sample droplet on platform

Electrothermal (Lvov or Graphite furnace) : advantages: - all sample used - longer time of sample in light beam - lower limit of detection (LOD) - can use less sample (0.5 10) disadvantage: - slow (can be several minutes per element or sample) - not as precise as flame (5-10% vs. 1%) - low dynamic range (< 102, range of detectable signal intensity) * use only when there is a need for better limit of detection or have less sample than Laminar flow can use Laminar Flow Burner advantages: - good b (5-10 cm) - good reproducibility disadvantages: - not sample efficient (90-99% sample loss before flame) - small amount of time that sample is in light path (~10-4 s) - needs lots of sample

Inductively Coupled Plasma - ICP

- involves use of high temperature plasma for sample atomization/excitation - higher fraction of atoms exist in the excited state, giving rise to an increase in emission signal and allowing more types of atoms to be detected - plasma electrically conducting gaseous mixture (cations & electrons) - temperature much higher than flame - possibility of doing multiple element analysis ~ 40-50 elements in 5 minutes Advantages - uniform response - multi-element analysis, rapid - precision & accuracy (0.3 3%) - few inter-element interferences - can use with gas, liquid or solids sample